April 2010
ii

TABLE OF CONTENTS 

PREFACE.....................................................................................................................................................................iv

ACKNOWLEDGEMENTS ........................................................................................................................................... v

GUIDE OVERVIEW .................................................................................................................................................... 1

1. CHARACTERISTICS OF VINYL ACETATE MONOMER ................................................................................. 4

1.1. Hazardous Properties ..................................................................................................................................... 4

1.1.1. Flammability .......................................................................................................................................... 4

1.1.2. Reactivity ............................................................................................................................................... 4

1.1.3. Health Effects ........................................................................................................................................ 5

1.1.4. Environmental Effects ........................................................................................................................... 6

1.2. Hazard Communication ................................................................................................................................. 7

1.2.1. General ................................................................................................................................................... 7

1.2.2. Hazard Classifications ........................................................................................................................... 7

1.2.3. Safety Data Sheets/MSDS ...................................................................................................................10

2. WORKPLACE SAFETY, PERSONAL PROTECTIVE EQUIPMENT AND FIRST AID ..................................11

2.1. Industrial Hygiene ....................................................................................................................................... 11

2.1.1. Occupational Exposure Limits .............................................................................................................11

2.2. Personal Protective Equipment ....................................................................................................................12

2.2.1. Availability and Use of Protective Equipment ....................................................................................12

2.2.2. Respiratory Protection .........................................................................................................................13

2.2.3. Hand and Skin Protection ....................................................................................................................14

2.2.4. Foot Protection .....................................................................................................................................15

2.2.5. Eye Protection ......................................................................................................................................16

2.2.6. Head Protection ...................................................................................................................................16

2.3. First Aid Treatment ......................................................................................................................................16

3. STORAGE, TRANSPORT AND HANDLING OF VINYL ACETATE MONOMER ........................................18

3.1. Storage Considerations ................................................................................................................................18

3.1.1. Bulk/Tank Storage ...............................................................................................................................18

3.1.2. Maintaining and Assessing Inhibitor Levels in Bulk Storage ..............................................................18

3.1.3. Containers and Drum Storage ..............................................................................................................20

3.2. Shipping Classifications and Regulations ....................................................................................................20

3.3. Loading and Unloading Bulk Shipments from Tank Rail Cars and Trucks ................................................21

3.4. Shipping Containers Damaged in Route ......................................................................................................23

3.5. Unloading into Storage Tanks .....................................................................................................................23

3.5.1. Storage Tank Vent Handling ...............................................................................................................23

3.5.2. Hoses ...................................................................................................................................................24

3.5.3. Sampling ..............................................................................................................................................24

3.6. Tank and Equipment Cleaning and Repairs ................................................................................................. 24

3.6.1. Preparing Personnel .............................................................................................................................24

3.6.2. Preparing Tanks and Equipment ..........................................................................................................25

3.7. Maintenance of Equipment ..........................................................................................................................26

3.8. Control of Vapors and Waste Disposal ........................................................................................................26

3.8.1. Air Pollution Control ...........................................................................................................................26

3.8.2. Discharge to Navigable Waters ...........................................................................................................26

3.8.3. Disposal of Wastes...............................................................................................................................26

4. HAZARD ANALYSIS AND EMERGENCY PLANNING FOR THE HANDLING OF VINYL ACETATE 

MONOMER ...........................................................................................................................................................27

4.1. Emergency Planning ....................................................................................................................................27

4.2. Risk Management/Process Safety Regulations ............................................................................................27

4.3. Emergency Response Planning: Acute Inhalation Guidance Values ..........................................................28

5. MANAGING EMERGENCIES .............................................................................................................................29

5.1. Fire and Explosion .......................................................................................................................................29

5.1.1. Preventing Fires ...................................................................................................................................29
iii

5.1.2. Fighting Fires .......................................................................................................................................30

5.2. Uncontrolled Polymerization .......................................................................................................................31

5.3. Managing Spills ...........................................................................................................................................32

5.4. Reporting Releases to the Environment .......................................................................................................33

REFERENCES ............................................................................................................................................................35

APPENDIX I: BULK STORAGE DESIGN ..............................................................................................................38

1. Building Design ...............................................................................................................................................38

2. Storage Tank Construction and Location ........................................................................................................39

3. Storage Tank Equipment ................................................................................................................................. 40

3.1. Temperature Measuring Device ...........................................................................................................40

3.2. Emergency Vent-Pressure Relief Devices ...........................................................................................40

3.3. Reducing Air Emissions ......................................................................................................................41

3.4. Tank Head Space Considerations ........................................................................................................41

3.5. Flame Arrester .....................................................................................................................................41

3.6. Overflow Protection .............................................................................................................................41

3.7. Liquid Level Measurement and Control ..............................................................................................41

3.8. Pumps ..................................................................................................................................................42

3.9. Pipe ......................................................................................................................................................42

3.10. Valves ..................................................................................................................................................43

3.11. Gaskets .................................................................................................................................................43

3.12. Filter.....................................................................................................................................................43

3.13. Prevention of Spills from Storage Tank Piping ...................................................................................43

3.14. Diagram of Storage Tank .....................................................................................................................44

APPENDIX II: CONTACTS: EMERGENCY RESPONSE, TRANSPORTATION AND 

OTHER REGULATORY AUTHORITIES ...........................................................................................................45

APPENDIX III: ACRONYMS AND ABBREVIATIONS USED THROUGHOUT GUIDE ...................................46

APPENDIX IV: GENERAL PROPERTIES OF VINYL ACETATE MONOMER ..................................................49

APPENDIX V: GUIDE 129 FROM 2008 EMERGENCY RESPONSE GUIDEBOOK ...........................................50

APPENDIX VI: EXAMPLE LIQUID CHROMATOGRAPHIC METHODS FOR 

HYDROQUINONE IN VINYL ACETATE MONOMER ....................................................................................52
iv

PREFACE 

Vinyl acetate monomer (VAM) is a high volume building block chemical used in the 

manufacture of polyvinyl acetate or vinyl acetate copolymers. These polymers are the base for 

many industrial and consumer products as well as for other polymers. When handled properly, 

VAM can be stored, transported and otherwise managed safely. However, if VAM is not 

properly managed, it can pose a serious fire and/or health hazard. 

The Vinyl Acetate Council (VAC) has developed this Safe Handling Guide to promote the safe 

and responsible use of VAM. This document is intended primarily for North American 

audiences though we have also attempted to include information on classifications, exposure 

limits and transportation regulations relevant to several other jurisdictions [see information in 

Appendix II]. Information contained in this updated Guide was developed based on procedures 

currently recommended by members of the VAC and reflects best practices on the safe handling, 

storage and transport of VAM. This Guide supersedes all previous editions of “Vinyl Acetate: 

Safe Handling Guide,” including the May 2009 and March 2005 editions and other earlier 

editions. Revisions since the May 2009 edition are primarily in Section 3 on storage times, 

conditions, and the addition of Appendix VI on liquid chromatographic methods for the analysis 

of hydroquinone (polymerization inhibitor) in VAM. 

The Guide is intended to supplement training, Material Safety Data Sheets (MSDSs), Safety 

Data Sheets (SDSs), and product labels for workers who handle, transport, process or may 

otherwise contact VAM, as well as for safety, engineering and health professionals responsible 

for implementation of safe management practices. There are also numerous national, regional 

and local regulations that need to be followed. All these documents should be consulted before 

handling VAM. 

No warranty or guarantee, either expressed or implied, is made with respect to any or all of the 

content of this document and neither the VAC nor its members assume any legal 

accountability. The Guide is not intended as a statement of legal requirements or remedies. 

While the VAC believes that the information contained in this Guide is current and accurate, 

ALWAYS CONSULT YOUR SUPPLIER’S SAFETY DATA SHEET, PRODUCT LABEL 

AND OTHER SAFE HANDLING INSTRUCTIONS FOR THE MOST CURRENT 

RECOMMENDATIONS. It is the responsibility of all persons handling VAM to respect 

proprietary rights and observe all existing laws. Consult with legal counsel and/or appropriate 

government authorities to ensure compliance with local, regional, national and international 

laws and regulations. 

Vinyl Acetate Council 

1250 Connecticut Avenue, NW, Suite 700 

Washington, DC 20036 

Phone: 202-419-1500 

www.vinylacetate.org

info@vinylacetate.org 
v

ACKNOWLEDGEMENTS 

The Vinyl Acetate Safe Handling Guide was developed by the Vinyl Acetate Council, a not-forprofit association of North American manufacturers, processors and users of vinyl acetate 

monomer. Current member companies of the Vinyl Acetate Council are listed below. Your 

manufacturing company should be contacted for any additional information or clarification of the 

content of this Guide. Ask your supplier for additional copies of this Guide or go to 

www.vinylacetate.org to request an electronic copy of this Guide. 

Celanese Corporation

Transportation Emergency: 800-424-9300

Product Information: 800-835-5235

www.celanese.com

www.chemvip.com/index/products_index/all_

products/all_products_acetyls/product-vinylacetate.htm

The Dow Chemical Company

North America: 800-447-4369

Europe: +800-3694-6367 

Asia Pacific (except China): +800-7776-7776

China: +800-600-0015

Other Global Areas: 989-832-1560

www.dow.com

www.dow.com/vam

DuPont Packaging and Industrial Polymers

Medical Emergency: 800-441-3637

Technical Information and VAM Safe 

Handling Guide Access: 800-628-6208, ext 6

www.dupont.com/

LyondellBasell Acetyls, LLC

Contact: 713-209-7000 

24-hour Emergency Number: 800-245-4532 

www.lyondellbasell.com

Wacker Chemie AG

Wacker Polymers

Contact: +49-89-6279-1646

International Emergency Information: +49-

621-60-43333 

www.wacker.com
1

GUIDE OVERVIEW 

Using this Guide

Section 1. Characteristics of Vinyl Acetate Monomer 

 Section 1 of the Guide contains an overview of the properties of VAM, including 

 its hazards: 

 Highly flammable 

 Vapor may cause flash fire 

 May polymerize spontaneously if cross contamination occurs, if the 

polymerization inhibitor is depleted, or if exposed to heat, radiation, 

oxidizing materials or strong acids or bases; may result in heat generation, 

rapid vaporization of VAM, and possible vessel rupture/explosion 

 May cause skin, eye and respiratory irritation 

 Harmful by inhalation 

 Possible cancer hazard. Lifetime inhalation and oral exposures have 

caused nasal and upper digestive tract (site of contact) cancers in 

laboratory animals exposed to high concentrations. Tumors can occur 

when exposure exceeds a threshold concentration such that tissue defense 

mechanisms are overwhelmed. 

Section 2. Workplace Safety, Personal Protective Equipment and First Aid 

Section 2 covers issues related to workplace training and safety, including 

appropriate personal protective equipment (PPE) for VAM and first aid measures. 

PPE requirements for VAM will vary depending on possible exposure 

circumstances and activities. Proper use of PPE requires adequate training. Any 

garments contaminated with VAM should be removed promptly and either 

decontaminated by a qualified in-house or reputable external industrial cleaning 

service or properly disposed. Contaminated leather articles such as shoes, 

clothing, belts or watchbands should be properly disposed as leather cannot be 

thoroughly decontaminated. 

 First Aid

If inhaled, move to fresh air. If breathing is difficult, give oxygen. If breathing 

has stopped, give artificial respiration, then oxygen as needed. Contact 

emergency medical personnel/physician immediately. Respiratory tract irritation, 

bronchitis, pneumonitis or delayed pulmonary edema may develop. 

Before using or handling vinyl acetate monomer (VAM), read the material safety data sheet 

(MSDS), safety data sheet (SDS) and any other materials provided by your supplier. This 

Guide is intended to be used in conjunction with the manufacturer’s information. 
2

In case of skin contact, immediately remove contaminated clothing and shoes. 

Wash affected areas with water and soap (if available) for at least 15 minutes. 

Call emergency medical personnel/physician if irritation and pain persist after 

thorough washing. 

In case of eye contact, remove contact lenses if worn. Immediately flush eyes 

with large amounts of room temperature water for at least 15 minutes. Contact 

emergency medical personnel/physician immediately. 

If ingested, slowly drink a glass (125-250 mL [4 to 8 oz]) of water or milk. Do 

not induce vomiting to prevent aspiration into lungs. Contact emergency medical 

personnel/physician immediately. 

In case of thermal burns, immediately cool affected skin for as long as possible 

with cold water. Do not remove clothing if adhering to skin. Keep individual 

warm and quiet. Contact emergency medical personnel/physician immediately. 

Section 3. Storage, Transport and Handling of Vinyl Acetate Monomer 

Section 3 covers the safe storage, transport and handling of bulk quantities of 

VAM including storage tank conditions such as temperature and inhibitor level 

monitoring, and proper loading/unloading operations. 

Cross contamination of VAM with other chemicals, especially oxidizing materials 

or strong acids or bases, may lead to spontaneous polymerization and fire. VAM

should be kept away from heat, sparks and flame. Prolonged or intense exposure 

to heat, sunlight, ultraviolet light or x-rays may also result in spontaneous 

polymerization. 

Section 4. Hazard Analysis and Emergency Planning for the Handling of Vinyl Acetate 

 Monomer 

Section 4 covers hazard analysis and emergency planning considerations, 

including Process Safety Management (PSM) and Risk Management Plans 

(RMPs). 

Section 5. Managing Emergencies 

Section 5 provides information on managing emergencies for situations including 

spills, fire fighting, uncontrolled polymerization responses and release reporting. 

In case of spill, eliminate ignition sources. Except for properly trained and 

equipped emergency responders, remove non-protected personnel from area. 

Provide adequate ventilation until area is clean. 

In case of fire, use CO2 or dry chemical for small fires (e.g., fires that can be 

extinguished using a portable fire extinguisher). Use alcohol-type aqueous filmforming foam for large fires. Water spray or fog may be ineffective in fully 

extinguishing a VAM fire, but can be used to cool fire-exposed structures and 
3

containers. Do not use high-velocity water stream since VAM floats on water and 

the stream may spread the fire. If potential exists for exposure to smoke, vapors 

or products of combustion, wear complete personal protective equipment and 

SCBA with full facepiece operated in pressure-demand or other positive-pressure 

mode. 

References 

Appendices 

Appendix I: Provides information for use in the design of facilities and operations handling 

and storing VAM. 

Appendix II: Contains emergency contact information. 

