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Safe Handling and Storage of Styrene Monomer
Safe Handling and Storage of Styrene Monomer
Styrene Monomer
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TABLE OF CONTENTS
INTRODUCTION .....................................................................……................2
Training ................................................................................................................................. 10
Recommended Practice for Sampling Styrene ..................................................................... 10
Sampling Devices ................................................................................................................. 11
Static Electricity and Grounding ............................................................................................ 11
Product Loading/Unloading Requirements ........................................................................... 11
Safety References ................................................................................................................ 12
PART 6 APPENDIX
The information contained in this technical bulletin is not intended to, nor
does it, amend or replace the Material Safety Data Sheet for Styrene (MSDS
No. 100000068536). The most current Material Safety Data Sheet can be
obtained from Chevron Phillips Chemical Company by calling (800) 231-1212
and should be carefully examined prior to working with this product.
Styrene undergoes polymerization by all the common methods used in plastics technology to produce
a wide variety of polymers and copolymers. Styrene is readily polymerized and copolymerized by both
batch and continuous mass polymerization, emulsion, suspension, and solution processes. The most
important products are polystyrene (PS), rubber-modified high impact polystyrene (HIPS), styrene
butadiene latex (SBL), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-
styrene/terpolymer (ABS), and styrene-butadiene copolymer (SBR, synthetic rubber). An approximate
breakdown of styrene’s markets are polystyrene 54%, expandable polystyrene 12%, ABS 10%, SBR
7%, SBL 6%, and other 11%. Other important uses of styrene are in styrene-polyester resins, latexes,
and styrenated oils and alkyls.
Polystyrene is primarily used in packaging, disposables, and low cost consumer products.
Expandable polystyrene beads (EPS) are primarily used in food and beverage packaging, insulation
and cushion packaging. Improved grades of resins are used in higher performance applications, such
as home electronics and appliances. ABS and SAN have many uses in the consumer durables
market. Styrene-based polyesters have lifetimes of over thirty years in both indoor and outdoor
applications, e.g., polyester boats typically last longer than boats made from conventional materials.
Thermoplastic elastomers are directly replacing natural and traditional synthetic rubbers in many
established applications and entering new markets. Other applications include carpet backing (SB
Latex), production of tires (SB Rubber) and castings for textiles and paper.
This publication addresses the need for an easy to use source of information describing the physical
properties, toxicity and first aid measures, safety, disposal, labeling and styrene storage information for
this relatively safe but perishable chemical. Styrene’s reactivity is such that it must be handled within a
range of specially prescribed conditions. This is necessary not only to avoid certain safety hazards but
also to prevent deterioration in the quality of the styrene. However, it has been well-demonstrated that
styrene can be used, handled, and stored without difficulty when its physical and chemical properties
are understood and the precautions associated with these properties are applied.
NOTE:
THIS BROCHURE DOES NOT AMEND OR REPLACE OFFICIAL PUBLICATIONS, SAFETY
REGULATIONS NOW IN USE, MATERIAL SAFETY DATA SHEETS OR COMMERCIAL TERMS OF
SALE. CHEVRON PHILLIPS CHEMICAL COMPANY LP MAKES NO GUARANTEE OF THE
ACCURACY OF THE CONTENTS OF THIS BROCHURE OR ANY WARRANTY OF ANY KIND,
EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THE USE OF THIS INFORMATION OR
ITS APPLICABILITY. THE USER ASSUMES ALL RISK AND LIABILITY ASSOCIATED WITH THE
INFORMATION IN THIS BROCHURE.
The data contained in this section have been obtained experimentally or derived from the chemical
literature referenced at the end of the section.
