2-propenoic acid, 2-methyl, butyl ester polymer
File No: PLC/106
February 1999
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION
AND ASSESSMENT SCHEME
FULL PUBLIC REPORT
2-propenoic acid, 2-methyl, butyl ester, polymer with butyl 2-propenoate, ethenylbenzene,
2-hydroxyethyl 2-methyl-2-propenoate, methyl 2-methyl-2-propenoate and 2-propenoic
acid
This Assessment has been compiled in accordance with the provisions of the Industrial
Chemicals (Notification and Assessment) Act 1989 (the Act) and Regulations. This legislation
is an Act of the Commonwealth of Australia. The National Industrial Chemicals Notification
and Assessment Scheme (NICNAS) is administered by the National Occupational Health and
Safety Commission which also conducts the occupational health & safety assessment. The
assessment of environmental hazard is conducted by the Department of the Environment and
the assessment of public health is conducted by the Department of Health and Family
Services.
F o r the purposes of subsection 78(1) of the Act, copies of this full public report may be
inspected by the public at the Library, National Occupational Health and Safety Commission,
92-94 Parramatta Road, Camperdown NSW 2050, between the following hours:
Monday ?Wednesday 8.30 am - 5.00 pm
Thursday 8.30 am - 8.00 pm
Friday 8.30 am - 5.00 pm
Copies of the full public report may also be requested, free of charge, by contacting the
Administration Coordinator.
Please direct enquiries or requests for full public reports to the Administration Coordinator
at:
Street Address: 92 Parramatta Road, CAMPERDOWN NSW 2050, AUSTRALIA
Postal Address: GPO Box 58, SYDNEY NSW 2001, AUSTRALIA
Telephone: (61) (02) 9577 9514
Facsimile: (61) (02) 9577 9465
Director
Chemicals Notification and Assessment
PLC/106
FULL PUBLIC REPORT
2-propenoic acid, 2-methyl, butyl ester, polymer with butyl 2-propenoate,
ethenylbenzene, 2-hydroxyethyl 2-methyl-2-propenoate, methyl 2-methyl-2-
propenoate and 2-propenoic acid
1. APPLICANT
Glasurit Pty Ltd of 231-233 Newton Rd WETHERILL PARK NSW 2164 has submitted a
limited notification statement in support of their application for an assessment certificate for
2-propenoic acid, 2-methyl, butyl ester, polymer with butyl 2-propenoate, ethenylbenzene,
2-hydroxyethyl 2-methyl-2-propenoate, methyl 2-methyl-2-propenoate and 2-propenoic
acid.
2. IDENTITY OF THE CHEMICAL
Chemical Name: 2-propenoic acid, 2-methyl, butyl ester, polymer with
butyl 2-propenoate, ethenylbenzene, 2-hydroxyethyl 2-
methyl-2-propenoate, methyl 2-methyl-2-propenoate
and 2-propenoic acid
Chemical Abstracts Service 57828-93-0
(CAS) Registry No.:
Other Names: 2-propenoic acid, 2-methyl-, hydroxyethyl ester,
polymer with 2-propenoic acid, 2-methyl-, methyl
ester, styrene, 2-propenoic acid, butyl ester, 2-
propenoic acid, 2-methyl-, butyl ester and 2-propenoic
acid
acrylic acid, butyl acrylate, butyl methacrylate, 2-
hydroxyethyl methacrylate, methyl methacrylate,
styrene copolymer
Trade Name: Glasurit HS-Multiclear 923-255
Cristal Top ZK 56-323F
Molecular Formula: (C8H14O2.C8H8.C7H12O2.C5H8O2.C6H10O3.C3H4O2)x
Structural Formula:
This depiction of the polymer shows the major structural features of the random copolymer.
The ratios of a,b,c,d,e are not known.
