MXPA97003223A - Polycarbonate and polyes compositions - Google Patents

Abstract

A polycarbonate, polyester or polyester carbonate composition prepared from a reaction mixture comprising at least one diol and at least one carbonate precursor or a precursor of the ether wherein at least 95 mol% of the diol are present is described. in the reaction mixture consists of one or more aromatic diols, at least 10 mol% of which consists of one or more stybenediols. The composition of the invention advantageously has a relatively high heat resistance, melting temperature, tensile and bending properties, and / or resistance to thermal cracking. In addition, the polymers of the invention, which are crystalline thermoplastic liquids also advantageously possess a wide temperature range for liquid crystallinity, good processability under melting, a low coefficient of thermal expansion, a high resistance to ignition, a high resistance to solvent, and / or good properties of barre

Description

POLYCARBONATE AND POLYESTER COMPOSITIONS DESCRIPTION OF THE INVENTION This invention relates to polycarbonates, polyesters, and polyester carbonates prepared from at least one aromatic diol, wherein a portion or all of the aromatic diol used in its preparation, is a stybenediol. Certain polymers derived from stilbendiols are known and are described, for example, by Cebe et al., Polvm. Preprints vol. 33, p. 331 (1992), Bluhm et al., Mol. Crvst. Lia Crvst .. vol. 239, p. 123 (1994), and Cheng et al., Macromolecules. vol. 27, p. 5440 (1994), which describe the preparation of mixed aromatic-aliphatic polycarbonates based on stilbendiols and alpha .omega-alkanediols of C4.12. Percec and others, J. Polvm. Sci. Polvm. Lett. , vol. 22, p. 637 (1984) and J. Polvm. Sci. Part A: Polvm. Chem .. vol. 25, p. 405 (1987) report the synthesis of mixed aromatic-aliphatic polyethers via the reaction of 4,4'-dihydroxy-allfa-methylstyrene with alpha.omega-dibromoalkanes of d-n. Blumstein and others, Mol. Crvst. Lia Crvst .. vol. 49, p. 255 (1979) and Polvm. Journal, vol. 17, p. 277 (1985) describe mixed aromatic-aliphatic polyesters of stybenediols and alpha.omega-alkanedicarboxylic acids. Roviello and Sirigu, Makromol. Chem .. vol. 180, p. 2543 (1979), Makromol. Chem .. vol. 183, p. 409 (1982) and Makromol. Chem .. vol. 183, p. 895 (1982) reported the preparation of liquid crystalline, thermotropic, aromatic-aliphatic mixed polyesters, of 4,4'-dihydroxy-alpha-methyl-ethyl-benzene and of alpha-mega-alkane-dicarboxylic acids of C8-14. Sato, J , Polvm. Sci.: Part A: Polvm. Chem., Vol. 26, p. 2613 (1988) reports the synthesis of mixed aromatic-aliphatic polyesters using 4,4'-dihydroxy-alpha, alpha'-diethylstilbene and adipoyl chloride, sebacoyl chloride, and mixtures of adipoyl chloride and sebacoyl. However, the physical properties and melting characteristics of such polymers may be less desirable for certain applications. In one aspect, this invention is a polycarbonate, polyester or polyester carbonate composition, prepared from a reaction mixture comprising at least one diol and at least one carbonate precursor or ester precursor, wherein: a) at least 95 mol% of the carbonate precursor or of the ester precursor present in the reaction mixture is selected from: (i) dialkyl carbonates, diaryl carbonates, carbonyl halides, or bis (trihaloalkyl) carbonates; (ii) aromatic dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, hydroxybiphenyl acids, hydroxy cinnamic acids, or the halides or metal salts of said acids; or (iii) oligomers and polymers of (i) or (ii) containing carbonate or ester groups, which are prepared by contacting a stoichiometric excess of at least one compound selected from (i) or (ii) with at least one monol or diol under sufficient reaction conditions to form the corresponding oligomer or polymer; or b) at least 95 mol% of the diol present in the reaction mixture, consists of one or more aromatic diols, at least 10 mol% of which consists of one or more stybendiols. Applicants have discovered that the composition of the invention has advantageous thermal resistance, melting temperature, tensile and flexural properties, and / or thermal cracking resistance. In addition, those polymers of the invention which are liquid thermotropic liquids also have an advantageous temperature scale for liquid crystallinity, melt processability, coefficient of thermal expansion, ignition resistance, solvent resistance, and / or barrier properties. These and other advantages of the invention will be apparent from the following description. The polymeric composition of the invention can be prepared by any suitable method for the preparation of polycarbonate polymers, polyester, or polyester carbonate, so that at least 95 mol% of the diol present in the polymerization reaction mixture consists of one or more aromatic diols, and at least 10 mol% of the aromatic diols consists of one or more stilbendioles. Such methods include interfacial, solution and fusion polymerization processes. In addition, the polymer composition of the invention can be prepared as a homopolymer, or as a random or block copolymer of the various monomers described below. The term "reaction mixture", as used herein, refers to the mixture of monomers that are polymerized to form the composition of the invention, using any of the polymerization methods described in any of the references cited herein. . The composition of the invention preferably comprises repeat units of the formulas: - [ROXO] - (I) and optionally - [R2-C (O) -O] - (II) wherein R, independently in each occurrence, is the divalent nucleus of an aromatic diol, X is selected from: -C (O) -, -C (O) -R1-C (O) -, or a mixture thereof, R1, independently in each occurrence, is the nucleus divalent of a difunctional aromatic carboxylic acid, and R2 is the divalent nucleus of an aromatic hydroxycarboxylic acid. As indicated by the above formulas, other monomers such as hydroxycarboxylic acids may also be present in the polymerization reaction mixture, in addition to the diols and carbonate precursors. The term "divalent nucleus" as used herein, refers to the described compound, minus its hydroxyl and / or carboxyl pendant groups. When the polymer composition of the invention is a polycarbonate, it can be prepared by the reaction of an aromatic diol or mixtures of aromatic diols with a carbon precursor. The term "carbon precursor", as used herein, refers to carbonyl halides, diaryl carbonates, dialkyl carbonates, bis (trihallogeoalkyl) carbonates, such as triphosgene, bishologenoformates, or other compounds that will react with the hydroxyl groups to form carbonate bonds (-OC (O) -O-). Examples of carbonyl halide include carbonyl bromide, carbonyl chloride ("phosgene") and mixtures thereof. Suitable halogen formates include the bischloroformates of dihydric phenols such as bisphenol A. Preferably, the carbonate precursor is phosgene or diphenyl carbonate, and most preferably is diphenyl carbonate. Examples of suitable methods for preparing polycarbonates are set forth in "Polycarbonates", Encvcopedia of Polvmer Science and Enaineerina (Second Edition), vol. 1 1, p. 648-718 (1988); U.A.A. Nos. 5, 142, 018; 5,034,496; 4,831, 105; 4,543,313; 3,248,414; 3, 153.008; 3,215,668; 3, 187.065; 3,028,365; 2,999,846; 2, 999, 835; 2,970, 137; 2,964,975; and 1, 991, 273. When the polymer composition of the invention is a polyester, it can be prepared by the reaction of an aromatic diol or a reactive derivative thereof (such as the corresponding diacetate), with an ester precursor. The term "ester precursor", as used herein, refers to C8-4o dicarboxylic acids, or their reactive derivatives (such as esters thereof or the corresponding acid halides), which will react with hydroxyl groups to form ester bonds (-OC (O) -R1-C (O) -O-, wherein R1 is the divalent nucleus of the ester precursor). Preferably, the ester precursor is an aromatic dicarboxylic acid. A portion of the ester component in these polymer compositions can optionally be derived from hydroxy carboxylic acids or their reactive derivatives, either by reaction with the other monomers or by autocondensation, to provide repeating units of the formula (II): - [ R2-C (O) -O] -, wherein R2 is the divalent nucleus of a hydroxycarboxylic acid. Examples of suitable methods for preparing polyesters are set forth in "Polyesters," Encvclopedia of Polvmer Science and Engineer (Second Edition), vol. 12, p. 1-75 (1988); "Liquid Crystalline Polymers", Encvclopedia of Polvmer Science and Engineering. (Second Edition), vol. 9, p. 1-61 (1988); "Polyesters, Main Chain Aromatic", Encvclopedia of Polvmer Science and Engineering. (Second Edition), vol. I, p. 262-279; U.A.A. Nos. 5,268,443; 5,237,038; 5,233,013; 5,221, 730; 5, 175.237; 5, 175.326; 5, 1, 10, 896; 5,071, 942; 5, 037, 938; 4, 987, 208; 4,946,926; 4, 945, 1 50 and 4, 985, 532. Similarly, when the polymer composition of the invention is a polyester carbonate, it can be prepared through the reaction of an aromatic diol with a combination of a carbonate precursor and a ester precursor, as described above. Suitable methods for the preparation of polyester carbonates are described in the patents of E.U.A. Nos. 5,045,610; 4,398, 018; 4,338,455; 4,374,973; 4,371, 660; 4,369,303; 4,360,656; 4,355, 150; 4,330,662; 4,287,787; 4, 260,731; 4,255,556; 4,252, 939; 4,238, 597; 4,238, 596; 4, 194, 038; 4, 156, 069; 4, 107, 143; 4, 105,633 and 3, 169, 121; and articles by Kilesnikov and others, published in Vvsokomol Soedin as B9, p. 49 (1967); A9, p. 1012 (1967); A9, p. 1520 (1967); and A10, p. 145 (1968). In the preparation of the composition of the invention, at least 95 mol% of the carbonate precursor or the ester precursor present in the reaction mixture, is (i) dialkyl carbonates, diaryl carbonates, carbonyl halides, or bis (trihaloalkyl) carbonates; (ii) aromatic dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, hydroxybiphenyl acids, hydroxy cinnamic acids, and the halides or metal salts of such acids; (iii) oligomers and polymers of (i) or (ii) containing carbonate or ester groups, which are prepared by contacting a stoichiometric excess of at least one compound selected from (i) or (ii) with less a monol or diol under sufficient reaction conditions to form the corresponding oligomer or polymer. The term "oligomer" as used herein, includes monoesters, diesters, monocarbonates, and dicarbonates of the monol or diol. Suitable stilbenediols for use in the preparation of the polymer composition of the invention include those of the formula: wherein R, independently in each occurrence, is selected from hydrogen, C?. β alkyl, chloro, bromo, or cyano, but is preferably hydrogen or C? 8 alkyl; R4, independently in each occurrence, is selected from hydrogen, halogen, alkyl, aryl, alkoxy, aryloxy, cyano, nitro, carboxyamide, carboximide, or R5-C (O) -, wherein R5 is C? -8 alkyl? "or aryloxy, but preferably it is hydrogen or C? -8 alkyl." Preferably, the phenolic groups are in a double-bond "trans" configuration. Preferably, the stybenediol is 4,4'-dihydroxystilbene; dihydroxy-alpha-methyl-ethyl-benzene: 4,4'-dihydroxy-alpha, alpha'-dimethyl-stilbene, or 4,4'-dihydroxy-alpha, alpha'-diethyl-ethylbenze The stybenediols described above can be prepared by any suitable method For example, the diol is prepared from a phenol and a carbonyl-containing precursor, using any of the methods described by SM Zaher et al., Part 3, J. Chem. Soc, pp. 3360-3362 (1954) V. Percec et al., Mol.Cryst. Liq. Crvst., Vol 205, pp. 47-66 (1991), Singh et al., J. Chem. Soc, pp. 3360 (1954), or H Efner et al., patent of E. U.A. No. 5,414, 150. If desired, the colored bodies, or the color-forming bodies, can be removed from the stybenediols by contacting them with an aqueous solution of one or more compounds selected from alkali metal carbonates, metal carbonates. alkaline earth, alkali metal bicarbonates (such as sodium bicarbonate), or alkaline earth metal carbonates. The stybenediols used to prepare the composition of the invention, preferably have a 4,4'-isomer purity of at least 95 mol%, preferably of at least 985 mol, and most preferably of at least 99 mol%.