Property Value
1
Autoignition temperature (in air) 490°C (914°F)
2,9
Boiling point: 760 mm Hg 145.14°C (293.25°F)
100 mm Hg 82.4°C
30 mm Hg 54.7°C
10 mm Hg 33.6°C
1 mm Hg -1.6°C
Color Colorless
gas at 25°C(∆Hf°)
2
Heat of formation: 35.22 kcal/(gm-mole)
7
Heat of polymerization at 90°C (∆H) -17.8 kcal/gm-mole
9
Heat of vaporization at 145.1°C 8.82 kcal/(gm-mole)
8
Solubility: Water in styrene Temp. (°C) (gms/100gms styrene)
0 0.020
20 0.060
40 0.100
60 0.140
80 0.180
9
Solubility in: Acetone ∞
CCl4 ∞
Benzene ∞
Ether ∞
n-Heptane ∞
Ethanol ∞
2
Relative Density/(Specific Gravity) (°C) gm/cc
0 0.9238
10 0.9151
20 0.9075
30 0.9009
40 0.8949
50 0.8897
60 0.8850
70 0.8809
80 0.8771
90 0.8738
100 0.8707
7
Specific Heat (°C) (cal/gm-°C)
0 0.4004
20 0.4131
40 0.4269
60 0.4421
80 0.4590
100 0.4774
Cp
2
Specific Heat (vapor) Temp. (°C) (cal/gm-°C)
0 0.256
25.0 0.280
Viscosity
4
Viscosity Temp. (°C) (Centipoise)
0 1.040
20 0.763
40 0.586
60 0.470
80 0.385
100 0.326
120 0.278
Vapor
Pressure
2
Vapor Pressure Temp. (°C) mm/Hg
0 1.15
10 2.34
20 4.50
30 8.21
40 14.30
50 23.87
60 38.41
70 59.78
80 90.31
90 132.82
100 190.63
110 267.62
120 368.22
130 497.39
140 660.64
150 864.00
160 1113.97
4. “Kirk-Othmer Encyclopedia of Chemical Technology,” (2nd Ed.), Vol. 19, Interscience, New
York, 1968, p. 56-57.
6. Manufacturing Chemists Association Chemical Safety Data Sheet SD-37 (Rev. 1971), p. 5.
7. R. H. Boundy and R. F. Boyer (Eds.), “Styrene: Its Polymers, Copolymers, and Derivatives,”
Reinhold, New York, 1952, Ch. 3.
10. Styrene Monomer: Environmental, Health, Safety, Transport and Storage Guidelines, Styrene
Producers Association, CEFIC Sector Group, Brussels, Belgium, 3 March 2008
Component
Styrene………………………………………………% 99.93
Benzene……………………………………………. ppm <1
Toluene…………………………………………….. ppm <1
Ethylbenzene………………………………………. ppm 50
α methylstyrene…………………………………… ppm 175
m + p-xylene……………………………………….. ppm 120
o-Xylene……………………………………………. ppm 125
Cumene……………………………………………. ppm 100
n-Propylbenzene………………………………….. ppm 60
m + p-Ethyltoluene……………………………….. ppm 20
Vinyltoluene……………………………………….. ppm 10
Phenylacetylene………………………………….. ppm 50
m + p-Divinylbenzene…………………………….. ppm <10
o-Divinylbenzene………………………………….. ppm <5
Polymer…………………………………………….. ppm 1
TBC…………………………………………………. ppm 12
Aldehydes as Benzaldehyde…………………….. ppm 15
Peroxides as Benzoylperoxides………………….. ppm 5
Chlorides as Cl……………………………………...ppm <1
Sulfur as S………………………………………..... ppm <1
1
This typical analysis is for information only, and does not necessarily represent specification
limits.
The following ASTM methods are recommended for the analysis of styrene monomer:
11. D7375 Trace Quantities of Water in Aromatic Hydrocarbons and Their Mixtures by
Coulometric Karl Fisher Titration
Inhibitors prevent polymerization in two ways. A TBC concentrate for use in increasing the
(1) They can react with and deactivate the free inhibitor level in styrene monomer can be
radical in a growing chain. (2) They can act as prepared by dissolving 704 grams of pure TBC
an antioxidant and prevent polymerization by in 1 gal of styrene monomer (186 gram/liter).
reacting with oxidation products in the At this concentration, 1 cc of the concentrate
monomer. It should be noted that sufficient will raise the level of inhibitor 1 ppm in a drum
oxygen must be present for inhibition. In the of styrene having a net weight of 410 pounds.
absence of oxygen polymerization will proceed Table 3A lists the amount of concentrate
as if no inhibitor were present. required to increase the inhibitor level of bulk
quantities by 10 ppm.
