NL8304450A - POLYCARBONATES WITH IMPROVED HEAT RESISTANCE. - Google Patents

Description

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- - S 2348-1263Ned / LE / WVR

Short designation: Polycarbonates with improved heat resistance.

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

Although currently available conventional polycarbonates are well suited for a 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 as well as greater resistance against heat 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 polycarbonate resins that exhibit substantially the most advantageous properties of conventional polycarbonate resins while at the same time improving heat resistance.

These polycarbonates generally contain at least one repeating structural unit according to the general formula (1) of the formula sheet, wherein: R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxo group; R * represents a monovalent hydrocarbon group; X represents a cycloalkylidene group having 8 to about 16 ring carbon atoms; n represents an integer with a value of 0-4; and 8304450 i * - 2 - m represents an integer ranging from 0 to the number of replaceable hydrogen atoms on X.

It has been found that carbonate polymers can be obtained which exhibit improved heat resistance and at the same time retain substantially the most beneficial properties of conventional polycarbonates.

These new polycarbonates are obtained from: (i) a carbonate precursor; and (ii) at least one new divalent phenol of the general formula (2) of the formula sheet, wherein: R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; R1 represents a monovalent hydrocarbon group; X represents a cycloalkylidene group having 8 to about 16 ring carbon atoms; n represents an integer with a value of 0-4; and m represents an integer ranging from 0 to the number of hydrogen atoms of X available for replacement.

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

The monovalent hydrocarbon groups represented by R are selected from alkyl groups, aryl groups, aralkyl greens, alkaryl groups and cycloalkyl groups. The preferred alkyl groups represented by R are those having 1 to about 8 carbon atoms. Some non-limiting examples of these alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and the like. The preferred aryl greens represented by R are those with 6-12 carbon atoms, for example phenyl, naphthyl and biphenyl. The preferred aralkyl and alkaryl groups represented by R are those having 7 to about 14 carbon atoms. Some non-limiting examples of these alkaryl and aralkyl groups are benzyl, tolyl, ethylphenyl and the like. The preferred cycloalkyl groups represented by R. are those having 4 to about 6 ring carbon atoms (cyclo-8304450 * 3 -butyl, cyclopentyl and cyclohexyl).

The monovalent hydrocarbonoxy groups represented by R are preferably selected from alkoxy groups and aryloxy groups. The preferred alkoxy groups are those carbon black from 1 to about 8 carbon atoms, for example, methoxy, butoxy, propoxy, isopropoxy and the like. The preferred aryloxy group is the phenoxy group.

Preferably, R is selected from monovalent hydrocarbon groups, with alkyl groups being the preferred hydrocarbon groups.

The monovalent hydrocarbon groups represented by R 1 are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. The preferred alkyl groups are those with 15 to about 8 carbon atoms. Some non-limiting examples of these alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and the like.

The preferred aryl groups are those with 6-12 carbon atoms (phenyl, naphthyl and biphenyl). The preferred aralkyl and alkaryl groups represented by 20 r1 are those with 7 to about 14 carbon atoms.

Some non-limiting examples of these preferred aralkyl and alkaryl groups are benzyl, tolyl, ethylphenyl and the like. The preferred cycloalkyl groups represented by R * are those having 4-6 ring carbon atoms (cyclobutyl, cyclopentyl and cyclohexyl).

The preferred monovalent hydrocarbon groups represented by R 1 are alkyl groups.

If more than one substituent R is present on the aromatic core in the divalent phenolic compounds of the formula (2), these substituents may be the same or different.

If more than one substituent R * is present on the cycloalkylidene group represented by X, these substituents may be the same or different.

In formula (2), m is preferably an integer carbon black a value from 0 to about 6.

The preferred divalent phenols of formula (2) are the 4,4'-bisphenols.

Some non-limiting examples of bivalent phenols of formula (2) are the compounds of the formulas (3), (4), (5), (6), (7), (8), (9) and (10 ) of the formula sheet.

The novel bivalent phenols of formula (2) are prepared by reacting a ketone with a phenol in the presence of an acidic catalyst, preferably in the presence of an acidic catalyst and a cocatalyst such as butyl mercaptan.

The ketone used as the reaction component is selected from ketones according to the general formula (11) of the formula sheet, wherein R1, m and X have the meanings given above. More specifically, the ketone of formula - (11) may be represented by the general formula (12) of the formula sheet, wherein R 1 has the meaning given above, Y is selected from alkylene groups of 7 to about 15 carbon atoms, which together with the -C (O) - group forms a 20 cyclic structure with 8 to about 16 carbon atoms and m 'represents an integer ranging from 0 to the number of replaceable hydrogen atoms on Y.

