VBC

Vinylbenzyl Chloride

A dual functional monomer you can polymerize or copolymerize before or after functional group reactions

General Information .........................................................................................................................4 Physical Properties ...........................................................................................................................5 Typical Reactions with VBC .............................................................................................................6 Typical Applications of VBC .............................................................................................................8 How to Get a VBC Sample ...............................................................................................................9 Polymerization of VBC ....................................................................................................................10 Homopolymerization In-Mass ................................................................................................10 Emulsion Polymerization ........................................................................................................11 Friedel-Crafts Polymerization.................................................................................................11 Polymerization of Vinylbenzyl Trimethyl Ammonium Chloride ..............................................11 Methods of Analysis ......................................................................................................................11 Storage and Handling ....................................................................................................................12 Toxicity ...........................................................................................................................................17 Patents Involving VBC Monomer ...................................................................................................20 Ion Exchange Resins ..............................................................................................................20 Photographic ..........................................................................................................................21 Plastics ...................................................................................................................................21 Elastomers .............................................................................................................................21 Chelation Agents ...................................................................................................................21 Silanes ...................................................................................................................................22 Combinatorial Chemistry .......................................................................................................22 Mordants................................................................................................................................22 Paper Manufacturing .............................................................................................................22 Fibers and Textiles .................................................................................................................23 Dyes .......................................................................................................................................23 Chromatography.....................................................................................................................23 Coatings .................................................................................................................................23 Catalysis.................................................................................................................................23 Membranes ............................................................................................................................23 Monomeric and Polymeric Synthesis ....................................................................................24 Specialty Polymers.................................................................................................................25

VBC - gives you a wide range of application possibilities

Lets you attach functional groups before or after polymerization

Vinylbenzyl chloride (VBC), also called chloromethyl styrene (CMS), consists of a polymerizable double bond and a benzylic

styrene at your facility are eliminated. The high purity of VBC from The Dow Chemical Company allows high molecular weights to be attained with a minimum of undesirable cross-linking. VBC will copolymerize with a wide variety of monomers such as acrylic esters, styrene, acrylamides, and more.

VBC a versatile building block that makes it easy to create your own special monomer and polymer systems

chloride group. The monomer is a mixture of meta (~57%) and para (~43%) isomers. Reactions can be carried out on the chloromethyl group before or after polymerization. The vinylbenzyl chloride can be reacted with primary, secondary, and tertiary amines, and many other nucleophiles. The ability to perform reactions to make a new monomer before the polymerization of VBC has advantages. This allows you to control more precisely the characteristics of the desired polymerized product. By starting with VBC, many of the problems, costs, and hazards associated with chloromethylating

VBC gives you flexibility in polymerization

VBC can be homopolymerized or copolymerized using solution, suspension, ionic, mass, emulsion, and other specialized techniques. This bifunctional monomer may be polymerized or chemically modified to achieve the desired product. VBC has been used to create products with a variety of structures such as films, beads, coatings, and many others.

Reacting VBC before or after polymerization

Typical Reactants

Typical Monomers

Vapor Pressure of VBC

Butadiene/Isoprene Acrylic Acid/Methacrylic Acid/ Fumaric Acid/Maleic Anhydride Acrylamide/Methacrylamide Fumarates/Maleates Styrene/ Methyl Styrene Isobutylene Acrylonitrile/Methacrylonitrile Acrylates/Methacrylates
Note: Polymerized by Catalysis Free Radical Mass Suspension Emulsion Solution Ionic Friedel-Crafts

Table 1 Physical Properties1

Appearance Purity Isomer Ratio Molecular Weight Freezing Point Range Boiling Point (at 760 mm Hg) Heat of Fusion, cal/gm Viscosity cps @ 25C Refractive Index, nD25 Density, gm/ml, 20C lbs/gal, 20C Thermal Expansion Coefficient Glass Transition Temperature, C Flash Point (Cleveland Open Cup) Fire Point (Cleveland Open Cup) Heat of Polymerization @ 195C Auto-Ignition Temperature Solubility of VBC in H2O @ 25C Solubility of H2O in VBC Heat of Vaporization Pale yellow to water white liquid ~96% ~43% para/57% meta 152.62 -26.2C to -42.3C 229C 15.73 1.832 1.5702 1.083 9.037 1.51x10-3 ml/g/C 82 220F (104.4C) 260F (126.6C) -15.4 K cal/mole 610620C 0.073 gm/l 0.6 gm/l C cal/gm 157.2 79.83 228.0 72.05

VBC is soluble in most common organic solvents

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These are typical properties and are not to be construed as specifications.

The chloromethyl group of VBC retains its reactivity after polymerization of the monomer. Illustrated below are some of the reactions VBC will undergo. There are many other chemicals that can be reacted with VBC.

The chemical versatility of VBC allows the development of unique polymers

Typical VBC Reactions

1. Vinylbenzylhalophenylether(A)
CH = CH 2 HO CH 2 Cl Br NaOH CH 2 O Br CH = CH 2

2. Vinylbenzyl Thioacetate(B)

3. Vinylbenzyl Alcohol(C)

4. Vinylbenzyl Diethyl Phosphonate(D)

5. Vinylbenzyl Trimethyl Ammonium Chloride(E, F)

6. N - (Vinylbenzyl)iminodiacetic Acid(G, H)

7. Vinylbenzyl Sulfonium Chlorides(I, J)

References

8. Vinylbenzyl Phosphonium Chlorides(K)

A. E. L. McMaster (to The Dow Chemical Company), U.S. 3,058,953 (1962). B. W. R. Nummy (to The Dow Chemical Company), U.S. 2,947,731 (1960). C. W. N. DeLano (to The Dow Chemical Company), U.S. 3,127,382 (1964).

9. Vinylbenzyl Sulfonate(L)

D. E. L. McMaster and W. K. Glesner (to The Dow Chemical Company), U.S. 2,780,721 (1961). E. J. T. Clarke and A. H. Hamerschlag (to Ionics, Inc.), U.S. 2,780,604 (1957). F. W. G. Lloyd (to The Dow Chemical Company), U.S. 3,178,396 (1965).

10. Vinylbenzyl Polyglycol Ethers(M)

G. R. A. Mock and L. R. Morris (to The Dow Chemical Company), U.S. 2,840,603 (1958). H. L. R. Morris, R. A. Mock, C. A. Marshall, and J.H. Howe, J. J. Am. Chem. Soc., 81, 377 (1959). I. M. J. Hatch, F. J. Meyer, and W. G. Lloyd, J. Appl. Polymer Sci., 13, 721 (1969). J. M. J. Hatch and E. L. McMaster (to The Dow Chemical Company), U.S. 3,078,259 (1963). K. A. Y. Garner, J. G. Abramo, and E. C. Chapin (to Monsanto Chemical Co.), U.S. 3,065,272 (1962). L. G. D. Jones (to The Dow Chemical Company), U.S. 2,909,508 (1959). M. S. C. Stowe (to The Dow Chemical Company), U.S. 3,190,925 (1965).
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Difficult application problems can be solved with VBC and a little imagination. While there is still much unexplored territory in the use of VBC, here are just a few of the ways it can be used.

4. The chloride of the chloromethyl group of VBC can also be replaced by biochemical, light-absorbent compounds such as chlorophyll, hemin, porphyrin, and metalloporphyrin to create photosensitive polymers. Using thionine or benzopyran to replace the chloride creates a photochromic polymer. VBC can also be used to create photoconductive polymers. 5. VBC can be used for a number of analytical applications such as partial resolution of alpha-amino acids, noble metal extraction, uranium recovery, phenol complexing resins, sulfur dioxide removal, copper, cobalt, or mercury complexing, and separation of nucleosides. 6. VBC can be used to combine and improve the characteristics of elastomers such as improving scorch time, and increasing temperature and weather resistance. It can be used to inhibit elastomer decomposition and even to produce photocurable, water soluble elastomers.

VBC gives you a wide range of application possibilities

1. VBC can be used to create polyelectrolytes with properties applicable to latex electrodeposition on metals. Other VBC-based polymers include polymeric surfactants, flocculating agents, phase transfer catalysts, electron carriers and viologens, ion exchange resins, and polymeric mordants for photographic dyes. 2. VBC can also make it easier to carry out reactions by acting as a polymeric support. After the molecular synthesis is completed, the modified molecule can be separated from the chloromethyl group. The polymeric support function of VBC can be used in peptide synthesis. 3. Used as a polymer reactant, the chloromethyl group of VBC can be modified by substitution of sulfinic acid, nicotinamide, tetrathiafulvalene, fluorinated ketone or amine, azide, oxyvanadium derivatives, Benders salt, and many others in place of the chloride.

