JPS6320852B2 - - Google Patents

Description

[Detailed description of the invention]

The invention is in accordance with German Published Patent Application No. 2651639.
A polyester diol from an aliphatic dicarboxylic acid and an aliphatic diol having a molecular weight n (number average) of 250 or more, preferably about 600 or more is combined with a carbonic acid bis-aryl ester in the presence of a catalyst and about 35 mm
Hg or less, preferably about 25 to 1 mmHg under vacuum.
heated to a temperature of 100 to 200°C, preferably about 110 to 180°C, with the exception of 1 per OH group of the polyester diol.
A polyester diol bis-aryl carbonate prepared by using more than mol of carbonic acid bis-aryl ester, preferably about 1.1 to 2.25 mol, and distilling off the resulting compound and excess carbonic acid bis-aryl ester. , in the presence of a catalyst and below about 35 mmHg, preferably about 25-0.1 mm
About 100~200℃ under Hg vacuum, preferably about 110~
react with diphenol at a temperature of 180° C., but using more than 1 mole, preferably about 1.1 to 2 moles of diphenol per mole of carbonate aryl ester groups of the polyester diol bis-aryl carbonate, and distill the resulting hydroxyaryl compound. The present invention relates to a method for producing polyester diol bis-diphenol carbonate. The invention furthermore relates to the polyester diol bis-diphenol carbonate prepared by the method described above and its use for the production of polyesters/polycarbonates and the resulting polyesters/polycarbonates. The reaction of transesterifying polyester diol bis-aryl carbonates with excess diphenol to produce the corresponding polyester diol bis-diphenol carbonates prepared according to DE 2651639 is carried out at reaction temperatures up to 200°C. The process proceeds surprisingly smoothly and without any side reactions, even in this case. Furthermore, the molecular weight distribution provided by the starting materials is not changed, the polyester polyol is not regenerated, and no polycondensation to polycarbonate takes place. A. Preparation of Polyester Diol Bis-Aryl Carbonates The polyester diol bis-aryl carbonates required for the preparation of the polyester diol bis-diphenol carbonates according to the invention are prepared according to DE 2651639 A1. DE 2651639 discloses the use of polyester diols having a molecular weight n (number average) of about 250 or more, preferably about 600 or more together with carbonate bis-aryl esters in the presence of a catalyst and up to about 35 mmHg, preferably from about 25 to About 100~200 under 0.1mmHg vacuum
°C, preferably from about 100 to 180 °C, provided that more than 1 mole, preferably about 1.25 to 2.25 moles of bis-carbonate per OH group of the polyester diol
The present invention relates to a process for producing carbonic aryl esters of polyester diols having n of about 250 or more, preferably about 600 or more, using an aryl ester and distilling off the formed hydroxyaryl compound and excess bis-aryl ester. Furthermore, DE 26 51 639 also relates to carbonate esters of polyester diols prepared in this way. Particularly suitable polyester diols for the present invention are polyester-diols from aliphatic dicarboxylic acids and aliphatic diols. The polyester diol used in the method of the invention is a reaction product of a dihydric alcohol and a dibasic carboxylic acid. In place of the free dicarboxylic acids, corresponding dicarboxylic acid anhydrides or esters of the corresponding dicarboxylic acids with lower alcohols and mixtures thereof can also be used in the production of polyester diols. Examples of dicarboxylic acids are oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid and dimeric and trimeric acids. Fatty acids such as oleic acid and optionally mixtures with monomeric fatty acids. Possible dihydric alcohols include ethylene glycol, propylene 1,2- and 1,3-glycol, butylene 1,
4- and 2,3-glycol, hexane-1,6
-diol, octane-1,8-diol, neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,
These are thiodiglycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol. The content of terminal hydroxyl groups and thus the "average" molecular weight n is determined by choosing a limited excess of alcohol. Polyesters from aliphatic starting compounds are preferably used. Furthermore, polyester diols may be prepared, for example, by polymerization of lactones, such as ε-caprolactone, or by condensation of hydroxycarboxylic acids, such as ω-hydroxycaproic acid, and hydroxy-containing starting compounds. n is determined as described above. The carbonate bis-aryl esters used are particularly of the formula [In the formula, Ar is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.] Possible substituents are in particular _C1 - _C4 alkyl, and also nitro and halogen, such as chlorine or bromine. Examples of bisaryl carbonate esters are diphenyl carbonate, alkyl-substituted diphenyl carbonates such as ditolyl carbonate, halogen-substituted diphenyl carbonates such as dichlorophenyl carbonate, dinaphthyl carbonate and alkyl- and halogen-substituted dinaphthyl carbonates. In these compounds, the nitro, alkyl or halogen substituents on the two phenyl or naphthyl nuclei of the diaryl carbonate may be the same or different and may be symmetrical or asymmetrical with respect to each other. Thus, for example, phenyltolyl carbonate, phenylchlorophenyl carbonate, 2-tolyl-4-tolyl carbonate or 4-tolyl-4-chlorophenyl carbonate are also suitable for the process of the invention. That is, polyester bis-aryl carbonate is particularly suitable for the simplified formula [In the formula, Ar has the same meaning as above, and -(polyester)- is one divalent group of the above-mentioned polyester diol]. Catalysts suitable for the process of the invention are basic transesterification catalysts, such as alkali metal phenolates or alkaline earth metal phenolates, alkali metal alcoholates or alkali metal alcoholates, and tertiary amines, such as triethylenediamine, morpholine, pyrrolidine, Pyridine and triethylamine, or metal compounds, antimony trioxide,
These are zinc chloride, titanium tetrachloride, and titanate tetrabutyl ester. The catalyst is about 10 to 10% based on the total weight of polyester diol and carbonate bis-aryl ester
The amount is 300ppm. The catalyst may be used in smaller amounts than those stated above when the starting compound is free of basic impurities when using an acid catalyst and free of acid impurities when using a basic catalyst. For the carbonate esters prepared according to the process of the invention, as little catalyst as possible should be used in order to minimize the inherent color. The process according to the invention is preferably carried out in bulk, ie in the absence of solvents. however,
Solvents which are inert under the reaction conditions, such as aliphatic or aromatic hydrocarbons which may contain nitro groups, can optionally also be used. The reaction time depends on the reaction temperature and the type and amount of catalyst used and is usually about 1/2 to 24 hours. After the completion of the reaction, in the case of a discontinuous process, the hydroxyaryl compound and excess biscarbonate produced during the process are removed by distilling off the hydroxyaryl compound and unreacted diaryl carbonate during the reaction. - Aryl esters can be removed. If the transesterification reaction is carried out in a continuous manner, the hydroxyaryl compound is separated from the reaction mixture by fractional distillation. According to a particularly preferred embodiment of the process, the reaction uses sodium phenolate as a catalyst and the polyester diols and carbonic acid bis-aryl esters from aliphatic dicarboxylic acids and aliphatic diols are reacted with hydroxy groups to carbonic acid bis-aryl esters. It is carried out at about 150°C using a molar ratio of about 1:2. The average molecular weight shown in the examples is number average n,
Determined by measuring OH number. The Scheutaudinger index [η] shown in the example is
Measured in THF at 25°C and expressed in dl/g. The definition of the Scheutaudinger index can be found in HG Elias, “Makromolekule”, Huthig
& Wepf—Verlag Basle, p. 265. Examples Example 1 n-hexane with average molecular weight n=800
800 parts by weight of polyester diol of 1,6-diol and adipic acid, 856 parts by weight of diphenyl carbonate and 0.05 part by weight of sodium phenolate were heated to 150° C. under nitrogen with stirring at 15 mm Hg for 3.5 hours; during this period 187 parts of phenol Part by weight was distilled off. Excess diphenyl carbonate is then removed using a wet wall evaporator.