The phenol used as the reaction component is selected from phenols according to the general formula "(13) of the formula sheet, wherein R and n have the meanings given above.

To obtain the new bivalent phenols of formula (2), one mole of a ketone of formula (12) is reacted with 2 moles of a phenol of formula (13) in the presence of an acid catalyst, and preferably in the presence of a acidic catalyst and a co-catalyst such as butyl mercaptan. In general it is like. reaction component of phenol used is present in excess. Instead of just one phenol, a mixture of two different phenols can be used.

Some non-limiting examples of suitable acidic 9304450 - 5 -

catalysts that can be used are chlorinated water

dust, hydrogen bromide, poly (styrene sulfonic acid), sulfuric acid, I.

benzenesulfonic acid, and the like. The phenol according to formula I.

(13) is converted with the ketone full cream formula (12) into I.

Presence of an acidic catalyst and under such I.

conditions of temperature and pressure that the phenol and I.

the ketone reacting together to form a dihydric I

dig phenol according to formula (2). In general, the I

reaction satisfactory at a pressure of about 1 atmosphere and at temperatures ranging from about room temperature (25 ° C) to about 100 ° C.

The amount of the acidic catalysts used is a catalytic amount. Under a catalytic I

quantity means an amount that is active I.

15 is about catalyzing the reaction between the I.

ketone and the phenol to form the divalent phenol. I

In general, this amount is about 0.1-10%. I

In practice, however, this amount is usually somewhat

slightly larger since the water formed as a by-product in the reaction dilutes the acid catalyst and the catalyst slightly

makes it less effective (making the reaction slower) I

compared to the undiluted catalyst.

In the preparation of the carbonate polymers of the I

The invention may only use one divalent phenol of formula (2) or a mixture of two or more compounds

various divalent phenols of formula (2).

The carbonate precursor produced with the divalent I.

phenol of formula (2) may be a carbonyl halide, a diaryl carbonate or a bishalogen formate. The carbonate precursors are preferably carbonyl halides. The carbonyl halides are selected from carbonyl chloride, carbonyl bromide and mixtures thereof. The preferred carbonyl halide is carbonyl chloride, also referred to as phosgene.

The novel carbonate polymers of the invention contain at least one repeating structural unit of the general formula (1), wherein R, R1, X, m, and n have the meanings given above 8304450 vv-6.

These high molecular weight aromatic carbonate polymers generally have a "weight" average molecular weight of from about 10,000 to 200,000 and preferably from about 20,000 to 100,000.

The invention also includes thermoplastic branched polycarbonates with random distribution of the branches. These random branching polycarbonates can be prepared by reacting (i) a carbonate precursor, (ii) at least one bivalent phenol of formula (2) and (iii) a small amount of a polyfunctional organic compound.

The polyfunctional organic compound is generally aromatic and acts as a branching agent. This poly-functional aromatic compound contains at least three functional groups selected from hydroxyl, carboxyl, haloformyl, carboxylic anhydride and the like. Some representative polyfunctional aromatics are disclosed in U.S. Pat. Nos. 3,635,895 and 4,001,184. Some non-limiting examples of these polyfunctional aromatic compounds are trimellitic anhydride, trimellitic acid, trimellitric trichloride, mellitic acid and the like.

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 according to formula (2), a carbonate precursor such as phosgene, a catalyst and a molecular weight regulator are used.

According to another suitable method for preparing the carbonate polymers. of the invention, an organic solvent system which can also act as an acid acceptor is used, at least one divalent phenol of formula (2), an agent for controlling the molecular weight. 8 3 0 4 4 5 0 - - * - 7 - weight , a catalyst and a carbonate precursor such as phosgene.

Any suitable catalyst which contributes to the polymerization of a bivalent phenol with a carbonate precursor such as phoscrene to form a polycarbonate may 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, chroman-I and the like.

The temperature at which the phosgenation reaction proceeds may range from below 0 ° C to above 100 ° C. The reaction proceeds satisfactorily at temperatures from room temperature (25 ° C) to about 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 modifying means; ultraviolet ray absorbers such as benzophenones, benzotriazoles, cyanoacrylates and the like; softeners; Stabilizers against hydrolysis, such as the epoxides described in U.S. Pat. Nos. 3,489,716, 4,138,379, and 3,839,247; color stabilizers such as the organophosphites disclosed in U.S. Pat. Nos. 3,305,520 and 4,118,730; flame retardants; and such.

