DE1808562A1 - Linear thermoplastic silicon-containing aromatic poly - esters - Google Patents

Abstract

Preparing linear silicon containing polyarylesters Transesterification of diarylesters of of terephthalic and/or isophthalic acid with dihydric phenols in presence of known transesterification catalysts at 80-220 degrees C, followed by polycondensation at up to 350C under pressure 0.01-4 Torr, characterised in that 0.001-0.2 mol% of diaryloxydiphenylsilanes (with respect to amt of phenol used) are added to the reaction mass before or during transesterification or polycondensation. The aryl residue of the diaryl ester and the diaryloxydiphenylsilane may be the same. The dihydric phenol may be 2,2-bis-(4-hydroxyphenyl)-propane. The aryl residue may be phenyl or cresyl. Presence of the diaryloxydiphenylsilane makes removal of any excess of the other reactants from the polyester easier.

Description

Process for the production of linear, thermoplastic, silicon-containing Polyaryl ester The invention relates to a process for the production of linear, thermoplastic, silicon-containing polyaryl ester through conversion of diaryl esters of tere- and / or isophthalic acid with dihydric phenols in the presence of known ones Transesterification catalysts at temperatures of 80 - 2200C and subsequent polycondensation at temperatures up to 3500C and a pressure of 0.01-4 Torr. The procedure is particularly characterized in that the approaches before or during the transesterification or polycondensate 0.001 to 0.2 mol r diaryloxydiphenylsilanes, based on the dihydric phenol.

Linear, from aromatic dicarboxylic acids and dihydric phenols Manufactured polyesters have excellent properties. They are transparent and extremely tough; in addition, they have excellent impact strength on.

These polyaryl esters can be formed by melt condensation from exactly equimolar Amounts of terephthalic acid and isophthalic acid diaryl ester with bis-phenol A (2; 2-bis- (4-hydroxyphenyl-).

propane).

The diaryl esters of tere- and isophthalic acid as well as the divalent ones Phenols, such as bis-phenol A, are extremely difficult to volatilize, so that an excess of one or the other component during the Polgkondensation usually cannot be completely removed and in many cases only too due to chain termination a low molecular weight polyester. Reproducibility of the products of such Approach is also difficult.

It has now been found that the disadvantages of the known processes for the production of linear, thermoplastic polyaryl esters by transesterification of diaryl esters of tere- and / or isophthalic acid with dihydric phenols in the presence of known ones Transesterification catalysts at temperatures of 80 - 2200C and subsequent polycondensation at up to 350ob and a pressure of 0.01-4 Torr so that the approaches before or during the transesterification or polycondensation 0.001 to 0.2 mol% of diaryloxydiphenylsilanes, based on the dihydric phenol, added.

The particular advantage is that there is an excess of acrylic esters or dihydric phenols, which are otherwise difficult to remove by distillation and bring about the above-mentioned disadvantages with which diphenyldiphènoxysilane react, while, in addition, diphenyldiphenoxysilane is present due to its lighter weight Volatility can be removed by distillation.

A starting component for the production of the polyaryl ester containing silicon are the diaryl esters of tere- and isophthalic acid. The phenol are used as aryl radicals and the various cresyl radicals are preferred. Mixtures can of course also be used of diaryl esters of tere- and isophthalic acid can be used. The ratio of Diaryl esters to one another is not critical; however, a mixture of molar ratio of 1: 1.

As starting products for the implementation of the manufacturing process the polyaryl esters are suitable, optionally alkyl-substituted, mononuclear or polynuclear, dihydric phenols, which can be both condensed and non-condensed.

Suitable dihydric phenols are, for example, the mononuclear, such as hydrochloride, resorcinol, brenzetechin.

Polynuclear, dihydric phenols, the nuclei 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 dihydroxydi-phenyl, for example. 2,2'-, 2,4'-, 3,3'-, 4,4'-dihydroxydiphenyl, 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, dihydroxybenzophenone, such as 2,2'-, 2,3'-, 2,4'-,), 3'-, 3,4'-, 4,4'-, 4,6'-, 6,6'-dihydroxybenzophenone and the like, dihydroxydiphenyl sulfide, such as 2,2'-., 4,4 '-J) iliydroxydiphenylsulfid, Dihydroxydiphenyldisulfide, Dihydroxydiphenylsulfid, such as 2,2'-, 4,4'-dihydroxydiphenyl sulfones, Dihydroxydiphenylalkane or cycloalkane, 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'-, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxydiphenylmethyl methane, 4,4'-dihydroxydiphenylphenyl methane, 4,4'-dihydroxydiphenyldiphenyl methane, Bis- (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis (4-hydroxyphenyl) -cycolohexane, bis- (4-hydroxyphenyl) -cyclohexylmethane, 1,1-bis- (4-hydroxyphenyl) -ethane i.a.

The polynuclear, condensed, dihydric phenols include the Dihydroxynaphthalenes or anthracenes etc.

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 2s2-bis (4-hydroxyphenyl) propane.

The transesterification or polycondensation approaches can be 0.001-0.2 Mol% of diaryloxydiphenylsilanes, based on the amount of dihydric phenol, were added will. Particularly suitable are those which have a phenoxy or aryloxy radical Wear cresyl residue. Those which have the same aryl radical are particularly preferred like the diaryl esters of tere- or isophthalic acid.

The transesterification is initially carried out at normal pressure at temperatures of 80-220C, preferably 150-200 ° 0. Then if necessary the temperature gradually increased up to approx. 3500C. This reaction phase is preferred carried out at a pressure of 0.01 to 4 torr in the final stage of the reaction. In The transition area can also be used at normal pressure.