It was removed at 200°C/0.1mmHg. This resulted in a colorless viscous oil. [η] _THF = 0.072 OH number = 0 Analysis: Calculated value: C, 66.5%; H, 8.2% Experimental value: C, 63.3%; H, 8.3% Example 2 n-hexane with average molecular weight n = 800
800 parts by weight of polyester-diol of 1,6-diol and adipic acid, 750 parts by weight of diphenyl carbonate and 0.1 part by weight of antimony trioxide were heated to 170°C for 4.5 hours at 15 mmHg with stirring under nitrogen, during which time the phenol 188 parts by weight were distilled off. Excess diphenyl carbonate was then removed according to Example 1. This resulted in a colorless viscous oil identical to the product prepared in Example 1. Example 3 Adipic acid with average molecular weight n=1900 and equimolar ethylene glycol and butane-1,4
-1000 parts by weight of polyester diol,
385 parts by weight of diphenyl carbonate and 0.1 part by weight of sodium phenolate were heated at 12 mmHg with stirring under nitrogen.
and heated to 150°C for 4.5 hours. During this period, 100 parts by weight of phenol were distilled off. Excess diphenyl carbonate was then removed in a wet wall evaporator at 200°C/0.1 mmHg. A colorless viscous oil was obtained. [η] _THF = 0.112 OH number = 0 Analysis: Calculated value: C, 55.0%; H, 7.6% Experimental value: C, 54.8%; H, 7.5% Example 4 Adipic acid with average molecular weight n = 1.828 and moles 1000 parts by weight of polyester diol of a mixture of n-hexane-1,6-diol/neopentyl glycol with a ratio of 65/35, 385 parts by weight of diphenyl carbonate and 0.12 parts by weight of sodium phenolate were stirred under nitrogen at 12 mmHg for 5 hours. Heated to 160°C. During this period, 101 parts of phenol were distilled off.
Excess diphenyl carbonate was then removed using a wet wall evaporator for 200 ml.
It was removed under ℃/0.1 mmHg. A viscous oil was obtained. [η] _THF = 0.118 OH number = 0 Analysis: Calculated value: C, 58.3%; H, 7.7% Experimental value: C, 58.1%; H, 7.6% B Manufacture of polyester diol bis-diphenol carbonate German published patent According to No. 26516392, polyester diols from aliphatic dicarboxylic acids and aliphatic diols and formula [wherein Ar is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, preferably phenyl] and is produced from a carbonic acid bis-aryl ester of [In the formula, -(polyester)- represents a divalent group of polyester diol] Polyester diol bis-aryl carbonate represented by the following is reacted with diphenol to produce polyester diol bis-diphenol carbonate. In practice, particularly with regard to the conversion of polyester diol bis-diphenol carbonate to polyester/polycarbonate, it is possible to convert polyester diol bis-aryl carbonate to diphenol together with excess carbonate bis-aryl ester, i.e. without distilling it off. It can be reacted to form polyester diol bis-diphenol carbonate. During this reaction, biscarbonate that had not been distilled off in advance
Aryl ester reacts with diphenol to form OH
A monomeric or low weight polymeric carbonate of diphenol containing groups is provided. Suitable diphenols for the preparation of the polyester diol bis-diphenol carbonate according to the invention are: hydroxy, resorcinol, dihydroxydiphenyl, bis-(hydroxyphenyl)-alkane, bis-(hydroxyphenyl)-cyclo Alkanes, bis-(hydroxyphenyl) sulfide, bis-(hydroxyphenyl) ether, bis-(hydroxyphenyl) ketone, bis-(hydroxyphenyl) sulfoxide, bis-(hydroxyphenyl) sulfone and α,α -Bis-(hydroxyphenyl)-
Diisopropylbenzene and their nuclear alkylated and nuclear halogenated compounds. These and further suitable aromatic hydroxy compounds are described in U.S. Pat.
No. 3271368, No. 2991273, No. 3271367, No.
3280078, 3014891 and 2999846 and German patents 2063050 and 2211957. Examples of suitable diphenols are bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, α,α- Screw-
(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-chloro-4-
hydroxyphenyl)-propane and 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane. Suitable diphenols are, for example, 2,2-bis-
(4-hydroxyphenyl)-propane, 1,1
-bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3,5-dichloro-4
-Hydroxyphenyl)-propane and 2,2-
It is bis-(3,5-dibromo-4-hydroxyphenyl)-propane. According to the invention, one or more suitable diphenols can be used. Suitable catalysts for the preparation of the polyester diol bis-diphenol carbonates according to the invention are basic transesterification catalysts, such as alkali metal phenolates or alkaline earth metal phenolates, alkali metal alcoholates or alkaline earth metal alcoholates, tertiary amines. , such as triethylenediamine, morpholine, pyrrolidine, triethylamine and tributylamine, and pyridine, or metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and tetrabutyltitanium. The catalyst is used in an amount of about 10 to 200 ppm based on the total weight of polyester diol bis-aryl carbonate and diphenol used. When using an acid catalyst when the starting material is free of basic impurities and when using a basic catalyst when the starting material is free of acid impurities, smaller amounts of catalyst than those mentioned above can optionally be used. In the interest of minimizing the inherent color of the products of the invention, as little catalyst as possible is preferred. The process for preparing polyester diol bis-diphenol carbonates according to the invention is preferably carried out in bulk, ie in the absence of solvents. However, it is optionally also possible to use solvents which are inert under the reaction conditions, such as unsubstituted and, for example, aliphatic or aromatic hydrocarbons substituted with nitro groups. The reaction time for transesterification for the production of polyester diol bis-diphenol carbonate is from about 1/2 to about 24 hours depending on the reaction temperature and the type and amount of catalyst. Polyester diol bis-diphenol carbonate is prepared by preparing a mixture of polyester diol bis-carbonate monoaryl ester, diphenol and catalyst prepared, for example, according to DE 2651639, at a temperature of from about 100 to about 200°C, preferably from about 110 to 180°C.
