NL8304322A - POLYCARBONATES WITH IMPROVED HEAT RESISTANCE. - Google Patents

Description

P & c * .Γ

t S 2348-1273 Ned / LE / WVR

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Short designation: Polycarbonates with improved heat resistance.

Polycarbonates are well-known thermoplastic materials which, because of their many excellent properties, are used as thermoplastic construction materials for many commercial and industrial applications. For example, poly-5 carbonates exhibit excellent toughness, flexibility, impact strength and the like. Polycarbonates are generally prepared by reacting a divalent phenol, such as bisphenol-A, with a carbonate precursor, such as phosgene.

Although conventional carbonates are generally well suited to a wide variety of applications, there is nevertheless a need, especially for a high temperature environment, for polycarbonates which exhibit substantially the most advantageous properties of conventional polycarbonates and at the same time have greater heat resistance than conventional polycarbonates.

The invention therefore provides polycarbonates which exhibit to a considerable extent the most advantageous properties of conventional polycarbonates and at the same time have improved heat resistance.

The invention provides new polycarbonates that exhibit substantially most or all of the beneficial properties of conventional polycarbonates while at the same time improving heat resistance.

The novel polycarbonates of the invention are prepared by reacting a carbonate precursor with a divalent phenol selected from divalent phenols of formulas (1) and (2) of the formula sheet, wherein: R 1 and R 3 independently of propose to each other a monovalent hydrocarbon group; R 1 represents flivalent hydrocarbon group or a hydrogen atom, with the proviso that if R is a hydrogen atom at least one of those represented by R and R

8t * r \ r,: J

0 W "» vtj * - 2 - I 4 monovalent hydrocarbon groups contain at least two carbon atoms; g R represents a divalent hydrocarbon group which, 6 together with the carbon atom in which R is bonded, forms a 5 cyclic hydrocarbon group; 7 R represents a hydrogen atom or a monovalent hydrocarbon group; R * represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; introduce.

The invention provides new polycarbonates which exhibit to a considerable extent the most advantageous properties of conventional polycarbonates and also good thermal properties, such as good heat resistance.

The novel polycarbonates of the invention are obtained from (i) a carbonate precursor and (ii) at least 20 one divalent phenol selected from divalent phenols of the general formulas (1) and (2) of the formula sheet.

4 5

In formula (1), R and R independently represent 3 monovalent hydrocarbon groups; R is a hydrogen atom or a monovalent hydrocarbon group, provided that if R is hydrogen, at least one of the monovalent hydrocarbon radicals represented by R and R contains at least two carbon atoms; R1 represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxy group; R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; and n and n 'are independently integers with a value of 0-4.

1 2

In formula (2), the definitions of R, R, n and n 'are the same as in formula (1); R represents a hydrogen atom or g 35 a monovalent hydrocarbon group; and R is a divalent hydrocarbon group which, together with the carbon atom to which it is bonded, forms a cyclic hydrocarbon structure.

V. * * .ζ cm ^ ssr-% '• i * * - 3 - 1 2

The halogen atoms represented by R and R are preferably chlorine and bromine.

1 2

The monovalent hydrocarbon groups represented by R and R are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. The preferred alkyl groups represented by 12 R and R are those having 1 to about 6 carbon atoms. These preferred alkyl groups include straight and branched chain alkyl groups. Some non-limiting examples of these preferred alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like.

1 2

The aryl groups preferably represented by R and R are those with 6-12 carbon atoms, for example phenyl, naphthyl and 1 2 biphenyl. The preferred alkaryl and aralkyl groups represented by R and R are those having 7 to about 14 carbon atoms, for example, benzyl, tolyl, ethylphenyl and the like. The preferred cycloalkyl groups represented by R and R are those having 3 to about 8 ring carbon atoms, for example cyclopropyl, cyclopentyl, cyclohexyl and the like.

The monovalent hydrocarbonoxy groups represented by R and R are preferably alkoxy groups and aryloxy groups. The alkoxy groups preferably contain 1 to about 6 carbon atoms. The preferred aryloxy group is the phenoxy group.

When more than one substituent R1 is present in the divalent phenols of formulas (1) and (2), ie when n is 2-4, these groups may be the same or different. The same goes for the substituent R. When n or n 'is 0, 4 of the ring carbon atoms of the respective aromatic nucleus carry only hydrogen atoms.

3 4 5 7

The monovalent hydrocarbon groups represented by R, R, R and R are selected from alkyl groups, cycloalkyl groups, aryl groups, alkaryl groups and aralkyl groups.

3 4 5 7

The preferred alkyl-35 groups represented by R, R, R and R are those having 1 to about 8 carbon atoms. These alkyl groups include branched alkyl groups and straight chain alkyl groups. Some non-limiting examples of these alkyl groups, preferably 8304322 r, are +, - + - - 4 -, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and the like.

The aryl groups preferably represented by R, R, R ° and R are those with 6-12 carbon atoms, namely phenyl, 5 naphthyl and biphenyl. The preferred alkaryl and aralkyl groups are those with 7 to about 14 carbon atoms, for example, benzyl, tolyl, ethylphenyl, etc.