The TBC level should be checked at regular
intervals. (See Table 2B of this section) Styrene vapors in storage tanks are not
Additional inhibitor should be added to inhibited and can polymerize on roofs of
maintain a safe level. storage tanks and around vents. Vapor
space inhibitors are available but are not
The time required for TBC concentrations to viewed as being adequately effective.
fall to a dangerously low level varies greatly
because of different storage and handling
conditions. The depletion rates in actual
storage may be appreciably faster or slower
depending on the set of environmental
conditions. Factors which affect depletion of
Table 1
Table 2A
Table 2B
Inspection Frequency
Air Vents Quarterly
Vacuum pressure relief
Flame arrester
Foam reservoir should be
inspected for polymer
Tank interior Every 3 years, if coated
Annually, if uncoated
OXYGEN REQUIREMENTS
Complete elimination of oxygen from the vapor
The problem presented by air is complex. space will lead to depletion of dissolved
TBC is not an effective inhibitor for styrene oxygen from the liquid monomer. If this
monomer in the complete absence of dissolved oxygen is greatly reduced, the TBC
dissolved oxygen. Excessive amounts of inhibitor becomes ineffective and rapid
oxygen in the storage tank, on the other hand, polymerization of the stored monomer will take
may lead to other serious storage and place. If an inert gas blanket such as nitrogen
handling problems. is used, provisions should be made to aerate
the monomer once a week for approximately
Monomer vapors above the liquid level in the 30 minutes, or until the oxygen level again
tank are uninhibited. These uninhibited reaches saturation. An alternative is to
vapors and condensed monomer droplets are recirculate product and inject air at a rate
3
readily oxidized on contact with air. These approximately 1-2 ft /hr/million pounds of
droplets containing oxidation products will styrene monomer. (Orbisphere Laboratories
polymerize quite rapidly and adhere to the Oxygen Analyzer is suitable for measuring
rusted, porous surfaces of unlined steel tanks. dissolved oxygen content.)
They form stalactites on the roof and coat the
sidewalls above the liquid level.
Gallons → 100 200 300 400 500 600 700 800 900
1,000 184 202 221 239 258 276 294 313 331 350
2,000 368 386 405 423 442 460 478 497 515 534
3,000 552 570 589 607 626 644 662 681 699 718
4,000 736 754 773 791 810 828 846 865 883 902
5,000 920 938 957 975 994 1012 1030 1048 1067 1086
6,000 1104 1122 1141 1159 1178 1196 1214 1233 1251 1270
7,000 1288 1306 1325 1343 1362 1380 1398 1417 1435 1454
8,000 1472 1490 1509 1527 1546 1564 1582 1601 1619 1638
9,000 1656 1674 1693 1711 1730 1748 1766 1785 1803 1822
10,000 1840 1858 1877 1895 1914 1932 1950 1969 1987 2006
Gallons
0 100 200 300 400 500 600 700 800 900
Styrene
CC of TBC Required
0 --- 0.39 0.78 1.17 1.56 1.96 2.35 2.74 3.13 3.52
1000 3.91 4.30 4.69 5.09 5.48 5.87 6.26 6.65 7.04 7.43
2000 7.82 8.22 8.61 9.00 9.39 9.78 10.17 10.56 10.95 11.34
3000 11.74 12.13 12.52 12.91 13.30 13.69 14.08 14.47 14.87 15.26
4000 15.65 16.04 16.43 16.82 17.21 17.60 18.00 18.39 18.78 19.17
5000 19.56 19.95 20.34 20.73 21.13 21.52 21.91 22.30 22.69 23.08
6000 23.47 23.86 24.25 24.65 25.04 25.43 25.82 26.21 26.60 26.99
7000 27.38 27.78 28.17 28.56 28.95 29.34 29.73 30.12 30.51 30.91
8000 31.30 31.69 32.08 32.47 32.86 33.25 33.64 34.03 34.43 34.82
9000 35.21 35.60 35.99 36.38 36.77 37.16 37.56 37.95 38.34 38.73