It is produced by heating under vacuum to a temperature of 0.degree. C. and distilling off the phenol formed from the reactor as the reaction progresses. In this process, diphenol is used in excess, more than 1 mole, preferably from about 1.1 to about 2 moles, of diphenol per carbonate phenyl ester group of the polyester diol bis-carbonate monoaryl ester.
According to a particularly preferred embodiment, the molar ratio of biscarbonate monoaryl ester to bisphenol A is 1:3.
The reaction of the polyester diol biscarbonate monoaryl ester and bisphenol A is carried out at 150 DEG C. and under a vacuum of 25 to 0.1 mmHg using disodium phenolate of bisphenol A as a catalyst. In particular, according to the present invention, polyester diol biscarbonate monoaryl ester is prepared by the following formula: [In the formula, X is -CH ₂ -,

【formula】

[Formula] represents O, S or SO ₂ , and Y ₁ to _{Y 4} may be the same or different and represent hydrogen or a halogen, such as chlorine or bromine] to form the simplified formula [In the formula, -(polyester)- represents a divalent group of polyester diol, and X and Y ₁ to Y ₄ have the same meanings as above] A polyester diol bis-diphenol carbonate is produced. The polyester diol bis-diphenol carbonates according to the invention are, i.e.
belongs to: In the above formula, -(polyester)- is a divalent group of formulas a to h of the polyester diol described above. C. Process for producing polyester/polycarbonate The polyester diol bis-diphenol carbonate according to the present invention is a starting bis-diphenol carbonate in the production of carbonate by the known two-phase interfacial polycondensation method.
Can be used as a phenol. Polyester/polycarbonates of various structures are thus obtained. The method for producing polyester/polycarbonate according to the invention comprises two methods known for the production of polycarbonate.
According to the phase interfacial polycondensation method, polyester diol bis-diphenol carbonate is combined with other diphenols, especially those of the formula, and phosgene with a pH of about 9 to 14.
It is characterized in that the reaction is carried out at a temperature of about 0 to 80°C, preferably about 15 to 40°C. The polyester/polycarbonates obtained according to the invention are characterized by the presence of an amorphous (elastic) polyester phase and a crystalline (hard) polycarbonate phase or an amorphous/crystalline (hard) polycarbonate. From a morphological point of view, the polyester/polycarbonate has two distinct spatially separated phases: a zone of continuous amorphous polyester and a zone of crystalline or amorphous/crystalline polycarbonate. Because they are multiphase, the polyesters/polycarbonates according to the invention have higher heat distortion temperatures than comparable single-phase polyesters/polycarbonates. Single phase polyester/polycarbonate is described, for example, in US Pat. No. 3,151,615. They are produced by various methods, preferably by the "pyridine" method known from the production of polycarbonates. For example, the production of two-phase polycarbonate/polycaprolactone polymers has hitherto been carried out only by using bischloroformates of polycaprolactone and polycarbonate oligomers (see FR 2 235 965). This means that 2
German patent no. 1162559 not identified as a phase polymer
This is also true for polyester/polycarbonate of No. The use of polyester diol bis-diphenol carbonates according to the invention, compared to the use of the corresponding bischloroformates, has a low sensitivity to hydrolysis, i.e. good storage stability and a well-defined diphenol carbonate.
Provides the advantage of organoleptic reactivity. In particular, the polyester/polycarbonate according to the invention has a high heat distortion temperature due to its crystalline polycarbonate phase. The different phases of the polyester/polycarbonate according to the invention can be detected by differential thermal analysis. Thus, for example, the polyester phase has a deformation temperature of <20°C, the amorphous component of the polycarbonate phase has a deformation temperature of about 100-150°C, and the crystalline component of the polycarbonate phase has a crystalline melting point of about 170-250°C. have The high molecular weight segmented polyesters/polycarbonates produced by the method of the invention and which can be processed as thermoplastics, in addition to their special thermal properties, have good transparency, high elasticity and >400
%. Suitable diphenols for preparing the polyester/polycarbonates of the invention from the polyester diol bis-diphenol carbonates of the invention are those already mentioned for the preparation of the polyester diol bis-diphenol carbonates, in particular those of the formula 4, 4'-dihydroxy-diphenyl, bis-(4-hydroxyphenyl)-methane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, α,α-bis(4-hydroxyphenyl)- p-diisopropylbenzene, 2,2-bis-(3-chloro-4-
hydroxyphenyl)-propane, bis-(hydroxyphenyl) sulfide and 2,2-bis-
(3,5-dimethyl-4-hydroxyphenyl)
-Propane is suitable. For the production of the polyester/polycarbonate according to the invention, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-
dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibrom-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane, and others It can be suitably used as a diphenol. Desired mixtures of these and other diphenols can also be used. The branched main component, which has good flow properties during processing, preferably contains small amounts of trifunctional or more than trifunctional compounds, in particular compounds with 3 or more phenolic hydroxyl groups (the diphenols used). from about 0.05 to about 2 mole percent). Suitable trifunctional or more than trifunctional compounds include:
Phloroglucinol, 4,6-dimethyl-2,4,
6-tri-(3-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-heptane,
1,3,5-tri(4-hydroxyphenyl)
-benzene, 1,1,1-tri-(3-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-(4,4'-dihydroxy) phenyl)cyclohexyl]-propane, 2,4-bis-(4
-hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2'-hydroxy-5'-methylbenzyl)-4-methylphenol 2,4-
Dihydroxybenzoic acid, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, 1,4-bis-(4,4″-dihydroxytriphenyl-methyl)-benzene and 3 ,3-bis-(4-hydroxyphenyl)-2
-oxo-2,3-dihydroindole and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. The polyester/polycarbonate according to the invention is produced through a polyester component and in particular according to DE 2651639 and containing a polyester diol biscarbonate monoaryl ester having 3 or 4 aryl carbonate groups, the diphenols mentioned above, The polyester diol is reacted with triphenol and/or tetraphenol in the process of the invention to produce the corresponding polyester polyol poly(polyphenol carbonate) and the polyphenol obtained is used in the synthesis of the polyester/polycarbonate of the invention. Branching can be achieved by co-using small amounts up to about 50 mole percent per mole of bis-diphenol carbonate. The chain length of the polyester/polycarbonate can be adjusted by adding chain terminators such as monofunctional phenols such as phenol, 2,6-dimethylphenol, p-bromophenol or p-tert-butylphenol. The amount used may be from about 0.1 to about 10 mole percent per mole of diphenol used. The chain length of the polyester/polycarbonate can be adjusted at any time, for example, by adding polyester monol mono-diphenol carbonate in an amount of up to about 50 mol % per mol of polyester diol bis-diphenol carbonate used. High molecular weight segmented polyester/polycarbonates which can be processed as thermoplastics are produced by a two-phase interfacial polycondensation process. For this purpose, the other phenols mentioned above or mixtures thereof are dissolved in an aqueous alkaline solution. The polyester diol bis-diphenol carbonate according to the invention, in particular of the formula or a mixture thereof, is then dissolved in an inert organic solvent which is likewise immiscible with water and this solution is added. Phosgene is then added to the mixture at a temperature of about 0-80°C, preferably about 15-40°C and a pH value of about 9-80°C.