7. Substituting oxyphosphorated or silicated compounds for the chloride in VBC produces fire-resistant polymers. Similar fire resistance is observed when VBC is copolymerized with cyclic phosphazene or poly-VBC is cross-linked with stannous chloride, SnCl2. 8. Copolymerizing VBC containing a hydroxybenzophenone group with methyl methacrylate produces a transparent, UV-resistant polymer. 9. Poly-VBC can be used in lithographic processes because it resists proton and electron beams.

10. Modified VBC has also been used as bioactive templates and to fix carbohydrates.

How to get started on your own unique polymers using VBC

Samples are available from your nearby Dow sales office. If you have a specific application in mind, our sales representative can put you in contact with the Dow research personnel who can best answer your questions.

References 1. M. Camps, M. Chatzopoulos, J. P. Montheard, J. Macromol. Sci, Rev. Macromol. Chem. Phys., C22(3), 343-407 (1982-83).

Table 2 Monomer Reactivity Ratios

M1 = Vinylbenzyl Chloride Monomer Acrylic acid Acrylonitrile Chloroprene M-diisopropenyl benzene Divinylbenzene Ethyl acrylate 2-Hydroxyethyl acrylate 2-Hydroxypropyl acrylate Isobutylene (cationic) Isoprene Methacrylic acid Methyl methacrylate r1 0.65 0.6 0.67 0.05 0.28 0.27 1.51 0.754 0.712 0.7 0.53 0.4 0.283 1.02 0.82 0.976 1.08 1.31 1.41 36.8 r2 0.25 0.2 0.06 3.50 0.25 1.24 0.423 0.372 0.334 4.5 1.14 0.73 1.115 0.46 0.37 0.496 0.72 0.72 0.71 0.0233 ref (4) (2) (3) (5) (6) (6) (2) (2) (2) (2) (7) (4) (2) (8) (9) (2) (2) (10) (11) (2)

2. M. A. Askarov, A. Dzhalilov, M. N. Nabiev, Deposited Doc., 1974; C. A. 86, 121856 (1977). 3. Dow unpublished data. 4. A. T. Dzhalilov, G. A. Babakhanov, M. Nabiev, Dokl. Akad. Nauk. Uzb. SSR 3, 42 (1978); C. A. 93, 95969 (1980). 5. M. A. Askarov, A. T. Dzhalilov, S. M. Khashimova, Deposited Doc., 1975; C. A. 87,86146 (1977). 6. S. M. Khashimova, A. T. Dzhalilov, M. A. Askarov, Vysokomol. Soedin., Ser. B, 16 (1), 53 (1974); C. A. 81,26023 (1974). 7. M. A. Askarov, A. T. Dzhalilov, G. A. Babakhanov, Deposited Doc., 1975; C. A. 87,68718 (1977). 8. G. A. Babakhanov, A. T. Dzhalilov, M. A. Askarov, M. Nabiev, Vysokomol. Soedin., Ser. B, 20 (11) 850 (1978); C. A. 90,88027 (1979). 9. K. Shuji, O. Toshiyuki, O. Kiyoshi, T. Kazuich, J. Macromol. Sci.-Chem. 13 (6), 767, (1979). 10. M. Negree, M. Bartholin, A. Guyot, Angew. Macromol. Chem., 80, 19 (1979).

Styrene

Vinyl acetate

Polymerization
Vinylbenzyl chloride has been homopolymerized and copolymerized using solution, mass, emulsion, and ionic polymerization techniques. Excellent results were obtained using emulsion polymerization systems. Advantages found for the emulsion systems, when compared with mass or suspension systems, were higher molecular weights, higher rate of polymerization, better conversion within a reasonable length of time, and ease of handling. High molecular weights can be obtained by removing inhibitors by caustic washing. Further information on removing inhibitors is given in the Storage and Handling section of this brochure. The monomer reactivity ratios of VBC shown below were obtained experimentally from copolymerization studies. The values of the Price-Alfrey copolymerization parameters Q and e (below) were calculated from these ratios.

Homopolymerization In-Mass: The homopolymerization of VBC by a mass process can be carried out with or without the presence of a free radical initiator. The procedure described next does not employ an initiator although free radical initiators such as benzoyl peroxide, t-butylperoctoate, and azobisisobutyronitrile can be used. Before polymerization of vinylbenzyl chloride, remove the inhibitors using the procedure described in the handling section; dry the monomer using anhydrous potassium carbonate. For laboratory work, a small reaction vessel such as a glass tube or ampule is recommended. A small amount of the monomer is placed in the vessel and nitrogen is allowed to bubble through the liquid for 23 minutes. After purging with nitrogen, the sample is sealed under vacuum. The vessel is then placed in a controlled temperature water bath at 80C until the monomer has solidified, after which it is transferred to an air oven for 24 hours at 115C. If it is desirable to remove the volatiles, the polymer can be dissolved in methyl ethyl ketone (5% solution) and

Price-Alfrey Copolymerization Parameters VBC Q Value 1.06 e Value -0.45

precipitated into alcohol. The polymer can then be removed by filtration and dried.

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When free radical initiators are employed, it is not always necessary to first remove the inhibitor. Caution must be used to avoid violent polymerizations. Emulsion Polymerization: The following procedure outlines a method for preparing high molecular weight linear and lightly cross-linked copolymers of vinylbenzyl chloride.

After agitation, the bottles are cooled to room temperature in the tumbler and removed. Remove the caps carefully (Caution: unpolymerized monomer may be present). The emulsion is poured through a fine screen to remove agglomerates. A biocide should be added to prevent mold and fungus growth if the emulsion is to be stored and not used immediately. Friedel-Crafts Polymerization: This

Polymerization of Vinylbenzyl Trimethyl Ammonium Chloride: To a reaction vessel equipped with a stirrer, condenser, and nitrogen inlet tube, add an aqueous solution containing 20 percent vinylbenzyl trimethyl ammonium chloride. Adjust this solution to a pH of 5. Add 1,000 ppm VERSENE* 100 chelating agent (based on monomer) as a 1 percent aqueous solution. Then add 500 ppm azobisisobutyronitrile (based on monomer). Purge the flask with nitrogen for 20 minutes. Heat the solution to 60C with stirring and constant nitrogen purge. Continue heating for 16 hours. The gel that is formed can be titrated to determine the amount of unpolymerized monomer. The gel can be dried in trays or by using heated rolls on a flaking device.

Vinylbenzyl chloride (60 g), methyl acrylate (20 g), and varying percentages of divinylbenzene (0.00, 0.05, 0.3, 1.0) are weighed into clean bottles containing deionized water (175 ml), 20 ml of aqueous 20 percent sodium lauryl sulfate, 9.6 ml of aqueous 5 percent NaHCO3, and 9.6 ml of aqueous 5 percent K2S2O8. The ingredients are then cooled in an ice bath for one hour after which 6.8 ml of aqueous 5 percent Na2S2O5 are added. The bottle contents are purged with prepurified nitrogen for 20 minutes in an ice bath, and the bottle sealed. Before placing the bottles in a tumbler, shield them with canvas bags or socks to prevent breakage in the tumbler. The bottles are placed in a tumbler at 30C and agitated at 12 rpm for 18 hours.

method of polymerization of VBC has been used to produce a foam that is exceptionally hard to ignite. Be extremely careful when attempting this type of polymerization. Large quantities of hydrogen chloride gas are evolved in this reaction and adequate precautions must be taken. Under no circumstances should the inhibitor present in VBC be removed prior to this reaction.

Methods of Analysis
Most of the derivatives of vinylbenzyl chloride can be titrated for unsaturation by methods commonly used for styrene.1 Quaternary amines fail to give satisfactory analyses except in coulometric titrations. Direct titration with bromide-bromate solution in acetic acid-sulfuric acid solution, using polarized electrodes to detect the presence of excess bromine is the most generally useful method.

*Trademark of The Dow Chemical Company

1

Styrene, Its Polymers, Copolymers and Derivatives; Edited by, R.H. Boundy and R.F. Boyer, Reinhold Publishing Corp. (1952), pp. 129-194.
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Unloading
Vinylbenzyl chloride is sold by Dow in the following quantities: 1-pint samples 16 liters (four glass bottles) 55-gallon HDPE drums A one-half inch valve is recommended for use in removing VBC from 55-gallon drums. The valve should be constructed of unanodized aluminum. Valve seats and stem seals should be coated with Teflon nonstick resin. The valve should be connected to the drum with a one-half inch unanodized aluminum pipe. Individual circumstances are important in establishing appropriate unloading procedures. For unloading information specific to your operation, contact The Dow Chemical Company, Midland, MI 48674.