3 4 5 7

The preferred cycloalkyl groups represented by R, R, R and R are those having 4 to about 8 ring carbon 10 atoms. Some non-limiting examples of these preferred cycloalkyl groups are cyclobutyl, cyclopyl, cyclohexyl, etc.

g

As mentioned above, R is a divalent group which, together with the group of formula (3) of formula sheet 15, forms a cyclic hydrocarbon structure. This cyclic structure can be monocyclic or bicyclic. Preferably g is R a divalent alkylene group with 3 to about 8 carbon atoms, for example propylene, butylene, pentylene and the like.

Some non-limiting examples of the cyclic structure formed by R and the group of formula (3) are the groups of formulas (4), (5), (5a) and the like.

Particularly suitable and sometimes even preferred divalent phenols of formula (1) are those in which all groups R, R and R are independently selected from monovalent hydrocarbon groups.

The new bivalent phenols of formulas (1) and (2) are prepared by reacting an aldehyde with a phenol in the presence of an acidic catalyst. The aldehyde used as the reaction component is selected from aldehydes according to the general formulas (6) and (7) of the 2 S 6 7 formula sheet, wherein R, R 4, R, R 0 and R 'have the definitions given above. The phenol used as the reaction component is selected from phenols according to the general formulas (8) and (9) of the formula sheet, wherein R, R, n and n * have the definitions given above.

In order to obtain the new bivalent phenols of formula 8304322-5 - k »Λ (1), 1 mole of an aldehyde of formula (6) is reacted with 1 mole of a phenol of formula (8) and 1 mole of a phenol of formula (9) in the presence of an acidic catalyst. Some non-limiting examples of suitable acidic catalysts that can be used are hydrogen chloride, hydrogen bromide, poly (styrene sulfonic acid), sulfuric acid, benzene sulfonic acid, and the like.

The phenols of formulas (8) and (9) are reacted with the aldehyde of formula (6) in the presence of the acidic catalyst under temperature and pressure conditions such that the phenols and the aldehyde react with each other to form the divalent phenol according to formula (1). The reaction generally proceeds satisfactorily at a pressure of about 1 atmosphere and at temperatures from room temperature to about 100 ° C.

The amount of the acid catalyst used is a catalytic amount. By "catalytic amount" is meant an amount that catalyzes the reaction between the aldehyde and the phenol. Generally, this amount is about 0.1-10%. In practice, however, this amount is usually slightly greater since the water formed as a by-product in the reaction dilutes the acidic catalyst and makes the catalyst slightly less active (slows down the reaction) compared to the undiluted catalyst.

The phenols of formulas (8) and (9) can of course be the same. In that case, 1 mole of the aldehyde of formula (6) is reacted with 2 moles of the phenol.

To obtain the divalent phenols of formula (2), 1 mole of an aldehyde of formula (7) is reacted with 1 mole of the phenol of formula (8) and 1 mole of the phenol of formula (9), or, if the phenols of formulas (8) and (9) are the same, with 2 moles of the phenol, in the presence of an acidic catalyst and under the above reaction conditions, to form the divalent phenol of formula (2).

Some non-limiting examples of the divalent 8304322 ψ - 6 phenols of formula (1) are the phenols of formulas (10), (11), (12), (13), (14), (15), ( 16), (17), (18), (19) and (20) of the formula sheet.

Some non-limiting examples of the divalent phenols of formula (2) are the phenols of formulas (21), (22), (23) and (24) of the formula sheet.

In the preparation of the carbonate polymers of the invention, only one divalent phenol of formula (1) or (2) is used or a mixture of two or more different divalent phenols of formula (1) and / or (2). For example, one or more different bivalent phenols of formula (1), two or more different bivalent phenols of formula (2) or at least one bivalent phenol of formula (1) and at least one bivalent phenol of formula (2) to apply.

The carbonate precursor can be a carbonyl halide, a diaryl carbonate or a bishalogen formate. The carbonate precursors are preferably carbonyl halides. The preferred carbonyl halides are carbonyl chloride, carbonyl bromide and mixtures thereof. The most preferred carbonyl halide is carbonyl chloride, also referred to as phosgene.

The novel carbonate polymers of the present invention contain recurring structural units of the general formulas (25) and / or (26) wherein R, Rr, R, R, 5 6 7 R, R, R, n and n 'possess the definitions given above.

These high molecular weight aromatic carbonate polymers generally have a "weight" average molecular weight of from about 10,000-150,000 and preferably from about 20,000-100,000.

According to a method of preparing the present high molecular weight aromatic carbonate polymers, a heterogeneous interfacial polymerization system is employed, wherein an aqueous solution of a base, an organic water-immiscible solvent such as dichloromethane, at least one divalent phenol is selected from the phenols of formulas (1) and (2), a carbonate precursor such as 8304322 * -7-phosgene, a catalyst and molecular weight regulator are used.

Another suitable method for preparing the carbonate polymers of the invention uses an organic solvent system which can also act as an acid acceptor, at least one divalent phenol of formula (1) and / or (2), an agent for controlling the molecular weight, a catalyst and a carbonate precursor such as phosgene.

