DE1927938A1 - Polyarylesters - Google Patents

Abstract

Polyarylesters. Reaction of dibasic acid chlorides with dihydric phenols, in inert high-boiling org. solvent, at 110 to 220 degrees C., HCl being split off. The catalyst used is vanadium pentoxide. The dibasic acid chloride may be a terephthaloyl chloride and/or isophthaloyl chloride. The dihydric phenol may be 2,2-bis-(4-hydroxyphenyl)-propane, phenolphthalein, resorcinol, bis-(4-hydroxydiphenyl)-sulphone, bis-(4-hydroxydiphenyl-)diphenylmethane or mixtures thereof. The catalyst may be in finely divided form, adsorbed on activated carbon. The claimed catalyst is more efficient than other known catalysts, reaction being more rapid. Since it is insoluble, it can easily be filtered off the reaction solution and re-used. The polyester is practically free of catalyst residues.

Description

Process for the preparation of polyaryl esters The subject of the invention is the use of vanadium pentoxide as a catalyst in the manufacture of polyaryl esters from aromatic dicarboxylic acid chlorides and dihydric phenols according to known Methods.

Polyaryl esters can essentially be obtained by various condensation processes manufacture: 1. Transesterification of diacetates of dihydric phenols with dihydric carboxylic acids or DlearbonsKurediphenylestern with dihydric phenols, 2nd interfacial condensation of dicarboxylic acid chlorides with phenolates of dihydric phenols, 3rd solution condensation with dicarboxylic acid chlorides at room temperature with salts tertiary amines of divalent Phenols and 4th solution condensation of dicarboxylic acid chlorides with dihydric ones Phenols in inert, high-boiling solvents at temperatures above 150 ° C with simultaneous expulsion of the hydrogen chloride that forms.

The latter method has been particularly detailed by Korshak and co-workers examined. The decomposition rate depends primarily on the reaction temperature addicted. Below 15,000 the reaction proceeds too slowly without a catalyst; The esters formed discolor slightly above 210 ° C. The optimal temperature range for carrying out the reaction in the absence of catalysts lies between 170-210 ° C.

The conversion of the acid chlorides with dihydric phenols can, however also catalyze. So far, the following catalysts have been mentioned: Magnesium, calcium and aluminum chloride as well as the halides of heavy metals and tertiary amines.

Condensation experiments in o-dichlorobenzene have found that Magnesium and calcium chloride accelerate the reaction only insignificantly. With aluminum chloride the elimination of hydrogen chloride is greatly accelerated. The polyaryl esters obtained However, they only have low mean molecular weights (<-10,000), which is likely may be caused by side reactions of the Friedel-Crafts type.

Some heavy metal halides also accelerate the implementation.

In no case were reaction times of less than 24 Hours measured at a reaction temperature of 18,000.

Surprisingly, it has now been found that the implementation of aromatic dicarboxylic acid chlorides, such as tere- and / or isophthalyl chloride with dihydric phenols to polyaryl esters in the presence of catalysts in inert, high-boiling, organic Solvents at temperatures between 110-220 ° C, preferably 140-18000, with elimination of hydrogen chloride considerably can be accelerated by using vanadium pentoxide in the known method used as a catalyst.

This finding is particularly surprising because vanadyl chloride (VOCI3) and vanadyl ester behave completely differently as pentavalent vanadium compounds than vanadium pentoxide. This is how men achieved in a reaction in boiling o-dichlorobenzene (180 ° C) a mixture of 50 mol% each iso- and terephthaloyl chloride with 2,2-bis- (4-hydroxyphenyl -) - propane of 0.1% by weight of vanadyl chloride or of 0.1% by weight of vanadyl tri-n-butoxide a complete Conversion after 24 hours at the earliest, while when 0.1% by weight of V2O5 is used the reaction has ended after just 1.5 hours.

With VOCl3 only insufficient mean molecular weights (<10 000) obtained with a corresponding polyaryl ester.

