i

2010 RIGID AND FLEXIBLE FOAMS REPORT

TABLE OF CONTENTS

Page

1) EXECUTIVE SUMMARY ES – 1

2) FOREWORD 1

3) CHAPTER 1 – TRANSITIONAL STATUS 3

4) CHAPTER 2 – TECHNICAL OPTIONS 40

5) CHAPTER 3 – BANKS AND RECOVERY OPTIONS 56

Appendices

APPENDIX 1 – REVIEW OF ALTERNATIVE BLOWING AGENTS A1 – 1

APPENDIX 2 – ALLOCATION OF COUNTRIES TO REGIONS A2 – 1

APPENDIX 3 – UNEP FOAMS TECHNICAL OPTIONS COMMITTEE A3 – 1
ES - 1

2010 RIGID AND FLEXIBLE FOAMS REPORT

EXECUTIVE SUMMARY

Executive Summary

E.1 Introduction

Not since the initial decision to phase-out CFCs in the early 1990s has the foam sector

faced a period of such uncertainty. Although a large proportion of the industry has previously

settled on hydrocarbons or CO2 (water) as their blowing agent of choice, there are increasing

pressures to improve the thermal performance of foams – primarily in the appliance sector, but

also in some construction and transport applications. Coupled with this, there are pressures to

limit future use of saturated hydrofluorocarbons (s-HFCs) because of their high global warming

potential, and to phase these down where possible. Finally, there is the time-certain schedule for

phasing out HCFC use in Article 5 countries, but substantial uncertainties remain about the

optimal choice of alternatives. These three trends are placing unparalleled stresses on the sector

and there is a significant divergence of opinion at this time about the most appropriate way

forward, particularly as there are a growing number of emerging alternatives to consider. The

following sections provide further background on the issues being faced.

E. 2 Foam Market Dynamics

Growth in thermal insulation foams continues to be driven by increasing energy

efficiency requirements in appliances, transport and buildings. Space constraints in the built

environment (e.g. cavity dimensions) have driven dramatic shifts from fibrous products to foam

products in some localised markets to meet the required thermal performance. However, fibre has

largely maintained its share through growth in the residential refurbishment sector where cost is a

prime issue. An additional downward trend on foam use in non-Article 5 countries has been the

on-going shift of appliance and refrigerated equipment manufacture to other regions where costs

of manufacture are lower. The latest extension of a graph for Western Europe shown in previous

reports (see overleaf) indicates that this combination of factors has led to only a small net shift to

the overall foam/fibre balance despite the turbulence of individual sectors.

Nonetheless, the same region saw overall growth in thermal insulation sales to the

domestic and commercial building sector of over 20% in the period between 2001 and 2008

despite the impact of the global downturn in 2008, thereby driving demand for appropriate

blowing agents. This is likely to be representative of other non-Article 5 regions responding to

the parallel drivers of climate change policy and energy security.

In Article 5 countries, the growth in demand for thermal insulation has been even starker

than for non-Article 5 countries in view of the increasing manufacturing base for global

appliances and the recognition that energy efficient buildings have a major contribution to make

in combating climate change for Article 5 countries. As an example, the use of PU Spray Foam
ES - 2

in China is understood to have grown to 70,000-80,000 tonnes, making it already the second

largest market in the world for PU Spray Foam, with only the United States market larger.

66.5%

62.0% 59.5% 59.2%

32.0% 36.6% 39.2% 39.7%

1.5% 1.4% 1.3% 1.1%

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1990 1995 2001 2008

Market Share

Year

Variation of Insulation by Product Type (1990-2008) in Western Europe

Other

Cellular polymer

Fibrous

Source; IAL

E.3 Transitional Status

As of 2010, HCFC phase-out is virtually complete in all non-Article 5 countries, with

XPS in North America being the last major sector to make the transition. In this instance, the

technology choice has been saturated HFCs, reflecting the demanding product range and process

requirements that the XPS industry has in the region. Experience from this transition has made

the industry wary about committing to any further transitions in the medium term, since proving

emerging alternatives in these applications will involve substantial further effort. As shown in the

graph below, the main growth in blowing agent use between 2005 and 2008 had occurred with

hydrocarbons, although there was also some additional use of HFCs. By contrast, only a very

marginal further decline in HCFC use had taken place, highlighting the fact that the XPS sector

in North America was not able to address its usage of HCFCs in the period to 2008, but was able

to do so prior to the phase-out deadline in 2010.
ES - 3

-120000

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

CFC HCFC HFC HC CFC HCFC HFC HC

Developed Developing

Changes in Blowing Agent Consumption (toones)

Changes in Blowing Agent Use by Type/Region

Changes in Blowing Agent Use 2001-2005 compared with 2001-2008

2001-2005

2001-2008

In Article 5 countries, the phase-out of remaining CFC use has been completed with the

main replacement for these residual applications being HCFCs. Growth has also continued in

hydrocarbon use, largely driven by a further increase in the appliance manufacturing base in these

regions.

Overall, the comparison between 2001-2005 and 2001-2008 time periods illustrates that

the changes in the last four years have been relatively moderate compared with those of the

previous four years.

Although hydrocarbons continue to be the primary solution in non-Article 5 countries,

there is pressure in some sectors to further optimise these solutions by blending. While

cyclopentane continues to play an important role in optimising blend performance, other

components such as unsaturated HFCs (u-HFCs or HFOs) and methyl formate are also being

assessed at this time. Early work on unsaturated HFCs suggests that they deliver better thermal

performance than their saturated counterparts, although toxicological work remains to be

completed for those substances yet to be commercialised. In the interim, there is evidence that

some enterprises manufacturing appliances in developing countries are already blending

saturated HFCs with hydrocarbons to meet energy requirements.

Decisions need to be made at short notice within HCFC Phase-out Management Plans

(HPMPs) on the choice of alternative to HCFCs in Article 5 countries. The prioritisation of

‘worst first’ embodied within Decision XIX/6 puts a strong focus on dealing with HCFC-141b
ES - 4

applications in the early phases of implementation. Nevertheless, some countries are finding it

easier to manage their compliance issues by phasing the foam sector transitions according to the

ease with which projects can be implemented and the magnitude of their impact. Shortfalls are

then being made up from other sectors.

E.4 Likely Future Scenarios

In general terms, the future technology selections in both Article 5 and non-Article 5

countries continue to be uncertain. This makes it particularly difficult to forecast the precise

blowing agent mix in the period to 2020 and the impact that this may have on bank composition

at that time.

As noted above, HCFC phase-out in Article 5 countries continues to be a serious source

of unease. In several sectors, particularly in rigid PU foams, previously identified low-GWP

alternatives to HCFCs have yet to be fully proven in the field or require high investments. This is

particularly important since many of the enterprises expected to take up these technologies are

small medium enterprises (SMEs) and have little, if any, internal capacity to optimise

formulations. There is evidence that measures to manage flammability for methyl formate may

require system houses to reformulate with more compatible polyols in order to reduce the risk.

However, in a limited number of cases it may be more productive to blend methyl formate in the

isocyanate component to obtain the required foam properties whilst avoiding flammable blends.

There continues to be a need to characterise the performance of foams made from lowGWP alternatives in the range of applications envisaged. This is an on-going exercise, but is

particularly important for technologies that do not have a significant history of use in non-Article

5 countries. The role of the Pilot Projects sponsored under the Multilateral Fund are especially

relevant here and the work of UNDP on methyl formate, for example, has already cleared the

way for wider use in the flexible moulded and integral skin sectors with potential for others to

follow.

In non-Article 5 countries, the primary future interest is in further improving energy

efficiency. However, an additional pressure may arise from proposals to see the phase-down in

use of saturated HFCs. Apart from initiatives signalled under the Montreal Protocol itself, there

is growing interest in seeing such a measure as part of the re-cast F-Gas Regulation in Europe.

This may serve to strengthen research efforts in non-Article 5 countries towards low-GWP

solutions and, in particular, towards the intelligent use of blends. There may be added spin-offs

for Article 5 countries from this work, but these are unlikely to emerge in time for incorporation

within relevant HPMPs.

For the immediate challenge of phasing out HCFC-reliance in Article 5 countries, there

are a number of obstacles. The time pressure to resolve these only serves to add to the complexity

of the situation and it may be that a number of not fully proven solutions need to be adopted in

the short-term, with the potential downside risk to enterprises and investors alike. Another

consequence could be that enterprises choose to minimise their risks by choosing proven, but
ES - 5

sub-optimal, technology solutions (e.g. high GWP or less energy efficient solutions) with the

intent of making a second conversion when more appropriate solutions have become established.

E.5 Banks, Emissions and Destruction

The management of ODS banks in appliance foams is currently being addressed by a

variety of regulatory and voluntary frameworks and using a range of fully automated, semiautomated and manual technologies. Although there is evidence to suggest that fully automated

approaches provide the most comprehensive recovery potential, the relevant cost-abatement

curves would suggest that some semi-automated processes will have a place in the on-going

management of ODS banks, particularly in areas where population densities are low or

investment is restricted.

Efforts have been made to further characterise foam inventories in a number of regions.

The flow of ODS-containing foams into the demolition waste stream from buildings is currently

low and is likely to remain so for at least the next decade for most product types. Although the

economics of recovery vary by region and are influenced by wider demolition waste management

frameworks, even the most favourable circumstances lead to costs of above $100 per tonne CO2

saved on average. There will be a need for further innovation in the longer-term if recovery from

this source is going to become economically feasible.

Considerations will continue into the most appropriate strategies for ODS bank

management in foams, with particular focus on ensuring that CFC capture from existing

appliance-based banks is optimised before those opportunities are lost. This may involve the

need to look at efficient ways of transferring existing technologies from non-Article 5 to Article

5 environments. The most appropriate funding mechanisms for such action are still under

discussion, but a conclusion needs to be reached soon if opportunities are going to be grasped.

Although less emissive than the refrigeration and air conditioning sector, the foam sector

continues to represent a substantial bank of long-lived ODS which provide opportunities for

future management. Time pressures for management initiatives vary by sector, but ultimate

policy decisions will depend on the emerging cost abatement curves on a wide range of other

ozone layer protection and climate measures. It remains to be seen whether or not the recovery of

ODS from buildings will become a viable option given the scattered nature of the sources

involved and the efforts required for recovery.

E.6 Specific Regional Messages

Developed Countries

 The growth of appliance foams and blowing agent use will continue broadly with general

economic drivers, since markets are largely saturated. However, there may continue to be

shifts in manufacturing location which will influence regional blowing agent consumption

trends.
ES - 6

 Hydrocarbons are now almost fully optimised for appliances, but the relentless drive for

energy efficiency is encouraging more focus on cyclo-pentane as a component of blends and,

beyond that, interest in unsaturated HFCs (HFOs), which themselves are showing better

potential thermal performance than current liquid HFCs. It may be that there is some switch

from hydrocarbons to HC/u-HFC blends in future as well as a possible switch in North

America from liquid HFCs directly to unsaturated HFCs over time depending on the future

HFC policy in the United States.

 The growth in blowing agent demand for construction applications is driven by energy

efficiency in new and existing buildings; there has been a slow-down in the construction of

new buildings because of global recession but retrofitting continues with spray foam and

other foam products (boards, etc). Nevertheless, growth in the demand for insulation foams

has been dramatic over the last ten years with changes in market share between foam and

fibrous insulation over that period, driven by the requirement for increased thicknesses and a

relatively buoyant construction market.

 Hydrocarbons are the dominant blowing agent in the construction sector, with the exception

of spray foam where s-HFCs continue to dominate due to safety issues, although there is

likely to be a further proliferation of blends – perhaps with u-HFCs (HFOs) and/or methyl

formate – particularly where the thickness requirements for insulation are perceived to be

becoming unmanageable.

 In extruded polystyrene, the long-term future for blowing agent selection is still unclear, with

a significant range of technologies in current use. The emergence of u-HFCs (HFOs) may

prove of interest as a replacement for gaseous HFCs, particularly as a component of blends.

Pressure for transition is likely to be greater in Europe where the F-Gas Regulation is

currently under review. However, in North America there are no further plans to make

transitions in the next 10 years since the transfer to gaseous s-HFCs has only just been

implemented as of 2010.

Developing Countries

 Economic growth rates in several key developing countries are likely to drive demand for

appliances and other consumer goods over the coming years which will be reflected in the

expected growth in demand for blowing agents.

 Since the appliance market is becoming largely a globalised market, future blowing agent

selection is largely expected to follow the same patterns as in developed countries.

 Some appliance manufacturers have been or are considering moving from cyclopentane to

blends of cyclopentane and HFCs to meet emerging energy efficiency standards and to better

meet existing energy standards for products exported to developed countries.
ES - 7

 Focus on insulation materials for the construction market and, in particular, foam products

varies substantially by developing country region, influenced primarily by climatic aspects

and the ability to invest in infra-structure.

 There is evidence of considerable effort to insulate both new and existing buildings in China

and this has driven demand for PU spray foam as one of the most energy efficient options.

Substantial growth in EPS/XPS has also been observed. However, in recent years, a few high

profile fires in cities such as Beijing and Shanghai have resulted in stricter regulations that

may limit the future use of organic insulation materials for residential buildings.

 There is much less clarity about the choice of blowing agent for the small/medium size

enterprises in the construction sector and a variety of technology options (including preblended hydrocarbons, methyl formate, CO2(water), liquid s-HFCs and u-HFCs) could all be

used to some degree.

 Although methyl formate has SNAP approval by the US EPA for PU spray foam

applications, it is still not clear whether the market will view the flammability issues as

sufficiently differentiated from hydrocarbons to drive uptake. There is likely to be some use

of methyl formate in those integral skin applications where CO2(water) is not already

established.

 Although commercialisation of the various u-HFCs (HFOs) under consideration is likely to

occur slightly earlier than previously expected (perhaps 2013-2015), these technologies are

still likely to be too late for the bulk of HCFC-141b transitions. Therefore two-step

transitions may be necessary to take advantage of their properties. Since the investment costs

are likely to be minimal for such technologies, a two-step strategy might be appropriate

where the economics support it.

 Work on ‘three-stream’ technologies for spray foam (e.g. super-critical CO2 and gaseous uHFCs) may allow an earlier transition in some instances, although the investment

implications are still being assessed.
1

FOREWORD

DATA AVAILABILITY

There is no single reference source for the consumption of blowing agents on a global basis. This

is because most bottom-up quantitative assessments are carried out at country or regional level.

However, supply-side information is available for some blowing agent types at the global level.

For example, the fluorocarbon industry has published this data on relevant fluorocarbons at

hemispherical level through the AFEAS project. However, this activity was recently

discontinued. There has been an understandable reluctance by blowing agent manufacturers to

provide supply-side information at greater levels of disaggregation because of disclosing valuable

confidential information and ultimately the risk of contravening competition law.

Without a reliable, comprehensive source of data, the Foams Technical Options Committee

(FTOC) has developed its own set of data based on information gained from a variety of the

above sources over a period of years. From this a model has been assembled to characterise

consumption – past, present and future. During each Assessment period, FTOC members are

encouraged to research information at regional level. However, this is never expected to result in

a comprehensive picture of usage patterns at any one juncture, but the information gained

provides a cross-check on the projections contained in the existing FTOC model. Adjustments

can then be made based on the robustness of the information obtained.

In this Assessment, the outputs of this process are reported for 2008, which is the latest year for

which data could be accessed by the Committee. However, anecdotal qualitative information is

conveyed for the subsequent period to 2010 where this is known.

The data is reported by blowing agent type and by region, with developed countries being divided

into four regions and developing countries into the seven. The country allocation is provided in

Appendix 3. It should be noted that ‘Russia and the Former Soviet countries’ is a new

designation, which replaces ‘Countries with Economies in Transition (CEIT)’. Although not all

of these countries would now be classified as ‘developing’ the allocation is maintained in order

to provide continuity with previous Assessments.

LEVELS OF CONSENSUS

The Assessment has proved the most challenging to date in which to reach consensus for the

FTOC. This is partly because there is a high level of uncertainty in the likely success of

competing alternative blowing agents. This, in turn, arises from the fact that there is little

previous experience with many of these alternatives in developed countries. With the future of

some blowing agent options resting in the balance and pressures to make choices in a number of

developing countries, there has been and understandable culture of claim and counter-claim. The

FTOC has not been immune from these claims and counter-claims and, in the absence of sound

scientific evidence or practical experience, it has been impossible to resolve some differences of
2

opinion. However, in most instances a strong majority view has emerged. One of the focal points

of these differences has been methyl formate technology, which has become something of a

‘cause célèbre’, since its promotion in some quarters has influenced the funding basis for many

MLF projects. The FTOC remains sceptical about some of the claims made for the technology,

but a minority believe that these claims either have been, or can be, substantiated. In dealing with

this situation, the following statement has been agreed as an appropriate expression of the status:

Although the majority view of the Committee is that the use of methyl formate

in rigid foam is unproven, a minority of members - particularly the protagonists

of the technology - contest this view, arguing that usage is already occurring or

has been sanctioned. A further aspect on which there is a discrepancy of view is

over the significance of the flammability issue, with the majority aligning with

the text of this report. Key areas of dispute are annotated by footnotes.

The co-chairs of the FTOC advocate that readers approach the relevant sections of this report

with this caveat in mind.
3

CHAPTER 1: TRANSITIONAL STATUS

POLYURETHANE FOAMS

RIGID POLYURETHANE FOAM

NON-CONSTRUCTION APPLICATIONS

This sector includes domestic refrigerators and freezers, commercial refrigeration units, water

heaters and refrigerated transport applications. It does not include miscellaneous non-insulating

applications.

REFRIGERATION EQUIPMENT AND APPLIANCES

Developed Countries

Domestic Refrigerators and Freezers

- Current market trends

The manufacture of domestic refrigerators and freezers continues across most of the developed

world, although there is an increasing shift of production from developed to developing

countries. Current estimates suggest that the split is now 45%:55%.

Polyurethane foam continues to dominate the market for refrigerator and freezer insulation, with

more sophisticated technologies such as vacuum panels still being limited to very specialist

applications. However, it is noted that one manufacturer [Panasonic] has recently re-introduced a

model containing such panels into Europe and there is also some continuing use of vacuum

panels (based on open-celled foams) in Japan for the walls of some models. One of the shortcomings observed with vacuum panels is that they have low thermal inertia when compared to

foam, which leads to more rapid warm-up in the event of a power outage.

Further increases in the thermal performance of domestic refrigerators in Europe are expected to

continue, but it is not yet clear whether this will lead to increased foam use, bearing in mind that

space is usually at a premium. However, continued trends towards North American styles of

cabinet refrigerator will permit increased foam usage per unit. In Japan the market is relatively

static, although showing little sign of decline, partly because the country continues to be a net

importer of white goods (1.9 million produced versus 4.5 million sold). As in Europe, North

America will see further increases in energy efficiency requirements over the next five years. In

the United States of America, the Department of Energy had already set a new rule for domestic

appliances being manufactured in 2014 and onwards. These requirements are likely to be met by

a combination of compressor efficiencies, increased foam use and potential changes to the

blowing agent selection.
4

- Current blowing agent selection

The choice of blowing agent in developed countries as a whole is illustrated in the graph below.

