Note: Descriptions are shown in the official language in which they were submitted.
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C~OS~-LINKED WATER-SWELLABLE INDENE-MALEIC
ANHYDRIDE INTERPOLYMERS
This invention relates to water-swellable polymers of
an indene-maleic anhydride-cross-linking monomer and to a method
for preparation of same.
We have discovered that water thickeners of excellent
efficiency can be prepared by polymerization of monomeric
mixturesof maleic anhydride, indene and a cross-linking agent
containing a plurality, i.e. more than one of polymerizable
CH2= C/ groupings. Such polymeric compounds are useful as
water thickeners and suspending agents which have utility in
cosmetics, pharmaceuticals, cleaning and polishing compounds,
latex coating applications, textile printing, well drilling
and water purification.
In addition to the maleic anhydride and indene, a
third essential monomer for use in the preparation of the
compositions of this invention may be any polymerizable
material which contains a plurality of polymerizable CH2'C~
groupings and which is reactive with maleic anhydride and
indene in their copolymerization. Polyunsaturated hydrocarbons,
esters, amides, nitriles, acids, sulfones, polyunsaturated acid
anhydrides, polyunsaturated ethers such as divinyl ether,
diallyl ether, diallyl ethylene glycol ether, 1,4,5,8-
naphthalene tetrol ethers, the vinyl, allyl, methallyl and
crotyl polyethers containing 2 to 7 or more alkenyl ether
groups per molecule, polyunsaturated ketones such as divinyl
ketone, diallyl ketone,allyl-beta-allyloxy propionate, allyl
methacrylyl sucrose, monoallyl maleate, and partial allyl
ethers of polyhydric alcohols such as diallyl glycerol ether.
A preferred group of polyolefinic monomers in the
present invention includes divLnyl benzene, trivinyl benzene,
diyinyl naphthalene~ tXi~llXl c~nux~te~ methylene-bis-
acrylamide, methylene-~is-methacrylamide, triacrylyl triazine,
trimethacrylyl triazine, hexaallyl trimethylene trisulfone,
tetraallyl methane, tetra~utenyl methane, tetraallyl silane,
tetravinyl silane, tetraallyl germane, tetravinyl germane,
ethylene glycol diacrylate, pentaerythritol tetraacrylate,
allyl acrylate, allyl cinnamate, diallyl maleate, diallyl
phthalate, divinyl ether, diallyl ether, 3,9-divinyl-
2,4,8,10-tetraoxospiro [5,5]undecane, divinyl ketone,
lQ polyalkenyl polyethers of polyhydric alcohols such as polyallyl
sucrose, tetraallyl pentaerythritol, and the like.
The amount of cross-linking agent can vary from 0.01%
to about 10% by weight of the other monomers.
Because maleic anhydride and indene evidence a strong
tendency to form alternating copolymers, it is not practical to
use monomeric proportions which vary far froma l:l molar ratio
of these materials. In the polymerization process of this
invention, it is greatly preferred to use monomeric mixtures in
which the maleic anhydride and indene are present in
substantially equimolar proportions and in which the cross-
linking agent can be varied in order to obtain the properties
desired in the terpolymer. If proportions of maleic anhydride
and indene other than equimolar are usedl the yield of polymer
is ~reatly reduced, and the polymer obtained will usually
contain a relatively greater proportion of cross-linking agent
than is represented in the original monomeric charge.
The polymers of this invention are prepared by
polymerization of maleic anhydride, indene and the cross-
linking agent in an inert diluent having some solubilizing
action on one or more of the monomeric ingredients but
substantially none of the resultant polymer. Polymerization
in mass may be employed but is not preferred because of the
)4.~
incomplete conve~sion~ And the di~iculty encounte~ed in the
work-up of the solid masses obtained. Polymerization in an
organic liquid ~hich is a solvent ~or the monomers but a
non-solvent for the polymer, or a mixture of such solvents, in
the presence of a solvent-soluble catalyst is most preferred
because the product is usually obtained as a very fine friable
and often fluffy precipitate which, after solvent removal,
seldom requires grinding or ot~er ~urther treatment before use.
Suitable solvents for the process of this invention include
benzene, xylene, tetralin, hexane, heptane, carbon tetrachloride,
methyl chloride, ethyl chloride, bromo trichloro methane, and
others, and mixtures thereof.
Polymerization in the organic diluent medium may be
carried out in the presence of a free-radical initiator in a
closed vessel in an inert atmosphere and under autogenous
pressure or in an open vessel under reflux at atmospheric
pressure. The temperature of polymerization may be varied from
0 C or lower to 1~0 C or higher depending to a large degree on
the molecular weight desired in the polymer.
The following examples are given to further illustrate
the products and process of this invention and are not meant to
limit the scope of this invention. The amounts of ingredients,
unless otherwise indicated, are given in parts by weight.
Example 1
A. A terpolymer of indene, maleic anhydride and
divinyl benzene was prepared from the following ingredients:
'Ingredient Parts
benzene 300
indene 54
maleic anhydride 46
divinyl benzene (active) 0.50
a,a'-azobisisobutyronitrile catalyst 0.3
X -3-
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The in~redients ~ere combined in a reactor which was
then purged with nitrogen and sealed. The polymerization
reaction was carried out at 60 C with agitation of the reaction
mixture for 4 hours. The solid white polymer which resulted was
isolated by filtration. The polymer was dried. A 1% by weight
solution of the polymer in dilute aqueous ammonia gave a
Brookfield viscosity (model LVT Spindle 4, 6 rpm) of 30,500
centipoises.
B. A repeat of A above in which no divinyl benzene
was employed gave a polymer which had the following Brookfield
viscosity: 10 centipoises.
C. A series of polymers in which the amount of
divinyl benzene was varied was prepared in accordance with A
above and the following aqueous Brookfield viscosities at 0.6 rpm
were obtained:
Divinyl Benzene Viscosity
Charged (Parts) (Centipoises)
0.25 6J500
0.50 112,000
0.75 23,000
.
Example 2
The procedure of Example lC was repeated using
N,N'-methylene-bis-acrylamide in place of divinyl benzene. The
resulting polymers at 1% in aqueous ammonia were found to have
the following Brookfield viscosities at 0.6 rpm:
N,N~-Methylene-Bis- Viscosity
Acrylamide (Parts) (Centipoises)
1.0 1,150
1.5 124,000
4~0 51,000
'Example 3
The procedure o~ Example lA was repeated except that
8 parts o~ triallyl cyanurate w~re used in place of the divinyl
--4-
X
(,r~
benzene. The Brook~ield Yi~C~sity of a 1% solution of the
resulting polymer in dilute aqueous ammonia was found to be
5,000 centipoises at 0.6 rpm.
... . ..
Example 4
The procedure of Example 3 was repeated using
3,9-divinyl-2,4,8,10-tetraoxospiro ~5,5]undecane in place of
triallyl cyanurate. The Brookfield viscosity of the resulting
polymer at 1% in dilute aqueous ammonia was found to be 170
centipoises at 0.6 rpm.
X ~5
