EXTENDING THE APPLICA

FOR POLYALKYLENE GLY

USING NEW TECHNOLOGY C

Martin Greaves, Ph.D

The Dow Chemical Company

The UEIL Annual Congress 2008"Lubricant raw materials - Technology and Supply"23-24 October 2008, Warsaw,
The Dow Chemical Company

Overview

• Diversified chemical company with annual sales of $54 billion 

employees worldwide serving customers in 160 countries

• Connecting chemistry and innovation with the principles of sus

provide everything from fresh water, food and pharmaceuticalpackaging and personal care products

• Combines the power of science and technology with the “Hum

constantly improve what is essential to human progress
Presentation Key Highlights & Desired Out

• Highlight the opportunities polyalkylene glycols (PAG) o

many of today’s lubrication challenges

• Share the enormous technology design options for deve

solutions

• Propose how PAGs can “upgrade” the performance of h

and vegetable oil technologies

• Demonstrate how more environmentally friendly solutio

achieved through improving friction control and energy well as providing biodegradable solutions that can minimenvironmental impact

• Show four examples where PAG application expansion • Summarize how REACH impacts PAGs
Equipme

Water Glycol 

Fluids 

Textile & 

Metalworking 

Fluids

Compressor 

and Gear Oils

Anhydrou

Hydraulic Fl

Historical Application Expansion of Polyalkylene 

Application growth

Fire safety

Production 

Efficiencies

Reduced fiber waste

Improved fiber quality

MWF cooling and 

lubrication efficiencies

Long life 

synthetic 

lubricants

Heavy duty 

industrial gears

Extended life 

air compressor 

lubricants

Equipme

Reliabilit

Anhydrous f

resistant flu

as ester alterna

Fluids 

& Quenchants
Chemistry & Versatility of PAGs
PAG Polymerization Technologies

Block

Polymerisation 

Random

Polymerisation

Inv

Pol

General reaction scheme for manufacturing PAGs

Polymer Design

Polymerisation Polymerisation Pol

Initiator

E

EO block 

PO block Initiator Initiator

....

PO

EO

MONOLSn-Butanol

2-Ethyl hexanol

Alkyl phenols

Fatty amines

DIOLS

Water

Ethylene glycol

Propylene glycol

1,4-Butanediol

TRIOLS

Glycerol Initiators Trimethylolpropan
Understanding Design Principles – Impact of EO/

EO/PO 

ratio

EO/PO 

ratio

EO/PO 

ratio

EO/PO 

ratio

Viscosity Index Pour Po

Oxidation rate Friction (control
Functional Performance of Conventional EO/PO 

Compared To Alternative Base Oils

↑

∆

Synthetic esterMineral oilPAGPAO

Diagram provides relative roils

↑

↑

↑

∆

Clear benefit of PAGs

Disadvantage of PAGs

Spider diagram 
Functional Performance of Conventional EO

Compared To Alternative Base Oil

Diagram provides relative ratings between base oils

↑

∆

Clear benefit of PAGs

Disadvantage of PAGs

Spide
Rotary Screw Com

• Widely used in air, n

refrigeration (R-134compression.

• PAGs eliminate slud

Applying the Benefits of PAGs – Applying the Benefits of PAGs – Deposit C

Deposit C

• PAGs eliminate slud

formation

• Thermo-oxidatively 

oxidation products aPAG base oil

• Technology used in 

air compressors woservice life >8000 hexceeded 50,000 ho

Mineral oil 

compressor lubricant

• Prone to varnish 

formation

• Short fluid life

PAG synthetic

compressor lubricant

• Deposit free and clean

• Long service intervals
Oxidation of PAGs – Oxidation of PAGs – Ether Oxidation Ether Oxidation