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

16,000

18,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - Dom. Appliances 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

The divide between the North American market and the rest of the developed world continues as

the domestic appliance industry continues its use of HFC-245fa and, to a lesser extent HFC-134a

in refrigerators and freezers. With the US Department of Energy continuing to demand increasing

minimum energy standards across the industry it seems unlikely that the bulk of the industry will

consider a move out of saturated HFCs until unsaturated HFCs (HFOs) such as 1234ze(Z) and

1336mzz and other still undisclosed molecules are commercially available. However, there are

some US manufacturers who have gained experience of manufacturing with hydrocarbon in

Mexico and may still consider a switch to HCs in the United States as their ultimate solution.

Indeed, one is already reported to have switched one plant to hydrocarbons.

Meanwhile, in Europe and elsewhere, the experience with hydrocarbons is well established and

increasing energy efficiency demands continue to be met, partly as a result of on-going

improvements in hydrocarbon technologies. It is therefore likely that European manufacturers

will stay with their choice for the foreseeable future, even though there is some interest in

evaluating unsaturated HFCs – particularly where these are exhibiting superior thermal

performance. In Japan, the market is fully settled on hydrocarbons with cyclo-pentane and

cyclo/iso blends being amongst the blowing agents of choice.
5

Other Appliances

- Current Market Trends

This sector covers a number of product types including water heaters, vending machines, display

cabinets and commercial freezers. The widespread use of vending machines across the hotel

industry in the United States and their relative size, makes the North American market for foams

more significant than other regions.

Despite the drive for improved energy efficiency, the market is seen as relatively static from a

technology perspective with size being a less significant constraining factor than it is in the

domestic sector. This has allowed the use of less efficient insulation types and has made the

choice of blowing agent less significant.

The situation is rather different for supermarket display cabinets, where occupied floor area is an

important factor. Nonetheless, the energy efficiency of such supermarket systems is often

dictated by the choice of refrigerant delivery system (distributed versus stand-alone). It is only in

the stand-alone cases, where the foam technology choices are likely to be critical.

- Current blowing agent selection

The graph below illustrates the spread of blowing agent choice as at 2008:

0

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

4,500

5,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - Other Appliances 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
6

At this point in time, there was some residual use of HCFCs in this sector in North America. This

was partly as a result of the fact that regulatory requirements were only just taking effect in the

US. However, there was also some continued use in Canada, since the phase-down there

continues to progress on a tradable allowance system.

In the North American vending machine sector, there has also been some use of CO2 (water)

systems as well as some emerging acceptance of methyl formate in the application. In 2008, the

use of methyl formate was nominal (perhaps 125 tonnes [3-4%]), but there is an understanding

that it may have grown further since then to perhaps about 5%.

Reefers and Refrigerated Transport

- Current Market Trends

This sector covers both the manufacture of reefers (refrigerated containers) and the manufacture

of other refrigerated transport bodies (e.g. insulated tanks and truck bodies). The sector is

distinguished from others by the fact that the polyurethane foam system is injected into a cavity

rather than constructed from pre-fabricated parts (e.g. discontinuous steel-faced panels). Over

50% of all foam in this sector is manufactured in developing countries indicating the dominant

position that China holds in the global manufacture of reefers.

- Current blowing agent selection

0

200

400

600

800

1,000

1,200

1,400

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - Reefers & Refr. Transport 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
7

The graph of consumption in developed countries shows the substantial variations in blowing

agent choice across the regions, with the European region focusing on the use of hydrocarbons,

whilst Japan and North America are largely reliant on HFCs. As with other appliances, there was

some residual reliance on HCFCs in 2008 in North America – primarily in Canada.

Developing Countries

Domestic Refrigerators and Freezers

- Current Market Trends

The manufacture of domestic refrigerators and freezers in developing countries is dominated by

production by North East Asia (including China and South Korea) and Latin America. In China

alone it is estimated that more than 300,000 tonnes of PU foam was consumed in 2008 in the

domestic refrigerator and freezer market alone. Growth rates are running at around 8% per

annum based on both domestic growth and the shift of production capacity from other countries.

In Latin America, the market has been growing at 5-7% per year, but has been influenced in the

post-2008 period by some Government intervention to increase refrigerator ownership and to

catalyse the replacement of old, inefficient units. The market, particularly in Mexico and

surrounding countries, also continues to be influenced by the relocation of production from the

United States and the export demand that this provides.

- Current Blowing Agent Selection

The choice of blowing agent in developed countries as a whole is illustrated in the graph below.

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

16,000

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - Dom. Appliances 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
8

The market in developing countries is split between the use of hydrocarbons and HCFCs. There

is also a small amount of HFC use for the export market to North America in the Latin American

region.

The original decision to invest in hydrocarbon technology was driven, in part, by the likely

demand arising from large populations, which in turn led to perceived economies of scale. An

additional factor in the direct transition from CFCs to hydrocarbons in the previous phase was the

active promotion and encouragement provided under the Multilateral Fund, which offered

additional support to leap-frog HCFCs in this sector.

Other Appliances

- Current Market Trends

In contrast with domestic appliances, only just over 25% of ‘other appliances’ manufactured

globally are made in developing countries, with the bulk of these being in China. As noted for

developed countries, the range of product types is very diverse. However, there is typically

greater demand for small-scale display cabinets in developing countries driven by the size of

retail outlets.

- Current blowing agent selection

0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - Other Appliances 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
9

As can be seen in the graph above, virtually the total blowing agent demand in this sector in 2008

was for HCFCs. There is now interest in hydrocarbons and methyl formate. Accordingly, this

sector is reliant on the delivery of HCFC alternatives under Decision XIX/6 initiatives. Options

are discussed further in Chapter 2.

Reefers and Refrigerated Transport

- Current Market Trends

Although refrigerated transport units (e.g. insulated tankers and refrigerated truck bodies) are

manufactured throughout the developed world for local use, the bulk of global refrigerated

container manufacture has shifted to China based on unit pricing – partially derived from

economies of scale. This market has grown relatively rapidly and, as an in-situ process has

needed to be based on proven technologies for the most part.

- Current blowing agent selection

0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - Reefers & Refr. Transport 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

As can be seen from the graph above, main blowing agents currently in use are HCFCs, and this

is almost exclusively HCFC-141b. There is also some reported use of HFC-134a in Latin

America, although the precise application is not known. It is expected that a froth foaming

process would be practised in this instance.
10

CONSTRUCTION APPLICATIONS

This sector covers all applications of rigid polyurethane foams in building and

construction, including the use of foamed panels in large-scale walk-in cold storage facilities,

which are typically considered as temporary buildings.

Developed Countries

PU Boardstock

- Current Market Trends

The growth in use of PU (incl. PIR) boardstock products has been dramatic in some markets,

particularly where cavity wall constructions are common and the minimum energy efficiency

requirements cannot be met with less efficient insulation types such as mineral fibre. There is a

trend toward incorporating boardstock products in external thermal insulation construction

systems (ETICS) for the refurbishment of solid walls. Although these typically have a payback

within their lifetimes (i.e. net negative whole life cost), they are amongst the more expensive

renovation options. Accordingly, fibre insulation has made ground in on-going residential loft

insulation upgrades as a more cost-effective renovation strategy, where it can be applied.

- Current blowing agent selection

0

5,000

10,000

15,000

20,000

25,000

30,000

35,000

40,000

45,000

50,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Boardstock 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
11

The bulk of the polyurethane boardstock market has transferred to hydrocarbon (initially cyclo

pentane but now more typically n- or iso-pentane), with only very minor use of HFCs in North

America. As can be seen, consumption levels in Japan are relatively low based on the fact that

PU Spray systems are a more prevalent way of insulating than PU boardstock in that region. No

further transitions are expected in developed regions in the near future.

PU Continuous Panels

- Current Market Trends

The growth of the polyurethane composite (sandwich) panel market has continued apace in the

period since the last Assessment. These panels can typically be faced with steel, aluminium or

other metallic surfaces and are increasingly being marketed as architectural panels. In some

instances, they are now being designed to incorporate PV solar panels and offer the potential of

contributing strongly towards zero-carbon building solutions now being demanded in some

countries.

- Current blowing agent selection

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

16,000

18,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Continuous Panel 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

There has been retention of HFCs in some countries in Europe based on the requirements to meet

certain regulatory and insurance criteria with respect to fire. However, increasingly, hydrocarbon
12

is seen as the long term solution in this sector, since the thickness of foam requirements is driven

more by panel strength requirements than it is by thermal performance per se. Typical panel

thicknesses for new buildings can be in the 80-100mm range. As can also be seen from the

relevant graph, this technology is far more established in Europe than elsewhere. However,

growth rates are rapid in parts of North America and in the Rest of the Developed World

(RODW). There was, in 2008, some residual use of HCFC technology in Canada.

PU Discontinuous Panels

- Current Market Trends

There has been a level of conjecture about the relative size of the discontinuous panel market

sector as a proportion of the total metal-faced panel industry. Some projections have the absolute

size of the discontinuous panel market staying relatively static – arguing that increased demand

will be met exclusively by the continuous sector as investments respond to economies of scale.

Others, including this Assessment, argue that, where market penetration is spreading

geographically, fledgling production facilities will always start in a discontinuous fashion. In the

end, it is the transport costs of finished products that probably dictates the final outcome and this

will be further reviewed in subsequent Assessments.

- Current blowing agent selection

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Discontinuous Panel 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
13

Again Europe has the bulk of this market with the blowing agent choice being split between

HFCs and hydrocarbons depending on the prevailing response to the risk of handling

hydrocarbons in discontinuous processes. As for the continuous panel scenario, there was some

residual use of HCFCs in North America as at 2008.

PU Spray Foam

- Current Market Trends

As noted under the PU boardstock section, this technology is a major component of the Japanese

insulation sector and spray foam remains the most significant market on a per-capita basis. In

North America, there are two distinct product types: - a low density infill product for gap-filling

between timber studs (primarily to avoid air infiltration) and a higher density thermal insulation

material for more technically demanding applications such as commercial flat-roofing. In Europe,

the product is typically used on flat-roofed residential buildings in Southern Europe (e.g. Spain

and Italy). The technology is seen to have a particular role in cost-effective renovations in these

regions.

- Current blowing agent selection

0

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

4,500

5,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Spray 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

The primary blowing agent choices for this technology in developed countries are HFCs. This

can be either HFC-245fa (primarily in the United States) or HFC-365mfc/227ea blends (more
14

prevalent in Europe). The low density in-fill foams used in North America are typically

CO2(water) blown. There is also significant use of super-critical CO2 in Japan, although this has

not been graphed separately at this stage, since CO2 consumption data has been harder to verify.

Nonetheless, it is estimated that CO2-based technologies as a whole represent the majority of

consumption in the Japanese market.

PU One Component Foam

- Current Market Trends

This is a predominantly European market arising from the construction methods used with brick

and block constructions. The product is based on a moisture-cured system (hence the term ‘onecomponent’) and is used primarily on site. The market is highly sensitive to construction activity,

particularly in the residential sector, but is likely to benefit from renovation activities also.

- Current blowing agent selection

0

1,000

2,000

3,000

4,000

5,000

6,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU One Component 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

Although hydrocarbons are noted as the primary blowing agent in Europe, this analysis needs to

be enhanced further in future Assessments since, although many formulations are based on

blends, one of the principle components is believed to be dimethyl either (DME) and other

similar products. Ethers would typically qualify as oxygenated hydrocarbons (HCOs) and would

be accounted accordingly in future analyses.
15

PU Pipe-in-Pipe (including moulding of pipe sections)

- Current Market Trends

This market has historically been strong in centralised economies where the provision of heat to

large residential complexes is delivered from a central heat source. These district heating systems

have become more significant now in other regions where the advent of combined heat and

power (CHP) systems has encouraged similar underground pipe solutions. Some of these systems

can now be on quite a small-scale (so-called micro-CHP).

- Current blowing agent selection

0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

2,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Pipe-in-Pipe 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

The major market for this approach is in Europe where hydrocarbon technologies have proved

fully operable for the pre-insulated pipes required. There is also some minor use of HFCs.

PU Block – Pipe Section

- Current Market Trends

Compared with other polyurethane markets, this sector remains fairly mature and tends to

fluctuate mostly with process-based investments. Polyurethane pipe sections (particularly PIR)
16

have a niche in cryogenic applications, where their resilience at these temperatures is important.

In other parts of the market they are under more pressure from other products offering better fire

performance (e.g. phenolic foam or mineral fibre).

- Current blowing agent selection

PU block can be made both continuously and discontinuous. Where market demand supports it,

continuous block offers less waste. However, cutting pipe sections from blocks is always an

inefficient process and the choice of blowing agent needs to reflect this, both economically and

environmentally. Accordingly, there has been increasing pressure on the use of hydrocarbons in

this sector despite the initial concerns over process safety. For the larger producers, the

management of hydrocarbon technology has proved both possible and cost-effective – once the

initial investment was made. For smaller manufacturers, HFCs have been a more obvious choice.

0

200

400

600

800

1,000

1,200

1,400

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Block-Pipe 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PU Block - Slabstock

- Current Market Trends

Again, this product type is relatively mature and is typically used for non-routine applications for

polyurethane foams where a degree of fabrication is necessary. The market for slabstock products

is typically higher than for pipe section – partly due to the lower losses resulting from the

fabrication step. This can be passed on in more competitive pricing.
17

- Current blowing agent selection

The processing is precisely as described for PU Block-Pipe and the blowing choice is identical as

a result. There are few applications for slabstock where the choice of a hydrocarbon blowing

agent does not suffice. Therefore, the final blowing selection is broadly driven by process

considerations.

0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

2,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Block-Slab 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

Developing Countries

PU Boardstock

- Current Market Trends

PU Boardstock has not been an historic part of the product mix in developing countries and the

only known production facility has been in Turkey (accounted for under MENA). This facility

has broadly been supplying the European market and does not really reflect indigenous demand.

That said, there is an increasing interest in all thermal insulation options for new buildings,

particularly in colder climates as the demand for energy efficiency, driven both by energy

security and climate change considerations, increases. It has been observed by the FTOC that

technology transfer from developed to developing countries relating to energy efficiency
18

solutions and standards has been on the increase during this Assessment period and may lead to

the adaptation of more developed country insulation strategies for both timber-framed and brick/

block constructions.

- Current blowing agent selection

In the one known facility, the choice of blowing agent has been consistent with the market served

(Europe) and no particular technological challenges have been observed.

0

20

40

60

80

100

120

140

160

180

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Boardstock 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PU Continuous Panels

- Current Market Trends

In view of the pre-fabricated nature of these products and the reproducibility that this brings, this

technology has been more transferable than others and multi-national interests have not been

afraid to invest directly in continuous plants where the overall population size and potential

economic growth are seen to justify it. One of the advantages of this type of construction is the

speed at which the erection of new buildings can take place around a steel frame. The technology

also has the advantage of having the thermal insulation characteristics in-built, thereby avoiding

the risk of under-insulation which can be associated with systems built up on site.
19

- Current blowing agent selection

The choice of blowing agent has largely been a measure of the timing of the investment. Once

the developed countries became comfortable with the use of hydrocarbons, it was inevitable that

this would be adopted for new investments in developing countries. However, earlier plants were

based on HCFCs (typically HCFC-141b) and will require conversion as part of the enactment of

Decision XIX/6. The choice of alternative will is quite widespread with both hydrocarbons and

HFCs being options.

0

200

400

600

800

1,000

1,200

1,400

1,600

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Continuous Panel 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PU Discontinuous Panels

- Current Market Trends

A similar argument exists to that in developed countries about the proportion of the PU panel

sector that will remain discontinuous as the market grows. However, an additional factor is in

play in the developing country scenario. This is simply that the investment cost for continuous

processing equipment is likely to be beyond many indigenous manufacturers. As is shown in the

following graph, the manufacture of steel-faced discontinuous panels is quite widespread within

the developing world and is likely to remain so for a significant period to come. Again, the value

of prefabrication in a factory environment has additional value in a developing country scenario.
20

- Current blowing agent selection

As with continuous panels, the primary blowing agents were HCFCs in 2008. However, the

proportion of the market based on this technology was higher, based on the lack of multi-national

influence on the chosen investment strategies.

0

500

1,000

1,500

2,000

2,500

3,000

3,500

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Discontinuous Panel 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

There have been reports from Latin America (notably Brazil) that this is an area where methyl

formate may have a role based on its basic performance. Some commercialisation has taken place

since 2008, although the longer-term prospects still need to be evaluated. Hydrocarbons and

saturated HFCs will be the other choices likely to be considered in the short-term, with

unsaturated HFCs (HFOs) unlikely to make inroads until commercialisation takes place and the

cost implications have been fully assessed.

PU Spray Foam

- Current Market Trends

The requirement for the refurbishment of residential properties in China has led to the

unprecedented growth of the PU Spray Foam market there. The centralised nature of parts of the

economy in that region means that this trend might not be replicated to the same extent in other

parts of the developing world. Nonetheless, the obvious value of PU Spray Foam in cost-
21

effectively improving the thermal performance of existing buildings will certainly ensure that it

has a major role in thermal insulation strategies around the world.

- Current blowing agent selection

The current estimate for the Chinese market alone is 70,000-80,000 tonnes per year currently.

However, in 2008, this was considerably lower (probably around 25,000 tonnes) leading to a

demand for blowing agent of between 2,500 tonnes and 3,000 tonnes for that year.

The sector is currently completely dependent on HCFCs (most typically HCFC-141b) and is

seeking to resist the transition to saturated HFCs with their climate dis-benefits. However, the

challenge for developing countries is to identify technologies that are largely unproven (at least

on a large scale) within developed countries. Methyl formate, methylal and super-critical CO2

have all been mentioned in this context and pilot projects have been targeted at evaluating each

in the spray foam environment. In Mexico, for example, the PU spray foam market represents

30% of all HCFC consumption in that country and the HPMP is currently proposing methyl

formate as the replacement of choice. However, the FTOC has concern that the evidence base is

currently too low to demonstrate that methyl formate can be used safely and effectively in PU

Spray applications1.

PU One Component Foam

- Current Market Trends

The PU One Component Foam market is prevalent in two developing country regions. The first

of these is ‘Russia and the former Soviet States’ primarily reflecting the extension of European

building practices into these regions. The second, and most significant, market is China where

approximately 150 million cans are produced annually. This accounts for approximately 100

ktonnes of PU chemical and up to 6,000 tonnes of blowing agent – making it a similar size to the

European market.