Storage
Vinylbenzyl chloride contains 50-100 ppm tertiary-butyl catechol (TBC) as a free radical polymerization inhibitor. Monomer containing TBC should contain oxygen at all times. VBC should never be stored at temperatures above 80F. For storage periods longer than thirty days, refrigerationeven down to freezing temperaturesis recommended. Care should be taken to slowly thaw frozen VBC. One method is to allow frozen VBC to stand at room temperature until thawed. In addition to TBC, vinylbenzyl chloride contains 700 900 ppm nitromethane to inhibit Friedel-Crafts reactions. If removal of TBC and nitromethane is desired, this may be done by extraction with 0.5 percent sodium hydroxide solution until a colorless extract is obtained. When this is complete, wash with water until neutral, followed by drying. Because the dried sodium salt of nitromethane is shock sensitive, the alkaline extract should be acidified and disposed of as the solution. Attempts to remove inhibitor by passing VBC through activated alumina or Drierite calcium sulfate are usually not successful because polymerization may occur. Without inhibitors, VBC has a very limited shelf life, but storage near 0C will extend its useful life significantly.

Storage and handling

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Uninhibited VBC will polymerize at ambient temperatures. Polymerization can be effected by free radical or ionic initiation through the vinyl group and by condensation of the chloromethyl group with loss of HCl. The condensation polymerization, as well as the cationic vinyl polymerization, is catalyzed by Friedel-Crafts type catalysts, as well as metals such as iron or materials like activated alumina. Cationic polymerization can take place in the presence of TBC.

polymer to form which will cause total degradation of the Teflon. The particles formed in this type of polymerization will cause further cross-linked polymer in virgin VBC. Plastic materials that have been used successfully are surface sulfonated polyethylene and Kynar2 polyvinylidene fluoride. Surface sulfonated polyethylene should be properly neutralized after sulfonation. Materials of unknown performance should be tested on a laboratory scale as a minimum before being put into service. Soluble plastic cap liners should not be used. To clean tools and equipment used with VBC, use a chlorinated solvent or isopropanol wash, followed by a soap and water wash to thoroughly remove the monomer. The chlorinated or isopropanol solvent should then be treated as if it were VBC with respect to skin and eye contact, etc. If equipment contaminated with VBC is washed in a sink with warm water, the vapors may cause throat and nasal irritation and may cause eye irritation (see section on eye contact).

Flammability
Although it has low flammability, vinylbenzyl chloride is combustible. Fires involving VBC can be extinguished with foam, dry powder, or CO2. When burning, VBC may give off toxic by-products such as hydrogen chloride (HCl) gas and carbon monoxide. Avoid breathing smoke or gas liberated by a fire in which VBC is involved. A potential hazard is the exothermic polymerization of VBC in a closed container due to surrounding fire. Warm containers should be vented or opened to prevent a pressure buildup from heat and/or polymerization.

Handling Materials and Equipment

Iron and heavy metals must not be allowed to contact VBC, because they may initiate uncontrollable Friedel-Crafts reactions and polymerizations with release of hydrogen chloride gas. Aluminum or titanium (grade II) are acceptable for containers and lines to be used at room temperature. Kynar plastic or glass-lined reaction equipment is recommended. VBC will penetrate most rubber and plastic products. Nylon, polyester, and polyvinyl alcohol are more resistant than most plastics. Although Teflon1 polytetrafluoroethylene is not soluble in VBC, the VBC is absorbed into Teflon and on subsequent heating may cause a cross-linked

1 2

Trademark of E.I. duPont de Nemours & Co. Trademark of Pennwalt Corp.

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Spills and Disposal

Personnel involved in spill cleanup should wear a self-contained breathing apparatus and resistant gloves and boots. (See pg. 19.) Small spills on a hard, nonporous surface can be removed for disposal by covering the spill with an adsorbent such as soda ash or ground corn cobs, or absorbent materials meeting ASTM F-716-82 performance specifications, such as IMBIBER BEADS. Adsorbents such as untreated clay and sorbent clays, diatomaceous earth, earth, oil adsorbing materials and mica may cause a polymerization reaction which could become uncontrollable and have been known to start fires due to the heat of polymerization. Wash area with soap and water only after all possible free VBC liquid has been absorbed. Due to the water insolubility of VBC, it may be necessary to solvent rinse with Chlorothene* solvent or isopropanol. Dispose of waste as required by applicable laws. For large spills, contact CHEMTREC or Dow Emergency Response for assistance.

Small amounts of VBC may be disposed of by burning in an approved incinerator. Polymerization of a dilute solution in a solvent such as isopropanol will provide a less reactive and hazardous material for disposal. VBC is toxic to fish and animals and should not be disposed into the sewer system or placed in a landfill area. All contaminated gloves, rags, and clothing should be disposed of by burning in an approved facility. In disposing of any wastes, all federal, state, and local laws and regulations must be met.

Distribution Emergency Response

Distribution Emergency Response (E/R) is the Dow system for advising and assisting carrier, warehouse, terminal, or public emergency service personnel confronted with an emergency involving Dow products. E/R, a part of Dows commitment to product stewardship, provides a quick and reliable resource for those facing a chemical emergency.

DISTRIBUTION EMERGENCIES AND CHEMICAL EMERGENCIES INVOLVING EXPOSURES, LEAKS, OR SPILLS Call: 1-989-636-4400 or CHEMTREC (day or night) Toll free 1-800-424-9300

*Trademark of The Dow Chemical Company

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Inhibition of styrenic monomers

TBC (4-tert-butylcatechol) is added to styrenic monomers to inhibit polymer formation and oxidative degradation during shipment and subsequent storage. If sufficient oxygen is

To prevent runaway polymerization of stored monomer, carefully monitor the inhibitor level, the temperature of the storage facility, and the oxygen content of the monomer.

Note: The information presented here is derived from observed properties of TBC with styrenic monomers. VBC is expected to behave in a similar manner.

present, TBC prevents polymerization by reacting with oxidation products (monomer peroxy-free radicals) in the monomer. However, in the absence of oxygen, polymerization will proceed at essentially the same rate as if no inhibitor were present. The inhibitor level of the styrene-type monomers must be maintained above a minimum concentration or danger level at all times. If inhibitor level drops below 20 ppm, add TBC to adjust to specification. If TBC concentration is allowed to drop to below 10 ppm, an exothermic, runaway polymerization may result.

Standard inhibition levels in Dow styrenic monomers

The time required for TBC concentrations to fall to a dangerously low level varies greatly for different storage and handling conditions. The graph at right shows typical depletion rates in styrene monomer stored at room temperature in a laboratory experiment. The data obtained for TBC levels in vinyl toluene are almost identical and it is expected that VBC will have a similar depletion rate. Remember, however, that the depletion rates in actual storage may be much faster or slower depending on environmental conditions.

Effect of Inhibitor and Oxygen on the Shelf Life of Styrene at Various Temperatures
12 ppm TBC Saturated with Less Than Oxygen 3 ppm Oxygen 6 mo. 10 to 15 days 3 mo. 4 to 5 days 8 to 12 days Less than 24 hours 50 ppm TBC Saturated with Oxygen More than 1 year 6 months Less than 30 days

Temp. 60F 85F 110F

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Most importantly, if the inhibitor has been depleted and polymerization has already begun, TBC should be added immediately, and The Dow Chemical Company or its representative should be notified as soon as possible. If unstable monomer is not treated promptly, it may become unsalvageable and may also cause serious consequences such as excessive heat and pressure buildup.

Other factors affecting inhibitor level

Other factors that affect the depletion of TBC are heat, water, and air, with heat being the most important. In hot climates or during hot seasons where temperatures greater than 80F are normally encountered, the monomer bulk storage installation should be refrigerated. For storage of more than six months, temperatures 45F are recommended.

Typical TBC Depletion Rates

In addition, drums of monomer should not be kept in the sun. As soon as monomer is received, it should be placed in a cool, shaded area. In very hot weather, drums can be temporarily cooled by water spray. It is advisable to keep monomer inventories to a minimum during hot weather, and to use drums in the order in which they are received so that monomer is not stored any longer than necessary.

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Toxicity
Vinylbenzyl chloride is a mixture of meta- and para-isomers. VBC has been shown to be negative in some in vitro (test tube) mutagenicity tests and positive in others.