Any suitable catalyst which contributes to the polymerization of a divalent phenol with phosgene can be used as the catalyst. Non-limiting examples of suitable catalysts are tertiary amines such as triethylamine, quaternary ammonium compounds and quaternary phosphonium compounds.

As a molecular weight regulator, any known compound which controls the molecular weight of the carbonate polymer according to a chain growth arrest mechanism can be used. Non-limiting examples of these compounds are phenol, tertiary butylphenol and the like.

The temperature at which the phosgenation reaction proceeds can range from below 0 ° C to above 100 ° C. The reaction proceeds satisfactorily at temperatures from room temperature, about 25 ° C, up to 50 ° C. Since the reaction is exothermic, the addition rate of phosgene or a low boiling solvent, such as dichloromethane, can be used to control the reaction temperature.

The carbonate polymers of the invention may optionally be mixed with certain conventional additives such as antioxidants; anti-static agents, fillers such as glass fibers, mica, talc, clay and the like? impact modifiers, ultraviolet ray absorbers such as benzophenones and benzotriazoles; softeners? stabilizers against hydrolysis, such as the epoxides described in U.S. Pat. Nos. 3,489,716, 4,138,379 and 8304322-8-f3,839,247; color stabilizers, such as the organophosphites disclosed in U.S. Pat. Nos. 3,305,520 and 4,118,370; and flame retardants.

Particularly suitable flame retardants 5 are the alkali and alkaline earth metal salts of sulfonic acids. These types of flame retardants are described in U.S. Patents 3,933,734, 3,948,851, 3,926,908, 3,919,167, 3,909,490, 3,953,396, 3,931,100, 3,978,024, 3,953,399, 3,917,559, 3,951. 910 and 3,940,366.

Another embodiment of the invention is formed by a carbonate copolymer obtained by converting the following essential components together: (i) a carbonate precursor, (ii) at least one divalent phenol selected from divalent phenols of the formulas (1) and (2), and (iii) at least one bivalent phenol according to the general formula (27) of the formula sheet, wherein A is an alkylene group, a cycloalkylene group, an alkylidene group, a cycloalkylidene group -S (0) -, - S-, -SS-, -SC ^ -, -O- or -C (O) -.

The divalent phenols of formula (27) are known compounds and are generally used for preparing conventional polycarbonates.

In formula (27), X 'and X are independently a halogen atom, such as chlorine or bromine, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group.

The monovalent hydrocarbon groups are selected from alkyl groups, preferably those having 1 to about 6 carbon atoms; aryl groups, preferably those with 6-12 carbon atoms, such as phenyl, naphthyl and biphenyl; alkaryl and aralkyl groups, preferably those with 7 to about 14 carbon atoms; and cycloalkyl groups, preferably those with 4 to about 8 ring carbon atoms.

The monovalent hydrocarbon oxy groups represented by X and X 'are preferably selected from alkoxy groups and aryloxy groups. The letters a and a 'independently represent integers with a value of 0-4. The letter b is a number with the value 0 or 1.

8304322 - 9 -

The alkylene groups represented by A contain 2 to about 6 carbon atoms. The alkylidene groups represented by A contain 1 to about 6 carbon atoms. The cycloalkylene and cycloalkylidene groups represented by A contain from 4 to about 7 ring carbon atoms. The alkylene and alkylidene groups represented by A are straight-chain alkylene and alkylidene groups.

When more than one substituent X is present in the divalent phenolic compounds of formula (27), these substituents may be the same or different. The same applies to the substituents X '. When b in formula (27) is 0, the aromatic rings are directly bonded together without an alkylene group or any other bridging group. The hydroxyl group and the groups X and X 'may be on the aromatic rings on the ortho, meta or para sites and the groups may be in a vicinal, asymmetric or symmetrical relationship with respect to each other.

Some non-limiting examples of suitable divalent phenols of formula (27) are: 2 0 1, i-bis- (4-hydroxyphenyl) cyclohexane; 2.2-bis (4-hydroxyphenyl) propane (bisphenyl-A); 3.3-bis (3-methyl-4-hydroxyphenyl) pentane; 1.1-bis (3-methyl-4-hydroxyphenyl) ethane; 2.2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 3,3'-dichloro-4,41-dihydroxydiphenyl; bis (3-chloro-4-hydroxyphenyl) sulfone; 3,3'-diethyl-4,41-dihydroxydiphenyl; bis (4-hydroxyphenyl) sulfide, and the like.

The amount of the divalent phenols of formulas (1) and / or (2) used in this embodiment is effective in improving the heat resistance, for example the transition state to the glass state, of the copolymers. This amount is generally about 10-90% by weight and preferably 35-70% by weight, based on the total amount of divalent phenol used, i.e. the total amount of divalent phenol of formula (1) and / or present. or (2) and 8304322-10 - divalent phenol of formula (27) ♦ The preferred divalent phenol of formula (27) is 2,2-bis (4-hydroxyphenyl) propane.