In addition to the stybenediol, one or more additional aromatic diols may also be used to prepare the composition of the invention. Suitable aromatic diols include any aromatic diol that will react with a carbonate precursor or ester precursor. Preferred diols include 2,2-bis (4-hydroxyphenyl) propane ("bisphenol A"); 9,9-bis (4-hydroxyphenyl) fluorene; hydroquinone; resorcinol; 4,4'-dihydroxybiphenyl; 4,4'-thiodiphenol; 4,4'-oxydiphenol; 4,4'-sulfonyl diphenol; 4,4'-dihydroxybenzophenone; 4,4"-dihydroxylphenyl; 1,4-dihydroxynaphthalene; 1,5-dihydroxynaphthalene; 2,6-dihydroxynaphthalene; bis (4-hydroxyphenyl) methane (" bisphenol F "); and its substantially substituted derivatives, as well as mixtures of Preferably the diol is 2,2-bis (4-hydroxyphenyl) propane ("bisphenol A"). In the preparation of the composition of the invention, at least 95 mol% of the diols present in the mixture of The reaction consists of one or more aromatic diols, preferably at least 95 mol% and most preferably 1005 mol of said diols are aromatic diols and at least 10 mol% of the aromatic diol present in the reaction mixture. , consists of one or more stybenediols, preferably at least 25 mol%, and most preferably at least 50 mol% of said aromatic diols are stybenediols Examples of aromatic dicarboxylic acids that can be used to prepare the polyester compositions or polyester carb The invention includes terephthalic acid; isophthalic acid; 2,6-naphthalenedicarboxylic acid; 1,4-naphthalene dicarboxylic acid; 1, 5-naphthalene dicarboxylic acid; 4,4'-biphenyl dicarboxylic acid; 3,4'-biphenyl dicarboxylic acid; 4,4'-terphenyldicarboxylic acid; 4,4'-stilbene dicarboxylic acid; 4,4'-dicarboxy-alpha-methylstyrene; its inertially substituted derivatives, as well as mixtures thereof. Examples of the hydroxycarboxylic acids that can be used to prepare the polyester or polyester carbonate polymer compositions of the present invention include 4-hydroxybenzoic acid; 3-hydroxybenzoic acid; 6-hydroxy-2-naphthoic acid; 7-hydroxy-2-naphthoic acid; 5-hydroxy-1-naphthoic acid; 4-hydroxy-1-naphthoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 4-hydroxy-4'-carboxydiphenyl ether; 4-hydroxycinnamic acid; its inertially substituted derivatives, as well as mixtures thereof. The processes for the preparation of polycarbonates, polyesters and polyestercarbonates typically employ a chain-stopping agent during the polymerization step to control the molecular weight. The amount of chain stop agent has a direct effect on both the molecular weight and the viscosity of the prepared polycarbonate, polyester, or polyester carbonate. Chain stop agents are monofunctional compounds, which react with a carbonate or ester precursor site on the end of the polymer chain and stop the propagation of the polymer chain. Examples of such suitable chain stop agents include monofunctional aromatic alcohols, thiols, and amines, as well as mixtures thereof. Preferably, the chain stop agent is a monofunctional aromatic alcohol, thiol, amine, aliphatic alcohol, aromatic carboxylic acid, aliphatic carboxylic acid, or a mixture thereof. The compositions of the present invention are preferably of the following formula: F-O- (R-O-X-O-) n-R-O-G and optionally contain repeat units of Formula (I I): (-R2-C (O) -O-) "; and / or end groups of the formulas: -R2-C (O) -O-G; or F-O-R2-wherein R, X, R1 and R2 have the descriptions provided above; n is an integer from 5 to 300; and F and G are, independently, either hydrogen or other common terminating groups for polycarbonates, polyesterscarbonates or polyesters.