Health Hazards
The suggested precautions for safe handling which follow are necessarily general in nature and cannot cover all possible situations, as customers specific use conditions are often unknown. The Dow Chemical Company will help customers establish safe work practices, but cannot accept responsibility for circumstances not under its direct control. Each user is fully responsible for establishing and following safe practices for use, handling, and storage. Persons handling, storing, or using

Toxicity, safety precautions, and first aid

Long-term animal studies on this material have shown no carcinogenic effects. However, repeated exposure to excessive vapor concentrations may cause lung, kidney, and liver effects. Persons handling, storing, or using VBC should be thoroughly familiar with its hazards and be trained in safe work practices. A Material Safety Data Sheet (MSDS) for VBC is available from Dow to help customers handle, store, and use this product safely. These sheets are updated regularly. Obtain current MSDS for all Dow Products from your Dow representative before using these products. Keep current MSDS on hand for use by physician in case of emergency.

VBC should prevent skin and eye contact with the liquid and avoid breathing vapors or exposure of eyes to vapors. If any ill effects occur, seek medical attention.

Ingestion
Acute oral toxicity of the isomeric mixture is low to moderate. The LC50 for male rats is between 630 and 1,260 mg/kg body weight. Amounts ingested incidental to industrial handling are not likely to cause serious injury. If VBC is swallowed, induce vomiting immediately by giving two glasses of water and sticking a finger down the throat. Seek medical attention.

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Skin Contact
VBC, either as a liquid or vapor, is irritating to skin; it causes a slightly delayed, but intense painful, burning response. Skin sensitization is also possible. Prolonged or frequent skin contact causes severe irritation, perhaps even a burn, as well as possible absorption of toxic quantities through the skin. The LD50 for skin absorption in rabbits is between 500 and 1,000 mg/kg.

Eye Contact
Eye contact with even small quantities of VBC will cause intense pain and severe lacrimation and may cause eye injury. The extent of injury will depend upon the concentration of VBC and the diluent used. Vapors may also irritate the eyes and will cause intense pain with consequent inability to see in bright light. Chemical workers goggles are the recom-

When handling VBC, wear clean, bodycovering clothing. Resistant gloves, boots, apron, and gauntlets, and a full face shield worn over chemical workers safety goggles are also recommended, depending on the extent and severity of likely exposure. In case of contact, immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash skin with isopropyl alcohol if available. Wash clothing before reuse. Destroy contaminated shoes.

mended minimum eye protection. A full face shield should be worn over goggles when exposure is likely. If vapor exposure causes eye or respiratory irritation, use a full face respirator. In addition, an eye fountain and safety shower should be easily accessible from the work area. If eye contact occurs, flush the eyes with flowing water immediately and continuously for at least 15 minutes. Seek medical attention.

Inhalation
Call a physician if irritation persists. NOTE TO PHYSICIAN: If burn is present, treat as any thermal burn, after decontamination. There is no specific antidote. Skin or eye contact with trace quantities of the material may cause extreme pain in the absence of significant irritation. Because vinylbenzyl chloride is poorly soluble in water, isopropanol is useful in decontaminating the skin. Supportive care is recommended. Treatment should be based on the judgment of the physician in response to symptoms of the patient. Vinylbenzyl chloride is an eye and respiratory irritant in the vapor state. Vapors of VBC at concentrations less than 1 ppm are capable of causing eye or nasal irritation, lacrimation, and light sensitivity. Repeated excessive exposures to high amounts may cause lung, kidney, and liver effects.

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VBC has good warning properties. It is easily detected at concentrations of 0.10 to 0.50 ppm, allowing exposures to be controlled by comfort level under most circumstances. An internal industrial Hygiene Guideline (HG) has been established. It is 0.5 ppm ceiling with a skin notation. In the absence of proper environmental control, wear an approved full face organic vapor-type respirator. For emergencies, use a positive-pressure, self-contained breathing apparatus. If effects occur, move the victim to fresh air and seek medical attention.

As shown, most rubber and plastic products are rapidly penetrated by VBC. Because of its thickness, butyl rubber showed a longer breakthrough time than the other materials tested. A thin butyl rubber glove may show similar values as Neoprene or NBR. Laboratory experience with VBC has also shown that polyvinylalcohol gloves are more resistant as are certain polyamides and polyesters.

Respirators
Four respirators were tested: U.S. Safety organic vapor, U.S. Safety organic vapor/acid gas, AO organic vapor/acid gas, and Willson organic vapor/acid gas respirators. Each was subjected to a 65 ppm concentration of VBC (~197 ppm constitutes a saturated atmosphere) at humidity levels of 20% and 80%. All of the respirator cartridges tested provided a minimum of 40 hours of service before breakthrough.

Gloves
Composition Breakthrough Time 16 hrs. 70 min. 70 min. 40 min. 6 min. 3 min.

North B161 Pioneer AF-18 Edmont 9-924 Edmont 29-865 Pioneer U-5 (Quixam) Edmont 35-725

Butyl Rubber NBR Lined Neoprene Unlined Neoprene PVC (disposable) Polyethylene (disposable)

Environmental Monitoring
Dow has a validated method for monitoring VBC in an industrial environment. Contact Dow for detailed information about this monitoring technique.

Suits
Composition Breakthrough Time 10 hrs.

Protective Clothing and Equipment

Industrial hygiene studies were conducted on protective gloves, suits, and cartridge respirators to determine the degree of protection provided. Listed are the results. Each item was tested for VBC permeation with respect to breakthrough time.
SARANEX* Film Marathon Slicker Suit (400 series) Uniroyal 2000 Suit Marathon Slicker Suit (800 series)

SARANEX Film coating Tyvek1 nonwoven fabric Neoprene/ Nylon PVC/Nylon Neoprene/ Nylon (flame retardant)

14 min.

11 min. 9 min.

NOTE: Seams should be heat sealed not sewn. *Trademark of The Dow Chemical Company 1 Trademark of E.I. duPont de Nemours & Co.

Reference paragraph on Skin Contact, page 18.

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This section is based primarily on numerous references to the patent literature. No efforts were made to validate claims or statements of the literature cited and space does not permit a listing of all such references. The utility of VBC in many applications is based on the chloromethyl group, which retains its reactivity even in the polymeric form. This enables VBC to be homopolymerized or copolymerized with other vinyl monomers and then post-modified.

8. M. J. Hatch (to The Dow Chemical Company), U.S. 3,277,023 (1966). 9. M. J. Hatch (to The Dow Chemical Company), U.S. 3,300,416 (1967). 10. M. J. Hatch (to The Dow Chemical Company), U.S. 3,041,292 (1962). 11. Copolymerization of vinylbenzyl chloride with divinylbenzene and m-diisopropenylbenzene, Khashimova, S. M.; Dzhalailov, A. T.; Askarov, M. A., Tashk. Politekh. Inst., Tashkent, USSR, Vysokomol. Soedin., Ser. B. 16(1), 53-5, Russian. 12. Synthesis and cross-linking polymerization of

Patents and references involving VBC monomer

Ion Exchange Resins

The preparation of ion exchange resins involving VBC has proven to be an extremely interesting application for this monomer. Although these resins have been prepared by various procedures, one that has proven attractive is to first prepare VBC polymer beads cross-linked with divinylbenzene and then treat this resin with a tertiary amine. Several references relating to this application are listed below.
1. G. F. DAlelio (to Koppers Company, Inc.), U.S. 2,631,127 (1953). 2. J. T. Clarke, A. H. Hamerschlag (to Ionics, Inc.), U.S. 2,780,604 (1957). 3. E. L. McMaster (to The Dow Chemical Company), U.S. 2,992,544 (1961). 4. M. J. Hatch (to The Dow Chemical Company), U.S. 3,030,317 (1962).

some N-vinylbenzyl quaternary salts, Janovic, Z.; Saric, K., Rest. Inst., INA, Zagreb, Yugoslavia, Croat. Chem. Acta, 51(1), 93-6, English. 13. Basic imidazolylmethylstyrene compound, its polymer, and its use as an ion exchange resin, Miyake, Tetsuya; Takeda, Kunihiko; Tada, Keishi, Asahi Chemical Industry Co., Ltd., Japan, U.S. US 4430445 A, 7 Feb 1984, 31 pp., English. 14. Imidazole derivatives, Asahi Chemical Industry Co., Ltd., Japan, Jpn. Kokai Tokkyo Koho JP 56/ 32462 {81/32462}, 1 Apr 1981, 6 pp., Japanese. 15. Synthesis of chelate resin having an affinity for heavy metal ions, Hong, Sung II; Jeong, Dong Won; Suh, Jeong Ok, Coll. Eng., Seoul Natl. Univ., Seoul, S. Korea, Hanguk Somyu Konghakhoechi, 21(2), 100-12, Korean. 16. Synthesis and characteristics of microspheres of polystyrene derivatives, Shahar, Michal; Meshulam, Haim; Marge, Shlomo, Dep. Mater. Res., Weizmann Inst. Sci., Rehovot, Israel, J. Polym. Sci., Part A: Polym. Chem., 24(2), 203-13, English. 17. Grafted Methylenediphosphonate Ion Exchange

5. L. R. Morris (to The Dow Chemical Company), U.S. 3,037,944 (1962). 6. L. A. Mattano (to The Dow Chemical Company), U.S. 3,162,608 (1964). 7. M. J. Hatch (to The Dow Chemical Company), U.S. 3,205,184 (1995).

