DE1495335B2 - PROCESS FOR MANUFACTURING LINEAR, THERMOPLASTIC POLYESTERS WITH FREEZING TEMPERATURES OVER 100 DEGREES C. - Google Patents

Description

Antimony oxide and 30 mg triphenyl phosphite melted with stirring in a nitrogen atmosphere, _{held at 180 ° C. for 2} hours, heated to 280 ° C. in 3 hours and kept at 280 ° C. and 0.2 torr for 2 hours. A very tough, pale yellow-brown colored product with a viscosity number (measured on a solution of 1 g of substance in 100 ml of solution at 25 ° C., solvent: phenol-tetrachloroethane 60/40 [percent by weight]) of 0.633 dl / g was obtained. The viscosity number increased to 0.79 dl / g in a further hour. The softening point, measured with the aid of a penetrometer (needle base area 1 mm ^2, the total load 35Og, 0.1 mm penetration depth) was 127 ⁰ C. A comparison experiment in which each 15.9 g of diphenyl terephthalate and diphenyl isophthalate, 18.2 g of bisphenol A, 3 g of triethylene glycol, 30 mg of antimony oxide and 50 mg of triphenyl phosphite were reacted with one another in the manner indicated above, yielded a brittle, darker colored polycondensate, the viscosity of which reached a maximum after about 3 hours at 280 ° C and 0.2 Torr, which was only 0 .41 dl / g was.

Example 2

There were 15.9 g of diphenyl terephthalate (0.05 mol), 14.3 g of diphenyl isophthalate (0.045 mol), 16.0 g of bisphenol A (0.07 mol), 3.1 g of technical-grade neopentyl glycol (2,2-dimethyl propanediol-1,3) (0.03 mol) and 1.3 g of diphenyl carbonate (0.006 mol) in the presence of 30 mg of antimony oxide and 40 mg of triphenyl phosphite transesterified and polycondensed in the above-mentioned manner. After a polycondensation time of 4V ₂ hours at 280 ° C. and 0.2 torr, a pale yellow, tough product with a viscosity number of 0.769 dl / g and a softening point of 145 ° C. was obtained.

When this experiment is repeated using equimolecular amounts of diphenyl terephthalate and diphenyl isophthalate in a molar ratio of 0.5: 0.5 on the one hand and bisphenol A and neopentyl glycol (technical) in a molar ratio of 0.7: 0.3, on the other hand, a viscosity number of the polycondensate of 0.31 was not exceeded for any polycondensation time.

Claims (1)

1 2 It has now been found that the described Claim: Disadvantages can be avoided by the invention. The invention relates to a method of manufacture A process for preparing linear, thermoplastic linear, thermoplastic polyester having Einfrierplastischer polyesters with glass transition temperatures above 5 temperatures above 100 ° C by heating aryl 100 ⁰ C by heating aryl esters of terephthalic esters of terephthalic acid, of isophthalic acid or phthalic acid, isophthalic acid or their mixtures with equimolecular amounts of a mix with equimolecular amounts of a mixture of 90 to 70 mol percent of a diphenol mixture of 90 to 70 mol percent of a diphenol and 10 to 30 mol percent of a dialcohol in counter and 10 to 30 mol percent of a dialcohol in In the presence of polycondensation catalysts and in the presence of polycondensation catalysts, the presence of solvents, until a product with and in the absence of solvents, until a viscosity number above 0.5, measured in a phenol product with a viscosity number above 0.5, tetrachloroethane -Solutions (60: 40 mol percent) when measuring iq phenol-tetrac chloroethane solutions 25 ° C, formed according to patent application P 14 95 (60:40 mol percent) at 25 ° C, 15 265.9-44, characterized in that 1 to according to patent application P 14 95 265.9-44, d a- 10 mole percent of the aryl esters of terephthalic acid characterized in that 1 bis and / or isophthalic acid is replaced by excess amounts of 10 mole percent of the aryl esters of terephthalic acid of aryl esters of volatile dibasic acids and / or isophthalic acid with excess men-. genes of aryl esters of highly volatile dibasic 20 In practice, the total amount of all aryl esters Acids replaced. of a batch maximum 110 mol percent, based on the total amount assumed to be 100 mole percent of diphenols and dietary alcohols, while the total amount of aryl esters of terephthalic acid, the Subject of the German patent application P 14 95 25 isophthalic acid or mixtures thereof about 95 mol 265.9-44 is a method of making linear, percent can be. It must be taken into account thermoplastic polyester with glass transition temperatures that with the accumulation of ester groups above 100 ° C by heating esters of terephthalic, highly volatile dibasic acids in the polycondensate acid, isophthalic acid or mixtures thereof with sat in general its hydrolytic stability a mixture of diphenols and dialcohols in 30 is reduced, so that advantageous the amount of Presence of polycondensation catalysts and aryl esters of terephthalic acid, isophthalic acid in the absence of solvents that thereby become or mixtures thereof taking into account the indicates that the aryl esters of the acids are expediently close to 1Q0 mol- equimolecular amounts of the mixture should be from 90 to percent. A considerably larger excess 70 mole percent of the diphenol and 10 to 30 mole percent of aryl esters of highly volatile dibasic acids cent of the dialcohol is heated until a product fails, however, for the success of the polycondensation with a viscosity number above 0.5, measured in phenol- a disadvantage when talking about the extension of the Tetrachloroethane solutions (60:40 mol percent) refrains from the reaction time. 25 ° C. There are already mixed polyesters made of low molecular weight with the exclusive use of the aforementioned 40 larem polyethylene terephthalate and a polycar starting materials, the above-mentioned method bonat dihydric phenols is known. Such products have the disadvantage that not all products with certainty differ significantly from those of the polyesters produced according to this invention to achieve sufficiently good mechanical properties. The required degree of polycondensation, namely negotiated in the case of the known polyesters due to the viscosity number, is 45 typical BJoek copolymers, while the invented can. This difficulty arises from the fact that polyesters produced in accordance with the invention are not necessarily block polyesters in equivalent amounts of the diphenols and the mers. The latter contain the built-in di-dialcohols on the one hand and the diaryl ester of the terephthalic radicals of the glycols and phenols in statistical distribution of thalic acid, isophthalic acid or mixtures thereof. On the other hand, the known polymers also contain nuts. Any 5 ° in contrast to the excess of aryl esters of the acids mentioned, polyesters leads to polyesters no phenyl ester groups of the tere or only to low molecular weight poly groups of carbonic acid which are unsuitable for most uses, but only phenyl esters. In the condensates according to the invention, during a possible excess of polyesters produced, the phenyl carbonate diphenols or dialcohols are only present in minor amounts, causing severe discoloration. But even with extremely precise weights. The reactants produced by the process according to the invention are, surprisingly, guaranteed to achieve a prepared polyester compared to the above-described high degree of polycondensation, which is not always known polyesters, because under the reaction conditions they have a special technical advantage; they are known to occur side reactions that are considerably more resistant to hydrolysis,
the equivalence of the reactants to one another would disturb. Another disadvantage of the example 1 above
given method is that most of the Commercially available dietary alcohols are not completely pure, 15.9 g of di- but impurities, often in the form of 65 phenyl terephthalate (0.05 mol), 14.3 g diphenyl iso- Moisture or from dialcohol ethers, contain phthalate (0.045 mol), 1.3 g diphenyl carbonate so that corresponding cleaning operations are required (0.006 mol), 18.2 g bisphenol A (0.08 mol), 3 g tri- are lich. ethylene glycol (single distilled) (0.02 mol), 30 mg