Preferably, F and G are represented by the formulas: R6-O-C (O) -; or R6-C (O) -where R6 is hydrogen, halogen, or the nucleus of an alkyl, aryl, or alkyl substituted with aryl, or carboxylic acid. The polymers of the present invention preferably have a weight-average molecular weight (Mw, determined through exclusion chromatography using a polycarbonate bisphenol A calibration curve) of at least 10,000, most preferably at least 20,000. Preferred polymers according to the present invention have inherent viscosities, measured in methylene chloride (for an amorphous polymer) at 0.5 grams per deciliter (g / dl_) and 25 ° C, or in pentafluorophenol (for a crystalline or crystalline polymer) liquid) at 0.1 g / dL and 45 ° C, of at least 0.2 dL / g, and most preferably at least 0.35 dL / g. The liquid crystalline polymeric compositions can be identified using one or more normal techniques, such as heating the composition in a differential scanning calorimeter and characterizing it in the molten state through optical microscopy under cross polarized light. Thermotropic liquid crystalline polymers will exhibit optical anisotropy under fusion. Other techniques that can be used to characterize the polymer as a liquid crystalline include scanning electron microscopy, X-ray diffraction, visible light diffusion techniques, electron beam diffraction, infrared spectroscopy, and nuclear magnetic resonance. If the composition is liquid crystalline, it preferably has a nematic order in the liquid crystalline melting state. As mentioned above, the compositions of the invention advantageously have a relatively high technical strength, a melting temperature, tensile and bending properties, and / or resistance to thermal cracking. In addition, those polymers of the invention which are liquid thermotropic liquids also advantageously possess a wide temperature range for liquid crystallinity, good processability under melting, a low coefficient of thermal expansion, a high resistance to ignition, a high resistance to solvent, and / or good barrier properties. The thermal resistance of the composition can be characterized by its Vicat softening temperature and the temperature at which it can be deformed under load, as illustrated in Example 2. The tensile and flexural properties of the composition can be characterized and measured in accordance with ASTM D-638, as illustrated in the examples. The resistance of the composition to thermal cracking refers to its tendency to become brittle at elevated temperature, and can be characterized by measuring its subsequent remaining strain charge drop, as illustrated in Example 7. The composition of the invention, when liquid thermotropic crystalline, preferably also has thermal characteristics, which allow it to be easily processed in the liquid crystal state and heated above its melting temperature. The temperature scale over which said polymers can be processed, above their melting temperature in the liquid crystal state, is preferably as wide as possible, but preferably is at least 25 ° C, preferably at least 25 ° C. minus 50 ° C, and most preferably at least 100 ° C. In most cases, the composition will be isotropic above this scale, in which case, the scale can be expressed as the difference between the clarification temperature (TC |) and the melting temperature (Tm) of the composition. The clarification temperature is the temperature at which the composition undergoes a transition from anisotropic liquid crystalline state to an isotropic state (see, for example, The Encvclopedia of Polvmer Science and Engineering, vol., p . 55 (1988)). The melt processability of the polymer composition can be characterized by its melting temperature and its melt viscosity, as illustrated in the examples. The melting temperature of the composition (Tm, as determined by Differential Scanning Calorimetry) when it is thermotropic liquid crystalline, is preferably at least 200 ° C, most preferably at least 250 ° C, but preferably not higher than 350 ° C. The coefficient of thermal expansion of the composition of the invention can be measured according to ASTM D-2236, as illustrated in the examples below. The ignition resistance of the polymers can be measured by determining the Limiting Oxygen Index of the composition, testing the composition according to the Underwriters Laboratories No. UL-94 test, or measuring the calcination resistance of the composition through of thermal gravimetric analysis. The solvent resistance of the composition of the invention can be characterized as shown in the examples.