The carbonate copolymers obtained by reacting (i) a carbonate precursor, (ii) at least one divalent phenol selected from divalent phenols of formulas (1) and (2), and (iii) at least one divalent phenol of formula (27) contain recurring structural units of formulas (25); 10 and / or (26); and (28), wherein X, X ', a, a', A and b are as defined above.

When only the divalent phenols of formula (1) and (27) are used, the carbonate polymer obtained contains repeating structural units of formulas (25) and (28). When only divalent phenols of formulas (2) and (27) are used, the polycarbonate obtained contains only repeating structural units (26) and (28). When divalent phenols of formulas (1), (2) and (27) are used, the polycarbonate obtained contains recurring structural units of formulas (25), (26) and (28).

The relative amounts of the different repeating structural units in the copolymer generally depend on the amounts of the different bivalent phenols used in the preparation of the copolymer.

The methods of preparing the carbonate copolymers are generally similar to those described above for preparing the polymers of the invention. The carbonate copolymers can also be mixed with the various additives mentioned above.

Another embodiment of the invention is a polycarbonate resin mixture consisting of (i) at least one polycarbonate resin of the invention (hereinafter referred to as resin A); and (ii) at least one polycarbonate resin obtained from (a) a carbonate precursor and (b) at least one divalent phenol of "8304322-11 formula (27) (hereinafter referred to as resin B). These blends can generally contain about 10-90% by weight of resin A, based on the total amount of resins A and B in the mixture. These mixtures are prepared by first preforming the different resins and then physically mixing them together. These mixtures may optionally contain the above-mentioned additives.

Yet another embodiment of the invention is comprised of copolyester carbonates obtained from 10 (i) a carbonate precursor? (ii) at least one divalent phenol selected from divalent phenols following one of the general formulas (1) and (2); and (iii) at least / bi-functional carboxylic acid or a reactive derivative thereof.

The copolyester carbonates contain repeating carbonate groups (-0-C (0) -0-), carboxylate groups (-C (O) -O-) and aromatic carbocyclic groups in the linear polymer chain, with at least some of the carboxylate groups and at least some of the carbonate groups are directly bonded to ring carbon atoms of the aromatic carbocyclic groups.

These copolyester carbonate polymers contain ester and carbonate bridging groups in the polymer chain, the amount of ester bridging groups being about 25-90 mol% and preferably about 35-80 mol%.

Copolyester carbonates and methods of their preparation are generally described in U.S. Patent 3,169,121.

In general, any bifunctional carboxylic acid customary for the preparation of linear polyesters can be used to prepare the copolyester carbonates of the invention. The carboxylic acids that can be used include aliphatic carboxylic acids, aliphatic-aromatic carboxylic acids and aromatic carboxylic acids. These acids are described in the aforementioned U.S. Patent 3,169,121.

The carboxylic acids which can be used to prepare the copolyester carbonates of the invention are 8304322-12 - generally compounds of the formula (29) of

Q

the formula sheet, wherein R is an alkylene group, alkylidene group, aralkylene group, aralkylidene group or cycloaliphatic group; an alkylene group, alkylidene group or cyclo-aliphatic group with olefinic unsaturation; an aromatic group such as phenylene, biphenylene, substituted phenylene and the like; two or more aromatic groups joined by non-aromatic bridging groups such as alkylene or alkylidene groups; and the like.

10 R is a carboxyl group or a hydroxyl group. The letter q

O

has the value 1 when R is a hydroxyl group and the 0 value 0 or 1 when R is a carboxyl group.

Preferred bi-functional carboxylic acids are aromatic carboxylic acids, i.e. those wherein q is 8 9 15 1, R is a carboxyl or hydroxyl group and R is an aromatic group such as phenylene, biphenylene, naphthylene, substituted phenylene and the like. The preferred aromatic bifunctional carboxylic acids are those according to the general ones

O

formula (30) of the formula sheet, wherein R is as defined above; p is an integer with a value of 0-4; and R10 represents an inorganic atom such as chlorine, bromine and the like, an organic group such as a monovalent hydrocarbon group, for example alkyl, aryl, aralkyl, alkaryl or cycloalkyl, or an inorganic group such as a nitro group, an amino group and the like. When more than one substituent R 1 ^ is present, these substituents can be the same or different. R1 is preferably a lower alkyl group.

Mixtures of two or more different bifunctional carboxylic acids can be used, and the term "bifunctional carboxylic acid" as used herein therefore includes mixtures of two or more different carboxylic acids as well as separate carboxylic acids.

Preferred aromatic bifunctional carboxylic acids are isophthalic acid, terephthalic acid and mixtures thereof. A particularly suitable mixture of isophthalic acid and terephthalic acid has a weight ratio between isophthalic acid 8304322-13 and terephthalic acid of about 1:10-10 µl.

It is possible - and sometimes even preferred - to use their reactive derivatives, such as, for example, acid halides, instead of the bi-functional carboxylic acids. Particularly suitable derivatives of the bifunctional carboxylic acids are the acid halides. For example, instead of terephthalic acid, isophthalic acid or mixtures thereof, it is possible to use isophthaloyl dichloride, terephthaloyl dichloride or mixtures thereof.