CH3 CH3 CH3
H
CH2 C
C
CH2 C CH2 C CH2 CH CH2 CH CH2
C O
C O C O C O C O
O O
O O OH
CH3 CH2 CH2 CH2
a d
H 2C H 2C H 2C
e
CH3 CH2 CH2
H 3C H 3C
b c
f
Number-Average 2990
Molecular Weight (NAMW):
Weight-Average 5468
Molecular Weight:
Polydispersity: 1.8
Maximum Percentage of Low
Molecular Weight Species
Molecular Weight < 500: 0.004 %
Molecular Weight < 1 000: 3.7 %
Weight Percentage of
Ingredients:
Chemical Name CAS No. Weight %
2-hydroxyethyl 2-methyl-2-propenoate 868-77-9 27.2 %
methyl 2-methyl-2-propenoate 80-62-6 21.4 %
butyl 2-propenoate 141-32-2 18.1 %
butyl 2-methyl-2-propenoate 97-88-1 13.1 %
2-propenoic acid 79-10-7 1.3 %
ethenylbenzene 100-42-5 18.9 %
Method of Detection The polymer is characterised by GPC and identified by
and Determination: IR spectroscopy.
Spectral Data: IR: 3511, 2954, 2874, 1729, 1600, 1453, 1385, 1168,
1146, 1075, 1028, 962, 905, 845, 760, 702 cm-1
3. PHYSICAL AND CHEMICAL PROPERTIES
T h e notified polymer will be imported as a component (40 % (w/v)) of a paint solution.
Solvents include up to 10 % (w/v) xylene and 10 % (w/v) ethylbenzene. The reported
properties are those of the solution.
Appearance at 20癈 clear colourless solution with a characteristic solvent
and 101.3 kPa: odour
Boiling Point: not stated
Specific Gravity: 1.026 at 20癈
Water Solubility: < 0.02 mg/L at 25癈
Partition Co-efficient not determined
(n-octanol/water):
Hydrolysis as a Function not determined
of pH:
Adsorption/Desorption: not determined
Dissociation Constant: the polymer contains a small percentage of carboxylic
acid groups likely to have a pKa around 4
Flash Point: 23癈
Autoignition Temperature: 200 - 300癈
Explosive Properties: not expected to be explosive
Reactivity/Stability: the polymer is expected to be stable
Comments on Physico-Chemical Properties
The notifier indicated that the polymer is present in a colourless solution. The structure of
the polymer does not indicate any reactive properties. Under the conditions of use the
polymer will not undergo photo or thermal degradation.
A water solubility study indicated that the water solubility of the polymer was significantly
l e s s than 1 mg/L. In the study, the polymer was agitated in water for 24 hours, then the
solution was decanted, condensed and the residual mass compared with a blank sample.
The ester linkages of the acrylate groups are inherently susceptible to hydrolytic cleavage, but
hydrolysis would not be expected, because contact between the ester groups and water will
be precluded by the low solubility of the polymer. The polymer contains a small percentage
of free carboxylic acid groups likely to have typical acidity.
4. PURITY OF THE CHEMICAL
Degree of Purity: 40 % in paint solution
Toxic or Hazardous
Impurities:
The identities of the hazardous components of the product, Glasurit HS-Multi-Klarlack,
containing the notified polymer, are disclosed in the Material Safety Data Sheet (MSDS) for
this product.
Chemical name: xylene (mixed isomers)
CAS No.: 1330-20-7
Weight percentage: 2.5 ?10 %
R20/21Harmful by inhalation and in contact with skin
Toxic properties:
R38 Irritating to skin
Chemical name: ethylbenzene
CAS No.: 100-41-4
Weight percentage: 2.5 ?10 %
R20 Harmful by inhalation
Toxic properties:
The identity of the other components in the paint have not been disclosed.
Maximum Content
of Residual Monomers:
Chemical Name CAS No. Weight %
2-hydroxyethyl 2-methyl-2-propenoate 868-77-9 0.19 %
methyl 2-methyl-2-propenoate 80-62-6 0.18 %
butyl 2-propenoate 141-32-2 0.00 %
butyl 2-methyl-2-propenoate 97-88-1 0.57 %
2-propenoic acid 79-10-7 0.00 %
ethenylbenzene 100-42-5 0.00 %
5. USE, VOLUME AND FORMULATION
The notified polymer will not be manufactured in Australia, but will be imported from
Germany in an organic solvent mixture containing xylene and ethylbenzene. The MSDS
supplied with the notification indicates that the new polymer would comprise 40 % (w/v) of
t h e resin solution. The product is to be imported in either 5 L or 1 L cans. The notifier
indicated that during the first 5 years the anticipated annual import quantities for the resin
solution containing Glasurit HS-Multi Clear 923-255 is 10 - 100 tonnes annually ?this
e q u a t e s to between 4 - 40 tonnes of the polymer itself. A more precise figure of 12 - 20
tonnes of notified polymer is also given by the notifier.