Submit under 14. The amount of phosgene depends on the diphenol used, the cooling means and the reaction temperature;
Generally about 1.1 to 3.0 moles per mole of diphenol. After phosgenation, polycondensation is carried out by adding about 0.2 to 10 mole percent of tertiary aliphatic amine per mole of diphenol. This method requires a phosgenation time of about 5 to 90 minutes, with a
A polycondensation time of minutes to 3 hours is required. The present invention therefore provides a method for combining the polyester diol bis-diphenol carbonates of the present invention, especially those of the formula, with other diphenols, especially those of the formula, and phosgene in a liquid mixture consisting of an inert organic solvent and an aqueous alkaline solution at a temperature of about 0. The reaction is carried out at ~80°C, preferably about 15-40°C and a pH value of about 9-14, and after addition of phosgene about 0.2-10 mol% of tertiary amine is added based on the molar amount of diphenol. A process for producing polyesters/polycarbonates, in which a polycondensation reaction is carried out, and the weight ratio of polyester diol bis-diphenol carbonate to other diphenols is determined by the proportion of polycarbonate and the proportion of polyester in the polyester/polycarbonate. Also related. The invention furthermore relates to the polyester/polycarbonate obtainable by this method. The resulting solution of polyester/polycarbonate in an organic solvent is treated analogously to the solution of thermoplastic polycarbonate produced by the two-phase interfacial process, ie the polyester/polycarbonate is subjected to after-treatment. In particular they are separated by a) known methods, for example by precipitation with methanol or ethanol;
then dried or subjected to shear or dissolved in an organic solvent to gel, or b) already subjected to shear during the separation, e.g. in an extruder to remove volatiles, or c) before the separation 2 It is gelled in a solvent used in the production of polyester/polycarbonate by the phase interface method. Inert organic solvents suitable for the preparation of the polyester/polycarbonate according to the invention are water-immiscible aliphatic chlorinated hydrocarbons, such as methylene chloride,
Chloroform and 1,2-dichloroethane or chlorinated aromatic compounds such as chlorobenzene, dichlorobenzene and chlorotoluene or mixtures of these solvents. The alkaline aqueous solution suitable for the method of the present invention is Li
(OH) ₂ , NaOH, KOH, Ca(OH) ₂ and/or
It is an aqueous solution of Ba(OH) ₂ . Tertiary aliphatic amines suitable for the process of the invention are those having about 3 to 15 carbon atoms, ie, for example trimethylamine, triethylamine, n-tripropylamine and n-tributylamine, depending on the diphenol used. It varies from 0.2 to 5 mol % and when tetramethyl-substituted diphenols are used, it varies from about 5 to 10 mol %, based on the total amount of diphenols used (=sum of polyester diol bis-diphenol carbonate and other diphenols). . The polyester/polycarbonate produced by the method of the invention can be separated in the following manner: a. Distilling off the organic solvent to a certain concentration,
(30-40% by weight) polymer solution is prepared, followed by slow evaporation of the remaining solvent to gel the polyester/polycarbonate. b Precipitating the polyester/polycarbonate with an organic solvent by using a suitable solvent for precipitation, such as methanol, ethanol, isopropanol, acetone, aliphatic hydrocarbons and alicyclic hydrocarbons. c Separation of the polyester/polycarbonate in a devolatilizing extruder at about 160-240°C under conditions known for polycarbonate and application of shear forces. The polyester/polycarbonate produced by the process of the invention can be prepared as a highly concentrated polymer in the treated organic phase of a two-phase reaction mixture without separation or in a separate organic solvent liquid solution of the polyester/polycarbonate previously separated. A gel is formed by cooling the solution. The gelation time depends on the proportion of polyester or polycarbonate, but is about 5 minutes to 12 hours at about 0 to 40°C. The gelled product can be processed to form a powder-grain mixture and the resulting polyester/polycarbonate is dried under vacuum at 50°C for about 48 hours and at 100°C for 24 hours. Suitable solvents for the separate gelling of the separated polyester/polycarbonate are organic solvents, such as methylene chloride, benzene, toluene or xylene. Heat treatment of the separated polyester/polycarbonate is carried out at about 40 DEG to 170 DEG C. for about 5 minutes to 24 hours. The separated polyester/polycarbonate contains approx.
The shear force is applied at a temperature of 130-240° C. for about 0.5-30 minutes, and a shear force of about 0.2-0.7 KWh/Kg of polymer is applied. The reaction of the present invention between the polyester diol bis-diphenol carbonate of the present invention, diphenol and phosgene by the two-phase interfacial method proceeds quantitatively. The reactant ratio of polyester diol bis-diphenol carbonate to other diphenols is therefore determined by the polycarbonate and polyester components of the polyester/polycarbonate to be synthesized. The proportion of polycarbonate in the polyester/polycarbonate produced by the process of the invention is from about 30 to 95, preferably from about 35 to 95, depending on the desired properties.
It is 80% by weight. Here the hardness and heat distortion temperature, and the elasticity and elongation at break increase and decrease, respectively, with increasing proportion of polycarbonate. The proportion of polycarbonate in the polyester/polycarbonate according to the invention is determined by the following formula: [wherein D represents a diphenolate group in the polyester/polycarbonate], especially an aromatic polycarbonate structural unit of formula a It is to be understood as the amount by weight of the aromatic polycarbonate structural unit in which X and Y ₁ to _{Y 4} have the same meanings as in the formula. The proportion of polyester in the polyester/polycarbonate according to the invention is correspondingly to be understood as the amount by weight of one polyester diolate block unit of the polyester/diol of the simplified formula -O-(polyester)-O- . Accordingly, the present invention comprises from about 30 to 95% by weight, preferably from about 35 to 80% by weight, of aromatic polycarbonate structural units of the formula, particularly a, and from about 70 to 5% by weight, preferably from about
Concerning polyester/polycarbonate consisting of 65-20% by weight. The polyester/polycarbonate according to the invention may be of the formula b from about 30 to about 95% by weight, preferably from about 35 to 80% by weight, and from about 70 to about 5 polyester dioleate block units, wherein Y is H, Cl, Br, or _CH3 . The weight percent preferably consists of about 65 to about 20 weight percent. The polyester/polycarbonate according to the invention has a molecular weight of about 25,000 to 200,000, preferably about 70,000 to 200,000 as determined by light scattering using a light scattering photometer.
