CS262091B1 - Copolymers of dimethylalkyl/3-maleinimidophenyl/ammonium halogenide and process for preparing them - Google Patents

Description

The present invention provides copolymers of dimethylalkyl (3-maleinimidophenyl) ammonium halide containing repeating units of formula I,

CHCHX (n in which

R ¹ is hydrogen or OH 3,

^Rz is CH3 or C2H5, and X is iodo, bromo or · chlorine with unsaturated compounds containing terminal group - CY = CH 2 in which Y is 262,091 hydrogen or methyl group, selected from vinyl aromatic and acrylic monomers, conjugated marrow and isobutylene, wherein the molar ratio of the units of formula I to the comonomer units is from 1 to 0.01.

The unsaturated compounds may be monomers that are radically homopolymerized or copolymerized, such as styrene, methyl methacrylate, acrylonitrile, isobutylene, N- (3-dimethylaminoaryl) maleimide and butadiene.

The copolymers according to the invention can be prepared according to the desired composition in the following ways:

Process for preparing the copolymers of the present invention containing repeating units of formula I wherein R ¹ is as defined above, R ² is CH 3 and X is iodo, characterized in that the monomer mixture obecněného formula II

where

R ¹ , R ² and X are as defined above, with unsaturated compounds having a terminal group -CY = CH 2 in which Y is hydrogen or CH 3 selected from vinylaromatic monomers, acrylic monomers, conjugated dienes and isobutylene, wherein: the molar ratio of units II to comonomer units is from 1 to 0.01, acting as a initiator of radical polymerization at the initiator decomposition temperature to initiate polymerization centers. Any conventional initiator or initiator system used in the free-radical polymerization of known monomers with olefinic C = iC bonds in the molecule can be used to initiate the copolymerization. The molar ratio of trimethyl (3-maleimidimidophenyl) ammonium iodide to comonomer may vary from 1 to 0.01. A solvent such as dimethylformamide, acetonitrile or dimethyl sulfoxide is added to homogenize the reaction mixture. Depending on the nature of the initiator used, the polymerization temperature is chosen such that the active initiator centers are formed at a sufficient rate.

Process for preparing the copolymers of the invention contain units of formula I wherein R ¹ and R ² are as defined above and. X is iodine or bromine, characterized in that the copolymers of N- (3-dimethylanunofenyljmaleinimidu comprising repeating units of the general formula III ,

(III) where

R ¹ has the abovementioned meaning, with compounds containing unsaturated end group -CY = CH 2 in which Y is as defined above, selected from vinylaromatic monomers, acrylic monomers, conjugated dienes and isobutylene, the molar ratio of units to units III comonomer from 1 to 0.01, quaternizes alkyl halides of the formula R ² X, wherein R ² is as defined above and X is an iodine or bromine atom. The quaternization is carried out at room or elevated temperature in the presence of a polar solvent such as acetone, dimethylformamide, acetonitrile and methanol. The concentration of the alkylating agent can be varied according to the desired degree of quaternization.

Process for preparing the copolymers of the present invention containing repeating units of formula 1 wherein R ¹ and R ² are as defined above and X represents chlorine, characterized in that the copolymers of the invention wherein in formula IR ¹ and R ² have the above and X represents bromine or iodine, acting with an aqueous solution of ammonium hydroxide or sodium hydroxide, first converting bromine or iodine to a hydroxyl group, which is then exchanged for chlorine with dilute hydrochloric acid. The concentrations of the aqueous solutions of ammonium hydroxide (NH 3 OH) and sodium hydroxide (NaOH) and hydrochloric acid (HCl) used are between 2 and 5% by weight.

The process for preparing dimethylalkyl (3-maleimidophenyl) ammonium halide copolymers is illustrated by the following examples.

He did

Polymer feedstock containing 1 g of trimethyl (3-maleinimldo-4-methylphenyl) ammonium iodide of mp 192 ^Q C, 2 g of styrene and 0.03 g of 2,2'-azobis (lsobutyronitrilui) in 10 cm ² with DMF in a glass ampoule, it is freed of air oxygen by alternate evacuation and flushing with nitrogen, the ampoule is sealed and left in a thermostat for 24 hours at 50 ° C. The reaction mixture was then concentrated in a vacuum evaporator and a white copolymer (1.37 g, i.e. a 45.7% conversion) precipitated with a 6-fold amount of ethanol. After extraction with ethanol, washing with water and drying, it contains 17.39% J, corresponding to 51% (22.55% by weight) of trimethyl (3-maleimido-4-methylphenyl) ammonium iodide in the copolymers.