The notified polymer is intended as a component of clear coat lacquer for spray painting of
automotive crash repairs, and will be sold under the name of Glasurit HS-Multi Clear 923-
255. The resin will be stored in the imported 5 L or 1 L cans in a Sydney warehouse and will
be sold to automotive repair shops in Australia. The stock will be dispatched to the
commercial user by road transport as needed.
Preparation of the ready-to-spray mixture will be completed at the customer facility by the
operator immediately prior to application. The quantity of the lacquer required for each
a p p l i c a t i o n can vary up to 3 L for a full vehicle respray. Application of the lacquer to
vehicles is performed in a spray booth with a fume extraction system.
6. OCCUPATIONAL EXPOSURE
The cans of product containing the notified chemical will be imported in shipping containers
a s part of a mixed load. The containers will be transported to a paint supply warehouse
where the product will be stored and dispatched as required. Two dock workers and one
transport worker will be involved in handling the product containing the polymer, two times a
month. These workers would not be expected to be exposed to the notified polymer except in
the case of an accident involving rupture of the cans.
At the warehouse, the individual cans will be unpacked and dispatched as required. Individual
customers will generally only purchase one or two cans at a time. The individual cans are
dispatched by road transport. The warehouse and courier workers would again only be
exposed in the event of an accident.
T h e notifier estimates that the polymer will be used by up to 1000 spray painters on a
regular basis.
At each crash repair shop, one operator would be involved in using the product containing the
notified chemical. The product will be mixed with hardener and reducer just prior to use, then
loaded into a high pressure spray gun or high volume low pressure spray gun. These steps
will be carried out manually and therefore there is a risk of dermal exposure to spills and
d r i p s . This procedure is estimated by the notifier to take between 5 and 10 minutes per
application.
The spraying of the automobile will be carried out in a laminar flow downdraft spray booth
which is designed to rapidly remove aerosol particles and solvent vapour from the
atmosphere. Several possible booth designs may be used. In a dry floor booth, the overspray
will be collected in filters contained in the floor of the booth; any unremoved particulates will
reach the exhaust stack with the solvent vapours. In a wet floor booth, overspray will collect
in a pool of water below the grill floor or in a wet scrubber in the exhaust and will be removed
with a filter. The residual solids will be disposed of to secure landfill. The spray booths are
subject to AS/NZS/4114.1:1995 Spray Painting Booths ?Design, Construction and Testing
and AS/NZS/4114.1:1995 Spray Painting Booths ?Selection, Installation and Maintenance.
The notifier estimates that the application of the paint will take between 10 and 45 minutes
per automobile, depending on the size of the job. The volume of lacquer required per car is
expected to be 2 ? L, with approximately 500 mL required for touch-up jobs.
Residual paint mixture will be washed from the equipment manually, using recycled paint
solvent.
Once residual final paint mixture has dried, the notified polymer will be irreversibly bound
within the cured matrix and not separately available for either exposure to workers, or for
dermal absorption.
The notifier states that generally a spray painter would be exposed to the notified polymer
for a maximum of 5 hours per week.
Local exhaust ventilation will normally be provided where natural ventilation is inadequate to
keep the solvent vapour concentrations below the recommended exposure levels. Spray
painters will wear appropriate personal protective equipment at all times; neoprene, nitrile or
PVC gloves and overalls while mixing the paint, and, in addition, a full face shield and
respirator while inside the spray booth.
7. PUBLIC EXPOSURE
There is negligible potential for public exposure to the notified polymer arising from use,
waste disposal, or transport. Public exposure through environmental dispersion of the
polymer is also unlikely.
The uncured polymer is only used in an industrial environment. The notified polymer will
only enter the public domain incorporated into automotive finish lacquers, where it will be
cross-linked as a component of a continuous unreactive film. Although there will be public
contact with the lacquer on automobiles, the notified polymer will not be bioavailable.
8. ENVIRONMENTAL EXPOSURE
Release
The new polymer will be exclusively used as a component of an automotive repair lacquer.
T h e polymer has the potential for environmental release during the thinning process for
lacquer preparation and during application. Such environmental release losses are expected to
be minimal since the polymer is non-volatile and overspray would be trapped in the spray
booth and soaked up with inert absorbent material.
