DE1495839C - Process for the production of high molecular weight poly 1,3 benzoxazinediones 2,4 - Google Patents

Description

It is known l, 3-Benzoxazinedione-2,4 of the formula

-Ck

, N

ΊΙ

R = H, alkyl, aryl by condensing salicylic acid amides with derivatives of carbonic acid, such as Phosgene, chlorocarbonic acid esters or diesters of carbonic acid. The same connections can also be obtained by reacting salicylic acid esters with isocyanates or carbamic acid chlorides (A. E i η h ο r η and C. M e 111 e r, reports, 35 [1902], p. 3647).

The invention relates to a process for the preparation of high molecular weight poly-l, 3-benzoxazinedione-2,4, which is characterized in that polyamides obtained by condensing di- (o-hydroxy) -aryldicarboxylic acids or their esters, optionally together with other dicarboxylic acids or aminocarboxylic acids, and diamines with phosgene, alkyl or aryl chlorocarbonic acid esters or diesters of carbonic acid at temperatures between 0 and 350 ° C.

As starting materials for the production of the polyamides used are such. B. the following dio-hydroxyaryldicarboxylic acids or their esters: 4,4-dihydroxydiphenyldicarboxylic acid - 3,3 ', 3,6 - dihydroxyphthalic acid, resorcinol dicarboxylic acid-2,4, resorcinol dicarboxylic acid - 4,6, 2,5 - dihydroxyterephthalic acid, 4,4 '- dihydroxydiphenylmethanedicarboxylic acid - 3,3', 4,4'-dihydroxy-5,5'-dimethyldiphenylmethanedicarboxylic acid-3,3 ' and 1,1- (4,4'-dihydroxy-5,5'-dimethyldiphenyl) ethane dicarboxylic acid-3,3 '.

Suitable diamines are, for. B. 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, benzidine, 4,4'-diaminodiphenylmcthan, 2,2- (4,4'-diaminodiphenyl) propane, m-xylylenediamine, p-xylylenediamine, m-bis (2-aminoethyl) benzene and p-bis (2-aminoethyl) benzene.

The polyamides are produced by the processes customary for polyamide production. This Polyamides are then mixed with phosgene, alkyl or aryl chlorocarbonic acid esters or diesters of carbonic acid, such as ethylchlorocarbonate, phenylchlorocarbonate or diphenyl carbonate, ' implemented. .

The conversion with diaryl carbonates goes particularly smoothly with elimination of the oxyaryl compound. Because of the high melting temperatures of the polyamides or polybenzoxazinediones, it is often useful to work in solvents. Phenol and cresols, for example, are suitable as such. the Conversion of the polyamides in the melt to the polybene / oxa / .indiones can be removed at temperatures Stir through 150 "C. The reaction is preferably made at temperatures of 250 to 350 ° C. The reaction can take place with basic substances such as sodium methylate, Ni-phenolate and Na-acetate, catalyzed will.

Audi aliphatic amines, such as Ν, Ν'-dimethylstearylamine, Ν, Ν ', Ν, Ν'-Tetramethyltetramethylenediamine and Ν, Ν', Ν, Ν'-Tetramethylhexamethylenediamine, are suitable as catalysts.

The conversion of the polyamides to polybenzoxazinediones with alkyl or, better still, aryl chlorocarbonic acid esters is also advantageous in solution in the presence of an acid binding agent such as pyridine at temperatures between about 0 and 50 ° C. As a solvent, for example, tetrahydrofuran, dimethylformamide, Tetrachloroethane and dichlorobenzene can be used.

The initially formed polyaryl carbonate of the polyamide condenses with elimination of phenol to form Polybenzoxazinedione, which is then isolated from the reaction mixture.

A preferred embodiment of the above process is as follows: Dissolve the polyamide in a mixed solvent of pyridine and o-dichlorobenzene and drops at a temperature of

about 0 ° C phenylchlorocarbonic acid ester, dissolved in o-dichlorobenzene, to. One works z. B. after a the following procedures:

Either you filter off the precipitated pyridine hydrochloride and then distill off the solvent in vacuo until all the still dissolved pyridine hydrochloride is distilled over - by adding z. B. Me-. THANOL can Polybenzoxazindione be obtained in solid form, - or added to the reaction mixture with an equal volume of methanol, stirred for ¹ I ₂ hour filtered off from the precipitated reaction product and washing it still give few times with methanolic aqueous hydrochloric acid, then methanol and dried .