Example 2

1 g of trimethyl (3-maleimido-4-methylphenyl) ammonium iodide, 2 g of methyl methacrylate and 0.03 g of 2,2'-azobis (isobutyronitrile) in 7 cm ^{3 of} dimethylformamide are polymerized in the same manner as in Example 1. 1.61 g (53.7% conversion) was precipitated with ethanol from a chloroform solution, and the content of 5.67% J found was 16.63% (by weight (4.51%)) of trimethyl (3-maleimido-4-). methylphenyl) ammonium iodide in copolymers.

Example 3

A solution of 0.7 g of trimethyl (3-maleimidophenyl) ammonium iodide, mp 199 ° C, 2 g of acrylonitrile and 0.03 g of 2,2'-azobis (isobutyronitrile) in 8 cm is polymerized in the same manner as in Example 1. ³ dimethylformamide. The prepared copolymer (2.55 g, i.e. 94.4% conversion) contains, after extraction with ethanol, 8.22 percent J, i.e. 23.20 wt% (4.28 percent molar) trimethyl (3-maleimidophenyl) ammonium iodide.

202091

Example 4

In the same manner as in Example 1, a batch of 0.8 g of trimethyl-5-maleimido-4-methylphenyl jamonium iodide, 0.28 g of isobutylene and 0.03 g of 2,2'-a, z-bis (isobutyronitrile) was polymerized. in 8 cm ^{3 of} dimethylformamide. 0.60 g (65.2% conversion) of the alternate copolymers are obtained having a content of 29.63% J.

Example 5

According to MS. No. 176 842, a copolymer of N- (3-dimethylamino-6-methylphenyl) maleimide with styrene containing 56.85% by weight (37.34% by mol) of an imide having a viscosity limit of 20 ° C in dimethylformamide of value of ⁵ g 53.0 cm ^_1. To 0.80 g of this copolymer in 10 cm ^{3 of} acetone is added 0.42 g of methyl iodide and the solution is allowed to stand at room temperature for 24 hours. The precipitated product (0.90 g) was extracted with ethanol. The content of 5.35% N and 15.76% J found was 46.22% (22.18% by weight) of trimethyl (3-maleimido-4-methylphenyl jamonium iodide), 38.42% (65.90% by weight) styrene and 15.36% (11.92 mole%) of unreacted imide in the copolymers.

Example 6

A copolymer containing 39.89% (21.28% by weight) of N- (3-dimethylaminophenyl) maleimide and 60.11% (78.72% by weight) of methyl methacrylate is prepared and quaternized in the same manner as in Example 5; the limit viscosity number in dimethylformamide at 20 ° C is 30.7 cm ³ g ^-1 . From 1 g of this copolymer in 10 cm ^{3 of} acetone with 1 g of methyl iodide, after 48 hours, 1.20 g of quaternized product is obtained. According to the found content of 3.87% N and 16.02% J, the prepared copolymer after extraction with ethanol contained 45.22% by weight (17.28% by mole) of trimethyl (3-maleimimidophenyl) ammonium iodide, 5'2.50% by weight ( 81.09 mol% of methyl methacrylate and 2.58 wt% (1.63 mol%) of unreacted imide.

Example 7

In the same manner as in Example 5 was prepared and quaternized alternance kopolymler N- (3-dimethylamino-6-methylphenyl) maleimide-butadiene copolymer whose intrinsic viscosity in dimethylformamide at 20 ^Q C has a value of 19.3 cm ³ g ^-1. Treatment of 1 g of methyl iodide with 0.65 g of this copolymer in 5 cm ^{3 of} acetone gives 0.80 g of product in 70 hours at room temperature which, after extraction with ethanol, contains 6.55% N and 29.7% J. trimethyl (3-maleimido-4-methylphenyl) ammonium iodide with butadiene.

Example 8

In the same manner as in Example 5, an alternate copolymer of N- (3-dimethylamino-6-methylphenyl) maleimide with isobutylene was prepared and quaternized whose viscosity limit in dimethylformamide at room temperature was 8.4 cm ³ g ^-1 . This copolymer is obtained by treatment with 1 g of methyl iodide for 48 hours at room temperature of 1.35 grams of the quaternized product.The content of 6.51% N and 29.50% J corresponds to the alternating copolymers of trimethyl (3-maleimido-4-methylphenyl) ammonium iodide with isobutylene.

Example 9

1 g of the N- (3-dimethylamino-6-methylphenyl) maleimide-styrene copolymer described in Example 5 is dissolved in 10 cm ³ and 1.10 g of ethyl bromide are added to the solution, and the reaction mixture is allowed to stand at room temperature for three days. then concentrated to dryness in a vacuum evaporator and the remaining copolymer extracted with ethanol containing 2.511% Br and 6.84% N, corresponding to 10.69% by weight (4.98% mole) of dimethylethyl (3-maleimido) 4-methylphenyl) ammonium bromide, 40.34 wt% (61.34 wt%) styrene and 48.97 wt% (33.68 wt%) of the imide.