O CH2 CH

CH3

O CH2 CH

CH3

O

O CH2 C

CH3

O CH2 CH

CH3

O

OOH

CH Peroxide

Like all ocan oxidtemp. op

OOH Oxidatio

O CH2 C

CH3

O

+ O CH2 CH

CH3

O + OH

C CH

O

H

CH3

O + H2O

Peroxide

Aldehyde

ketone

Oxidatioinclude aketonesacids

Oxidation by- Oxidation by-products are products are SOLUBLE in the base oil & un

DO NOT FORM DEPOSITS AND VARNISH – key bene

– key bene
Applying the Benefits of PAGs – Applying the Benefits of PAGs – Water Solu

Water Solu

Hydraulic Fluids

Play a major role in the use of fire resistanhydraulic fluids (HF

-C) 

Extending applications for water based lubricants may he

dependency on oil

PAGs – only major class of water soluble base oil only major class of water soluble base oil

hydraulic fluids (HF

-C) 

PAGs used as viscosity builders to provide lubrication

Metalworking Fluids

PAGs used in premium water based cutting fluidsFunction by unique inverse solubility mechanism (cloud point) forming thin film at cutting interface
Wind Turbine Lubricants

Trends

• Growth rates 15- Growth rates 15-30 % per annum to 2014 30 % per annum to 2014

• Demand for higher energy output and larger turbines• Increased loading on gears and higher operating 

temperatures

• Off-shore turbines requiring longer service intervals shore turbines requiring longer service intervals

Lubrication Chall

• Eliminate micro- Eliminate micro-pitting 

pitting 

seen with PAOs and m

• Eliminate sludging

• Improve corrosion per

Improve corrosion per

wind turbines

• Extend fluid life, drain 
Traction Measurements at 40oC 

Contact Pressure of 1.25GPa, speed 1m/sec

Comparison of ISO-VG320 for PAG and PAO Wind Tur

0.060.070.080.09

Traction Coefficient

PAOPAG-1 (100% PO)

PAG-2 PAG-3 

Mini-traction Machine - Steel ball on steel disk

0 20 40 60 8

Slide Roll Ratio in %

0

0.01

0.020.030.040.05

0.06

Traction Coefficient
Traction Measurements at 80oC 

Contact Pressure of 1.25GPa, speed 1m/sec

Comparison of ISO-VG320 for PAG and PAO Wind Turb

0.040.050.06

Traction Coefficient

PAOPAG-1 (100%PO)

PAG-2 PAG-3 

Mini-traction Machine Steel ball on steel disk

0 20 40 60 8

Slide Roll Ratio in %

0

0.01

0.020.03

Traction Coefficient
0.03

0.04

Traction Coefficient

PAOPAG-1 (100% PO)

PAG-2 (60/40 EO/PO)PAG-3 (50/50 EO/PO)

Traction Measurements at 120oC 

Contact Pressure of 1.25GPa, speed 1m/sec

Comparison of ISO-VG320 for PAG and PAO Wind Turb

0 20 40 60 80 

Slide Roll Ratio in %

0

0.01

0.02

Traction Coefficient

Mini-traction Machine - Steel ball on steel disk
Wind Turbine Lubricants

• Industry has been reticent in us

• Small percentage of turbines c

• Provide excellent high load car

• Excellent friction control • EO-rich PAG’s offer high VI an

rich PAG’s offer high VI an

values across a wide operating 

• PAGs offer improved thermo- PAGs offer improved thermo-p

p

than hydrocarbon products than hydrocarbon products

• Offer an alternative to PAO an
Applications For Polyalkylene Glyco

Automotive Fluids And Lubrican

• Intrinsic tribological properties of PAGs are excellent

• Thermo- Thermo-physical aspects are attractive physical aspects are attractive 

• Ecologically more favourable than hydrocarbon oils

• However conventional PAGs are NOT hydrocarbon comp
Application Development By Polymer D