It should have an average molecular weight w (weight average) of 150,000. Relative solution viscosity ηrel of polyester/polycarbonate according to the invention (0.5 g in 100 ml CH ₂ Cl ₂
(measured at 25°C below) is about 1.3-3.0, preferably about
It is 1.4-2.6. The high molecular weight segmented polyester/polycarbonate produced by the method of the present invention and which can be processed as a thermoplastic has a polyester component present in an amorphous form and a temperature between about -100°C and +100°C as determined by differential thermal analysis. , preferably about -80°C
deformation of the amorphous polycarbonate portion, having a deformation temperature of ~+20°C, and in which the polycarbonate component is partially present in crystalline form and the crystalline polycarbonate portion has a crystalline melting point of at least 160°C, preferably from about 165 to 250°C. The temperature is about 80℃ or higher,
It is characterized in that the temperature is preferably about 100°C or higher. The above-mentioned differences in the deformation temperature of the polyester component and the deformation temperature and crystalline melting point of the polycarbonate component are characteristic for the presence of phase separation between the polyester component and the polycarbonate component. The degree of partial crystallinity of the polycarbonate component of the polyester/polycarbonate of the invention, which can be detected by a measurable melting enthalpy of at least 1 to 8 cal/g of polymer, is determined by stretching and subsequent heat treatment at 40 to 170°C (5 25 hours) or by the action of shear forces in thermoplastic processing in a multi-screw extruder by a further 50%. At this time, the heat distortion temperature of the product increases, and the appearance changes from transparent to translucent to opaque. The partially crystalline elastic polyester/polycarbonate can be processed as a thermoplastic at temperatures from about 130 to up to 250° C. below or near the crystalline melting point of the crystalline polycarbonate portion. In this case a substantial part of the crystallinity is retained. Amorphous, transparent products are obtained at processing temperatures above the crystalline melting point of the crystalline polycarbonate portion. That is, the crystalline proportion of the polycarbonate portion of the polyester/polycarbonate according to the present invention can be varied and may be about 1 to 8 cal/g polymer, preferably about 2.5 to give the polyester/polycarbonate a high heat distortion temperature for use. ~5.5cal/
g is sufficient to impart an enthalpy of melting to the polymer. If the polyester/polycarbonate is processed and separated according to the invention without heat treatment, without gel and without application of shear forces, the polyester/polycarbonate is of a single phase, i.e. has only one deformation temperature that can be measured by differential thermal analysis. A product is obtained. The stability against UV light and the stability against hydrolysis of the polyester/polycarbonate according to the present invention is higher than that of thermoplastic polycarbonates with conventional UV light.
Agents which confer stability against hydrolysis by means of stabilizers, such as substituted "benzophenones" or "benztriazoles", such as monocarbodiimides and especially polycarbodiimides [see,
W. Neuman, J. Peter, H. Holtschmidt andW.
Kallert, Proceeding of the 4th Rubber
Technology Conference, London, May 22-25
Japan, 1962, pp. 738-751], for example by 0.2 to 5% by weight, based on the weight of the polyester/polycarbonate, and by anti-aging agents known in the chemistry of thermoplastic polyesters and thermoplastic polycarbonates. can. Furthermore, substances such as carbon black, diatomaceous earth, kaolin, clay, CaF ₂ , CaCO ₃ , aluminum oxide and common glass fibers can also be added in amounts of about 2 to 40% by weight relative to the total weight of the molding composition, and Inorganic pigments can be added as fillers and nucleating agents;
As a result, the powder produced according to the invention can be modified. If a flame-retardant product is desired, flame retardants known in the chemistry of thermoplastic polyesters and thermoplastic polycarbonates, such as antimony trioxide, tetrabromophthalic anhydride, hexabromocyclododecane, tetrachlor or tetrabromobisphenol, are used. A is or tris-(2,3-
Dichloropropyl) phosphate can be incorporated in an amount of about 5 to 15% by weight based on the weight of the polyester/polycarbonate. Tetrachlor and tetrabromophenols, which are statistically incorporated into the polycarbonate part of the polycarbonate according to the invention, also exhibit flame retardancy. Furthermore, processing aids known in thermoplastic polyester and thermoplastic polycarbonate chemistry, such as mold release agents, can also be used to advantage. The polyester/polycarbonate produced according to the invention can be used in all cases where a combination of hardness and elasticity, especially cold flexibility, is desired, for example in car bodies, in the production of low-pressure car tires.
It can be advantageously used in the skins of hoses, seats and tubes and in flexible drive pulleys. The average molecular weight n is shown in the following example, and OH
Determined by counting numbers. The relative solution viscosity η _rel of Examples 7(a) to 7(f) is defined as the viscosity at 25° C. of a solution of 0.5 g of polyester/polycarbonate in 100 ml of methylene chloride. Tensile strength and elongation at break comply with DIN No. 53455,
Corresponding measurements were made according to ASTM No. D-638.
Gel chromatography was performed using tetrahydrofuran and styragel columns (separation range 1.5).
×10 ⁵ Å, 1 × 10 ⁵ Å, 3 × 10 ⁴ Å and 2 × 10 ³ Å)
The test was carried out at room temperature using A correction curve for bisphenol A polycarbonate was used for the determination. No significant deviations were found compared to w determined by light scattering methods. Differential thermal analysis was performed using "Dupont 900 model" manufactured by EI DuPont. When interpreting the deformation temperature, approximately the midpoint of the softening temperature range was chosen according to the tangential method, and for the crystalline melting point, approximately the midpoint of the endothermic peak of the melting curve was chosen. Scheutaudinger index [η] shown in Example 5
is measured in tetrahydrofuran at 25℃, dl/g
Display in . For the definition of the Schyutaudinger index, see HG Elias,
“Makromolekule”, Huthig & Wepf-verlag
See Basle, p. 265. Example 5 Preparation of polyester diol bis-carbonate monoaryl ester Hexane-1 with average molecular weight n=800,
800 parts by weight of a polyester diol from 6-diol and adipic acid, 856 parts by weight of diphenyl carbonate and 0.05 parts by weight of sodium phenolate were heated to 150° C. under nitrogen with stirring and a vacuum of 15 mm Hg for 3.5 hours. During this period the phenol is extracted from the reaction mixture.