- Current blowing agent selection

Although HFCs are understood to be the primary choice in the former Soviet States, the Chinese

market has followed the European technology move into hydrocarbons. The following graph

demonstrates this trend.

1

The ‘minority view’ challenges this statement and cites the number of project submissions made to the MLF

Secretariat in support of this position. However, the FTOC is conscious that the decision to submit or approve such

products cannot be used as a ‘proxy’ for technology endorsement.
22

0

1,000

2,000

3,000

4,000

5,000

6,000

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU One Component 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PU Pipe-in-Pipe (including moulding of pipe sections)

- Current Market Trends

As noted in the developed country section for this application, the more centralised economies

have tended to adopted district heating systems as a means of distribution and, with it, have made

good use of pre-insulated polyurethane pipes. As with PU One Component Foams, China is the

dominant market for these, although there is considerable use in Russia and Former Soviet States

as well.

- Current blowing agent selection

The current foam systems are based on HCFC technology, but there is a clear option to switch to

hydrocarbon, based on the substantial experience gained in Europe using this technology. This

will be particularly the case in China, where the economies of scale should make investment a

rational proposition. The situation will be less clear in Russia and the former Soviet States, where

some use of HFC-based technologies is also possible – particularly in smaller manufacturers.
23

0

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Pipe-in-Pipe 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PU Block – Pipe Section

- Current Market Trends

These markets (both for pipe section and slabstock) are relatively mature in nature. In developing

countries, the PU Block processes are almost exclusively discontinuous. This reflects the fact that

investment costs are lower and small operations can be scattered across regions where larger

scale investments would not be cost-effective. However, for the same reasons, it is particularly

difficult to track the split between pipe section demand and slabstock demand, since the only

distinction occurs at the block fabrication stage.

For the purposes of this report, it is assumed that the split between the two sectors is 50/50. This

is largely an arbitrary split at this point and further bottom-up research would certainly help in

validating this assumption. The main significance of the separation of the two product types is in

the waste levels from each, with pipe section fabrication resulting in up to 50% waste in some

instances.
24

- Current blowing agent selection

The dominant blowing agent choice at present is HCFCs. This sector therefore represents one of

those requiring to be addressed under Decision XIX/6. It is also one that accounts for a large

number of the really small consuming enterprises. The technology choices are therefore s-HFCs,

or those potentially flammable blowing agents that can be shown to be managed at this scale.

This may include pre-blended hydrocarbons, methyl formate and others, but pilot projects are yet

to deliver conclusive messages for these technologies.

0

100

200

300

400

500

600

700

800

900

1,000

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Block-Pipe 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PU Block - Slabstock

- Current Market Trends

Comments for this sector are the same as those for PU Block – Pipe.

- Current blowing agent selection

Comments for this sector are the same as those for PU Block – Pipe.
25

0

100

200

300

400

500

600

700

800

900

1,000

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PU Block-Slab 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

FLEXIBLE POLYURETHANE FOAM

PU - Flexible Slabstock

The use of CFCs in flexible slabstock has been completely phased out over this

Assessment period, if not before. There was little, if any, substitution with HCFCs as an auxiliary

blowing agent and therefore the issues with respect to ozone depleting substances (ODS) are

virtually fully resolved.

However, the Montreal Protocol through its Technical Options Committees has a duty of

care to maintain an overview of the replacement technologies - particularly where there may be

on-going health, safety or environmental concerns. These remaining paragraphs therefore briefly

review the current status.

The main technologies now in use are methylene chloride and carbon dioxide (CO2

(LCD)). Other, more minor technologies also exist and, between them all, they cover all

applications. However, processing is sometimes more challenging and in some cases more

expensive. This is specifically the case for low density/ ‘high hardness’ foams where the high

process temperature (“exotherm”) limits the effectiveness of some current replacement

technologies.
26

Methylene chloride continues to be under scrutiny from a health and safety perspective.

However, the pressure for replacement has not grown substantially since 2001.

Liquid carbon dioxide, while successful in developed countries, specifically when the use

of methylene chloride is restricted or forbidden, proved to be a serious challenge in most Article

5(1) countries. The combination of a complicated technology with virtually unchallenged use of

easy-to-process methylene chloride proved a major burden for an initially enthusiastic embrace of

the environmentally preferable LDC option. In the USA there is also considerable use of acetone

and in Europe some use of variable pressure technology. On a smaller scale, special additives are

used—frequently as co-technology to limit the amount of methylene chloride required. There is

also very limited use of n-pentane, formic acid and MDI based foams—the latter generally for

speciality products. Forced cooling, a previously popular technology in the USA has virtually

disappeared because of perceived increased emissions of TDI and fire risk. The further uptake of

Exotherm Management Technologies (EMT) continues to be monitored, although little has been

published recently on the subject. There is also some recent, but unsubstantiated, information that

methyl formate may be acting as a replacement for pentane, acetone and methylene chloride.

PU – Flexible Moulded

All-water-based technology is predominant in cold cured foams. In hot-cure applications

there is also use of methylene chloride. In very low density/soft foams (e.g pillows) there is

some use of LCD or GCD but generally, this technology did not get the same attention as in

slabstock applications—most likely because there is no exotherm problem and water-based

technology performs well in most cases. HCFC-141b is used in exceptional circumstances such

as highly filled acoustical foams but is not essential as a replacement in this industry. The use of

HCFCs in this industry is not allowed in most developed countries. Methyl formate has emerged

as a legitimate replacement for HCFC-141b where it is still used and may also provide

advantages over CO2(water) where this technology has already been adopted.

PU – Integral Skin and Miscellaneous

This sector includes both rigid and flexible integral skin applications and also noninsulating rigid foam applications for packaging, leisure (e.g. surf boards), floatation and floral

foams.

A variety of blowing agents has been identified as alternatives to HCFCs in this sector.

These include CO2 (water), various s-HFCs, n-pentane and methyl formate. With some

drawbacks associated with skin formation using CO2 (water) technologies, methyl formate may

offer a particularly attractive alternative and there has already been considerable uptake in Latin

America (most notably Brazil) already.
27

POLYOLEFIN FOAMS

There are three prime product types in the uncross-linked polyethylene foam sector:

sheet, plank and tubular. All of these have used CFCs in the past. This is in contrast to crosslinked polyethylene foams which are produced for specialist applications and have typically been

blown with inert gases such as nitrogen. The transition issues facing sheet, plank and tubular

products are broadly similar and these are therefore considered together in this review.

Developed Countries

- Current Market Trends

The market for polyethylene pipe section continues to be buoyant based on the demand for lowcost, easy-to-install pipe insulation in the residential sector, where fire performance is less

regulated in many regions. The product is particularly suited to do-it-yourself activities, since it is

easy handled and manipulated. However, the actual thermal performance can be variable

depending on the quality of installation.

- Current blowing agent selection

Hydrocarbons (typically iso-butane) are the dominant blowing agents in Europe and predominate

in other regions too (see graph below)

0

50

100

150

200

250

300

350

400

450

500

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PE Block-Pipe 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
28

0

100

200

300

400

500

600

700

800

900

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PE Block-Slab 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

For PE Block-Slab, the market is split between construction, leisure and packaging applications,

with packaging dominating on some regions (e.g. Japan).

Developing Countries

- Current Market Trends

Although the markets are similarly characterised in developing countries as those in developed

countries, the geographic distribution is limited rather more in this case by historic technology

transfer, with Latin America embracing PE pipe section more significantly than other regions.

Latin America also has significant involvement with PE slab production, again with a similar

application portfolio to that in developed countries. However, the larger market for slab in

developing countries is found in South East Asia. As with Japan, this is understood to be

underpinned by a larger use in the packaging sector.

- Current blowing agent selection

In all developing country regions, the dominant blowing agent is now hydrocarbon.
29

0

100

200

300

400

500

600

700

800

900

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PE Block-Pipe 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

0

50

100

150

200

250

300

350

400

450

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PE Block-Slab 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
30

EXTRUDED POLYSTYRENE FOAMS

Developed Countries

Sheet

- Current Market Trends

The XPS sheet market has a number of similarities with the PE Slab market in that a large

proportion is used for leisure and packaging. In some instances, the packing requires some

thermal performance (e.g. fast foods and hot drinks), but the thermal properties are no required to

be persistent in the same way as thermal insulation applications in construction, transport or

appliances. The market has been less studied quantitatively by the FTOC since the phase-out of

CFCs and almost universal switch to hydrocarbons.

- Current blowing agent selection

As noted above, hydrocarbons (butane, isobutane, pentane, isopentane), HFCs (HFC134a, HFC-152a); and hydrocarbon / CO2 (LCD) blends, have found a range of commercial use

with hydrocarbons being the dominant selection in most regions. HFC-152a also been used

significantly in the United States to overcome local VOC emission regulations.

Few future developments are expected. However, capital investment required for the

handling of flammability issues and on-going concerns over VOC emissions will be limiting

factors in further expansion of hydrocarbon containing systems.

Board

- Current Market Trends

Extruded polystyrene board has effectively emulated the growth of PU/PIR products in the

thermal insulation sector as markets have been stimulated by increased energy efficiency in

buildings. The product’s competitive position is underpinned by its particularly good moisture

resistance, which has been responsible for widespread use as a floor insulation material in

Europe. In North America, the product is typically competing with PIR (“polyiso”) products in

the residential sheathing market, as well as in a number of commercial and industrial building

applications.

- Current blowing agent selection

The following graph illustrates the rather bizarre situation in terms of blowing agent selection by

region as it was in 2008.
31

0

5,000

10,000

15,000

20,000

25,000

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - XPS Board 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

In Europe, the primary replacement technologies have been HFC-134a, HFC-152a and

CO2 (or CO2/alcohol), while in Japan there has also been significant use of hydrocarbons (notably

isobutene). In North America, the transition away from HCFCs has been more difficult because

of particular product requirements, especially in the residential sector. HCFC-142b, therefore,

remained the dominant blowing agent as at 2008. However, since then, transition to s-HFCs has

occurred, as companies have mastered the adoption of HFC technology for sheathing products

and also achieved the relevant building code requirements.

Investment criteria continue to be a barrier to further use of CO2-based technologies in

Europe, although pressures are likely to increase concerning the on-going use of HFCs. A review

of the F-Gas regulation is on-going in the EU and will be completed before the end of 2011.

There may be some future interest in the use of HFOs for this application, but cost considerations

may necessitate the use of these substances as blends with HCs and possibly HCOs (e.g. dimethyl ether).

Developing Countries

Sheet

- Current Market Trends

The market drivers are very similar to those described for developed countries.
32

- Current blowing agent selection

Technologies have also shifted almost universally to hydrocarbon despite earlier concerns about

the flammability of both the blowing agent and the substrates on high temperature extrusion

lines. There is no immediate expectation for this sector to make any further blowing agent

transitions.

Board

- Current Market Trends

There has been substantial growth in markets for XPS board in a number of Article 5

countries, most notably in China and some middle-eastern countries. This has increased the

demand for HCFCs by in excess of 15,000 tonnes per annum since 2001. However, latest

information suggests that some recent fires in major Chinese cities may result in some

retrenchment for both new and existing buildings, driven by new fire standards. Although EPS

and some EPS might be the primary culprits, the impact could be seen across all organic foam

products.

- Current blowing agent selection

The industry was totally based on HCFCs in 2008, although the split between HCFC142b and HCFC-22 continues to remain unclear.

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

16,000

18,000

20,000

Russia &

Former

Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - XPS Board 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
33

For other Article 5 countries, the relatively low cost of investment in locally produced

manufacturing plant and the high demand for improved thermal performance in buildings is

expected to drive further rapid growth of XPS board production. Prior to 2015, the predominant

blowing agents are expected to continue to be HCFCs. Ultimately, hydrocarbons may prove the

dominant blowing agents in these territories.
34

PHENOLIC FOAMS

Developed Countries

PF Boardstock

- Current Market Trends

Phenolic Foam boardstock has continued to make progress in the buoyant European market, with

the key manufacturers being able to switch between PU boardstock and PF boardstock products,

at will, against the same market specifications. This has meant that capacities can be better

utilised and PU raw material shortages offset.

In Japan, the market has continued to be supportive of phenolic boardstock in view of its superior

fire performance and highly competitive insulation values. However, the recent earthquake and

tsunami have created interruptions in production which may have some short-term impact on

supply.

- Current blowing agent selection

The bulk of the sector is now fully switched to hydrocarbon technologies, although this was

slightly less the case in 2008 (see graph below):

0

100

200

300

400

500

600

700

800

900

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PF Boardstock 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
35

There is still some use of 2-chloro-propane at one facility in Europe, but otherwise the industry is

expected to normalise even further around the hydrocarbon option.

PF Pipes and Blocks

- Current Market Trends

The market for phenolic pipe insulation continues to be highly regionalised with the United

Kingdom representing the major market in Europe and, perhaps, the world. This results from a

specific combination of ‘reaction-to-fire’ requirements which rules out competitive materials

such as PU/PIR. The future direction of other markets in Europe will depend on the extent to

which individual countries adopt maximum smoke requirements, which can now be specified

through the European classification system.

The production economics have also been improved by the introduction of continuous process

technologies for the more common sizes of pipe.

- Current blowing agent selection

The choice of blowing agent for the continuous process has been hydrocarbon. This has had little

effect on the overall fire performance of the product or its market acceptance. For discontinuous

block processes, the choice remains s-HFCs, particularly for the smaller manufacturers. This is

reflected in the graph below:

0

100

200

300

400

500

600

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PF Block-Pipe 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
36

0

20

40

60

80

100

120

140

160

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PF Block-Slab 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

Technology choices are the same for PF Block-Slab Foam, although hydrocarbon is less

prevalent because no continuous process exists for this product group. Accordingly, s-HFCs are

the most significant blowing agents in use, with the exception of Japan, where hydrocarbon

solutions have been effectively engineered.

PF Panels

- Current Market Trends

The market for metal-faced phenolic foam panels is relatively mature in Japan. The primary

products are for residential siding and office partitioning. These are usually discontinuously

produced. The market in Europe is still in a fledgling state and is targeted at niche panel

applications such as clean rooms, cold stores and computer safe rooms.

- Current blowing agent selection

Reflecting the size and maturity of the Japanese market, the technology has been able to be

adapted for hydrocarbon blowing agents. In Europe, (most notably the UK), the size of

production operations is insufficient to support hydrocarbon investments at present and s-HFCs

are typically used.
37

0

100

200

300

400

500

600

Europe N. America Japan RODW

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PF Panel 2008 - Developed

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

Developing Countries

PF Boardstock

- Current Market Trends

At the present time, there are no known PF Boardstock manufacturers in developing countries.

- Current blowing agent selection

There is currently no blowing agent consumption.

PF Pipes and Blocks

- Current Market Trends

Historically, there was some PF Block Foam manufacture in India, but this is understood to have

ceased as a consequence of limited market penetration and conversion costs out of ozone

depleting substances. The only developing country consumption is now in South Africa, where
38

European block foam technology continues to be operated – partially supplying products for the

mining sector.

- Current blowing agent selection

It is understood that HCFC-141b remains the blowing agent of choice in South Africa at present,

although considerations are underway for a transition to non-ODS alternatives. Further

investigations are on-going into potential choices, but the scale of the operation might leave sHFCs as the only viable alternative in the short-term.

0

5

10

15

20

25

30

35

40

45

50

Russia &

Former Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PF Block-Pipe 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs
39

0

5

10

15

20

25

30

35

40

45

50

Russia &

Former Soviets

NE Asia SE Asia S Asia SS Africa MENA Latin America

Annual Consumption (tonnes)

Region

Blowing Agent Consumption by Type - PF Block-Slab 2008 - Developing

HFOs

CO2

HCOs

HCs

HFCs

HCFCs

CFCs

PF Panels

- Current Market Trends

At the present time, there are no known PF Discontinuous Panel manufacturers in developing

countries.

- Current blowing agent selection

There is currently no blowing agent consumption.
40

CHAPTER 2: TECHNOLOGY OPTIONS

POLYURETHANE FOAMS

Developments on blowing agents in the PU foam sector

The primary challenge for the foam sector continues to be the phase-out of HCFCs in

developing countries under Decision XIX/6. HPMPs are being developed to meet the 2013 freeze

and the 10% use reduction in 2015. In developed countries HCFCs were completely eliminated

by the middle of the last decade in the polyurethane (PU) foam sector and the substitute

technologies and the usage patterns have reached a relatively mature status. The analysis of this

experience along with the proper considerations associated with the markets differences and the

scope of Decision XIX/6 focused on alternatives that minimize the climate change impact,

provides a valuable insight for the HCFC phase-out in developing countries.

Developed Countries

The section describes the blowing agents currently used in developed countries:

Table 1. Blowing Agents currently used in developed countries

PU RIGID FOAM

Domestic refrigerators and freezers c-pentane, cyclo/iso pentane blends, HFC- 245fa, HFC-134a

Other appliances c-pentane, cyclo/iso pentane blends, HFC- 245fa, HFC365mfc/227ea blends, HFC-134a, methyl formate, CO2 (water)

Transport & reefers c-pentane, cyclo/iso pentane blends, HFC- 245fa, HFC365mfc/227ea blends, HFC-134a

Boardstock

c-pentane, n-pentane, iso pentane, cyclo/iso pentane blends, npentane/iso pentane blends, HFC- 245fa, HFC-365mfc/227ea

blends

Panels – continuous

c-pentane, n-pentane, iso pentane, cyclo/iso pentane blends,

cyclo/n-pentane blends, n-pentane/iso pentane blends, HFC245fa, HFC-365mfc/227ea blends

Panels discontinuous

HFC- 245fa, HFC-365mfc/227ea blends, HFC-134a, c-pentane, npentane, iso pentane, cyclo/iso pentane blends, n-pentane/iso

pentane blends, CO2 (water), formic acid, methyl formate

Spray HFC- 245fa, HFC-365mfc/227ea, Supercritical CO2, CO2 (water),

Blocks

c-pentane, n-pentane, iso pentane, cyclo/iso pentane blends, npentane/iso pentane blends, HFC- 245fa, HFC-365mfc/227ea

blends, methyl formate

Pipe-in-pipe c-pentane, n-pentane, HFC- 245fa, HFC-365mfc/227ea blends,

CO2 (water), methyl formate

One Component Foam Mixtures of propane, butane and dimethyl ether, HFC-134a, HFO1234ze

PU FLEXIBLE FOAM

Integral Skin CO2 (water), HFC-134a, HFC- 245fa, HFC-365mfc/227ea blends,

n-pentane, methyl formate

Shoe Soles CO2 (water), HFC-134a

Flex moulded CO2 (water), methyl formate
41

It is important to notice the different roles of the blowing agent in PU rigid and flexible

foams. Although in both it has the primary function to physically expand the foaming mixture to

produce the foam, in the case of rigid foam it should remain within the closed cells and

contribute to the insulating performance. To fulfil this latter function, the blowing agent should

have a low gaseous thermal conductivity plus a low rate of diffusion of the gas through the foam

(matrix) so that the good insulating properties are retained for many years. A low solubility of the

blowing agent in the PU matrix is also require to ensure that it is retained as a gas in the foam

cell avoiding the solid plasticisation and the loss of thermal insulation. In the case of domestic

refrigeration high solubility of the blowing agent in the thermoplastic material of the inner lining

may result in a severe deterioration of the mechanical strength.