10000 39.12 39.51 39.90 40.29 40.69 41.08 41.47 41.86 42.25 42.64
11000 43.03 43.42 43.81 44.21 44.60 44.99 45.38 45.77 46.16 46.55
12000 46.94 47.34 47.73 48.21 48.51 48.90 49.29 49.68 50.07 50.47
13000 50.86 51.25 51.64 52.03 52.42 52.81 53.20 53.60 53.99 54.38
14000 54.77 55.16 55.55 55.94 56.33 56.72 57.12 57.51 57.90 58.29
15000 58.68 59.07 59.46 59.85 60.25 60.64 61.03 61.42 61.81 62.20
16000 62.59 62.98 63.38 63.77 64.16 64.55 64.94 65.33 65.72 66.11
17000 66.50 66.90 67.29 67.68 68.07 68.46 68.85 69.24 69.63 70.03
18000 70.42 70.81 71.20 71.59 71.98 72.37 72.76 73.16 73.55 73.94
19000 74.33 74.72 75.11 75.50 75.89 76.28 76.68 77.07 77.46 77.85
20000 78.24 78.63 79.02 79.41 79.81 80.20 80.59 80.98 81.37 81.76
21000 82.15 82.54 82.94 83.33 83.72 84.11 84.50 84.89 85.28 85.67
22000 86.07 86.46 86.85 87.24 87.63 88.02 88.41 88.80 89.19 89.59
23000 89.98 90.37 90.76 91.15 91.54 91.93 92.32 92.72 93.11 93.50
24000 93.89 94.28 94.67 95.06 95.45 95.85 96.24 96.63 97.02 97.41
25000 97.80 98.19 98.58 98.97 99.37 99.76 100.15 100.54 100.93 101.32
Example: Current TBC level = 8 ppm; desired TBC level = 15; Difference = 7 ppm; Volume = 5,900 gallons of styrene
2 6 8 12 16 18 22 26 30 32
Initial Target TBC Level in truck or vessel
TBC level 15 20 25 30 35 40 45 50 55 60
10.0 11 12 13 14 15 16 17 19 20 21
10.5 11 13 13 15 16 17 18 19 21 21
11.0 12 13 14 15 16 17 18 20 21 22
11.5 12 14 14 16 17 18 19 20 22 22
12.0 13 14 15 16 17 18 19 21 22 23
12.5 13 15 15 17 18 19 20 21 23 23
13.0 14 15 16 17 18 19 20 22 23 24
13.5 14 16 16 18 19 20 21 22 24 24
14.0 15 16 17 18 19 20 21 23 24 25
14.5 15 17 17 19 20 21 22 23 25 25
15.0 16 17 18 19 20 21 22 24 25 26
This table shows resulting TBC if required amount is added to the nearest 2 oz of the exact amount
This table shows resulting TBC if one amount is added to the nearest 2 oz of the exact amount for all starting TBC levels
lbs. of styrene x PPM TBC - PPM TBC required in product x 503 5. Styrene lying stagnant in a line may
1,000,000 develop color and, if flushed into a tank, may
make the entire tank off color.
POLYMER BUILDING IN STORAGE
Color problems in storage can be minimized
The polymer deposited under storage by:
conditions will be discolored, cross-linked, and
high in peroxides, aldehydes, and other 1. Avoiding use of copper or copper
oxidation products. Deposits of contaminated alloyed material in contact with styrene
polymer could eventually produce serious monomer.
color and polymer problems in monomer
stored under air in unlined steel tanks. 2. Paying careful attention to the oxygen
Internal reflux, (the vaporization and level in the styrene and in the vapor space
condensation due to normal temperature above the styrene.
differentials) will dissolve small amounts of this
polymer and carry it back into the tank, 3. Employing proper tank design and
thereby increasing both the polymer content maintenance to avoid rust and polymer build-
and the color of the stored monomer. up on tank walls and roof.
Polymer deposits in tanks also create difficult 4. Applying good transfer practices.
removal and cleaning problems. If stalactites
Baked Phenolic
1. Heresite P403 Heresite Chemical Co.
822 South 14th Street
Manitowac, WI 54220
All electrical equipment associated with the with nitrogen. Do not leave styrene in blocked
tank should conform to the National Electrical lines because thermal expansion could
Code (NFPA 70). damage valves and seals and the monomer is
more likely to become oxygen and inhibitor
PIPING depleted.
