DE1595556A1 - Process for the production of polyesters from halogenated, dihydric phenols - Google Patents

Description

Process for the production of polyesters from halogenated, divalent ones Phenols The invention relates to a process for the production of polyesters from halogenated, dihydric phenols and acid chlorides of dibasic carboxylic acids. The process is particularly characterized in that the dicarboxylic acid chlorides with the halogenated, dihydric phenols in the presence of catalytic amounts tertiary amines whose amino group is not part of an aromatic ring system is, optionally using solvents at a temperature of 50-2500C, preferably 80-1800C.

The production of polyesters from halogenated, dihydric phenols has already been described in the literature. Such polyesters are widely used by transesterification of dialkyl dicarboxylates of alcohols which have up to 4 e atoms can own made with diphenols. The transesterification of such reaction mixtures However, it is relatively slow. In contrast, the conversion of acid chlorides runs faster with phenols. When using halogenated phenols, however, this reaction is so delayed that the reaction stops at a conversion rate of 40%.

It has now been found that the disadvantages mentioned can be found in the manufacture of polyesters made from halogenated bivalent penols, if you look at the Production of polyesters from halogenated, dihydric phenols and acid chlorides Two-valued carboxylic acids proceed in such a way that the dicarboxylic acid chlorides are mixed with the halogenated, dihydric phenols in the presence of catalytic amounts of tertiary Amines whose amino group is not part of an aromatic ring system, optionally using inert solvents at a temperature of 50 - 250 ° C, preferably 80-180 ° C.

The reaction according to the above invention is preferably carried out at Normal pressure carried out. However, it can also be carried out at negative or positive pressure will.

Dicarboxylic acid chlorides are used to produce the polyesters of the halogenated diphenols and halogenated diphenols are preferably used in a stoichiometric ratio, i.e., per mole of dicarboxylic acid chloride becomes 1 mole of halogenated dihydric phenol used. An up to 5 molar excess of the phenol can be used to adjust the serve the desired molecular weight.

For the implementation of the method according to the invention are uniform and mixed tert-amines with aliphatic, cycloaliphatic, aromatic and heterocyclic radicals or mixtures thereof are suitable.

Suitable tertiary amines with aliphatic radicals are, for example: Trimethylamine, TriäthylUin, Triisopropylamin, Triisobutylamin, Monoäthyldiisopropylasmin, Monoethyl-di-n-butylamine, Tri-n-butylamine, N, N, N ', N'-tetramethylbutanediamine- (1,4), N, N, N, ', N'-Tetramethylethylenediamine, optionally substituted, tertiary, aliphatic Amines, such as B-chloropropyldipropylamine, tris- (ß-ethoxyethyl) amine, N, N-di-n-butylaminoacetonitrile, N, N-Diisopropylaminoacetonitrile, N-n-Butyl-N-methyaminicaetonitril, From the series of the amines with cycloaliphatic radicals would be called dimethylcylohexylamine. Furthermore, suitable amines with aromatic radicals should be mentioned, such as N, N-dialkylaniline, N, N-dimethylaniline and N, N-diethylaniline and others, p-bromophenyldimethylamine, 2,4-dinitrophenyldimethylamine and benzyldimethylamine, p-nitrophenyl-di-n-butylamine 2, 4-dichlorophenyl-diethylamine, N, N, N ', N'-tetramethylbenzidine.

Suitable heterocyclic nitrogen compounds are, for example, -N-alkyl- or N-arylmorpholines, such as N-n-butylmorpholine, N-phenylmorpholine, N- (4-methylphenyl) -morpholine, Morpholine acetic acid morpholide, N, N-dialkyl- or N, N-diarylpiperazines, e.g.