In addition to the significantly higher catalytic effectiveness of vanadium pentoxide Its special value as a catalyst lies in the fact that it is more heterogeneous, insoluble The catalyst acts, which is advantageous by simply filtering off the reaction solution can be completely removed with the addition of a little charcoal and for another Approach can be reused. It could be shown by X-ray fluorescence analysis be that the polyaryl ester obtained does not contain any measurable amounts of vanadium, d, h. less than 3 ppm.

The better advantage for the obtained polyesters is that they are Do not contain any heavy metal ions, which at high temperatures *) during use doors can accelerate degradation.

In addition, colorless reaction solutions are obtained even at high temperatures and correspondingly colorless polyesters.

The lower limit for the amount of V205 to be used can be 0.001 Weight (based on the amount of acid chlorides used) are given. One there is no upper limit, since the reaction can also be carried out over a fixed bed, e.g. from V2O5 on carbon.

It was also observed that the degree of purity of the used V2 V205 is not insignificant for the catalytic efficiency. So were with a technical quality response times of 6-10 hours measured, while a 99 % pure oxide which produced an extremely short reaction time of 1.5 hours.

Suitable aromatic dicarboxylic acid chlorides are primarily isophthaloyl chlorides and terephthaloyl chlorides. However, it is also possible to use substituted, aromatic dicarboxylic acid chlorides of the general formula use, in which R can be an alkyl group of 1-4 carbon atoms, halogen, -NO2 '-COOR. The acid chlorides can be used as mixtures.

As a second output product for carrying out the manufacturing process the polyaryl esters are suitable, optionally alkyl-substituted, mononuclear or polynuclear, dihydric phenols, the both condensed and uncondensed can be.

Suitable dihydric phenols are, for example, the mononuclear, such as hydroquinone, resorcinol, catechol.

Polynuclear, dihydric phenols, the cores of which are not condensed, can be given, for example, by the following general formula in which Y can be oxygen or sulfur, a carbonyl, disulfide or sulfone bridge or an optionally phenyl-substituted alkylene or cycloalkylene radical.

Basic types are the dihydroxydiphenyl, of which the 2,2'-, 2,4'-, 3,3'-, 4,4'-dihydroxy-2-diphenyl, 4,4'-dihydroxy-2-methyldiphenyl, 4,4'-dihydroxy-2,2'-dimethyldiphenyl, 4,4'-dihydroxy-3,3'-dimethyldiphenyl, 6,6'-dihydroxy-3,3'-dimethyl-diphenyl and others are derived.

Dihydroxybenzophenones, such as 2,2'-, 2,3'-, 2,4'-, 3,3'-, 3,4'-, 4,4'-, 4,6'-, 6,6'-dihydroxytenzophenone and the like, dihydroxydiphenyl sulfides such as 2,2'-, 4,4'-dihydroxydiphenyl sulfides fid, dihydroxydiphenyl sulfones, such as 2,2i-, 4,4'-dihydroxydiphenyl sulfone, dihydroxydiphenyl ether, such as bis (4-hydroxyphenyl) - ether, dihydroxydiphenylalkane or -cycloakan, such as 2,2'-, 4,4'-dihydroxydibenzyl, 2,2'-, 2,3'-, 2,4'-, 2,5 ', 2,6'-, 3,3'-, 3,4'-, 3, 5'-, 3,6'-, 4,4'-, 4,5'-, 4,6'-, 5,5'-, 5,6'-, 6,6'-, dihy droxydiphenyl-2,2-propane, 2,2-bis- (4-hydroxy-3-chlorophenyl) - propane, 2,2'-, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihyldroxydiphenylmethylmethane, 4,4'-dihydroxydiphenylphenylmethane, 4,4'-dihydroxydiphenyldiphenylmethane, bis- (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, bis- (4-hydroxyphenyl) -cyclohexylmethane, 1,1-bis- (4-hydroxyphenyl) -ethane, 1,1-bis (4-hydroxyphenyl) - 2,2-2, trichloroethane, 1,1-bis (4-hydroxyphenyl) -4'-methylphenylmethane, Phenolphthalein et al.