 

Appendix III: Includes a list of the acronyms and abbreviations.

Appendix IV: Includes a table of general properties of VAM. 

Appendix V: The recommended guide (Guide 129) for VAM from the 2008 Emergency 

Response Guidebook (ERG) developed by the US DOT, Transport Canada, and 

the Secretariat of Transport and Communications of Mexico. Readers should 

check the ERG website to see if a more current version is available. 

Appendix VI: Several example methods for using liquid chromatography to analyze for the level 

of hydroquinone in vinyl acetate monomer. Liquid chromatographic (LC) 

methods are recommended for the analysis of VAM that has exceeded its storage 

time or when the presence of soluble polymer is suspected. 
4

1. CHARACTERISTICS OF VINYL ACETATE MONOMER 

Vinyl acetate monomer (VAM) is a flammable, reactive, colorless liquid that is partly 

soluble in water. It has a sweet, fruity smell in small quantities, but the odor may become 

sharp and irritating at higher levels. It is usually shipped and stored in clearly marked 

bulk containers. 

VAM is a chemical building block used to manufacture a wide variety of (co)polymers 

that are used in a range of consumer and industrial products. There is no direct consumer 

use of VAM. 

 Chemical Name: Vinyl Acetate 

 Common Name: Vinyl Acetate 

 Synonyms: Vinyl Ester Acetic Acid; 

 Ethenyl Ester Acetic Acid; 

 Vinyl Acetate Monomer (VAM);

 Ethenyl Acetate; 

 1-Acetoxyethylene; 

 Acetic Acid Ethenyl Ester 

 CAS Name: Ethenyl Ester Acetic Acid 

 CAS Registry No.: 108-05-4 

 Chemical Formula: CH3COOCH=CH2

 Chemical Structure: 

 See Appendix IV for physicochemical properties. 

1.1. Hazardous Properties 

 

1.1.1. Flammability 

VAM has a flash point below 37C (100F) and as such is considered a 

“flammable” liquid. When mixed with air at room temperature, VAM can form a 

flammable vapor. Its vapors are heavier than air and may travel a long distance to 

an ignition source such as a flame or electric spark and then flash back (see 

information on flammability classification in Section 1.2.2). 

1.1.2. Reactivity 

VAM is a reactive molecule. Unless inhibited, or if proper handling and storage 

precautions are not met, VAM can polymerize uncontrollably. VAM is typically 

shipped with a polymerization inhibitor, generally hydroquinone (HQ). Properly 

inhibited, VAM is stable under recommended storage conditions. Prolonged or 

intense exposure to heat, sunlight, ultraviolet light or x-rays may result in 

polymerization. Spontaneous polymerization may also result from exposure to 

amines, strong acids, alkalis, silica, alumina, oxidizing agents (e.g., peroxides, 

hydroperoxides, hydrogen peroxide) or polymerization initiators. Heat and 
5

pressure generated during such polymerization may rupture insufficiently vented 

containers, leading to liquid spill, vapor generation and possibly fire. 

See Section 3 for information about storage conditions and inhibitor levels for 

VAM. 

VAM is hydrolyzed in water. This reaction is typically not violent in nature and 

as such, is not considered as a hazardous reaction. While VAM has a National 

Fire Protection Association (NFPA) instability classification of 2 (yellow section 

of NFPA diamond - see Section 1.2.2) due to its ability to polymerize and to react 

with other chemicals, this classification and associated warnings do not apply to 

the mixing of VAM and water. 

1.1.3. Health Effects 

As with all chemical substances, the health effects associated with exposure to 

VAM depend largely on the exposure level and duration. VAM is irritating to the 

upper respiratory tract, skin and eyes so contact with vapors and liquids should be 

avoided. If VAM contacts the eyes, it may cause irritation, redness and swelling. 

VAM vapors have been reported to be intolerably irritating to the eyes at 21 ppm 

but not at approximately 5-10 ppm. The odor detection threshold is reported to be 

about 0.5 ppm. VAM is not considered to be a skin sensitizer. 

Based on studies in laboratory animals, VAM is considered to have low acute 

toxicity by all routes of exposure: the oral LD50 in rats is approximately 2920 

mg/kg; the inhalation 4-hour LC50 in rats is approximately 4000 ppm (14 mg/L); 

and the dermal LD50 in rabbits is >2000 mg/kg. High level inhalation exposure 

to VAM in animals results in deaths from pulmonary edema. At less than lethal 

exposure concentrations, single or repeated exposure to VAM may produce 

irritation or injury to upper respiratory tract tissues. The exposure concentrations 

in repeat dose studies below which adverse effects were not seen were 50 ppm in 

mice and 200 ppm in rats. 

No selective reproductive or developmental toxicity was seen in a two-generation 

drinking water study or in pregnant rats exposed to VAM; no observed effect 

levels were 1000 ppm in drinking water and 200 ppm in air, respectively. 

Lifetime drinking water or inhalation exposure to VAM have shown cancer 

effects in laboratory animals. Tumors were localized to tissues that were directly 

in contact with VAM (i.e., the nose and upper respiratory tract if inhaled or in the 

mouth, esophagus and stomach if ingested). A threshold-based tumor mechanism 

is believed to exist with a key event involving the enzymatic conversion of VAM

by tissue carboxylesterases to acetaldehyde and acetic acid. Acetaldehyde is 

ubiquitous in the environment and present in the body at low levels as a byproduct 

of food metabolism. If threshold exposure levels of VAM are exceeded, 

acetaldehyde may accumulate above background levels. Acetaldehyde is also 

mutagenic and thought to mediate the genotoxicity associated with VAM. 

However, the body of evidence indicates that carcinogenicity is not expected to 

occur when the levels of VAM (and acetaldehyde) are below a practical 
6

concentration threshold (EU 2008a; Canada 2009). Occupational exposure limits 

(see Section 2.1.1 Occupational Exposure Limits) are below the threshold level 

for tumors in laboratory animals (EU 2008b). Thus, tumors observed at high 

exposure concentrations are not considered to be relevant to humans exposed to 

low concentrations under typical use conditions. 

The International Agency for Research on Cancer (IARC) has designated VAM

as a Group 2B carcinogen, meaning “possibly carcinogenic to humans.” 

Classification has not been reevaluated since 1995. 

See information on hazard classifications in Section 1.2.2. 

1.1.4. Environmental Effects 

If released into the environment, VAM will tend to partition into the 

environmental compartment to which it is released. 

If released to air, VAM tends to stay in the air where it is rapidly degraded by 

photochemical pathways. The VAM atmospheric half-life has been calculated to 

be 0.6 days. Some volatilization can occur following releases of VAM to soil or 

water. 

If released to water, VAM partitions mostly to the water where it undergoes 

hydrolysis. The hydrolytic half-life of VAM is estimated to be approximately 7 

days at pH 7 and 25oC (77°F). Acetic acid and acetaldehyde are hydrolysis 

products of VAM. In general, hydrolysis increases in basic conditions. VAM is 

not expected to adsorb to sediments or soils to a great extent. 

VAM is readily biodegraded by either anaerobic or aerobic mechanisms. VAM is 

also subject to biotic and abiotic hydrolysis in soils and sediments. 

Microorganisms from sludge, soil and wastewater treatment facilities can utilize 

VAM as a carbon source so that VAM is readily biodegraded. Rates of 

transformation are higher under aerobic conditions. Anaerobic and aerobic 

biodegradation pathways yield acetaldehyde (transient) and acetic acid (final). 

An aerobic transformation half-life of 12 hours was obtained with one bacterial 

isolate, whereas a half-life of 60 hours was found for non-enzymatic hydrolysis of 

VAM in a sterile medium. 

VAM is considered to be moderately toxic to aquatic organisms. Acute aquatic 

toxicity values range from approximately 12-18 mg/L for freshwater fish, algae 

and invertebrates over an exposure period of 48-96 hours. Chronic toxicity has 

been evaluated in freshwater fish with a no-observed effect concentration of 

approximately 0.6 mg/L. 

Given the susceptibility of VAM to be readily biodegraded and the low level of 

acute aquatic toxicity, VAM is not considered to represent a significant 

environmental or ecotoxicological risk (EU 2008a, Canada 2009). 
7

Bioaccumulation, which is the increase in a chemical‟s concentration in an 

organism relative to the environmental concentration under steady state 

conditions, of VAM is unlikely. In the European Union (EU) and Canada, VAM 

is not classified as an environmental hazard or persistent, bioaccumulative or 

toxic (PBT) in the environment (EU 2008a, Canada 2009). 

1.2. Hazard Communication 

1.2.1. General 

So that workers, emergency responders and the public are aware of the potential 

hazards associated with chemicals, there are hazard communication requirements 

throughout the world. In the US, chemicals are subject to the labeling 

requirements of the Occupational Safety & Health Administration (OSHA) 

Hazard Communication Standard (Code of Federal Regulations (CFR) 29 CFR 

1910.1200); the Department of Transportation (DOT) requires labeling and 

placarding during shipment (DOT, 49 CFR 172.400). Comparable requirements 

can be found in Canada (Workplace Hazardous Materials Information System 

(WHMIS)) and in the European Union (Regulation on Classification, Labeling 

and Packaging (CLP) of Substances and Mixtures, EC 1272/2008). 

The Globally Harmonized System of Classification and Labelling of Chemicals 

(GHS) (UN 2007, GHS 2nd ed.) was developed to provide a common basis for 

chemical classification and labeling throughout the world. The GHS is in the 

process of being implemented in the US, Canada and elsewhere in the world and 

will result in changes to existing national/regional hazard communication 

regulations. In the European Union, GHS is being implemented through 

Regulation EC 1272/2008 (see above) which entered into force in January 2009 

and has an implementation deadline of December 2010 for VAM. Information on 

how the EU implementation of the GHS impacts hazard classification and 

labeling is presented in Section 1.2.2. The US is still evaluating potential changes 

to the Hazard Communication Standard based on the GHS. 

Consult your supplier for appropriate labeling information. 

1.2.2. Hazard Classifications 

Hazard communication programs require that a substance‟s hazard be classified 

and specific precautionary symbols or safety phrases be used. Some VAM hazard 

classification information for various regions are provided below, though consult 

your MSDS/SDS for complete information. 

US Hazard Classification

VAM is addressed under several US regulations (both state and federal) and 

programs covering toxic, chemical and fire hazards. Below are some of the 

common VAM hazard classifications. 
8

VAM hazard classifications under Sections 311, 312 of the Emergency Planning 

and Community Right-to-Know Act (EPCRA) are as follows: 

Acute: Yes 

Chronic: Yes 

Fire: Yes 

Reactivity: Yes 

Pressure: No

VAM is listed on the following: 

 EPCRA Section 313, the Toxics Release Inventory (TRI) 

 Clean Air Act Section 112(r) 

 Comprehensive Environmental Response, Compensation, and Liability 

Act (CERCLA) Hazardous Substance 

 EPCRA Section 302 Extremely Hazardous Substances (EHS) 

The American Conference of Governmental Industrial Hygienists (ACGIH) has 

classified VAM as an “A3” carcinogen - confirmed animal carcinogen with 

unknown relevance to humans. 

US DOT regulations, require that containers of VAM bear a label in the shape of 

a diamond with a red background showing the flame symbol with the words 

“Flammable Liquid” and a number “3” signifying its designation as a flammable 

liquid (49 CFR 172.419(a)). 

The National Fire Protection Association (NFPA) hazard, reactivity, flammability 

label and classification for VAM is shown below: 

Flammable!

 Warning Flammable liquid flash point below 100°F (37.78°C)

 Warning May be harmful if inhaled or absorbed

 Warning Violent chemical change at high temperature and pressures

Refer to Section 1.1 Hazardous Properties for information on the specific hazards 

of VAM. 

2

3

2
9

Canada Hazard Classification 

The Canadian classifications for VAM under WHMIS are presented in the table 

below. The disclosure level for VAM in substances is 0.1 percent. 

Table 1.1: VAM Classifications in Canada (WHMIS) 

Classification Statement

B2 Flammable Liquid

D1B Toxic Material Causing Immediate and Serious 

Toxic Effects

D2A Very Toxic Material Causing other Toxic Effects

F Dangerously Reactive Material

EU Hazard Classification

In Europe, VAM is classified under the classification system of EU Directive 

67/548/EEC as: 

Classification Risk Phrase Definition

F R11 Highly Flammable

In September 2007, the EU's Technical Committee on Classification and 

Labelling decided that VAM should be classified as presented in Table 1.2. This 

classification will not be legally binding until published in an Adaptation to the 

Technical Progress (ATP) under the new CLP regulation and will enter into force 

after a transition period.

Table 1.2: VAM Classifications in Europe 

Classification Risk Phrase Definition

F R11 Highly Flammable

Carcinogen Category 3 R40 Limited Evidence of a 

Carcinogenic Effect

Xn R20 Harmful by Inhalation

Xi R37 Irritating to Respiratory 

System

The corresponding classification under the new GHS CLP classification 

regulation (see Section 1.2.1) is presented in Table 1.3. 

Table 1.3: GHS European CLP Classification 

Classification Category Risk Phrase Definition

Flammable 

Liquid 2 H225 Highly Flammable Liquid and Vapor

Acute Toxicity 4 H332 Harmful if Inhaled

STOT, Single 

Exposure 3 H335 May Cause Respiratory Irritation

Carcinogen 2 H351 Suspected of Causing Cancer 
10

1.2.3. Safety Data Sheets/MSDS 

Material safety data sheets (MSDSs) and safety data sheets (SDSs) provide 

detailed information about the hazards and precautions required for handling 

hazardous chemicals. MSDSs are provided by suppliers; please consult your 

supplier for the latest MSDS. 
11

2. WORKPLACE SAFETY, PERSONAL PROTECTIVE EQUIPMENT AND FIRST 

AID 

2.1. Industrial Hygiene 

VAM is an eye, skin and respiratory tract irritant. Workers should be warned to avoid 

skin and/or eye contact with VAM and to avoid breathing its vapors. 

Safety showers and eyewash facilities should be provided in areas where VAM is being 

handled. Workers should be trained to promptly wash any area of the skin exposed to 

VAM with large amounts of water. All contaminated footwear and clothing should be 

removed immediately. 

2.1.1. Occupational Exposure Limits 

VAM should be handled in a well-ventilated area or in a completely closed 

system. Appropriate respiratory protection should be worn when exposure to 

vapors or mists above the established exposure limit may occur. Workers should 

be familiar with the location and operation of respiratory protective equipment 

and instructed to immediately report any incident that could result in exposure to 

VAM above permissible exposure limits. 