In particular, suitable flame retardants are the alkali metal and alkaline earth metal salts of sulfonic acids. These types of flame retardants are described in U.S. Pat. Nos. 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 reacting (i) a carbonate precursor, (ii) at least one divalent phenol of formula (2) and (iii) at least one divalent phenol according to the general formula (14) of the formula sheet, wherein: R represents a haloene atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy growth; a represents an integer with a value of 0-4; b 0 or lis; and A is selected from alkylene groups, alkylidene groups, -S-, -O-, -S-S-, -C (O) -, -S (O) - and -SCL-.

Δ 2

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

2

The monovalent hydrocarbon groups represented by R are alkyl groups, aryl groups, aralkyl groups, alkaryl-20 groups and cycloalkyl groups. The preferred alkyl groups represented by R are those having 1 to about 8 carbon atoms. Some non-limiting examples of these alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and the like. The preferred aryl groups represented by R are those with 6-12 carbon atoms (phenyl, naphthyl and biphenyl).

2

The preferred aralkyl and alkaryl groups represented by R are those having 7 to about 14 carbon atoms.

Some non-limiting examples of these aralkyl and alkaryl groups are benzyl, tolyl, ethylphenyl and the like.

2

The preferred cycloalkyl groups represented by R are those having from 4 to about 6 ring carbon atoms, for example cyclobutyl, cyclopentyl, cyclohexyl, methylvcyclohexyl and the like.

The monovalent hydrocarbon oxy groups represented by R are preferably alkoxy greens and aryloxy greens.

2

The preferred alkoxy greens represented by R are those with 1 to about 8 carbon atoms. Some non-limiting examples of these alkoxy groups are methoxy, butoxy, isopropoxy, propoxy and the like. The preferred aryloxy group is the phenoxy group.

Preferably R is a monovalent hydrocarbon group; the alkyl groups are the preferred monovalent hydrocarbon groups.

The preferred alkylene groups represented by A are those having 2 to about 6 carbon atoms. Some non-limiting examples of these alkylene groups are ethylene, propylene, butylene and the like. The preferred alkylidene groups represented by A are those having 1 to about 6 carbon atoms. Some non-limiting examples of these alkylidene groups are ethylidene, 15 l, 1-propylidene, 2,2-propylidene and the like.

The preferred bivalent phenols of formula (14) are those wherein b is 1 and A is selected from alkylene groups and alkylidene groups.

When more than one substituent R is present on the aromatic core in the divalent phenol of formula (14), these substituents may be the same or different.

Particularly preferred bivalent phenols of formula (2) are the 4,4 * bisphenols.

The divalent phenols of formula (14) are known compounds and generally these compounds are commercially available or can be prepared by known methods. These phenols are generally used to prepare known and conventional polycarbonate resins.

Some non-limiting examples of the divalent phenols of formula (14) are: 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A); 1.1-bis (3-methyl-4-hydroxyphenyl) ethane; 2.2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; bis (4-hydroxyphenyl) sulfone; 3.3-bis (3-methyl-4-hydroxyphenyl) pentane; 3,3'-diethyl-4,4'-dihydroxydiphenyl; and such.

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> V

- 10 -

The amount of the divalent phenol of formula (2) used in this embodiment is an amount effective to improve the heat resistance, for example the transition temperature to the glass state, of the copolymers. Generally, this amount is about 5-90 wt%, and preferably about 10-80 wt%, based on the total amount of divalent phenols of formulas (2) and (14) used.

The preferred divalent phenol of formula (14) is 2,2-bis (4-hydroxyphenol) propane.

The carbonate copolymers obtained by reacting (i) a carbonate precursor, (ii) at least one divalent phenol of formula (2) and (iii) at least one divalent phenol of formula (14) contain at least the repeating structural units of formulas (1) and (15) of the formula sheet.

In this embodiment of the invention, only one divalent phenol of formula (14) or a mixture of two or more different divalent phenols of formula (14) can be used.

The methods of preparing the copolymers of this embodiment are generally similar to those used to prepare the polycarbonates of the invention as described above. The subject carbonate copolymers may optionally be mixed with the various additives mentioned above.

Yet another embodiment of the invention is a polycarbonate resin mixture of (i) at least one poly-30 carbonate resin obtained from (a) at least one divalent phenol of formula (2) and (b) a carbonate precursor (hereinafter referred to herein) as resin A); and (ii) at least one conventional polycarbonate resin obtained from (a) at least one divalent phenol of formula (14) and (b) a carbonate precursor (hereinafter referred to as resin B). These blends contain an amount of resin A which is effective in improving the heat resistance of these blends. Generally, this amount is about 5-90 wt%, and preferably about 10-80 wt%, of resin A, based on the total amount of resins A and B present in the mixture.

