SU674677A3 - Method of obtaining polyesteramides - Google Patents

Description

(54) THE METHOD OF OBTAINING POLYESTERMS C and where XsCyH y -, - C -, - O - and -S-; and .1; and an organic diamine of the formula D Hj, NR-NHj, where E is a bivalent organo radical selected from the group consisting of aromatic hydrocarbon radicals having 6-20 carbon atoms and their halogenated derivatives, alkylene radicals Cj-Cg, terminated with an alkylene polydioorganosiloxane cycloalkylene radical, and having polydiorganosiloxane cycloalkylene radicals of alkylene radicals having alkylene polydioorganosiloxancycloalkylene radicals, having alkylene hydrocarbon radicals having 2-20 carbon atoms and bivalent radicals of the general formula III O O II II-C-, H2, -, where q,. ABOUT . where X 1-5 m 0-1. The method of preparing polyetherimide consists in carrying out the reaction between an aromatic bis-ester dicarboxylic acid of formula 1 and an organic diamine of formula II in the presence of a non-polar organic solvent, 30 liters of phenol solvent, removing the reactive moisture and separating the polyether imide from the resulting mixture. Compounds of aromatic bis-ether-35 dicarboxylic acids of general formula I have the following formulas IV-VI O-O-0-, 15 20 25 45 50. 55 ®, Tetracarboxylic acids of formula IV include, for example: 2, 2-bis-4- (2, 3-dicarboxyphenoxy) -phenyl propane; 4, {2, 3-dicarboxyphenoxy) diphenyl ether; 1,3-bis- (2,3-dicarboxyphenoxy) benzene; 4, 4-bis- (2, 3-dicarboxyphenoxy) diphenyl sulfide; 1,4-bis- (2,3-dicarboxyphenoxy) -benzene. , Tetracarboxylic acids of formulas and VI include, for example: 2,2-bis-4- (3,4-dicarboxyphenoxy) phenyl propane; 4,4-bis- (3,4-dicarboxylphenoxy) diphenyl ether; 4,4-bis- (3,4-dicarboxyphenoxy) -diphenylsulfide; 1,3-bis- (3,4-dicarboxyphenoxy) -benzene; 1,4-bis (3,4-dicarboxxyphenoxy) benzene; 4- (2, 3-dicarboxyphenoxy) -4- (3, 4-dicarboxyphene. Oxy) -diphenyl-2,2-propane. These tetracarboxylic acids can be obtained by hydrolysis of the product of the reaction of nitro-substituted phenyldinitrile with a metal salt of a diatom of the phenol compound in the presence of „„ „„ „„ „„ „„ „„, „„ effect of dipolar aprotic solvent. For example, a benzoyl compound of the formula where the group is —NO2, can be located anywhere on the benzene ring, can react in dimethylformes with an alkali metal salt of an amide, a diatomic phenol of the basic formula 2 Ek-OPO-AEk where R is a divalent aromatic radical, and Slk is an alkali ion metal. The organic diamines of formula II are, for example: m - phenylenediamine; p - phenylenediamine; 4,4-diaminodiphenylpropane; 4,4-diaminodiphenylmethane; benzidine; 4,4-diaminodiphenylsulfide; 4,4 diaminophenylsulfone, 4, 4-diaminodipheny 1,5-diaminonaphthalene ester; 3 3 -dimethylbeneidine; 3, 3-dimethoxybenzyl; 2, 4-bic- (| ll-a mn-tert-butyl) -toluene; Bis-pp-amino tert-butylphenyl ester; bis (p-methyl-o-aminopentyl) benzene; 1,3-diamino-4-isopropylbenzral; 4,4-dis1minodiphenylbenzophenone; 1,2-bis- (3-aminopropoxy) ethane; m-xylylenediamine n-xylylenediamine; 2,4-diaminotoluene 2,6-diaminotoluene; bis (4-aminocyclohexyl) methane; 3-methylphenylamine) zmin; 4,4-dimethylheptamethylenediamine; 2.11-lodecanediamine; 2,2-dimethylpropylene diamine; octamethylenediamine; 3-methoxy hexamethylenediamine; 2,5-dimethylhexa methylenediamine; 2,5-dimethylheptamethylenediamine; 3-methylheptamethylenediamine 5-methylnonamethylenediamine; 1,4-cyclohexanediamine; 1,12-octadecandiamine; bis-3-aminopropyl sulfide; N-methyl-bis- {3-aminopropyl) -amine; hexamethy lendiamine; heptamethylenediamine