The National Institute for Occupational Safety and Health (NIOSH), the 

American Conference of Governmental Industrial Hygienists (ACGIH), Canadian 

provinces, the EU SCOEL and other regulatory bodies have recommended 

exposure limits for VAM. Consult your supplier‟s MSDS for any applicable 

occupational exposure limits on VAM for your area. 

Everyone working with VAM, or in the vicinity of VAM, should be fully aware of its 

hazards and informed of appropriate safe handling and emergency response 

procedures. 

Every workplace handling VAM is advised to have an established emergency 

response plan in place prior to bringing the chemical on-site. All personnel 

responsible for handling VAM should be thoroughly trained on the storage and 

handling requirements, including all applicable occupational safety, health and 

environmental regulations. Training should be conducted by persons with 

knowledge and experience in these areas and in conformance with all required 

local, regional and/or national regulations. 

Workers engaged in the handling, storage or transport of VAM should be aware of 

the telephone number(s) or other emergency contacts for securing immediate 

assistance in response to a VAM event. Workers should also be authorized to 

summon emergency response personnel. Workers and supervisors should be 

aware of the requirements for reporting accidents and accidental releases to local, 

state and federal or national agencies. (An overview of these requirements is 

discussed in Section 4.) 
12

Table 2.1: VAM Occupational Exposure Limits 

Organization/Agency Limit

NIOSH 15 minute Ceiling Limit of 4 ppm 

ACGIH

8 hour Threshold Limit Value (TLV) Time-Weighted 

Average (TWA) of 10 ppm

15 minutes Short-term Exposure Limit (STEL) of 15 

ppm

Canada (Alberta, 

British Columbia, 

Ontario)

8 hour Time-Weighted Average (TWA) of 10 ppm

15 minutes Short-term Exposure Limit (STEL) of 15 

ppm

Mexico

8 hour Time-Weighted Average (TWA) of 10 ppm

15 minutes Short-term Exposure Limit (STEL) of 20 

ppm

EU SCOEL Proposed OEL of 5 ppm (17 mg/m3)

China

8 hour Time-Weighted Average (TWA) of 10 mg/m3

15 minutes Short-term Exposure Limit (STEL) of 15 

mg/m3

2.2. Personal Protective Equipment 

2.2.1. Availability and Use of Protective Equipment 

A hazard analysis should be performed for each work activity to determine what 

specific personal protective equipment (PPE) should be worn by anyone working 

with VAM. 

PPE is not an appropriate substitute for safe working conditions, such as 

engineering controls and compliance with safety procedures. However, in some 

instances PPE is the only practical means of protecting the worker, particularly in 

emergency situations. The proper use of PPE requires adequate training of 

workers. The PPE described in the following sections should be readily available 

for use when there is potential exposure to VAM. 

For routine operations where vapor exposure is below established exposure limits, 

PPE typically would consist of: 

 Flame retardant clothing, splash goggles, hard hat and safety shoes 

 Gloves are also recommended for handling hoses or drums. 

For routine operations with potential for minor liquid exposure (from splashes, 

drips or minor spills) and where vapor exposure is below established exposure 

limits, PPE typically would consist of: 

 As above but use impervious gloves, clothing, boots and a face shield 

 Wear protective clothing made of chemical- and fire-resistant materials in 

process areas. When both are needed, the chemical resistant clothing 

should be worn over flame retardant clothing. 
13

For routine operations with potential vapor exposure up to 40 ppm, NIOSH 

recommends: 

 Use of approved organic vapor respirators or respirators with full face 

pieces, goggles and chemical resistant gloves (NIOSH) 

For spills, emergencies and activities with the potential for substantial or 

unknown exposure use: 

 Supplied air respirator with full protective clothing, including a wholebody, chemical- and fire-resistant suit, impervious gloves and boots, and 

eye, head and respiratory protection 

For large spills where the potential exists for uncontrolled high-level exposure to 

VAM vapor, wear: 

 Complete protective suit that includes SCBA with full facepiece operated 

in pressure-demand or other positive-pressure mode and impervious 

gloves 

Permeation testing indicated that the materials in Table 2.2 may afford protection 

against VAM penetration. Other materials or products from other suppliers may 

be suitable for use with VAM if documented permeation test results are available 

to the user. See your supplier‟s MSDS or contact your supplier for additional 

information. 

2.2.2. Respiratory Protection 

Respiratory protection per OSHA 29 CFR 1910.134/ANSI Z88.2-1992 should be 

a type approved by NIOSH. Guidelines for the use of any personal protective 

equipment must be followed, including medical evaluation and approval, worker 

fit testing, training for use and care of respiratory equipment. 

Very high exposures to VAM may occur during: emergency situations; 

equipment cleaning and repairs; when decontaminating areas after a spill or; in 

case of failure of piping or equipment containing VAM. In these situations, 

workers need to be provided with approved full-face self contained or supplied air 

respiratory protection and full protective suits. 

NIOSH recommended respiratory protection levels are: 

 Situations where potential exposure is unknown or could be up to 4,000 

ppm: Use self-contained breathing apparatus (SCBA), which permits the 

wearer to carry a supply of breathing air in a cylinder or appropriate 

supplied air respirator. The SCBA should have a full face piece and 

operate in a pressure-demand or other positive pressure mode. A supplied 

air respirator is also acceptable providing it has a full face piece and is 

operated in a pressure demand or other positive pressure mode. 
14

 For escape: Use SCBA with full face piece or any respirator specifically 

 approved for escape. 

 Situations where potential exposure could be up to 100 ppm: Use full face 

piece supplied air respirators, either continuous flow or positive pressure 

or a powered, air-purifying respirator with organic vapor cartridge. Air 

purifying element should have an end of service life indicator or defined 

replacement schedule. 

 Situations where potential exposure could be up to 40 ppm: Use air 

purifying respirators (low level concentrations only) with organic vapor 

cartridge or air purifying respirator with full face piece and organic vapor 

cartridge. Note that eye irritation has been noted to occur at 

concentrations of 20 ppm and higher. The air purifying element should 

have an end of service life indicator or defined replacement schedule. A 

supplied air respirator is also acceptable. 

SCBAs allow considerable mobility and maximal protection where exposure 

concentrations are unknown. The length of time this apparatus provides 

protection varies according to the amount of air carried and its rate of 

consumption. Where mobility is required, only SCBA should be used. 

Supplied air respirators use breathing air from banks of compressed air cylinders 

or from other reliable respirable air sources. Conventional air compressors or 

plant air systems not specifically designed for breathing air may introduce 

respirable contaminants and should not be used as a source of breathing air. 

Air purifying respirators are convenient and provide considerable mobility but 

afford limited protection. They should be used only when exposure 

concentrations are known to be at low levels. 

For all respiratory protective equipment, follow the manufacturer‟s 

recommendations for use. 

2.2.3. Hand and Skin Protection 

Avoiding skin contact with the VAM is very important. Using appropriate and 

properly fitting PPE is essential to avoid skin contact. Clothing and glove 

materials should be selected for suitability for the intended application prior to use 

and properly worn to be effective. Many common clothing and glove materials 

are not suitable for workplaces were VAM exposure is possible. Some potentially 

suitable materials are shown in the following table. 
15

 Table 2.2: VAM Permeation Test Results for Protective Clothing Materials1

Material Common Uses Results2

Barricade

Suits > 8 hours

Teflon

Suits > 8 hours

Responder

Suits > 4 hours

North Butyl B161 

(16 mil) (or equivalent) Gloves 5 hours

North Butyl B324R (32 mil) (or equivalent) Gloves > 8 hours

Ansell Edmont Laminate (2.5 mil) (or 

equivalent) Gloves 6 hours

North Silver Shield/4H(2.7 mil) (or 

equivalent) Gloves > 8 hours

If other chemicals are used in conjunction with VAM, material selection should 

be based on protection for all chemicals present. These recommendations do not 

take into account the physical demands (e.g., puncture or heat resistance, 

flexibility) that may be required for the protective clothing. Alternative materials 

with shorter breakthrough times (e.g., Neoprene) may also provide acceptable 

protection as long as adequate permeation test data are available for the use 

scenario envisioned. 

Contaminated Clothing/Apparel 

Whenever garments become contaminated with VAM, they must either be 

cleaned by an industrial cleaning service familiar with VAM or properly disposed. 

Contaminated leather articles (e.g., boots, belts, gloves) must be properly 

discarded as contaminated leather cannot be thoroughly cleaned. Other 

contaminated articles (e.g., non-leather watch bands, belts) may or may not be 

able to be properly decontaminated; seek a reputable, professional cleaner 

experienced with VAM contaminated clothing. 

2.2.4. Foot Protection 

To prevent crushing-related injuries, safety footwear with built-in steel toe caps in 

accordance with (OSHA 29 CFR 1910.136/ASTM F2412-05 and ASTM F2413-

05) is recommended for most industrial operations. For added protection against 

chemical contact, safety footwear of chemically-resistant materials should be 

worn over safety shoes. 

All footwear contaminated with VAM, except those that are chemical-resistant to 

VAM, should not be reused and should be properly disposed. Chemical-resistant 

safety foot coverings should be thoroughly cleaned before reuse. 

 

1

 Testing conducted according to the American Society for Testing and Materials (ASTM), Standard Test Method 

for Resistance of Protective Clothing Materials to Permeation by Liquids or Gases Under Conditions of Continuous 

Contact. ASTM F 739-99a. Annual Book of ASTM Standards, Vol. 11.03. 

2

 Results are given as resistance time to breakthrough after continuous contact. 
16

2.2.5. Eye Protection 

Safety glasses must be worn as minimum eye protection (OSHA 29 CFR 

1910.133/ANSI/ASSE Z87.1-2003) but provide little protection against facial 

injury. Side shields and/or chemical splash goggles provide some additional 

protection. When handling VAM, full eye and face protection is preferred and 

should include face shields (full length, 20 cm [8 in.] minimum) with forehead 

protection in addition to chemical splash goggles. If vapor or mist exposure is 

likely, eye protection can be provided through the use of a full face mask in 

conjunction with appropriate respiratory protection. 

Each user of VAM should determine appropriate procedures for employees 

wearing contact lenses given the potential for VAM to irritate the eyes. 

2.2.6. Head Protection 

Hard hats (OSHA 29 CFR 1910.135/ANSI/ISEA Z89.1-2009) are recommended 

for protection from falling objects. Additional chemical resistant head covering 

may be required to protect against overhead liquid leaks and chemical splashes. 

2.3. First Aid Treatment 

The following first aid procedures should be started immediately in the event that VAM

is ingested, inhaled or comes into contact with an individual‟s skin or eyes. Exposed 

individuals should be referred to emergency medical personnel, who should be provided 

with the details of the incident, exposure and symptoms. 

Inhalation (Breathing)

 Remove individual from contaminated area to fresh air and monitor for sign of 

respiratory distress. 

 Provide supplemental oxygen if breathing is difficult. 

 Start artificial respiration if breathing stops, then oxygen as needed. 

 If there are signs of respiratory distress or breathing difficulty, immediately 

contact emergency medical personnel/physician. (Respiratory tract irritation, 

bronchitis, pneumonitis or delayed pulmonary edema may develop.) 

Skin Contact 

 Immediately remove all contaminated clothing (e.g., garments, gloves, belts, 

watch bands, shoes). 

 Wash exposed skin thoroughly with water and soap (if available) for at least 15 

minutes or else blistering may develop 24-48 hours later. 

 Contact emergency medical personnel/physician if irritation and pain persist after 

thorough washing. 
17

Eye Contact

 Remove contact lenses if worn. Immediately, flush exposed eye(s) with large 

amounts of room temperature water for at least 15 minutes. 

 Hold eyelid(s) open and away from eyeball during irrigation to ensure water 

contacts all tissue surfaces of eye and lid. 

 Contact emergency medical personnel/physician immediately. 

Ingestion (Swallowing)

 Slowly drink a glass (125-250 mL [4 to 8 oz]) of water or milk in small sips. 

Larger volumes of liquids may induce vomiting. 

 Do not induce vomiting as VAM can be aspirated into the respiratory tract leading 

to severe respiratory symptoms. 

 Immediately contact emergency medical personnel/physician. 

Thermal Burns

 Immediately cool affected skin for as long as possible with cold water. 

 Do not remove clothing if adhering to skin. 

 Keep individual warm and quiet. 

 Contact emergency medical personnel/physician immediately. 
18

3. STORAGE, TRANSPORT AND HANDLING OF VINYL ACETATE MONOMER 

3.1. Storage Considerations 

3.1.1. Bulk/Tank Storage 

Bulk storage systems for VAM should be evaluated prior to use to ensure that 

appropriate systems (e.g., temperature monitors, systems to add inhibitor and mix 

content of tanks) are available if necessary. 

Bulk storage of VAM at ambient temperature is an acceptable practice when 

appropriate procedures and controls have been put in place to prevent 

spontaneous or uncontrolled polymerization. Most VAM shipped from the 

manufacturer will contain an inhibitor, typically 3-5 ppm hydroquinone3

 (HQ) for 

regional shipments and up to 25 ppm HQ for long-range (e.g., transoceanic) 

shipments. VAM storage tanks should be equipped with temperature measuring 

devices to monitor for unexpected VAM polymerization. The ability to sample 

and analyze tank contents for polymerization inhibitor concentration may be 

needed. See Appendix I for more information about tank design and monitoring 

equipment and Figure 1 (in Appendix I) for a diagram of a typical VAM bulk 

unloading system. 

3.1.2. Maintaining and Assessing Inhibitor Levels in Bulk Storage 

The rate at which the polymerization inhibitor HQ is consumed is dependent on 

storage conditions with temperature, oxygen concentration and presence of 

reactive contaminants being the key factors. Under normal storage and use 

conditions, routine sampling of HQ concentration should not be required 

 

3

 Hydroquinone is the main inhibitor used for VAM. There are other known inhibitors though these are not typically 

used because of their impact the color of VAM/VA-based polymers. 

Vinyl acetate monomer (VAM) can be stored, transported and handled safely if its 

hazards are understood. Two guiding principles for the proper storage, transport and

handling of VAM are to avoid:

 Situations such as inhibitor depletion, excess heat or cross contamination that 

could result in spontaneous or uncontrolled polymerization.