Resins, Andrzej W. Trochimcznk (to ARCH Development Corp.), US 5,712,347 (1998). 18. Process for the Production of a Permselective and Flexible Anion Exchange Membrane, Andreas Reiner, (to Frauhofer-Gesellschaft zur Foderung der angerwandten Forshung e.V.), US 4,871,778 (1989).

20

Additional references relating to the preparation of the trimethyl ammonium salt of VBC that may be of interest are:
1. G. D. Jones (to The Dow Chemical Company), U.S. 2,694,702 (1954). 2. J. H. Rassweiler, D. R. Sexsmith (to American Cyanamid), U.S. 3,068,213 (1962). 3. G. R. Geyer (to The Dow Chemical Company), U.S. 3,335,100 (1967). 4. W. G. Lloyd (to The Dow Chemical Company), U.S. 3,178,396 (1965).

Plastics
1. 2-Hydroxybenzophenone derivatives, UV absorbents for plastics, Kamogawa, Hiromi, Agency of Industrial Sciences and Technology, Japan, Japan JP 50/20059 {75/20059}, 11 Jul 1975, 3 pp., Japanese. 2. Flame-resistant alkenyl aromatic compounds and polymers containing chemically bonded phosphorus and blends with polyphenylene, Axelrod, Robert Jay; Cooper, Glenn Dale, General Electric Co., USA, Eur. Pat Appl. EP 147724 A2, 10 Jul 1985, 16 pp. Designated States: DE, FR, GB, IT, NL, English.

6. Method and Material for Producing High Green strength Rubber Compounds, Tom C. H. Tsai, (to Copolymer Rubber & Chemical Corp.), US 4,454,304 (1984). 7. Curable Acrylic Rubber containing Dibutylaminotriazine thiol and 9,10-Dihydro-9-oza10-phosphaphenathrene-10-oxide, Kunio Mori, (to Nippon Zeon Co. Ltd.), US 5,270,398 (1993). 8. Silica-grafted polyisobutylene and butyl rubber. I. Synthesis and characterization of silica-grafted polyisobutylene, Vidal, A.; Guyot, A.; Kennedy, J. P., Cent. Rech. Phys. -Chim. Surf. Solides, Mulhouse 68200, Fr., Polym. Bull. (Berlin), 2(5), 315-20, English.

Photographic
1. Novel polymeric derivatives of tetrazole-5-thiols and their metal and ammonium salts, Grasshoff, J. Michael; Reid, Jerome L., Polaroid Corp., U.S. 3936401, 3 Feb 1976, 6 pp., English. 2. Photochromic 5-(vinylbenzyloxycarbonyl)-1,3, 3-trimethylindolino-spirobenzopyrans and their copolymers, Nagakubo, Kuniharu; Miura, Masatoshi; Wakamatsu, Jiro, Fujikura Kasei Co., Ltd., Japan. Japan Kokai JP 50/4077 {75/40777}, 16 Jan 1975, 6 pp., Japanese. 3. New practical materials and their syntheses, Oda, Ryohei, Kyoto Univ., Kyoto, Japan, Kagaku Kogyo, 30(12), 1289-93, Japanese. 4. Coating Compositions for Antistatic Layers for Photographic Elements, Ronald M. Stimson, (to Eastman Kodak Company), US 5,326,688 (1994). 5. Silver halide photographic photosensitive materials, Fuji Photo Film Co., Ltd., Japan, Jpn. Kokai Tokkyo Koho JP 57/73735 A2 {82/73735}, 8 May 1982, 11 pp., Japanese. 6. Photosensitive resin for photomechanical printing platemaking, Mitsubishi Petrochemical Co., Ltd., Japan, Jpn. Kokai Tokkyo Koho JP 58/216242 A2 {83/216242}, 15 Dec 1983, 8 pp. Japanese.

Elastomers
1. Latex polymer with built-in surface-active composition, Killam, Harrison S., Rohm and Haas Co., USA, Ger. Offen. DE 2447611, 17 Apr 1975, 22 pp., German. 2. Mixed polymers, The Dow Chemical Company, Ger. Offen. DE 2352938, 21 Feb 1974, 36 pp., Division of Ger. Offen. 2,333,301 (CA 81:92212u), German. 3. Acrylic Vinylbenzyl Chloride Elastomers, Robert D. De Marco, (to The B.F. Goodrich Company), US 3,763,119 (1973). 4. Elastomer with Improved Heat and Oil Resistance Based on Modified Chlorinated Polyethylene, Yong S. Rim, (to Uniroyal Inc.), US 4,238,578 (1980). 5. Diphenylamine Derivatives and Degradation Inhibitors for Rubber Polymers, Mitsuhiro Tamura, (to Nippon Zeon Co. Ltd.), US 4,298,5 (1981).

9. Diphenylamine derivatives and their use in decomposition inhibitors for elastomers, Tamura, Mitsuhiro; Ohishi, Tetsu; Sakurai, Hiroshi, Nippon Zeon Co., Ltd., Japan, Ger. Offen. DE 3022952, 22 Jan 1981, 20 pp., German.

Chelation Agents
Excellent chelation agents for heavy metal ions based on polymeric salts of VBC have been prepared. References in this area include:
1. L. R. Morris (to The Dow Chemical Company), U.S. 3,118,831 (1964). 2. R. A. Mock, L. R. Morris (to The Dow Chemical Company), U.S. 2,840,603 (1958). 3. M. J. Hatch (to The Dow Chemical Company), U.S. 3,300,416 (1967). 4. L. R. Morris (to The Dow Chemical Company), U.S. 2,888,441 (1959).

21

Silanes
1. Cationic Unsaturated Amine-Functional Silane Coupling Agents, Edwin P. Plueddemann, (to Dow Corning Corporation), US 3,819,675 (1974). 2. Chemically Treated Fibers and Method of Preparing and Method of Using to Reinforce Polymers, Johnson C. Watkins, (to PPG Industries, Inc.), US 5,085,938 (1992). 3. Organosilane Polycondensation Products, Burkhard Standke, (to Hls Aktiengesellschaft), US 5,591,818 (1997). 4. Method for Producing Retroreflective Sheeting Using a Coupling Agent, Katsura Ochi, (to Nippon Carbide Kogyo Kabushiki Kaisha), (1998).

4. Ink Jet Printing Process, Charles E. Romano (to Eastman Kodak Company), US 6,367,922 B2 (2002). 5. Method of Preparing a stable Coating, Sridhar Sadasivan, (to Eastman Kodak Company), US 6,335,395 B1 (2002). 6. Jet Ink Composition, Charles E. Romano (to Eastman Kodak Company), US 6,156,110 (2000). 7. Photographic Elements Containing Cross-linked Mordants and Process of Preparing said Elements, Gerald A. Campbell (to Eastman Kodak Company), US 3,958,995 (1976). 8. Ink Jet Recording Sheet, Yung T. Chen, (to Polaroid Corporation), US 6,068,373 (2000). 9. Copolymeric Mordants and Photographic Products

Combinatorial Chemistry
1. Resin-Linker Combination for the solid-Phase Synthesis of Peptides and Intermediates, Monika Mergler, (to Bachem Feinchemikalein A.G.), US 4,914,151 (1990). 2. Organosilicion Compounds and Uses Thereof, Younghee Lee, (to Northwestern University), US 6,416,861 B1 (2002). 3. Processes for Electrochemical Production of a Carbon-Containing Material Whose surface is Modified with Organic Groups, and Use of the Modified Material, Oliver Fagebaume, (to Centre National de la Recherche Scientifique (CNRS)), US 6,435,240 B1 (2002).

and Process Utilizing same, Edwin H. Land, (to Polaroid Corporation), US 4,322,489 (1982).

Paper Manufacturing
Homopolymers and copolymers of VBC derivatives have found utility as wet and dry strength additives in paper manufacturing processes.
1. L. H. Wilson, J. J. Padbury (to American Cyanamid Co.), U.S. 2,884,057 (1959). 2. Y. Jen, R. R. House (to American Cyanamid Co.), U.S. 3,015,605 (1962). 3. J. H. Daniel, Jr. (to American Cyanamid Co. ),

Mordants
1. Ink Jet Recording Element, Suresh Sunderranjan (to Eastman Kodak Company), US 6,447,882 B1 (2002). 2. Ink Jet Printing Method, Suresh Sunderrajan (to Eastman Kodak Company), US 6,447,114 B1 (2002). 3. Ink Jet Printing Method, Elizabeth A. Gallo (to Eastman Kodak Company), US 6,447,111 B1 (2002).

