MXPA96001898A - Method for modifying polymeri resin skeleton - Google Patents

Abstract

The present invention relates to a process by which a polymeric resin (containing a linker and / or carbonate) is easily converted into a resin having a modified molecular structure. Accordingly, a cyclic carbonate (a monomer or oligomer) is transesterified with the polymer resin in the melt, preferably after extrusion, optionally in the presence of a catalyst. Significantly, the cyclic carbonate, which can include any of a variety of functional groups, can, by the process of the invention, be inserted into the polymer structure, effecting a modification in the structure and properties of the resin. Among the beneficial modifications described as well as the resin, are the thermal stability, the altered rheology and the optical properties

Description

METHOD FOR MODIFYING THE POLYMER RESIN SKELETON The invention relates to a transesterification process for modifying a polymer resin; more specifically, the process relates to a transesterification reaction in the melt between a cyclic carbonate and a polycarbonate or a polyester resin. A process is described by which a polymer resin (containing ester and / or carbonate linkages) is easily converted into a resin having a modified molecular structure. Accordingly, a cyclic carbonate (a monomer or oligomer) is transesterified with the polymeric resin in the melt, preferably after extrusion, optionally in the presence of a catalyst. Significantly, the cyclic carbonate which can include any of a variety of functional groups can be inserted, by the inventive method, into the polymer structure, effecting a modification in the structure and properties of the resin. Among the described beneficial modifications thus imparted to the resin are better thermal stability, an altered rheology and optical properties. Polycarbonate polyesters and polyester carbonate resins and methods for their manufacture are known. Transesterification is also well known as a method for preparing polyesters and polycarbonates. See in this sense Chemistry and Physics of Polycarbonate, by Hermann Schnell Interscience Publishers, John iley & Sons, Inc., 1964, pp. 44-51 and Polycarbonate, by illia F. Christopher and Daniel. Fox, Reihhold Publishing Corporation, New York, 1962, pp. 13-15. Three different exchange reactions have been described for esters, carbonates and mixed esters / carbonates (Porter et al., In Polym, Eng. Sci., 1989, 29, 55).

Intermolecular alcoholysis, HO- intermolecular acidolysis, and transesterification.

Alcoholysis and acidolysis occur, by definition, between a terminal group and the main chain. In general, transesterification refers to an intermolecular reaction between chains. In the present context, transesterification refers to exchanges between a cyclic carbonate and a carbonate and / or ester bond. Stabilizers are commonly incorporated, among other functional additives, into polycarbonates, polyesters and polyestercarbonates by physical mixing. Due in part to their relatively small size, issues of interest with respect to such stabilizers include their toxicity, volatility, bloom, diffusion rate, leaching, plasticization and distribution within the matrix. Some of these problems have been investigated. In the area of polymeric antioxidants, for example, attention can be drawn to an article by Coleman et al. in Macromolecules 1994, 27, 127 and references cited therein. Researchers from Bayer, Schnell and Botten-bruch, for the first time, prepared cyclic oligomeric aromatic carbonates with low yields during the first 60 years. The preparation and mentioned use of cyclic precursors of low molecular weight and low viscosity that can have the ring opened for forming high molecular weight polymers has been published by Brunelle et al. in Indian Journal of Technology, Vol. 31, April-June 1993, pp. 234-246 and in J. Amer. Chem. Soc., 1990, 112, 2399. It has been said that the ring opening polymerization of said cyclics leads to complete conversion into high molecular weight linear polymers. The use of in situ polymerization of cyclic oligomers of bisphenol-A carbonate in the preparation of mixtures with styrene-acrylonitrile copolymer has also been published - Arren L. Nachlis in Polymer, Vol. 36, Nd 17, 1994, pp. 3643 et seq. The technique also includes US Pat. No. 5,281,669, which described easy flow mixtures containing polymers and linear oligomers with a cyclical overall structure and US Pat. 4,605,731, which described a method for the preparation of polycarbonate resins from cyclic polycarbonate oligomers, the reaction being catalyzed by a particular borate compound. The US patent is more relevant in the present context. No. 5,162,459, which described a polycarbonate blend with a cyclic polycarbonate oligomer containing hydroquinone carbonate structural units and a ring-opening polycarbonate forming catalyst. A process including the transesterification of a resin containing carbonate and / or ester bonds with a cyclic oligocarbonate has not been described anywhere, a process that results in the insertion of the cyclic carbonate into the preferably linear, high molecular mesocarbonate polycarbonate. resulting in a structurally modified resin. While the following text describing the invention refers primarily to polycarbonate resins, it is to be understood that the invention is directed to the modification of any polymeric resin whose repeating units contain carbonate and / or ester linkages. The present invention is based on the discovery that cyclocarbonates can be advantageously inserted, which optionally contain a radical, residue or group whose inclusion in the structure of the resin effects a change in the properties of the resin (here Group), by means of a transesterification reaction, in the melting, in the structure of polycarbonates, polyesters