187 parts by weight were distilled off. Excess diphenyl carbonate was then removed in a wet wall evaporator at 200°C/0.1 mmHg. A colorless viscous oil was obtained. [η] Tetrahydrofuran = 0.072 OH number = 0 Analysis: Calculated value: C, 66.3%; H, 8.2% Experimental value: C, 63.8%; H, 8.3% Example 6a Bisphenol A 18.5% by weight and Bisphenol A Preparation of polyester diol bis-(bisphenol A) carbonate containing also the reaction product of diphenyl carbonate and diphenyl carbonate Average molecular weight n=
446.3 parts by weight (0.2 mol) of biscarbonate monoaryl ester of polyester diol 1900, mixed with about 26.3 parts by weight of diphenyl carbonate (residual content 5.9% by weight based on the total amount), 2,2 -Bis-(4-hydroxyphenyl)-propane (bisphenol A) 191.7
parts by weight and 0.2 parts by weight of catalyst (sodium bisphenolate of bisphenol A: bisphenol A = 1:100) at 0.05 mmHg while stirring under nitrogen.
The mixture was heated to 150°C for 4 hours. During this period, 57.3 parts by weight of phenol were distilled off. Example 6b Preparation of polyester diol bis(bisphenol A) carbonate containing 18.7% by weight of bisphenol A and also the reaction product of bisphenol A and diphenyl carbonate Hexane-1,6-diol and adipic acid according to example 5 Average molecular weight n=
800 polyester diol mixed with about 27.0 parts by weight of diphenyl carbonate (residual content 4.3% by weight based on the total amount), 627 parts by weight of the polyester diol biscarbonate monoaryl ester, 2,
431.5 parts by weight of 2-bis-(4-hydroxyphenyl)-propane (bisphenol A) and catalyst
0.43 parts by weight (sodium bisphenolate of bisphenol A: bisphenol A = 1:100)
first for 1 hour at 0.5 mmHg with stirring under nitrogen.
Heated to 125°C then 150°C for 6 hours. During this period, 123 parts by weight of phenol were distilled off. Example 6c Preparation of polyester diol bis(bisphenol A) carbonate containing 26.1% by weight of bisphenol A and also the reaction product of bisphenol A and diphenyl carbonate Hexane-1.6 in a molar ratio of 65/35 according to Example 5
A polyester diol with an average molecular weight n = 1828 produced from diol/neopentyl glycol and adipic acid, which is mixed with about 164.5 parts by weight of diphenyl carbonate (residual content 8.8% by weight based on the total amount). 1870 parts by weight of biscarbonic acid monoaryl ester, 986 parts by weight of 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) and 1.5 parts by weight of catalyst (sodium bisphenolate of bisphenol A: bisphenol A) = 1:100) was heated at 0.25 mm Hg with stirring under nitrogen, first for 1 hour at 125°C and then for 5 hours at 150°C. During this period, 246 parts by weight of phenol were distilled off. Example 6d Preparation of polyester diol bis(bisphenol A) carbonate containing 15.6% by weight of bisphenol A and also the reaction product of bisphenol A and diphenyl carbonate Hexane-1 in a molar ratio of 65/35 according to Example 5
A polyester diol with an average molecular weight n=1828 produced from 6-diol/neopentityl glycol and adipic acid, containing about 12.8 parts by weight of diphenyl carbonate (residual content of 4.1 parts based on the total amount).
313 parts by weight of the biscarbonate monoaryl ester of the polyester diol mixed with 2.2% by weight)
-Bis(4-hydroxyphenyl)-propane (bisphenol A) 120.5 parts by weight and sodium phenolate 0.02 parts by weight were stirred under nitrogen.
0.06mmHg for first 1 hour at 125℃ then 3 hours
Heated to 150°C. During this period, phenol 31.5
Part by weight was distilled off. Example 6e Preparation of polyester diol bis(bisphenol A) carbonate containing 16.8% by weight of bisphenol A and also the reaction product of bisphenol A and diphenyl carbonate Prepared from neopentyl glycol and adipic acid according to Example 5 A polyester diol with an average molecular weight n = 2000, containing about 18.1 parts by weight of diphenyl carbonate (residual content 5.2 parts based on the total amount).
348.1 parts by weight of the biscarbonate monoaryl ester of the polyester diol mixed with
139.5 parts by weight of 2-bis(4-hydroxyphenyl)-propane (bisphenol A) and 0.14 parts by weight of catalyst (sodium bisphenolate of bisphenol A: bisphenol A = 1:100) were mixed under nitrogen with stirring. 125℃ for 1 hour at 0.5mmHg
It was then heated to 150°C for 5 hours. During this period,
37.6 parts by weight of phenol was distilled off. Example 6f 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane and diphenyl carbonate Preparation of a polyester diol bis-diphenol carbonate of the formula f which also contains the reaction product in an amount of 14.8% by weight Average molecular weight n = prepared from hexane-1,6-diol and adipic acid according to Example 5
800 polyester diol, 303 parts by weight of biscarbonate monoaryl ester of the polyester diol mixed with about 3 parts by weight of diphenyl carbonate (residual content 1% by weight based on the total amount), 2,
232.2 parts by weight of 2-bis-(4-hydroxyphenyl)-propane and 0.22 parts by weight of catalyst (sodium bisphenolate of bisphenol A: bisphenol A = 1:100) were mixed under nitrogen with stirring.
125°C for 1 hour first at 0.1mmHg then 150°C for 4.5 hours
heated to ℃. During this period, 49 parts by weight of phenol were distilled off. Example 7a Preparation of polyester/polycarbonate with 50% by weight polyester fraction 40.2 parts by weight of bisphenol A and p- dissolved in 70 parts by weight of 45% NaOH and 1300 parts by weight of distilled water
To a solution of 0.885 parts by weight of tert-butylphenol were added 151.5 parts by weight of the viscous oil from Example 6a dissolved in 1725 parts of methylene chloride. Then, 58.3 parts by weight of phosgene was added at 20 to 25°C for 30 minutes with stirring under nitrogen.
It was fed for a minute. During this period, after the introduction of phosgene to which 111 parts by weight of 45% NaOH were simultaneously added dropwise so that the pH value was constant at 13, 39.8 parts by weight of 1% triethyleneamine solution were added and the mixture was
Stir for hours. The organic phase was separated and washed successively with 2% phosphoric acid and finally with distilled water until free of electrolyte. After separation of the water, the organic phase was treated in the following manner. [ _7a.1 ] A high concentration (approximately _30-40 % by weight) of A polymer solution was obtained. The polyester/polycarbonate was then gelled by slow evaporation of the remaining methylene chloride or chlorobenzene, which was then further processed into a powder particle mixture. Obtained polyester/
Polycarbonate at 50℃ for 48 hours and 100℃ for 24 hours
Dry under vacuum for an hour. [7a.2] Distill the solvent and collect the residue at 15 mmHg and approx.