U.S. 3,022,214 (1962). 4. R. W. Morgan, M. J. Hatch (to The Dow Chemical Company), U.S. 3,146,157 (1964). 5. C. G. Humiston, F. J. Meyer, D. L. Kenaga (to The Dow Chemical Company), U.S. 3,130,117 (1964).

22

Fibers and Textiles

VBC has found use in a number of different fiber and textile applications. These include resins for improving dimensional stability, dye receptivity, and antistatic properties of textiles; VBC has also been grafted on fibers of various types.
1. W. G. Lloyd, T. Alfrey, Jr. (to The Dow Chemical Company), U.S. 3,022,199 (1962). 2. S. A. Murdock (to The Dow Chemical Company), U.S. 3,094,505 (1963). 3. H. T. Patterson, I. D. Webb (to E.I. duPont de Nemours & Co.), U.S. 2,691,640 (1954). 4. S. A. Murdock (to The Dow Chemical Company), U.S. 3,075,947 (1963). 5. C. S. H. Chen, E. F. Hosterman, R. F. Stamm (to American Cyanamid Co.), U.S. 3,218,117 (1965). 6. C. S. H. Chen, E. F. Hosterman, R. F. Stamm (to American Cyanamid Co.), U.S. 3,278,255 (1966). 7. C. S. H. Chen, E. F. Hosterman, R. F. Stamm (to American Cyanamid Co.), U.S. 3,423,161 (1969).

Chromatography
1. High Performance Affinity Chromatography Column Comprising Non-Porous, Nondisperse Polymeric Packing Material, Marsha D. Bale, (to Eastman Kodak Company), US 5,043,062 (1991). 2. Attachment of Compounds to Polymeric Particles Using Carbamoylonium Compounds and a Kit Containing Same, Richard C. Sutton, (to Eastman Kodak Company), US 5,397,695 (1998). 3. Pore-Size Selective Modification of Porous Materials, Jean M. J. Frechet, (to Cornell Research Foundation Inc.), US 5,593,729 (1997).

Catalysis
1. Functional polymers and sequential copolymers by phase-transfer catalysis. 18. Synthesis and characterization of -bis(2,6-dimethylphenol)-poly (2,6-dimethyl-1,4-phenylene oxide) and bis(vinylbenzyl)-poly (2, 6-dimethyl-1,4-phenylene oxide) oliogomers, Nava, Hildeberto; Percec, Virgil, Dep. Macromol. Sci., Case Western Reserve Univ., Cleveland, OH 44106, USA, J. Plym. Sci., Part A: Polym. Che., 24(5), 965-90, English. 2. Synthesis of polystyrenes having 2-pyridylthio group and their use as phase-transfer catalysts for the reduction of carbonyl compounds by sodium borohydride, Kondo, Shuji; Nakanishi, Minoru; Yamane, Kazuyuki; Horibe, Atsushi; Tsuda, Kazuichi, Nagoya Inst. Technol. Nagoya 466, Japan, J. Appl. Polym. Sci., 32(3), 4255-62, English. 3. Catalytic/Co-Catalytic Production of Bisphenol A, Jean-Roger Desmurs, (to Rhone-Poulenc Chimie), US 5,105,027 (1992).

Coatings
References related to the use of polymers prepared from VBC in coatings include:
1. J. F. Vitkuske, F. C. Rutledge (to The Dow Chemical Company), U.S. 3,072,588 (1963). 2. F. A. Miller (to The Dow Chemical Company), U.S. 3,306,871 (1967). 3. J. F. Vitkuske, F. C. Rutledge (to The Dow Chemical Company), British 880,338 (1961). 4. Electrostatographic liquid developers, Fuji Photo Film Co., Ltd., Japan, Jpn. Kokai Tokkyo Koho JP 58/105235 A2 {83/105235}, 12 Jun 1983, 6 pp., Japanese. 5. Vinylarylalkyl polysulfide polymers, Meyer, Victor E.; Dergazarian, Thomas E., The Dow Chemical Company, USA, U.S. 4438259 A, 20 Mar 1984, 8 pp., Cont.-in-part of U.S. Ser. No. 339,820, abandoned, English. 6. Electron transfer to anionic reactants incorporated within polycationic coatings on glassy carbon electrodes. Comparison of random and block copolymers, Sumi, Katsuhiro; Anson, Fred C., Arthur Amos Noyes Lab., California Inst. Technol., Pasadena, CA 91125, USA J. Phys. Che., 90(16), 3845-50, English.

Membranes
1. Copolymerization of chloromethylstyrene and divinylbenzene in the absence or presence of poly(vinyl chloride), Takata, Kuniaki; Kusumoto, Koshi; Sata. Toshikatsu; Mizutani, Yukio, Tokuyama Soda Co., Ltd., Tokuyama 745, Japan, J. Macromol. Sci., kChe., A24(6), 645-59, English. 2. Method of Making a Coating and Permselective Membrane, Ionic Polymer Therefor, and Products Therof, Hamish Small, (to The Dow Chemical Company), US 4,705,636 (1987). 3. Novel Polyamide Reverse Osmosis Membranes, Richard F. Fibiger, (to Filmtec Corp.; Dow Chemical Company), US 4,859,384 (1989). 4. Reverse Osmosis Membrane, Donald L. Schmidt, (to The Dow Chemical Company), US 5,464,538 (1995).

Dyes
1. Strong cationic group-containing polymeric colors, Shigehara, Kiyotaka; Tsuchida, Eishun, Japan, Jpn. Kokai Tokkyo Koho JP 53/137228 {78/137228}, 30 Nov 1978, 6 pp. Japanese.

23

Monomeric and Polymeric Synthesis

1. Vinyl benzyl ethers and their polymers, Evani, Syamalarao; Corson, Frederick P.; Lalk, Robert H.; Fiero, Terry H., The Dow Chemical Company, Ger Offen. DE 2333301, 31 Jan 1974, 34 pp., German. 2. Chemical modification of polymers. VI. Displacement of reactive halogens by isoquinoline Reissert compound anions, Gibson, Harry W.; Bailey, F. C., Webster Res. Cent., Xerox Corp., Webster, NY, USA, English. 3. Enhanced reactivity and affinity of polymeric 3-carbamoylpyridinium toward cyanide ion, Shinkai, S.; Tamaki, K.; Kunitake, T., Fac. Eng., Kyushu Univ., Fukuoka, Japan, J. Polym. Sci., Polym. Lett. Ed., 14(1), 1-3, English. 4. ar-Vinylbenzyl iodide, McKinley, Suzanne V., The Dow Chemical Company, USA, U.S. 3923911, 2 Dec 1975, 2 pp., English. 5. Polymerizable porphyrin derivatives, Kamogawa, Hiroyoshi, Agency of Industrial Sciences and Technology, Japan. Kokai JP 49/127999 {74/127999}, 7 Dec 1974, 3 pp., Japanese. 6. Styrene derivatives having a formyl group, Satomura, Masato, Fuji Photo Film Co., Ltd., Japan. Kokai JP 49/95930 {74/95930}, 11 Sep 1974, 3 pp., Japanese. 7. Spontaneous polymerization during the reaction of halogen-containing vinyl monomers with tertiary amines, Dzhalilov, A. T.; Asharov, M. A., Tashk. Politekh. Inst., Tashkent, USSR, Uzb. Khim. Zh., 18(1), 56-9, Russian. 8. Study of polymerization occurring in the reaction of vinylbenzyl chloride with triethylamine, Rakhmatullaev, Kh.; Chulpanov, K.; Dzhalilov, A. T.; Askarov. M. A., Tashkent, Politekh. Inst., Tashkent, USSR, Vysokomol. Soedin., Ser. B. 21(5), 369-71, Russian. 9. Study of polymerization occurring in the reaction of vinylbenzyl chloride with dimethylaniline, Rakhmatullaev, Kh.; Chulpanov, K.; Dzhalivov, A. T.; Askarov, M. A., Tashkent, Politekh. Inst., Tashkent, USSR, Vysokomol. Soedin., Ser. B. 20(11), 871-3.