The mixtures may optionally be mixed with the above additives.

The blends can generally be prepared by first preparing resins A and B and then physically mixing these resins. These mixtures may optionally contain the additives described above.

Yet another embodiment of the invention is comprised of copolyester carbonates obtained from (i) a carbonate precursor, (ii) at least one bivalent phenol of formula (2) and (iii) at least 15 one bi-functional carboxylic acid or a reactive derivative thereof.

The copolyester carbonates contain repeating carbonate groups, carboxylate groups and aromatic carbocyclic groups in the linear polymer chain, at least some of the carboxylate groups and at least some of the carbonate groups being directly bonded to the ring carbon atoms of the aromatic carbocyclic groups .

These copolyester carbonates contain ester bridging groups and carbonate bridging groups in the polymer chain, the amount of ester groups being about 25-90 mol% and preferably about 35-80 mol%. For example, 5 moles of bisphenol-A, which react completely with 4 moles of isophthaloyl dichloride and 1 mole of phosgene, give a copolyester carbonate with 80 mole% ester groups.

Conventional copolyester carbonates and methods for their preparation are 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 carbonate resins of the invention. The carboxylic acids that can be used include aliphatic carboxylic acids, aliphatic carboxylic-aromatic carboxylic acids and aromatic carboxylic acids.

These acids are described in the aforementioned U.S. Patent 3,169,121.

The bifunctional carboxylic acids which can be used to prepare the copolyester carbonate resins of the invention are generally compounds of formula (16) of the formula sheet wherein R is an alkylene group, alkylidene group, aralkylene group, aralkylidene group or cycloaliphatic group. an alkylene group, alkylidene group 10 or cycloaliphatic group with olefinic unsaturation; an aromatic group such as phenylene, biphenylene, substituted biphenylene and the like? -two or more aromatic groups linked by non-aromatic bridge groups such as 3 alkylene or alkylidene groups? and the like. R 15 is a carboxyl group or a hydroxyl group. The letter q has the value 1 when R is a hydroxyl group and the value 0 or 3 has 1 when R is a carboxyl group.

Preferred bifunctional carboxylic acids are aromatic bifunctional carboxylic acids, i.e., 3 <RTIgt; 20 </RTI> acids of formula (16) wherein q is 1, R is a carboxyl-4 or hydroxyl group and R is an aromatic group such as phenylene, naphthylene, biphenylene, substituted phenylene and the like. The preferred aromatic bifunctional carboxylic acids are those according to the general formula (17) of the formula sheet wherein R is as defined above? R5 represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group? and p is an integer with a value of 0-4.

The preferred halogen atoms represented by R1 are chlorine and bromine. The hydrocarbon groups represented by R ** are alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. The preferred alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups are the same as mentioned above for R. The monovalent hydrocarbonoxy groups represented by R 1 are alkoxy and aroxy groups. The preferred alkoxy and aryloxy groups represented by R 3 are the same as mentioned above for R 1.

5

Preferred groups represented by R are monovalent hydrocarbon groups, the alkyl greens being the preferred monovalent hydrocarbon groups.

Both individual bi-functional carboxylic acids and mixtures of two or more different bi-functional carboxylic acids can be used. The term "bi-functional carboxylic acid" as used herein, therefore, includes mixtures of two or more different bi-functional carboxylic acids as well as separate bi-functional carboxylic acids.

Particularly suitable 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 of isophthalic acid and terephthalic acid of 1:10 - 10: 1.

It is possible - and sometimes even preferred - to use reactive derivatives thereof, such as, for example, acid halides, instead of the functional carboxylic acids. Particularly suitable acid halides are the acid chlorides. For example, instead of terephthalic acid, isophthalic acid or mixtures thereof, 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, comprising an aqueous solution of a base, an organic water-immiscible solvent, at least one divalent phenol according to formula (2), at least one bi-functional carboxylic acid or a reactive derivative thereof, a catalyst, a molecular weight regulator and a carbonate precursor are used. In a preferred heterogeneous interface polymerization system, phosgene is used as the carbonate precursor and dichloromethane or chlorobenzene as the organic solvent.

The reaction conditions used, catalysts and 3304450-14 chain stoppers or molecular weight reagents are generally the same as those noted above to prepare the polycarbonates of the invention.

The copolyester-carbonate resins of the invention may optionally be mixed with the above additives.