EO/PO EO Solder assis

Textile lubricants

Gear lubricants

Bearing oils Surfac

Water glycol fluids

Refrigeration oils Quenchants

water soluble PAGs

PAGs today are predominantly used in the Industrial Lubricants segment

PO

PO/BO

BO/EO

BO

Air Compressor fluids

Hydraulic oils

B

flu

Aut

T

Polymer design 

space

oil soluble PAGs

Introducing BO for OIL SOLUBLE PAGs could open the “application envelope” to include automotive
PAGs As Future Base Oil Components Of 

PAG 

or PAG blends

Bio-renewables

High performance synsimplified technology offering biodegradabil

Renewabl

Environmental 

sustainability

Modern synthetics

Incremental 

mprovement

Performance 

Mineral oils

Synthetics

e.g. PAO

Well established but limited fluid longevity

Higher performance and highly engineered Longer drain intervals but weak environmen

Breakthrough technology

offering biodegradabil(BIO-NO-TOX)

Investm

(developmen

time

Performance 
Engines Oils – Options in using PAGs

Hydrocarbon base oilDispersant

Modern engine oil formulations are highly complex

Can the fundamental tribological and thermo- Can the fundamental tribological and thermo- physical properties of PAGs eliminate that 

complexity?

DispersantAnti-oxidantZinc A/W additiveVI ImproverDetergentsFriction modifiersCorrosion inhibitors

Base oil using PAG

Base oil of Mineral oil a
Technology Options for Engine Oils

Utilize PAG as the primary base oil – Utilize PAG as the primary base oil – option to use wate

option to use wate

(EO/PO), water insoluble (PO) and oil soluble (BO) P

• Thermal conductivity of PAGs > mineral oils • Eliminate need for VI Improvers• Reduce detergent and dispersant treat levels

• Reduce A/W and friction modifier treat levels

Utilize oil soluble PAGs (OSP) based on, for example, b

homo-polymers polymers

• Incorporate OSP’s in formulations at levels of 10-

the performance of hydrocarbon oil containing pro
Validation of Technical Concept for PAGs in 

Phase I – Phase I – Technical Validation of Hypothesis (Near Com

Technical Validation of Hypothesis (Near Com

• Vehicle studies ongoing • Primarily monitoring fluid condition, reliability and fuel e• Exceeded expectations so far

Phase II Phase II – Next phase/ R&D ongoing Next phase/ R&D ongoing

• Defining application needs per market segment • Optimization of thermo-physical properties • Building structure properties maps based on chemistry • Confirm initial research showing unique tribo-film forma

Phase III

• To work with industry partners to implement technolog
Specialty Marine Lubricants

1. Cost2. Performance3. Environmental acceptability

Do PAGs have the functionality to serve the challenges o

marine market?

Application for PAGs as specialty marine lubricants

 Sub-sea Motion Compensators sea Motion Compensators

 Hydraulics 

 Gears

 Stern Tube Lubricants
Expanding PAGs into Specialty Marine Lubri

Known PAG Benefits for Ma

Water soluble

Non-sheeningBiodegradableLow eco-toxicityHydrolytic stabil

Preferred Additional Benefits.......

• Constant rheology (viscosity) control at high water contamination levels 

for sub-sea systems)

• Minimum loss of friction control and lubrication with water contaminatio

EO/PO 

ratio

Water solubility

M.W.
PAG Base Oil Formulation Design – Controlling R

Random Copolymers - Water Impact on Viscosity

0

20406080

100

0 10 20 30 40 50

V is c o s ity a t 4 0 o C , c S t

New Biodegradable PAGs - 

0

200400600800

1000

0 10 20 

Viscosity at 40oC , cSt

0 10 20 30 40 50

% Water in PAG

0 10 20 

% Wate

Combining the rheology properties of PAGs to optimize base oil design and provide fluids which are:

• readily biodegradable• non-sheening• thermo-oxidatively stable

Novel blends - Impact 

0

20406080

100120140

0 10 20 

% Water 

Viscosity at 40oC Stable rheology c
Traction Performance of New PAG Marine Lubric

(e.g. ISO-100 viscosity grade)