nonamethylenediamine; decamethylenediamine; bis (3-aminopropyl) tetramethyldisylo san; bis (4-aminobutyl) tetramethyldi siloxane. The non-polar organic solution of bodies that can be used in pure form or as a mixture to carry out the reaction between the aromatic bis-ether dicarboxylic acids of the formula D and the organic diamines of the formula II include, for example, benzene, toluene, xylene, xylene, ethyl benzene , propylbenzene, chlorobenzene dichlorobenzenes, trichlorobenzenes, biphenyl, terphenyl, acetophenone, benzophenitrobenzene, anisole, phenetol, diphenyl ether, diphenylsulfide, chlorinated biphenyls, chlorinated diphenyl ethers, dichloroethane, tetherhene, tetrafenone, tetrafenone, chlorinated biphenyls, chlorinated diphenyl ethers, dichloroethane, tetherhene, tetrafenone, tetrafenone chloroethylene, tetrachlorethylene, methyl cyclohexane, octane, isooctane, decane. Phenol solvents are, for example, phenol, o-, m- and p-chlorophenol O-, P-, and m-cresol, and mixtures thereof known as cresic acid; mixtures of phenol and cresic acid; ethylphenols isopropylphenols, tert-butylphenols, xylenols, phenylphenol .. Polyethyrimide products of the reaction of aromatic bis-ether dicarboxylic acids of the formula I and organic diamines of the formula II are soluble in certain organic solvents and can be cast at temperatures down to the thermoplastic film from the organic solvent solution The preferred class of materials for injection molding are the organic and diamine-derived products of formula II and the aromatic bis-ester dicarboxylic acids of formulas 1V-VI. Pouring temperature is 200-400 ° C, products are soluble in such organic solvents as methylene chloride, chloroform, K, K-dimethylformamide, N, N-dimethyl acetamide metacresol. These reaction products can be enhanced by conventional silicon fillers, for example, perlite, smoky silicon, carbon spirals, glass fibers in proportions of 10-60 parts of filler per 100 parts of polyetherimide. The order of addition of the reagents is not essential. It is preferred to react the tetracarboxylic acid and the organic diamine in an inert atmosphere such as nitrogen. The organic solvent is used in an amount sufficient to provide a solids content of 1-90%. The reaction is carried out at 130-300 0, preferably 1 5 O - 2 5 O C. To ensure optimal contact between the aromatic bis-ether dicarboxylic acid and the organic diamine, the reaction mixture is stirred. The optimum molecular weight of the polymer is achieved by an equal number of moles of reactants; however, 0.5-2 mol, preferably 0.9-1.1 mol of aromatic bis-estercarboxylic acid per 1 mol of organic diamines can be used to obtain effective results. It has been found that the polyetheramide can have 5-500 repeated reaction products of an aromatic bis-ether carboxylic acid-organic diamine, preferably 10-50. May contain end amino groups or phthalic acid groups. The reaction time tetracarboxylic. The acids of formula 1 and the organic diamine of formula II can vary from 0.5 to 20 hours depending on the temperature, the depth of agitation, the nature of the reagents, the solvent used. During the formation of the polymer, the reaction moisture is continuously removed. The course of the reaction is controlled by the true amount of water produced as a percentage of the theoretical amount. In special cases, a mixed solvent system consisting of a low boiling azeotropic solvent and a high boiling solvent can be used. Upon completion of the reaction, the polyetherimide is recovered from the cooled polymer solution by precipitation, for example, with methanol. Example 1. From the