 Situations that could result in uncontrolled releases (spills, overfills, runaway 

polymerization) which create potential fire risks. 

VAM may be subject to rapid spontaneous polymerization if the inhibitor is not 

present or becomes depleted during prolonged storage. Spontaneous polymerization 

is especially likely if cross contamination occurs. The stability of VAM is finite and 

depends on the concentration of inhibitor present, the temperature of the storage 

vessel and other conditions. To avoid polymerization, ensure that cross 

contamination does not occur, that the temperature is not increasing and that the 

inhibitor concentration does not decrease below a minimum effective level (3 ppm).
19

providing the initial HQ inhibitor concentration is at least 3 ppm. Normal storage 

conditions include: 

 An HQ concentration of 3 ppm or higher. 

 A maximum storage temperature of no more than 30oC (86oF). 

 A dry blanket gas in the tank headspace 

o The blanketing gas should be nitrogen (preferred) or air. 

 The absence of reactive contaminants. 

 Turnover of the tank contents every 60 days or less. 

 A rust free storage environment. 

Blanketing with dry gas is important because the presence of water initiates a 

hydrolysis reaction of the VAM to acetic acid and acetaldehyde. Nitrogen is 

preferred as the blanket gas for two reasons. First, it minimizes flammability 

concerns. Second, the presence of oxygen promotes formation of organic 

peroxides, which are polymerization initiators. This leads to more rapid depletion 

of HQ and more rapid onset of polymerization. However, storage under dry air is 

acceptable with a 60-day or shorter turnover. 

Turnover of the tank involves the addition of fresh, inhibited VAM with sufficient 

mixing in the tank to maintain a uniform HQ concentration of at least 3 ppm 

throughout the tank. 

Under laboratory conditions, experimental data indicates that VAM stored at a 

temperature of 38oC (100oF) with a dry air blanket and containing 3-5 ppm HQ in 

a carbon steel container is stable for at least 7-8 months. Stable storage times 

using a nitrogen blanket were even longer (Levy 1993, Levy and Hinojosa 1992).

Despite evidence for stability over 6 months without polymerization, the 60 day 

turnover time for VAM is recommended to provide conservatism when 

accounting for varying transit times and storage conditions. 

Analysis of Inhibitor Concentrations in Bulk Storage

Under conditions that deviate from these normal storage and use conditions, 

periodic analysis of the HQ concentration and tank temperature monitoring may 

be needed to insure that polymerization is not occurring. The HQ concentration 

should be measured at least once every 30 days until sufficient historical data is 

available to define a HQ sampling schedule based on actual storage conditions. 

A commonly used analytical method for HQ analysis of fresh VAM is a titration 

method established by the ASTM – D2193 “Standard Test Method for 

Hydroquinone in Vinyl Acetate” (ASTM 2006). However, for analysis of VAM 

that has exceeded its recommended storage time or when the presence of soluble 

polymer is suspected, a liquid chromatographic (LC) method is recommended. 

This is because in these circumstances it is possible for a solid polymer film to 

form during the evaporation stage included in the ASTM method, blocking the 

HQ and preventing its further dissolution with water during the sample 

preparation procedure (see Appendix VI for several sample LC HQ analytical 
20

methods). The supplier should be consulted for more information on inhibitor 

analysis. 

Precautions Regarding Recycled/Recovered VAM

Special transfer and storage procedures must be used for recycled vinyl acetate 

monomer, such as unreacted VAM recovered from an incomplete polymerization 

process. Recycled VAM will not contain sufficient levels of inhibitor to prevent 

polymerization and may even contain traces of polymerization initiator (Gustin 

2002, 2005). Recycled or recovered VAM must not be returned to a storage tank 

unless special precautions are taken to ensure that adequate polymerization 

inhibitors have been added and that cross contamination of storage tanks does not 

occur. 

There have been documented polymerization events that have occurred in tanks of 

recovered VAM. In one circumstance, VAM recovered from a polymerization 

operation at a polyvinyl acetate plant caused a violent, uncontrolled 

polymerization, resulting in catastrophic tank failure, after being stored in hot 

summertime conditions (Gustin 2002, 2005). 

3.1.3. Containers and Drum Storage 

To prevent hazardous polymerization, drums and small containers should be 

stored in a cool, well-ventilated area. Use only approved containers (per US 

Department of Transportation (DOT), Transport Canada or other appropriate 

authority). Drums of VAM should be stored out of direct sunlight. 

Sealed drums of VAM inhibited with 14-17 ppm hydroquinone may be stored at 

temperatures up to 30oC (86oF) for approximately one year from the date of 

packaging. Sealed drums of VAM inhibited with 3-5 ppm hydroquinone may be 

stored at temperatures up to 30oC (86oF) for up to six months from the date of 

packaging. 

3.2. Shipping Classifications and Regulations 

VAM is commonly transported by highway, rail and water. In the United States, 

regulations for movement of VAM are established by the DOT. Based on United Nations 

Recommendations on the Transport of Dangerous Goods, the DOT established 

Hazardous Materials Regulations for hazard communication, classification and packaging 

requirements (http://phmsa.dot.gov/hazmat/regs). Shipping specifications for VAM were 

listed in the DOT Hazardous Materials Table, 49 CFR 172.101. 
21

Table 3.1: US DOT, Canadian TDG, and EU Shipping Requirements for VAM 

US DOT Canadian TDG EU

Shipping Name

Vinyl Acetate, 

Inhibited

Vinyl Acetate, 

Stabilized

Vinyl Acetate, 

Stabilized

Hazard Class 3 (Flammable 

Liquid) 3 3

UN/NA ID 

Number UN 1301 UN 1301 UN 1301

Packing Group II II II

Reportable 

Quantity 5,000 lb (2270 kg) 200 L (187 kg)

Tank Car 

Specification 111A100W

Tank Truck 

Specification

MC 307, 312, DOT 

407, 412

Barge 

Specification

USCG Certified for 

VAM

Placard Flammable Flammable 

Liquid Flame

Label Flammable Liquid Flammable 

Liquid

Highly Flammable 

Liquid and Vapour

3.3. Loading and Unloading Bulk Shipments from Tank Rail Cars and Trucks 

There are national and regional regulations regarding tank cars (e.g., rail cars) and tank 

trucks for transporting chemicals like VAM, see Section 3.2 for more information. 

The use of rail tank cars with top unloading fittings is recommended to minimize the 

chance of leakage or spillage. If the tank rail car does not have a suction pipe or dip tube4

for top unloading, one can be inserted through a nozzle or opening on top of the tank car 

or through the manway (an opening in the tank car through which a person can enter the 

tank). However, appropriate fittings for the opening or manway should only be used to 

minimize the opening for the suction pipe or dip tube so as to minimize the opportunity 

for volatilization of VAM to the atmosphere. 

There are two common types of tank trucks for VAM transport-center loaders/unloaders 

and rear loaders/unloaders; both types utilize closed system loading (open loading is 

inappropriate for VAM due to the potential for vapor generation). Tank trucks should be 

equipped with two valves and with wash out caps, one of which should be used for the 

vapor recovery and/or nitrogen purge. Tank trucks should also be equipped with a relief 

valve. This protects the integrity of the tank in an over pressure condition. 

Tank trucks or rail tank cars should not be loaded or unloaded during severe electrical 

storms. 

 

4

 A dip tube or suction pipe is a pipe which extends from the top of the railcar at the multi-housing plate to 

approximately 3” from the bottom of the railcar. It allows for loading without causing splashing or turbulence that 

can lead to the build-up of static electricity. 
22

For both tank cars and tank trucks, a dry nitrogen blanket for the head space should be 

used on the tank to make the transfer or to provide suction to a pump. 

Upon arrival at the delivery site, the tank car or tank truck should be inspected for leaks 

and damage. If there are any problems, notify the supplier, the owner of the tank car or 

tank truck and the trucking or railroad company, even if the tank can be unloaded safely. 

Always ensure that the damaged tank car or tank truck is in safe condition before it leaves 

the property. 

When a tank car or tank truck arrives: 

Complete Safety Check Preparing to Load/Unload

 Dedicated equipment is recommended, otherwise special care is required to avoid 

cross contamination. 

 Ensure only appropriately trained and equipped personnel perform loading/ 

unloading operations. 

 Check the shipping papers against the placards, labels and seals as appropriate to 

ascertain proper identification. 

 Check that the car or truck is parked within the designated containment area and 

that the transfer hose has the correct fittings and is of appropriate length. 

 Chock the wheels, set the brakes and shut down the truck engine. 

 Check that the tank truck driver is out of the truck during loading/unloading. 

 If derails (a blocking device placed on the track to prevent unauthorized 

movements of the rail car) are necessary, ensure that they are in place on tank rail 

car tracks. 

 Set up warning signs as appropriate. 

 If hoses are run across vehicular byways, set up protective barricades. 

 Ensure that the transfer equipment contains nothing to contaminate the VAM, 

especially oxidizers, acids or bases. 

Check and Have Ready Necessary Safety Equipment 

 Be aware of emergency procedures. 

 Prior to opening any covers, check the availability and proper operating condition 

of the emergency water, eye wash and shower for washdown. 

 Don personal protective equipment appropriate for the task(s). 

 Emergency equipment should be readily available and checked to confirm it is in 

proper working condition. 

 Use electrical bonding and grounding to prevent static electricity buildup. 

 Use grounded pumps or appropriately regulated, pressurized dry nitrogen (not air) 

for transferring VAM. 

 Have vapor control systems available if regulations require. 

 A flame arrester is recommended if the tank is open to the atmosphere during 

loading/unloading. 
23

Preliminary Procedures

 Before opening a tank car manway cover, outlet valve cap or plug, the car should 

be relieved of pressure through the vent valve. 

 Before removing caps on nozzles, be sure the valves are closed. In some cases a 

valve may have leaked, building pressure between valve and cap. Always use 

caution in removing caps even after having vented the tank car. 

 Confirm that the tank to receive the material has sufficient room to hold the entire 

contents of the truck or tank. 

 If sample purging is done, a metal container (not plastic or other non-conducting 

container) that is electrically bonded to the sample line should be used. 

 Before beginning transfer, check that any necessary samples have been taken and 

check for proper alignment of valves in the line from the car or truck to the tank. 

Making the Transfer

 VAM transfers should be continuously attended and monitored by trained 

personnel equipped with appropriate PPE. 

 Make transfers through piping and into receiving vessels that have been properly 

designed to prevent the generation and accumulation of static charges. Refer to 

Appendix I Bulk Storage Design. 

 Do not make VAM transfers during an electrical storm. 

Your supplier may be consulted for advice on particular situations. Also, the Association 

of American Railroads provides information on methods of loading and unloading nonpressure tank cars in its Pamphlet 34 (AAR 2008). 

3.4. Shipping Containers Damaged in Route 

The following procedure should be followed if a tank car or tank truck containing or 

transporting VAM becomes damaged in route so that it cannot proceed safely to its 

destination: 

 Contact local police and fire departments, the shipper, the supplier and the 

regional transportation emergency centers (e.g., Chemical Transportation 

Emergency Center (CHEMTREC) – see Appendix II for contact information). 

 Remove public from the immediate area. 

 Assess whether damaged tank car or tank truck can be moved to a safe location to 

transfer material to another container. 

 Procedures should be in place to determine whether a reportable quantity has been 

released and whether the loss needs to be reported to the appropriate authorities. 

3.5. Unloading into Storage Tanks 

3.5.1. Storage Tank Vent Handling 

When bulk shipments are loaded or unloaded, the storage tank vent gas may be 

returned to the shipping vessel through a dedicated vapor return line, or may be 
24

sent to a flare or incinerator. In each of these cases, the vent line should have 

flame and/or detonation arresters properly installed and, in some cases, may have 

inert gas added to render the vent gas non-flammable. See Appendix I-Figure 1 

for more details. 

 

3.5.2. Hoses 

The preferred practice is to utilize dedicated equipment when unloading VAM. 

Prior to use, hoses should be checked for cleanliness and integrity. If hoses are 

used for multiple services, they should be thoroughly cleaned after each use to 

avoid cross-contamination. 

Caution is necessary when VAM is bled from hoses to minimize employee 

exposure and to minimize environmental emissions of volatile organic 

compounds. 

To help prevent static electric charge buildup, dedicated electrically continuous 

chemical transfer hoses should be used. Hose materials must be compatible for 

VAM service (see Section 1 on VAM reactivity and incompatible materials). 

Dry-disconnect hose connections are available, which have internal values that 

allow only a few drops of spillage when disconnected. These also prevent 

excessive spillage if the connection is broken during transfer. 

3.5.3. Sampling 

The preferred practice is the use of a „closed loop‟ sampling device such as a 

DopakTM. If closed-loop sampling is not available and a direct collection method 

(e.g., via a purge line) is required, procedures should be used to insure a clean, 

representative sample is collected. Appropriate PPE should be utilized during the 

sample collection process to avoid inhalation, skin and eye contact and/or clothing 

contamination. 

3.6. Tank and Equipment Cleaning and Repairs 

The following are general guidelines and suggestions for the preparation and cleaning of 

VAM tanks and equipment prior to entering for inspection and repair. These guidelines 

are not intended to replace detailed written procedures for a specific job and situation. 

3.6.1. Preparing Personnel 

Tank and equipment cleaning should be performed by trained personnel who are 

familiar with all of the hazards and the safeguards necessary for the safe 

performance of the work. All precautions pertaining to education, protective 

Caution: These hoses should not be relied on to be the primary electrical 

bond; separate bonding and grounding cables must be used.
25

equipment and health and fire hazards, as detailed elsewhere in this Guide and in 

company guidelines and response plans, should be reviewed and understood. 

A stepwise procedure addressing all relevant tasks should be written and used to 

train all personnel involved with the work. The procedure should include specific 

instructions regarding possible hazards, and describe safe procedures and 

protective equipment for dealing with these hazards. 

3.6.2. Preparing Tanks and Equipment 

The tank, equipment and associated lines to be cleaned should first be electrically 

grounded and then emptied of all liquid. In the case of large tanks, it is 

imperative that the tank vent and make-up system be in good working condition 

to keep from over-pressuring or collapsing the tank. 

The bulk of the liquid should be transferred to another vessel (for recovery or 

reprocessing, if necessary) so that any remaining liquid (i.e., heel) is minimized. 