The suitable polynuclear, condensed, dihydric phenols are including the D1 hydroxynaphthaligv or -anthracene-etc. from, like the 1: 3-, 1: 4-, 1: 5-, 1: 6-, 1: 7, 1: 8, 2: 6-, and 2: 7-dihydroxynaphthalene.

In addition to alkyl groups, the phenyl groups of the abovementioned divalent ones can be used Phenols also carry alkoxy, carboxy and phenoxy groups as substituents. Of course Mixtures of the aforementioned phenols can also be used according to the invention for the reaction will. The preferred dihydric phenol is 2,2-bis (4-hydroxphenyl) propane, which is sometimes referred to in the literature as bisphenol A or Dian will.

The dihydric phenols can be used alone or as mixtures ground in place.

Inert, highly resistant, organic. Solvent in the sense of the present Invention are those that neither with the starting materials nor with the formed Polyarylates react and the Polyaryl ester completely or largely to solve. Typical solvents are chlorinated, aromatic hydrocarbons, such as chlorobenzene, dichlorobenzene, trichlorobenzene and tetrachlorobenzenes, chlorinated diphenyls or diphenyl ethers, chlorinated naphthalenes, but also unchlorinated aromatics, such as Terphenyl, benzophenones, dibenzylbenzenes and others, Kcmmen in question.

The reaction between the aromatic dicarboxylic acid chlorides and The dihydric phenols start at approx. 110 ° C. At 130 ° C is the uncatalyzed Reaction not yet complete after 200 hours; When catalyzed with V-205, the elimination of hydrogen chloride takes a long time approx.

24 hours. At 180 ° C the uncatalyzed reaction takes approx.

100 hours, the V2O5-catalyzed 1.5-2 hours; at 210 ° C it is 30 hours or 1 hour for the uncatalyzed or catalyzed R @ action. Higher In the uncatalyzed reaction, temperatures lead to permanently discolored polyesters.

The polyaryl esters obtained are isolated according to known methods Methods by precipitation with non-solvents such as methanol, acetone, aliphatic substances etc. You can, however, also by evaporating the solvent at high temperatures, possibly un @ er vacuum, obtained from vacuum twin screw extruders as a melt strand will. To achieve useful mechanical properties, the viscosity number should (z @) must be at least 0.6. The viscosity number is determined by Mot solution of a 0.5 sew. Polymer solution (0.5 g of substance per 100 ml of solution) in Phenol / tetrechloroethane mixture (60 G.T./40 G.T.) at a temperature of 25 ° C.

The linear ones, made up of aromatic dicarboxylic acids and dihydric phenols produced, thermoplastic polyaryl esters have excellent properties. They are transparent and extremely tough; They also have an excellent Impact strength on. They are suitable for the production of high quality foils for Special purposes.

The process ger'.äß the present invention is carried out by the following Examples illustrated.

Example 1: In a 5 l three-necked round bottom flask with stirrer, reflux condenser and the gas inlet pipe, 101.75 g of isophthaloyl chloride (0.5 mol), 101.75 g of terephthaloyl chloride (0.5 mol) and 228 g of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) in 1500 ml of o-dichlorobenzene dissolved by heating with an oil bath to approx. 80 ° C. This solution became 100 mg vanadium pentoxide (o, c5% by weight based on the amount of acid chlorides used) admitted; the solution turns greenish-brown. With good stirring and Passing a little nitrogen was quickly heated to 1800C.

The elimination of hydrogen chloride continued at an internal temperature of about 11,000 a, is berelts strong at 1400C and becomes violent up to 18000. While stirring well the o-dichlorobenzene was further brought to the boil (18,000) after 1.5 hours the elimination of hydrogen chloride completely ended. The solution became clearly viscous. Then approx. 5 g of activated charcoal were stirred in and the solution was increased to approx. 10000 cooled. The solution was filtered through a glass frit. The filtrate is completely colorless.

