0901b803804d9caf

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

Viny

lben

zyl C

hlor

ide

3

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

4

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

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

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 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.

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

Reacting VBC before or after polymerization

5

Typical Monomers

• Butadiene/Isoprene • AcrylicAcid/MethacrylicAcid/ FumaricAcid/MaleicAnhydride • Acrylamide/Methacrylamide • Fumarates/Maleates • Styrene/α – Methyl Styrene • Isobutylene • Acrylonitrile/Methacrylonitrile • Acrylates/Methacrylates

Note: Polymerized by Catalysis Free Radical – Mass – Suspension – Emulsion – Solution Ionic Friedel-Crafts

Typical Reactants Vapor Pressure of VBC

Table 1 Physical Properties1

Appearance Pale yellow to water white liquid Purity ~96% IsomerRatio ~43%para/57%metaMolecular Weight 152.62 Freezing Point Range -26.2°C to -42.3°C Boiling Point (at 760 mm Hg) 229°C HeatofFusion,cal/gm 15.73Viscosity cps @ 25°C 1.832 Refractive Index, nD

25 1.5702 Density, gm/ml,20°C 1.083 lbs/gal,20°C 9.037Thermal Expansion Coefficient 1.51x10-3ml/g/°CGlass Transition Temperature, °C 82 Flash Point (Cleveland Open Cup) 220°F (104.4°C) Fire Point (Cleveland Open Cup) 260°F (126.6°C) HeatofPolymerization@195°C -15.4Kcal/moleAuto-Ignition Temperature 610–620°C Solubility of VBC in H2O@25°C 0.073gm/lSolubility of H2OinVBC 0.6gm/lHeatofVaporization °C cal/gm 157.2 79.83 228.0 72.05VBC is soluble in most common organic solvents1These are typical properties and are not to be construed as specifications.

6

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)

2. Vinylbenzyl Thioacetate(B)

3. Vinylbenzyl Alcohol(C)

4. Vinylbenzyl Diethyl Phosphonate(D)

5. Vinylbenzyl Trimethyl Ammonium Chloride(E, F)

CH = CH2

CH2Cl

HO NaOHBr

CH = CH2

CH2O Br

7

References

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).

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).

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


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).

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

7. Vinylbenzyl Sulfonium Chlorides(I, J)

8. Vinylbenzyl Phosphonium Chlorides(K)

9. Vinylbenzyl Sulfonate(L)

10. Vinylbenzyl Polyglycol Ethers(M)

8

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.

1. VBC can be used to create polyelectro-

lytes 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,

Bender’s salt, and many others in place of

the chloride.

4. The chloride of the chloromethyl group of

VBC can also be replaced by biochemical,

light-absorbent compounds such as chloro-

phyll, 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 photocon-

ductive 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

9

7. Substituting oxyphosphorated or silicated

compounds for the chloride in VBC produces

fire-resistant polymers. Similar fire

resistance is observed when VBC is copoly-

merized 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.

Table 2 Monomer Reactivity Ratios

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

References

1. M. Camps, M. Chatzopoulos, J. P. Montheard,

J. Macromol. Sci, Rev. Macromol. Chem. Phys.,

C22(3), 343-407 (1982-83).

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).

10. Modified VBC has also been used as

bioactive templates and to fix carbohy-

drates.

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.

10

Polymerization

Vinylbenzyl chloride has been

homopolymerized and copolymerized using

solution, mass, emulsion, and ionic polymer-

ization 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 2–3 minutes. After purging with

nitrogen, the sample is sealed under vacuum.

The vessel is then placed in a controlled

temperature water bath at 80°C until the

monomer has solidified, after which it is

transferred to an air oven for 24 hours at

115°C. If it is desirable to remove the

volatiles, the polymer can be dissolved in

methyl ethyl ketone (5% solution) and

precipitated into alcohol. The polymer can

then be removed by filtration and dried.

Price-Alfrey Copolymerization Parameters

Q Value e Value VBC 1.06 -0.45

11

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.