The formation of the polybenzoxazinediones can easily be demonstrated by infrared spectra.

The bands of the NH or OH groups and the NH - CO groups that appear in polyamide disappear in the conversion to the polybenzoxazinedione.

For the polybenzoxazinedione, on the other hand, a band is characteristic, that of the CO - NH - CO group is assigned.

It is also possible to produce polybenzoxazinediones by adding copolyamides, their carboxylic acid component partly from bis-o-hydroxyaryldicarboxylic acid, partly from one customary dicarboxylic acid or aminocarboxylic acid, with one of the amounts of bis-o-hydroxyaryldicarboxylic acid used converts an equimolar amount of a carbonic acid derivative.

It is also possible to use only some of the hydroxyl or amide groups contained in the polyamide to be converted into oxazine rings. This gives polybenzoxazinediones, the free hydroxyl and amide groups contain.

The Polybenzoxazindiones can be from the melt and from the solution to films, threads and process other moldings and coatings. It is also possible to use the polyamides to form moldings

or coatings and then convert them to polybenzoxazinediones implement by z. B. a polyamide solution prior to processing into moldings the appropriate amount of a diaryl carbonate is added, the solution to coatings or moldings, such as foils or threads, processed and then brought to such a high temperature that under Cleavage of the hydroxyaryl compound ring closure to the oxazine occurs.

There are high molecular weight compounds in ethyl acetate, dimethyl sulfoxide, ethylene chloride, o-Difolgender Structure obtained: chlorobenzene, dimethylformamide, tetrahydrofuran and

Benzene, with the film - except for the action of the first two solvents mentioned - through

5 crystallization becomes cloudy. H ,

Γ O OH H

Il 11 T I

OH [—C — R — C ^ N-R'— Ν—

wherein R is a mononuclear or polynuclear aromatic b) production of a polyamide from 4,4'-dihydroxy

Is a remainder, the nuclei of which may also be replaced by 3,3-dimethyld.phenylmethane-dicarboxylic acid diphenyl-

Alkylidene, ether, sulfide, sulfoxide, or sulfone ^ester - ^{5 '5} and m-Xylylendiamm

bridges can be connected, in the adjacent position 100.33 g 4,4'-dihydroxy-3,3'-dimethyldiphenylme-

have an OH group to the carboxyl group and diphenyl than-dicarboxylate-5,5 '(1.0 mol), 30.04

in addition to these substituents, other inert substituents m-xylylenediamine (1.03 mol) and 10Q g of cresol

such as alkyl, halogen may have; R 'a two- (DAB 6) are prepared as described under a),

valent aliphatic, cycloaliphatic araliphatic ^ was obtained which at 250 ⁰ C pale yellow, high-

tic or aromatic radical and / i a whole 15 viscous melt. The product has a relative

Number from 50 to 200. Viscosity from 1.295 *). By failures from a

The high molecular weight polybenzoxazinediones draw a cresol solution with methanol giving a crystalline solution

through high melting points, high chemicals ·. Product that melts at 220 to 225 ° C. It dissolves

resistance and low solubility in organic in dimethylformamide, tetrahydrofuran, dimethyl

Solvents from _; Their properties can be 20 sulfoxide, cresol, pyridine, methanolic-aqueous Na-

by choosing different di-o-hydroxyaryldicarbon hydroxide solutions. It is insoluble in methylene chloride,

acids and different diamines vary. Ethylene chloride, tetrachloroethane, o-dichlorosnzene,

a) Production of a polyamide from 4,4'-dihydroxy

S.S'-dimethyldiphenylmethane-dicarboxylic acid diphenyl- Example 2

ester-5,5 'and Hexamethylendiarniu-1,6 _{χ25 g} ^ ₈ ^ _{b) obtained Po} i _yarn jds are in

97.36 g of 4,4'-dihydroxy-3,3'-dimethyldiphenylme- 50 g of pyridine dissolved. The solution is with 62.5 g

than-dicarboxylic acid diphenyl ester-5,5 ', 24.87 g of hexa- o-dichlorobenzene and diluted with stirring at 2 to

methylenediamine-1,6 and 98.0 g of cresol (DAB 6) are mixed at 3 ° C with a solution of 9.88 g of phenylchlorocarbon

into one with a distillation head, receiver and 30 acid esters and 25 g of o-dichlorobenzene in 15 minutes