The filter cake was recovered and used for the next batch reused.

In the still hot filtrate were stirred vigorously at at least 700C 1500 ml of cyclohexane stirred in. The solution becomes cloudy. Among other things while stirring vigorously, the mixture was cooled. The polyaryl ester began to form at 20 ° C to be deposited gritty. The solid polyester was suction filtered and mixed with methanol washed thoroughly. The yield was positive, the polyaryl ester obtained has a viscosity number of 1.48.

In a repeat run, the carbon-bound catalyst was used the end used the first approach. The polyester solution obtained was completely colorless. the obtained viscosity number of the polyaryl ester is 1.44.

In the samples of the two polyester batches, after filtration of the catalyst before precipitation with cyclohexane by X-ray fluorescence analysis the remaining amount of vanadium is determined.

In both cases it is <3 ppm, as this value is the limit value for is the ability of the analyzer to determine.

Example 2: In a replicate of Example 1 were used as Catalyst 100 mg V0013 used. The elimination of hydrogen chloride was after 24 Hours ended. The viscosity number of a sample of the polyaryl ester is 0.48. Of the The batch was kept at 180 ° C. for a further 24 hours; the viscosity number increased no longer.

Example 3: In a repetition of example 1 were 100 mg of vanadyl tri-n-butoxide (VO (OC4Hg) 5) were used as the catalyst. The elimination of hydrogen chloride was over after 24 hours. The solution of the polyaryl ester in o-dichlorobenzene was dark green and completely clear; it could not be discolored with charcoal.

The polyaryl ester obtained has a viscosity number of 1.44.

The following examples were carried out analogously to Example 1.

The test conditions and the results are shown below Tabel.

Table c: Bei- Diphenol acid chlo- V2O5 sol. Temp. Time Z2 play (Mcl%) ride (Mol%) (wt.%) (° C) (hrs.) 4 bisphe- TDC 50 0.05 dibenzyl- 210 1 1.21 nol A IDC 25 benzene 5-Cl-IDC- 25th 5 bisphe-TDC 0.05 o-dichloro-180 1.5 1.56 nol A 50 benzene + Pheno] - phthalic in 50 6 Bisphe- TDC 30 0.1 Tetra- 210 1 1.08 nol A 50 chlorobenzene + Diphe- TDC 70 zol-Ge nylolsulmisch fon 50 7 Resor- TDC 100 0.01 chlorobenzene 130 24 0.92 @@@ zol 8 bis- (4-TDC 80 0.05 o-dichloro-180 1.5 0.72 hydroxy-TEC 20 benzene phenyl diphenyl methane TDC = terephthaloyl chloride IDC = isophtheloyl chloride 5-CI-IPC = 5-chloro-isophth @ lcyl chloride

Claims (5)

P a t e n t a n 5 p r Ü c h e 1. Process for the production of polyaryl esters by reacting aromatic dicarboxylic acid chlorides with dihydric phenols in the presence of catalysts in inert, high-boiling, organic solvents at temperatures between 110-220 ° C, preferably 140-180 ° C, with elimination of hydrogen chloride in a known manner, characterized in that the catalyst used is vanadium pentoxide used. 2. The method according to claim 1, characterized in that terephthaloyl chloride and / or isophthaloyl chloride is used as the dicarboxylic acid chloride. 7. The method according to claim 1, characterized in that 2,2-bis (4-hydroxyphenyl) propane, Phenolphthalein, resorcinol, bis (4-hydroxydiphenyl) sulfone, bis (4-hydroxydiphenyl) diphenylmethane used alone or in a mixture as dihydric phenols. 4. The method according to claim 1, characterized in that as inert, high-boiling, organic solvents chlorinated aromatics are used. 5. The method according to claim 1, characterized in that nan a high-purity vanadium pentoxide in finely divided form, adsorbed on activated carbon as catalyst used.