The heel should then be drained into a suitable container for proper reuse or 

disposal. In the case of large storage tanks, it may be helpful to add about six 

inches of water to the tank to recover any VAM remaining in the low spots of the 

tank. All waste liquids should be properly disposed. 

The vessel(s) and piping to be cleaned should be isolated from all other systems 

by closing the proper valves. Wash and flush the equipment three or four times 

with hot (preferably 49-66C [120-150F]), demineralized water. The dirty wash 

water should be collected in a sump or other suitable vessel for proper disposal, 

taking into consideration potential environmental effects. Steam may be used to 

remove final traces of VAM. Providing VAM is not present, a strong aqueous 

detergent or caustic solution can be used to help loosen and remove polymer 

residues. All wastes should be properly disposed. 

The lines in and out of the tank or equipment should be disconnected and 

grounded for entry. Note: Even though the equipment has been flushed with 

water, proper protective equipment should be worn when opening flanges. The 

equipment should then be purged with fresh air and the air should be tested for 

VAM vapor and oxygen content by an approved method before permitting 

personnel to enter. Tank entry is governed by the OSHA standard for Confined 

Space Entry, 29 CFR 1910.146 and the Lockout/Tagout Rule for Control of 

Hazardous Energy, 29 CFR 1910.147. 

Caution: Do not use caustic or alkali detergent solutions when liquid 

VAM is present or with aluminum equipment.

Caution: The vapor space above even dilute aqueous solutions of VAM 

may be flammable.
26

3.7. Maintenance of Equipment 

Routine maintenance is critical to ensuring that equipment performs as designed and 

constructed. A maintenance schedule and program should be implemented in accordance 

with equipment utilized at the facility and applicable local, regional and national 

regulations. 

3.8. Control of Vapors and Waste Disposal 

VAM is volatile and may give rise to odorous vapors. As such, emphasis should be 

placed on the prevention of leaks and spills through careful design and good operating 

procedures. Because of the low odor threshold (about 0.25-0.5 ppm), leaks and spills 

may elicit complaints from workers and neighbors downwind. 

If a spill occurs, only properly trained and equipped response personnel should remain in 

the area for cleanup. The spilled VAM should be collected and disposed of properly (see 

Section 5.3 for guidance on spill response). 

3.8.1. Air Pollution Control 

Atmospheric emissions of VAM are subject to local, regional and/or national 

regulations. 

3.8.2. Discharge to Navigable Waters 

Discharge of pollutants to any body of water is subject to local, regional and/or 

national regulations. 

3.8.3. Disposal of Wastes 

Wastes containing VAM must be treated or disposed of at an authorized facility. 

As a liquid, this material cannot be disposed of directly into a hazardous waste 

landfill. The recommended management practice for waste VAM is incineration 

or burning for heat recovery. 

Typical plant-processed aqueous VAM waste streams can be treated in the plantsite wastewater treatment system. Plant-site wastewater treatment systems should 

be adequately engineered to handle the volume and concentration of VAM 

process waste streams. 

Though adequate dilution of concentrated wastes can reduce odor problems and 

fire hazard, direct discharge of dilute wastes to municipal wastewater treatment 

systems is not appropriate. The treatment method and its impact on sewage 

sludge should be considered. 
27

4. HAZARD ANALYSIS AND EMERGENCY PLANNING FOR THE HANDLING 

OF VINYL ACETATE MONOMER 

4.1. Emergency Planning 

Facilities that handle large quantities of VAM, will likely need to develop an emergency 

plan in order to respond to situations such as: fires, releases to environment, off-site 

incidents, natural disasters, medical emergencies, loss of utilities, etc. Key elements of 

an emergency plan include: 

 Each facility should maintain a written emergency plan outlining response 

procedures to incidents. 

 Responsibilities for internal and external resources are defined and appropriate 

training provided. 

 Emergency procedures are tested periodically, reviewed and revised, as necessary 

to maintain effective response. 

 The emergency plan is periodically communicated to employees/contractors and 

responsible officials in the local community. 

 Emergency response equipment is operated by qualified individuals and is 

available at the facility or locally. 

4.2. Risk Management/Process Safety Regulations 

Depending on where your facility is located there may be regulations that determine what 

specific elements need to be in your emergency plan. Examples of possible regulations 

that should be considered are: 

 US: EPA Clean Air Act, Section 112(r) - Risk Management Plan; 40 CFR 68.130 

 US: OSHA Process Safety Management of Highly Hazardous Chemicals (HHC); 

29 CFR 1910.119(n) 

 US: OSHA Emergency Action Plan; 29 CFR 1910.38 

 US: OSHA Hazardous Waste Operations and Emergency Response; 29 CFR 

1910.120 

Each step in handling and using VAM should be reviewed for possible hazards. The 

review should include the appropriateness of the equipment and the proper 

procedures for using the equipment. The review team should include personnel 

directly involved in all relevant activities, as well as technical and safety specialists. 

The safety review must meet the requirements of governmental regulations, and may 

include evaluations of:

 Process design and controls 

 Operational safety equipment such as ventilation, pressure relief 

devices, grounding devices, etc.

 Prevention of cross contamination sources as this could result in 

spontaneous polymerization
28

 Europe: SEVESO II 2003/105/EC, 12/2003 & 96/82/EC, 1/1997 

 Mexico: NOMO-28 

Some of these regulations include specific “threshold quantities” of VAM that trigger 

regulatory requirements. For the US EPA CAA 112(r) RMP, the threshold quantity for 

VAM is 15,000 pounds. For the US OSHA Process Safety Management regulation, the 

threshold quantity for VAM is 10,000 pounds. Additional information about the CAA 

112(r) regulations and other EPA programs designed to prevent and respond to 

emergencies can be found at http://www.epa.gov/emergencies/index.htm. More 

information on the OSHA Process Safety Management standard can be found at 

http://www.osha.gov/SLTC/processsafetymanagement/index.html. 

4.3. Emergency Response Planning: Acute Inhalation Guidance Values 

In emergency planning, acute inhalation guidance values are used to determine adverse 

health effect levels in populations that might be impacted by an emergency release. The 

American Industrial Hygiene Association‟s Emergency Response Planning Guidelines5

(ERPG) and the US EPA draft Acute Exposure Guideline Levels (AEGLs), listed in 

Table 4.1, provide guidance on air concentrations that may cause effects in the general 

population. In the event that an accidental or unscheduled release results in community 

exposures at these levels, sheltering, evacuation or other actions may be required. 

Table 4.1: ERPG and AEGL Values for VAM

AEGL/ 

ERPG Value

ERPG-1 5 ppm (1-hour) Threshold for Mild, Transient Adverse Health Effects 

AEGL-1

(interim) 6.7 ppm (up to 8-hours) Threshold for Irritation

ERPG-2

75 ppm (1-hour) Threshold for Irreversible Health Effects and Escape 

Impairment

AEGL-2

(interim) 180 ppm (1-hour)

ERPG-3 500 ppm (1-hour) Threshold for Lethality

AEGL-3

(interim) 610 ppm (1-hour)

 

5

 Emergency Response Planning Guidelines are health-based threshold values used to assist health and safety 

professionals in the development of emergency response strategies for protecting workers and the general public 

against the harmful effects of specific chemical substances. They represent the concentration that nearly all 

individuals could be exposed to for up to one hour without experiencing or developing the indicated effect.
29

5. MANAGING EMERGENCIES 

5.1. Fire and Explosion 

5.1.1. Preventing Fires 

Since VAM vapors are heavier than air, they may concentrate and travel along the 

ground some distance to an ignition source. Therefore, every precaution should 

be taken to prevent exposure to flames, sparks or other ignition sources. The 

following are general guidelines for preventing VAM fires (see Section 3 for 

more detailed handling information): 

 Locate VAM storage, handling and processing equipment outside or in a 

non-combustible or fire-resistant building. 

 Do not allow combustible material such as brush or weeds to accumulate 

around storage tanks or drums. 

 Provide adequate venting for emergency conditions in vessels used for 

storage, handling and processing. (As described elsewhere, relief devices 

must be sized according to engineering calculations.) 

 Provide proper electrical equipment and adequate grounding for static 

electrical discharge. 

An essential component of Emergency Management is incident prevention. 

Through adequate facility design, safe storage and handling practices, personnel 

training and disaster preplanning, many of the consequences of an emergency can 

be minimized or avoided altogether.

In the event of a major release of VAM, the area should be evacuated immediately 

based on the facility risk management plan (RMP) or other emergency response 

plan. Only trained personnel equipped with appropriate safety equipment should 

enter the area. Full protective clothing (Section 2.2) should be worn when it is 

necessary to work in an environment containing VAM where exposure may occur at 

levels in excess of permissible limits. 

As part of the emergency response plan, regular communications and/or disaster 

training sessions with the local/municipal fire departments are encouraged in 

anticipation of fires, spills or emergencies. 

The following sections describe the materials and procedures to be used in the event 

of emergency situations involving VAM, including fires, spills or first aid 

requirements. Much of this information comes from the 2008 Emergency Response 

Guidebook (ERG 2008), which may be obtained from the US DOT at

http://phmsa.dot.gov/hazmat/library/erg or from Transport Canada at 

http://www.tc.gc.ca/CANUTEC/en/GUIDE/guide.htm. Guide 129 is specific to 

VAM (see Appendix 5).
30

 When filling, circulating or agitating VAM in a storage tank, care should 

be taken not to vigorously disrupt the liquid surface (causing a static 

charge). 

 Regularly inspect equipment and storage facilities for corrosion and leaks, 

especially vents and flame arresters. 

 Immediately fix any leaks in equipment. 

 Provide adequate local exhaust and general ventilation in the working area 

and carry out regular tests with a combustible gas indicator in any area 

where vapors might accumulate. 

 Provide proper facilities to handle any accidental spillage. 

 Provide adequate fire extinguishing equipment including automatic 

sprinklers in storage and work areas.

5.1.2. Fighting Fires 

In the event of a fire involving VAM, the following extinguishing materials 

should be used and procedures followed: 

Extinguishing Materials

 Use carbon dioxide or dry chemical extinguishers for small fires.6

 Use dry-chemical or alcohol type foam for large fires. When these 

extinguishing materials are not immediately present, the fire can be fought 

with water spray, especially to keep fire-exposed containers and structures 

cool and to reduce vaporization. However, water spray may not be 

completely effective in fully extinguishing the fire.

 Use of high-velocity water stream should be avoided in order to prevent 

the spread of burning monomer or the accumulation of fire-fighting water. 

Since VAM is lighter than water and does not appreciably mix with water, 

it will float on water, thereby spreading the fire. 

Procedures

 Firefighting individuals should wear SCBA and complete personal 

protective equipment (PPE) for protection from smoke, fumes or 

hazardous decomposition products (see Section 2 for more information on 

PPE). 

 Use water spray to cool fire-exposed structures and containers. 

 Use water spray to disperse vapor cloud if fire is not present and to flush 

spills. 

 Firefighters must stay well away from involved vessels since explosion 

may be possible. 

 Any drums or containers of VAM exposed to fire should be kept cool by 

water spray to prevent uncontrolled polymerization, which in turn can 

cause auto-ignition and explosion. 

 

6 A “small fire” is a fire that can be extinguished using a portable fire extinguisher.
31

 If the involved VAM storage vessel is no longer venting, it could still be 

dangerous. Unless the vent is obviously unobstructed, other indications 

such as pressure, temperatures and no longer making normal venting 

sounds must be considered to avoid undetected pressure buildup and 

possible container rupture. 

 Have the proper MSDS ready for arriving municipal emergency 

responders along with directions from the Incident Commander (IC) onscene. 

 In the event of a massive fire, use unmanned hose holder or monitor 

nozzles; if this is impossible, withdraw from area and let fire burn (ERG 

2008). 

Evacuation

 If tank, rail car or tank truck is involved in a fire, US DOT (ERG 2008) 

recommends that the area be isolated for 800 meters (1/2 mile) in all 

directions. 

5.2. Uncontrolled Polymerization 

As discussed in Section 3, VAM is typically inhibited with hydroquinone and is stable 

under recommended storage conditions (see Section 1.1.2 on polymerization hazards). 

Polymerization of VAM is highly exothermic and a rapid release of heat may cause a 

rapid increase in pressure resulting in an uncontrolled release and/or vessel rupture. The 

only reliable method to stop an uncontrolled polymerization is the addition and proper 

mixing of an inhibitor. Cooling water sprayed on the exterior of a storage tank to remove 

heat will retard, but not stop, an uncontrolled polymerization. As conversion increases, 

increased viscosity of tank contents may prevent effective addition and distribution of 

inhibitor and may limit heat transfer. In addition, the hazards of approaching a container 

or vessel of VAM that is undergoing an uncontrolled polymerization must be considered 

in the response plan. 

 

An abnormally high and increasing storage tank temperature trend indicates that VAM 

polymerization may be occurring. In this situation, additional polymerization inhibitor 

should be promptly added to the tank. The specific inhibitor quantity to be added will 

depend upon your specific situation. Where the polymerization rate is low and the 

temperature is gradually increasing, enough HQ should be added to raise the 

concentration in the tank by 5 ppm to replace HQ that has been consumed. For more 

rapid or continuing polymerization and increasing temperature, it may be necessary to 

add more inhibitor initially until polymerization is stopped as indicated by temperature 

stabilization in the tank. However, until the storage tank temperature can be brought 

back to normal conditions, more frequent monitoring of tank temperature and inhibitor 

concentration is recommended due to the increased potential for recurring polymerization 

due to inhibitor depletion at higher temperatures. The ability to mix the inhibitor with the 

entire contents of the tank is critical and must be considered during the design of storage 

tanks and supporting equipment. The system for adding the inhibitor should be designed 

to prevent personnel exposure to the inhibitor and VAM vapors. 
32

5.3. Managing Spills 

Only professionally trained personnel provided with full personal protective gear should 

be involved in a VAM spill response and cleanup. The following procedures should be 

followed for cleaning VAM spills: 

Initial Response

 Call emergency response telephone number provided from facility, supplier, 

MSDS, shipping paper or other source. 

 As an immediate precautionary measure, isolate the spill or leak area for at least 

50 meters (150 feet) in all directions (ERG 2008). Larger spills will likely 

involve the need to isolate larger areas and/or the potential for downwind 

evacuation. 

 Evacuate non-protected and non-professional personnel from the affected area. 

 Keep non-emergency response personnel away. 

 Stay upwind. 