N, N-Dimethylpiperazine, N, N-Di-n-butylpiperazine, N, N-Diphenylpiperazine, N-substituted piperidine derivatives, N-aryl or N-alkyl tetrahydroquinolines or Tetrahydroisochionolines, e.g. B. N-n-propyl-tetrahydroquinoline, N-phenyl-tetrahydroisochionoline, N-alkyl and N-aryl pyrrolidines and their derivatives, e.g. B. N-methylpyrrolidine, N-n-butylpyrrolidine, N-phenylpyrrolidine, and optionally substituted derivatives of the aforementioned compounds. Of the above tertiary amines, those containing nitrile groups have proven to be particularly suitable proven. The tertiary amines described can of course also by the corresponding hydrochlorides and the salts from the halogenated phenols and the tertiary amines in corresponding mol percent as a catalyst be replaced. The tertiary amines used as catalysts are used in quantities from 0, - 20 mol, preferably 0.2 - 2 mol 1>, based on the amount of acid halide, used.

The reaction can be carried out either in the melt or in the presence of inert solvents are carried out. Suitable inert solvent in the sense of the present invention are both aliphatic and aromatic hydrocarbons as well as simple and cyclic ethers. Aliphatic hydrocarbons are both- to name uniform compounds as well as mixtures thereof, such as isooctane and Petrol fractions, for example, those with a boiling range of .120 - 20,000. Cycloaliphatic compounds such as decahydronaphthalene can also be used will. Benzene, orthodichlorobenzene, toluene and xylene are examples of suitable ones aromatic hydrocarbons. As an ether suitable for carrying out the reaction are, should be mentioned, diisopropyl ether, di-isoamyl ether, dimethyl ether of the ethylene and diethylene glycol, diphenyl ether, 1,4-dioxane, etc. This list shows that both aliphatic and aromatic, and open-chain ethers are used can be. But also polar solvents, such as dimethyl sulfoxide and dimethylformamide, can be used.

As starting products for carrying out the process according to the invention are suitable, optionally alkyl-substituted; single or polynuclear, halogenated, dihydric phenols, which can be both condensed and uncondensed.

Suitable halogenated, dihydric phenols are, for example mononuclear ones derived from hydroquinone, resorcinol and catechol such as: 2-chloro- or 2-bromohydroquinone, tri- and tetrachlorohydroquinone, 2,4,6-tribromoresorcinol. etc.

Polynuclear, bivalent, halogenated phenols, the nuclei of which are not condensed, are derived from the general formula in which X are identical or different halogen atoms, a or b is an integer from 1 to 4 and Y is oxygen, a carbonyl sulfide or. Sulfonic group or an optionally phenyl-substituted alkylene radical. Basic types of these phenols are the dihydroxydiphenyls, for example 2,2'-, 2,4'-, 3,3'-, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxy-2-methyldiphenyl, 4,4'-dihydroxy -2,2'-dimethyldiphenyl, 4,4'-dihdyroxy-3,3'-dimethyldiphenyl, 6,6'-dihdyroxy-3,3'-dimethyldiphenyl, among others; Dihydroxybenzophenones such as: 2,2'-, 2,3'-, 2,4'-, 3,3'-, 3,4'-, 4,4'-, 4,6'-, 6,6 ' -dihydroxybenzophenone and the like; Dihydroxydiphenyl sulfides such as: 2,2'-, 4,4'-dihydroxydiphenyl sulfide; Dihydroxydiphenyl sulfones such as: 2,2'-, 4,4'-dihydroxydiphenyl sulfones; Dihydroxydiphenylcans 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'-dihydroxydiphenyl-2,2-propane, 2,2'- or 4,4'-dihydroxydiphenyl-methane, 4,4'-dihydroxydiphenylphenylmethane, 4,4'-dihydroxydiphenyldiphenylmethane, 4,4'-dihydroxydiphenylmethylmethane among others

The halogenated, used according to the invention, are derived from these types dihydric phenols, such as: 2,2-bis- (3,5-dichloro-4-hydroxypehnyl) propane, 2,2-bis- (3,5-dirbomo-4-hydroxyphenyl-) - propane, 4,4'-dihydroxy-5,5'-difluoridophenylmethane, 1,1-bis- (3,5-dichloro-4-hydroxyphenyl) -1-phenylethane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -hexane, 4,4'-dihydroxy-3,3 ', 5,5'-tetrachlorodiphenyl.