The pump manufacturers can recommend the Nitrile, Grafoil GHE, or its equivalent is
proper pump if the following parameters are satisfactory for flanged connections at ambient
known: 1) flow rate, 2) size and length of conditions. Reinforced graphite composite
suction and discharge lines, 3) suction and gaskets are also recommended. Gaskets
discharge pressures and, 4) the styrene made of rubber or other styrene-soluble
monomer temperature. A drain valve should materials should not be used.
be installed at the lowest point in the system
so that the pump and all piping can be FILTERS
completely drained before any maintenance
work is done. Totally closed fan cooled Since small amounts of foreign matter may
motors are recommended; however local fire enter storage tanks from various sources, a
and insurance codes should be consulted to filter in the transfer piping between the tank
determine if an explosion proof motor must be and processing equipment is recommended.
used. Cartridge type filters with a fine or medium
replaceable cartridge or bag filters are
All pump motors should meet National suggested. Polyester, Nomex, Rayon and
Electrical Code standards (NFPA 70). Nylon fiber filters are compatible with styrene.
The following practices are recommended to Filter cartridges should be inspected and
minimize the possibility of pump leakage. renewed periodically.
1. Mechanical seals in conformance with API HOSES
RP 682. Tandem seals with barrier fluid
are recommended. If hoses are needed for loading or unloading
operations, they should be flexible and
2. Pumps in conformance with API Standard chemical-resistant. A satisfactory type is
610. Goodyear, rough-bore, style WH-7 with Viton
®
Part I - Design
Part II - Installation
Although the handling of styrene is considered incident involves a Chevron Phillips Chemical
to present a low degree of health risk, material, CHEMTREC will immediately contact
exposure to this product should always be the on-call Chevron Phillips Chemical
minimized. Extensive experience has shown Company LP Crisis Management Team (CMT)
that this monomer can be handled safely if its member at 1-866-4HAZMAT (442-9628). The
toxicological properties are clearly understood contacted Chevron Phillips Chemical CMT
and proper precautions are practiced. member will then be responsible for
coordinating an appropriate response to the
Material Safety Data Sheets for styrene are transportation incident. In addition, if the CMT
available from Chevron Phillips Chemical member determines that the incident involves
Company LP to help customers further satisfy exposure or potential health effects, the on-
their own safe handling and disposal needs call Chevron Phillips Chemical toxicologist will
and OSHA Hazard Communication Rule also be contacted.
requirements. Such information should be
requested and studied prior to working with Eliminate all sources of ignition in the vicinity
this product. Please call Chevron Phillips of the spill or released vapor. Stop the source
Chemical Company LP at (800) 231-1212 to of the leak or release. Clean up releases as
request the MSDS for styrene. NOTE: This soon as possible, observing personal
booklet does not substitute for the MSDS. protection precautions (see below). Contain
liquid to prevent further contamination of soil,
The following briefly summarizes the surface water or groundwater. Styrene is
toxicological information. The precautions expected to be toxic to aquatic organisms.
recommended are, of necessity, general in Avoid contaminating soil or releasing this
nature, because specific recommendations material into sewage or drainage systems and
can be made only when the conditions of bodies of water. Clean up small spills using
handling are known. appropriate techniques such as sorbent
materials or pumping. Where feasible and
ACCIDENTAL RELEASE MEASURES appropriate, remove contaminated soil.
Follow prescribed procedures for reporting
If a transportation incident involving styrene and responding to larger releases. The
does occur, the Chemical Transportation Reportable Quantity (RQ) under CERCLA
Emergency Center (CHEMTREC) should be Section 302.4 is 1000 lbs. USA regulations
contacted for immediate assistance. require reporting spills of this material that
CHEMTREC is a public service organization could reach any surface waters. The toll free
established by the American Chemistry number for the U.S. Coast Guard National
Council to provide assistance in hazardous Response Center is (800) 424-8802.