Given a stirrer-equipped flask. The apparatus moves. The mixture is heated to 50 ⁰ C, the reac-

is solidified to a gel three times after evacuation to about 20 Torr with an ion mixture. One stops for 2 hours

Charged with nitrogen. Then it is heated below the at this temperature, then stirred with 100 ecm

Stirring at normal pressure to 75 ⁰ C and increases the methanol, whereby the polybenzoxazinedione formed

Temperature around 25 ° C every 15 minutes. One turns out to be powdery. It is washed a few times with methanol

holds 30 minutes at about 250 ° C, with phenol / after and dries at 120 ° C / 20Torr. The product

Cresol distilled off. The pressure is reduced after a relative viscosity of 1.44 ¹ ), it melts

15 minutes at 150 Torr and stirs at about 240 to 250 ° C. A tetrachloroethane

10 Torr another 30 minutes. The resulting melt solution, cast film, dissolves in cresol and pyridine,

is yellowish and highly viscous. After cooling, however, it is insoluble in o-dichlorobenzene, dimethyl

The product held has a relative viscosity of 1.3I ¹ ). formamide, tetrahydrofuran, dimethyl sulfoxide, benzene

The polyamide can be separated by precipitation from one and acetone.

Cresol solution crystallized with methanol and obtained. _TT ". _n ,.,. '., _.,,

then melts at 215 ^° C. It dissolves in dimethyl ^c > Production of a polyamide from 4,4'-dihydroxy

formamide, tetrahydrofuran, dimethyl sulfoxide, Kre- 45 ³ ' ³ -d'metjiyldiphenylmeü ^ -dicarbonsaurediphenyl-

sol, pyridine or methanolic aqueous sodium hydroxide solution ester-5,5 and bis-p- (2-aminoethyl) -benzene.

and is insoluble in ethylene chloride, chlorobenzene or 97.17 g of 4,4'-dihydroxy-3,3'-dimethyldiphenylme-

Benzene. Than-dicarboxylic acid diphenyl ester-5,5 '(1.0 mol), 35.11g

Example 1 bis-p- (2-aminoethyl) - benzene (1.03 mol) and 98 g

5 ° cresol (DAB 6) are poured into a flask with de-

15.0 g of the polyamide prepared according to a) are added to the still unit, receiver and stirrer. The apparatus in 60 g of pyridine with stirring at room temperature is dissolved three times after evacuation to about. The solution is filled with 73 g of o-dichlorobenzene 20 torr with nitrogen. The mixture is then heated, diluted and with stirring at 3 ° C. in 15 minutes with stirring to 75 ° C. and the temperature is increased by 25 ° C. after every 15 minutes with a solution of 13.63 g of phenylchlorocarbons. It holds 30 Misäureester (1.15 mol) in 30 g o-dichlorobenzene comparable utes at 250 ⁰ C, wherein Pheiiol / cresol is distilled off, sets. It then is stirred for 3 hours at 50 ⁰ C, it reduces the pressure at 15 minute sucks the precipitated pyridine hydrochloride from, comparable to 150 Torr and stirred at 10 Torr after ³ / «hours, diluted mit.25Og o-dichlorobenzene, distilled at a the product crystallized when about 95% of the phenolic bath temperature of 150 ⁰ C and a pressure of 60 cresol mixture are distilled off, whereby it trilchigetwa 50 Torr 250 g of solvent from. The remaining becomes cloudy. A solution dissolved in cresol in the heat is mixed with 150 g of methanol. After 30 minutes of precipitation with methanol and thorough stirring, the precipitated, crystalline poly- benzoxazinedione, dried in vacuo at 120 "C, is filtered off and the sample has a melting point of 190 to 2 () 2 ° at 120 ° C / 20 Torr C. dried. The relative viscosity is 1.34 '). It 65 The relative viscosity is 1.10'). From a phenol melt at 210 to 215 "C. Fine film cast from a tetra solution dissolves in cresol, pyridine and chlorithane solution; cast film dissolves in methylene chloride, cresol and pyridine, but is insoluble i) Viscosity: measured in 1% solution in cresol at 25 ° C.