Another embodiment of the invention is a copolyester carbonate resin prepared from (i) a carbonate precursor, (ii) at least one bi-10 functional carboxylic acid or a reactive derivative thereof, (iii) at least one divalent phenol of formula (2) and (iv) at least one divalent phenol of formula (14). In this copolyester carbonate resin, the amount of divalent phenol of formula (2) is effective in improving heat resistance of the resin. Generally, this amount is about 5-90 wt%, and preferably about 10-80 wt%, based on the amount of the divalent phenols of formulas (2) and (14) present. These resins may optionally also be mixed with the additives described above.

Yet another embodiment of the invention is a copolyester-carbonate resin mixture containing (i) at least one copolyester-carbonate resin of the invention, that is, 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 (2) (hereinafter further referred to as copolyester carbonate resin C); and (ii) at least one conventional copolyester carbonate resin obtained from (a) a carbonate precursor, (b) at least one bi-functional carboxylic acid or a reactive derivative thereof and (c) at least one divalent phenol of formula (14 ) (hereinafter referred to as copolyester-carbonate resin D).

The blends of this embodiment contain an amount of resin C which is effective in improving the heat resistance of the blends. In general, this amount is about 5-90 wt.%, And at 8 3 G 4 4 * 0 - 15 - preferably about 10-80 wt.%, Based on the amount of copolyester-carbonate resins C and D present in the mixtures. .

These mixtures may optionally also contain the above-mentioned additives.

5 Preferred embodiment

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 new bisphenols of the invention.

Example I

This example describes the preparation of 4,4 * -cvclo-dodecylidenebis phenol.

Into a 3 liter round bottom flask equipped with a stirrer, reflux condenser, thermometer and gas inlet tube, 1647 grams (17.5 moles) of phenol, 478 grams (2.62 moles) of cyclododecanone and 15 ml of n-butyl mercaptan were charged. It was heated by means of a heating mantle? when the reaction mixture became liquid at 58 ° C, anhydrous chlorine water was fed. dust until the solution is saturated. Stirring was continued at a temperature between 52 ° C and 60 ° C for several hours, during which time a white solid was separated from the reddish-orange reaction mixture. When gas chromatographic analysis of the samples taken from the slurry showed that macrocyclic ketone was no longer present, the hot reaction mass was filtered by suction and the resulting filter cake was washed with dichloromethane to remove much of the excess phenol. The filter cake was then slurried with fresh dichloromethane, filtered and washed again with a further amount of solvent. Gas chromatographic analysis of the dried filter cake, which weighed 849.8 grams (2.41 mol), corresponding to a yield of 92%, 35 and melted at 207.0-208.5 ° C, showed that this material had purity of 99.9% and a retention time of 26.07 minutes, compared to p.cumvlphenol, which appeared after 13.91 minutes.

3304430 —- -----— * - 16 -

Example II

This example describes the preparation of 4,4'-cyclooctylidene bis (2,6-dimethylphenol).

In a molten mixture consisting of 6.3oram (0.05 mol) 5 cyclooctanone, 122.1 grams (1.0 mol) 2,6-xylenol and 5 ml mercaptoacetic acid, gaseous hydrogen chloride was introduced until a saturated solution was obtained, while keeping the temperature between 50 ° C and 78 ° C for about 26 hours. At the end of this period solid had formed in the molten xylenol, which solid was filtered off, washed with dichloromethane and methanol and air dried. The new white crystalline diphenol, which was obtained in a yield of 9.1 grams, melted at 253 ° -254 ° C and had gas chromatography (the elution time was 24.35 minutes, compared to 13.5 minutes for p.cumylphenol) a purity of 98.5%. The structure was confirmed by proton and 13C nmr spectroscopy.

The examples below illustrate the preparation of the polycarbonate resins of the invention.

Example III

In a mixture of 352.2 grams (1.0 mol) 4,4'-cvclo-dodecylidene bisphenol, 2052 grams (9.0 mol) bisphenol-A, 7 liters of dichloromethane, 6.5 liters of water, 28 ml of triethylamine and 104 1.2 grams (3.5 mol%) of chroman-I (bisphenol-A content 10%), 1180 grams of phosgene were introduced over a period of 97 minutes at room temperature, while the pH of the two-phase system was approx. 11-11.2 was maintained by addition of a 25% aqueous sodium hydroxide solution. After completion of the addition of the phosene, the dichloro-50 methane phase was separated from the aqueous phase, washed with excess dilute (0.01 N) aqueous HCl and then washed three times with deionized water. The polymer was precipitated with steam and dried at 95 ° C. The resulting polycarbonate, which had an intrinsic viscosity of 0.475 dl / g in dichloromethane at 25 ° C, was fed into an extruder with an operating temperature of about 288 ° C; the extrudate was comminuted into granules.