Example 10

For 0.5 g of copolymers containing 46.22% by weight (22.18% by weight) of trimethyl (3-maleimido-4-methylphenyl) ammonium iodide, 38.42% by weight of (65.90% by weight) styrene and 15 36% by weight (11.92 mole%) of N- (3-dimethylamino-6-methylphenyljmaleinimide, the preparation of which is described in Example 5) are treated alternately at four-hour intervals at room temperature of 100 cm ^{3 of} 0.05 N ammonium hydroxide (NH 4 OH) ) and 100 cm @ ^{3 of} 1N hydrochloric acid (HiCl) After the procedure is repeated three times, the copolymer is washed with water until neutral. The concentration of chloride ions exchanged with iodide ions in the starting copolymers is determined by titration: The copolymer is allowed to stand for 16 hours. 100 cm ^{3 of a} 4% neutral aqueous sodium nitrate solution (NaOH 3), which is then titrated with 0.01 N mercuric perchlorate [Hg (C104] 2], found at 1.2 milliequivalents g ^-1 Cl indicates complete conversion of the starting iodide to chloride .

Example 11

In the same manner as in Example 10 was carried out an ion exchange reaction with 0.8 g kopo262091 interpolymer dimethylethyl (3-maleimido-4-methylfenylj ammonium bromide jebož preparation described in Example 9. The designated content mlliekvivalentu 0.3 g ^_1 Cl corresponds to complete conversion of the starting bromide to chloride.

Copolymers of dimethylalkyl (3-maleimidoaryl jammonium halide) may find use as ion exchange materials (anion exchange materials and materials for selectively permeation and electrochemically active membranes. They can also be used as adhesives, flocculating, emulsifying and dispersing agents.

The quaternized copolymers of N- (3-dimethylaminoarylmaleinimide containing unreacted tertiary amino groups) can be crosslinked by the action of peroxides and halogenated compounds. Bezděk M., Hynek V., Bouchal K., Hraibák F.: Europ, Polymer J. 8, 1333 (1972) In addition to copolymerization of dimethylalkyl (3-maleimidoaryl) ammonium halide with ethylenically unsaturated compounds in the presence of known crosslinkers (divinylbenzene, glycol dimethacrylate), this method represents another possibility for obtaining three-dimensional anionic polymers.

Claims (4)

Subject JX ^ Copolymers of dimethylalkyl (3-maleimido-phenyl) ammonium halide containing the repeating units of formula I, IN INVENTION (!) In <which R ¹ is H or CH 3, ^R2 is CH3 or C2H5, and X is an iodine, bromine or chlorine atom, with unsaturated compounds containing the term —CY = CH2, wherein Y is hydrogen or methyl, selected from vinyl aromatic and acrylic monomers, conjugated dienes and isobutylene, wherein the molar ratio of units of formula I to the comonomer units are from 1 to 0.01. 2. Process for preparing the copolymers according to claim 1 containing repeating units of formula I wherein R ¹ is as defined in claim 1, ^R2 is CH3 and X is iodine, wherein the mixture of a monomer of Formula II wherein R ¹ , R ² and X are as defined above, with unsaturated compounds having a terminal group -CY = CH 2 wherein Y is hydrogen or CH 3 selected from vinylaromatic monomers, acrylic monomers, conjugated diapers and isobutylene, wherein the molar molar the ratio of units II to comonomer units is from 1 to 0.01, causing a radical polymerization initiator to initiate polymerization centers at the initiator decomposition temperature. 3. Process for preparing the copolymers according to claim 1, comprising units of the general, formula I, wherein R ¹ and R ² are as defined in claim 1 and X is iodine or bromine, characterized in that the copolymers of N ^J (3-dimethylamlnofenyljmaleinlmldu comprising repeating units of formula III, (III) wherein R ¹ is as defined in item 1, with unsaturated compounds having a terminal group —C'Y = H2H2, in which Y is as defined above, selected from vinyl aromatic monomers, acrylic monomers, conjugated dienes and isobutylene, wherein the molar molar the ratio of units III to comonomer units is from 1 to 0.01, quaternizing the alkyl halides of the general formula R ² X, wherein R ² is as defined in item 1 and X is an iodine or bromine atom. 4. Process for preparing the copolymers of claim 1 comprising repeating units of formula I wherein R ¹ and R ² are as defined in claim 1 and X represents chlorine, characterized in that the copolymers are characterized in claim 1, where formula IR ¹ and R ² are as defined in claim 1 and X is bromo or iodo, with an aqueous solution of ammonium hydroxide or sodium hydroxide, which was first exchanged bromine or iodine for a hydroxyl group which is then replace the effect of dilute hydrochloric acid chlorine.