The notifier estimates a 70% consumption of the final product in its end use pattern and a
30% wastage as a result of the application procedures and residue remaining in packs after
use. Taking into account an import volume of 10-100 tonnes of the new product, 3-30 tonnes
of waste is estimated to be produced per year. Given a 40% polymer content in the product,
the maximum amount of new polymer that may be released into the environment is estimated
as 1.2-12 tonnes per year. Most of this would be contained within the control equipment at
the automotive repairer, and would be collected and disposed of appropriately, most likely to
landfill.
Once applied to the metal panels of vehicles the notified polymer will be incorporated in an
inert film and would not present a significant hazard. Any fragments, chips or flakes of the
lacquer will be of little concern as they are expected to be inert. The metal panels coated with
the polymer are likely to be either recycled for steel reclamation or placed into landfill at the
end of their useful life.
Fate
When deposited into landfill as overspray, residue in used paint cans or on discarded panels,
the organic components of the lacquer including the new polymer would be inert and
immobile, but could nevertheless be expected to be very slowly degraded through the
biological and abiotic processes operative in these facilities. When recycled the polymer
would be destroyed in the blast furnaces and converted to water vapour and oxides of carbon.
9. EVALUATION OF TOXICOLOGICAL DATA
The polymer in Glasurit HS-Multi Clear 923-255 has been notified as a Polymer of Low
Concern. Polymers which satisfy the criteria for this category are unlikely to have significant
toxic effects because of the high molecular weight and the absence of reactive functional
groups. For this reason toxicological studies are not required as part of the notification
process.
The notifier states that there have been no reports of adverse symptoms in humans exposed
to the notified polymer.
10. ASSESSMENT OF ENVIRONMENTAL EFFECTS
No ecotoxicological data were provided, which is acceptable for polymers of low concern
with a NAMW > 1000 according to the Industrial Chemicals (Notification and Assessment)
Act.
11. ASSESSMENT OF ENVIRONMENTAL HAZARD
The majority of the polymer would be encapsulated in an inert film after application. It is
possible that up to 30% (i.e. a maximum of 12 tonnes per annum) of the polymer could be
released as a consequence of lacquer preparation and application. This is expected to be
primarily in automotive repair facilities. The procedures in place at the repair facility ensure
that any released material is properly contained and disposed of, most likely to landfill.
The polymer is unlikely to present a hazard to the environment when it is incorporated into
the lacquer and applied to solid substrates. The physical characteristics of low water
solubility and low volatility suggest that the mobility of the polymer in the environment will
be very limited.
The low environmental exposure of the polymer as a result of the proposed use indicates the
overall environmental hazard should be low.
12. ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS
Occupational Health and Safety
There is little potential for significant occupational exposure to the notified polymer in the
transport and storage of the lacquer containing this polymer. The greatest exposure is in the
mixing and use of the paints.
The lacquers including the pre-prepared paint containing the notified polymer could contain a
wide variety of additional ingredients once fully mixed. This is likely to introduce human
health hazards because, apart from a range of potentially toxic solvents, there may be
components containing resins with pendant isocyanate groups. The spraying procedure also
produces a dense aerosol which would adversely affect human health even in the absence of
additional hazardous components. It is also probable that professionals involved in the spray
painting industry will use a number of different paint formulations.
For these reasons, the notified polymer must be assessed for the contribution it makes to the
hazards associated with spray application of the lacquer. The presence of many potential and
actual hazardous substances in the formulations requires the use of stringent engineering
controls, such as a correctly constructed and maintained spray booth, and of a high level of
personal protective equipment, such as impermeable overalls and gloves and a full face shield
and respirator. The use of the paint containing the notified polymer should be in accordance
with the NOHSC Draft National Code of Practice for Spray Painting (National Occupational
Health and Safety Commission, 1991). The level of protection from exposure afforded by the
standard protective measures will provide adequate protection from the notified polymer,
which is likely to be less intrinsically toxic than most of the solvents, pigments and other
paint resins.
Once the applied final paint mix has hardened, the polymer will not be separately available
for exposure or absorption.
There are NOHSC exposure standards for ethylbenzene and xylene, identified as ingredients
in the pre-prepared paint Glasurit HS-Multi Clear 923-255. The employer is responsible for
ensuring that these exposure standards, and exposure standards pertaining to other final paint
mix additives, are not exceeded in the workplace.