corresponding bis-imide on the basis of hydrolysis followed by oxidation of the corresponding salt with a mineral acid, tetracarboxylic acid, 2,2-bis-4- (3,4-dicarboxxy-phenoxy) -phenyl-propane is obtained. Bis-imide is prepared from the corresponding H-phenyl. L-4-nitro-phthalimide with the sodium diphenoxide salt of bis-phenol-A using the following procedure. A mixture of 29.8 g (0.131 mol) of bis-phenol .a-A, 10.44 g of sodium hydroxide in the form of a 50% aqueous solution, 1250 cm of dimethyl sulfoxide and 66 cm of toluene is stirred under nitrogen at reflux for 7 The final drying is carried out by refluxing toluene over a ladder filled with recirculating calcium hydride. The toluene is distilled off and the reaction mixture is cooled to. Then 70.0 g (0.26 mol) of n-phenyl-4-nitrophthalixed and 250 cm of dimethyl sulfoxide are added, the resulting solution is stirred at 60 ° C for 45 minutes and 25 cm 5 of ice neoylacetic acid are added. The reaction mixture is diluted with 1400 g of water, the fine solids are separated and isolated by filtration, washing with water and drying. After recrystallization from acetonitrile and benzene, 44.4 g of white needles are obtained, m.p. ..Dialysis: Calculated,%: C 77.0; H 4.51; N 4.18 C 45 From N06 H 4.5; Found,%: C 76.7; N 4.1. The final product is 2,2-bis-4- (L-phenylphthalimide-4-hydroxy) -phenyl-1-propane. A mixture of 60.2 g of 2,2-bc-4- {N-phe nylphthalimide-4-oxy) -phenyl) -propane, 57.37 g of an aqueous 50% sodium hydroxide solution and 350 cm of water is heated for 25 at 160-175 ° C under a pressure of 150 pSi (10.54 kg / cm. Then the mixture is distilled with steam for 45 minutes. The aqueous residue is acidified with hydrochloric acid, the product is separated from the aqueous solution, washing Example 2, following the procedure of Example 1, 2,2-bis-4- (K-phenyl phthalimide-3-oxy) -feuyl propane is hydrolyzed in the presence of aqueous alkali at 170 ° C / 115 pSi (8.08 kg / cm2) with the formation at 9% yield of the corresponding 9th tetracarboxylic acid , analysis:.: Calculated,%: C, 66.9; H4, 3; Cj flj. Found,%: C, 66.5; H, 4.5. The final product is 2,2-bis-4- (2, 3-dicarboxyphenoxy) -phenyl-propane with water and recrystallized from 50% acetic acid. 32.9 g of product are obtained; mp 208-216 ° C Analysis: Calculated,%: C, 66.9; H 4.3 Cz1 NgdOi - Found,%: C 66.5; H 4.4. The final product is 2,2-bis-4- (3,4-dicarboxyphenoxy) -phenyl-proPan. Equal molar amounts of tetracarboxylic acid and 4,4-diaminodiphenylether are heated to reflux (140 ° C) for 4 hours under a nitrogen atmosphere in the presence of o-dichlorobenzene and toluene. Mixed solvents are used with an o-dichlorobenzene and toluene volume ratio of about 3: 1, which is sufficient for the polymerization of a mixture having about 90% by weight solvents. Then the toluene is removed by distillation of the mixture with heating for an additional 0.5-2 hours at 182 ° C, cooled to room temperature, and the polymer is precipitated in methanol. 94% of polymer having an internal viscosity in dimethylformamide 0.40 is obtained. The final product, polyetherimide, has a repeating unit. A mixture of 3,000 parts of the above-mentioned tetracarboxylic acid, 1.068 parts of 4,4-diaminodiphenylmethane, 40 parts of m-cresol and 5 parts of toluene are heated to reflux for 2 hours. continuously removed by azeotropic distillation. The resulting viscous reaction mixture is drunk in methanol, and the product is precipitated. The internal viscosity of the product is 0.71 in dimethylformamide, ie glass. 232C. The final product, polyether amide, has a repeating unit,. ,