The barrier properties of the composition of the invention can be measured in accordance with ASTM D-3985 (oxygen transmission rate) and ASTM F-372 (carbon dioxide and water vapor transmission rate). The composition of the invention can be subjected to postcondensation in the solid phase (also known as solid state advance), preferably under reduced pressure, at a temperature in the range of 150 ° C to 350 ° C. After 1 to 24 hours, the molecular weight was increased and the resulting polymers exhibited improved additional properties. The composition of the present invention can be manufactured using any of the known thermoplastic molding processes, including compression molding, injection molding, and extrusion to provide manufactured articles, including molds, boards, sheets, tubes, fibers and films. The procedures that can be employed to maximize the orientation of the liquid crystal portions, contained in the articles made from the polymers of the invention, are summarized in the patent of E. U.A. 5,300,594, as well as in all references cited therein. The composition of the present invention can also be used with other thermoplastic polymers to prepare thermoplastic polymer blends. Thermoplastics suitable for this purpose include polycarbonates, polyesters, polyethers, polyetherketones, polysulfides, polysulfones, polyamides, polyurethanes, polyimides, polyalkylenes such as polyethylenes and polypropylenes, polystyrenes, copolymers thereof and mixtures thereof. The polymers of this invention can, in addition to being used for molding purposes, be employed as the basis for preparing thermoplastic molding compositions by being combined with antioxidants, antistatic agents, inert fillers and reinforcing agents such as glass fibers, carbon fibers, talc, mica, and clay, hydrolytic stabilizers, colorants, thermal stabilizers, flame retardants, mold releasing agents, plasticizers, UV radiation absorbers, and nucleating agents, as described in the U.A. Nos. 4, 945, 150 and 5,045,610, and the other references cited above. The following examples are presented to illustrate the invention and should not be construed as limiting in any way. Unless otherwise specified, all parts and percentages are given by weight.

EXAMPLE 1 Preparation of 4,4'-dihydroxy-alpha-methyl-ethyl-benzene polycarbonate (DHAMS). The polymerization was carried out in a 1 L single-necked round bottom flask equipped with a two-neck adapter on which a glass vane stirrer and a 13 cm Vigreaux distillation column were mounted. distillation with a thermometer, condenser and a receiver. DHAMS (1.75 mol, 403.6 g) and diphenyl carbonate (1.93 mol, 412.7 g) were added to the reaction flask. The apparatus was evacuated and refilled with nitrogen, three times. The flask was immersed in a bath of molten salt preheated to 200 ° C. When the solid reagents were melted to form a molten reaction mass, stirring was started and an aqueous solution of lithium hydroxide (0.82 ml, 0.06 M) was added as a catalyst. The reaction temperature was increased to 290 ° C over a period of 1 hour and the pressure was reduced from atmospheric pressure to 2 x 10'3 atmospheres. The last pressure was maintained for 1 hour at 290 ° C. After an additional 5 minutes, the reaction mass formed a ball on the shaft of the agitator. Then, the vacuum was removed under nitrogen and the reaction vessel was removed from the salt bath. The reaction apparatus was cooled and disassembled. The distillation receiver EEI contained 337 g of phenol. The flask was separated from the white opaque polycarbonate plug. The plug was cut into pieces and then ground in a Wiley mill. The product was dried in a vacuum oven at 100 ° C for 2 hours to give 408 g of the product (91% yield). The polycarbonate had an inherent viscosity (IV) of 2.6 dL / g, measured at 45 ° C, using a solution of 0.1 g of polycarbonate in 100 ml of pentafluorophenol. Differential scanning calorimetry (DSC), conducted at 20 ° C / minute using a Du Pont Instruments DSC 2910, showed a peak melting point of 273 ° C (first heating scrutiny, operation from 25 ° C to 320 ° C) and a crystallization temperature of 202 ° C (first cooling scrutiny, operation from 320 ° C to 50 ° C). A second heating scrutiny showed a peak endotherm at 272 ° C, and a second cooling scrutiny showed a crystallization temperature at 194 ° C. When the initial heating scrutiny was performed from 25 ° C to 400 ° C, a second endotherm was observed at 375 ° C. Examination through hot-cap cross-polarized microscopy (described below) indicated that the first endotherm was a transition from liquid crystalline to liquid nematic crystalline and the second endotherm was a transition from nematic liquid crystalline to isotropic liquid clarification. The 1 H NMR and 13 C NMR spectra of DHAMS polycarbonate are determined in pentafluorophenol at 45 ° C. The 1 H NMR spectrum (300 MHz) showed the presence of aliphatic, aromatic and vinyl hydrogen atoms. The infrared spectrum showed the presence of groups C = O, C = C, and C-O. The apparent molecular weights were determined through gel permeation chromatography (GPC) using refractive index detection. The calibration was performed using both BA (BA) polycarbonate and polystyrene with a narrow molecular weight distribution, with chloroform as the mobile phase. The preparation of the sample was carried out by dissolving a 40 mg sample in 1 ml of pentafluorophenol at 45 ° C, followed by the addition of 10 ml of chloroform. Using the polycarbonate BA for calibration, the polycarbonate sample from DHAMS had an Mw = 66,000 and an Mn = 13,000. Using polystyrene as the calibration, DHAMS polycarbonate had an Mw = 154,000 and an Mn = 20,000.

Characterization through Optical Microscopy under Light of Cross-Polymerization. The apparatus used to determine the optical anisotropy included a THM 600 heat stage (Linkham Scientific Instruments LTD, Surrey, England) and a Nikon Optiphot microscope equipped with crossed polarizers and a 35 mm camera (Nikon Instrument Group, Nikon, I nc. Garden City, N. Y.). The observation of a bright field at temperatures above the melting point indicated that the polycarbonate melt of DHAMS was optically anisotropic. The sample was placed on the programmable heat stage and a heating rate of 50 ° C / minute initially from 25 ° C to 180 ° C was used, then 10 ° C / minute from 180 ° C to 250 ° C was used and finally, 5 ° C / minute from 250 ° C to 300 ° C was used. The observation of the samples showed a nematic phase at ambient temperature and a nematic phase under fusion. The polymer formed a cloudy melt bath that exhibited a strong shear opalescence. The following observations were made for the DHAMS polycarbonate sample, using the polarization microscope.

Temperature (° C) Remarks 25 white opaque solid 150 white opaque solid 180 compressed between coverslips and slides 260 highly birefringent, nematic texture, viscous fluid 290 highly birefringent, nematic texture, flow-directed domains 300 anisotropic fusion, cross-polymerization light continues to pass . The sample remains anisotropic above 300 °, indicating that DHAMS polycarbonate was a liquid crystalline. Clarification (transition from liquid crystalline to isotropic phase) was not observed until 370 ° C.

Solubility Characterization The DHAMS polycarbonate prepared in this example was insoluble in conventional organic solvents, both at room temperature and at elevated temperatures. Solvents that do not dissolve this polycarbonate include methylene chloride, chloroform, carbon tetrachloride, tetrahydrofuran, acetone, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine, and trifluoroacetic acid / methylene chloride (volume ratio 4/1). The polycarbonates were soluble in pentafluorophenol at high dilutions (0.1 g / dL).

Determination of Viscosity under Fusion The viscosity under fusion of the polycarbonate sample of DHAMS was determined using an Instron 321 1 capillary rheometer, with a capillary length of 2,562 cm, a capillary diameter of 0.1271 cm, a shear rate scale of 3.5 to 350 sec'1, and a temperature of 290 ° C. Samples for the rheometer were prepared by placing a sample of polymer (1 g), pre-drying (100 ° C drying in a vacuum oven), in a stainless steel die, compressing in a hydraulic press at a platen pressure of 1362 kg, during some minutes and obtaining cylindrical pellets. The melt viscosity of DHAMS polycarbonate was determined as 810 poises at 100 sec'1, and 250 poises at 400 sec'1.