The corresponding tetrabromo or tetrachloro derivatives of 4,4'-dihydroxydiphenyl ether, 4,4'-Dihydroixybenzyophenns and 4,4'-Dihydroxydiphenylsulfons.

The polynuclear, condensed, dihydric phenols are derived essentially from the Dihdroxyaphantlainen, such as from the 1: 3-, 1: 4-, 1: 5-, 1: 6-, 1: 7-, 1: 8-, 2: 6-. and 2: 7-dihydroxynaphthalenes.

Suitable halogenated phenols are, for example, the dichloro and Dibromo compounds and the tetrabromo- and tetrachloridihydroxynaphthalenes.

In addition to alkyl groups, the phenyl groups of the aforementioned divalent, phenolic compounds also include alkoxy, carboxy and phenoxy groups as substituents wear. Mixtures of the abovementioned halogenated phenols can of course also be used be used according to the invention for the implementation.

According to the invention, both the Acid chlorides aliphatic, cycloaliphatic and also aromatic, saturated or unsaturated Dicarboxylic acids are used. Suitable aliphatic, saturated and unsaturated Dicarboxylic acid chloride are, for example, those of the oxalic, malonic, amber, glutaric, Adipic, pimeline, cork, azelaic, sebacic, fumaric, itaconic acid and the like.

Examples of suitable cycloaliphatic carboxylic acids are tetrahydrophthalic and hexahdrophthalic acid, hexachloroendomethylenetetrahydrophelic acid and the like which are produced by Diene synthesis of unsaturated dicarboxylic acids or their chlorides on 1,4-dienes, if necessary can be represented with after hydrogenation of the double bond has taken place.

Suitable aromatic dicarboxylic acids would be the terephthalic, phthalic, Isophthalic, tetrachlorophthalic, diphenyl-4,4'-dicarboxylic acid, diphenyl-2,2'-dicarboxylic acid to be called.

The aforementioned aliphatic, cycloaliphatic and aromatic Dicarboxylic acid chlorides can also be halogenated or alkyl, alkoxy and Contain aryl residues as well as sulfur and ketone bridges, such as: acetone dicarboxylic acid, Dibromosuccinic acid, dichlorosebacic acid, methylene bis (thioglycolic acid) and others. Mixtures of the aforementioned dicarboxylic acid chlorides can also be used to prepare the Polyester can be used.

The condensation proceeds rapidly under the conditions according to the invention and with the release of almost stoichiometric amounts of gaseous HCl.

A residual content of chlorine, which results from the acid halide, can by post-treating the polyester with amines, alkali phenolates or alcoholates are eliminated.

The end products can be worked up by methods known per se take place. If solvents are used as the Eondengationsmedium the isolation of the polyester by stripping off the solvent or by precipitation of the polymer be won.

The polymers produced according to the invention have high thermal stability and can be used, for example, as molding compounds. They are fire retardant, fungicidal and bactericidal.

The following examples illustrate the process according to the invention: Belspiel-1 : In a three-necked flask equipped with a stirrer, condenser and inlet tube were 55 g of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 18.3 g of adipic acid dichloride, 0.3 ml of N, N-di-n-butylaminoace tonitril in 250 ml of xylene reacted. That The reaction mixture was kept at the boiling point of xylene with stirring.

After about 22 hours, about 92% of the theoretical amount was hydrogen chloride cleaved. A white precipitate formed on cooling. Subsequently were 5 ml of pyridine were added and the reaction mixture was boiled for a further 2 hours.

The deposited precipitate was filtered off and washed with H 2 O.

The dry product has a melting point of 2600C and a red. viscosity of 0.28. Yield: about 95%. The reduced viscosity was measured with a falling ball viscometer certainly. A 0.5 percent by weight solution in chlorine form was measured at 250C.