A finely ground solid product was obtained by drying in a vacuum dryer at 80-110°C and subsequent grinding. [7a.3] Precipitating the polyester/polycarbonate from the organic phase using e.g. methanol, ethanol, isopropanol, acetone, aliphatic and cycloaliphatic hydrocarbons, followed by precipitation at 80~
It was dried in a vacuum oven at 110°C and 15mmHg. [7a.4] The organic phase was concentrated in an evaporative extruder and subsequently extruded at about 160-240°C under conditions known for extrusion of polycarbonates. The relative viscosity η of the polyester/polycarbonate obtained in Examples 7a.1 to 7a.4 was 1.64 (measured in CH ₂ Cl ₂ at 25° C. and d=5 g/). According to gel chromatography, polyester/polycarbonate showed the highest value at 56,000. It contained 50% by weight polyester and 50% by weight polycarbonate portion. The mechanical properties of the film cast from methylene chloride were as follows: Tensile strength 22.7 ((MPa) (DIN No. 53455)
According to ASTM No. D-368) Elongation at break 413% (DIN No. 53455 - ASTM No. D)
According to differential thermal analysis of granular polyester/polycarbonate (according to No. 638), the polyester component has a glass transition temperature (deformation temperature) of -28°C, and the amorphous polycarbonate portion has a glass transition temperature (deformation temperature) of 125°C. and the crystalline polycarbonate portion had a crystalline melting point of about 190°C. The enthalpy of melting of the crystalline polycarbonate portion was 2.5 to 5.5 cal/g polymer. Example 7b Preparation of a polyester/polycarbonate with a polyester fraction of 45% by weight 2,2-bis-(4-hydroxyphenyl)-propane (2,2-bis-(4-hydroxyphenyl)-propane ( Bisphenol A) 20.3 parts by weight and p-tert-butylphenol
To 1.3 parts by weight of the solution were added 171.6 parts by weight of the viscous oil from Example 6b dissolved in 1725 parts by weight of methylene chloride. While stirring the mixture under a nitrogen atmosphere, 85.6 parts by weight of phosgene were introduced over a period of 45 minutes, and at the same time 195 parts of 45% sodium hydroxide solution were added dropwise to keep the pH at a constant value of 13. After charging the phosgene, 0.44 parts by weight of triethylamine was added. This mixture became viscous. After 1 hour, the organic phase was separated and the polyester/polycarbonate was separated as in Example 7a (7a.1-7a.4). The relative viscosity η _rel of the polyester/polycarbonate was 1.82 (in CH ₂ Cl ₂ ). According to gel chromatography, the polymer
The highest value was 93,000. Contains 45% polyester and 55% by weight
It has a polycarbonate part. The mechanical properties of the film cast from methylene chloride were as follows: Tensile strength 61.5 MPa Elongation at break 265% Example 7c Preparation of polyester/polycarbonate with 50% by weight polyester fraction 1300 parts by weight of distilled water and 45% by weight 28.5 parts by weight of 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) and p-tert-butylphenol dissolved in 70 parts by weight of % sodium hydroxide solution.
To 0.89 parts by weight of the solution were added 163.2 parts by weight of the viscous oil from Example 6c dissolved in 1725 parts by weight of methylene chloride. While stirring this mixture under nitrogen atmosphere, 58.3 parts by weight of phosgene was introduced over 40 minutes.
At the same time, 131 parts of 45% sodium hydroxide solution was added dropwise to maintain the pH at a constant value of 13. After charging the phosgene, 0.4 parts by weight of triethylamine was added. This mixture became more viscous. 1 hour later
The organic phase was separated and the polyester/polycarbonate was separated as in Example 7a (7a.1-7a.4). The relative viscosity η _rel of the polyester/polycarbonate was 1.62 (in CH ₂ Cl ₂ ). According to gel chromatography, the polymer
The highest value was 51,000. Contains 50% polyester and 50% by weight
The mechanical properties of the film cast from methylene chloride with a polycarbonate portion of The amorphous polycarbonate portion had a glass transition temperature (deformation temperature) of 130°C, and the crystalline polycarbonate portion had a crystalline melting point of about 185°C. The enthalpy of melting of the crystalline polycarbonate portion was 2.5 to 5.5 cal/g polymer. Example 7d Preparation of polyester/polycarbonate with 45% by weight polyester fraction 2,2-bis-(4-hydroxyphenyl)-propane ( Bisphenol A) 59.8 parts by weight and p-tert-butylphenol
To 0.98 parts by weight of the solution were added 130.6 parts by weight of the viscous oil from Example 6d dissolved in 1725 parts by weight of methylene chloride. This mixture is added to 1,4-bis-(4',
0.58 parts by weight of 4"-dihydroxytriphenylmethyl)-benzene and 5 parts by weight of 5% NaOH solution were added. The mixture was stirred under nitrogen atmosphere.
64.3 parts by weight of phosgene were introduced over a period of 30 minutes, and at the same time the pH was kept at a constant value of 13 by dropwise addition of 146 parts of 45% sodium hydroxide solution. After charging the phosgene, 0.44 parts by weight of triethylamine was added. This mixture became more viscous. 1 hour later
The organic phase was separated and the polyester/polycarbonate was separated as in Example 7a (7a.1-7a.4). The relative viscosity η _rel of the polyester/polycarbonate was 1.81 (in CH ₂ Cl ₂ ). According to gel chromatography, the polymer
The highest value was at 53,000, and an additional highest value for polymers was at 200,000. Contains 45% polyester and 55% by weight
The mechanical properties of the film cast from methylene chloride with polycarbonate portions were as follows: Tensile strength 39.6 MPa Elongation at break 286% Differential thermal analysis of the granular polyester/polycarbonate showed that the polyester component was at -28°C. The amorphous polycarbonate portion had a glass transition temperature (deformation temperature) of 130°C, and the crystalline polycarbonate portion had a crystalline melting point of about 185°C. The melting enthalpy of the crystalline polycarbonate portion was 2.5 to 5.5 cal/g polymer. Example 7e Preparation of polyester/polycarbonate with 50% by weight polyester fraction 2,2-bis-(4-hydroxyphenyl)-propane (2,2-bis-(4-hydroxyphenyl)-propane ( Bisphenol A) 42.4 parts by weight and p-tert-butylphenol
To 0.89 parts by weight of the solution were added 149.2 parts by weight of the viscous oil from Example 6e dissolved in 1725 parts by weight of methylene chloride. 58.3 parts by weight of phosgene are introduced into this mixture under stirring under a nitrogen atmosphere over a period of 40 minutes, and at the same time 135 parts of 45% sodium hydroxide solution are added dropwise to maintain the pH at a constant value of 13. Ta. After charging the phosgene, 0.4 parts by weight of triethylamine was added. This mixture became more viscous. After 1 hour, the organic phase was separated and the polyester/polycarbonate was separated as in Example 7a (7a.1-7a.4). The relative viscosity η _rel of the polyester/polycarbonate was 1.56 (in CH ₂ Cl ₂ ). According to gel chromatography, the polymer
It peaked at 49,000. Contains 50% polyester and 50% by weight
The mechanical properties of the film cast from methylene chloride with polycarbonate portions were as follows: Tensile strength 17.5 MPa Elongation at break 228% Differential thermal analysis of the granular polyester/polycarbonate showed that the polyester component was at -19°C. The amorphous polycarbonate portion had a glass transition temperature (deformation temperature) of 125°C, and the crystalline polycarbonate portion had a crystalline melting point of about 185°C. The melting enthalpy of the crystalline polycarbonate portion was 2.5 to 5.5 cal/g polymer. Example 7f 2,2- with 50% by weight polyester portion
Preparation of polyester/polycarbonate from bis-(3,5-dimethyl-4-hydroxyphenyl)-propane Dissolved in 1725 parts by weight of methylene chloride in a solution of 1300 parts by weight of distilled water and 66 parts by weight of 45% sodium hydroxide solution. 197.1 parts by weight of the viscous oil from Example 6f and 0.61 parts by weight of tributylamine (=1 mol % per mole of bisphenol units) were added. 98 parts by weight of phosgene were introduced into this mixture with stirring under a nitrogen atmosphere over a period of 30 minutes, and at the same time 225 parts of 45% sodium hydroxide solution were added dropwise to keep the pH at a constant value of 13. After introducing the phosgene, 5.5 parts by weight of tributylamine (=9 mol % per mole of bisphenol units) were added to complete the reaction.