8 3 0 4 Λ s η · »* * v, · '- 17 -

The beads were then injection molded at about 316 ° C into test bars of about 12.7 cm by about 1.3 cm by about 0.16 cm (thickness). The load deformation temperature (VTOB) of the test bars was determined according to ASTM D-648 5 at about 1820 kPa. The VTOB of the test bars was 142.5 ° C.

Example IV

In a mixture of 42.1 grams (0.125 mol) 4,4'-cyclo-dodecylidene bisphenol, 28.5 grams (0.125 mol) bisphenol-A, 10.7 ml triethylamine, 0.12 grams (0.5 mol% phenol, 400 ml of dichloromethane and 300 ml of water were fed at ambient temperature and a pH of about 11, namely 10.2-11.4, over a period of 27 minutes of phosgene at a rate of 1 gram per minute , while the pH of the two-phase system. 15 was maintained at about 10.2-11.4 by addition of a 25% aqueous sodium hydroxide solution. After completion of the addition of the phoscreen, the dichloromethane phase was separated from the aqueous phase, washed with excess dilute (0.01 N) aqueous HCl and then washed three times with deionized water. After this, the polymer was precipitated with methanol. The resulting polymer had a second order over glass to glass state (Tg) temperature of more than 186 ° C.

The following example illustrates the preparation of a conventional polycarbonate not covered by the invention. This example is given for comparison.

Example V

This example describes the preparation of a bisphenol-A type polycarbonate. In a mixture of 2283 cram 30 pure 4.4 * -isopropylidene bisphenol (bisphenol-A) (melting point 156 ° C-157 ° C; 10.0 grammes), 5700 grams of water, 9275 grams of dichloromethane, 32.0 grams of phenol and 10.0 grams of triethylamine were fed 1180 grams of phoscene at ambient temperature over a period of 97 minutes, while the pH of the two-phase system was kept at about 11, i.e. 10-12.5, by simultaneously Add 25% waterice sodium hydroxide solution. After this addition, the 83 04 pH of the aqueous phase was 11.7 and the content of this phase of bisphenol A was less than 1 part per million (ppm) as determined by ultraviolet analysis.

The dichloromethane phase was separated from the aqueous phase, washed with excess dilute (0.01 N) aqueous HCl and then washed three times with deionized water.

The polymer was precipitated with steam and dried at 95 ° C. The resulting pure bisphenol-A polycarbonate, which had an intrinsic viscosity 10 (IV) of 0.572 dl / g in dichloromethane at 25 ° C, was fed into an extruder with an operating temperature of about 288 ° C; the extrudate was comminuted into granules.

Then, the granules were injection molded at about 316 ° C into test bars with a thickness of about 12.7 cm by about 1.3 cm by about 0.16 cm (thickness). The VTOB of the test bars was found to be 128 ° C. The Tg of this polycarbonate was 149 ° C.

From the data in Examples II-V, it is clear that the polycarbonate resins of the invention (Examples 20 iii-iv) exhibit improved heat resistance over known and conventional polycarbonate resins (Example V) as determined by the second-order temperature to the ala state and the deformation temperature under load.

The example below illustrates the preparation of a copolyester carbonate resin of the invention.

Example VI

400 ml of dichloromethane, 300 ml of water, 35.2 grams of 4,4'-cyclododecylidenebisphenol, 0.09 grams of phenol and 0.28 ml of triethylamine were placed in a reactor vessel. At a pH of about 11, 5.1 grams of isophthaloyl dichloride were added over a period of 15 minutes, while the pH was simultaneously kept at about 11 by adding a 35% aqueous caustic solution. After the addition of the isophthaloyl dichloride 35 was completed, 8.9 grams of phosgene were introduced over a 15 minute period while the pH was kept at about 11 by adding the 35% aqueous caustic solution.

83 0 4 4 5 0 - 19 -

The polymer-containing mixture was diluted with methylene chloride and the salt-containing phase separated. The resulting polymer-containing phase was washed with HCl and then with water; the polymer was isolated by precipitation with 5 methanol. The resulting copolyester carbonate polymer had an intrinsic viscosity of 0.472 dl / σ in dichloromethane at 25 ° C and a Tg of 240.0 ° C.

The following example illustrates the preparation of a known and conventional copolyester carbonate resin not covered by the invention. This example is given for comparison.