The lacquers containing the notified polymer are flammable due to their solvent content.
Precautions must be taken to avoid sources of ignition, e.g. use of earthing leads. Operators
should wear antistatic overalls and footwear.
Similar considerations apply in the cleaning of spray equipment and disposal of the polymer.
The wastes containing the notified polymer may be hazardous materials on the basis of the
solvent and other resin content, and the precautions used on the basis of these additional
materials should be adequate for protection from the notified polymer. In addition, much of
the polymer will be crosslinked and hardened by the time of disposal and this will immobilise
the notified polymer.
Public Health
There is negligible potential for public exposure to the notified polymer arising from use in
lacquers for use in the automotive crash repair industry. There may be public contact with the
notified polymer on the lacquered surface of automobiles, but its adhesion to the substrate
and the physico-chemical properties of the cured lacquer will be sufficient to preclude
absorption across the skin or other biological membranes. Therefore, based on its use pattern
and physico-chemical characteristics, the notified chemical will not pose a significant hazard
to public health.
13. RECOMMENDATIONS
To minimise occupational exposure to the polymer in Glasurit HS-Multi Clear 923-255 the
following guidelines and precautions should be observed:
Employers should ensure that NOHSC exposure standards for all of the components
?br>
of the final paint mix are not exceeded in the workplace;
Safety goggles should be selected and fitted in accordance with Australian Standard
?br>
(AS) 1336 (Standards Australia, 1994) to comply with Australian/New Zealand
Standard (AS/NZS) 1337 (Standards Australia/Standards New Zealand, 1992);
Industrial clothing should conform to the specifications detailed in AS 2919
?br>
(Standards Australia, 1987) and AS 3765.2 (Standards Australia, 1990);
Impermeable gloves or mittens should conform to AS 2161 (Standards Australia/
?br>
Standards New Zealand, 1998);
All occupational footwear should conform to AS/NZS 2210 (Standards Australia/
?br>
Standards New Zealand, 1994);
Spillage of the notified chemical should be avoided. Spillages should be cleaned up
?br>
promptly with absorbents which should then be put into containers for disposal;
Good personal hygiene should be practised to minimise the potential for ingestion;
?br>
A copy of the MSDS should be easily accessible to employees.
?br>
14. MATERIAL SAFETY DATA SHEET
The MSDS for the notified chemical was provided in accordance with the National Code of
Practice for the Preparation of Material Safety Data Sheets (National Occupational Health and
Safety Commission, 1994).
This MSDS was provided by the applicant as part of the notification statement. It is
reproduced here as a matter of public record. The accuracy of this information remains the
responsibility of the applicant.
15. REQUIREMENTS FOR SECONDARY NOTIFICATION
Under the Act, secondary notification of the notified chemical shall be required if any of the
circumstances stipulated under subsection 64(2) of the Act arise. No other specific conditions
are prescribed.
16. REFERENCES
National Occupational Health and Safety Commission (1991) Draft National Code of Practice
for Spray Painting. Australian Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1994) National Code of Practice for
the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)]. Australian
Government Publishing Service, Canberra.
Standards Australia (1987) Australian Standard 2919-1987, Industrial Clothing. Standards
Association of Australia, Sydney.
Standards Australia (1990) Australian Standard 3765.2-1990, Clothing for Protection against
Hazardous Chemicals Part 2 Limited protection against specific chemicals. Standards
Association of Australia, Sydney.
Standards Australia (1994) Australian Standard 1336-1994, Eye protection in the Industrial
Environment. Standards Association of Australia, Sydney.
Standards Australia/Standards New Zealand (1992) Australian/New Zealand Standard 1337-
1992, Eye Protectors for Industrial Applications. Standards Association of Australia/
Standards Association of New Zealand, Sydney/Wellington.
Standards Australia/Standards New Zealand (1994) Australian/New Zealand Standard 2210-
1994, Occupational Protective Footwear. Standards Association of Australia/Standards
Association of New Zealand, Sydney/Wellington.
Standards Australia/Standards New Zealand (1998) Australian/New Zealand Standard 2161.2-
1998, Occupational protective gloves, Part 2: General requirements. Standards Association of
Australia/Standards Association of New Zealand, Sydney/Wellington.
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