Thermoaravimetric Analysis ÍTGA) The TGA was conducted using a Du Pont thermal analyzer 2100, a temperature scrutinizing scale of 25 ° C to 1000 ° C, a heating rate of 10 ° C / minute, and a nitrogen purge. The residue remaining at 1000 ° C, also known as the calcination resistance, is 38% for the DHAMS polycarbonate. The importance of calcination resistance and its relation to ignition resistance were discussed by Van Krevelen, Properties of Polvmers. p . 731 (3rd edition, 1990).

EXAMPLE 2 Invention Molding and Properties of DHAMS Polycarbonate. DHAMS polycarbonate, prepared according to the procedure of Example 1, was milled in a Thomas-Wiley laboratory mill, model 4, dried at 100 ° C in a vacuum oven for 2 hours, and then molded by injection using an Arbug injection molding machine. Test specimens with a normal thickness of 0.3175 cm were injection molded, at a barrel temperature of 300 ° C, a mold temperature of 125 ° C, and using 275 bar of injection pressure. The tensile strength at break (Tb), the modulus of tension (TM), the elongation at break (Eb), the resistance to bending (FS), and the flexural modulus (FM), were determined. with the method D-638 test of American Society for Testing and Materials (ASTM) (American Society for Testing and Materials). Slit Izod impact strength was determined in accordance with ASTM D-256, where a slot radius of 0.0254 cm was used. The Vicat softening temperature for the polymer was determined in accordance with ASTM D-1525 using a 1 kg load. The coefficient of linear thermal expansion (CLTE), in the direction of flow, was measured in accordance with ASTM D-2236. The limiting oxygen index (LOI) was determined in accordance with ASTM D-2863-87. The UL-94 Flammability Resistance determinations were conducted as specified by Underwriters Laboratories. Water absorption was measured at 25 ° C after an immersion time of 24 hours. The relative density was measured according to ASTM D-570. The results were as follows: relative density - 1 .27; H2O absorption (percentage) - 0.002; LOI (percentage of oxygen) - 37; value of U L-94 V-0; CLTE (ppm / ° C) - 25 to 35; Vicat (° C) - 188; Tb (kg / cm2) - 1 122,691; TM (kg / cm2) - 40478.74; Eb (percentage) - 5; FS (kg / cm2) - 1333,591; FM (kg / cm2) - 46158.98; N. lzod (kg-m / cm) - 0.4752. The thermal resistance of DHAMS polycarbonate was also evaluated using a probe with a diameter of 0.0635 cm, carrying a load of 10 g. No penetration of the sample was observed until a temperature of 270 ° C was reached.

EXAMPLE 3 Solid State Advance of DHAMS Polycarbonate A polycarbonate sample of DHAMS, having an IV of 0. 42 dL / g (measured in pentafluorophenol at 0.1 g / dL and 45 ° C), was synthesized by the general procedure of Example 1. The DSC analysis showed a melting temperature of 231 ° C and a crystallization temperature of 157 ° C, determined during the first heating and cooling cycles according to the procedure described above. Then, DHAMS polycarbonate was advanced to solid state with agitation at 220 ° C under a reduced pressure of 2 x 10"4 atmospheres for 48 hours, resulting in an IV increase of 2.2 dL / g, a melting point at 271 ° C, and a crystallization temperature of 192 ° C.

EXAMPLE 4 Preparation of DHARS Polycarbonate Mixture and Glass Fibers. DHAMS polycarbonate (prepared as in Example 1) (417 g) was mixed dry with Owens-Corning glass fibers (125 g, nominal length 0.3175 cm, # 492). The mixture was then blended using a conical twin-screw extruder, Brabender, (reverse rotation), at a screw speed of 40 rpm, with the feed zone at 255 ° C and all other zones at 300 ° C. The mixture was fed into the extruder using a K-Tron volumetric screw, having a feed setting at 10.0, venting any volatiles from the polymer melt under vacuum, and one die was maintained. The torque measured was approximately 2.500 gram-meters and the upper pressure was less than 140.6 kg / cm.sup.2. As the mixture came out, the die extinguished it with a sprinkling of water and cut it into pellets with a conventional strand cutter. The resulting pellets were dried for approximately 16 hours in a vacuum oven set at 100 ° C and then injection molded to normal test specimens (as specified by ASTM D-638 to determine the stress properties) on a machine of Arburg molding using a barrel temperature of 300 ° C, a mold temperature of 125 ° C, and 275 bar of injection pressure.

EXAMPLE 5 Preparation of a Blend of Polycarbonate of DHAMS v Polycarbonate of BA. The polycarbonate of DHAMS with an IV of 1.5 dL / g (measured in pentafluorophenol at 0.1 g / dL and 45 ° C) and polycarbonate of BA, with a flow rate under fusion of Condition O of 10 g / 10 minutes, they were ground, separately, cryogenically to a fine powder. A portion (0.501 1 g) of the DHAMS polycarbonate and a portion (4.50 g) of the BA polycarbonate were combined and mixed. The resulting mixture (4.76 g) was added over a period of 8 minutes to the stirred tank of a molder by injection, which was preheated to 260 ° C. After the addition of the mixture was complete, the stirred mixture was maintained for an additional 12 minutes at a temperature of 260 ° C before the stirring was stopped. The mixture was then injected into a 7.62 cm by 1.27 cm by 3.17 cm stainless steel mold, which was preheated to 260 ° C. The resulting molding was allowed to slowly cool to 23 ° C before removing it from the molding machine. The molded specimen was opaque when it was removed. The instantaneous vaporization recovered from the edges of the injection molded mixture was examined through optical microscopy under cross-polymerization light at both 75X and 300X amplifications. For instantaneous vaporization, birefringent fibers were observed in both amplifications, and were oriented in the direction of flow in an isotropic matrix. A sample of the residual mixture remaining in the injection molder reservoir was removed and heated to 260 ° C using a heat stage and then examined through optical microscopy under cross polarized light. The birefringent fibers were observed in both amplifications, and these fibers were randomly oriented in an isotropic matrix.

EXAMPLE 6 Preparation of DHAMS / BA Copolycarbonates using Transesterification Under Fusion. The copolymerization was carried out in a 250 ml single-neck round-bottomed flask equipped with a two-neck adapter under which a glass paddle stirrer and a 13 cm Vigreaux distillation column were mounted. distillation with a thermometer, condenser and a receiver. DHAMS (0.1 1 mole, 24.19 g), BA (0.012 mole, 2.71 g) and diphenyl carbonate (0.12 mole, 24.46 g) were added to the reaction flask. The apparatus was evacuated and refilled with nitrogen, three times. The flask was immersed in a bath of molten salt preheated to 220 ° C.