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 30°C and agitated at

12 rpm for 18 hours.

*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.

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

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.

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 60°C 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.

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.

12

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® non-

stick 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 and handling

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 80°F. For storage periods longer than

thirty days, refrigeration—even down to

freezing temperatures—is 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 0°C will

extend its useful life significantly.

13

1Trademark of E.I. duPont de Nemours & Co.

2Trademark of Pennwalt Corp.

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.

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 recom-

mended. 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

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 polyethyl-

ene 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

pressurebuildupfromheatand/or

polymerization.

14

DISTRIBUTION EMERGENCIES AND CHEMICAL EMERGENCIES

INVOLVING EXPOSURES, LEAKS, OR SPILLS

Call: 1-989-636-4400or

CHEMTREC (day or night)Toll free 1-800-424-9300

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. Polymer-

ization 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

DistributionEmergencyResponse(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,apartofDow’scommitmentto

product stewardship, provides a quick and

reliable resource for those facing a

chemical emergency.

*Trademark of The Dow Chemical Company

15

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

present, TBC prevents polymerization by

reacting with oxidation products (monomer

peroxy-free radicals) in the monomer.

However, in the absence of oxygen, polymer-

ization 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 min-

imum 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.

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

Effect of Inhibitor and Oxygen on the Shelf Life of Styrene at Various Temperatures

12 ppm TBC 50 ppm TBC Saturated with Less Than Saturated with Temp. Oxygen 3 ppm Oxygen Oxygen 60°F 6 mo. 10 to 15 days More than 1 year 85°F 3 mo. 4 to 5 days 6 months 110°F 8 to 12 days Less than 24 hours Less than 30 days

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.

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.

16

Typical TBC Depletion Rates

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

80°F are normally encountered, the

monomer bulk storage installation should

be refrigerated. For storage of more than

six months, temperatures ≤ 45°F are

recommended.

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.

17

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.

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.

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

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

between630and1,260mg/kgbodyweight.

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.

Toxicity, safety precautions, and first aid

18

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

and1,000mg/kg.

When handling VBC, wear clean, body-

covering 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.

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.

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-

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

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.

19

†Reference paragraph on Skin Contact, page 18.

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.

Environmental Monitoring

Dow has a validated method for monitoring

VBC in an industrial environment. Contact

Dow for detailed information about this

monitoring technique.

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.

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. Labora-

tory experience with VBC has also shown

that polyvinylalcohol gloves are more

resistant as are certain polyamides

and polyesters.

Gloves

Composition Break- through TimeNorth B161 Butyl Rubber 16 hrs.

Pioneer AF-18 NBR 70 min.

Edmont 9-924 Lined Neoprene 70 min.

Edmont 29-865 Unlined Neoprene 40 min.

Pioneer U-5 PVC 6 min. (Quixam) (disposable)

Edmont Polyethylene 3 min. 35-725 (disposable)

Suits

Composition Break- through TimeSARANEX* SARANEX Film 10 hrs. Film coating Tyvek1 nonwoven fabric

Marathon Neoprene/ 14min. Slicker Suit Nylon (400 series)

Uniroyal PVC/Nylon 11min. 2000 Suit

Marathon Neoprene/ 9min. Slicker Suit Nylon (flame (800 series) retardant) NOTE: Seams should be heat sealed not sewn. *Trademark of The Dow Chemical Company1Trademark of E.I. duPont de Nemours & Co.

Respirators

Four respirators were tested: U.S. Safety

organicvapor,U.S.Safetyorganicvapor/acid

gas,AOorganicvapor/acidgas,andWillson

organicvapor/acidgasrespirators.Eachwas

subjected to a 65 ppm concentration of VBC

(~197 ppm constitutes a saturated atmo-

sphere) at humidity levels of 20% and 80%.

All of the respirator cartridges tested

provided a minimum of 40 hours of service

before breakthrough.

20

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.

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. D’Alelio (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).

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).