In the case of flexible foam, particularly in integral skin and shoe soles, the blowing agent

has a critical role in forming a robust/aesthetic skin as a result of its condensation during the

high-pressure injection process. For this application a relatively low boiling point of the blowing

agent is desirable. During the CFC phase-out most of the shoe sole market migrated to all water

blown formulations along with the use of polyester polyols to meet the abrasion resistance

requirements From table 1, there is wide scale use of hydrocarbons in PU foams together with

HFCs in some specific applications, such as HFC 245fa in most North American domestic

refrigerators and freezers, and HFC-365mfc/227ea blends to meet the most stringent fire tests in

panels. Formulations based on hydrocarbons have been refined over the years and their insulation

performance, as expressed by foam thermal conductivity, is now similar to those for HCFC- 141b

based foams. They can now also meet very stringent fire test requirements as panels or boards.

There is a clear exception to the trend to use hydrocarbons for PU foams; despite trials,

HCs are not used in spray foams for safety reasons. Instead, HCFC 141b has been replaced by

HFC 245fa or HFC365mfc/227ea blends, often in combination with significant amounts of CO2

(water) – “reduced-HFC” technology. CO2 (water) may be used when increasing foam thickness

can compensate for the higher thermal conductivity of the foam. In Japan, supercritical CO2

technology has been developed and is used. The strengths and weaknesses of the HC and HFC

technologies are described in table 2.
42

Table 2. Strengths & Weaknesses of HC and HFC technologies

SECTOR/OPTION STRENGTHS WEAKNESSES COMMENTS

Rigid Foam

Hydrocarbons (c-pentane &

n-pentane & cyclo/iso

blends)

Low GWP Highly

flammable

High conversion

costs, uneconomic

for SMEs. Not

suitable for spray

Low unit costs Low operating costs

Acceptable foam

properties

Global industry

standard

HFC-245fa, HFC365mfc/HFC-227eaNon-flammable High GWP Low conversion

costs. Industry

standard for spray

High unit costs High operating costs,

could be improved

by using “HFC

reduced” HFC/

CO2 (water)

formulations

Good foam properties Improved insulation

(versus HC)

Flexible Foam (Integral Skin & Shoe soles)

n-pentane Low GWP Highly

flammable

High conversion

costs, uneconomic

for SMEs

Low unit costs Low operating costs

Good skin quality

HFC-134a, HFC-245fa,

HFC-365mfc/HFC-227ea

Non-flammable High GWP Low conversion

costs

High unit costs High operating costs

Good skin quality

The major drawback of the hydrocarbon family is their flammability. This has a strong

impact on both the capital costs for processing -to ensure that safety is properly engineered- and

on product handling, which is particularly problematic for smaller enterprises. Efforts have been

made to reduce costs at the foam manufacturers by pre-blending the hydrocarbons into polyols at

systems houses. The challenge is to develop a long-term stable formulation with no phase

separation. A successful industrial case has been reported in Northern Europe where a system

house, for some years, has been delivering formulated polyols containing c-pentane in one-tonne

containers and 200 l drums to different industries in Eastern and North-Eastern Europe

(PROKLIMA, 2009). This approach allows reduced investments on the user’s side without

compromising the insulating efficiency and the long-term dimensional stability performance.

This experience shows that investment in one blending facility may make it possible to reduce

investments in manufacturing plants. While the cost of HC storage tanks, pumps and premixing

stations can be avoided, the safety modifications for the polyol blend storage and foaming line

and the installation of proper monitoring and ventilation systems will still be required. It is

estimated that savings in increased capital cost (ICC) for the end user are in the order of 25 to

35%.
43

The technology based on CO2, derived from the isocyanate-water reaction, has been used

with limited success for commercial refrigeration (displays, vending machines) where insulation

performance is not critical. Its major drawbacks are the relative poor insulating performance

resulting from the relatively high lambda value of CO2; the required increase in foam moulded

density caused by the high permeability values of CO2 through the polyurethane matrix; and the

reduced “adhesion” to the substrates where it is applied (metal, thermoplastics), a consequence of

the high amount of polyurea present in the polymer. In the Japanese spray market, the use of

water blown foam along with patented super-critical CO2 technology has been developed and

commercialised; however, there may be limitations in some applications that require an improved

insulating performance.

There is also a small use in developed countries of methyl formate (United States,

Australia) particularly for commercial refrigeration, an application where the insulating

performance is not critical and some global beverage players (i.e. Coca-Cola) are requesting

foams based on non-HFCs, 0 ODP substances. Further discussion on this technology can be

found below.

Although a large proportion of the industry in developed countries has settled on

hydrocarbons or HFCs as their blowing agent of choice, there are increasing pressures -in the

case of HCs- to improve the thermal performance of foams, particularly in the appliance sector,

and to limit the future use of saturated hydrofluorocarbons (s-HFCs) and to phase these down

where possible.

In this context, there is a growing interest in the potential role of the recently developed

unsaturated HFCs (HFOs) in the domestic refrigeration sector and other rigid foam applications,

particularly in North America, where saturated HFCs have a significant market, and in PU Spray

foam both in Europe and North America. One of these (HFC-1234ze) has found some initial use

in Europe as a replacement for HFC-134a in PU One Component Foams.

These compounds represent an emerging group of blowing agents that exhibit a number

of the characteristics also displayed by saturated HFCs, but have considerably lower GWPs (<

15). The prime reason for these lower values relates to the shorter lifetime of the molecules in the

atmosphere caused by the presence of a double bond between adjacent carbon atoms. Early work

suggests that they deliver better thermal performance than their saturated counterparts, although

toxicological work remains to be completed for those yet to be commercialised. Cost predictions

are similar to saturated HFCs. Their main characteristics are presented in table 3.
44

Table 3. Saturated HFCs (HFOs)

HFO-1234ze FEA-1100 HBA-2 AFA-L1

Chemical Formula Trans- CF3CH=CHF Cis- CF3-CH=CH-CF3 Undisclosed Undisclosed

Molecular Weight 114 164 Undisclosed Undisclosed

Boiling Point ( 0C ) -19 32 15.3<T<32.

1

10.0<T<30.

0

Gas Conductivity

(mW/mK @ 100C) 13.0 10.7 NotReported 15.9

Flammable Limits

in Air (vol.%) None to 28oC^ None None None

TLV or OEL (ppm)

(USA) Unpublished 9.7 Undisclosed Undisclosed

GWP (100 yr time

horizon) 6 9.4 <15 <15

^ Flame limits of 7.0-9.5 at 30oC are quoted

Developing Countries

One of the major challenges of the foam industry is the HCFC phase-out in developing

countries under Decision XIX/6. This Decision calls for an accelerated phase-down of the use of

HCFCs leading to their replacement, in the foam sector, by zero ODP blowing agents. At the

same time, the Executive Committee (ExCom) of the Montreal Protocol is requested, when

applying funding criteria, to give priority to cost effective projects with focus on substitutes that

minimize other environmental impacts, including on the climate, taking into account globalwarming potential, energy use and other relevant factors.

Today two types of polymeric foams use HCFCs as blowing agents: Polyurethane (PU)

Foams (mainly HCFC-141b and some HCFC-22) and Extruded Polystyrene (XPS) Board Foams

(HCFC-142b and HCFC-22). They compete with other materials, such as mineral fibres, EPS in

thermal insulation and other applications. The PU foam sectors using HCFCs are insulating

foams, integral skin foams and microcellular foams (shoe soles). In the last two sectors the usage

is much less than in the insulating market because of the smaller overall market and the higher

foam density. XPS board foams are mainly used for insulation purposes.

The main route for PU foams is to use hydrocarbons (HC), principally pentanes (npentane, c-pentane and cyclo/iso-pentane blends). This is particular true for the sectors where the

large size of the companies (HCFC use > 50 tonnes/year) benefits the economics despite of the

high conversion cost: domestic refrigeration, continuous panels and some commercial

refrigeration and discontinuous panels manufacturers. In the case of medium size enterprises (50

tonnes/year >HCFC use >10 tonnes/year) the option of pre-blending hydrocarbons into polyols -

described above- may represent a sustainable long-term approach. The Multilateral Fund and the

Implementing Agencies have taken up the matter and two pilot projects have been sponsored and

are under development (China and Egypt); one of them along with the introduction of a third HC

stream at the mixing point. The results will be ready during 2011.
45

Although the use of HC technology provides lower operating costs than other alternatives

such as HFCs, the significant capital costs for conversions make unviable its application for

small size enterprises (HCFC use < 10 tonnes/yr). It is estimated that the minimal Incremental

Capital Costs (ICC) for the conversion to HC are in the range of USD300,000 to USD500,000.

On the other side, in addition to their high GWP, the use of saturated HFC-based

technologies (HFC 245fa, HFC-365mfc/HFC-227ea) may result in significant increases in

operating costs owing to their higher unit prices and molecular weights. It is also clear that,

despite of the promising results, their unsaturated counterparts (HFOs) are unlikely to be

available in time to meet the early stages (pre-2015) of the HCFC phase-out as required under

Decision XIX/6. In the interim, there is evidence that some enterprises manufacturing appliances

in developing countries are already blending saturated HFCs with hydrocarbons to meet energy

requirements.

From the above considerations, HCFC phase-out in sectors that include a large number of

SMEs (a typical industry characteristic in the Article 5 countries) represents the most significant

challenge. Many of the enterprises have little, if any, internal capacity to optimise formulations

and their capacity to handle flammable compounds is limited. There continues to be a need to

characterise the performance of foams made from low-GWP alternatives in the range of

applications envisaged. This is an on-going exercise, but is particularly important for

technologies that do not have a significant history of use in non-Article 5 countries. The role of

the Pilot Projects sponsored under the Multilateral Fund are especially relevant here and the work

of UNDP on methyl formate, for example, has already cleared the way for wider use in the

flexible moulded and integral skin sectors with potential for others to follow.

In the case of rigid foam applications, perhaps the most critical case, a conventional testing

programme for a new blowing agent includes2:

 Toxicology and ecotoxicology testing (ODP, GWP, toxicology)

 Processing characteristics:

 Stability in polyol blends

 Miscibility with polyols

 Flow properties (flow index, minimum fill density)

 Reaction times including jig dwell times

 Atmospheric concentrations during processing and comparison with flammable limits in

air

 Effects on equipment – seals and metal parts

 Physical & Fire properties:

 Closed cell content

 Density/strength (compression strength) relationships

 Dimensional stability versus temperature and ageing using accepted accelerated methods

2

For a more fundamental approach tending to provide a performance explanation tests like cell gas analysis with

time, water vapour transmission, glass transition temperature over time at different temperatures, etc., are

desirable.
46

 Thermal conductivity versus temperature and ageing using accepted accelerated methods

 Foam friability

 Adhesion to different substrates

 Fire code testing for construction industry foam-based components

 Trials under commercial production conditions and long term testing of articles

For integral skin and shoe-soles, open celled applications where the blowing agent does

not remain in the product, the testing programme on physical properties should include the skin

appearance and related properties like abrasion resistance.

In addition to the option of pre-blended HCs into the polyols, new technology alternatives

for the SMEs are emerging or have recently emerged: methylal, methyl formate and modified

water blown formulations.

Methylal, also called dimethoxymethane, is a flammable liquid with a negligible GWP

and a boiling point of 42 oC. To date, it has been marketed primarily within the thermoplastic

foam sector (extruded polystyrene and polyolefin) as a co-blowing agent with HFC-134a to date.

The use of methylal as a co-blowing agent in conjunction with hydrocarbons and HFCs

for PU rigid foam applications (domestic refrigeration, panels, pipe insulation and spray) has

been described in the literature. It is claimed (Lambiotte, 2006) that in continuous panels it

promotes blending in the mixing head and improves the miscibility of pentane, the foam flow

and uniformity, the adhesion to metal surfaces and the insulation properties by reducing the cell

size. In discontinuous panels, the addition of a low percentage of methylal to HFCs (245fa,

365mfc or 134a) would make it possible to prepare pre-blends with polyols of low flammability

with no detrimental effect on the fire performance of the foam. As in the case of hydrocarbons

Methylal would reduce the cost and improve the miscibility, the foam flow and uniformity the

adhesion to metal surfaces.

There is no known use of methylal as sole auxiliary blowing agent in PU foam. By

decision 58/30 the ExCom approved a demonstration project to assess its use as a possible

replacement of HCFCs in developing countries. The final report will be issued during 2011 but

the partial results in integral skin/microcellular foams already released show an excellent skin

formation compared to HCFC-141b.

However, the flammability of the methylal/polyols blends is a major point of concern.

Data recently reported shows that the addition of more than 3 parts of methylal brings the flash

point of the blend down to values lower than 35 oC, similar to those obtained with hydrocarbons

(InterTox, 2010). According to the Global Harmonised System such type of blends are classified

as a flammable liquid of category 3. The impact of the increased capital cost needed to handle a

blend of these characteristics at the end user can make the use of methylal prohibited for the

SMEs.
47

Methyl Formate (MF), also called methyl-methanoate, is a flammable liquid with a

negligible GWP and a boiling point of 31.5 oC. Foam Supplies, Inc. (FSI) has promoted its use as

a blowing agent in PU foams from 2000 onwards. The company filed on December 18th, 2001,

for a US patent, which was issued on June 22nd, 2004. The use of this technology has grown

significantly in the last four years, although continues to be very small in size. For all foam

applications 365 tones were consumed worldwide in 2009 and around 1,000 in 2010, replacing

over 2,000 tonnes of HCFC-141b3.

It is reported that MF is finding increased use in the flexible moulded and integral skin

foam applications. Consumption in Australia, South Africa and Brazil has been established.

Table 4 describes the strengths and weaknesses of the low GWP alternatives for these

applications.

The use of MF is also occurring in rigid foam applications, particularly in commercial

refrigeration and discontinuous steel-faced panels. Additional work is progressing in the US, UK

and elsewhere to broaden this range of use, but with mixed levels of success.

Table 4. Alternate technologies for Integral Skin Foam & Shoe-soles

SECTOR/OPTION STRENGTHS WEAKNESSES COMMENTS

Methyl formate (MF) Low GWP Flammable Conversion costs to be

determined

Moderate unit costs Flammability of

polyol/MF blends

should be checked

Good skin quality Moderate operating

costs

Patented technology.

Commercial restriction

CO2 (water) Low GWP Poor skin quality Suitable skin may

require in-mouldcoating – added

expense

Low conversion costs Well proven in shoesoles - used with

polyester polyols

n-pentane Low GWP Highly flammable High conversion,

uneconomic for SMEs

Low unit costs Low operating costs

Good skin quality Well proven in

application

There are some technical issues that would seem to act as barriers to the use in rigid

polyurethane insulating foams of MF as a sole blowing agent and would also inhibit its use as a

co-blowing agent in systems such as those primarily blown with CO2 (water)-blown. These issues

can be documented as follows:

3

In its 2006 assessment report the FTOC estimated the global market of blowing agent for the incumbent foam

applications in the year 2005 at around 360,000 tonnes.
48

 There is concern that measures to manage flammability for MF may require system houses to

reformulate with more compatible polyols for rigid foam applications in order to reduce the

risk. In some cases it may be more productive to blend methyl formate in the isocyanate

component to obtain the required foam properties whilst avoiding flammable blends. The

additional health risk associated with the isocyanate handling needs to be managed.

According to the United Nations Global Harmonised Systems a liquid blend is

classified as flammable in the number 3 category when exhibits a flash point between 23 and

60 oC. Additionally, it is stated that “liquids with a flash point of more than 35 °C may be

regarded as non-flammable liquids for some regulatory purposes (e.g. transport) if negative

results have been obtained in the sustained combustibility test (which is the MF case)...” The

current fully formulated polyols used in developing countries have HCFC-141b

concentrations around 18 %, which -applying the ideal gas law- correspond to a MF

concentration of 10.1 %4. At this concentration, according to the supplier ́s data, virtually all

type of polyols will result in MF/polyol blends with flash points lower than 35 oC (Foam

Supplies, Presentation given to the FTOC, Salt Lake City, 2006). To avoid the implied safety

risk a significant reformulation work is required. This is particularly important for spray

foam, an application where the foam injection process is not controlled.

 The gaseous thermal conductivity of MF is intermediate between HCFC-141b and c-pentane

and would suggest the potential for foams with good thermal performance. However, MF is

a potent solvent for the polyurethane matrix and the addition of MF either on its own or as a

co-blowing agent with CO2 (water) results -as recently reported- in a significant reduction in

compressive strength (shrinkage). Such effects can be countered either by reducing the level

of the MF component present, or by increasing the density of the foam. The former reduces,

or even nullifies, any incremental benefit in thermal performance, while the latter increases

weight and cost and, in doing so, may not be technically or economically viable. If co-blown

with CO2 (water) the rapid aging of thermal conductivity, characteristic of CO2 (water)

systems, is also likely to be evident. Where shrinkage occurs, insufficient adhesion to metal

substrates is typically observed within discontinuous sandwich panel trials. Again, the

plasticising effect may be countered by increasing density where this is a commercial option.

 There is a need for further aged data to assess the trends in thermal insulation performance

and dimensional stability with time. As has already been noted, the current analysis suggests

that there will be a very fine balance between these two characteristics even in the short-term.

Therefore, long-term behaviour patterns are a particular area of focus at this time. There is a

possibility that the operational window could be too narrow for commercial viability in some

applications. The elucidation of the long-term performance is critically important in

applications where the thermal performance is expected to be maintained for periods of up to

50 years.

4

The ‘minority view’ contends that applying the ‘ideal gas law’ is not correct in practice. However, it is

acknowledged that the flash points associated with these polyol blends can be below 35oC, creating the need to split

the methyl formate component between the polyol and isocyanate streams.
49

 When MF is used as a co-blowing agent with other added blowing agents (e.g.

hydrocarbons), it has the potential to improve thermal performance by favourably impacting

the morphology of cells – usually by making the average cell size smaller and the cell size

more uniform. This is an effect beyond the gaseous thermal conductivity itself and may

result in the increasing use of MF as a component of blends, particularly in place of cpentane if this continues to remain in short supply.

 There does not yet appear to be evidence available related to the levels of MF in the

atmosphere for several production processes. In particular, there is little experience of using

MF-based systems for spray foam.

 There is a further concern about the stability of MF owing to the observed (by cell gas

analysis) hydrolysis to formic acid, CO2 and CO. This would serve to reduce the

concentration of MF in the foam cells and potentially contribute to further deterioration in

thermal performance.