or polyestercarbonate resins. The reaction results in a structurally modified resin, which shows altered properties. The resulting properties of the resin are determined by the efficiency of the process and by the identity and relative amount of the cyclocarbonate and / or Group thus inserted. It is an object of the present invention to describe a process for the modification of resins, whose repeating unit contains carbonate and / or ester bonds, which allows the preparation of modified resins having chemistries and properties according to the order. This and other objects are achieved by the presently described invention, as will be described in detail below. DETAILED DESCRIPTION OF THE INVENTION Schematic representations of the inventive process are shown below: the polycarbonate being a representative of the resins which can thus be modified and the cyclic oligocarbonate representing the cyclic carbonates useful in the inventive reaction. In the context of the present invention, transesterification refers to an intermolecular chain reaction; more specifically, to exchanges between a cyclic carbonate and a polycarbonate, preferably a linear polycarbonate. According to the schematic representation, a polycarbonate resin is transesterified in the melt, for example in an extruder, optionally in the presence of a suitable transesterification catalyst, with a cyclic carbonate oligomer, the process giving rise to a modified polycarbonate. Schematically, the method of the invention can be represented by and in the following manner: and by JV ?? PC-? -0-C- or- ~, PC - ??? ~ "_ ^ WS PC- ~ O - C 0 ~ ~ * PC II II oo Cyclic carbonates which are suitable in the presently described invention can be synthesized by an interface procedure in any of the following three ways: (A) a bisphenol can first be converted to its corresponding bischloroformate, which is then cyclized, the result is that a bisphenol is present in each repeating unit; ) the compositions can be given proportions to achieve the desired composition, and (C) a desired residue in its bisphenolic form (up to 20 mol%) can be reacted with bisphenol A bischloroformate. These can be represented schematically as: Synthesis A: Synthesis B: Synthesis C: where X and R independently represent residues and n and m are the respective degrees of cyclization. The term "residue" as used herein refers to the structure of a bischloroformate without its carbonyl groups or its chlorine atoms and to the structure of a dihydroxy compound without the hydroxy groups. Monocyclic carbonates are known, which are suitable in the process of the present invention and their preparation is conventional. An example of a suitable oncyclic is 1,3-dioxolan-2-one (ethylene carbonate). The present invention relates to a transesterification process, by reacting a polycarbonate resin with at least one cyclic carbonate, optionally in the presence of a suitable catalyst, carried out in the melt, preferably in an extruder or in another apparatus that allows the processing melting of the reactants, preferably at temperatures in the range of 250 to 350 ° C and with a residence time sufficient to allow the transesterification reaction, preferably up to about 5 minutes, resulting in the insertion of said carbonate into the resin. The cyclic carbonate optionally contains a Group, as previously defined. The resulting properties of the resin are determined by the efficiency of the process and by the identity and relative amount of the cyclocarbonate and / or Group thus inserted. In the present context, the term "functionalized cyclic carbonate" refers to cyclic carbonates whose structure includes Group (s). Any one or a combination of functionalized cyclic carbonates can be inserted in this way, giving rise to a modified resin, in this case the modification being responsible for conferring the function of the Group included in the functionalized cyclic carbonate to the resin, the cyclic carbonate. Functionalized may include groups whose functions impart to the resin better mechanical and / or physical properties, mold release properties, optical properties, such as UV stability or anti-oxidation characteristics, to name a few. Examples of a suitable group include triphenylphosphine, benzophenone and BHT, whose groups impart stability to the resin; radicals containing phosphorus and / or sulfur atoms, which impart flame retardancy to the resin, and groups which have an effect on the compatibility of the resin in mixtures with other resins. One or more of these functionalized cyclic carbonates may be inserted, optionally simultaneously, according to the invention, to modify a conventional commercial resin. The methods of preparing functionalized cyclic carbonate suitable in the practice of the present invention are known. Information regarding cyclic oligocarbonates is included in the article entitled "Preparation of Ring-Opening Polymerization of Cyclic Oligomeric Aromatic Carbonates", by Daniel J. Brunelle et al., In Indian Journal of Technology, Vol. 31, April-June 1993 , pgs. 234-246, whose text is here incorporated by way of reference. Also incorporated herein by reference are the relevant disclosures of US Pat. 4,727,134 and in Preparation and Polymerization of Bisphenol A Cyclic Oligomeric Carbonates, by D.J. Brunelle and T.G. Shannon, Macromolecules, 1991, 24, p. 3035-3044 and from Ring-Opening Polymerization: Mechanisms, Catalysis, Structure, Utility (1993), Hanser Publishers, Chapter 11, pgs. 309-336. A method for the preparation of cyclic oligocarbonates involves a triethylamine catalyzed hydrolysis / condensation reaction of bischloroforptiate. The suitable cyclic carbonate of the present invention is a member selected from the group consisting of wherein X and R independently represent an aliphatic, cycloaliphatic or aromatic residue of a dihydroxy or a