This mixture became more viscous. After 3 hours, the organic phase was separated and the polyester/polycarbonate was separated as in Example 7a (7a.1-7a.4). The relative viscosity η _rel of the polyester/polycarbonate was 1.58 (in CH ₂ Cl ₂ ). Although the invention has been described in detail for purposes of illustration, it is understood that such details are for that purpose only and that no modifications may be made without departing from the spirit of the invention and the scope of the claims. Should.

Claims (1)

[Claims] 1. The following formula [In the formula, -(polyester)- represents a divalent group of polyester diol from an aliphatic dicarboxylic acid and an aliphatic diol, X represents -CH ₂ - or [Formula], and Y ₁ to _{Y 4} are the same polyester diol bis-diphenol carbonate having a weight average molecular weight of 750 to 20,000, which may be different in size and represent hydrogen or methyl. 2 The following formula [In the formula, -(polyester)-- represents a divalent group of a polyester diol from an aliphatic dicarboxylic acid and an aliphatic diol acid.] The polyester diol bis-diphenol carbonate according to claim 1. 3 The following formula [In the formula, -(polyester)-- represents a divalent group of a polyester diol made from an aliphatic dicarboxylic acid and an aliphatic diol.] The polyester diol bis-diphenol carbonate according to claim 1. 4 The following formula [In the formula, Ar is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and -(polyester)- is 250
is a divalent group of a polyester diol from an aliphatic dicarboxylic acid and an aliphatic diol having a larger molecular weight n. [In the formula, X represents -CH ₂ - or [Formula], and Y ₁ to _{Y 4} may be the same or different and represent hydrogen or methyl] together with the diphenol, a At a temperature of about 100 to about 200 ° C. b) using more than 1 mole of diphenol per mole of carbonate aryl ester groups of the polyester diol biscarbonate monoaryl ester during heating under a vacuum of not more than about 35 mmHg, and c) in the presence of a catalyst. A method for producing polyester diol bis diphenol carbonate. 5. The method for producing polyester diol bis diphenol carbonate according to claim 4, wherein the produced hydroxyaryl by-product is distilled off. 6. The method according to any one of claims 4 to 5, wherein the polyester diol has a molecular weight of 600 or more. 7. The method according to any one of claims 4 to 6, wherein the reaction temperature is about 110 to 180°C. 8. The method according to any of claims 4 to 7, wherein the pressure is about 25 to 0.1 mmHg. 9. The method of any of claims 4 to 8, wherein the amount of diphenol is from about 1.1 to about 2 moles per carbonate aryl ester group of the polyester diol biscarbonate monoaryl ester. 10. The method according to any one of claims 4 to 9, which is carried out in the absence of a solvent. 11. The method according to any one of claims 4 to 9, which is carried out in the presence of an inert solvent. 12 polyester diol biscarbonate monoaryl ester with bisphenol A, a molar ratio of biscarbonate monoaryl ester to bisphenol A of about 1:3, b in the presence of disodium phenolate of bisphenol A as a catalyst; 12. A method according to any of claims 4 to 11, characterized in that c) the reaction is carried out at a temperature of about 150<0>C and d) under a vacuum of about 25 to 0.1 mmHg. 13 A polyester diol made from an aliphatic dicarboxylic acid and an aliphatic diol having a molecular weight n (number average) of 250 or more is prepared by the following formula: [wherein Ar is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms] with the carbonic acid bisaryl ester of a) at a temperature of about 100 to about 200°C, b under a vacuum of about 35 mmHg or less, and c of a catalyst. Using more than 1 mole of biscarbonate-aryl ester per mole of OH groups of the polyester diol upon heating in the presence of [In the formula, Ar has the same meaning as above, -
(Polyester) - Molecular weight n greater than 250
is a divalent group of a polyester diol from an aliphatic dicarboxylic acid and a fatty acid diol having the following formula: [In the formula, -CH ₂ - or [Formula], Y ₁ to _{Y 4} may be the same or different and represent hydrogen or methyl] together with a diphenol at a temperature of about 100 to about 200°C, b using more than 1 mole of diphenol per mole of carbonate aryl ester groups of the polyester diol biscarbonate monoaryl ester upon heating under a vacuum of about 35 mm Hg or less and in the presence of a catalyst. Method for producing diol bis diphenol carbonate. 14. The method of claim 13, wherein the resulting polyester diol bis-carbonate monoaryl ester and excess carbonate bis-aryl ester are reacted with diphenol. 15. The method according to any one of claims 13 to 14, wherein the polyester diol has a molecular weight of 600 or more. 16. The method according to any one of claims 13 to 15, wherein the reaction temperature is about 110 to 180°C. 17. The method of any of claims 13-16, wherein the pressure is about 25-0.1 mmHg. 18. The method of any of claims 13-17, wherein the amount of diphenol is from about 1.1 to about 2 moles per carbonate aryl ester group of the polyester diol biscarbonate monoaryl ester. 19. The method according to any one of claims 13 to 18, which is carried out in the absence of a solvent. 20. The method according to any one of claims 13 to 18, which is carried out in the presence of an inert solvent. 21 polyester diol biscarbonate monoaryl ester with bisphenol A, a in a molar ratio of biscarbonate monoaryl ester to bisphenol A of about 1:3, b in the presence of disodium phenolate of bisphenol A as a catalyst, c 21. A process according to any of claims 13 to 20, wherein the reaction is carried out at a temperature of about 150<0>C and under a vacuum of about 25 to 0.1 mmHg.