10. Spontaneous polymerization during the reaction of p-vinylbenzyl chloride with pyridine, Askarov, M. A.; Dzhalilov, A. T.; Muminov, K. M.; Muminova, Z. K., Tashk. Politekh. Inst. im. Beruni, Tashkent, USSR, Zh. Vses. Khim. O-va., 19(6), 705-7, Russian. 11. Preparation and polymerization of p-fluoromethylstyrene, Asami, Ryuzo; Gy, Maung; Takaki, Mikio; Ikuta, Toshiaki, Dep. Synth. Chem., Nagoya Inst. Technol. Nagoya, Japan, Polym. J., 10(3), 301-6, English. 12. Vinylbenzyl esters of N-tert- butyloxycarbonylamino acids, Harris, Nicholas D., Morton-Norwich Products, Inc., USA, Ger. Offen. DE 2706883, 1 Sep 1977, 9 pp., German. 13. Vinylbenzyl ester of an N-BOC amino acid, Harris, Nicholas D., Morton-Norwich Products, Inc., USA, U.S. 4033998, 5 Jul 1977, 3 pp., English. 14. Vinylbenzyl ethers and nonionic water soluble thickening agents, Evani, Syamalarao; Corson, Frederick P., The Dow Chemical Company, USA, U.S. 4029872, 14 Jun 1977, 4 pp. Division of U.S. 3,963,684, English. 15. Vinylbenzyl ethers and nonionic water soluble thickening agents, Evani, Syamalarao; Corson, Federick P., The Dow Chemical Company, USA, U.S. 4029873, 14 Jun 1977, 4 pp. Division of U.S. 3,963,684, English. 16. Vinyl benzyl ethers and nonionic water soluble thickening agents, Evani, Syamalarao; Corson, Frederick P., The Dow Chemical Company, USA, U.S. 4029874, 14 Jun 1977, 4 pp. Division of U.S. 3,963,684, English. 17. Synthesis and polymerization of some new carbazole and phthalimide monomers, Gibson, Harry W.; Bailey, F. C., Webster Res. Cent., Xerox Corp., Webster, N.Y., USA, Macromolecules, 10(3), 602-4, English.

24

18. Functional polymers and sequential copolymers by phase transfer catalysis, 4. A new and convenient synthesis of p- and m-(hydroxymethyl)phenylacetylene, Percec, Virgil; Rinaldi, Peter L., Dep. Macromol. Sci., Case West. Reserve Univ., Cleveland, OH 44106, USA, Polym. Bull. (Berlin), 10(5-6), 223-30, English. 19. Synthesis of functional monomers by vinylbenzylation and polymerization of these monomers, Asami, R.; Kondo, Y.; Watanabe, I.; Sagiura, T.; Nakajima, M.; Yamada, N., Dep. Synth. Chem., Nagoya Inst. Technol., Nagoya, Japan, Jpn.- USSR Polym. Symp. {Proc.}, 2nd, 249-59. Soc. Polym. Sci., Jpn.; Tokyo, Japan, English. 20. 4-Isobutylstyrene, Mitsubishi Petrochemical Co., Ltd., Japan, Jpn. Kokai Tokkyo Koho JP 59/1431 A2 {84/1431}, 6 Jan 1984, 4 pp., Japanese. 21. Spontaneous polymerization in the reaction of vinylbenzyl chloride with polyethylenepolyamine, Babakhanov, G. A.; Dzhalilov, A. T.; Karimova, A. M., Tashk. Politekh. Inst., Tashkent, USSR, Dokl. Akad. Nauk Uzb. SSR, (2), 36-7, Russian. 22. Preparation of (p-vinylbenzyl)polystyrene macromer, Asami, Ryuzo; Takaki, Mikio; Hanahata, Hiroyuki, Dep. Synth. Chem., Nagoya Inst. Technol, Nagoya 466, Japan Macromolecules, 16(4), 628-31, English. 23. Syntheses of polymerizable phenol derivatives having a carbonyl-containing group as a ring substituent, Kamogawa, Hiroyoshi; Sugiyama, Kinya; Hanawa, Hidehito; Nanasawa, Masato, Dep. Appl. Chem., Yamanashi Univ., Kofu, Japan, J. Polym. Sci., Polym. Chem. Ed., 14(2), 511-14, English. 24. Polystyrene-based deblocking-scavenging agents for the 9-fluorenylmethyloxycarbonyl aminoprotecting group, Carpino, Louis A.; Mansour, E. M. E.; Cheng. C. H.; Williams, James R.; MacDonald, Russell; Knapczyk, Jerome; Carman, Mark; Lopusinski, Andrzej, Dep. Chem. Univ. Massachusetts, Amherst, MA 01003, USA, J. Org. Chem., 48(5), 661-5, English.

25. Polymer-supported bases. 1. Synthesis and catalytic activity of polymer-bound 4-(N-benzyl-Nmethylamino)pyridine, Tomoi, Masao; Akada, Yuzo; Kakiuchi, Hiroshi, Fac. Eng., Yokohama Natl. Univ., Yokohama 240, Japan, Makromol. Chem., Rapid Commun., 3(8), 537-42, English. 26. Styrene polymers and their use as resist materials, Fujii, Tsuneo; Inukai, Hirosi, Daikin Kogyo Co., Ltd., Japan, Ger. Offen. DE 3414104 A1, 25 Oct 1984, 13 pp, German. 27. Process for Preparing Cationic Polymers, Irena Y. Bronstein-Bonte (to Polaroid Corporation), US 4,340,522 (1982). 28. Synthesis of polymers containing acetamide structure and their use as phase transfer catalyst, Kondo, Shuji; Minafuji, Makoto; Inagaki, Yasuhito; Tsuda, Kazuichi, Dep. Appl. Chem., Nagoya, Inst. Technol., Nagoya, Japan, Polym, Bull. (Berlin), 15(1), 77-82, English. 29. Reactive monomers and polymers containing chiral groups. Synthesis and copolymerization of N-p-methylstyryl-(1R,2S)-ephedrine, VilledonDenaide, F.; Lecavalier, P.; Frechet, J. M. J., Dep. Chem., Univ. Ottawa, Ottawa, ON K1N 9B4, Can., Polym. Bull. (Berlin), 15(6), 491-5, English. 30. A new grafting method using polymeric sulfonium salt. Grafting of bicyclo ortho ester onto polystyrene, Uno, Hitomi; Endo, Takeshi, Res. Lab. Resour. Util., Tokyo Inst. Technol., Yokohama 227, Japan, Chem. Lett., (11), 1869-70, English.

Specialty Polymers
Additional applications suggested for VBC include flocculants, membranes, selfextinguishing films and electroconductive resins. References to these applications and others are listed below.
1. Vinylbenzyl Sulfonium Salt, G. R. Geyer (to The Dow Chemical Company), U.S. 3,335,100 (1967). 2. Vinylbenzyl Sulfonium Salt, J. H. Rassweiler, D. R. Sexsmith (to American Cyanamid), U.S. 3,060,156 (1962). 3. Vinylbenzyl Sulfonium Salt, M. J. Hatch, E. L. McMaster (to The Dow Chemical Company), U.S. 3,078,259 (1963). 4. Vinylbenzyl Sulfonium Salt, D. R. Sexsmith, E. J. Frazza (to American Cyanamid), U.S. 3,216,979 (1965). 5. Vinylbenzyl Sulfonium Salt, J. L. Lang, U.S. 3,272,782 (1966). 6. Vinylbenzyl Sulfonium Salt, G. D. Jones (to The Dow Chemical Company), U.S. 2,909,508 (1959). 7. Flocculation of Sewage Having Controlled Solids Concentrations, C.P. Priesing and S. Mogelnicki (to The Dow Chemical Company), U.S. 3,259,569 (1966). 8. Dewatering Aqueous Suspensions of Organic Solids, C. P. Priesing and S. Mogelnicki (to The Dow Chemical Company), U.S. 3,259,570 (1966). 9. Chemical Manufacture (Elastomeric Copolymers of Vinylbenzyl Alcohol and 1,3 Diene), J. G. Abramo, E. C. Chapin (to Monsanto Chemical Company), U.S. 3,038,890 (1962).