 The presence of formic acid, either from breakdown of methyl formate, or through deliberate

addition, can lead to corrosion of dispensing machine components (Cannon, Brazil, 2010)5.

Machinery suppliers have investigated this effect and identified a number of components that

would need to be monitored and replaced at regular intervals.

Water Blown Formulations. As mentioned before, historically the development of water

blown foams has been a real challenge due to its intrinsic physical hurdles such as higher thermal

conductivity, lower foam dimensional stability -which requires and increased moulded density-,

and higher surface brittleness, resulting in a potentially weaker adhesion to metal facings. As

result, the use of all water blown foam in the industry is today still limited.

However, global system houses have recently reported the development of new water

blown technology characterized by an improved performance that can now be considered in line

with HCFC low-level technologies -characterized by relative high foam lambda values- (3rd

Polyurethane Exhibition & Conference in India - PU TECH 2011). This solution, focused on

addressing the discontinuous panels and commercial refrigeration applications, leaves the

opening to be converted later on into co-blowing with physical blowing agents by the time when

new proven low ODP low GWP non-flammable solutions will be available.

It is claimed that, as a result of improved flow and optimized density distribution, applied

densities are now in the same range of HCFC low-level technology with minimum impact on

foam dimensional stability and mechanical properties. The systems would allow easy filling of

the cavities and could be processed with a mould temperature of 40°C. Typical initial thermal

conductivity is in the range of 22-23 mW/mK (measured at 10°C), relatively higher compared to

5

The ‘minority view’ continues to challenge this assertion, although, as the text explains, the machinery suppliers

are already taking action.
50

pentane and/or some HFCs blown systems but still acceptable for commercial refrigeration and

discontinuous panels.

It is also reported that the addition of formic acid as chemical blowing agent to these

systems can result in quantified improvements in foam aesthetic, flow, density distribution and

adhesion even at low mould temperatures. Nevertheless, some drawbacks have been identified

and need to be taken into consideration. They are linked to potential corrosion, which requires

the involvement of equipment suppliers to check the equipment suitability, and the eventual

release of carbon monoxide that makes it necessary the checking of the atmospheric

concentrations and proper ventilation. Despite these drawbacks, this technology is being used in

developed countries where enhanced flow, lower density and improved aesthetics are key

requirements, i.e. the production of sandwich panels for cold store applications.
51

PHENOLIC FOAMS

Historically significant phenolic foam markets were developed in Europe and Japan based

on a combination of Boardstock and Block/Pipe products. The development of similar markets in

North America was thwarted by poor experience with a specific roofing board technology

(Koppers) that created corrosion problems on steel-decks.

A further traditional application of phenolic foam has been as floral foam. The primary

brand globally is known as ‘Oasis’. However, this material has never significantly been blown

with ozone depleting substances, except in the case of small ‘me too’ producers. It is therefore

not the prime focus of attention in this report.

PF Boardstock

The traditional blowing agent for phenolic boardstock was CFC-11, although this was

rapidly superseded by HCFC-141b. The use of HCFC-141b presented a particular challenge for

the phenolic emulsion chemistry because of its solubility and the major technology holders found

it necessary to modify the blowing agent with additives to make it less soluble in the foam mix.

In the transition that took place from HCFC-141b in Europe, it became self-evident that

the phenolic product itself was sufficiently robust in its fire performance to accommodate

hydrocarbon blowing agents for the bulk of end-uses. Therefore, the bulk of continuous

processes are now based on n-pentane, either on its own or in blends with other hydrocarbons.

One technology in Europe had moved directly from CFC-11 to 2-chloro-propane and continues

to use this blowing agent as the basis for its product range.

There is limited use for saturated HFCs in these continuous processes, since thermal

performance based on optimised hydrocarbon formulations is seen as sufficient for most enduses. Although it is not yet clear how the emergence of unsaturated HFCs might affect the

blowing agent choices for future phenolic boardstock formulations, the overall performance of

the various hydrocarbon-based technologies make it unlikely that there will be further technology

transitions in the short term.

There has been little, if any, implementation of phenolic foam boardstock facilities in

developing countries to date, so any future investment is likely to be based completely on

technology transfer from Europe or elsewhere.

PF Blocks & Pipe Sections

As with other phenolic foam product/process types, except for the floral foam industry,

CFC-11 was the basic blowing agent of choice. In some cases, the boiling point of the blowing

agent was modified by using CFC-11/CFC-113 blends in order to ensure the appropriate rise/cure

profile. This was particularly important for phenolic chemistry where the sensitivity between
52

temperature and cure rate is high. The reduction in the latent heat of evaporation in the early

stages of the reaction helped to ensure appropriate processing times.

In similar fashion to the phenolic boardstock sector, the first transition was to HCFC141b, with the same use of additives to reduce solubility of the blowing agent. In moving from

HCFC-141b under the regulatory pressures in both Europe and North America, the industry

initially moved to saturated HFCs. The choice was typically HFC-365mfc/227ea for boiling point

reasons (as for CFC-11/CFC-113 blends). There is still a lack of widespread use of hydrocarbons

in phenolic block processes for insulation purposes, although its use continues for floral foams.

The introduction of a continuous pipe section process has enabled reduction in foam losses, but

has also enabled a switch in blowing agent to hydrocarbons, based on the more controllable

environment. The bulk of phenolic pipe section supply in the UK is now based on this

technology.

It should be noticed that phenolic foam continues to be something of a niche product in

most global markets and has seen little success to date in developing countries. However, its

innate potential continues to be recognised in a number of important and growing markets. In

general terms, it is believed that any further development of a manufacturing base in developing

countries will be supported by comprehensive technology transfer from one of the current

technology holders.

As a consequence, there seems to be little requirement for support for the transition of

existing phenolic foam facilities in developing countries.
53

THERMOPLASTIC FOAMS (POLYOLEFIN & XPS)

Extruded thermoplastic foams are the only ones that have historically used ozone

depleting substances. In the case of extruded polystyrene, products fall into two categories:

‘board’ and ‘sheet’, with ‘board’ being used for a variety of insulation, buoyancy and recreational

activities, while ‘sheet’ has been focused on food and other packaging. Polyolefin (both

polyethylene and polypropylene) foams have also found uses in these sectors, but the use of

polyolefin foams in insulating applications has been more limited.

Equipment for the manufacture of extruded thermoplastic products varies substantially by

region and application. In North America, the manufacturing lines tend to be long, for optimum

speed and also capable of producing wide boards (typically 1.2 metres) at thicknesses down to

25mm. This requirement necessitates a substantial engineering solution and makes the transfer

from one blowing agent to another very challenging. In Europe, the requirements are more

modest, with many lines generating product at a maximum of 0.6 metres in width and at greater

thicknesses. In South East Asia (most notably China), where the demand for extruded

polystyrene foam is growing at its fastest, the technical and processing requirements are still

more limited. In many cases, the polystyrene being used for extrusion has a high recycled

content, making it less easy to process. Products generated in this scenario tend to be lower grade

than in North America and Europe and are typically processed on 0.6 metre lines.

Most thermoplastic foams still depending on HCFCs have used a combination of HCFC142b and HCFC-22. The proportions of each have varied considerably depending on the

application and, in some instances, each blowing agent has been used in isolation. Alternatives to

HCFC-142b/22 include, saturated and unsaturated HFCs, hydrocarbons, CO2 and CO2/ethanol.

CO2, in isolation, has been found to be particularly difficult to process, which is one of the

reasons why combinations with oxygenated hydrocarbons have been explored. Even then, there

have been some shortcomings in the technology that have limited processing speeds and product

ranges.

The unsaturated HFCs have the potential to provide the best solution from a purely

technical and environmental perspective. Hydrocarbons also offer a significant solution provided

that the flammability issues can be managed at both product and process level. The extruded

foam industry has had significant experience of managing hydrocarbons in the ‘sheet’ sector,

which tended to bypass HCFCs and move straight to hydrocarbons when phasing out of CFCs.

However, the experience of fires was commonplace and led some to conclude that this was not

really a sustainable solution. Nevertheless, few ‘sheet’ manufacturers have stepped back from

their choice and have presumably found coping strategies.

There is an additional challenge for ‘board’ products, however. “Board” products are

relatively thick for both construction and packaging applications. In developed countries where

hydrocarbons have been adopted (particularly in polyolefin foams), this led to a particular

problem with boards in storage and transport. In essence, the rate of diffusion of hydrocarbon out

of the products was not sufficiently fast after production to avoid the build-up of flammable
54

gases in the post-production areas. This led to some incidents. The matter was finally addressed

by most manufacturers through the use of perforating equipment to release the hydrocarbon

blowing agent physically.

Another major challenge for the thermoplastic foams sector lies in dealing with

investment costs and/or blowing agent availability. The following table illustrates the fact that

penalties are likely to be faced either in the context of investment cost (e.g. hydrocarbons or CO2)

or in operating costs and availability (saturated and unsaturated HFCs). However, it should be

noted that HFC-134a is relatively widespread because of its existing use as a refrigerant.

Blowing Agent Criterion HCFC142b/22 Hydrocarbons Saturated

HFCs

Unsaturated

HFCs (HFOs) CO2

CO2

/ethanol

Investment Costs + ++/+++ + + +++ ++/+++

Operating Costs ++ + ++/+++ +++ +/++ +/++

Widespread Availability ++ ++ +/++ + +/++ +/++

Potential to blend ++ ++/+++ +++ ++ ++/+++ ++/+++

+++ High; ++ Medium; + Low;

An additional factor to consider is the lead time that would be required for further

conversion, especially for non-Article 5 countries, bearing in mind the testing necessary to meet

strict building codes.

Extruded Polystyrene (XPS) Board

The use of extruded polystyrene is primarily in the construction sector where it is used for

a variety of insulation purposes, both in walls and roofs, but most notably in floors, where the

product has specific competitive advantages. The product has competed successfully against both

rigid polyurethane foams and mineral fibre in all the major regions of the world, although its

mode of success has varied depending on the regional demand patterns. This point speaks to the

versatility of extruded polystyrene in its application.

The whole extruded thermoplastic foam sector was established on the ease of use of CFC12 as a blowing agent. It was only when the phase-out of CFCs was required that the split

between choices for ‘board’ and ‘sheet’ materials occurred. Sheet products moved predominantly

to hydrocarbons, while board products chose to use HCFC-142b/22 blends for the most part, in

order to retain the requisite thermal performance.

When the blend was chosen, it was known that the cell wall permeability of HCFC-142b

was significantly lower than that of HCFC-22. Therefore, the long-term thermal performance of

products would largely be determined by the proportion of HCFC-142b in the blend and its

subsequent retention. Since HCFC-22 is a major refrigerant, its availability has been greater, and

its price lower, throughout its period of use. This has been particularly important in some

developing country regions where access to HCFC-142b has been more difficult and the cost

significantly higher. Since some product and building codes will have been written around the
55

sole use of HCFC-22, it may make the transitional hurdle a little easier when phase-out of

HCFCs is finally embraced.

The extruded polystyrene sector is continuing to grow rapidly in China and elsewhere in

Asia and practical transitional solutions will be essential. It seems unlikely that either saturated or

unsaturated HFCs will make major in-roads in the markets for reasons of cost and availability.

Therefore, the most likely solution will be based on hydrocarbons, on their own or in blends. The

level of investment needed to support this is unclear, but, since the plants are relatively small,

and there is parallel experience with extruded polystyrene sheet, it may be that the transition will

be less challenging than currently envisaged. CO2 seems unlikely as a solution in isolation.

The extrusion process remains highly emissive, and this puts a particular burden on the

avoidance of high GWP solutions, such as saturated HFCs. The only time when such an approach

might be justified is in applications and jurisdictions where thermal performance is absolutely

paramount. In these cases, it may be possible to make further transitions from saturated to

unsaturated HFCs in due course.

Polyolefin Foams

Polyolefin foams have made less penetration into the construction markets that have been

the bedrock of the extruded polystyrene industry. The one exception to this has been in the pipe

insulation sector, where the added resilience offered by the product has proved of substantial

value. The primary use for polyolefin foams has been as a high performance packaging material –

particularly when used for the packaging of delicate, high value equipment.

The choice of blowing in the polyolefin foam sector has followed a very similar pattern to

that of extruded polystyrene foam. However, because of the lack of a large demand for insulating

properties, the industry switched more fully to hydrocarbons when transitioning from CFCs. The

remaining use of HCFCs in this product sector is much more limited than in the extruded

polystyrene sector. Nevertheless, where use does exist -possibly in goods related to recreational

applications- technical assistance may be necessary to ensure that appropriate precautions are

taken in any final switch to hydrocarbons.

The polyolefin foam sector is only seen to present a limited challenge in the efforts to

phase of HCFCs under Decision XIX/6. It would appear that relevant climate-positive solutions

are available and that widespread experience exists concerning their use. There may be some, as

yet, unidentified niche applications that could present more of a challenge, but no evident has yet

emerged to this effect.
56

CHAPTER 3: BANKS AND RECOVERY OPTIONS

RECENT TEAP WORK ON THIS ISSUE

The Technology and Economic Assessment Panel (TEAP) of the Montreal Protocol has

been actively quantifying and locating banks of ODS in a series of studies responding to

decisions of the Parties. The latest of these was Decision XX/7 which initiated the most

comprehensive review of banks and potential mitigation options yet.

The Task Force convened by the TEAP to complete this work reported in two separate

reports: Phase 1 in June 2009 and Phase 2 in October 2009. The second of these reports focused

particularly on the quantification of savings that could be achieved, the timing at which recovery

and destruction would be required and the cost of so doing. As had been the case in earlier

studies, the TEAP Task Force divided the ODS Banks into three major categories of ‘effort’:

low, medium and high. Although ‘effort’ is partially a synonym for ‘cost’, this is not completely

the case, since there is some adjustment for the fact that the relative costs of some sectors, such

as foams, will always be higher than other sectors, such as refrigeration. Rather than having all

refrigerant recovery in the ‘low’ category and all foam in the ‘high’ category, there is some

offsetting to allow a level of differentiation within each sector. Note that although the emphasis

of the research was on reducing ODS emissions, most of the conclusions could also apply to

reducing HFC emissions as well.

The TEAP analysis also recognized that recovery from densely populated (urban) areas

would be easier than from sparsely populated (rural) areas. Its full analysis is summarized in the

following table:

Sector Low Effort Medium Effort High Effort

Domestic Refrigeration – Refrigerant DP SP

Domestic Refrigeration – Blowing Agent DP SP

Commercial Refrigeration – Refrigerant DP SP

Commercial Refrigeration – Blowing Agent DP SP

Transport Refrigeration – Refrigerant DP/SP

Transport Refrigeration – Blowing Agent DP/SP

Industrial Refrigeration – Refrigerant DP/SP

Stationary Air Conditioning – Refrigerant DP SP

Other Stationary Air Conditioning – Refrigerant DP SP

Mobile Air Conditioning – Refrigerant DP SP

Steel-faced Panels – Blowing Agent DP SP

XPS Foams – Blowing Agent DP/SP*

PU Boardstock – Blowing Agent DP/SP*

PU Spray – Blowing Agent DP*/SP*

PU Block – Pipe DP SP

PU Block – Slab DP SP

Other PU Foams – Blowing Agent DP/SP*

Halon – Fire Suppression DP SP

DP = Densely Populated Areas; SP = Sparsely Populated Areas

* Still technically unproven
57

This table underlined the fact that, even before cost elements were explicitly addressed,

the management of existing ODS banks, in foams, was seen as representing the most significant

challenge (largely high effort). Indeed, in some instances (e.g., PU Spray Foams) it was

acknowledged that recovery and destruction of blowing agents from those sources was still

globally unproven technically. This reflects the fact that flows of ODS into building demolition

waste streams are still in their infancy and there is little global experience as yet in managing

such materials. Even in Japan, where the regulation of demolition processes attracts high levels

of compliance, a study on ODS Bank Management in the built environment conducted by the

Japan Technical Committee on Construction Materials (JTCCM) in the period 2002-2005

concluded that it was not possible to mandate the recovery and destruction of ODS in buildings

because of continuing uncertainties about technical feasibility and economic impacts. Of course,

this is not to rule out the likelihood that experience will spawn innovation and technological

development in this area. However, the Japanese view was that this is best achieved by voluntary

action, often supported by incentives, rather than unenforceable legislation.

The main conclusions from this work were that the refrigerant banks represented the most

cost-effective ODS bank management options (as measured in $ per tonne of CO2 saved),

partially because of their easier accessibility and partially because the baseline emissions for

refrigerants are higher than for foams, which tend to display relatively low emissions during the

majority of their lifecycles.

For appliances, it was clear that measures to manage ODS banks would need to be

implemented within the next five years, even in developing countries, if the main ozone and

climate benefits arising from CFC recovery and destruction were to be realised. This fact is

highlighted in the next section where the location of ODS banks on foams is analysed for 2008.

For foams, the main areas where recovery at end-of-life could be legitimately expected at

low/medium effort, were identified as:

 Domestic Appliances

 Commercial Refrigeration

 Steel-faced panels

 Block Pipe Section & Slab

Progress on recovery and destruction from these product areas are reviewed further in the

later sections of this chapter.

BANK ESTIMATES IN 2008

In the period leading up to the preparation of this report, it had been anticipated that the

Committee would provide baseline bank estimates for 2020. However, in view of the large

uncertainties still associated with the selection of alternatives and the sensitivities involved in

making quantitative predictions about future consumption, it was decided to limit this chapter to

the assessment of banks as at 2008.
58

The following tables provide a summary of the banks of blowing agents contained within

foams in developed and developing countries for 2008.