material incidents. FOR A CHEMICAL
EMERGENCY CALL CHEMTREC AT (800) SPILLS
424-9300 toll free in the United States,
Canada, Puerto Rico, and the Virgin If styrene has been spilled, it can be removed
Islands. For emergency calls outside the safely for disposal. Before attempting to clean
United States call + (703) 527-3887. Collect up the spill be sure that the flow of liquid has
calls are accepted. been stopped and that all sources of ignition
are eliminated. Small spills (non-marine) can
CHEMTREC will provide the caller preliminary be removed by covering the spill with sand or
emergency assistance in the form of Material a suitable absorbent. Some absorbing agents,
Safety Data Sheet (MSDS) information. In all such as untreated clays and micas, will cause
cases once CHEMTREC determines the an exothermic reaction which might ignite the
All disposal procedures are to be carried out in Burning Rate: 5.2 mm/min.
strict conformance to federal, state and local
regulations. Styrene monomer and absorbent- NFPA Fire Hazard Rating: 3
containing styrene must be incinerated in an
approved designated furnace. Please contact FLAMMABILITY
Chevron Phillips Chemical Company
Aromatics Technical Service Group at (877) Styrene monomer is classified by both OSHA
771-7176 if additional assistance is required. 29 CFR 1910.26 and National Fire Protection
Association (NFPA) Code 30 as a Class IC
FIRE HAZARDS flammable liquid. The National Electric Code
(NFPA 70) refers to styrene as a Class I,
This product presents a fire hazard. The liquid Group D material.
evaporates, and forms vapor (fumes) which
can catch fire and burn with explosive Styrene will burn and requires the same
violence. Invisible vapor spreads easily and precautions against fire and explosion hazards
can be set on fire by many sources such as that commonly apply to other combustible and
pilot lights, welding equipment, and electrical flammable liquids. The flammability properties
motors and switches. of styrene are given in the Physical Properties
section (Part 1, Pages 3-6).
For fires involving this material, do not enter
any enclosed or confined fire space without
proper protective equipment. This may
4-TERT-BUTYLCATECHOL (TBC):
CHEMICAL DESIGNATIONS:
SHIPPING INFORMATION:
Code of Federal Regulations: Flammable liquid NAS Hazard Rating for Bulk Water Transportation:
Category Rating
Fire 3
Health
Vapor Irritant 2
Liquid or Solid Irritant 2
Poisons 2
Water Pollution
Human Toxicity 1
Aquatic Toxicity 3
Aesthetic Effect 2
Reactivity
Other Chemicals 2
Water 0
Self Reaction 3
Category Rating
Health Hazard (Blue) 2
Flammability (Red) 3
Reactivity (Yellow) 2
WATER POLLUTION:
Styrene
2) TSCA: Is this product or its components subject to any of the following TSCA requirements of 40
CFR, Part:
Have there been any Section 8(e) submissions for this material? YES
3) International Registration: Are all components of this material listed on the following
international inventories?:
4) FDA: Do FDA regulations permit use of this material as a direct or indirect food additive?
5) HAZARDOUS METALS: Does the sum of the concentration levels of lead, cadmium, mercury
and hexavalent chromium present in this material exceed 100 ppm by weight? NO
APPENDIX
Bonding The connection of two or more conductive objects by means of a conductor (most
commonly a wire or metal plate)
CG Coast Guard
Confined Space An area that by design has limited openings for entry and exit. A confined space
has unfavorable natural ventilation and is not intended for continuous worker
occupancy.
EU European Union
Flashpoint The minimum temperature at which a liquid gives off vapor in sufficient
concentrations to form an ignitable mixture with air near the surface of a liquid.
Grounding The connection of one or more conductive objects to the ground: a specific form of
bonding. Grounding is also referred to as earthing.
IDLH Immediately dangerous to life and health, the airborne concentration of a toxic
material from which one could escape within 30 minutes without any escape-
impairing symptoms or irreversible health effects.
MIL Military
PM Preventative Maintenance
QA Quality Assurance
QC Quality Control
UL Underwriters Laboratory
UN United Nations
Vapor Pressure The pressure exerted by a volatile liquid while under defined equilibrium
conditions. Vapor pressure is usually measured in millimeters of mercury (mm
Hg).