When the solid reagents were melted to form a molten reaction mass, stirring was started and a solution of lithium hydroxide was added as a catalyst (0.36 ml, 0.06 M). The reaction temperature was increased to 265 ° C for a period of 1 hour from atmospheric pressure to 2 x 10"3 atmospheres The last pressure was maintained for 1 hour at 265 ° C. After an additional 5 minutes, the reaction mass Then the vacuum was released under nitrogen and the reaction vessel was removed from the salt bath The reaction apparatus was cooled and disassembled The flask was separated from a clay block copolycarbonate stopper The cap was cut into pieces and then ground in a Wiley mill.The polycarbonate had an inherent viscosity of 0.91 dL / g, which was measured at 45 ° C using a solution of 0.1 g polycarbonate in 100 ml. of pentafluorophenol The peak melting point was 250 ° C in the first heating scrutiny, as measured by scanning calorimetry (DSC) in a sample operation at 10 ° C / minute. The sample showed only a Tg at 84 ° C, and no melting point transition was observed. The polycarbonate was characterized through optical microscopy under cross-polarized light. Observation of a bright field at temperatures above the melting point indicated that the copolycarbonate melt was optically anisotropic. In accordance with the general procedure described above, additional DHAMS and BA copolycarbonates were prepared. These copolycarbonates were based on molar ratios of DHAMS / BA from 90/10 to 50/50. The copolycarbonates were characterized through DSC for the determination of the glass transition temperature (T ") and the melting temperature (Tm), IV, TGA (percentage of calcination), and optical microscopy under cross-polarized light, such as described above. These results are shown in Table I.

TABLE I Ratio IV Tg Tm% Fusion Molar of (dL / g) (° C) (° C) Nematic Calcination DHAMS / BA TGA 90/10 0.91 to 84 250 35 Yes 75/25 0.36 1 05 216"31 Yes 70/30 0.59 124 213"31 No 65/35 0.38 1 30 210"30 No 60/40 0.59 1 34 218"30 No 50/50 0.31 137 c 29 No Operation in pentafluorophenol at 45 ° C. After annealing for 2 to 12 hours at 175 ° C under nitrogen. No fusion transition was observed.

EXAMPLE 7 Preparation of DHAMS / BA Copolycarbonates (Molar Ratio of 50/50 and 25/75) Using the Solution Procedure. The following procedure was used to prepare DHAMS / BA copolycarbonate (molar ratio of 50/50). A 2-L, four-necked round bottom flask, equipped with a thermometer, condenser, phosgene / nitrogen inlet, and a paddle stirrer connected to the Serveino Colé Parmer, was charged with DHAMS (26.80 g, 0.1 18 moles) , BA (27.04 g, 0.1 18 moles), 4-tert-butyl phenol (0.71 g, 4.7 mrnoles, a chain terminator), pyridine (48.5 g, 0.614 moles), and methylene chloride (0.5 L). The mixture was stirred at 250 rpm and slowly purged with nitrogen, as phosgene (24.8 g, 0.251 mol) was bubbled in for 28 minutes, while the reactor temperature was maintained at 17 ° C to 26 ° C. The reaction mixture was processed by adding methanol (5 ml) and then a solution of 20 ml of concentrated HCl in 60 ml of water. After stirring for 15 minutes at 200 rpm, the mixture was emptied into a 2 L separating funnel. The methylene chloride layer was separated and washed further with a solution of 5 ml of concentrated HCl in 100 ml of water, followed by 100 ml of water, and then passed through a column (bed volume 0.2 L) of macroporous cation exchange resin. The product was isolated by adding the clear methylene chloride solution to a mixture of hexane (2 L) and acetone (0.2 L) in an explosion-resistant mixer. The product was filtered, dried in a dome overnight, and then dried for 48 hours in a vacuum oven at 10 ° C. The dry product weighed 55.6 g and had an IV of 0.846 dL / g (determined in methylene chloride at 0.5 g / dL and 25 ° C). DSC analysis (first scrutiny, heating rate of 20 ° C / minute, scrutiny of 50 ° C to 250 ° C) showed an extrapolated glass transition temperature (Tg) of 144 ° C. The second scrutiny showed a Tg at 141 ° C. The 1 H NMR spectrum of the product was in agreement with the copolycarbonate target composition. Size exclusion chromatography, using narrow fraction polystyrene filaments, gave the following molecular weight analysis: Mw = 98.446 and Mw / Mn = 2.361. The general procedure of this example was used to prepare additional DHAMS / BA copolycarbonates, having molar ratios of DHAMS / BA of 50/50 and 25/75.Compression and Properties Molding of DHAMS / BA Copolycarbonates. Compression molded plates of approximately 15.24 cm x 15.24 cm x 0.3175 cm were prepared at molding temperatures 100 ° above the Tg using a Tetrahedron MTP-14 press. These transparent plates were machined into test specimens. Tension resistance to loosening (Ty), elongation to deformation (Ey), and post-strain strain drop (PYSD) were determined in accordance with ASTM D-638. A reduction of PYSD was correlated with improved resistance to physical aging and fatigue, resulting in improved maintenance of long-term property: see, R. Bubeck et al., Polvm. Eng. Sci .. vol. 24, p. 1 142 (1984). As described above, IV, Tg and Slotted Izod were determined. These results are shown in Table I I.