According to one of the methods of preparing the copolyester carbonates of the invention, a heterogeneous interfacial polymerization system is used, wherein an aqueous solution of a base, an organic water-immiscible solvent, at least one divalent phenol, is selected from the divalent phenols of formulas (1) and (2), at least one bifunctional carboxylic acid or a reactive derivative thereof, a catalyst, a molecular weight regulator and a carbonate precursor. In a preferred heterogeneous interface.

The polymerization system uses phosgene as the carbonate precursor and dichloromethane or chlorobenzene as the organic solvent.

The reaction conditions, catalysts and chain stoppers or molecular weight regulators employed are generally the same as those noted above for the polycarbonates of the invention.

The copolyester carbonates of the invention may optionally be mixed with the above additives.

Another embodiment of the invention is comprised of a copolyester carbonate resin prepared from (i) a carbonate precursor, (ii) at least one bi-functional carboxylic acid or a reactive derivative thereof, (iii) at least one divalent phenol selected from the divalent phenols of formulas (1) and (2), and (iv) at least one divalent phenol of formula (27). In this copolyester carbonate, the amount of divalent phenol of formula (1) and / or (2) is effective in improving the heat resistance of the resin, for example, the transition temperature to the glass condition. Generally, this amount is about 10-90% by weight, based on the total amount of divalent phenols present. These resins may optionally be mixed with the above additives.

Yet another embodiment of the invention is a copolyester carbonate resin mixture containing (i) at least one copolyester carbonate resin of the invention; And (ii) at least one copolyester carbonate resin obtained from (a) a carbonate precursor, (b) at least one bifunctional carboxylic acid or a reactive derivative thereof and (c) at least one divalent phenol of formula (27) . These blends contain an amount of the copolyester-15 carbonate resin of the invention which is effective in improving the heat resistance of the blends. In general, this amount is approx.

10-90% by weight, based on the total amount of copolyester carbonate resins present in the mixture.

These mixtures may optionally be mixed with the above additives. The present blends can be prepared by first preforming the various resins and then thoroughly mixing them together to form an intimate physical mixture thereof.

The invention also includes thermoplastic polycarbonates and high molecular weight copolyester carbonates with random distribution of the branches. The randomly branched polycarbonates can be prepared by reacting the following materials together: (i) a carbonate precursor, (ii) at least one divalent phenol selected from the phenols of formulas (1) and ( 2), and (iii) a branching agent. The copolyester carbonates can be prepared by reacting the following materials together: (i) a carbonate precursor, (ii) at least one bi-functional carboxylic acid or a reactive derivative thereof, (iii) at least one divalent phenol, selected from the phenols of formulas (1) and (2), and (iv) a branching agent.

8304322 - 15 -

The branching agent is used in a small amount and is generally a polyfunctional organic compound having at least three functional groups. These functional groups are, for example, carboxyl groups, hydroxyl groups, carboxylic anhydride groups, haloformyl groups and the like. Some representative polyfunctional compounds are described in U.S. Pat. Nos. 3,635,895 and 4,001,184. Some examples of these polyfunctional compounds are trimellitic anhydride, trimellitic acid, trimellityl chloride, mellitic acid and the like.

Preferred Embodiments

The invention is further illustrated by the non-limiting examples below. In these examples, all parts and percentages are by weight unless otherwise stated.

The following examples illustrate the preparation of the novel bivalent phenols of the invention.

Example I

This example describes the preparation of 4,4 '- (cyclohexylmethylene) bisphenol (a divalent phenol of formula (2)).

In a warm solution of 658.7 grams (7 moles) of molten phenol and 78.9 grams (0.7 moles) of cyclohexane carboxaldehyde (hexahydrobenzaldehyde) in a 2-liter three-necked flask equipped with a stirrer, thermometer, reflux The cooler and gas inlet tube, which emanated below the surface of the liquid, were fed hydrogen chloride gas, while using a cooling bath with cold water, the temperature of the reaction mixture, which obtained a reddish-orange color, was ensured between 34 ° C and 45 ° C were kept. After the solution was saturated with hydrogen chloride, the solution was left overnight at ambient temperature, during which time a white solid was formed which was filtered by suction and triturated with dichloromethane and filtered again.

The resulting white crystals, which melted between 216 ° C and 218 ° C, were recrystallized from methanol-water, having a melting point of 221-222 ° C and a purity of 99.9% according to gas chromatography. . and nmr confirmed the structure of the 4,4 '- (cyclohexylmethylene) bisphenol.

The gas chromatography retention time (GC retention / ref. In minutes) was 24.3 / 16.6.

Examples II-XII

The procedure described in Example I was followed using different amounts of phenol and aldehyde as reaction components to obtain various new bivalent phenols of the invention. The various divalent phenols prepared, their melting points, gas chromatography retention times and purity are listed in Table A. Table A also lists the various phenols and aldehydes used to prepare the divalent phenols, as well as the amounts of these phenols and aldehydes used.

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The examples below illustrate the preparation of the polycarbonates of the invention.