Example 2: In a three-necked flask equipped with a stirrer, condenser and Inlet tube, 37 g of 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 18.3 g of adipic acid dichloride, 0.3 ml of N, N-di-nibutylaminoacetonitrile in 250 ml of xylene brought to reaction. The reaction mixture was stirred at the boiling point of xylene held.

After about 22 hours, about 90% of the theoretical amount was hydrogen chloride cleaved and a white precipitate formed on cooling. Afterward 3 ml of pyridine were added and the reaction mixture more Cooked for 2 hours.

The deposited precipitate was filtered off and washed with H2O.

The dry product has a melting point of 247-2500C and a red.

Viscosity of 0.36.

Example 3: As in Example 1, 55 g of 2,2-bis (9,5-dibromo-4-hydroxyphenyl) propane, 18.3 g of adipic acid dichloride and 0.5 ml of tri-n-butylamine as a catalyst in 250 ml Xylene reacted.

The end product has a melting point of 2620C and a red. Viscosity of 0.28.

Example 4: As in Example 2, 37 g of 2,2-bis (3,5-dibromo-4-hydroxyphennyl) propane, 18.3 g of adipic acid dichloride and 0.5 ml of N-methylpyrrolidine as a catalyst in 250 ml of xylene reacted.

The end product has a PP of 249 - 2510 and a red. viscosity of 0.37.

Example 5: In a three-necked flask equipped with a stirrer, condenser and inlet pipe, 36.6 g of 2,2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 22.5 g of azelaic acid dichloride, 0.5 ml of N, N-di-iso-butylamine acetonitrile in 250 ml of xylene brought to reaction. The reaction mixture was stirred at the boiling point of xylene held.

After 48 hours, approx. 98-99% of the theoretical amount was hydrogen chloride cleaved. The xylene was distilled off under vacuum and the The polyester continued to condense for 2 hours at approx. 1 mm Hg and 2400C with stirring Product has a softening point of 145 - 15,000 and a red. Viscosity ton 0.71. Yield / 95%.

Example 6: -In a three-necked flask equipped with a stirrer, condenser and inlet tube, 219.6 g of 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 143.5 g of sebacic acid dichloride, 2 ml of tri-n-butylamine in 500 ml of xylene for the reaction brought. The reaction mixture was brought to the boiling point of the xylene with stirring held. After 48 hours, approx. 98% of the theoretical amount was hydrogen chloride cleaved. The xylene was distilled off under vacuum and the polyester for 1 hour condensed further at 240 ° C and 2 mm Hg with stirring. The product has a softening point from 142-145 ° C, a red. Viscosity of 0.72 and a yield of 98%.

Example 7: In a three-necked flask equipped with a stirrer, condenser and Inlet tube, were 219.6 g of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 101.4 g glutaric acid dichloride, 2 ml N, N-di-n-butylamine acetonitrile in 500 ml xylene for the reaction wired. The reaction mixture was stirred at the boiling point of xylene held.

After 48 hours, approx. 98% of the theoretical amount was hydrogen chloride flaked off. The xylene was distilled off under vacuum. The product has a softening point from 185 - 19000, one red. Viscosity of 0.47 and a yield of 98 96, example 8: In a three-dimensional flask, equipped with a cooler, stirrer and inlet pipe for N2, 37 g (0.1 mol and 0.4 g excess) of 2.2 bis (3,5-dichloro-4-hydroxyphenyl) propane and 20.3 g of o-phthalyl dichloride (0.1 mol) in 250 ml of xylene in the presence of 0.5 g N phenylmorpholine reacted. The resulting HCl gas was by means of N2 flushed out of the boiling reaction mixture and collected in NaOH solution. The reaction had ended after 48 hours. To remove the last traces of HC1, 5 ml of pyridine were added and the mixture was boiled for a further 1 hour.

The xylene was evaporated.

The resulting product was washed with water and dried.