The reaction is expediently carried out under a dry inert gas, such as nitrogen, carbon dioxide, etc. carried out.

The first phase required depending on the dimensions of the equipment and the Amount of reactants approx. 3 - 5 hours, during the second stage in general approx. 1 - 3 hours are required.

For the transesterification, the known catalysts, such as z.3. Oxides, Hydroxides, hydrides, amides and alcoholates of the alkali and alkaline earth metals, as well Zinc oxides, sieioxyde and antimony trioxide, for example sodium ethylate or magnesium ethylate, or titanates, such as tetra-n-butyl titanate and tetraphenyl titanate, can be used.

The silicon-containing polyesters have antistatic properties.

The method according to the present invention is carried out by the following Examples illustrated.

Example 1: A mixture of 15.9 g (0.05 mol) of diphenyl terephthalate, 14.51 grams (0.045 moles) of diphenyl isophthalate and 2.027 grams (0.05 moles) of diphenyldiphenoxysilane was treated with 22.8 g (0.1 mol) of bisphenol A in the presence of 32 mg of Sb2O3 while gassing with nitrogen interesterified at 1800 C. After 3 hours the temperature rose to 2300 for 1 hour C, then increased to 2500 C for 1 hour and the reaction under phenol distillation continued.

The temperature was then increased to 3100 for the polycondensation C increased and the condensation vessel evacuated. At a pressure of 0.1-0.2 torr the polycondensation took place with a marked increase in the viscosity of the melt Fast forward and was over after 1 hour.

A slightly brownish polyester was obtained.

Melting range: 240 - 2900 ¢ Reduced viscosity: 0.52 (determined as 0.5 % By weight B6 solution in phenol / tetrachloroethane 60/40% by weight at 25 ° C).

Example 2: 15.9 g (0.05 mol) diphenyl terephthalate, 15.1 g (0.0425 Mol) diphenyl isophthalate, 1.014 g (0.0025 mol) diphenyldiphenoxysilane were in Presence of 92 mg Sb2O3 with 22.8 g (0.1 mol) of bisphenol A below transesterified and polycondensed under the conditions of Example 1. It became an easy one brownish polyester obtained.

Melting range: 235 - 280 ° C Reduced viscosity: 0.70 (determination according to Example 1) Example 3: Starting mixture and conditions correspond to the example 1, but instead of 32 mg Sb2O3 24.5 mg PbO were used. The reaction ended after 5 hours.

The polyester obtained has a melting range of 245 to 290 ° C on, the red. Viscosity was 0.55 (determination according to Example 1).

Examples 4-7: As in Example 1, further experiments were carried out. The proportions, catalysts and other reaction conditions can can be found in the table below.

Tabel: @sp. Starting products mol% transesterification transesterification Torr polycondensation melting Red.Vis. Beginning range (0.5 wt.% change catalyst poly- i.Phenol / Ge Duration temp. Duration temp. Pressure Sator ester tetrachloro weight (h) (° C) (h) (° C) (Torr) Koffler ethane 60 / loss Bank (° C) 40% by weight. *) at 25 ° C) (° C) 4 diphenylteres- 0.05 3 180 Sb2O3 760 phthalate, di- 0.04875 1 210 phenylisophtha- lat, diphenyldi- 0.00125 1 250 760 230-280 0.64 about 415 phenoxysilane Bisphenol A 0.1 1,320 0.15 325 0.2 5 diphenylteres- 0.05 3 180 Sb2O3 760 phth.Diphenyl- 0.0425 1 210 isophthalate, Diphenyldiphe- 0.0025 1 250 760 235-280 0.70 about 425 noxysilane Bisphenol A 0.1 1 1/4 335-0.2 340 6 Diphenylteres- 0.05 3 180 Sb2O3 760 phth., diphenyl- 0.045 1 210 isophthalate, Diphenyldiphe- 0.005 1 250 760 240-290 0.52 about 445- noxysilane 450 Bisphenol A 0.1 1 330- 0.2- 335 0.3 7 Diphenylteres- 0.05 3 180 Sb2O3 760 phth., diphenyl- 0.0425 1 210 isophthalate, Diphenyldiphe- 0.075 1 250 760 noxysilane Bisphenol A 0.1 1 325- 0.1- from 260 0.52 about 450 330 0.2 *) using a thermal balance at a heating rate of 8 ° C / min. certainly.

Claims (7)

Claims 1. Process for the production of linear, thermoplastic, silicon-containing Polyaryl esters by transesterification of diaryl esters of tere- and / or isophthalic acid with dihydric phenols in the presence of known transesterification catalysts at temperatures from 80 to 220 ° C, preferably 150 to 200 ° C, and subsequent polycondensation at temperatures up to 35,000 and a pressure of 0.01 to 4 Torr, characterized in that that before or during the transesterification or polycondensation 0.001 to 0.2 mol% Diaryloxydiphenylsilane, based on the amount of dihydric phenol used, is added. 2e method according to claim 1, characterized in that one diaryl ester and diaryloxydiphenylsilane with the same aryl radical are used. 3. The method according to claim 1 and 2, characterized in that one 2,2-bis (4-hydroxyphenyl) propane is used as the dihydric phenol. 4. The method according to claim 1-3, characterized in that the Diaryl ester of tere- or isophthalic acid is a diphenyl ester. 5. The method according to claim 1-3, characterized in that the Diaryl ester of tere- or isophthalic acid is a dicresyl ester. 6. The method according to claim 1-5, characterized in that the Diaryloxydiphenylsilane is a diphenoxydiphenylsilane. 7. The method according to claim 1-5, characterized in that the Diaryloxydiphenylsilane is a dicresyldiphenyl silane.