TABLE II Ratio IV t8 Izod Ty Ey PYSD Molar of (dL / g) (° C) Slotted (kg / cm2) (° C) (%) DHAMS / BA (kg-m / cm) 25/75 0.71 1 50 13.3 7,802 7.8 14.6 50/50 0.64 1 35 1 1 .2 7,459 7.6 8.1 50/50 0.76 1 38 12.7 7,354 8.9 6.2 EXAMPLE 8 Preparation of DHAMS / BA Copolycarbonate (75/25 Molar Ratio) Using the Solution Procedure. The same equipment, described in Example 7, was charged with DHAMS (40.30 g, 0.178 moles), BA (13.55 g, 0.059 moles), 4-tert-butylphenol (0.71 g, 4.7 mmol), pyridine (48.7 g, 0.616 moles) , and methylene chloride (0.5 L). The mixture was stirred at 250 rpm and slowly purged with nitrogen, as phosgene was bubbled (24.4 g, 0.247 mole) for 21 minutes, while maintaining the reactor temperature from 18 ° C to 26 ° C. The product began to precipitate out of the reaction solution, when 13 g of phosgene was added. The same work procedure shown in Example 7 was followed, except that the product was not passed through an ion exchange resin column. For this composition, the product was made slurry in the methylene chloride, instead of a solution. The product was isolated by adding the mud to 3 L of methanol in an explosion-resistant mixer. The product was filtered, dried in a dome overnight, and then dried for 48 hours in a vacuum oven at 10 ° C. The product weighed 59.6 g and was insoluble in the following solvents that dissolved the polycarbonate of BA: methylene chloride, chloroform, tetrahydrofuran, dimethylformamide, and sim-tetrachloroethane. A compression molded plate (with a thickness of approximately 0.0508 cm) prepared at 250 ° C (molding time 3 minutes, plate pressure 4, 540 kg) melted well, was opaque, collapsible, insoluble in the solvents listed above , and did not crack due to tension when flexed and exposed to acetone. The DSC analysis of the product showed a T8 of a first scrutiny of 135 ° C and a fusion endotherm of 175 ° C to 220 ° C with a peak transition at 194 ° C. A sample of this copolycarbonate was characterized by optical microscopy under cross polarized light, as described above. The sample was applied between a glass slide and covers glass objects and then placed on the programmable heat stage of the microscope. A heating rate of 10 ° C / minute was used and the following results were obtained: Temperature (° C) Remarks 30 birefringent crystalline solid 145 light softening observed when compressed between the coverslip and carrier 1 68 is fused to a highly birefringent, opaque, viscous liquid when compressed 1 84 highly birefringent, viscous fluid 200 highly birefringent, viscous fluid , agitation opalescence, nematic texture, is oriented with shear stress to give domains directed by the flow 245 some observed isotropic fluid 285 isotropic fluid containing diffused birefringent regions 291 complete isotropy EXAMPLE 9 Preparation of DHAMS / 9.9-bis (4-hydroxy-phenefluorene copolicarbonate (BHPF1) The general procedure of Example 7 was used to prepare DHAMS / DHP copolicarbonate (75/25 mole ratio) The resulting copolycarbonate was insoluble in methylene chloride The DSC analysis showed a Tß at 173 ° C (first scrutiny, heating rate of 20 ° C / minute).

EXAMPLE 10 Preparation of Polyestercarbonate from DHAMS. Diphenyl Terephthalate and Diphenyl Carbonate. The polymerization was carried out in a 250 ml single-neck round bottom flask equipped with a two-neck adapter on which a glass paddle stirrer, a 13 cm Vigreaux distillation column, a head were mounted. of distillation with a thermometer, a condenser and a receiver. Diphenyl terephthalate (0.0143 mol, 3.64 g, a derivative of terephthalic acid ester), DHAMS (0.1 mol, 25.84 g), and diphenyl carbonate (0.10 mol, 22.02 g) were added to the reaction flask. The apparatus was evacuated and refilled with nitrogen, three times. The flask was immersed in a bath of molten salt preheated to 220 ° C. When the solid reagents were melted to form a molten reaction mass, stirring was started and lithium hydroxide (0.36 ml of 0.06 M aqueous solution) was added. The reaction temperature was increased to 265 ° C for a period of one hour and the pressure was reduced from atmospheric pressure to 2 x 10'3 atmospheres. The last pressure was maintained for 1 hour at 265 ° C. After an additional 5 minutes, the reaction mass formed a ball on the shaft of the agitator. Then, the vacuum was released under nitrogen and the reaction vessel was removed from the salt bath. The reaction apparatus was cooled and disassembled. The volume of phenol recovered was 20.1 ml. The flask was separated from an opaque white clay product. The plug was cut into pieces and then ground in a Wiley mill. The polyester carbonate had an inherent viscosity of 1.05 dL / g (pentafluorophenol, 45 ° C, 0.1 g / dL). The DSC analysis, conducted at a scanning speed of 10 ° C / minute, showed a melting transition at 213 ° C.

EXAMPLE 1 1 Preparation of Polyester from 4.4'-diacetoxy-alpha-methyl-ethyl-benzene (DAAMS) v terephthalic acid. The following procedure was used to convert DHAMS to DAAMS. A DHAMS (0.133 mol, 30 g) and acetyl chloride (0.665 mol, 48 ml) in chloride were added to a 500 ml round bottom flask equipped with a condenser and a nitrogen inlet. of methylene (200 ml). The reaction mixture was refluxed for 3 hours and a clear solution was obtained, at that point, by analysis of High Pressure Liquid Chromatography (HPLC), the reaction reached completion. The reaction mixture was cooled, and then concentrated to remove excess methylene chloride and unreacted acetyl chloride, leaving a white powder as the product. The crude product was recrystallized from methyl isobutyl ketone, resulting in 20.16 g of DAAMS as a white crystalline solid with a melting point of 126 ° C. Polymerization was carried out in a 250 mL single-neck round bottom flask equipped with a two-neck adapter, in which a glass paddle stirrer and a 13 cm Vigreaux distillation column were mounted, Distillation head with a thermometer, a condenser and a receiver. Terephthalic acid (0.084 mol, 13.99 g) and DAAMS (0.084 mol, 26.12 g) were added to the reaction flask. The apparatus was evacuated and refilled with nitrogen, three times. Then, the flask was immersed in a bath of molten salt preheated to 260 ° C. The white suspension became a mud during the next 2 hours, as the temperature slowly rose to 360 ° C. The pressure was slowly reduced to 2 x 10"3 atmospheres.After an additional 30 minutes, the apparatus was cooled, and the vacuum was released under nitrogen.The isolated amount of opaque, pale yellow polyester was 26 g. receiver contained 9.7 ml of acetic acid.The polyester was ground to a powder and found to be insoluble in pentafluorophenol at 0.1 g / dL and 45 ° C. DSC analysis of the polymer resulted in no endotherm or exotherm observable on the scale of analysis from 25 ° C to 400 ° C.

EXAMPLE 12 Preparation of Copolyester from DAAMS. isophthalic acid. 4-acetoxybenzoic acid (ABA) and 2,6-naphthalene-dicarboxylic acid (NDCA). Polymerization was carried out in a 250 mL single-neck round bottom flask equipped with a two-neck adapter, in which a glass paddle stirrer and a 13 cm Vigreaux distillation column were mounted, Distillation head with a thermometer, a condenser and a receiver. To the reaction flask, ABA (0.102 moles, 18.232 g), isophthalic acid (0.0169 moles, 2.80 g), NDCA (0.017 moles, 3.65 g), and DAAMS (0.034 moles, 10.46 g) were added. The apparatus was evacuated and refilled with nitrogen, three times. Then, the flask was immersed in a bath of molten salt preheated to 260 ° C. When the melt bath of the solid reagent formed a molten reaction mass, stirring was started and lithium hydroxide (0.36 mL of 0.06 M aqueous solution) was added. The reaction temperature was increased to 340 ° C over a period of 2 hours at atmospheric pressure. Afterwards, the pressure was reduced to 2 x 10"3 atmospheres, and this pressure was maintained for an additional hour at 340 ° C. After an additional 5 minutes, the reaction mass formed a ball on the shaft of the agitator. Then the nitrogen was freed under nitrogen, and the reaction vessel was removed from the salt bath The reaction apparatus was cooled and disassembled The volume of acetic acid recovered was 9.67 ml The flask was separated from the opaque yellow copolyester plug The stopper was cut into pieces and then ground in a Wiley mill.The DSC analysis, conducted at a scanning speed of 10 ° C / minute, showed a melting transition at 280 ° C.