bischloroformate compound and where R may optionally contain a Group; Y represents a trifunctional or tetrafunctional nucleophile; n, n n2 and n3 independently represent an integer from 0 to 16. It is specifically understood that, in view of the description of US Pat. No. 5,162,459, the scope of the present invention does not include, and specifically excludes, the free transesterification of polycarbonate resin catalyst with a functionalized cyclic oligocarbonate conforming to (I), wherein R is the hydroquinone residue; the product of this reaction is also excluded here. An illustrative example of the process of the invention is the insertion, in a polycarbonate resin, of a functional cyclic oligocarbonate where the Group conforms to The polycarbonate thus modified exhibits UV filtration properties. The optional catalyst useful in the process of the present invention is selected from the group consisting of dibutyltin oxide, cobalt (II) acetate tetrahydrate, antimony (III) oxide, manganese (II) acetate tetrahydrate, titanium butoxide (IV) ), zinc acetate dihydrate, dibutyltin dilaurate, tin acetate (II), tetramethyldiacetoxiestannoxane, tin oxide (IV), lead (II) acetate trihydrate, dibutyltin diacetate and titanium (IV) bis (ethylacetoacetate). The polycarbonates modified according to the inventive process are homopolycarbonates and copolycarbonates and their mixtures. The polycarbonates generally have a weight average molecular weight of 10,000-200,000, preferably 20,000-80,000, and their melt flow rate, according to ASTM D-1238, at 300 ° C is from about 1 to about 65 g / 10 min., preferably about 2-15 g / 10 min. They can be prepared, for example, by the known diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by polycondensation (see German Patent Publications 2,063,050, 2,063,052, 1,570,703, 2,211 .956, 2,211,957 and 2,248,817, French Patent 1,561,518, and H. Schnell's monograph "Chemistry and Physics of Polycarbonates," Interscience Publishers, New York, New York, 1964, all incorporated herein by way of reference). The dihydroxy compounds suitable for the preparation of the polycarbonates of the invention conform to structural formulas (1) or (2). where A represents an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloalkylidene group with 5 to 15 carbon atoms, carbonyl group, an oxygen atom, a sulfur atom, or S02, or CH3 1 1 CH3 CH, g and e represent 0 or 1; Z represents F, Cl, Br or C or o-1-4 alkyl and, if several Z radicals are substituents on an aryl radical, they can be identical or different from each other; D represents an integer from 0 to 4, and f represents an integer from 0 to 3. Among the dihydroxy compounds useful in the practice of the invention are hydroquinone, resorcinol, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) ethers, bis ( hi-droxyphenyl) ketones, bis (hydroxyphenyl) sulphoxides, bis (hydroxyphenyl) sulphides, bis (hydroxyphenyl) sulfones and, a-bis (hydroxyphenyl) diisopropylbenzenes, as well as their nuclear alkylated compounds. These and other suitable aromatic dihydroxy compounds are described, for example, in U.S. Patent Nos. 3,028,356, 2,999,835, 3,148,172, 2,991,273, 3,271,367 and 2,999,846, all incorporated herein by reference. reference. Other examples of suitable bisphenols are 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis (4-hydroxy-phenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane , a, a'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2, 2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-1,4-hydroxyphenyl) propane , is (3, 5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, dihydroxybenzophenone, 2 , 4-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, β-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene and 4,4'-sulfonyldiphenol. Examples of particularly preferred aromatic bisphenols are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxy-phenyl) -cyclohexane. . The most preferred bisphenol is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). The polycarbonate resins suitable as reactants in the process of the invention can carry in their structure units derived from one or more of the suitable bisphenols. Suitable resins in the practice of the invention include polycarbonate based on phenolphthalein, copolycarbonates and terpolycarbonates, such as those described in US Pat. 3,036,036 and 4,210,741, both incorporated herein by reference. Polycarbonates suitable as reactants in the process of the invention can also be branched by condensing therein small amounts, for example 0.05-2.0 mol% (relative to bisphenols), of polyhydroxyl compounds. Polycarbonates of this type have been described, for example, in German Patent Publications 1,570,533, 2,116,974 and 2,113,374.; in British patents 885,442 and 1,079,821 and in US Pat. 3,544,514. The following are some examples of polyhydroxyl compounds that can be used for this purpose: phloroglucinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1, 3, 5-tri (4- hydroxyphenyl) benzene, 1,1,1- tri (4-hydroxy-phenyl) ethane, tri (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4- (4,4'-dihydroxydiphenyl)] cyclohexylpropane, 2 , 4-bis (4-hydroxy-1-isopropylidine) phenol, 2,6-bis (2'-dihydroxy-5'-methylbenzyl) -4-methylphenol, 2,4-dihydroxybenzoic acid, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. Some of the other polyfunctional compounds are 2,4-dihydroxy-benzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (4-hydroxyphenyl) -2-oxo-2,3-dihydroindole. In addition to the above-mentioned polycondensation process, other processes for the preparation of the polycarbonates of the invention are polycondensation in a homogeneous phase and transesterification. Suitable procedures are described in US Pat. 3,028,365, 2,999,846, 3,153,008 and 2,991,273, incorporated herein by reference. The preferred method for the preparation of