U.S. 3,205,184 (1995).


U.S. 3,277,023 (1966).


U.S. 3,300,416 (1967).


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

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.KokaiTokkyoKohoJP56/

32462{81/32462},1Apr1981,6pp.,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, Han’guk 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

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).

Patents and references involving VBC monomer

21

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).

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.JapanKokaiJP50/4077{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.

KokaiTokkyoKohoJP57/73735A2{82/73735},

8 May 1982, 11 pp., Japanese.

6. “Photosensitive resin for photomechanical printing

platemaking,” Mitsubishi Petrochemical Co., Ltd.,

Japan,Jpn.KokaiTokkyoKohoJP58/216242A2

{83/216242},15Dec1983,8pp.Japanese.

Plastics

1. “2-Hydroxybenzophenone derivatives, UV

absorbents for plastics,” Kamogawa, Hiromi,

Agency of Industrial Sciences and Technology,

Japan,JapanJP50/20059{75/20059},11Jul

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.

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).

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-oza-

10-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.

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:


U.S. 3,118,831 (1964).

2. R. A. Mock, L. R. Morris (to The Dow Chemical

Company), U.S. 2,840,603 (1958).


U.S. 3,300,416 (1967).


U.S. 2,888,441 (1959).

22

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 Hüls 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).

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).

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


(2002).

3. Ink Jet Printing Method, Elizabeth A. Gallo


(2002).

4. Ink Jet Printing Process, Charles E. Romano


(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

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. ),

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).

23

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).





Dyes

1. “Strong cationic group-containing polymeric

colors,” Shigehara, Kiyotaka; Tsuchida, Eishun,

Japan,Jpn.KokaiTokkyoKohoJP53/137228

{78/137228},30Nov1978,6pp.Japanese.

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).

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

58/105235A2{83/105235},12Jun1983,6pp.,

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.

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-CatalyticProductionofBisphenolA,

Jean-Roger Desmurs, (to Rhone-Poulenc Chimie),

US 5,105,027 (1992).

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).

24

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.KokaiJP49/127999

{74/127999},7Dec1974,3pp.,Japanese.

6. “Styrene derivatives having a formyl group, “

Satomura, Masato, Fuji Photo Film Co., Ltd.,

Japan.KokaiJP49/95930{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


Federick P., The Dow Chemical Company, USA,


3,963,684, English.

16. “Vinyl benzyl ethers and nonionic water soluble


Frederick P., The Dow Chemical Company, USA,


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.

25

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.-USSRPolym.Symp.{Proc.},2nd,249-59.Soc.

Polym. Sci., Jpn.; Tokyo, Japan, English.

20. “4-Isobutylstyrene,” Mitsubishi Petrochemical Co.,

Ltd.,Japan,Jpn.KokaiTokkyoKohoJP59/1431

A2{84/1431},6Jan1984,4pp.,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 amino-

protecting 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-N-

methylamino)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,” Villedon-

Denaide, 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, self-

extinguishing films and electroconductive

resins. References to these applications and

others are listed below.

1. Vinylbenzyl Sulfonium Salt, G. R. Geyer (to The


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


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


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).

26

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


18. Vinylbenzyl Dialkyl Phosphonates and Preparation

Thereof, E. L. McMaster, W. K. Glesner (to The


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


(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


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


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).

27

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-ThiopseudoUreaCompounds,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-yl-

Benzylthio)-Alanine, C. W. Roberts, D. H. Haigh


(1966).

39.Polyhalobicyclo-{2.2.1}-Hept-5-en-2-yl-Benzyl

Guanidines, C. W. Roberts, D. H. Haigh (to The


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


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).

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 Customer’s use and for ensuring that Customer’s 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

Printed in U.S.A. *Trademark of The Dow Chemical Company Form No. 504-00026-0610AMS

VBC Vinylbenzyl Chloride

A dual functional monomer you can

polymerize or copolymerize before or after

functional group reactions

To learn more… 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

0901b803804d9caf

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