Example XIII

In a mixture of 14.1 g (0.05 mol) 4.4 '- (cyclo-5-hexylmethylene) bisphenol, 300 ml of water, 400 ml of dichloromethane, 0.12 g of phenol and 0.28 ml of triethylamine were introduced for 10 minutes of phosgene at a rate of 0.5 g / min, while the pH of the two phase system was kept at 11 (i.e. 10-12.5) by simultaneous addition of 25% aqueous sodium hydroxide solution. At the end of the phosgenation, the pH of the aqueous phase was about 11.7.

The dichloromethane phase was separated from the aqueous phase, washed with excess dilute (0.0IN) aqueous HCl and then washed three times with deionized water.

The polymer was then steam-precipitated and dried at 95 ° C. The resulting polycarbonate had a 1 V. (intrinsic viscosity determined in dichloromethane at 25 C) of 0.368 and a second order glass temperature (T) transition temperature of 197.8 ° C.

^ Example XIV

The procedure of Example XIII was repeated with a mixture of 14.1 g (0.05 mol) 4.4 '- (cyclohexylmethylene) bisphenol and 11.4 g (0.05 mol) bisphenol-A, using 0 , 12 g (1.25 mol%) phenol and 0.28 ml (1.0 mol%) triethyl

O C

amine? a polycarbonate with an I.V. was obtained of 0.697 dl / g and a Tg of 183.3 ° C.

Example XV

The procedure of Example XIV was repeated, except that a mixture of 19.77 g (0.07 mol) of 4,4'-cyclohexylmethylene) bisphenol and 6.85 g (0.03 mol) of bisphenol-A was applied? a polycarbonate with an I.V. was obtained of 0.670 dl / g and a T of 190.1 ° C.

Example XVI

The procedure of Example XIV was repeated, however with the difference that a mixture of 8.5 g (0.03 mol) 4.4 '- (cyclohexylmethylene) bisphenol and 16.0 g (0.07 mol) bisphenol-A was applied? a polycarbonate was obtained with ----- - * 8304322 9 - 26 - an I.V. of 0.733 dl / g and a Tg of 172.4 ° C.

Example XVII

The procedure of Example XIII was repeated, except that a mixture of 14.1 g (0.05 mol) of 4.4 '- (cyclohexyimethylene) bisphenol and 5.75 g (0.0125 mol) of 4.4 - (cyclohexyimethylene) bis (2,6-dimethylphenol) was used? a polycarbonate with a T of 189.7 ° C was obtained.

Example XVIII

The procedure of Example XIII was repeated, except that 31.0 g (0.1 mol) 4.4 '- (cyclohexy1-methylene) bis (2-methylphenol), 0.25 g (2.5 mol %) phenol and 0.28 ml (2.0 mol%) triethylamine in 400 ml dichloromethane and 300 ml water were used? a polycarbonate was obtained with an I.V. of 0.374 dl / g and a T of 170.1 ° C.

Example XIX

The procedure of Example XIII was repeated, except that 13.4 g (0.05 mol) of 4,4 '- (2,2-dimethyl-propylidene) bisphenol, 0.1 g of phenol and 0.2 g of triethylamine 20 were applied? a polycarbonate with an intrinsic viscosity of 0.544 dl / g and a T 2 of 200.4 ° C was obtained.

Example XX

The procedure of Example XIII was repeated, but with the difference that 14.2 g (0.05 mol) 4,4 '- (2,2-dimethyl-propylidene) bis (2-methylphenol), 0.1 g phenol and 0.14 ml of triethylamine were used? a polycarbonate with an I.V. was obtained of 0.353 dl / g and a T of 162.2 ° C.

For comparison, only the transition temperatures to the second order glass state of various known and conventional polycarbonates obtained from corresponding known and conventional bivalent phenols are given in Table B below. The polycarbonates and the divalent phenols listed in Table B from which these polycarbonates are obtained are not included in the invention. Table B

gives the divalent phenol used for the preparation of the polycarbonate and the Ti value of the polycarbonate.

8304322 * - 27 -

Table B

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H

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H

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HO C OH 119.4 ° C

H

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A comparison of the T values in Table B with those of Examples XIII-XX clearly shows that the polycarbonates of the invention have an improved transition. temperature to the glass state relative to the known polycarbonates listed in Table B, Table 8. This improvement in the is very surprising.

As can be seen from the data in Table B, there is no discernible relationship between the structure of the bivalent phenol and the value of the corresponding polycarbonate. In order to determine which bivalent phenols give polycarbonates with high T values, an empirical approach should be used. Thus, the fact that the divalent phenols of the invention result in polycarbonates 10 with improved Ti values is unpredictable and surprising.

The examples below illustrate the preparation of copolyester carbonate resins of the invention.

Example XXI

14.1 g (0.05 mol) of 4.4 '- (cyclohexylmethylene) bisphenol, 0.12 g (2.5 molS) phenol, 0.28 ml (2.0 mol%) of triethylamine were added to a reaction vessel. 400 ml of dichloromethane and 300 ml of water. A 25% aqueous solution of sodium hydroxide was added to adjust the pH of the reaction mixture to about 11, which value was then maintained.