polycarbonate coughs is the interface polycondensation process. Other methods of synthesis can be used in the formation of the polycarbonates of the invention such as those described in U.S. Pat. 3,912,688, incorporated herein by reference. Suitable polycarbonate resins can be obtained commercially, for example Makrolon FCR, Makrolon 2600, Makrolon 2800 and Makrolon 3100, all of which are bisphenol-based homopolycarbonate resins which differ in terms of their respective molecular weights and are characterized in that their molten flow (VFF) according to ASTM D-1238 are approximately 16.5-24, 13-16, 7.5-13.0 and 3.5-6.5 g / 10 min., Respectively. These are products of the Bayer Corporation of Pittsburgh, Pennsylvania. A suitable polycarbonate resin is known in the practice of the invention and its structure and methods of preparation have been described, for example, in US Pat. 3,030,331, 3,169,121, 3,395,119, 3,729,447, 4,255,556, 4,260,731, 4,369,303 and 4,714,746, all incorporated herein by reference. The preferred embodiment of the inventive process is carried out using a linear polycarbonate resin. The (co) polyester suitable in the present invention consists of repeating units of at least one aromatic dicarboxylic acid C6_20, aliphatic C3_20 or alicyclic and repeating units of at least one aliphatic glycol C2_2o > Examples of the dicarboxylic acids include malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, 1,4-, 1,5- and 2,6-decahydronaphthalenedicarboxylic acid and cis- or trans-1 acid, 4-cyclohexanedicarboxylic acid. Examples of useful aromatic dicarboxylic acid are terephthalic acid, isophthalic acid, 4'-biphenyldicarboxylic acid, trans-3,3'- and trans-4,4'-stilbenedicarboxylic acid, 4,4'-dibenyldicarboxylic acid , 1,4-, 1,5'-, 2,3'-, 2,6- and 2,7-naphthalenedicarboxylic acid. Preferred dicarboxylic acids are terephthalic and isophthalic acid or mixtures thereof. The preferred glycol of the (co) polyester includes 2 to 8 carbon atoms. Examples include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butane diol, 1,5-pentanediol, 1,6-hexanediol, 1,2-, 1,3- and 1, 4-cyclohexanedimethanol, neopentyl glycol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Preferred diols are 1,4-cyclohexanedimethanol, ethylene glycol and mixtures thereof. Preferred (co) polyesters include resins having repeating units of poly (ethylene terephthalate) or poly (1,4-cyclohexylene dimethyl-terephthalate). The preferred (co) polyesters consist of repeating units of terephthalic acid, isophthalic acid or mixtures thereof and 1,4-cyclohexanedimethanol. Other preferred (co) oliesters consist of repeating units of terephthalic acid and 1,4-cyclohexanedimethanol, ethylene glycol or mixtures thereof. The preparation of the (co) polyesters follows conventional procedures well known in the art, such as the process described in U.S. Pat. 2,901,466, the description of which is hereby incorporated by reference. The (co) polyesters of the invention have, as a rule, an inherent viscosity of about 0.4 to 1.0 dl / g, preferably about 0.6 to 0.8 dl / g, at 25 ° C in a solvent that it contains 60% by weight of phenol and 40% by weight of tetrachloroethane. Among the other polymer resins suitable for modification according to the inventive process, mention may be made of the polyester carbonates and thermoplastic polyurethanes containing ester segments. The inventive process is preferably carried out in an extruder, preferably a twin-nut extruder. In the work described here, the molecular weights (both the number average molecular weight and the weight medium) were determined by Gel Permeation Chromatography (CPG) Gel Permeation Chromatography (CPG) Molecular weight determination For the determination of molecular weight , samples were analyzed in a 150C high temperature gel permeation chromatography equipped with a differential refractive index detector. Tetrahydrofuran served as the mobile phase. The conditions for the analysis by CPG were as follows. Four stainless steel columns (7.8 x 300 mm) were packed with PL Gel SDVB (2 mixed beads + lx500A + lxlOOÁ) having an average particle diameter of 10 μm. The flow rate was 1.0 ml / min and the injection volume was 75 μl. A temperature of 35 ° C was used for both the CPG and the IR detector. Samples prepared at a known concentration were dissolved (-0, 5%) in the mobile phase and toluene was added as the flow pattern. They were filtered through 0.5 μm disposable PTFE filters before analysis. The determination of the molecular weight means and the distribution of the polycarbonate samples was based on polycarbonate standards using the Hamelic Wide Pattern Calibration Method. The data analysis was performed using a PE-Nelsons' ACCESS * CHROM SEC program in a VAX-based system. Characterization of cyclic insertion Samples were analyzed in a Perkin Elmer HPLC equipped with the 235C Diode Array Detector, with monitoring of the wavelengths 265 nm and 300 nm. The same conditions for the CPG analysis as those described above were followed with the following exceptions. Samples were prepared at a known concentration of 1% and no flow pattern was added. The injection volume was 100 μl and the system was operated at room temperature. The analysis of the chromatograms (coating, etc.) was performed using an ACCESS * CHROM GC / LC program in a VAX-based system. High Performance Liquid Chromatography (CIAR) The analysis was performed on a Perkin Elmer HPLC equipped with the Perkin Elmer 235C Diode Array Detector. The following chromatographic conditions were used for this model polymerization study: Column: Hypersil MOS-2, RP C-8 (Keystone Scientific) 5 μm, 150 x 4.6 mm. Flow: 0.5 ml / min. Concentration of the sample: 1.0%, filtered with a PTFE filter of 0.5 μm. Injection volume: 10 μm. Detector: Perkin Elmer 235C Diode Array Monitored wavelengths = 254, 285 and 300 nm.