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10. Recovery of Iodine from Aqueous Iodide Solutions, J. F. Mills (to The Dow Chemical Company), U.S. 3,050,369 (1962). 11. Production of Ion Selective Permeable Membrane, M. Mindick, H. L. Parzelt (to National Aluminate Corp.), U.S. 3,069,728 (1962). 12. Self-Extinguishing Plastic Film, M. D. Longstreth, E. L. McMaster, F. B. Nagle (to The Dow Chemical Company), U.S. 3,108,016 (1963). 13. Removal of Microorganisms from Fluids, K. W. Guebert, J. D. Laman (to The Dow Chemical Company), U.S. 3,242,073 (1966). 14. Vinylidene Polymers: Achieving High Molecular Weight Vinylidene Polymers by Addition of Ethylenically Unsaturated Compounds, M. Baer (to Monsanto Chemical Co.), Fr. 1,447,176 (1966). 15. Vinylphenyl Aliphatic Aminocarboxylic Acids, R. A. Mock, L. R. Morris (to The Dow Chemical Company), U.S. 2,840,603 (1958). 16. Vinylphenyl Aliphatic Aminocarboxylic Acid Polymers, L. R. Morris (to The Dow Chemical Company), U.S. 2,875,162 (1959). 17. Vinylbenzyl Thiolesters of Carboxylic Acids and Polymers Thereof, W. R. Nummy (to The Dow Chemical Company), U.S. 2,947,731 (1960). 18. Vinylbenzyl Dialkyl Phosphonates and Preparation Thereof, E. L. McMaster, W. K. Glesner (to The Dow Chemical Company), U.S. 2,980,721 (1961). 19. Vinylbenzyloxybenzophenones, J. P. Milionis, F. J. Anthen (to American Cyanamid), U.S. 3,049,503 (1962). 20. Process for Producing Vinyl Aromatic Oxymethyl Compounds, J. G. Abramo (to Monsanto Chemical Co.), U.S. 3,055,947 (1962). 21. Vinylbenzylhalophenylether and Polymers and Method of Making the Same, E. L. McMaster (to The Dow Chemical Company), U.S. 3,058,953 (1962).

22. Copolymers of Vinylbenzyl Alcohol and Vinylbenzyl Alkyl Ethers, J. G. Abramo, A. Y. Garner, E. C. Chapin (to Monsanto Chemical Co.), U.S. 3,063,975 (1962). 23. Ethylenically Unsaturated Ionic Phosphonium Salts, J. G. Abramo, A. Y. Garner, E. C. Chapin (to Monsanto Chemical Co.), U.S. 3,065,272 (1962). 24. Method for Separating Thorium and Yttrium Values, W. N. Vanderkooi (to The Dow Chemical Company), U.S. 3,067,004 (1962). 25. Copolymers of Styrene, Vinylbenzyl Alcohol and Allyl Alcohol, J. G. Abramo, E. C. Chapin (to Monsanto Chemical Co.), U.S. 3,069,399 (1962). 26. Vinylbenzyloxy Phenylbenzotriazoles, J. P. Milionis, W. B. Hardy (to American Cyanamid), U.S. 3,072,585 (1963). 27. Alkylene-Aromatic-Acetamides, J. G. Abramo, E. C. Chapin (to Monsanto Chemical Co.), U.S. 3,073,862 (1963). 28. Ethylencially Unsaturated Benzyl Phosphorus Amides, A. Y. Garner, E. C. Chapin, J. G. Abramo (to Monsanto Chemical Co.), U.S. 3,075,011 (1963). 29. Polymers of Hydroxyalkyl Vinylbenzyl Ethers, J. G. Abramo (to Monsanto Chemical Co.), U.S. 3,079,369 (1963). 30. Coploymers of Vinylbenzyl Alcohol with Vinyl Compounds, J. G. Abramo, E. C. Chapin (to Monsanto Chemical Co.), U.S. 3,093,622 (1963). 31. Vinyl Aromatic Oxymethyl Oxy Compounds, J. G. Abramo, (to Monsanto Chemical Co.) U.S. 3,100,804 (1963). 32. Condensation Polymers of Chloromethyl Aromatics, E. E. Harris (to Olin Mathieson Chemical Corp.), U.S. 3,105,054 (1963).

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33. Monomeric Alkenyl Benzyl Polyglycol Ethers, S. C. Stowe (to The Dow Chemical Company), U.S. 3,190,925 (1965). 34. Preparation of Lithium Substituted Polystyrene Polymer, F. C. Leavitt (to The Dow Chemical Company), U.S. 3,234,196 (1966). 35. S-(4-Vinylbenzyl)-Isothiourea and Isothiouranium Chloride, S. J. Nelson (to United States Rubber Co.), U.S. 3,260,748 (1966). 36. 2-Aryl-Polyhalo-Bicyclohept-5-enes, C. W. Roberts, D. H. Haigh (to The Dow Chemical Company), U.S. 3,378,580 (1968). 37. 2-{p-(Halogenated-Bicyclo-{2.2.1}-Hept-5-en-2-yl) Benzyl}-2-Thiopseudo Urea Compounds, C. W. Roberts, D. H. Haigh (to The Dow Chemical Company), U.S. 3,283,004 (1966). 38. 3-(Polyhalobicyclo-{2.2.1}-Hept-5-en-2-ylBenzylthio)-Alanine, C. W. Roberts, D. H. Haigh (to The Dow Chemical Company), U.S. 3,293,287 (1966). 39. Polyhalobicyclo-{2.2.1}-Hept-5-en-2-yl-Benzyl Guanidines, C. W. Roberts, D. H. Haigh (to The Dow Chemical Company), U.S. 3,238,259 (1966). 40. Soil and Method of Improving, W. G. Lloyd, C. W. Roberts, B. J. Thiegs (to The Dow Chemical Company), U.S. 3,121,972 (1964). 41. Cross-linked Chelating Resins, D. P. Sheetz (to The Dow Chemical Company), U.S. 3,134,740 (1964). 42. Process for Water-Soluble Sulfonium Polymers, W. G. Lloyd (to The Dow Chemical Company), U.S. 3,236,820 (1966). 43. Isobutylene Copolymers of VBC and Isopropenylbenzyl Chloride, G. D. Jones, J. R. Runyon, and J. Ong. J. Appl. Polymer Sci., 5, 452 (1961).

44. High Molecular Weight Polycationics, W. G. Lloyd and J. F. Vitkuske, J. Appl. Polymer Sci., 6, S57-S59 (1962). 45. Grafting of Vinylbenzyl Chloride to Polypropylene Fibers by the Use of Ionizing Radiation, U.S. Atomic Energy Comm. TID-7643, pp. 345-97 (1962). 46. Chemical Reactions of Poly-p-Vinylbenzyl Chloride Resin in Dimethyl Sulfoxide, J. T. Ayres and C. K. Mann, J. Polymer Sci., Pt B-3(6), 505 (1965). 47. Chemical Structure and Electrostatic Property of Polymers, E. Tsuchida, M. Kitajima, T. Yao, I. Shinohara, Kogyo Kagaku Zasshi, 69(10), 1978 (1966). 48. Synthesis and Reactions of Polymers Containing Nicotinamide, Y. Kurusu, K. Nakajima, M. Okawara, Kogyo Kagaku Zasshi, 74(6), 934 (1968). 49. Sulfonium Polymers Derived from ar-Vinylbenzyl Chloride, M. J. Hatch, F. J. Meyer, W. G. Lloyd, J. of Appl. Polymer Sci., 13, 721 (1969). 50. p-Vinylbenzyltrialkyl Ammonium Salts in Vinyl Polymerization, G. D. Jones, S. J. Goetz, J. of Polymer Sci., 25, 201 (1957). 51. A Conductometric Study of Polycation-Polyanion Reactions in Dilute Aqueous Solution, A. S. Micheals, L. Mir, and N. S. Schneider, J. of Physical Chemistry, 69(5), 1447 (1965). 52. Polymers of Ethylenimine and Its Derivatives, G.D. Jones, N.B. Tefertiller, B.P. Thill, Polymer Preprints, 10(2), 1368 (1969).

53. Kinetic Observations of the Quaternization of Poly-(ar-vinylbenzyl chloride) with Trimethylamine, W. G. Lloyd, T. E. Durocher, J. Appl. Polymer Sci., 8, 953 (1964). 54. Partial Amino Acid Resolutions on a New Resolving Resin, C. W. Roberts, D. H. Haigh, J. Org. Chem., 27, 3375 (1962). 55. Electroconductive Coated Paper and Method of Making Same, L. H. Silvernail, M. W. Zembal (to The Dow Chemical Company), U.S. 3,011, 918 (1961).

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VBC Vinylbenzyl Chloride

A dual functional monomer you can polymerize or copolymerize before or after functional group reactions

In the U.S. and Canada, call 1-800-447-4369 or fax 989-832-1465 In other areas of the world, call 989-832-1560 or fax 989-832-1465 www.dow.com
Notice: No freedom from any patent owned by Dow or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customers use and for ensuring that Customers workplace and disposal practices are in compliance with applicable laws and other government enactments. The product shown in this literature may not be available for sale and/or available in all geographies where Dow is represented. The claims made may not have been approved for use in all countries. Dow assumes no obligation or liability for the information in this document. References to Dow or the Company mean The Dow Chemical Company and its consolidated subsidiaries unless otherwise expressly noted. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED. Published June 2010

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