VBC A dual functional monomer you can polymerize or copolymerize before or after functional group reactions Vinylbenzyl Chloride
Oct 25, 2014
VBCA dual functional monomer you can polymerize or copolymerize before or after functional group reactions
Viny
lben
zyl C
hlor
ide
2
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
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).
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
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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.
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.
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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® 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).
7. M. J. Hatch (to The Dow Chemical Company),
U.S. 3,205,184 (1995).
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
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:
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).
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
(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).
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
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).
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).
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
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.
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
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).
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
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).
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
(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).
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