Solvent gradient (linear gradient changes) Total operating time = 37 min.

With this technique, the formation of cyclic carbonates was determined. In addition, the use of this technique with detection at various known wavelengths allows confirmation that chromophores (eg, binaphthol) have been incorporated into the cyclic carbonates. Nuclear Magnetic Resonance (NMR) The proton NMR spectra (1H) were obtained in a 200 MHz Varian instrument in a combination of CDC13 solvents and deuterated DMSO. All spectra were referenced to tetramethylsilane (TMS) at 0 ppm. The Makrolon 2408 is a commercial topped polycarbonate. This method was used to characterize the phenolic end groups formed during processing, which can lead to the formation of quinone, hence the color instability in polycarbonate. An integral ratio of the protons of the phenoxy terminal group (8.3-8.4 ppm) was determined in relation to the six aliphatic protons of bisphenol A isopropylidine (1.6-1.8 ppm) in the polycarbonate of bisphenol A. This integral ratio allows a qualitative comparison of the phenoxy end groups formed during the processing. The melt flow rates were determined according to ASTM 1238. This invention is further illustrated, but is not intended to be limited, by the following examples, in which all parts and percentages are by weight, unless otherwise indicated. another way. EXAMPLES Example 1 The synthesis of a cyclic carbonate containing binaphthol represents a modification of the procedure described in Ring-Opening Polymerization: Mechanisms, Catalysis, Structure, Utility, Brunelle, DJ, Ed., Hanser Publishers: Munich, Vienna, New York, Barcelona , 1993, pgs. 309-335, also in Brunelle, D.J. et al., "Preparation and Polymerization of Bisphenol A Cyclic Oligomeric Carbonates", Macromolecules 1991, 24, pgs. 3035-3044 and Brunelle D.J. et al., "Recent Advances in the Chemistry of Aromatic Cyclic Oligomers", Makromol. Chem., Macromol. Sy p., Vol. 64, pp. 65-74, here incorporated by reference. A 1.0 liter Morton flask equipped with a mechanical stirrer and a condenser was charged with CH2C12 (200 ml), water (7 ml), 9.75 M NaOH (3 ml, 29 mmol) and triethylamine (2.4 ml). , 17.25 mmol). The resulting solution was heated to reflux, stirred vigorously and a 1.0 M solution in CH2C12 of bisphenol A-bischloroformate (0.18 moles, 63.58 g) and 1.1 '-bi-2-naphthol- was added. here binaphthol- (0.02 moles, 5.72 g) below the surface on the tip of the propellant at 6.7 ml / min, using a peristaltic pump. At the same time, 9.75 M NaOH (59 mL, 575 mmol) was administered over 25 minutes, using a dropping funnel, and triethylamine (2.4 mL) was added over 28 minutes using a pump. of syringe. In the time of 10 minutes after the complete addition of bischloroformateThe phases were separated, washed with 1.0 M HCl and then with water three times. The concentration of the product under vacuum gave an almost quantitative yield of product, with a content of 85% of cyclics by HPLC analysis. To isolate the cyclics from the polymer, they were dissolved again in CH2C12 and precipitated in 5 volumes of acetone. As a result, the cyclics were dissolved in acetone, while the polymer was precipitated and separated by filtration. Removal of the acetone in vacuo afforded practically pure cyclooligomers, which contained ~ 10% moles of binaphthol and conformed to Contains - 10% moles of binaphthol The product represents a mixture in which n varies up to approximately 16. The incorporation of binaphthol in the cyclic was confirmed by CLAR-UV / vis at different wavelengths. Example 2 Cyclic oligocarbonates containing binaphthol (3 g) were dried and Makrolon 2608 (27 g) was added to resin. The mixture was then processed in a Haake Kneader, without catalyst, under the following conditions: 15 minutes, 200 rpm, nitrogen atmosphere. It was determined by CPG equipped with a UV-vis detector that the rest binaphthol was uniformly distributed in all the molecular weights in the polycarbonate skeleton. The following diagram represents the procedure: or «VW-PC? -0-C-O? -PC ???? ~ > II wwwpc ^ vO-C-O- ^ PC - ^^^ * ^ + - Merger procedure or Example 3 The process of the invention has been demonstrated by carrying out the experiment described in Example 2, except for the addition of 300 ppm of dibutyltin oxide. In comparison with the product obtained in Example 2 above, an increase in the speed of insertion of the cyclic compounds in the polycarbonate backbone was observed. The speed of the cyclic insertion reaction was determined by taking aliquots of the fusion during the processing and analyzing the degree of incorporation of cyclics by CPG-UV / vis. The molecular weight determined by Gel Permeation Chromatography (CPG) was maintained. It is believed that it is because the cyclics had been inserted into the PC skeleton by a transesterification mechanism; it was determined that the binaphthol moiety was uniformly distributed at all molecular weights in the polycarbonate backbone, as determined by CPG equipped with a UV-vis detector. Example 4 (Comparative Example) A schematic representation of the intermolecular hydrolysis of the polycarbonate backbone by a bisphenol, a process outside the scope of the present invention, is shown below. In this example, the binaphthol was processed in fusion with polycarbonate resin at a level of 1% by weight. As shown in Table 1, the molecular weight had decreased, as determined by Gel Permeation Chromatography. It is believed that this is due to excision of the chains by intermolecular alcoholysis.