 Keep personnel out of low areas, where VAM may collect. 

 Immediately turn off or remove all possible sources of ignition. 

 Ensure containers and transfer lines are grounded during loading/offloading. 

 Implement initial downwind evacuation based on consequence analysis of 

accidental catastrophic releases from the risk management plan. The 2008 

Emergency Response Guidebook recommends an evacuating area of at least 300 

meters (1,000 feet), though this recommendation expands to 800 meters (2,600 

feet; 1⁄2 mile) in all directions if fire is involved (see Section 5.1.2 on Fire 

Fighting/ Evacuation). 

 Provide adequate ventilation until area is clean. 

 Prevent VAM from contacting peroxides, hydroperoxides, hydrogen peroxide, 

azo compounds and other polymerization initiators, as well as strong acids, alkalis 

or oxidizing agents. 

 

Containing and Managing Small Spills

 Place leaking containers in well ventilated areas with spill containment. 

 Cover liquid VAM with nonflammable absorbent material (e.g., diatomaceous 

earth, absorbing pads) and allow it to soak up the spilled material. 

 Commercially available spill cleanup kits are suggested for small spills. Choice 

of spill kit should be appropriate for amount of VAM handled, size of containers 

and site conditions. 

 If odor problems persist after a small spill has been thoroughly cleaned, lime or 

other alkaline material may be used to deodorize the area. 

Containing and Managing Large Spills

 Locate and correct source of spill or leak, if possible to do so safely. 

 Contain the spill in a diked area if possible. 
33

 Cover the liquid with alcohol type foam to decrease vaporization and/or chance of 

ignition. Water spray may be used to reduce vapors. 

 Keep the material out of sewers (explosion danger) and surface waters. Should 

accidental spillage reach surface waters or the municipal sewer system, notify 

appropriate pollution control and water supply agencies. 

 Floating booms should be kept on hand where the possibility of spillage to water 

exists for use in pulling the floating monomer into a smaller area where it can be 

skimmed off. 

 Determine if release is reportable under applicable laws and regulations and 

notify appropriate authorities. 

Disposal 

 Dispose of spilled material by biological oxidation if initial VAM concentration is 

below toxic levels for microorganisms, otherwise dispose of by controlled 

incineration. 

 Properly dispose of contaminated dirt or absorbent material in compliance with 

applicable local, regional, and/or national waste regulations. 

 Do not wash spillage or leakage into sewer system. Prevent runoff into storm 

sewers and ditching leading to natural waterways. 

5.4. Reporting Releases to the Environment 

Under the US Federal Comprehensive Environmental Response, Compensation, and 

Liability Act (CERCLA) of 1980 and EPCRA, unauthorized releases of listed substances 

to the environment above their “Reportable Quantity” (RQ) must be reported. 

Transportation spills greater than the reportable quantity are also reportable. In the US, 

the RQ for VAM is set at 5,000 pounds. As such, any single unauthorized release above 

5,000 pounds must immediately be reported to the appropriate authorities. Facilities that 

have on-site more than 1,000 pounds of VAM are subject to this reporting requirement. 

Reports are to be filed with the National Response Center (see Appendix II for contact 

information), the appropriate State Emergency Response Commission (SERC) and the 

Local Emergency Planning Committee (LEPC). (Appendix II identifies sources of 

additional information on these reporting requirements.) 

Some states or regional authorities have established their own environmental reporting 

programs that can be more stringent than the national requirements. As such, facilities 

handling VAM should be familiar with all regulatory requirements. 

In Canada, under the Canadian Transportation of Dangerous Goods (TDG) regulations, 

the RQ for Class 3 substances like VAM is 200 liters (187 kg). In the event of an 

accidental release of that quantity or more, an “immediate report” is required to be made 

with the following: 

 Appropriate provincial authority 

 Employer of the person who has possession of the dangerous goods 

 Consignor of the dangerous goods 

 For a road vehicle, the owner, lessee or charterer of the road vehicle 
34

 For a railway vehicle, Canadian Transport Emergency Centre of the Department 

of Transport (CANUTEC); see Appendix II for contact information 

 For a ship, CANUTEC, a Vessel Traffic Services Centre or a Canadian Coast 

Guard radio station 

 For an aircraft, an aerodrome or an air cargo facility, CANUTEC and the nearest 

Regional Civil Aviation Office of the Department of Transport and, if the 

aerodrome is an airport, the operator of the airport 

 For an accidental release from a cylinder that has suffered a catastrophic failure, 

CANUTEC 

Follow-up reports may be required in both the US and Canada after initial notification of 

a release. Some state and local governments in the US have additional requirements. 
35

REFERENCES 

American Conference of Governmental Industrial Hygienists (ACGIH). (2007). Industrial 

Ventilation: A Manual of Recommended Practice for Operation and Maintenance. Available 

for purchase at http://www.acgih.org/store/ProductDetail.cfm?id=1874

American Industrial Hygiene Association (AIHA). (1992). Emergency Response Planning 

Guidelines (ERPG), Vinyl Acetate. AIHA Press, Fairfax, VA. 

American Institute of Chemical Engineers (AIChE). http://www.aiche.org/

AIChE Center for Chemical Process Safety http://www.aiche.org/ccps/

AIChE Design Institute for Emergency Relief Systems 

http://www.aiche.org/TechnicalSocieties/DIERS/index.aspx 

AIChE Design Institute for Physical Properties (DIPPR®): www.aiche.org/DIPPR/

American National Standards Institute (ANSI). (1992). Z88.2: Practices for Respiratory 

Protection. Note: ANSI Z88 Committee states that this standard has been administratively 

withdrawn by ANSI. The standard is currently under appeal, and appeals are expected to be 

resolved in 2009. Updates can be obtained on the Z88 Committee webpage: 

http://www.aiha.org/Content/InsideAIHA/Standards/z88.htm 

American National Standards Institute (ANSI)/American Society of Safety Engineers (ASSE). 

(2003). Z87.1-2003: Occupational and Educational Personal Eye and Face Protection Devices. 

American National Standards Institute (ANSI)/International Safety Equipment Association 

(ISEA). (2009). Z89.1-2009: American National Standard for Industrial Head Protection. 

American Petroleum Institute (API). (2002, February). API 620: Design and Construction of 

Large, Welded, Low-Pressure Storage Tanks. Tenth Edition. 

American Petroleum Institute (API). (2001). API 650: Welded Steel Tanks for Oil Storage. 

Tenth Edition, November 1998. Addendum 1, January 2000. Addendum 2, November 2001. 

Association of American Railroads (AAR). (2008). Pamphlet 34: Recommended Methods for the 

Safe Loading and Unloading of Non-Pressure (General Service) and Pressure Tank Cars. 

http://nar.aar.com/nar/pdfs/ref-material/pamphlet_34_from_boe_tariff.pdf 

ASTM International. (2005). F 2412-05 Test Methods for Foot Protection. 

ASTM International. (2005). F 2413-05 Specification for Performance Requirements for 

Protective Footwear. 

ASTM International. (2006). ASTM D2193 - 06 Standard Test Method for Hydroquinone in 

Vinyl Acetate. 

Canada. (2009). Screening Assessment for the Challenge: Acetic Acid Ethenyl Ester (Vinyl 

Acetate Monomer). Environment Canada, Health Canada. 
36

Canada (Transport Canada). Transportation of Dangerous Goods Regulations 

http://www.tc.gc.ca/tdg/clear/tofc.htm 

Emergency Response Guidebook (ERG). (2008). http://phmsa.dot.gov/hazmat/library/erg

EU (European Union). Directive for Classification, Packaging and Labelling of Dangerous 

Substances (67/548/EEC). 

EU (European Union). Regulation on Classification, Labeling and Packaging of Substances and 

Mixtures. EC No. 1272/2008. 

EU (European Union). Directive 94/9/EC on Equipment and Protective Systems Intended for 

Use in Potentially Explosive Atmospheres (ATEX 95).

EU (European Union). Directive 99/92/EC on Minimum Requirements for Improving the Safety 

and Health Protection of Workers Potentially at Risk from Explosive Atmospheres (ATEX 

137). 

EU (European Union). (2008a.) Risk Assessment Report (RAR) of Vinyl Acetate. May 2008. 

EU (European Union). (2008b). European Commission Directorate-General for Health and 

Consumers. Scientific Committee on Health and Environmental Risks (SCHER). Risk 

Assessment Report on Vinyl acetate: Human Health Part. November 2008. 

Gustin, Jean-Louis. (2002). “Influences of Trace Impurities on Chemical Reaction Hazards.” 

Journal of Loss Prevention in the Process Industries. 15(2002): 37-48. 

Gustin, Jean-Louis. (2005). “Understanding vinyl acetate polymerization accidents.” Chemical 

Health & Safety, November/December 2005, pp 36-46. 

IEEE 81: IEEE Guide for Measuring Earth Resistivity, Ground Impedance, and Earth Surface 

Potentials of a Ground System, 1983 edition. 

IEEE 142: IEEE Recommended Practice for Grounding of Industrial and Commercial Power 

Systems. (Color Book Series - Green Book), 2007 edition. 

International Agency for Research on Cancer (IARC). (1995). IARC Monographs on the 

Evaluation of Carcinogenic Risks to Humans, vol. 63, p. 443. World Health Organization. 

Lyon, France. http://www.inchem.org/documents/iarc/vol63/vinyl-acetate.html 

Levy, L.B. and Hinojosa, L. (1992). “Effect of Oxygen on Vinyl Acetate Polymerization.” 

Journal of Applied Polymer Science, Vol. 45, 1537-1544 (1992). 

Levy, L.B. (1993). “Vinyl Acetate Shelf Life.” Celanese Internal Company Memo. Hoechst 

Celanese Corporation, Chemical Group. LBL-0908-93. January 21, 1993. 

NFPA 30: Flammable and Combustible Liquids Code, 2008 edition. 

NFPA 68: Standard on Explosion Protection by Deflagration Venting, 2007 edition. 
37

NFPA 70: National Electrical Code®, 2008 edition. 

NFPA 70b: Recommended Practice for Electrical Equipment Maintenance, 2006 edition. 

NFPA 77: Recommended Practice on Static Electricity, 2007 edition. 

NFPA 101: Life Safety Code®, 2009 edition. 

NIOSH. (2007, September). Pocket Guide to Chemical Hazards. US Department of Health and 

Human Services, Publication No. 2005-149. http://www.cdc.gov/niosh/npg/pdfs/2005-149.pdf

OECD. Test No. 301. Guideline for the Testing of Chemicals: Ready Biodegradability. 

United Nations (UN). (2007). Globally Harmonized System of Classification and Labelling of 

Chemicals (GHS). Second Revised Edition. 

http://www.unece.org/trans/danger/publi/ghs/ghs_rev02/02files_e.html

United Nations (UN) Recommendations on the Transport of Dangerous Goods. Available for 

purchase at the United Nations Publications page: www.un.org/Pubs/ 

Workplace Hazardous Material Information System (WHMIS) (Canada). http://www.hcsc.gc.ca/ewh-semt/occup-travail/whmis-simdut/index-eng.php
38

APPENDIX I: BULK STORAGE DESIGN 

1. Building Design 

Equipment and vessels containing vinyl acetate monomer (VAM) should be isolated 

from other facilities by good design practices and the use of fire resistant materials. 

Standard firewalls are recommended for the isolation of larger equipment and storage 

tanks, while partitions of plaster on metal framing may be used to isolate smaller 

equipment from other combustible materials. 

At least two means of exit should be provided from each room or building in which 

VAM is stored or used. No area of such a room or building should be further than 75 

feet from the nearest exit. Additional exits should be provided depending on the number 

of persons in the building (see NFPA 101). All exit doors should open out in the 

direction of travel and should be provided with panic hardware (e.g., emergency exit bar 

door). Fire doors should be of an approved type. A fire resistant stairwell with selfclosing fire doors should be provided where hazardous operations are carried out on 

upper floors. 

Operations where large quantities of VAM are used should preferably be processed in 

outdoor type structures or housed in one-story buildings protected by automatic 

sprinkler systems. Explosion vents may be used to reduce destructive damage to 

buildings, ducts, mixers, blenders, dryers and similar equipment in places where 

flammable vapors of VAM are liable to concentrate. Explosion venting windows, roof 

and wall panels, skylights, light windows, diaphragms, etc., may be used to minimize 

building damage due to explosion. 

Since the required surface area of explosion vents depends upon such factors as the 

intensity of an explosion, vapor temperature, type of structure, type of vent closure, etc., 

the determination of required vent capacity should be made by experienced engineers. 

Consideration may be given to explosion suppression systems (see NFPA 68). 

Static electricity is a particular problem when handling flammable materials. 

Consequently, shipping and storage containers, reaction vessels and transfer lines should 

be electrically grounded and bonded. NFPA 77: Recommended Practice on Static 

Electricity provides instructions for proper grounding procedures. Electrical devices and 

installations in areas where VAM is handled should be suitable for Class I, Group D 

hazardous locations (as defined by Articles 500 and 501 of the National Electrical 

Code). In setting up storage and handling facilities and procedures, care should be taken 

to conform with local ordinances and any regulations of underwriters and insurance 

companies. The need to segregate floor drains from sanitary or process sewer systems 

should be considered as well as the question of adequate distances between chemical 

storage buildings and other buildings and processing equipment. 

Buildings used for processing or storing VAM should be well ventilated to prevent 

accumulation of vapors and exposure to personnel. Ventilation methods include local 

exhaust and general dilution procedures. Regional standards and regulations governing 

air exchange rates in buildings that handle toxic and/or flammable gases should be 

consulted. Local exhaust is most effective where vapors are emitted from point sources, 

such as liquid transfer points, pump houses and the reactor area. General dilution 
39

ventilation may be used when vapors are emitted from scattered points throughout an 

area. Because of VAM‟s low odor threshold, the ventilated air may require odor 

abatement. 

2. Storage Tank Construction and Location 

Type: Suitable for flammable liquids 

Material: Rust free steel, cured phenolic-lined steel, stainless steel or aluminum 

Design: American Petroleum Institute (API 620 and 650) 

Fittings: Nozzles for temperature and level sensors, manhole cover, dip pipe, vent 

 line, pressure and vacuum relief valve, emergency relief valve, 

 manometer level gauge, high level alarm, overflow, fill and discharge 

In addition to the steel, carbon and aluminum materials listed above, certain passivated 

zinc-based coatings may be acceptable for storing VAM. However, many other 

common lining materials such as copper, copper alloys (e.g., brass and admiralty metal), 

zinc and galvanized steel should not come into contact with VAM because these can 

have adverse effects on end uses. 

