Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
  • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds

Definitions

• 6,323,291 describes blends of polycarbonate with a melt flow index greater than 18 g/10 min and polyesters derived from phthalic acid and a diol portion of 1,4-cyclohexanedimethanol and ethylene glycol.
• polyesters used in the blends each of the patents above refers solely to U.S. Pat. No. 2,901,466, which teaches the use of ester interchange catalysts in the production of polyesters but does not specify a particular catalyst type or catalyst level.
• Fifty-four of the polyester examples in the '466 patent show the use of titanium based catalysts. The titanium concentration in these examples is uniformly greater than 35 parts per million (ppm) elemental titanium, typically in the range of 50 to 200 ppm.
• step (ii) polycondensing the product of step (i) at temperatures and pressures sufficient to effect polycondensation in the presence of a titanium-containing catalyst compound in an amount of from about 1 to about 30 ppm elemental titanium, with ppm based on the total weight of the polyester;
• thermoplastic composition comprises the step of compounding:
• an acid component comprising repeat units from about 80 to 100 mole percent terephthalic acid, isophthalic acid, and mixtures thereof, based on 100 mole percent acid component;
• a diol component comprising repeat units from about 40 to 100 mole percent 1,4-cyclohexanedimethanol and about 0 to about 60 mole percent ethylene glycol, based on 100 mole percent diol component;
• a polyester composition comprises
• the amount of elemental titanium is from about 1 to about 20 ppm, and more preferably from about 1 to about 15 ppm, with ppm are based on the total weight of the polyester.
• an ester exchange catalyst in an amount of from about 1 to about 150 ppm of an active element is utilized in preparing the polyester when an acid component of the polyester is derived from a diester of a dicarboxylic acid.
• This level of elemental titanium in the present invention is a lower level of titanium as compared to prior art polyester/polycarbonate blends, typically prepared using a polyester having 50 ppm or greater elemental titanium.
• the acid component of the polyester comprises repeat units from at least one aromatic, aliphatic, or alicyclic dicarboxylic acid, wherein the aromatic portion of said aromatic dicarboxylic acid has 6 to 20 carbon atoms and wherein the aliphatic or alicyclic portion of said aliphatic or alicyclic dicarboxylic acid has 3 to 20 carbon atoms.
• the diol component comprises repeat units from about 40 to 100 mole percent 1,4-cyclohexanedimethanol, from 0 to about 60 mole percent ethylene glycol, and from 0 to about 20 mole percent of other diol units having from 3 to about 12 carbon atoms.
• Exemplary of the other diols suitable for use herein are propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, diethylene glycol and the like, or mixtures thereof.
• the polyesters as described herein are based on an acid component of 100 mole percent and a diol component of 100 mole percent.
• the polyester used for the miscible blend comprises from about 95 to 100 mole percent of terephthalic acid, from about 58 to about 66 mole percent 1,4-cyclohexanedimethanol and from about 42 to about 34 mole percent of ethylene glycol.
• Another most preferred polyester comprises 100 mole percent 1,4-cyclohexanedimethanol, from about 22 to about 30 mole percent isophthalic acid, and from about 78 to about 70 mole percent terephthalic acid.
• Suitable pre-polycondensation phosphorus-containing compounds for use in preparing polyesters of the invention include, but are not limited to, phosphates, organic phosphate esters, organic phosphite esters, phosphoric acid, diphosphoric acid, polyphosphoric acid, phosphonic acid and substituted derivatives of all the above.
• the polyesters of each of the embodiments herein comprise toners to impart a desired neutral color to the resulting polyester.
• a preferred method of including colorants is to use a colorant having thermally stable organic colored compounds having reactive end groups such that the colorant is copolymerized and incorporated into the polyester to improve the hue of the polyester.
• colorants such as dyes possessing reactive hydroxyl or carboxyl groups, including but not limited to, blue and red substituted anthraquinones may be copolymerized into the polymer chain. Suitable colorants and dyes are described in detail in U.S. Pat. Nos.
• the inherent viscosity of the polyester of the present invention may range from about 0.3 to about 1.5 dl/g, the preferred range being about 0.6 to about 1.2 dl/g, at 25° C. in a solvent mixture consisting of 60% by weight phenol and 40% by weight tetrachloroethane determined in accordance with ASTM Test Method D2857-70.