- HO-R-O Table 1 Characterization of the molecular weight of modified polycarbonates a Carried out in a Haake b Mixer Determined by CPG c 10% cyclic weight = 1% by weight of binaphthol functionality.

The results show that, when Makrolon 2408 homopolycarbonate resin end-capped with phenol is thermally processed (15 min at 300 ° C), the polycarbonate is stable in molecular weight (within 2-5%). Similarly, by incorporating (10 mol%) the bisphenolic additive through a cyclic oligocarbonate (according to the invention) by a process molten with Makrolon 2408 resin (10% cyclic weight = 1% by weight of binaphthol functionality), The molecular weight was maintained as shown in Table 1. In contrast, in a process in which a binaphthol (1% weight) is directly processed in a melt with Makrolon 2408 resin under the same conditions, a significant reduction in the molecular weight together with an increase of ~ 6 fold in the formation of phenoxy end groups, as determined by NMR. EXAMPLE 5 The synthesis of cyclic carbonates containing a Group designated to impart an antiplas tifying effect to the polycarbonate resin is based on a modification of the procedure described in the documents of Brunelle et al., Cited in relation to Example 1 above . Anti-plastifying, as used in the present context, refers to imparting a higher melting strength to a material. A 1.0 liter Morton flask equipped with a mechanical stirrer and a condenser was charged with CH2C12 (200 ml), water (7 ml), 9.75 M NaOH (3 ml, 29 mmol) and triethylamine (2 ml)., 4 ml, 17.25 mmol). The resulting solution was heated to reflux, stirred vigorously and a 1.0 M solution in CH 2 Cl 12 of bisphenol A-bischloroformate (0.18 mole, 63.58 g) and 1,1 l, tris (4-hydroxyphenyl) was added. ) ethane-here, trisphenol- (0.02 mole, 6.13 g) under the surface on the tip of the propellant at 6.7 ml / min, using a peristaltic pump. At the same time, 9.75 M NaOH (59 ml, 575 mmol) was administered over 25 min., Using a dropping funnel, and triethylamine (2.4 mL) was added over 28 min. using a syringe pump. Within 10 min. After the complete addition of bisclo-roformate, the phases were separated and washed with 1.0 M HCl and then with water three times. Concentration of the product in vacuo gave an almost quantitative yield of product containing 85% cyclics by HPLC analysis. To isolate the cyclics from the polymer, they were dissolved again in CH2C12 and precipitated in 5 volumes of acetone. As a result, the cyclics were dissolved in acetone, while the polymer precipitated and separated by filtration. Removal of the acetone in vacuo gave practically pure cyclooligomers, which contained ~ 10 mol% trisphenol. The incorporation of the additive to the cyclic was confirmed by CLAR. The cyclics were decomposed hydrolytically with a KOH / MeOH solution and trisphenol was determined to be part of the structure. Example 6 The melt processing according to the inventive method of a 10% weight cyclic carbonate [containing 10 mol% trisphenol] with Makrolon 2408 resin resulted in a branched resin having a modified rheology. A transesterifi cation catalyst, dibutyltin oxide (ODBE), was used in the reaction. The schematic representation of this procedure has been shown above. The modification of the rheology was determined by CPG and by measuring the molten flow velocity (VFF). The CPG measurements show an increase in molecular weight. The results (Table 2) showed that the ODBE catalyst produced a significant reduction of the VFF.