The powdery product has a melting point of 258-261 ° C, mol Weight: 3980, red. Viscosity: 0.16; Yield about 95%.

Example 9: Analogously to Example 5, 73.2 g (0.2 mol) of 2,2-bis (3,5-di-chloro-4-hydroxyphenyl) propane were obtained with a mixture of 30.95 g (0.14 mol) of azelaic acid dichloride and 0.5 ml of N-methylpyrolidine reacted in 120 ml of xylene. After the elimination of hydrochloric acid has ended 92 g (0.06 mol) of fumaric acid dichloride were added to the reaction mixture. To The reaction was complete for a total of 46 hours. The xylene was distilled off in a peter vacuum. The polyester has a melting range of 160 - 162 ° C and a red.

Viscosity (0.5 wt% in chloroform at 25 ° C) of 0.7.

Example 10: In accordance with Example 6, 36.6 g (0.1 mol) of 2,2-bis- (3,5-dieblor-4-hydroxpyphenyl) propane, 19.13 g (0.08 mol) sebacic acid dichloride, 4.06 grams (0.02 moles) of terephthalic acid dichloride and 0.5 ml of N, N-di-n-butylaminocacetonitrile in 120 ml of tetrachloroethane for the reaction brought.

The reaction had ended after 18 hours. The polymer was made with methanol failed. Melting range 250 - 2800C, reduced viscosity (0.5% by weight in chloroform at 250C) 0.7.

Example 11: According to Example 6, 36.6 g (0.1 mol) of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, a mixture of 19.13 (0.08 mol) sebacic acid dichloride and 0.5 ml uri-n-butylamine reacted in 120 ml of tetrachloroethane. After 60% of the hydrochloric acid has been split off was, 4.06 g (0.02 mol) of terephalic acid dichloride were added to the reaction mixture. The splitting off of HCl was complete after 18 hours. The polymer was made with methanol precipitated and freed from the catalytic amount of amine hydrochloride.

Melting range 250 - 280 ° C, red. Viscosity (0.5 wt% in chloroform at 25 ° C) 0,?.

Example 12.

According to Example 6, 73.2 g (0.2 mol) of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 33.48 grams (0.14 moles) of sebacic acid dichloride, 10.98 grams (0.06 moles) of adipic acid dichloride and 0.5 ml of tri-n-butylamine in 100 ml of xylene reacted. After completion the elimination of hydrochloric acid, the xylene and the polymer were sucked off in a water jet vacuum condensed further for a further 2 hours at 2600C and approx. 4 mm Hg.

The resulting product has a melting range of 138 - 1400C and a reduced viscosity of 0.6 (measured in chloroform at 250C as 0.5 weight percent solution).

Example 13: According to Example 7, 36.6 g (0.1 mol) of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane were obtained with a mixture of 19.13 g (0.08 mol) sebacic acid dichloride, 3.1 g (0.02 mol) Succinic acid dichloride, and 0.5 ml of pyrrolidine acetonitrile in 120 ml of o-dichlorobenzene brought to reaction. After the elimination of hydrochloric acid had ended, the polymer became precipitated with ethanol. The polymer has a melting range of 210-2300C and a reduced viscosity (0.5% by weight in chloroform at 250C) of 0.5.

Example 14: In a three-neck flask equipped with a stirrer, condenser and inlet pipe, 658.8 g of 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 304.2 g of glutaric acid dichloride and 2 ml of di-n-butylcyclohexylamine in 3 l of o-dichlorobenzene brought to reaction.

The theoretical amount of hydrogen chloride had been split off after about 48 hours. The polymer was precipitated with methanol.

Melting range 205 - 27000, reduced viscosity (0.5% by weight in chloroform at 25 ° C) 0.73.

Example 15: In a three-neck flask equipped with a stirrer, cooler and inlet pipe, there were 36.6 g of 2,2-bis (3,5-dichloro-4-hydroxypehnyl) propane (0.1 mole), 16.74 g sebacic acid dichloride (0.075 mole), 6.09 g terephthalic acid dichloride (0.03 mol) and 0.5 ml of tri-n-butylamine in 120 ml of o-dichlorobenzene reacted.