Example 3. In accordance with the above procedure, (s-phenylphthalimide-4-hydroxy) -diphenylsulfide is hydrolyzed to form the corresponding tetracarboxylic acid at the 9450-HOM yield. M.p. lll-iaO C (decomposition),

A mixture of 5.565 parts of 4, 4-bis- (3,4-dicarboxyphenoxy) diphenylsulfide, 1.162 hours, hexamethylenediamine, 40 parts of trichlorobenzene and 5 parts of toluene is heated to reflux for 3 hours, which is formed with ethyl acetate and water removed as an azeotropic mixture. After

cooling the product precipitated. The reaction mixture was diluted with 200 parts of meta-, nola, and the product was filtered off. You764677JO

product run 96. The final product is polyetherimide - it has a repeating unit.

- (Ng) b Example 4, Following the procedure of Example 1, 1,4-bis- (N-phenylphthalimide-4-hydroxy) -benzene is hydrolyzed to obtain tetracarboxylic acid at a yield of 97%. After heating, the product is dehydrated at 200-210 ° C and melted at 262-26 ° C. The final product is 1,4-bis- (3,4-dicarboxyphenoxy) benzene.

A mixture of 4.343 parts of the above-mentioned tetracarboxylic acid, 2.700 parts of bis- {4-aminobutyl) -tetramethyldisiloxane, 50 parts of phenol and 10 hours, toluene is heated to reflux for 4 hours. Bis (N-phenylphthalimide-3-hydroxy) -diphenyl ether is hydrolyzed with sodium hydroxide under pressure. After oxidation of the reaction mixture, a white product precipitates, which is filtered, washed and dried. The material is melted at 252-255 ° C. The final product is 4,4-bis- (2,3-dicarboxylphenoxy) diphenyl ether. I5 mixture 5,304 parts of the above ± tetracarboxylic acid, 1,081 parts Fe Example 6. Blend from 2,782 parts of 2,2-bis-4- (2,3-dicarboxyphenoxy) -phenyl-propane, 2.782 parts of 2,2-bis-4- (3,4-dicarboxy-phenoxy) -phenyl-propane, 1,982 hours 4,4-diaminodiphenyl methane, 60 h. Of phenol and 10 h, toluene is heated to reflux for 2 h. Formed during T-S-f-S

After 1 hour, the water formed during this time is removed by aerootropic distillation. The yellow fibrous product is separated by precipitation in methanol.

Calculated: With 63.5; H 6.0; N 4.4; . Si 8.7

Cj4 HjgNjjSi Ov

Found,% J C 63.1; H 6.3; N 4.8; Si 9.4.

The product has a conversion temperature. The final product is a polyetherimide consisting of the following repeating unit.

SNS SNZ

1- "1Hr - -0- $ 1- (CHg) 4liHj Lnz nola and 10 parts of toluene are distilled off and heated to reflux for 1.5 h, and during this time the water formed is removed by azeotropic distillation. The resulting viscous solution is poured into methanol and a white fibrous product is collected by filtration. Exit 97%. The internal viscosity of the product in m-cresol is 0.34 dl / g. T. Stekl. 234 ° C. The final product is a polyetherimide, consisting of the following repeating unit. ULe, and water are continuously removed by azeotropic distillation. The reaction mixture is precipitated with methanol, and the white, white polymer is collected by filtration. polymer yield Y4%. T. glass 227p. The single polymer product consists of the following repeating units.

; "- .-.

-

. - -V

j "- Formula

The method of producing polyetherimides by polycondensation of imide-forming compounds containing ether groups and diamines in organic solvents, characterized in that, in order to simplify and cheapen the process, tetracarboxylic acids of formula I are used as imide-forming compounds containing ether groups

BUT -

BUT -

Where

674677

Where

diamines are used as diamines

Formula HNR

-NH

ZR where R is a divalent organic radical selected from the group consisting of aromatic hydrocarbon radicals having 6-20 carbon atoms and their halogenated derivatives, alkylene radicals of C2-C terminated with alkylene polydiorganosiloxane cycloalkylene radicals having 2-20 carbon atoms, divalent radicals of formula III

gdes1 -0 -, - C -, - & -, - 6- V.)

II Oh

X t 1-5;

Where

m 0-1,

a non-polar or phenolic solvent is used as an organic solvent and the reaction is carried out at 130-300 s.

Sources of information taken into account in the examination

1. USSR author's certificate 257010, cl. C 08 G 73/10, 1969.