A newly constructed carbon steel tank should be prepared for service by sandblasting 

and vacuum cleaning. If the cleaned tank is not to be immediately filled with monomer, 

it should be closed and blanketed with dry air or inert gas to retard rusting. 

VAM is typically stored in a vertical (API 620 or 650 design) above ground tank. There 

may be local regulations that require additional design aspects (e.g., internal floating 

roofs). The design selected should allow for mixing of the contents with new deliveries 

or when additional inhibitor is added in order to achieve uniform distribution of the 

inhibitor. The tank should be set on a concrete pad within a concrete dike of sufficient 

capacity capable of holding a minimum of the entire tank‟s contents. Storage tanks 

containing materials that are incompatible with VAM must not be placed in the same 

dike. A tank well with a bottom drain line through the tank pad will provide complete 

tank drainage. 

Tanks normally used for VAM storage may be coated with a heat or light reflective 

coating (e.g., white or reflective paint) in order to minimize heat absorption and to 

reduce possible air emissions. 

Tanks must be electrically grounded to prevent accumulation of static electricity, which 

could discharge and ignite flammable VAM vapors. The design, testing and 

maintenance of grounding systems are beyond the scope of this document. Refer to 

applicable regulations and design standards (e.g., NFPA 70, 70B and 77, IEEE 

Standards 81 and 142). 

When filling, circulating or agitating VAM in a storage tank, care should be taken to not 

vigorously disrupt the liquid surface, which will cause generation and accumulation of a 

static charge within the liquid. This applies even if the tank vapor space is made inert 

with nitrogen. If VAM is fed into a storage tank through a dip pipe, the dip pipe must be 

electrically grounded to prevent the buildup of a static electrical charge. 
40

Equipment such as emergency vents and instrumentation that are attached to a VAM

storage tank should be designed to prevent polymerization of VAM. Vapors of VAM

can condense in equipment such as emergency vents, vacuum breakers, instrumentation 

tubing, nozzles and piping. 

Polymerization will occur and could affect performance of critical safety and operational 

devices. Therefore, equipment attached to a tank should be designed such than all 

condensate drains into the tank. In the case of instrumentation tubing, VAM vapors can 

be kept out of the tubing with a small nitrogen purge. VAM storage tanks and 

supporting equipment (e.g., pipes, pumps, and valves) should be designed and operated 

to prevent stagnant areas where liquid VAM could remain for long periods of time and 

lead to polymerization. 

3. Storage Tank Equipment 

3.1. Temperature Measuring Device 

An unusual increase in temperature may be an indication of VAM

polymerization. Therefore, continuous temperature monitoring with the ability to 

observe trends in tank temperature is a valuable tool for early detection of 

polymerization. One temperature sensing element should be placed near the tank 

bottom to ensure that it is always in liquid. In large bulk storage tanks, 

additional sensing elements should be installed at different elevations in the tank 

as localized polymerization can occur in tanks that are poorly mixed. 

Additionally, a high temperature alarm should also be installed to warn of 

polymerization. It should activate at a temperature of about 5oC above the 

normal maximum temperature of the stored liquid, however this value may be 

revised based on historical experience and as needed to account for ambient and 

process conditions. Refer to Section 5.2 on addition of inhibitor if tank 

temperature exceeds alarm level. 

3.2. Emergency Vent-Pressure Relief Devices 

Storage tanks containing VAM should be equipped with one or more emergency 

vents sized according to local, regional and/or national regulations (e.g., NFPA 

30 or ATEX 95). It should be noted that despite conformance with engineering 

standards, such devices may not provide sufficient pressure relief in the event of 

an uncontrolled or runaway polymerization. Runaway polymerization can be 

prevented by maintaining an adequate concentration of polymerization inhibitor 

and preventing exposure to high temperature and reactive contaminants. 

Vacuum relief is also required to prevent collapse or rupture of the tank should 

the tank pressure control system fail during withdrawal of liquid from the tank. 

For further guidance on emergency pressure relief device designs, contact 

organizations such as the AIChE Design Institute for Emergency Relief Systems 

(DIERS) or the AIChE Center for Chemical Process Safety (CCPS). 

Caution: It is critical to note that the condensate will not contain any 

polymerization inhibitor and may begin to polymerize.
41

3.3. Reducing Air Emissions 

VAM emissions from point sources can be reduced by vapor recovery systems 

that recapture the monomer or emission control devises such as flares or 

incinerators. These (or other) emission reduction systems should only be 

installed after consulting with appropriate technical experts. 

3.4. Tank Head Space Considerations 

Although storage of VAM with either air or nitrogen in the headspace is 

acceptable, nitrogen is the preferred gas. By excluding oxygen, the flammability 

of the tank‟s vapor space is reduced and the potential for polymerization is 

minimized. 

In cases where air is used instead of nitrogen in the tank headspace, the air 

should be dry. Drying agents (typically, molecular sieves or calcium chloride) 

can be used. The drying agent should be renewed as needed to maintain a dry 

headspace. Silica and alumina are not recommended due to incompatibility with 

VAM. 

3.5. Flame Arrester 

Flame arresters should be used on vent lines for tanks holding flammable liquids 

and are frequently required by regulation. They are not used on emergency vents 

that vent directly to the atmosphere. Flame arresters should be regularly 

inspected for blockage by vinyl acetate polymer deposits. Initial inspection 

frequency should be at least once every 6-12 months and then can be modified 

based on experience and performance history. When using closed circuit 

unloading, an additional flame arrester should be installed in the vapor return 

line. 

3.6. Overflow Protection 

Safe guards such as high-level interlocks or other systems should be used to 

prevent overfilling the tank. If the capacity of the tank is exceeded during 

transfer of monomer from a delivery vehicle, the excess monomer should flow 

through a properly designed overflow protection system such as an overflow 

vent, seal pot/loop (collection devises connected to the tank) into a suitable 

receiver. 

3.7. Liquid Level Measurement and Control 

A differential pressure transmitter is the preferred method for measuring liquid 

level. The transmitter tap to the tank vapor space should be purged using dry 

nitrogen to prevent condensation of VAM vapor in the tap, which would cause 

an erroneous level measurement. Use of a differential pressure transmitter also 

allows continuous readout of the liquid level at remote locations (e.g., control 

room). 

A separate high level switch or differential pressure transmitter should be used to 

trigger liquid flow shut off into the tank in cases where overfilling the tank 
42

would create unsafe (e.g., spill) or undesirable (e.g., tank damage) consequences. 

The measurement device used for the high level shutoff should not be the same 

device used to control the tank level so that both control and shut off functions 

are not disabled by a single instrument failure. The high level sensor should be 

set based on tank capacity, fill rate and time required for manual intervention 

should the automated shut off fail to work (e.g., shut off at 90 percent of tank 

maximum liquid level). A high level alarm (e.g., 85 percent level) can provide a 

warning that the shutoff level is being approached. While alarm levels can vary 

from these values, users are responsible for determining the maximal safe tank 

levels and alarm settings consistent with safe operating conditions. 

3.8. Pumps 

Double mechanical seals are typically used as the sealing mechanism for VAM

process pumps. Double mechanical seals, specifically the barrier fluid seal pot, 

provide containment of the VAM in the event of a seal failure. Seal-less (e.g., 

mag-drive) or canned pumps are also acceptable. If tank cars or tank trucks are 

to be unloaded from the top, a self-priming centrifugal pump is recommended. 

Consult your pump supplier to match material compatibility with VAM. 

Care should be taken to prevent dead-heading (i.e., running pump with a blocked 

discard line) of any pump used with VAM. Pump discharge piping and any 

related components must be capable of handling the maximum pump dead-head 

pressure, or suitable over pressure protection (e.g., a relief valve discharging to a 

safe location) can be provided. To prevent heat buildup, a pump should not be 

allowed to circulate through a relief valve or other recirculation line for extended 

periods of time. Dead-heading of the pump or continued circulation without 

adequate cooling will lead to polymerization of VAM over time. Dead-heading 

a pump may result in a seal leak, pump failure, loss of containment and possibly 

a fire. An automated pump shut-off system should be considered where pump 

dead-heading could create safety and material quality issues. 

3.9. Pipe 

Steel piping should be cleaned of all grease and scale adhering to the inner walls. 

All pipes should be painted white or otherwise protected from the heat of direct 

sunlight. All pipes should be pitched to drain and not retain VAM that could 

subsequently polymerize. Pipelines and associated systems that will be dormant 

should be drained and cleared as any VAM remaining in the lines may 

polymerize. Nitrogen should be used to blow pipelines clean, due to the 

potential for generating flammable vapors and static charges. 

Caution: If seal-less or canned pumps are used, heat generation can 

cause polymerization in the pump if flow is stopped.
43

3.10. Valves 

Type: Polytetrafluoroethylene (PTFE)-sleeved plug valves, globe 

 valves, gate valves, ball valves 

Material: Carbon steel, ductile iron or stainless steel 

Ball valves with PTFE seals are suggested for on-off service. 

3.11. Gaskets 

Consult your gasket supplier to ascertain material and design compatibility. 

Note: The impact of heat from external fires may compromise gasket integrity 

and should be considered in gasket selection given VAM‟s flammability. 

 

3.12. Filter 

Rust particles or other particulate matter can be satisfactorily removed from 

VAM by means of a cartridge filter. 

 Type: In-line cartridge filter 

 Material: White cotton fiber or polypropylene wound on a stainless core or 

 stainless steel mesh 

 3.13. Prevention of Spills from Storage Tank Piping 

Designers and operators of VAM storage tanks should consider the potential for 

large releases of liquid due to failure of piping connected to the tanks. Check 

valves on inlet lines and remote shutoff valves on outlet lines may be used to 

minimize the risk of emptying tanks through failed piping. Some localities may 

require the installation of fusible link valves to stop the flow of monomer from 

storage tanks in case of a fire in the vicinity of the tank. Valves used to prevent 

releases from VAM storage tanks should be located close to the tanks to 

minimize the amount of unprotected piping between the valves and tanks. Other 

considerations include the proper design, installation and inspection of piping 

and adoption of safe work practices to prevent damage to piping. 
44

3.14. Diagram of Storage Tank 

Figure 1 – Typical VAM Unloading and Storage Facility 

2 3

5 7 4

1 * LT TT 9

* 3

DIKE AREA RAIL CAR OR TANK TRUCK

TO PROCESS TO VAPOR CONTROL DEVICE 8

6 6 Level transmitter(s) providing level indication in control room. High level alarm(s) and automated shutoff(s) of liquid feeds to prevent overfilling tank. Low level alarm(s) and automated shutoff(s) of liquid flow to internal mixing nozzle to prevent generation of static electricity due to spray above liquid surface. Separate transmitters may be required for level control and safety shutoff(s). Temperature transmitter at bottom of tank providing temperature indication and high temperature alarm(s) in control room. Multiple measurements at different tank elevations may be needed for large tanks. Typical options for liquid feeds with internal dip tubes and mixing nozzles. Pressure control device and detonation arrestor in vent to control device. Emergency vent(s), vacuum vent with flame arrestor, and overflow vent. Grounding systems. Dry nitrogen (preferred) or dry air supply for maintaining positive pressure in head space of tank.

Vapor return line from tank to shipping container. Inhibitor addition tank.

5

1

2

3

4

6

7

8

9
45

APPENDIX II: CONTACTS: EMERGENCY RESPONSE, TRANSPORTATION AND 

OTHER REGULATORY AUTHORITIES 

North America

 CHEMTREC: 800-424-9300 or http://www.chemtrec.com/Chemtrec/

Canada

 CANUTEC: 613-996-6666 

United States

 National Response Center: 800-424-8802 or http://www.nrc.uscg.mil/nrchp.html

 State Emergency Response Commission (SERC): obtain individual state contacts at: 

http://www.epa.gov/emergencies/content/epcra/serc_contacts.htm

 Local Emergency Planning Committee (LEPC): obtain contacts at: 

http://yosemite.epa.gov/oswer/LEPCDb.nsf/HomePage?Openform

 Federal Emergency Management Act (FEMA) State Offices and Agencies of Emergency 

Management: obtain contact information at: http://home.fema.gov/about/contact/index.shtm 

 National Emergency Management Association (NEMA): 

http://www.nemaweb.org/home.aspx

European Union

 ICE – European Emergency Response Network 

http://www.cefic.org/Templates/shwStory.asp?NID=492&HID=379
46

APPENDIX III: ACRONYMS AND ABBREVIATIONS USED THROUGHOUT GUIDE 

AAR Association of American Railroads 

ACGIH American Conference of Governmental Industrial Hygienists 

AEGL Acute Exposure Guideline Level 

AIChE American Institute of Chemical Engineers 

AIHA American Industrial Hygiene Association 

ANSI American National Standards Institute 

API American Petroleum Institute 

ASTM American Society for Testing and Materials 

ATEX ATmosphere EXplosive; ATEX 95 is an EU Directive on Equipment and 

Protective Systems Intended for Use in Potentially Explosive 

Atmospheres; ATEX 137 is an EU Directive on Minimum Requirements 

for Improving the Safety and Health Protection of Workers Potentially at 

Risk from Explosive Atmospheres 

CAA Clean Air Act 

CANUTEC Canadian Transport Emergency Centre of the Department of Transport 

CCPS Center for Chemical Process Safety 

CERCLA Comprehensive Environmental Response, Compensation, and Liability 

Act (also commonly known as “Superfund”)

CFR Code of Federal Regulations 

CHEMTREC Chemical Transportation Emergency Center 

DIERS Design Institute for Emergency Relief Systems 

DIPPR Design Institute for Physical Properties® 

DOT Department of Transportation 

EHS Extremely Hazardous Substances 

EPA Environmental Protection Agency 

EPCRA Emergency Planning and Community Right-to-Know Act (also commonly 

 known as “Superfund Amendments and Reauthorization Act (SARA) Title 

 III”) 
47

ERG Emergency Response Guidebook 

ERPG Emergency Response Planning Guidelines 

EU European Union 

FEMA Federal Emergency Management Act 

GHS Globally Harmonized System of Classification and Labelling of 

 Chemicals 

HHC Highly Hazardous Chemicals 

HQ Hydroquinone 

IARC International Agency for Research on Cancer 

IC Incident Commander 

IEEE Institute of Electrical and Electronics Engineers, Inc. 