Foam Banks - Developed Countries - 2008

CFCs HCFCs HFCs HCs Other Total % CFC*

Available

% HCFC*

Available

PU - Dom. Appliances 283528 144834 55607 224807 0 708776 21.59% 99.80%

PU - Other Appliances 27324 68954 22953 17789 255 137275 46.30% 99.88%

PU - Reefers 12342 18639 6816 6970 0 44767 28.33% 98.83%

Total Appliances 323194 232427 85376 249566 255 890818 23.94% 99.75%

36.28% 26.09% 9.58% 28.02% 0.03%

PU - Boardstock 616683 297973 7560 383219 0 1305435 100.00% 100.00%

PU - Continuous Panel 147619 56633 21552 116124 0 341928 100.00% 100.00%

PU - Disc. Panel 123785 85377 38707 20801 0 268670 100.00% 100.00%

PU - Spray 97608 102470 40733 0 523 241334 100.00% 100.00%

PU - Block-Pipe 10220 4660 1631 3379 0 19890 18.74% 98.15%

PU - Block-Slab 26168 12192 4110 8573 0 51043 27.11% 98.64%

PU - Pipe-in-Pipe 38950 15506 3531 10767 0 68754 100.00% 100.00%

XPS - Board 250016 369145 26339 28113 0 673613 100.00% 100.00%

PE - Block-Pipe 8033 5183 516 8055 0 21787 18.74% 98.15%

PE - Block-Slab 8057 3317 643 9234 0 21251 27.11% 98.64%

PF - Boardstock 10699 6724 1772 13741 0 32936 100.00% 100.00%

PF - Disc. Panel 4364 3640 559 3399 0 11962 100.00% 100.00%

PF - Block-Pipe 3865 3153 1038 2849 0 10905 18.74% 98.15%

PF - Block-Slab 1185 987 626 606 0 3404 27.11% 98.64%

Total Constr./Other 1347252 966960 149317 608860 523 3072912 96.75% 99.95%

43.84% 31.47% 4.86% 19.81% 0.02%

Grand Total 1670446 1199387 234693 858426 778 3963730 82.66% 99.91%

42.14% 30.26% 5.92% 21.66% 0.02%

* Availability based on correction for banks already in waste stream

The table shows that only around 24% of CFC blowing agent banks remains available in

Domestic Appliance Foams with the remainder already in landfill. By contrast, most the HCFC remains

available. For the ‘construction and other’ foams, only the products produced from block foams have

significantly reached their end-of-life and entered into the waste stream. The opportunity for recovery

from products is, therefore, still substantial if appropriate techniques can be developed to recovery and

destroy blowing agents economically.
59

Foam Banks - Developing Countries - 2008

CFCs HCFCs HFCs HCs Other Total % CFC*

Available

% HCFC*

Available

PU - Dom. Appliances 241750 108607 1217 181904 0 533478 72.98% 100.00%

PU - Other Appliances 7977 16902 0 0 0 24879 85.93% 100.00%

PU - Reefers 14850 23767 531 0 0 39148 81.91% 100.00%

Total Appliances 264577 149276 1748 181904 0 597505 73.87% 100.00%

44.28% 24.98% 0.29% 30.44% 0.00%

PU - Boardstock 1709 0 0 784 0 2493 100.00% N/A

PU - Continuous Panel 22306 9092 0 2621 0 34019 100.00% 100.00%

PU - Disc. Panel 55536 34961 0 4205 0 94702 100.00% 100.00%

PU - Spray 60232 37146 0 0 0 97378 100.00% 100.00%

PU - Block-Pipe 8011 2953 0 0 0 10964 67.58% 100.00%

PU - Block-Slab 12509 4562 0 0 0 17071 75.55% 100.00%

PU - Pipe-in-Pipe 42387 21122 0 227 0 63736 100.00% 100.00%

XPS - Board 70311 184277 0 44 0 254632 100.00% 100.00%

PE - Block-Pipe 8815 0 0 4898 0 13713 67.58% N/A

PE - Block-Slab 10975 0 0 5324 0 16299 75.55% N/A

PF - Block-Pipe 782 198 0 0 0 980 67.58% 100.00%

PF - Block-Slab 782 198 0 0 0 980 75.55% 100.00%

Total Constr./Other 294355 294509 0 18103 0 606967 96.04% 100.00%

48.50% 48.52% 0.00% 2.98% 0.00%

Grand Total 558932 443785 1748 200007 0 1204472 85.55% 100.00%

46.40% 36.84% 0.15% 16.61% 0.00%

* Availability based on correction for banks already in waste stream

By way of contrast to the developed country scenario, approximately 73% of banked CFCs in

domestic appliance foams were still available for recovery and destruction in 2008. There are no

significant HCFCs already in the waste stream and these remain available for recovery and destruction

where economically viable.
60

RECOVERY ACTIVITIES IN THE APPLIANCE SECTOR

Experiences to date – Developed Countries

In contrast to the challenges of the building sector, there is considerably more experience

in managing foams from appliances and commercial refrigeration equipment. In several regions

of the world, including Europe and Japan the recovery of blowing agents from domestic

refrigerators and freezers has been required. This has been extended over time to cover other

types of appliance. In the case of Europe this has been driven by product lifecycle legislation

such as the WEEE6 Regulation rather than the ozone regulations per se, although efforts have

been made to ensure that both regulatory strands are complementary to one another.

This said, there have been on-going concerns in Europe about the percentage of end-oflife appliances being de-manufactured in line with the legislative requirements as well as the

maintenance of adequate standards for recovery and destruction within those operations

designated to manage the process. Even in Germany, a recent study uncovered a number of

failures to uphold the existing standards. Further investigation revealed that the most likely cause

of these malpractices has been the over-capacity in the sector, with prices for the de-manufacture

of domestic refrigerators dropping from their initial levels in excess of $25/unit to values as low

as $8/unit.

Another factor to consider here is that voluntary carbon finance cannot be leveraged in

the region, even though the relevant methodologies (Voluntary Carbon Standard (VCS) and

Climate Action Reserve (CAR)) apply to these recovery and destruction operations. This is

because the market sees no ‘additionality’ from ODS recovery and destruction in regions where

the measure is already mandated. Even if such funding were to be available, its contribution

would be less substantial for HCFC recovery and destruction than for CFC recovery and

destruction. This observation arises from the lower GWP of HCFCs in comparison with CFCs.

This issue is dealt with further within the following developing country discussion, where a

further analysis by TEAP is presented.

In North America, there is still no federal requirement for the recovery of blowing agent

from foams in appliances. However, there are a number of state level initiatives which encourage

recovery and destruction. California is looking at the option of using their wider cap-and-trade

mechanisms for the inclusion of ODS recovery, using the Climate Action Reserve methodology

as a basis. However, this methodology necessarily needs to take a conservative view on savings

and the uncertainties around anaerobic degradation of ODS in landfills has led to lower baseline

emission estimates and a reduction in the realisable savings from end-of-life measures. With the

low current valuation of carbon, even on exchanges with high reputations such as CAR, the

financial incentives may be insufficient to encourage widespread recovery and destruction of

foam blowing agents, despite the adoption of semi-automated processes with lower investment

costs.

6 WEEE – ‘Waste Electrical and Electronic Equipment’
61

The other driver for recovery of ODS in appliances in North America has been the

introduction of energy efficiency schemes, promoted by the energy supply companies to reduce

demand in vulnerable regions of the territory. However, these schemes are not obliged to recover

ODS and it is often left to the environmental consciousness of the individual companies to

influence decisions to include recovery from units. This is even more the case for blowing agents

than it is for refrigerants, since blowing agents are further along the cost-abatement curve.

Experiences to date – Developing Countries

An additional piece of analysis of the TEAP data for developing countries, as presented at

the July 2010 Geneva Workshop on ODS Bank Management, illustrated the significant

difference between CFC and HCFC recovery in terms of cost-effectiveness. Depending on

location (urban or rural) the cost of recovery and destruction of HCFCs in appliance foam can

range from $60-$90 per tCO2-eq. saved or even more in developed countries where transport and

labour costs are higher. This compares to a figure of $10 per tCO2-eq. saved for CFCs where the

opportunity exists for both the refrigerant and foam blowing agent to be recovered at the same

time. The analysis doesn’t take into account the recovery of HFC-134a refrigerant in the

appliance, which can, of course, provide additional climate benefit for a given investment under

appropriate circumstances.

Average Cost Effectiveness of Climate Savings

0

200

400

600

800

1,000

1,200

1,400

1,600

0 10 20 30 40 50 60 70 80 90 100

Cost Effectiveness ($ per tonne CO2 saved)

Total Potential Saving (Mtonnes CO2 saved)

CFC

HCFC

Potential for Recovery vs. Cost Effectiveness

The Impact of Dealing with Appliances (2010-2030)

Refrigerant only

Refrigerant & CFC Foam

HCFC Foam in Appliances
62

One of the other factors to consider is that waste streams are unlikely to be segregated by

blowing agent type and the cost-effectiveness will vary according to the product mix arriving at

end-of-life on an annual basis. The following graph illustrates how this might change with time

for appliances in developing countries. It can be seen that the period of greatest cost-effectiveness

is between now and 2020. After that time, higher carbon prices would be needed to support the

cost-effectiveness of recovery of predominantly HCFCs.

Cost Effectiveness Ranges for ODS & ODS Substitute Bank

Management in Developing Countries (Appliances & Foams)

0

10

20

30

40

50

60

70

80

90

100

201020112012201320142015201620172018201920202021202220232024202520262027202820292030

Year

Costs ($ per tonne CO2 saved)

Low Effort - Lower Bound

Low Effort - Upper Bound

Low/Medium Effort - Lower Bound

Low/Medium Effort - Upper Bound

RECOVERY ACTIVITIES IN THE BUILT ENVIRONMENT

Experiences to date by Region (incl. logistics)

As noted in the earlier sections of this Chapter, the only low/medium effort recovery

options for foams in the buildings sector are found in the building services (e.g. pipe and duct

insulation) and in certain forms of prefabricated construction (e.g. steel-faced panels).

In practice, the quantity of block manufactured and used globally for pipe insulation and

other building services products (e.g. duct insulation) is relatively small as a proportion of the

total. Where pipe section is produced from block (or, indeed, extruded from thermoplastic

foams), there is a potential for recovery during decommissioning. This may also be the case for

block foam prefabricated for use in composite panels.

For steel-faced panels there is also some relevant experience, since these products tend to

be used on buildings in Europe with shorter average life-times than traditional constructions

(typically 30 years). Although these are only now reaching the waste stream in any number, the
63

potential to use existing refrigerator de-manufacturing equipment or even direct incineration

exists. In most cases, the presence of the steel facings also adds to the economic case since these

can be recovered and recycled. Nevertheless, across the European Union’s 27 member states

(EU-27) there is a large range of demolition waste practice. Only where waste segregation is

already highly advanced (e.g., Austria) does the economics of recovery and destruction stack-up.

This is demonstrated in the following table, although it should be noted that the final relative

cost-effectiveness (in cost per tonne of CO2 saved) between appliances and panels will depend on

the blowing agent mix reaching the waste stream:

Cost effectiveness – Panels vs. Appliances

Tonnage

Band

Domestic

Appliance

JTCCM

(Japan)

Kingspan

Panels

(trial projects)

Austria

Study

Destruction

Transport

Sorting

Dismantling -------

-------

€ 40-50

€ 25-35

€ 55-65

€ 3-4

€ 20-25

€ 20-25

€65-90

€ 4-6

€ 25-35

€ 5-10

Discounted!

€ 20-30

(based on

steel-faced

panels @

€200/te)

Per kg of blowing agent

Discounted!

Total € 65-85 € 98-119 € 99-141 € 20-30

There is therefore some reticence within some Member States to see any move towards a

mandated recovery and destruction requirement for ODS in steel-faced panels. However, the

potential of an incentive-led approach, perhaps based on carbon valuation, may prove a more

mutually acceptable way forward.

Moving onto more general ODS banks in building foam, the most recent study completed

by the Building Research Establishment (BRE) in the United Kingdom, the assessment of cost

associated with the management of ODS in buildings was in the order of £200 ($300) per tCO2-

eq. saved (BRE, 2010). It should be stressed that the prime purpose of this study was not to

review costs in detail, but it is interesting to note that this assessment supports the view that

average recovery costs from the wider building sector would be proportionately higher than those

associated with steel-faced panels.
64

FUTURE TRENDS AND DRIVERS

Financing

The future trends in carbon financing are far from settled at this time following the failure

of the Copenhagen Conference of the Parties to meet a binding agreement on the way forward.

Although the Cancun meeting endorsed alternative bilateral and multilateral funding options via

the Nationally Appropriate Mitigation Actions (NAMAs), it is still not clear whether these will

sit alongside existing mechanisms or actually replace them. Either way, there is expected to be

wholesale reform of the current Clean Development Mechanism (CDM). In turn, this is leading

to considerable uncertainty about the valuation of carbon savings in the short to medium terms.

With this in mind, the valuation of carbon in the short-term depends on intrinsic valuations

placed on carbon mitigation at national level rather than a market-based carbon price per se. The

only region where this is not strictly true is in Europe, where the EU Emissions Trading Scheme

(EU ETS) continues to provide a direct monetary basis (around €17 per tonne of CO2 as at May

2011). However, as noted earlier in this chapter, there is no specific leverage for ODS recovery

from appliances, because the measure would not be additional to the regulatory base (WEEE and

the recast Ozone Regulation).

Other Regulatory Drivers

With continuing uncertainties about the cost-effectiveness of blowing agent recovery

from foams in a number of key sectors, it is unlikely that regulation will extend significantly in

the next five years, particularly because access to public or private finance is likely to be limited

under the current economic constraints. The link between proposed regulation and the cost has

been heightened considerably in recent years because of the need for Regulatory Impact

Assessments in a number of jurisdictions. There is concern amongst some industry sectors that

penalising the low/medium effort product base by the stigma of regulatory control, when other

high effort products are likely to remain unregulated would drive counter-productive market

behaviour.
A1 - 1

APPENDIX 1: REVIEW OF ALTERNATIVE BLOWING AGENTS

The major blowing agents being commercially used as substitutes for HCFCs in the foam

sector, or being considered for commercial introduction in the short-term, are shown in the subsections that follow – each of which contains a table with basic properties and supply information.

These tables are supplemented by descriptive paragraphs which provide technical information on

the blowing agents themselves and some information on usage patterns and commercial

availability. It should be noted that there are no references to regulatory constraints in this Section.

While the impact of ODS regulations is probably well known to the reading audience and does not

require further iteration here, it might be useful to note, for example, that other environmental

factors, such as classification as volatile organic compounds (VOCs) may have a bearing on local

acceptance. The reader is therefore encouraged to make a full evaluation of the national and local

circumstances when choosing blowing agent options.

The tables and the subsequent descriptive paragraphs provide technical information on the

blowing agents themselves and some information on usage patterns and commercial availability. It

should be noted that there are no references to regulatory constraints in this Appendix. While, the

impact of ODS Regulations is probably well known to the reading audience and does not require

further iteration here, it might be useful to note, for example, that all fluorocarbons in the United

States are not treated as Volatile Organic Compounds (VOCs) for regulatory purposes.

The blowing agents options have been divided in seven different families:

1.1 HCFCs

1.2 Hydrocarbons

1.3 Carbon Dioxide

1.4 Oxygenated Hydrocarbons (Methyl Formate, Methylal and Dimethyl Ether)

1.5 Chlorinated Hydrocarbons (Methylene Chloride, Trans-1,2 di-chloroethylene and 2-

chloropropane)

1.6 Saturated HFCs

1.7 Unsaturated HFCs (HFOs)
A1 - 2

1.1 HCFCs

HCFC-141b HCFC-142b HCFC-22

Chemical Formula CH3CFCl2 CH3CF2Cl CHCIF2

Molecular Weight 116.95 100.50 86.47

Boiling Point ( 0C ) 31.9 -9.2 -40.8

Gas Conductivity (mW/mK @ 100C) 8.8 8.4 9.9

Flammable Limits in Air (vol.%) 7.6-17.7 6.2-17.9 -

TLV or OEL (ppm) (USA) 500 1000 1000

GWP (100 yr time horizon) 725 2310 1810

Key Producers

Arkema, Cgangsu 3f,

Daikin, Hangzhou

Fist, Kangtai Fluorine

Chemical, Quzhou

Rongqiang, Shandong

Dongda, Solvay,

Zhejiang Lantian,

Zhejiang Sanmei

Arkema, Cgangsu

3f, Daikin,

Hangzhou Fist,

Kangtai Fluorine

Chemical,

Shandong Dongda,

Solvay, Zhejiang

Sanmei

Arkema, Cgangsu 3f,

Daikin, DuPont,

Honeywell, Produven,

Quimobasicos,

Quzhou Rongqiang,

Shandong Dongyue,

Solvay, Zhejiang

Sammei, Zhejiang

Quhua.
A1 -3

HCFC – 141b

Description & Usage

HCFC-141b is a liquid at room temperature and does not have a flash point. HCFC-141b

has been used as a foam blowing agent in almost all rigid and integral skin foam sectors.

Physical and Chemical properties7

Chemical name: 1,1-dichloro-1-fluoroethane

Formula: CH3CFCl2

Molecular Weight: 116.95

EC Number (EINECS): 605-613-2

CAS Number: 1717-00-6

Density (g/cm3) 1.25 (10 °C)

Boiling Point (°C) 31.9

Vapour pressure (mmHg) 525 (25 oC)

Gas Conductivity (mW/m. K) 8.8 (10 °C), 9.7 (25 °C)

Vapour density (air=1) 4.1

Solubility in water 1.7 g/L

HSE properties

Toxicological data:

WEEL, 8 hr. TWA, ppm 500

Autoignition temperature 550 °C

Flammable limits in air (vol. %) 7.6-17.7

VOC No

GWP8(100-yr Time Horizon) 725

ODP 0.11

Commercial status

Producers: Arkema, Changshu 3f, Daikin, Hangzhou Fist,

Kangtai Fluorine Chemical, Quzhou

Rongqiang, Shandong Dongda, Solvay,

Zhejiang Lantian, Zhejiang Sanmei.

7

http://ull.chemistry.uakron.edu/erd/Chemicals/2000/247.html. Consulted April 2011.

8

IPCC Fourth Assessment Report: Climate Change 2007.
A1 -4

HCFC – 142b

Description & Usage

HFC-142b is a gas at room temperature, highly flammable. It is used as a foam blowing

agent for extruded polystyrene foams. It can be used alone or as a blend with HCFC-22.

A blend of 60/40 HCFC-142b/HCFC-22 (60/40) is non-flammable.

Physical and Chemical properties9

Chemical name: 1-chloro-1,1-difluoroethane

Formula: CH3CF2Cl

Molecular Weight: 100.50

EC Number (EINECS): 200-891-8

CAS Number: 75-68-3

Density/Specific gravity 1.107 (25 oC)

Boiling Point (°C) -9.2

Vapour pressure (mmHg) 7786 (25 oC)

Gas Conductivity (mW/m. K) 8.4 (10 °C), 11.5 (25 °C)

Vapour density (air=1) 3.49

Solubility in water Slightly soluble

HSE properties

Toxicological data:

TLV or OEL (USA, ppm) 1000

WEEL, 8 hr. TWA, ppm 1000

Autoignition temperature 632 °C

Flammable limits in air (vol. %) 6.2-17.9

Flash Point -65 oC

VOC No

GWP10 (100-yr Time Horizon) 2310

ODP 0.066

Commercial status

Producers: Arkema, Changshu 3f, Daikin, Hangzhou Fist,

Kangtai Fluorine Chemical, Shandong

Dongda, Zhejiang Lantian, Zhejiang Sanmei.

9

http://ull.chemistry.uakron.edu/erd/Chemicals/2000/131.html. Consulted April 2011.

10 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -5

HCFC-22

Description & Usage

HCFC-22 is a non-flammable colourless gas liquefied under pressure. One main

application is as a non-flammable mixture with HCFC-142b for PU and XPS foams. In

rigid PU foam it has been used in combination with HCFC-141b.