Example VII

400 ml of dichloromethane, 300 ml of water, 34.2 grams of bisphenol-A, 0.35 grams of phenol and 0.42 ml of triethylamine were placed in a reactor vessel. At a pH of about 11, a solution of 7.6 grams of isophthaloyl dichloride in 10 ml of dichloromethane was added over a 15 minute period while the pH was kept at about 11 by adding 35% aqueous lye. After the addition of the isophthaloyl-20 dichloride was completed, 6 grams of phosgene were introduced over a period of 15 minutes, while the pH was adjusted to about 11 by addition of 35% aqueous loocol solution. The polymer-containing mixture was diluted with dichloromethane and the salt-containing phase separated. The resulting polymer-containing phase was washed with HCl and then with water; then the polymer was isolated by precipitation with methanol. The resulting copolyester carbonate was found to have an intrinsic viscosity of 0.530 dl / g and a Tg of 182.2 ° C.

3 ° From a comparison of the data of Examples VI and VII, it will be apparent that the copolvester carbonate resins of the invention (Example VI) have a much higher Tg value than the known and conventional copolyester carbonate resins (Example VII) .

Furthermore, the Tg value of 240.0 ° C of the present copolyester carbonate resin of Example V is also much higher than 8304450 - 20 - the Tg value of 199 ^ C of a known and conventional copolyester carbonate resin which is obtained from phosgene, isophthaloyl dichloride and cyclohexylidenebisphenol.

The invention is not limited to the above described embodiments, since numerous modifications are of course possible within the scope of the invention.

8304450

Claims (55)