2.5 g (0.0125 mol) of isophthaloyl dichloride dissolved in dichloromethane were added dropwise to the reaction mixture while the pH was kept at 11 by adding the aqueous caustic solution. After all the isophthaloyl dichloride was added and the pH of the reaction mixture stabilized at about 11, phosgene was introduced into the reaction mixture at a rate of 0.5 g per minute for 10 minutes while the pH was adjusted to 11 held by adding the aqueous caustic solution. The dichloromethane layer was separated from the alkaline aqueous layer, washed with 0.01 N hydrochloric acid, then washed twice with deionized water. The copolvester carbonate resin was precipitated with methanol and dried in a vacuum oven at 60 ° C.

The resulting copolyester carbonate resin had an I.v.

35 of 0.408 dl / g and a T 2 value of 201.1 ° C.

Example XXII

The procedure of Example XXI was repeated, however 1304322-29, except that 5.1 g of isophthaloyl dichloride was used instead of the 2.5 g amount of Example XXI.

f The copolyester carbonate resin obtained had a T-5 value of 208.1 ° C.

Example XXIII

8.5 g (0.03 mole) of 4,4 '- (cyclohexylmethylene) bisphenol, 16.0 g (0.07 mole) of bisphenol-A, 0.12 g (2.5 mole%) were placed in a reaction vessel. phenol, 0.28 ml (2.0 mol%) triethylamine, 400 ml dichloromethane and 300 ml water. A 25% aqueous solution of sodium hydroxide was added to adjust the pH of the reaction mixture to about 11, which value was then maintained. 5.1 g (0.025 mol) of isophthaloyl-15 dichloride dissolved in dichloromethane were added dropwise to the reaction mixture while the pH was kept at 11 by addition of the aqueous sodium hydroxide solution. After all the isophthaloyl dichloride was added and the pH of the reaction mixture stabilized at about 11, phosgene was introduced into the reaction mixture at a rate of 0.5 g per minute for about 16 minutes at a rate of 0.5 g per minute while the aqueous caustic solution was kept at 11. The dichloromethane layer was separated from the alkaline aqueous solution, washed with 0.01 N hydrochloric acid, then washed twice with deionized water. The copolyester carbonate resin was precipitated with methanol and dried in a vacuum oven at 60 ° C.

The resulting copolyester carbonate resin had an I.V. of 0.599 dl / g and a T 2 value of 179.4 ° C.

The invention is not limited to the above-described embodiments with regard to the methods and compositions, since numerous modifications are of course possible within the scope of the invention.

8304322

Claims (46)