Physical and Chemical properties11

Chemical name: Chlorodifluoromethane

Formula: CHCIF2

Molecular Weight: 86.47

EC Number (EINECS): 200-871-9

CAS Number: 75-45-6

Density (g/cm3) 1.41 (20 °C)

Boiling Point (°C) -40.8

Vapour pressure (mmHg) 6290 (25 oC)

Gas Conductivity (mW/m. K) 9.9 (10 °C), 11.0 (30 °C)

Vapour density (air=1) 2.98

Solubility in water 3 g/L

Soluble in most organic solvents

HSE properties

Toxicological data12

TLV (as TWA) 1000 ppm, 3540 mg/m3(ACGIH

1992-1993)

TWA (NIOSH REL) 1000 ppm (3500 mg/m3)

Decomposition temperature 480 °C

VOC No

GWP13 (100-yr Time Horizon) 1810

ODP 0.055

Commercial Status

Producers: Arkema, Changshu 3f, Daikin, DuPont,

Honeywell, Produven, Quimobasicos,

Quzhou Rongqiang, Shandong Dongyue,

Solvay, Zhejiang Sammei, Zhejiang Quhua.

11 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/83.html. Consulted April 2011.

12 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/83.html. Consulted April 2011.

13 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -6

1.2 Hydrocarbons

Cyclo-Pentane n-Pentane Iso-Pentane Iso-Butane n-Butane

Chemical Formula (CH2)5 CH3(CH2)3CH3 CH3CH(CH3)CHCH3

CH3CH(CH3)CH CH3CH2CH2CH3

Molecular Weight 70.1 72.1 72.1 58.1 58.1

Boiling Point ( 0C ) 49 36.1 28 -11.7 -0.45

Gas Conductivity (mW/mK

@ 100C) 11.0 14.0 13.0 15.9 13.6

Flammable Limits in Air

(vol.%) 1.5-8.7 1.4-8.0 1.4-8.3 1.8-8.4 1.8-8.5

TLV or OEL (ppm) (USA) 600 610 1000 800 800

GWP (100 yr time horizon) <25 <25 <25 <25 <25

Key Producers

Chevron

Phillips,

Haltermann

Products,

ExxonMobil,

Haldia

Petrochemical

Ltd., Maruzen

Petrochemical,

Puyang

Zhongwei Fine

Chemical

Beijing

Yanshan

Petrochemical

Co. Ltd.,

Chevron

Phillips,

Haltermann

Products,

ExxonMobil,

Maruzen

Petrochemical,

Shell

Chevron Phillips,

Haltermann

Products,

ExxonMobil, Jilin

Jinlong Industrial Co

Bayer, Chevron

Phillips,

ExxonMobil,

Refinery of

Jinling

Petrochemical

Chevron

Phillips,

ExxonMobil,

Shanghai

Petrochemical

Co. Ltd.

^ Measured at 0 oC
A1 -7

CYCLOPENTANE

Description and Usage

Cyclopentane is a colorless and flammable liquid with a gasoline-like odor. It is a

blowing agent for polystyrene and polyurethane foam processes.

Physical and Chemical properties14

Chemical name: Cyclopentane

Formula C5H10

Molecular Weight 70.13

EC Number (EINECS) 206-016-6

CAS Number 287-92-3

Density (g/cm3) 0.746 (20 °C)

Boiling Point (oC) 49

Melting point (oC) -93.3

Vapour pressure (mmHg) 318 (20 °C)

Gas Conductivity (mW/m.K) 11.0 (10 °C)

Vapour density (air=1) 2.42 (20 °C)

Solubility in Water Insoluble

HSE properties15

Toxicological data

TLV (as TWA) (ACGIH 1993-1994)

TWA (NIOSH REL)

600 ppm, 1720 mg/m3

600 ppm, 1720 mg/m3

Flammable limits in air (%) 1.5 - 8.7

Autoignition Temperature 380 °C

Flash Point (°C) -42

VOC Yes16

GWP (100-yr Time Horizon) <2517

ODP 0

Commercial Status

Producers Chevron Phillips, Haltermann

Products, ExxonMobil, Haldia

Petrochemicals Ltd., Maruzen

Petrochemical, Puyang Zhongwei Fine

Chemical Co., Ltd.

14 http://ull.chemistry.uakron.edu/erd/Chemicals/8000/6348.html. Consulted April

2011.

15 http://ull.chemistry.uakron.edu/erd/Chemicals/8000/6348.html. Consulted April

2011.

16 Subject to regulations that can vary from country to country and within a country even from

region to region.

17 Precise figure varies according to local atmospheric conditions.
A1 -8

ISOPENTANE

Description and Usage

Isopentane is a colorless and flammable liquid with a gasoline-like odor. It is a blowing agent for

polystyrene and polyurethane foam processes.

Physical and Chemical properties18

Chemical name: 2-Methylbutane

Formula C5H12

Molecular Weight 72.15

EC Number (EINECS) 201-142-8

CAS Number 78-78-4

Density (g/cm3) 0.620 (20°C)

Boiling Point (oC) 28

Melting point (oC) -160

Vapour pressure (mmHg) 727 (25 °C)

Gas Conductivity (mW/m.K) 13.0 (10 °C)

Vapour density (air=1) 2.48 (20 °C)

Solubility in Water < 0.1 g /100ml (23°C)

HSE Properties19

Toxicological data

TWA (ACGIH) 600 ppm

Odor threshold (ppm) 10

Flammable limits in air (%) 1.4 – 8.3

Autoignition Temperature (°C) 420

Flash Point (°C) -57

VOC Yes20

ODP 0

GWP (100-yr Time Horizon) <2521

Commercial Status

Producers Chevron Phillips, Haltermann Products,

ExxonMobil, Jilin Jinlong Industrial Co.

18 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/45.html. Consulted April 2011.

19 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/45.html. Consulted April 2011.

20 Subject to regulations that can vary from country to country and within a country

even from region to region

21 Precise figure varies according to local atmospheric conditions.
A1 -9

n-PENTANE

Description and Usage

n-Pentane is a colorless and flammable liquid with a gasoline-like odor. It is a blowing

agent for polystyrene and polyurethane foam processes.

Physical and Chemical properties22

Chemical name: n-Pentane

Formula C5H12

Molecular Weight 72.1498

EC Number (EINECS) 203-693-4

CAS Number 109-66-0

Density (g/cm3) 0.62 6 (20 °C)

Boiling Point (oC) 36.1

Melting point (oC) -129.7

Vapour pressure (mmHg) 512 (25 °C)

Gas Conductivity (mW/m.K) 14.0 (10 °C)

Vapour density (air=1) 2.48 (20 oC)

Solubility in Water 0.04 g /100ml (23 °C)

HSE Properties23

Toxicological data

TWA (OSHA PEL)

TWA (NIOSH REL)

C (NIOSH REL)

LEL (NIOSH IDLH)

1000 ppm, 2950 mg/m3

120 ppm, 350 mg/m3

610 ppm, 1800 mg/m3(15-minute)

1500 ppm

Flammable limits in air (%) 1.4 – 8.0

Autoignition Temperature (°C) 285

Flash Point (°C) - 49

VOC Yes24

ODP 0

GWP (100-yr Time Horizon) <2525

Commercial Status

Producers Beijing Yanshan Petrochemical Co.

Ltd., Chevron Phillips, Haltermann

Products, ExxonMobil, Maruzen

Petrochemical, Shell.

22 http://ull.chemistry.uakron.edu/erd/Chemicals/8000/7301.html. Consulted April

2011.

23 http://ull.chemistry.uakron.edu/erd/Chemicals/8000/7301.html. Consulted April

2011.

24 Subject to regulations that can vary from country to and from region to region

25 Precise figure varies according to local atmospheric conditions.
A1 -10

ISOBUTANE

Description and Usage

Isobutane is a colorless gas with a faint petroleum-like odor. It is a blowing agent for

polyethylene and polyurethane foam processes.

Physical and Chemical properties26

Chemical name: Isobutane

Formula C4H10

Molecular Weight 58.12

EC Number (EINECS) 200-857-2

CAS Number 75-28-5

Density/Specific gravity 0.557

Boiling Point (oC) -11.7

Melting point (oC) -255.3

Vapour pressure (mmHg) 2580 (25 oC)

Gas Conductivity (mW/m.K) 15.9 (20 oC)

Vapour density (air=1) 2.01 (20 oC)

Solubility in Water Slightly soluble

HSE properties27

Toxicological data

TWA (NIOSH REL) 800 ppm, 1900 mg/m3

Flammable limits in air (%) 1.8 – 8.4

Flash Point (°C) -107

Autoignition Temperature (°C) 460

GWP (100-yr Time Horizon) <2528

VOC Yes29

ODP 0

Commercial Status

Producers Bayer, Chevron Phillips, ExxonMobil,

Refinery of Jinling Petrochemical

26 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/24.html. Consulted April 2011.

27 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/24.html. Consulted April 2011.

28 Precise figure varies according to local atmospheric conditions.

29 Subject to regulations that can vary from country to country and within a country

even from region to region
A1 -11

n-BUTANE

Description and Usage

n-Butane is a colorless gas with a faint disagreeable odor. It is used It as blowing agent

for polyethylene and extruded polystyrene processes.

Physical and Chemical properties30

Chemical name: n-butane

Formula C4H10

Molecular Weight 58.12

EC Number (EINECS) 203-448-7

CAS Number 106-97-8

Density (g/cm3) 0.579 (20 °C)

Boiling Point (oC) -0.45

Melting point (oC) -138.35

Vapour pressure (mmHg) 1556 (20 °C)

Gas Conductivity (mW/m.K) 13.6 (0°C)

Vapour density (air=1) 2.046

Solubility in Water 61mg/L (20 °C)

HSE properties31

Toxicological data

TWA (ACGIH TLV)

TWA (OSHA PEL)

800 ppm

800 ppm

Odor threshold (ppm) 50000

Flammable limits in air (%) 1.8 - 8.5

Flash Point (°C) -60

Autoignition Temperature (°C) 405

GWP (100-yr Time Horizon) <2532

VOC Yes33

ODP 0

Commercial Status

Producers Chevron Phillips, ExxonMobil,

Shanghai Petrochemical Co. Ltd.

30 http://ull.chemistry.uakron.edu/erd/Chemicals/22000/20510.html. Consulted April

2011.

31 http://ull.chemistry.uakron.edu/erd/Chemicals/22000/20510.html. Consulted April

2011.

32 Precise figure varies according to local atmospheric conditions.

33 Subject to regulations that can vary from country to country and within a country

even from region to region
A1 -12

1.3 Carbon Dioxide

CARBON DIOXIDE

Description & Usage

Carbon Dioxide (chemical formula CO2) is a gas in normal conditions and exists in the

atmosphere in small concentrations. It is a colourless, odourless, non-flammable gas,

with very low chemical reactivity and toxicity.

Physical and Chemical Properties34

Formula CO2

Molecular weight 44.0

EC Number (EINECS): 204-696-9

CAS Number: 124-38-9

Triple point

Pressure (bar) 5.11

Temperature (°C) -56.6

Critical point

Pressure (bar) 75.2

Temperature (°C) 31

Specific volume (L/kg) 2.156

Density 1.56 g/cm3(20 °C)

Vaporisation Heat (Kcal/kg) 83.20 (triple point)

Sublimation Heat (Kcal/kg) 136.40 (1 atm)

Heat of formation of gas (Kcal/kg) 2.137 (25 °C)

34 http://ull.chemistry.uakron.edu/erd/Chemicals/8000/6241.html. Consulted April

2011.
A1 -13

Phase diagram for carbon dioxide
A1 -14

HSE Properties

Carbon dioxide is toxic only at very high concentrations (5000 ppm = 9000 mg/m3).

Commercial Data

Carbon dioxide is a generic chemical with numerous suppliers and wide availability in

most countries. There are two main supply sources:

 From mining sources (natural CO2). Carbon Dioxide exists in the underground and is

produced by the decomposition of carbonate compounds in presence of steam or by

the sudden cooling of magma which release CO2 as a gas.

 Chemically generated as a by-product of several chemical reactions in the main

industrial processes. One of the main sources is the process to produce ammonia and

urea. The main impurities are sulphurous products, inert gases and water.

Since CO2 is normally utilized as an additive in the food industry, it is supplied at very

high purity (some suppliers guarantee more than 99,9%).

CO2 is liquefied to be stored and transported. There are two are systems to store carbon

dioxide for industrial use: pressurized bottles for small consumption requirements and

bulk tanks for high consumptions. All mayor suppliers of liquid gases provide rental

contracts for the mentioned storage solutions.

 Pressurised bottles: Bottles of liquid CO2 are at pressures of 70 to 100 bar at normal

ambient temperature. Two types of pressure bottles are used – bottom feed, with an

internal bottom-feed pipe for delivering liquid CO2 or top-feed, for delivering gaseous

CO2. Avoid any heating of the bottles either by sun light or any heating source.

Bottles must be handled with care using gloves and avoiding any hard contact.

 Bulk tanks: CO2 is stored in insulated, pressurised tanks of capacity from 3 up to 50

m

3

, at a pressure of about 16-18 bar and temperature about –30 to –24 °C. The tank is

normally fitted with a CO2 level detector and cooling system to control the pressure

within the required limits. It is recommended that the tank is protected from adverse

weather conditions and to erect around it a guard rail, to restrict access. Any parts of

the electric installation should be placed under a roof or indoors.

Carbon Dioxide as blowing agent for polyurethane foams

In polyurethane foam (flexible slab-stock, flexible moulded, integral skin, rigid) the

carbon dioxide is generated chemically by the reaction between water and isocyanate.
A1 -15

1.4 Oxygenated Hydrocarbons

Methylal Methyl

Formate Di-methyl Ether

Chemical Formula CH3 OCH2OCH3 CH3(HCOO) CH3OCH3

Molecular Weight 76.1 60.0 46.07

Boiling Point ( 0C ) 42 31.5 -24.8

Gas Conductivity (mW/mK @ 150C) Not available 10.7 (@ 250C) 15.5

Flammable Limits in Air (vol.%) 2.2-19.9 5.0-23.0 3.0-18.6

TLV or OEL (ppm) (USA) 1000 100 1000

GWP (100 yr time horizon) <25 <25* 1

Key Producers

Spectrum

Chemicals,

Alcan

International,

Kimbester (China)

Caldic

Lambiotte & Cie

BOC

Foam Supplies

Multiple Chinese

producers

Air Liquide
A1 -16

METHYL FORMATE (ECOMATE®)

Description & Usage

Ecomate® is a colourless, flammable liquid with an ethereal odour. It is a registered

trademark of Foam Supplies, Inc. protected by Patent No. 6753357. It is being promoted

as blowing agent for PU rigid foams mainly but also for flexible foams and microcellular

elastomers with zero ODP and GWP. Use has been reported in commercial refrigeration.

Physical and Chemical properties35

Chemical composition: Methyl Formate 97.5 %, Methanol 2.5

%

Molecular Weight 60

EC Number (EINECS): 203-481-7

CAS Number: 107-31-3

Density (g/cm3) 0.98 (20 °C)

Boiling Point (°C) 32.1

Melting Point (°C) -100

Vapour pressure (mm Hg) 476.4 (20 °C)

Gas conductivity (mW/m. K) 10.7 (25 °C)

Water solubility (%) 33 (20 oC)

HSE Properties36

Toxicological data:

Methyl Formate

ACGIH, TWA (ppm) 100

ACGIH, TWA (ppm) 100

TWA, OSHA (ppm) 100

Flammable limits (vol. %) 5.0 - 23.0

Flash point (°C) approx. -28

Autoignition Temperature (°C) approx. 440 oC

VOC No

GWP (100 years) Negligible

ODP 0

Commercial Status

Current Supplier: BOC, Foam Supplies

35 http://www.ecomatesystems.com. Consulted April 2011.

36 MSDS, Foam Supplies, reviewed on 12.03.2010.
A1 -17

1.5 Chlorinated Hydrocarbons

Methylene Chloride Trans-1,2-

dichloroethylene 2-chloropropane

Chemical Formula CH2Cl2 ClHC=CHCl CH3CHClCH3

Molecular Weight 84.9 97 78.5

Boiling Point ( 0C ) 40 48 35.7

Gas Conductivity (mW/mK

@ 100C) Not available Not available Not available

Flammable Limits in Air

(vol.%) None 6.7-18 2.8-10.7

TLV or OEL (ppm) (USA) 35-100 200 50

GWP (100 yr time horizon) Not available <25 Not available

Key Producers Multiple Sources Arkema Alfa Aesar
A1 -18

METHYLENE CLORIDE

Description & Usage

Methylene chloride, or dichloromethane, is a clear, colourless liquid with a penetrating ether-like odour.

Pure, dry methylene chloride is very stable and will not produce corrosion in mild or galvanized steel,

copper, nickel, lead or tin. In the presence of water, however, it may undergo very slow hydrolysis to

produce small quantities of hydrogen chloride, which can lead to corrosion. This process is accelerated by

elevated temperatures and the presence of alkaline or metals. Commercially available methylene chloride is

normally inhibited with small quantities of stabilizers to avoid this process. Typical stabilizers are

propylene oxide and cyclohexane.

The low photochemical ozone creation potential (PCOP) and lack of ozone depletion potential (ODP) made

it a significant CFC-replacement in the manufacture of polyurethane flexible foam.

Physical and Chemical properties37

Chemical name: Dichloromethane

Formula: CH2Cl2

Molecular Weight: 84.93

EC Number (EINECS): 200-838-9

CAS Number: 75-09-2

Density (g/cm3) 1.322 (20 °C)

Boiling Point (°C) 39.8

Melting Point (°C) -95

Viscosity (cp) 0.41 (25 °C)

Refractive index 1.4244 (20 °C)

Vapour pressure (mmHg) 349 (20 °C)

Vapour density (air=1) 2.9

Water Solubility 10-50 mg/ml

HSE properties

Toxicological data:

TLV (ppm) 50

OSHA PEL (ppm) 25

Flash point -4 oC

Autoignition temperature 605 oC

LFL (%) 13

UFL (%) 223

GWP38 (100-yr Time Horizon) 8.7

The potential carcinogenicity of MC is a controversial issue. There is one study, performed for the National

Toxicology Program (NTP) that suggests carcinogenic effects of high lifetime doses in mice. Other

37 http://ull.chemistry.uakron.edu/erd/Chemicals/8000/6380.html. Consulted April

2011.

38 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -19

bioassays with different animals (rat, hamster) and at lower concentrations did not confirm these findings,

indicating that the association between MC exposure and carcinogenicity may be unique to mice and even

then concentration related. This was supported by subsequent research, concluding that important species

differences exist in metabolism between the mouse on one side, and rats, hamsters, or humans on the other

side. Evidence was provided that the GST pathway of metabolism is linked to the carcinogenic response

observed in mice. Since humans show a very limited ability to metabolize MC via the GST pathway, the

mouse is a poor surrogate for assessing human hazard.