Table 2 Characterization of molecular weight and molten flux for modified rheology polycarbonate. a Determined by CPG b VFF values taken at 300 ° C * 10% cyclic weight = 1% trisphenol functionality weight. Example 7 A 1.0 liter Morton flask equipped with a mechanical stirrer and a condenser was charged with CH2C12 (200 ml), water (7 ml), 9.75 M NaOH (3 ml, 29 mmol) and triethylamine -Et3N- (2.4 mL, 17.25 mmol). The solution was heated to reflux, stirred vigorously and a solution of bisphenol A-bischloroformate (200 ml of 1.0 M in CH 2 C 12) was added under the surface on the tip of the propellant at 6.7 ml / min., Using a peristaltic pump. At the same time, 9.75 M NaOH (59 ml, 575 mmol) was administered over 25 min. using a dropping funnel and Et3N (2.4 ml) was added in a time of 28 min. using a syringe pump. Within 10 minutes of the complete addition of bischloroformate, the phases were separated, washed with 1.0 M HCl and then with water three times. The concentration of the product under vacuum gave an almost quantitative yield of product with an 85% cyclic content by HPLC analysis. To isolate the cyclics from the polymer, they were dissolved in CH2C12 and precipitated in 5 volumes of acetone. As a result, the cyclics were dissolved in acetone, while the polymer precipitated and was separated by filtration. The removal of the acetone in vacuo gave practically pure cyclooligomers that conformed to The product represents a mixture in which n varies up to about 16. Example 8 The cyclic oligocarbonates based on bisphenol A prepared in Example 7 were melt blended with Makrolon 2608 polycarbonate resin in a Haake Kneader under the following conditions: 5 minutes, 300 ° C, 200 rpm. Transesterification catalysts (300 ppm) were introduced into the molten reaction to determine their relative efficiency in the incorporation of the cyclic carbonates in the linear polycarbonate by insertion by transesterification. Gel Permeation Chromatography (CPG) equipped with a refractive index detector was used to characterize the final resin in terms of molecular weight. The results are presented in Table 3. The table shows the molecular weight characterization of the polycarbonate resin that had been reacted with 10% by weight of cyclic oligocarbonates based on bisphenol A and the molecular weight dependence with respect to the catalyst used in the reaction. Table 3 It can be seen that three transesterification catalysts give rise to a polycarbonate with a narrower polydispersity than the control resin (Example a-polydispersity = 2.7). These are dibutyltin oxide, cobalt (II) acetate tetrahydrate and antimony oxide. The high value of Mn correlates directly with a low polydispersity value. The presence of cyclic carbonates gives a low value of Mn, as shown in Example B of the table. Once these cyclics are randomly incorporated into the high molecular weight polycarbonate by insertion by transesterifi cation, the Mn increases and the polydispersity becomes narrower.

Using common catalysts of polymer formation (for example tetrabutylane onium tetraphenyl borate, Example V), it can be seen that the Mn is very low and that the polydispersity is large. Therefore, ring opening polymerization catalysts are not effective in the transesterification insertion process of the present invention. Although it is not desired to be inclined to the theory, it is believed that, at levels of 10% by weight, there are not enough cyclics to undergo a ring-opening polymerization. As a result, cyclics interact mostly with linear polycarbonate. As a result, the catalysts that promote the insertion by transesterifi cation in the polycarbonate give rise to a final material with the cyclics incorporated randomly in all the molecular weights. Although the invention has been described in detail in the foregoing for illustrative purposes, it is to be understood that said detail has only that purpose and that those skilled in the art can make variations therein without departing from the spirit and scope of the invention, except in what may be limited by the claims.

Claims (37)

1. CLAIMS 1. A process for the preparation of modified resin consisting of the transesterification reaction in the melting of (i) a polymeric resin, whose repeating units contain at least one member selected from the group consisting of ester bond and carbonate bond, with ( ii) at least one cyclic carbonate having a molecular weight of about 80-10000 g / mol and conforming to where X and R independently represent an aliphatic, cycloaliphatic or aromatic residue of a dihydroxy compound or a bischloroformate; Y represents a trifunctional or tetrafunctional nucleophile, and n, n n2 n, independently represent an integer from 0 to 16, with the proviso that the transesterification of a polycarbonate resin with a cyclic carbonate conforming to (I) above , where R is the hydroquinone residue, be excluded.
2. 2. A process for the preparation of modified resin consisting of the transesterification reaction in the melting of (i) a polymeric resin, whose repeating units contain at least one member selected from the group consisting of ester bond and carbonate bond, with (ii) a cyclic carbonate having a molecular weight of about 80-10000 g / mol and conforming to where X and R independently represent an aliphatic, cycloaliphatic or aromatic residue of a dihydroxy compound or a bischloroformate; Y represents a trifunctional or tetrafunctional nucleophile, and n, n, n and n3 independently represent an integer from 0 to 16, in the presence of a catalyst selected from the group consisting of dibutyltin oxide, cobalt (II) acetate tetrahydrate, antimony (III), manganese (II) acetate tetrahydrate, titanium (IV) butoxide, zinc acetate dihydrate, dibutyltin dilaurate, tin acetate (II), tetramethyldiacetoxiestannoxane, tin oxide (IV), lead acetate (II) ) trihydrate, dibutyltin diacetate and titanium (IV) bis (ethylacetoacetate).