1. Thermoplastic polymeric materials with improved heat resistance, containing at least one thermoplastic polymer prepared from (a) a carbonate precursor; and 5 (b) at least one divalent phenol selected from divalent phenols of the general formulas (1) and (2), wherein * each of the symbols R1 represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group? 2 each of the symbols R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group? 4 5 R and R independently represent monovalent hydrocarbon groups? 3 15. represents a hydrogen atom or a monovalent hydrocarbon 3 group, provided that if R is hydrogen at least one of the monovalent hydrocarbon radicals proposed by R and R contains at least two carbon atoms? g r is a divalent hydrocarbon group which, together with the carbon atom to which R 2 is bonded, forms a cyclic structure? 7 R represents a hydrogen atom or a monovalent hydrocarbon group? and n and n independently represent integers with a value of 0-4. 1 2 The material of claim 1, wherein the monovalent hydrocarbon radicals represented by R and R are selected from alkyl groups, aryl groups, aralkyl groups, alkaryl groups and cycloalkyl groups. 1 2 The material of claim 1, wherein the halogen atoms represented by R and R are selected from chlorine and bromine. 1 2 The material of claim 1, wherein the monovalent hydrocarbonoxy moieties represented by R and R are selected from alkoxy and aryloxy groups. 3 4 The material according to claims 1-4, wherein the monovalent hydrocarbon radicals represented by R, R, R 7, R and R are selected from alkyl groups, aryl creams, alkaryl groups, 8304322-6-aralkyl groups and cycloalkyl groups. The material according to claims 1 to 5, wherein the divalent hydrocarbon groups represented by R are selected from alkylene groups. 3 4 A material according to claims 1-6, wherein R, R and R 4 are independently selected from monovalent hydrocarbon groups. 8. The material of claim 7, wherein the monovalent hydrocarbon groups are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. The material of claim 8, wherein the monovalent hydrocarbon groups are selected from alkyl groups. The material of claim 8, wherein the alkyl groups are 15 to about 8 carbon atoms, the aryl groups are 6 to 12 carbon atoms, the aralkyl and alkaryl groups are 7 to about 14 carbon atoms, and the cycloalkyl groups are 4 to about 8 ring carbon atoms. contain atoms. The material of claims 1-10, wherein n and n 'are 20.. The material according to claims 1-11, wherein the divalent phenol is selected from divalent phenols of the general formula (1). 13. The material of claims 1-11, wherein the divalent phenol is selected from divalent phenols of the general formula (2). 7 The material of claim 13, wherein the monovalent hydrocarbon radicals represented by R are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups, and cycloalkyl groups. The material of claim 13 or 14, wherein the divalent hydrocarbon group represented by R 6 is an alkylene group. The material of claim 15, wherein the alkylene group 35 is a pentylene group. 7 The material of claim 13 or 15-16, wherein R is hydrogen. 8304322 η - 32 - The material of claims 12-17, wherein the divalent phenols are 4,4'-phenols. The material of claims 1-18, wherein the carbonate precursor is phosgene. 20. The material of claims 1-19, wherein the thermoplastic polymer is obtained from (a)? (b); and (c) at least one divalent phenol of the general formula (27), wherein: een an unbranched alkylene group having 2 to about 6 carbon atoms, an unbranched alkylidene group having 2 to about 6 carbon atoms, a cycloalkylene group with 4 to about 7 ring carbon atoms, a cycloalkylidene group of 4 to 7 ring carbon atoms, -S-, -SS-, -O-, -C (O) -, -S {0) - or -SC ^ - represents; each of the symbols X represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; each of the symbols X 'represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; B is 0 or 1; and a and a 'independently represent integers with a value of 0-4. 21. The material of claim 20 containing an amount of divalent phenol (b) effective in improving the heat resistance of the material. The material of claim 21, wherein this amount is about 10-90% by weight, based on the total amount of divalent phenols present. 30 The material of claims 20-22, wherein the divalent phenol (c) is a 4,4'-bisphenol. The material of claim 23, wherein the 4,4'-bisphenol is bisphenol-A. The material of claims 1-24, further comprising at least 35 'thermoplastic polycarbonate obtained from: (d) a carbonate precursor; and (e) at least one divalent phenol of the general formula (27), wherein A, X, X ', b, a and a' have the meanings given in claim 9304322 * - 33 - 20. The material of claim 25, wherein the divalent phenol (e) is a 4,4'-bisphenol. The material of claim 26, wherein the bisphenol 5 is bisphenol-A. The material according to claims 1-27, wherein for the preparation of the polymer obtained from (a) and (b), also (f) at least one bifunctional carboxylic acid or a reactive derivative thereof is used. The material of claim 28, wherein the reactive derivative of the bi-functional carboxylic acid is an acid dihalide. The material of claim 29, wherein the acid dihalide is an acid dichloride. The material of claim 30, wherein the acid dichloride is selected from isophthaloyl dichloride, terephthaloyl dichloride and mixtures thereof. 32. The material of claims 1-31, further comprising at least one polymer obtained from (g) a carbonate precursor; (h) at least one bifunctional carboxylic acid or a reactive derivative thereof; and (i) at least one divalent phenol of the general formula (27), wherein A, X, X ', b, a and a' have the meanings given in claim 20. 33. Novel bivalent phenols of the general formulas (1) and (2), wherein: each of the symbols R * represents a halocene atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; Each of the symbols R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; 4 5 R and R independently represent monovalent hydrocarbon groups; 35 represents a monovalent hydrocarbon group or hydrogen with the proviso that if R is hydrogen, at least one of the monovalent - Cl represented by R 1 and R 5. 8304322 2 * - 34 - hydrocarbon groups contain at least two carbon atoms; 7 R is hydrogen or a monovalent hydrocarbon group; and g R represents a divalent hydrocarbon group which forms g 5 together with the C radical to which R is bonded, a cyclic structure; and n and n * independently represent integers with a value of 0-4. 34. Divalent phenols according to claim 33, wherein the monovalent hydrocarbon groups are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. 35. Divalent phenols according to claim 33 or 34, wherein the divalent hydrocarbon groups are selected from 15 alkylene groups. 36. Divalent phenols according to claims 33-35, wherein the monovalent hydrocarbon radicals represented by R and R are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. 37. Divalent phenols according to claims 33-35, wherein 1 2 the halogen atoms represented by R and R are selected from bromine and chlorine. 38. Bivalent phenols according to claims 33-35, 12 wherein the monovalent hydrocarbon oxy groups represented by R and R are selected from alkoxy and aryloxy groups. Bivalent phenols according to claims 33-38, wherein the phenols are 4,4'-bisphenols. 40. Bivalent phenols according to claims 33-39, wherein 3 4 5 JL, R and R independently represent an alkyl group, aryl-30 group, aralkyl group, alkaryl group or cycloalkyl group. 3 41. Bivalent phenols according to claim 40, wherein P, R, R and R independently represent an alkyl group. 42. Bivalent phenols according to claims 33-41, wherein 35 n and n 'are 0. Bivalent phenols according to claims 33-36 and 39-42, 12 wherein R and R independently represent alkyl groups. 8304322 «. «C-" - 35 - 44. Bivalent phenols according to claims 33-39 and 42-43, 3 4 ς in which R represents hydrogen and R and R independently represent an alkyl group or an aryl group, 45. Divalent phenols according to claims 33-44, wherein 7 is 5. hydrogen. Bivalent phenols according to claims 33-45, wherein g R is pentylene. 8304322