• polyesters For particular methods of producing polyesters, reference is made to U.S. Pat. Nos. 2,901,466 and 3,772,405, the contents of which are incorporated herein by reference.
• the polyesters may also be subjected to solid-state polymerization methods for further molecular weight build-up.
• the compounded polyester/polycarbonate blends of the present invention have reduced yellowness over similar conventional blends, minimal yellow coloration may still be present.
• the yellow coloration may be further suppressed by adding a blend stabilizer, typically a phosphorus-containing compound, to the blend.
• each of R 1 , R 2 , and R 3 represents a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an arylalkyl group containing 7 to 20 carbon atoms, or an OR group in which R is a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, and arylalkyl group containing 7 to 20 carbon atoms; R 1 , R 2 , and R 3 may be different from each other, or at least two of R 1 , R 2 , and R 3 may be the same, or at least two of R 1 , R 2 , and R 3 may form a ring, and metal salts of these phosphorous compounds;
• R 1 represents a divalent alkyl group having 2-12 carbon atoms or a divalent aryl group having 6-15 carbon atoms
• R 2 and R 3 are monovalent alkyl groups having 2-18 carbon atoms, or a monovalent aryl or substituted aryl group having 6 to 15 carbons
• R 1 and R 2 represent monovalent alkyl groups having 2-18 carbon atoms, or a monovalent aryl or substituted aryl groups having 6-15 carbon atoms.
• a preferred post-polycondensation phosphorus-containing compound of formula (e) is distearyl pentaerythritol diphosphite (R 1 and R 2 are C 18 H 37 ).
• the dihydric phenols employed are known, and the reactive groups are thought to be the phenolic hydroxyl groups.
• Typical of some of the dihydric phenols employed are bis-phenols such as 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,4-bis-(4-hydroxyphenyl)-2-methyl-butane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, .alpha.,.alpha.′-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxypheny
• the polycarbonates of the invention may entail in their structure, units derived from one or more of the suitable bisphenols.
• the most preferred dihydric phenol is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).
• the polycarbonates may be prepared by a variety of conventional and well known processes which include transesterification, melt polymerization, and interfacial polymerization.
• the polycarbonates are generally prepared by reacting a dihydric phenol with a carbonate precursor, such as phosgene, a haloformate or carbonate ester in melt or solution.
• a carbonate precursor such as phosgene, a haloformate or carbonate ester in melt or solution.
• Suitable processes for preparing the polycarbonates of the present invention are described in U.S. Pat. Nos., 2,991,273; 2,999,846; 3,028,365; 3,153,008; 4,123,436; all of which are incorporated herein by reference.
• the blends may comprise more than one polyester and more than one polycarbonate and can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
• the solution blending method includes dissolving the appropriate weight/weight ratio of polyester and polycarbonate in a suitable organic solvent such as methylene chloride, mixing the solution, and separating the blend composition from solution by precipitation of the blend or by evaporation of the solvent.
• a suitable organic solvent such as methylene chloride
• thermoplastic compositions of this invention may contain common additives such as colorants, mold release agents, flame retardants, plasticizers, nucleating agents, UV stabilizers, fillers, and impact modifiers.
• the impact modifiers may be added to the subject compositions in conventional amounts of from 0.1 to 25% by weight of the overall composition.
• typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers, styrene based block copolymeric impact modifiers, and various acrylic core/shell type impact modifiers.
• the present invention is directed to articles of manufacture formed from the blend compositions and films and sheets of the present invention.
• the articles can be produced utilizing any suitable technique such as injection molding.
• Extruded objects comprising the blends have a wide range of commercial uses.
• films and sheets are useful for signs, skylights, the packaging of foods, clothing, and pharmaceutical products.
• Extruded films/sheets may be used as is or thermoformed to provide packaging for foods, hardware and other items.
• the polyester/polycarbonate blends of this invention may be foamed during the extrusion operations using techniques well known in the art. For example, useful foaming techniques are disclosed in U.S. Pat. Nos. 5,399,595; 5,482,977; and 5,654,347.