5 6

methanolic-aqueous sodium hydroxide solution. It is insoluble and melts at 270 to 285 ° C. The relative viscosity

in methylene chloride, ethylene chloride, o-dichlorobenzene, is!, 45 ¹ ). The product can be made up of solutions,

Dioxane, dimethyl sulfoxide, benzene, acetone, the z. B. in tetrachloroethane to pour fo'ien.

Film cloudy in some cases due to crystallization. _TT ". _,.,. ,, _ ..,

• j ₅ e) Production of a polyamide from 4,4 -dihydroxy-

ijS'-dimethyldiphenylmethane-dicarboxylic acid diphenyl-

B e i s ρ i e 1 3 ester-5,5 'and 4,4'-diaminodiphenyl ethers

5.7 g of the polyamide prepared according to c) are 35.14 parts by weight of 4,4'-dihydroxy-3,3'-dimethyl

with stirring at room temperature in 22.8 g of pyridine diphenylmethane - dicarboxylic acid diphenyl ester - 5.5 ',

solved. The solution is mixed with 28.5 g of o-dichlorobenzene and 15.10 parts by weight of 4,4'-diaminodiphenyl ether

diluted and with stirring at 3 to 5 ° C in 15 Mi- 35 parts by weight of phenol in a with De-

nuten with a solution of 4.05 g of phenylchlorocarbon stilling attachment, receiver and stirrer

acid ester (1.05 mol) in 20 g of o-dichlorobenzene were added. Piston given. The apparatus is three times after

The reaction product separates out of the solution, evacuated to about 20 torr, charged with nitrogen, mixed with pyridine hydrochloride, partly powdery. It is mixed with 200 cc of methanol-2-η hydrochloric pressure at 75 ⁰ C and the temperature is raised to acid (2: 1), stirred for 30 minutes, filtered off with suction and washed in each case 15 minutes at 25 ° C. Is maintained for 2 hours at three times 30 minutes each with water, then this temperature and then reduced to twice with methanol and dried at 120 ⁰ C / pressure at _^3/4 hours at 600 torr, with a total of 20 Torr. Relative viscosity 1.395 ^X ), melting point 20 43.0 parts by weight of phenol are distilled off. The now -255 to 270 ^° C. A more viscous melt from a tetrachloroethane solution is cooled, the ground cast film dissolves in methylene chloride, cresol and extracted in an extractor for 15 hours. Man and methanolic aqueous sodium hydroxide solution is, however, dried in vacuo at 100 ° C. for 24 hours. The insoluble in o-dichlorobenzene, dioxane, benzene, acetone product dissolves in tetrahydrofuran, cresol, pyridine, and dimethyl sulfoxide, crystallizes in ethylene chloride, dilute sodium hydroxide solution. It melts at 310 to dimethylformamide and tetrahydrofuran. 330 ^° C. The relative viscosity is 1.41 ^× ).

d) Production of a polyamide from 4,4'-dihydroxy,

J ^ '- dimethyldiphenylmethan-dicarboxylic acid diphenyl- Example 5 "'*' ester-5,5 'and 4,4'-diaminodiphenylmethane

35.14 parts by weight of 4,4'-dihydroxy-3,3'-dimethyldi-12.5 parts by weight of the polyphenylmethane-dicarboxylic acid diphenyl ester - 5,5 ', amide in 50 parts by weight of pyridine are under 14.94 parts by weight of 4.4 Dissolved '-diaminodiphenylmethane and stirring at room temperature. The solution is 30.0 parts by weight of phenol are poured into a still unit, receiver and stirrer, which has been diluted with de- with 62.5 parts by weight of o-dichlorobenzene, and a solution of flasks is added with stirring at -2 ° C. The apparatus is charged with nitrogen three times after 12.98 parts by weight of phenylchlorocarbonic acid ester are evacuated to about 20 torr. 25 parts by weight of o-dichlorobenzene are added. The polybenzoxazinedione formed is then heated with stirring at normal pressure, crystallizes to 75 ° C. with formation and the temperature is increased after a gel. The mixture is heated to 50 ° C. for 2 hours and then cooled to 25 ° C. for 15 minutes each time. It holds 2 _^3/4 hour 40 room temperature, stirred with 200 parts by verbei this temperature and then lowers the dilute hydrochloric acid, decanted from the organic pressure in 2V ₄ hours at 220 Torr, and 39.5 overall layer, and then stirred with 200 Distill off parts of the volume of phenol. The viscous melt divides methanol. The now powdery Polybenzoxerstarrt after cooling is pulverized, washed three times with azindion washed neutral with water, even boiling methanol per Vz hour extracted and subsequently 45 washed twice with methanol and at 100 ° C-closing in a vacuum at 100 ⁰ C for 24 hours in Vacuum dried over 24 hours. It dissolves dry. The product is soluble in tetrahydro- in tetrachloroethane, cresol, pyridine. It melts over furan, cresol, pyridine, dioxane. It melts at 300 38O ⁰ C. The relative viscosity is 1.46 ^X). That up to 310 ° C. The relative viscosity is 1.35 ¹ ). Product can be derived from solutions, e.g. B. in tetrachlor