Thermoplastic polymeric materials with improved heat resistance, containing (i) at least one thermoplastic polymer made from: (a) a carbonate precursor; and (b) at least one divalent phenol of the general formula (2), wherein R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; R1 represents a monovalent hydrocarbon group; 10. represents a cycloalkylidene group having 8 to about 16 ring carbon atoms; n is an integer with a value of 0-4; and m is an integer ranging from 0 to the number of replaceable hydrogen atoms on X. 2 I formula (14), wherein R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group I; A is selected from alkylene groups, alkylidene groups, I -S-, -O-, -S-S-, -C (O) -, -S (O) - and -SO 2 ~; b is 0 or 1? and I a is an integer with a value of 0-4. I 2 I The material according to claim 1, wherein the monovalent hydrocarbon radicals represented by R 1 are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. The material of claim 2, wherein the monovalent hydrocarbon groups are selected from alkyl groups. The material of claim 3, wherein the alkyl groups contain 1 to about 8 carbon atoms. Material according to claims 1-4, wherein m is 0. The material according to claims 1-5, wherein the divalent phenol is a 4,4'-bisphenol. The material according to claims 1-6, wherein the monovalent hydrocarbon groups represented by R are selected from alkyl groups, aryl groups, aralkyl groups, alkaryl groups and cycloalkyl groups. A material according to claims 1-7, wherein the halogen atoms represented by R 30 are selected from chlorine and bromine. A material according to claims 1-8, wherein the monovalent hydrocarbonoxy groups represented by R are selected from alkoxy and aryloxy groups. The material of claims 1-9, wherein the carbonate precursor is phosgene. 8304450 - 22 - The material of claims 7-10, wherein R is selected from alkyl groups. The material of claims 1-11, wherein n is 0. The material of claims 1-12, wherein X is a cyclo-5 dodecylidene group. The material of claim 13, wherein the bivalent phenol is 4,4'-cyclododecylidene bisphenol. The material of claims 1-14, wherein the thermoplastic polymer (i) is obtained from (a); (b); and (c) at least one divalent phenol of the general formula 2 (14), wherein R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; A is selected from alkylene groups, alkylidene groups, -S-, -S-S-, -O-, -C (O) -, —S (0) - and -SC ^ ”? b is 0 or 1; and a 15 is an integer with a value of 0-4. The material of claim 15, containing an amount of divalent phenol (b) effective in improving the heat resistance of the material. The material according to claim 16, wherein this amount is about 5-90% by weight, based on the amount of divalent phenols (b) and (c) present. The material of claim 17, wherein said amount is about 10-80% by weight. The material of claims 15-18, wherein b is 1. The material of claims 15-19, wherein A is selected from alkylene groups and alkylidene groups. 2 21. The material of claims 15-20, wherein the halogen atoms represented by R are selected from chlorine and bromine. The material of claims 15-21, wherein the monovalent hydrocarbonoxy groups are selected from alkoxy groups and aryloxy groups. 2 The material of claims 15-22, wherein the monovalent hydrocarbon radicals represented by R35 are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups, and cycloalkyl groups. 8304450 V I - 23 - The material of claim 23, wherein the monovalent hydrocarbon radicals represented by P are selected from I alkyl groups. The material of claims 15-24, wherein the bivalent phenol (c) is a 4,4'-bisphenol. The material of claims 15-25, wherein a is 0. I The material of claim 26, wherein the divalent I phenol is bisphenol-A. I 28. The material of claims 1-27, further comprising: I 10 (ii) at least one thermoplastic polymer obtained from: I (d) a carbonate precursor? and I (e) at least one divalent phenol according to General I. 29. The material of claim 28, which contains an amount of polymer (i) effective to improve the heat resistance of the material. I The material according to claim 29, wherein said amount of I is about 5-90% by weight, based on the total amount of I polymers (i) and (ii) present. I A material according to claims 1-30, wherein polymer (i) I is obtained from: (a)? (b)? and (f) at least one bifunctional I carboxylic acid or a reactive derivative thereof. I 32. The material of claim 31, wherein the bifunctional carboxylic acid is isophthalic acid, terephthalic acid, or a mixture thereof. The material of claim 31, wherein the reactive derivative of the bifunctional carboxylic acid is isophthaloyl dichloride, terephthaloyl dichloride or a mixture thereof. I The material of claims 31-33, wherein polymer (i) I 35 is obtained from: (a)? (b)? (f)? and (g) at least one divalent phenol of the general formula (14), wherein 2 R represents a halogen atom, a monovalent hydrocarbon group, or 83 0 4 0 * e - 24 - a monovalent hydrocarbon oxy growth; A is selected from alkylene groups, alkylidene groups, -S-, -S-S-, -O-, -C (O) -, -S (0) - and -SC ^ -; b is 0 or 1; and a is an integer with a value of 0-4. 5 The material of claim 34, wherein A is an alkylene group or an alkylidene group. The material of claims 1-35, further comprising; (iii) at least one thermoplastic polymer obtained: (h) a carbonate precursor; (i) at least one bi-functional carboxylic acid or a reactive derivative thereof; and (j) at least one bivalent phenol of the general 2 formula (14), wherein R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxide group; A is selected from olefin groups, alkylidene groups, -S-, -S-S-, -O-, -S (O) -, "SO2", and -C (O) - ;. b is 0 or 1; and a is an integer with a value of 0-4. The material of claim 36, wherein A is an alkylene-20 group or an alkylidene group. The material of claim 36 or 37, wherein b is 1. The material of claims 36-38, wherein the divalent phenol (j) is bisphenol-A. A material according to claims 36-39, wherein the carbonate-25 precursor of (a) and (h) is phosgene. 41. Bivalent phenols of the general formula (2), wherein R represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxide group; R1 represents a monovalent hydrocarbon group; X represents a cycloalkylidene group having 8 to about 16 ring carbon atoms; n is an integer with a value of 0-4; and m is an integer ranging from 0 to the number of replaceable hydrogen atoms on X. 42. Divalent phenols according to claim 41, wherein the monovalent hydrocarbon radicals represented by R 1 are selected from alkyl groups, aryl groups, aralkyl groups, alkaryl groups and cycloalkyl groups. 8304450 - 25 - Divalent phenols according to claim 42, wherein the monovalent hydrocarbon groups are selected from alkyl groups. The bivalent phenols of claim 43, wherein the 5 alkyl groups contain 1 to about 8 carbon atoms. 45. Bivalent phenols according to claims 41-44, wherein the halogen atoms represented by R are selected from chlorine and bromine. 46. Divalent phenols according to claims 41-45, wherein the monovalent hydrocarbonoxy groups are selected from alkoxy groups and aryloxy groups. 47. Bivalent phenols according to claims 41-46, wherein the monovalent hydrocarbon radicals represented by R are selected from alkyl groups, aryl groups, aralkyl groups and cycloalkyl groups. 48. Two bisphenol phenols according to claim 47, wherein the monovalent hydrocarbon groups are selected from alkyl groups. 49. Divalent phenols according to claims 41-48, namely 4,4'-bisphenols. 50. Bivalent phenols according to claims 41-49, wherein m is 0. 51. Divalent phenols according to claims 41-50, wherein n is 0. 52. Two-valued phenols according to claims 41-51, wherein x 25 is a cyclododecylidene group. 53. Bivalent phenols according to claims 41-51, wherein X is a cycloctylidene group. 54. 4,4'-Cyclooctylidene bis (2,6-dimethylphenol). 55. 4.4 * -Cyclododecylidene bisphenol. 83040 |