• an acid component comprising repeat units from about 80 to 100 mole percent terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or mixtures thereof and from 0 to about 20 mole percent of other dicarboxylic acid units having from about 4 to about 40 carbon atoms, wherein the total mole percent of the acid component is equal to 100 mole percent,
• an improvement comprises the polyester comprising catalyst residues of (i) a titanium-containing catalyst compound in an amount of from about.1 to about 20 ppm elemental titanium, (ii) a pre-polycondensation phosphorus-containing compound in an amount of from about 1 to about 150 ppm elemental phosphorus, (iii) from about 1 to about 10 ppm of at least one copolymerizable compound of a 6-arylamino-1-cyano-3H-dibenz[f,ij]isoquinoline-2,7-dion or a 1,4-bis(2,6-dialkylanilino) anthraquinone in combination with at least one bis anthraquinone or bis anthrapyridone(6-arylamino-3H-dibenz[f,ij]isquinoline-2,7-done) compound, wherein the compounds contain at least one polyester reactive group; and (iv) optionally, a ester exchange catalyst in an amount of from about 1
• One embodiment of the present invention is a process for preparing a blend of a polyester and a polycarbonate.
• the polyester is produced comprising the steps of:
• step (i) polycondensing the product of step (i) at temperatures and pressures sufficient to effect polycondensation in the presence of a titanium-containing catalyst compound in an amount of from about 1 to about 20 ppm elemental titanium and a pre-polycondensation phosphorus-containing compound in an amount of from about 1 to about 150 ppm elemental phosphorus, with ppm based on the total weight of the polyester.
• polyester After producing the polyester, from about 1 to about 99 weight percent of the polyester is compounded with from about 99 to about 1 weight percent of a polycarbonate to form a blend, with the weight percent based on the total weight percent of the blend.
• catalyst residues consisting essentially of (i) a titanium-containing catalyst compound in an amount of about 1 to about 15 ppm elemental titanium, (ii) a pre-polycondensation phosphorus-containing compound in an amount of about 45 to about 100 ppm elemental phosphorus, (iii) from about 1 to about 5 ppm of at least one copolymerizable compound of a 6-arylamino-1-cyano-3H-dibenz[f,ij]isoquinoline-2,7-dione or a 1,4-bis(2,6-dialkylanilino) anthraquinone in combination with at least one bis anthraquinone or bis anthrapyridone(6-arylamino-3H-dibenz[f,ij]isquinoline-2,7-done) compound, wherein the compounds contain at least one polyester reactive group, and (iv) optionally, an ester exchange catalyst in an amount of from about 10 to about 65 ppm
• the glass transition temperatures (Tg's) of the pellets were determined using a TA Instruments 2920 differential scanning calorimeter (DSC) at a scan rate of 20° C./min.
• the color of the polymer pellets and plaques was determined in a conventional manner using a HunterLab UltraScan Colorimeter manufactured by Hunter Associates Laboratory, Inc., Reston, Va. The instrument was operated using HunterLab Universal Software (version 3.8). Calibration and operation of the instrument was done according to the HunterLab User Manual.
• polyester #2/polycarbonate blends have better thermal stability, with regards to color formation as represented by lower ⁇ b* values, than polyester #1/polycarbonate blends.
• the reduced yellowness seen in the blends is significantly larger than the reduced yellowness seen in neat polyesters (composition A).
• polyester #4/polycarbonate blends have better thermal stability as represented by lower ⁇ b* values, with regards to color formation, than polyester #3/polycarbonate blends.
• the reduced yellowness seen in the blends is significantly larger than the reduced yellowness seen in neat polyesters (composition A).
• thermoplastic compositions illustrate melt stability improvements in polyester #4/polycarbonate blends compared to polyester #3/polycarbonate blends.
• polyester/polycarbonate blends with different levels of Weston 619 were bag blended and then injection molded into 100 mil thick color chips with a Toyo Plastar Ti-90G injection molding machine equipped with a mixing screw and mixing nozzle to provide homogeneity.

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• 2002
  • 2002-03-27 US US10/107,674 patent/US6723768B2/en not_active Expired - Fee Related
• 2003
  • 2003-03-07 MY MYPI20030799A patent/MY140141A/en unknown
  • 2003-03-12 DE DE60301398T patent/DE60301398T2/de not_active Expired - Lifetime
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  • 2003-03-12 WO PCT/US2003/007679 patent/WO2003082979A1/en active IP Right Grant
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