0.040.050.060.070.080.09

Traction Coefficent

Traction experiments at 40oC, 1.25GPa and slide roll ratio 100% using steel ball on disk configuration

0

50

100

150

200

250

300

350

400

450

500

550

600

650

7

Mean Speed - mm/s

0

0.01

0.020.03

Traction Coefficent

At high speeds traction coefficients are improved with waAt lower speeds traction increases in the mixed EHL regi
Environmentally Friendly Hydraulic Fluids

AgricultureEquipment reliability and operability in cold climatesConstructionEquipment reliability 

ForestryBiodegradability (especially in Nordic countries)

Equipment reliability and operability in cold climates
Environmentally Friendly Hydraulic Fluids in 

Europe offers a diverse range of technologies m

on vegetable oils or synthetic esters.

New Accreditations have emerged (European Eco

-label)

Eco-label

- Renewable carbon content >50%- Fulfill hydraulic specification 

requirements (ISO-15380)

What options are available with PAGs for use in environm

areas?
PAG Based Anhydrous Flu

• Excellent hydrolytic and oxidation 

• Wide operating temp range. All se

due to high VI >200 and low pour 

due to high VI >200 and low pour 

• Excellent lubrication and wear pe

Excellent lubrication and wear pe

• Increasing use in mobile and statio

• Biodegradable

PAGs as Environmentally Friendly Fluids

• Biodegradable• Not derived from renewable resou

PAG & Natural Ester Blend

• Improved oxidation stability compa

esters

• Excellent intrinsic lubrication perfor• Clean and deposit free

• Biodegradable and based on renew
Benefits of PAG and H.O. Vegetable Oil Bl

PAGPAG + H.O. Veg oilH.O Veg oil

507090

110

K V 4 0, cS t

H.O. 

Accelerated oxidation test – ASTM D2893 (95

oC)

30

0 10 20 30 40 50

Time, days

be

af

• PAGs offer excellent thermo- PAGs offer excellent thermo-oxidative stability oxidative stability

• Thermo- Thermo-oxidative stability of vegetable oils can be impro oxidative stability of vegetable oils can be improved and 

upgraded in combination with PAGs upgraded in combination with PAGs

• Decomposition products of vegetable oils are soluble in the 

PAGs providing less varnish formation and valve sticking – cking – hence greater equipment reliability
Supply of PAGs - Supply of PAGs - Manufacture beyond lub

Manufacture beyond lub

Huge global infra- Huge global infra-structure existing today structure existing today 

for manufacturing PAGs, polyethers, polyglycols for wide variety of applications 

and industries:- and industries:-

Polyurethanes

Fuel additives

Surfactants

Pharmaceuticals

Personal care

Drilling fluids

as well as

Lubricants

Back integration into key oxides – Back integration into key oxides – E

EE

can offer improved security of supp
REACH - REACH - registration timeline took effect on J

registration timeline took effect on J
REACH & Polymers

• Polymers are exempted from registration under RE• REACH does require registration of raw materials, oth

and additives that are used in the manufacture of poly

• Monomers as well as other substances which have bee

polymer backbone must be registered if a polymer prodimported into the EU consists of 2% or more by weight or other substances in reacted form exceed one metric 

• Polymer additives need to be registered if they are man

imported on their own or in compounded form in volumtonne or more per annum.
Conclusions

• PAG innovation will continue in solving problems whic

oils can not 

• Upgrading hydrocarbon oils using oil soluble PAGs op

Upgrading hydrocarbon oils using oil soluble PAGs op

application envelope

• Application expansion is possible in new industrial app

wind turbine and marine) as well as new automotive fl

• Application expansion is possible in new industrial app

wind turbine and marine) as well as new automotive fl

• Environmental and energy efficient solutions are poss

which can offer better friction control and improved the

properties than alternative options.

• Back integration into EO, PO and BO can offer improv

supply from your PAG partner
THANK