After about 18 hours, the theoretical amount of hydrogen chloride had been split off. The xylene was drawn off under a water jet vacuum and the polymer with methanol failed.

The polymer has a melting range of 270-310 ° C, red.

Viscosity in chloroform of 0.56 (measured as a 0.5 weight solution at 25 ° C).

Examples 16 and 17: The batch was also carried out in the presence of N, N-di-n-butylaminoacetonitrile and N-methylpyrrolidine carried out as a catalyst. The result was similar achieved.

Example 18: In a three-necked flask equipped with a stirrer, condenser and inlet tube, 36.6 g of 2,2-bis- (3,5-dichloro-4-hydroxypheny) propane, 19.7 g of pimelic acid dichloride, 0.5 ml of N, N-dimethylaniline in 200 ml of xylene for reaction brought.

After about 22 hours, the theoretical amount of hydrogen chloride had been split off. The xylene was distilled off under a water jet vacuum and the polymer was distilled off for 2 hours condenses further at 24,000 and approx. 1 mm Hg; this left the last traces of amine hydrochloride removed. The polymer has a melting range of 180-220 ° C, red. viscosity as a 0.5% by weight solution in chloroform, measured at 25 ° C., 0.57.

Example 19: According to Example 12, 73.2 g (0.2 mol) of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 33.45 grams (0.14 moles) of sebacic acid dichloride, 10.98 grams (0.06 moles) of adipic acid dichloride and 0.5 ml -N-phenolmorpholine reacted in 100 ml of xylene.

After completion of the hydrochloric acid cleavage, the xylene was in vacuo distilled off and the polymer is further condensed for 2 hours at 2600C and approx. 4 mm Hg, as a result, the amine hydrochloride, which had arisen from the tertiary amine, removed.

The polymer has a melting range of 140 - 165 ° C and red.

Viscosity (in chloroform) 0.6 as a 0.5% by weight solution at 2500.

Example 20: According to Example 7, 36.6 g (0.1 mol) of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, a mixture of 19.13 g (0.08 mol) of sebacic acid dichloride and 0.5 ml of ethyl-di-n-butylamine, 3.1 g (0.02 mol) of succinic acid dichloride in 120 ml of o-dichlorobenzene for the reaction brought. After completion of the hydrochloric acid delay, the polymer was treated with methanol failed. The polymer has a melting range of 210-23000, red. viscosity (0.5% by weight solution in chloroform at 250C) of 0.5.

Examples 21 to 25: According to Example 6, 36.6 g of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane were obtained and 23.9 g of sebaoic acid dichloride in 100 ml of xylene in the presence of 1% by weight of the following Catalysts implemented: morpholine acetic acid morpholide, dimethylaniline, N-phenylmorpholine, N-methylpyrrolidine and tri-n-butylamine. The melting range of the polymers is between 145 - 1900C and reduced viscosities as a 0.5% by weight solution in chloroform determined at 250C, between 0.5 and 0.65.

Claims (4)

P a t e n t a n s p r ü c h e 1. Process for the production of polyesters from halogenated, dihydric phenols and acid chlorides of dibasic carboxylic acids, characterized in that the carboxylic acid chlorides with the halogenated, divalent Phenols in the presence of catalytic amounts of tertiary amines, their amino group is not part of an aromatic ring system, possibly using of inert solvents, at a temperature of 50-2500C, preferably from 80-180 ° C. 2. The method according to claim 1, characterized in that the tertiary amines in amounts of 0.1-20 mol%, preferably 0.2-2 mol on the acid halide. 3. The method according to claim 1 and 2, characterized in that one the tertiary amines are used in the form of their hydrochlorides. 4. The method according to claim 1 to 3, characterized in that one the tertiary amines are used in the form of their salts from halogenated phenols and amines.