The above mentioned research efforts led to the development of a physiologically based pharmacokinetic

(PB-PK) model to evaluate the carcinogenic risk to man from exposure to MC. Application of this model

on experimental animal data concludes to no significant risk for man under current hygiene standards.

The U.S. EPA has accepted the PB-PK model, and used in its draft Update to the Health Assessment

Document (HAD) for methylene chloride. Also EPA's Science Advisory Board indicated approval. OSHA,

however, indicated reservations, and has based its proposed revision of the occupational exposure standard

for MC on the before mentioned NTP study. The industry has submitted critical comments to this proposal,

and achieved reconsideration by the agency. The effected date for the new standard delayed accordingly.

Industrial mortality studies have shown no evidence of that methylene chloride, even at relatively high

concentrations (100-350 ppm, with peaks of up to 10,000 ppm) represents a carcinogenic or cardiovascular

ischemic risk to humans.

The US Occupational Safety and Health Administration (OSHA) in January 1997 adopted a comprehensive

standard for workplace exposure to methylene chloride. The standard establishes permissible exposure

limits (PELs) of 25 ppm as an 8-hour time-weighted average (TWA) and 125 ppm as a short-term exposure

limit (STEL). The compliance dates vary by industry sector and size of business; all companies must be in

compliance by April 2000 at the latest. The standard also requires medical surveillance and contains a

number of other ancillary provisions. The ACGIH threshold limit value (TLV) is 50 ppm for an 8-hour

TWA exposure. In 1987, the US Consumer Product Safety Commission (CPSC) published a Statement of

Interpretation and Enforcement Policy for household products containing methylene chloride. This policy

statement establishes labeling guidance for these products under the Federal Hazardous Substances Act. In

addition, the use of methylene chloride in cosmetic and food products is restricted by the Food and Drug

Administration (FDA).

The EU classification was established as Carc. Cat. 3 /Xn;R40 in the 23rd ATP in 1997. This classification

was implemented by member states by December 1998.

Commercial status

Methylene chloride is a generic chemical and available from numerous manufacturing and trading sources.

The use of recycled material in PU foam applications is discouraged because of a possible catalytic effect of

dissolved trace metals. Several manufacturers such as Dow Chemical and Solvay offer product versions

that have been specifically stabilized for the use in PU foam.
A1 -20

TRANS-1,2-DICHLOROETHYLENE

Description & Usage

Trans-1,2-dichloroethylene is a liquid at room temperature and is recommended for use in a variety of

polyurethane foam blowing applications primarily in combination with HFC-134a and HFC-245fa. Studies

have shown that trans-1,2-dichloroethylene moderates the frothing effect particularly with HFC-134a and

significantly improves its blowing efficiency.

Physical and Chemical Properties39

Chemical name: trans-1,2-dichloroethylene

Formula: C2H2Cl2

Molecular weight: 96.94

EC Number (EINECS): 205-860-2

CAS Number: 156-60-5

Specific gravity: 1.26

Boiling point (°C) 48

Vapor pressure @ 25°C (mm Hg) 333

Heat of vaporization (kJ/mol) 30.3

Vapor density (air = 1) @ 20°C 1.8

Solubility @ 25°C (g trans / 100 g water) 0.63

HSE properties40

Toxicological data:

TLV 200 ppm (ACGIH TLV®8-hr TWA)

Flammable limits in air (volume %) 6.7 - 18

Flash point (°C) -12

Minimum ignition energy @ 25°C (mJ) 40.5

Autoignition temperature (°C) 460°C

Volatile Organic Compound Yes

GWP (100-yr Time Horizon) Negligible

ODP 0

Commercial Status

Current Producers: Arkema

39 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/108.html. Consulted April 2011.

MSDS, Arkema, Revised 03.04.2006.

40 MSDS, Arkema, Revised 03.04.2006.
A1 -21

1.6 Saturated HFCs

HFC-134a HFC-152a HFC-245fa HFC-365mfc HFC-227ea

Chemical Formula CH2FCF3 CHF2CH3 CF3CH2 CHF2 CF3CH2 CF2 CH3 CF3CHF CF3

Molecular Weight 102 66 134 148 170

Boiling Point ( 0C ) -26.2 -25 15.3 40.2 -16.5

Gas Conductivity (mW/mK @ 100C) 12.4 14.3* 12.5* 10.6* 11.6

Flammable Limits in Air (vol.%) None 3.9-16.9 None 3.8-13.3 None

TLV or OEL (ppm) (USA) 1000 1000 N/A N/A 1000

GWP (100 yr time horizon)^ 1430 124 1030 794 3220

Key Producers

Arkema, Daikin,

DuPont, Honeywell,

Kangtai Fluorine

Chemical, Produven,

Quzhou Rongqiang,

Shandong Dongyue,

Solvay, Zhejiang

Guomao, Zhejiang

Lantian, Zhejiang

Sammei, Zhejiang

Quhua

Changshu 3f,

Daikin, DuPont,

Hangzhou Fist,

Solvay, Shandong

Dongyue, Zhejiang

Lantian, Zhejiang

Sammei.

Honeywell, Central

Glass, Zhejiang

Lantian

Solvay Solvay

* Measured at 24-250C
A1 -22

HFC-134a

Description & Usage

HFC-134a is a non-flammable gas at room temperature. It is the most widely used zero

ODP fluorochemical and is an established refrigerant. HFC-134a has been used as a

blowing agent in almost all foam sectors, particularly rigid and integral skin foam. It is

also being used for extruded polystyrene foam in Europe and North America.

Physical and Chemical properties41

Chemical name: 1,1,1,2-Tetrafluoroethane

Formula: CF3CH2F

Molecular Weight: 102.03

EC Number (EINECS): 212-377-0

CAS Number: 811-97-2

Density (g/cm3) 1.2076 (25 °C)

Boiling Point (°C) - 26.2

Vapour pressure (mmHg) 4730

Gas conductivity (mW/m. K) 12.4 (10 °C), 13.7 (25 °C)

Vapour density (air=1) 3.18

Solubility in water 1.5 g/L

HSE properties

Toxicological data42:

TLV or OEL (USA) (ppm) 1000

WEEL, 8 hr. TWA, ppm 1000

Flash Point -79 oC

Flammable limits in air (vol. %) None

VOC No

GWP43 (100-yr Time Horizon) 1430

ODP 0

Commercial status

Producers: Arkema, Daikin, DuPont, Honeywell, Kangtai

Fluorine Chemical, Produven, Quzhou

Rongqiang, Shandong Dongyue, Solvay,

Zhejiang Guomao, Zhejiang Lantian, Zhejiang

Sammei, Zhejiang Quhua.

41 http://ull.chemistry.uakron.edu/erd/Chemicals/6000/5730.html. Consulted April

2011.

42 MSDS, DuPont, Revised 18.04.2007.

43 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -23

HFC-152a

Description & Usage

HFC-152a is a flammable gas at room temperature. It has limited use in polyurethane

foam because it is flammable, and it diffuses out of the foam quickly, preventing it from

offering additional long term thermal insulation value. Yet, HFC-152a is widely used as

a blowing agent for one component PU foam system where the foam is mostly used to fill

a cavity and thermal insulation value is not the most critical parameter.

HFC-152a is used with HFC-134a in XPS boardstock. Although it does not offer long

term thermal insulation value for the product, it is mainly used to reduce the foam density

of HFC-134a foam, and improve processing conditions. It is also used as blowing agent

for extruded polystyrene sheets, mostly used in food packaging applications. It is the only

HFC that is approved by US food and drug administration (FDA) for this application.

Physical and Chemical properties44

Chemical name: 1,1-Difluoroethane

Formula: CH3CHF2

Molecular Weight: 66.05

EC Number (EINECS): 200-866-1

CAS Number: 75-37-6

Density (g/cm3) 0.886 (30 °C)

Boiling Point (°C) - 25

Vapour pressure (mmHg) 4100 (25 °C)

Gas conductivity (mW/m. K) 14.3 (25 °C)

HSE properties

Toxicological data:

AIHA recommended TWA (ppm) 1000

Flammable limits in air (vol. %) 3.7 - 10

Flash Point -81 oC

VOC No

GWP45 (100-yr Time Horizon) 124

ODP 0

Commercial status

Current Producers: Changshu 3f, Daikin, DuPont, Hangzhou Fist,

Solvay, Shandong Dongyue, Zhejiang Lantian,

Zhejiang Sammei.

44 http://ull.chemistry.uakron.edu/erd/Chemicals/2000/32.html. Consulted April 2011.

45 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -24

HFC-245fa

Description & Usage

HFC-245fa is a non-flammable liquid having a boiling point slightly below room

temperature. It is used for a wide variety of foam blowing applications.

Physical and Chemical properties46

Chemical name: 1,1,1,3,3-Pentafluoropropane

Formula: CF3CH2CHF2

Molecular Weight: 134.05

EC Number (EINECS): 610-280-1

CAS Number: 460-73-1

Density (g/cm3) 1.106 (97 °C)

Boiling Point47 (°C) 15.3

Freezing Point (°C) -103

Vapour Pressure (KPa) 123 (20 °C)

Gas Conductivity (mW/m. K) 12.05 (20 °C)

Water Solubility 0.13 g/L

HSE properties

Toxicological data:

WEEL, 8 hr. TWA (ppm) 300

Flammable limits in air48 (vol. %) None

Flash Point49 (°C) None

VOC No

GWP50 (100-yr Time Horizon) 1030

ODP 0

Commercial status

Current Producers: Honeywell, Central Glass, Zhejiang Lantian.

46 http://ull.chemistry.uakron.edu/erd/Chemicals/24000/22949.html. Consulted April

2011.

47 MSDS, Honeywell, Revised 28.08.2007.

48 Measured at ambient temperature and pressure using ASTM E681-85 with

electrically heated match ignition, spark ignition and fused wire ignition; ambient air.

49 ASTM D 3828-87; ASTM D1310-86.

50 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -25

HFC - 365mfc

Description & Usage

HFC - 365mfc is a liquid at room temperature with low gas phase thermal conductivity. It

is being used for a wide variety of foam blowing applications.

Physical and Chemical properties51

Chemical name: 1,1,1,3,3-Pentafluorobutane

Formula: CF3CH2CF2CH3

Molecular Weight: 148.09

EC Number (EINECS): 430-250-1

CAS Number: 406-58-6

Density/Specific gravity 1.26 (25 oC)

Boiling Point (°C) 40.2

Vapour pressure (kPa) 53 (25 °C)

Heat of vaporization (kJ/kg.K) 177

Gas conductivity (mW/m. K) 10.6 (25 °C)

Vapour density (air = 1) 5.11

Solubility in Water52 (mg/L) 26.1 (25 °C)

HSE Properties

Toxicological data:

SAEL (Solvay Acceptable Exposure Limit) 200753 (ppm) 1000

Flammable limits in air (vol. %) 3.6-13.3

Minimum Ignition Energy (mJ) 10.8 (25 °C)

Flash point (°C) < –27

Autoignition Temperature (°C) 594

GWP54 (100-yr Time Horizon) 794

ODP 0

Commercial Status

Current Producers: Solvay

Geographic Constraints

The use of HFC-365mfc might fall within the scope of European Patent 381 986 and its

counterparts, all held by Bayer. Solvay has acquired from Bayer the right to sublicense its

customers under these patents in all countries except in the USA and in Canada.

51 http://www.solvaychemicals.co.uk/product/datasheet/0,0,-_EN-1000798,00.html.

Consulted April 2011.

52 http://esc.syrres.com/interkow/webprop.exe?CAS=406-58-6. Consulted April 2011.

53 MSDS, Solvay, Issued 16.09.2008.

54 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -26

HFC 227ea

Description & Usage

HFC-227ea is used as a component in non-flammable HFC-365mfc blowing agent

blends. Its prime purpose is to suppress flammability (flash-point) of the blowing agent

and/or of the polyol system. Commercially available are blends with HFC-227ea ratios of

7% and 13% by wt.

Physical and Chemical properties55

Chemical name: 1,1,1,2,3,3,3 Heptafluoropropane

Formula: CF3CHFCF3

Molecular Weight: 170

EC Number (EINECS): 207-079-2

CAS Number: 431-89-0

Density/Specific gravity 1.54

Boiling Point (°C) -16.5

Vapour pressure @ 25 °C (bar) 4.6

Gas Conductivity (mW/m.K at 10 °C) 11.6

Gas Conductivity (mW/m.K at 25 °C) 12.7

Vapour density (air=1) 30.2 (25°C)

Solubility in Water ≈ 0.4 g/l (20°C)

Decomposition temperature 425 °C

Flammable limits in air (vol. %) none

HSE properties

Toxicological data:

AEL TWA 1000 ppm56

VOC No

GWP57 (100-yr Time Horizon) 3220

ODP 0

Commercial Status

Current Producers: Solvay

55 Manufacturer ́s information, Solvay Fluor GmbH, Germany.

http://www.solvaychemicals.com/EN/products/Fluor/Hydrofluorocarbons_HFC/Solk

ane227technicalgrade.a spx. Consulted April 2011.

56 Manufacturer ́s Information, Solvay Fluor GmbH, Germany. MSDS, Rem Tec

International, Revised 30.11.2009.

57 IPCC Fourth Assessment Report: Climate Change 2007.
A1 -27

1.7 Unsaturated HFCs (HFOs)

HFO-1234ze FEA-1100 HBA-2 AFA-L1

Chemical Formula Trans- CF3CH=CHF Cis- CF3-CH=CH-CF3 Undisclosed Undisclosed

Molecular Weight 114 164 Undisclosed Undisclosed

Boiling Point ( 0C ) -19 32 15.3<T<32.1 10.0<T<30.0

Gas Conductivity (mW/mK @ 100C) 13.0 10.7 Not Reported 15.9

Flammable Limits in Air (vol.%) None to 28oC^ None None None

TLV or OEL (ppm) (USA) Unpublished 9.7 Undisclosed Undisclosed

GWP (100 yr time horizon) 6 5 <15 <15

Key Producers Honeywell DuPont Honeywell Arkema

^ Flame limits of 7.0-9.5 at 30oC are quoted
A2 - 1

APPENDIX 2: ALLOCATION OF COUNTRIES TO REGIONS

Latin America and the Caribbean

(LAC) Antigua and Barbuda

Argentina

Bahamas

Barbados

Belize

Bolivia

Brazil

Chile

Colombia

Costa Rica

Cuba

Dominica

Dominican Republic

Ecuador

El Salvador

Grenada

Guatemala

Guyana

Haiti

Honduras

Jamaica

Mexico

Nicaragua

Panama

Paraguay

Peru

Saint Kitts and Nevis

Saint Lucia

Saint Vincent and The Grenadines

Suriname

Trinidad and Tobago

Uruguay

Venezuela

Middle East/North Africa

(MENA) Algeria

Bahrain

Egypt

Iran, Islamic Republic of
A2 - 2

Iraq

Israel

Jordan

Kuwait

Lebanon

Libyan Arab Jamahiriya

Mauritania

Morocco

Oman

Palestine

Qatar

Saudi Arabia

Syrian Arab Republic

Tunisia

Turkey

United Arab Emirates

Yemen

Sub-Saharan Africa

(SSA) Angola

Benin

Botswana

Burkina Faso

Burundi

Cameroon

Cape Verde

Central African Republic

Chad

Comoros

Congo

Congo, Democratic Republic of

Cote d'Ivoire

Djibouti

Equatorial Guinea

Eritrea

Ethiopia

Gabon

Gambia

Ghana

Guinea

Guinea-Bissau

Kenya
A2 - 3

Lesotho

Liberia

Madagascar

Malawi

Mali

Mauritius

Mozambique

Namibia

Niger

Nigeria

Rwanda

Sao Tome and Principe

Senegal

Seychelles

Sierra Leone

Somalia

South Africa

Sudan

Swaziland

Tanzania, United Republic of

Togo

Uganda

Zambia

Zimbabwe

South/Central Asia

(SCA) Afghanistan

Bangladesh

Bhutan

India

Maldives

Nepal

Pakistan

Sri Lanka

South-East Asia

(SEA) Brunei Darussalam

Cambodia

Indonesia

Lao People's Democratic Republic

Malaysia

Myanmar

Philippines
A2 - 4

Singapore

Thailand

Viet Nam

North-East Asia

(NEA) China (incl. Taiwan)

Mongolia

North Korea

South Korea

Japan

Japan

Europe Albania

Andorra

Austria

Bosnia and Herzegovina

Belgium

Bulgaria

Croatia

Cyprus

Czech Republic

Denmark

Estonia

Finland

France

Germany

Greece

Holy See

Hungary

Latvia

Iceland

Ireland

Italy

Liechtenstein

Lithuania

Luxembourg

Macedonia

Malta

Moldova

Monaco
A2 - 5

Netherlands

Norway

Poland

Portugal

Romania

San Marino

Slovakia

Slovenia

Spain

Sweden

Switzerland

United Kingdom

Yugoslavia

North America

Canada

USA

Australia, New Zealand & The Pacific

(ANZP) Australia

Cook islands

Fiji

Kiribati

Marshall Islands

Micronesia

Nauru

New Zealand

Niue

Palau

Papua New Guinea

Samoa

Solomon Islands

Tonga

Tuvalu

Vanuatu

Russia & Former Soviet Countries

Armenia

Azerbaijan

Belarus

Georgia

Kazakhstan

Kyrgyzstan
A2 - 6

Russian Federation

Tajikistan

Turkmenistan

Ukraine

Uzbekistan
A3 - 1

APPENDIX 3: UNEP FOAMS TECHNICAL OPTIONS COMMITTEE

Committee Member Affiliation Country

Mr. Terry Armitt Hennecke United Kingdom

Mr. Paul Ashford, Co-chair Caleb Management Services Limited United Kingdom

Mr. Chris Bloom Dow United States

Mr. Roy Chowdhury Australian Urethane Systems Australia

Mr. Kiyoshi Hara Japanese Urethane Manufacturers Assoc Japan

Mr. Mike Hayslett Maytag/AHAM United States

Dr. Mike Jeffs Consultant Belgium

Mr. Candido Lomba ABRIPUR Brazil

Mr. Yehia Lotfi Technocom Egypt

Mr. Christoph Meurer Solvay Germany

Ms. Francesca Pignagnoli Dow Italy

Mr. Miguel Quintero, Co-chair Consultant Colombia

Mr. Ulrich Schmidt Haltermann Products Germany

Mr. Enshang Sheng Huntsman Polyurethanes China

Ms. Helen Walter-Terrinoni Du Pont United States

Mr. Tom Werkema Arkema United States

Mr. Dave Williams Honeywell United States

Mr. Allen Zhang Owens Corning China