50 ethane, process into foils or threads.

B e 1 s ρ 1 e 1 4 _f ^ Production of a polyamide from 4,4'-dihydroxydi-

12.5 parts by weight of the polyphenylmethane-dicarboxylic acid diphenyl ester S.Si and

amides are in 50 parts by weight of pyridine under 1,6-hexamethylenediamine

Stirring dissolved at room temperature. The solution is 55 22.0 parts by weight of 4,4'-dihydroxydiphenylmethane

diluted with 62.5 parts by weight of o-dichlorobenzene and dicarboxylic acid diphenyl ester-5,5 ', 5.8 parts by weight

with stirring at about 0 ⁰ C in 14 minutes with a hexamethylenediamine-1,6 and 0.534 parts by weight

Solution of 10.63 parts by weight of phenylchlorocarbon stearylamine are poured into a with a distillation attachment,

acid ester in 25 parts by weight of o-dichlorobenzene added to a flask provided with a stirrer,

puts. The mixture is then stirred for 2 hours at 50 ^° C. The apparatus is opened three times after evacuation

After cooling to room temperature, the mixture is stirred for about 20 torr and charged with nitrogen. Subsequently

with 200 parts by volume of dilute hydrochloric acid, decanted and heated to 75 ^° C. with stirring at normal pressure

from the organic layer and stir with and increase the temperature every 15 minutes

200 parts by volume of methanol, with the poly- formed around 25 ° C. It is kept at this temperature for 2 hours,

benzoxazindione precipitates as a powder. It is filtered off with suction, 2.9 parts by weight of phenol distilling off. Man

and washed neutral with water. After drying, a viscous melt of the polyamide is obtained. One

12O ⁰ C in vacuum over 24 hours. The product __

dissolves in tetrachloroethane, cresol, pyridine. It ») Viscosity: measured in a 1% solution in cresol at 25 ° C.

A sample of the product gives a relative viscosity of 1.39 ¹ ).

Examples

To the obtained under f) melt 21.4 parts by weight of diphenyl carbonate, 0.04 part by weight N, N'-tetramethylhexamethylenediamine-1,6 and 35 weight parts of phenol are added at 250 ⁰ C. 53.5 parts by weight of phenol distill off from the mixture in 30 minutes. The now viscous melt of the polybenzoxazinedione formed solidifies after cooling to a solid mass which, after grinding and extraction with boiling methanol, ^{is dried at 100 °} C. in a vacuum. The product dissolves in tetrachloroethane, cresol, pyridine. It melts at 230 to 240 ⁰ C. The relative viscosity is 1.49 ^X). Foils or threads can be obtained from a solution in, for example, tetrachloroethane.

Claims (2)

Patent claims: 1. A process for the preparation of high molecular weight poly-l, 3-benzoxazinedione-2,4, characterized in that polyamides obtained by condensing di- (o-hydroxyj-aryldicarboxylic acids or their esters, optionally together with other dicarboxylic acids or Aminocarboxylic acids, and diamines have been obtained, with phosgene, alkyl or aryl chlorocarbonic acid esters or diesters of carbonic acid at temperatures between 0 and 350 ⁰ C is reacted. 2. The method according to claim 1, characterized in that that the reaction in the presence of solvents, basic catalysts or acid-binding agents. *) Viscosity: measured in 1% solution in cresol at 25 ° C. 109614/115