EXAMPLE 13 Preparation of Polycarbonate of 4.4'-dihydroxy-alpha.alpha'-diethylstilbene (DES). This polycarbonate was prepared according to the general procedure of Example 1, using DES (0.14 mol, 36.5 g) and diphenyl carbonate (0.15 mol, 32.1 g). During the synthesis, conducted from 220 to 290 ° C, the reaction mixture remained isotropic. Phenol (25 g) was removed as a distillate during the synthesis. The isolated production of DES polycarbonate is 37 g. This polycarbonate had an IV of 0.37 dL / g (determined in chloroform at 25 ° C). The DSC analysis showed a Tg at 87 ° C and no indication of a melting transition on the scrutiny scale from 25 ° C to 300 ° C. The polycarbonate was annealed at 125 ° C for 12 hours under a nitrogen atmosphere. The DSC analysis of the annealed sample showed a Tg at 92 ° C, no evidence of fusion transitions.

EXAMPLE 14 Preparation of DHAMS / DES Copolycarbonate (Relation Molar of 90/10). This copolycarbonate was prepared according to the general procedure of Example 1, using DES (0.016 moles, 4.19 g), DHAMS (0.14 moles, 31.76 g), and diphenyl carbonate (0.16 moles, 33.41 g). During the conducted synthesis of 220 ° C to 290 ° C, the reaction changed from an isotropic liquid to an opaque molten state at 270 ° C. Phenol (29 g) was removed as a distillate during the synthesis. The resulting polycarbonate was obtained as a white crystalline solid, in an isolated yield of 35g. The DSC analysis showed a Tg at 87 ° C and a melting transition at 237 ° C during the heating scrutiny, and a crystallization exotherm at 12 ° C during the cooling scrutiny. The polymer was soluble in methylene chloride and chloroform at 0.1 g / dL. The melt bath of the polymer was optically anisotropic, as determined by optical microscopy analysis, described above.

EXAMPLE 15 Preparation of DHAMS Copolycarbonate / 4.4'-dihydroxy-stilbene (DHS) According to the general procedure of Example 1, DHAMS / DHS copolycarbonate (90/10 molar ratio) was prepared, using DHS (0.02 moles, 3.35 g), DHAMS (0.14 moles, 32.5 g) and diphenyl carbonate (0.16 moles, 34.2 g) DHS was prepared according to the McMurry and Silvestri procedure, J. Org. Chem .. vol. 40, p. 2687 (1975). The polymerization was conducted from 220 ° C to 290 ° C. The reaction mixture was opaque at 280 ° C. Phenol (30 g) was removed as a distillate during the synthesis. The resulting copolycarbonate, 37 g, was isolated as a white fibrous solid. The polymer was insoluble in methylene chloride or chloroform at 0.1 g / dL. The DSC analysis showed an acute melting transition at 283 ° C and a crystallization exotherm at 200 ° C during the first heating and cooling scrutinizations. The second heating and cooling scrutinizations of the sample showed a melting transition at 283 ° C and a crystallization exotherm at 196 ° C. The fusion bath was optically anisotropic, as determined by the methods described above.

EXAMPLE 16 Preparation of DHAMS / DHS Copolycarbonate (Relation Molar of 75/25). This copolycarbonate was prepared according to the general procedure of Example 1, using DHS (0.04 mol, 8.45 g), DHAMS (0.12 mol, 27.3 g), and diphenyl carbonate (0.16 mol, 34.5 g). The reaction was conducted from 220 ° C to 320 ° C, and the reaction mixture became opaque at 285 ° C. Phenol (30 g) was removed as a distillate during the synthesis. The resulting copolycarbonate, 35 g, was isolated as a white fibrous solid. The polymer was insoluble in methylene chloride or chloroform at 0.1 g / dL. The DSC analysis showed an acute melting transition at 299 ° C and a crystallization exotherm at 228 ° C. The fusion bath was optically anisotropic, as determined by the methods described above.

Claims (10)

1 .- A composition of polycarbonate, polyester or polyestercarbonate prepared from at least one diol and at least one carbonate precursor or a C8 carboxylic acid. 40, wherein: a) at least 95 mol% of the carbonate or carboxylic acid precursor is selected from the group consisting of: (i) dialkyl carbonates, diaryl carbonates, carbonyl halides, or bis (trihaloalkyl) carbonates ); (ii) aromatic dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, hydroxybiphenyl acids, hydroxy cinnamic acids, or the halides or metal salts of said acids; and b) at least 95 mol% of the diol, from which the composition is prepared, consists of one or more aromatic diols, at least about 10 mol% of which consists of one or more stybendiols selected from the group consisting of 4,4'-dihydroxy-alpha-methyl-ethyl-benzene; 4,4'-dihydroxy-alpha, alpha'-diethyl-stilbene; and 4,4'-dihidorix-alpha, alpha'-dimethylstilbene.

2. The composition according to claim 1, wherein the product of the polymerization reaction of a) and b) is at least one crystalline, liquid, thermotropic polymer.

3. The composition according to claim 1, which is prepared from more than one diol, which includes 9,9-bis (4-hydroxyphenyl) fluorene, hydroquinone, 4,4-dihydroxybiphenyl, or 4,4'- Thiodiphenol.

4. The composition according to claim 1, which is prepared from more than one diol, including bisphenol A.

5. The composition according to claim 1, wherein at least 25 mol% of the aromatic diols, from which the composition is prepared, are stybenediols.

6. The composition according to claim 1, wherein at least 50 mol% of the aromatic diols, from which the composition is prepared, are stybenediols.

7. The composition according to claim 1, wherein 100 mol% of the aromatic diols, from which the composition is prepared, are stybenediols.

8. The composition according to claim 1, wherein the polymers therein have a weight average molecular weight of at least 10,000.

9. The composition according to claim 2, wherein the average difference between the clarification temperature and the melting temperature of the polymers, in it, is at least 50 ° C.

10. The composition according to claim 2, wherein the polymers have a melting temperature of at least 200 ° C. 1 - A composition comprising at least 1% by weight of the polycarbonate, polyester or polycarbonate composition of claim 1, and at least 1% by weight of a different thermoplastic polymer. 12. A molded or extruded article comprising the composition of claim 1. 13. The composition according to claim 1, wherein at least about 95 mol% of the carbonate or carboxylic acid precursor is diphenyl carbonate.