LC50 Median Lethal Concentration 

LD50 Median Lethal Dose 

LEPC Local Emergency Planning Committee 

MSDS Material Safety Data Sheet 

NA North America 

NEMA National Emergency Management Association 

NFPA National Fire Protection Association 

NIOSH The National Institute for Occupational Safety and Health 

OECD Organisation for Economic Co-Operation and Development 

OEL Occupational Exposure Limit 

OSHA Occupational Safety & Health Administration 

PPE Personal Protective Equipment 

PPM Parts Per Million 

PSM Process Safety Management 
48

PTFE Polytetrafluoroethylene 

RCRA Resource Conservation and Recovery Act 

RMP Risk Management Plan 

RQ Reportable Quantity 

SCBA Self-Contained Breathing Apparatus 

SCOEL Scientific Committee on Occupational Exposure Limits 

SERC State Emergency Response Commission 

STEL Short Term Exposure Limit 

STOT Specific Target Organ Toxicity 

TDG Transportation of Dangerous Goods 

TLV Threshold Limit Value 

TRI Toxics Release Inventory 

TWA Time-Weighted Average 

UN United Nations 

VAC Vinyl Acetate Council 

VAM Vinyl Acetate Monomer 

WHMIS Workplace Hazardous Material Information System (Canada) 
49

APPENDIX IV: GENERAL PROPERTIES OF VINYL ACETATE MONOMER 

Data presented in Appendix IV are largely extracted from the AIChE Design Institute for Physical 

Properties (DIPPR®) (www.aiche.org/DIPPR/) and also from the EU Risk Assessment Report on 

VAM (EU 2008a). 

PROPERTY VALUE

Formula Weight 86.09

Critical Temperature 246°C (474.8°F)

Critical Pressure 574.0 psia (39.0 atm)

Normal Boiling Point @ 760 mm Hg = 72.7°C 

(162.9°F)

Standard Heat of Formation Liquid @ 25°C = -83.5 

Kcal/mole

Heat of Combustion @ 25°C = -495 Kcal/mole

Refractive Index (nD

20) 1.3953

Flash Point

Tag Closed Cup = 

-8°C (18°F); 

Tag Open Cup = 

-4°C (25°F)

Autoignition Temperature 385-426.9°C (725-800°F)

Physical State Liquid

Relative Evaporation Rate 

(n-butyl acetate = 1)

8.9

Vapor Pressure @ 60°C 487.4 mm Hg

Vapor Pressure @ 40°C 222.1 mm Hg

Vapor Pressure @ 20°C 89.1 mm Hg

Antoine Equation Log P = A - [B/(T+C)]

 - Log = Base 10

 - T = °C 

 - P = mm Hg 

 - Range = 10 to 83°C

Equation Coefficients - A = 7.51868

 - B = 1452.058

 - C = 240.588

PROPERTY VALUE

Color Clear and colorless

Specific Gravity (20/20°C) 0.934

Vapor Density (Air = 1.00) 2.97

Viscosity @ 20°C 0.43 cps

Melting Point -92.8°C (-135°F)

Heat of Vaporization 

(1 atm) 87.6 cal/g

Heat of Polymerization 21.3 Kcal/mole

Specific Heat @ 20°C (liq.) 0.46 cal/g °C

Odor Not unpleasant, sweetish 

smell in small quantities

Odor Threshold Approx. 0.25-0.5 ppm

Reactivity

Reactive with self and 

variety of other chemicals. 

Stable when properly stored 

and inhibited. 

Water Solubility: 

 - VA in Water @ 20°C 2.3% by weight

 - Water in VA @ 20°C 1% by weight

Light Sensitivity Light promotes 

polymerization

Electrical Conductivity 

@ 23°C

2.6 x 104pS/m 

(1 S = 1 mho)

Surface Tension (20°C) 23.6 dynes/cm

Coefficient of Cubical 

Expansion 0.00137 per °C at 20°C

Upper Flammability Limit 13.4 vol% in air

Lower Flammability Limit 2.6 vol% in air
50

APPENDIX V: GUIDE 129 FROM 2008 EMERGENCY RESPONSE GUIDEBOOK 
51
52

APPENDIX VI: EXAMPLE LIQUID CHROMATOGRAPHIC METHODS FOR 

HYDROQUINONE IN VINYL ACETATE MONOMER 

Liquid Chromatic Method for HQ in VAM: Example 1 

SCOPE:

This method describes procedure for determining the concentration of Hydroquinone (HQ) in 

vinyl acetate monomer (VAM) by liquid chromatography. 

SAFETY

All of the reagents used in this method are hazardous. Consult the Material Safety Data Sheet 

for the reagents listed for hazard information. 

APPARATUS

1. Hewlett Packard 1100 Series HPLC with HP 1100 Autosampler and UV/VIS Variable 

Wavelength Detector. 

2. HPLC column: Phenomenex Synergi Polar-RP, 250 mm x 4.6 mm, 

 catalog # 00G-4336-E0

REAGENTS

1. Mobile Phase A: 0.1 % v/v Phosphoric acid in nanopure water (1 ml H3PO4 in 1L 

nanopure water). 

2. Mobile Phase B: HPLC grade Acetonitrile. 

3. Hydroquinone (HQ) 

4. Vinyl Acetate Monomer, purity 99%+ 

5. Ortho-phosphoric acid, purity 85% 

6. Acetonitrile, HPLC grade 

7. Water, purified by Barnstead Nanopure water purification system or equivalent. 

INSTRUMENT CONDITIONS

HP 1100 Quaternary Pump 

Control 

 Flow: 1.000 ml/min 

 Stoptime: 20.00 min 

 Posttime: 3.00 min 

Solvents 

 Solvent A : 80.0 % (H20, 0.1% H3PO4) 

 Solvent B: 20.0 % (Acetonitrile) 

PressureLimits 

 Minimum Pressure : 20 bar 

 Maximum Pressure: 400 bar 

Timetable 

 Time Solv.B (%) Flow 

 0.00 20.0 1.000 

 3.00 20.0 1.000 

 15.00 95.0 1.000 

 20.00 20.0 1.000 
53

HP 1100 Variable Wavelength Detector 

Signal 

 Wavelength: 294 nm 

 Peakwidth: > 0.1 min 

Time 

 Stoptime: As pump 

 Posttime: Off 

Autobalance 

 Prerun balancing: Yes 

 Postrun balancing: No 

HP 1100 Autosampler 

 Injection Mode : Standard 

 Injector volume: 7.0 μl 

RetTime (min) Name 

 4.932 HQ 

CALIBRATION AND STANDARDIZATION

As the HQ component in the standard is not very stable, the calibration must be carried out 

immediately after the standard is made from a freshly prepared stock standard. 

Prepare 100 ppm of HQ in Vinyl Acetate Monomer. 

1. Accurately weigh 0.05g of HQ into a 1000 ml standard flask. 

2. Add accurately Vinyl Acetate Monomer to have the final weight at 500 g. 

3. Cap and shake the content of the standard flask to ensure proper mixing of HQ. 

Prepare 3 ppm of HQ in Vinyl Acetate Monomer. 

1. Weigh 3 g of 100 ppm standard into a glass bottle. (Record the weight) 

2. Add 97 g of vinyl acetate monomer. (record the total weight). 

Prepare 8 ppm of HQ in Vinyl Acetate Monomer. 

1. Weigh 8 g of 100 ppm standard into a glass bottle. (Record the weight) 

2. Add 92 g of vinyl acetate monomer. (record the total weight). 

Determine HQ concentrations in the vinyl acetate monomer blank by Standard Addition. 

1. Analyze vinyl acetate monomer blank, 3 ppm standard, and 8 ppm standard. 

2. Plot peak area vs. 0, 3, 8 ppm. 

3. Use the equation obtained from the plot to calculate the HQ concentration in the vinyl 

acetate monomer blank. 

4. Calculate the final concentration of HQ in the standards by adding the concentration in the 

blank to the spiked HQ concentration. 
54

Blank Standard 

1

Standard 

2

HQ HQ HQ

Spiked Conc. 0 3.670 8.132

Peak Area 23.87 54.15 90.96

Final Conc. 2.894 6.564 11.026

HQ (x) concentration in the vinyl acetate monomer blank is calculated from the equation: 

y = 8.2497x + 23.874 

x = - 23.874/8.2497 = - 2.894 ppm 

Establish Calibration Curve. 

Plot the peak area against the final concentration in above standards to obtain the external 

calibration curve. 

Chart Title

y = 8.2497x + 23.874

R

2

 = 1

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

100.00

-3 -2 -1 0 1 2 3 4 5 6 7 8 9

ppm

Area
55

TYPICAL CHROMATOGRAMS OF HQ. Red trace is HQ spiked. 

SAMPLE ANALYSIS

1. Place the sample on the respective autosampler tray position. 

2. When the sample run is over, the computer prints out the data sheet with result. 

REPORTING

Report the HQ in part per million, ppm. 
56

Liquid ChromatographicMethod for HQ in VAM: Example 2 

HYDROQUINONE (HQ)

a) Analyze a portion of the sample using the following reverse phase

 high pressure liquid chromatographic procedure.

b) Instrument parameters

 Instrument Hewlett Packard Model 1090 High

 Pressure Liquid Chromatograph, or

 equivalent.

 Column Merck LiChrospher Reverse Phase High

 Pressure Liquid Chromatographic

 Column, LiChrospher 100 RP 18.

 12.5cm x 4.0 mm with 5 μm spherical

 particles. Available from VWR

 Scientific.

 Eluent (A) Phosphoric acid (0.01%) in water.

 Eluent (B) Acetonitrile.

 Gradient Program 90% A:10% B for 4 minutes;

 programmed to 50% A:50% B at 12

 minutes; programmed to 100% B at

 19 minutes. Hold at 100% B for 6

 minutes.

 Total Run Time 25 minutes.

 Instrument Equilibration

 Time (between analyses) 5 minutes.

 Column Temperature 40°C.

 Detectors Ultraviolet/Visible detector

 operated at 285 nm.

 Sample size 20 μL.

 Sparge gas Helium.

NOTE: The refined vinyl acetate monomer should not be filtered due to the

 possibility of contamination from the filter.

c) Procedure: Analyze a portion of the sample according to the

 parameters described in paragraph 6b.

d) Prior to running a sequence of VAM samples, or if the instrument

 has not been used for greater than 2 hours, perform an injector

 wash sequence.

e) If the UV lamp has been turned off for any length of time, turn on

 and allow about 15 minutes for warm-up and equilibrium.

f) Calibration: Hydroquinone standards are prepared by weighing

 about 0.2500 g of HQ into approximately 26 g of refined ethyl

 acetate. This gives a solution containing about 0.9 weight

 percent inhibitor. Sequential dilution of this material with

 ethyl acetate are made to obtain a series of standards containing

 about 0.45, 0.10, 0.015, 0.01, 0.001 and 0.0005 weight percent of

 inhibitor.

g) Analyze the standards according to the parameters shown in

 paragraph 6b.

h) On graph paper plot the known weight percent inhibitor (y-axis)

 versus peak area count. The calibration factor for HQ is the

 slope of its given calibration curve (y/x or weight percent/peak

 area count).

 i) Calculation: Calculate the concentration of inhibitor in the

 sample using the equation below:

 Weight percent inhibitor, i = Slope i x peak area count i x 100

 Where
57

 Slope i = slope of the calibration curve for HQ, generated in

 paragraph 6h.

 peak area count i = Peak area of HQ taken from chromatogram

 of the sample.

Alternate Method

j) Ceric sulfate, standard 0.002 N solution, Reagent number 29M12.2:

 Dissolve 1.096 g of ceric ammonium nitrate (NH4)2Ce3(NO3)6, in 

 28.0 mL of concentrated sulfuric acid. With stirring, slowly

 pour the ceric solution into 200 mL of distilled water contained

 in a 600-mL beaker. When the solution is complete, transfer to a

 1-liter flask and dilute to the mark with distilled water.

k) Diphenylamine indicator, Reagent number B7C3.2: Dissolve 0.1 g of

 diphenylamine in 100 mL of concentrated sulfuric acid. Store in

 a brown bottle.

l) Hydroquinone standard: Weigh 0.2000 g of hydroquinone to the

 nearest 0.1 mg. Dissolve and dilute with distilled water to

 exactly 1000 mL in a volumetric flask. This is an unstable

 solution. The HQ slowly oxidizes to benzoquinone which is inert

 to the reagent, hence the solution must be discarded after one

 week of normal use.

m) Reagent standardization: Pipet 10-mL portions of the hydroquinone

 solution into each of two 100-mL flasks. Add 3 drops of the

 diphenylamine indicator and titrate with the ceric sulfate

 reagent to a light-blue end point, using a 25-mL buret. The

 titrations should be approximately 20 mL and should agree within 

 0.5 mL. Average the two values and use in the calculations.

n) Procedure: Pipet 50 mL of the sample into a 250-mL flask.

o) Evaporate the sample at room temperature by passing a stream of

 nitrogen gas or clean air into the flask. Bench-line air should

 pass through a fiberglass filter before entering the sample

 flask. Maintain the flow of air just short of a level causing

 splattering of the sample. That part of the delivery tube in the

 flask must be metal, glass, or an inert plastic such as

 polyethylene or Teflon.

p) After complete evaporation, which requires 45 to 60 minutes,

 remove the gas stream and dissolve the hydroquinone in 25 mL of

 distilled water.

q) Add 3 drops of diphenylamine indicator, using the same dropper as

 in the reagent standardization, and titrate with the ceric

 sulfate solution to a light-blue end point, permanent for 15

 seconds. At the 4-ppm level, this requires approximately 2 mL

 titration.

r) Calculation:

 [(V x F)/(S)] x 1000 = ppm HQ in sample

 V = mL Ce(HSO4)4 reagent required for the sample titration, 

 from paragraph 6r.

 F = factor = (mg HQ in 10-mL aliquot, paragraph 6m) ÷

 (average mL Ce(HSO4)4 reagent, paragraph 6n).

 S = grams of sample used = 50 x specific gravity

s) Reference: ASTM Method D 2193.
VINYL ACETATE 

 COUNCIL

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 Suite 700 

 Washington, DC 20036 

 USA 

 202.419.1500 

 info@vinylacetate.org 

www.vinylacetate.org

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