3. The method of Claim 1, wherein said (i) is present in an amount of about 60 to 99.99 percent and said (ii) is present in an amount of about 0.01 to 40, 0 percent, said percentage being in relation to the total weight of said (i) and (ii).
4. The method of Claim 2, wherein said (i) is present in an amount of about 60 to 99.99 percent and said (ii) is present in an amount of about 0.01 to 40, 0 percent, said percentage being in relation to the total weight of said (i) and (ii).
5. The method of Claim 1, wherein said (i) is present in an amount of about 90 to 99.99 percent and said (ii) is present in an amount of about 0.01 to 10, 0 percent, said percentage being in relation to the total weight of said (i) and (ii).
6. 6. The method of claim 2, wherein said (i) is present in an amount of about 90 to 99.99 percent and said (ii) is present in an amount of about 0.01 to a 10.0 percent, said percentage being in relation to the total weight of said (i) and (ii).
7. The method of Claim 1, wherein said reaction in the melt is carried out in an extruder.
8. The method of Claim 1, wherein said reaction is carried out at temperatures in the range of 250 to 350 ° C and with a residence time sufficient to allow the transesterification reaction.
9. The method of Claim 2, wherein said reaction is carried out at temperatures in the range of 250 to 350 ° C and with a residence time sufficient to allow the transesterification reaction.
10. The method of Claim 9, wherein the dwell time is up to about 5 minutes.
11. 11. The method of Claim 1, wherein said resin is linear polycarbonate.
12. 12. The method of Claim 2, wherein said resin is linear polycarbonate.
13. The method of Claim 1, wherein said resin is polyester.
14. The method of Claim 2, wherein said resin is polyester.
15. 15. The process of Claim 12, wherein said catalyst is dibutyltin oxide.
16. 16. The method of Claim 12, wherein said catalyst is cobalt (II) acetate tetrahydrate.
17. 17. The method of Claim 12, wherein said catalyst is manganese (II) acetate tetrahydrate.
18. 18. The process of Claim 12, wherein said catalyst is antimony (III) oxide.
19. 19. The method of Claim 12, wherein said catalyst is titanium (IV) butoxide.
20. The process of Claim 12, wherein said catalyst is zinc acetate dihydrate.
21. 21. The method of Claim 12, wherein said catalyst is dibutyltin dilaurate.
22. 22. The method of Claim 12, wherein said catalyst is tin acetate (II).
23. 23. The method of Claim 12, wherein said catalyst is tetramethyldiacetoxy stannoxane.
24. 24. The method of Claim 12, wherein said catalyst is tin oxide (IV).
25. 25. The process of Claim 12, wherein said catalyst is lead (II) acetate trihydrate.
26. 26. The process of Claim 12, wherein said catalyst is dibutyltin diacetate.
27. 27. The process of Claim 12, wherein said catalyst is titanium (IV) bis (ethylacetoacetate).
28. 28. A process for the preparation of modified resin consisting of the transeste-rification reaction in the melting of (i) a polymeric resin, whose repeating units contain at least one member selected from the group consisting of ester bond and carbonate bond, with (ii) at least one cyclic carbonate having a molecular weight of about 80-10000 g / mol and conforming to O where X and R independently represent an aliphatic, cycloaliphatic or aromatic residue of a dihydroxy or bischloroformate compound and n represents an integer from 0 to 16, with the proviso that the transesterification of a polycarbonate resin with a cyclic carbonate where R is a hydroquinone residue is excluded.
29. 29. A process for the preparation of modified resin consisting of the transesterification reaction in the melting of (i) a polymeric resin, whose repeating units contain at least one member selected from the group consisting of ester bond and carbonate bond, with (ii) ) at least one cyclic carbonate having a molecular weight of about 80-10000 g / mol and conforming to where X and R independently represent an aliphatic, cycloaliphatic or aromatic residue of a dihydroxy compound or a bischloroformate; Y represents a trifunctional or tetrafunctional nucleophile, and n, nl r n2 and n3 independently represent an integer from 0 to 16.
30. 30. The method of Claim 1, wherein said R includes a radical or residue whose inclusion in the structure of said resin would effect a change in the properties of the resin.
31. 31. The method of Claim 2, wherein said R includes a radical or residue whose inclusion in the structure of said resin would effect a change in the properties of the resin.
32. 32. The method of Claim 28, wherein said R includes a radical or residue whose inclusion in the structure of said resin would effect a change in the properties of said resin.
33. 33. The method of Claim 29, wherein said R includes a radical or residue whose inclusion in the structure of said resin would effect a change in the properties of the resin.
34. 34. The method of Claim 28, wherein said resin is linear polycarbonate.
35. 35. The method of Claim 29, wherein said resin is linear polycarbonate.
36. 36. The method of Claim 28, wherein said resin is polyester.
37. 37. The method of Claim 29, wherein said resin is polyester.