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
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy 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
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/015—Biocides
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2286—Oxides; Hydroxides of metals of silver
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/321—Phosphates
  • C08K2003/328—Phosphates of heavy metals
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
  • C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/54—Inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• This invention relates to the preparation of blends of polyesters from terephthalic acid, 40 to 5 mol % 2,2,4,4-tetramethy-1,3-cyclobutanediol and 60 to 95 mol % 1,4-cyclohexanedimethanol with copolyestercarbonates.
• Blends of polyesters containing % 2,2,4,4-tetramethy-1,3-cyclobutanediol with copolyestercarbonates provide clear blends.
• the present polymer blend comprising (1) 5-95 weight % of a aliphatic-aromatic copolyester having repeat units 2,2,4,4, tetramethyl-1,3 cyclobutanediol, 1,4-cyclohexanedimethanol and terephthalic acid; (2) 5-95 weight % of an copolyestercarbonate comprising a bisphenol A diol component and 50-90 mole % isophthalic acid, 0-60 mole % terephthalic acid and 0 to 60 mole % carbonic acid wherein the total mole % of acid units is equal to 100 mole %.
• the invention relates to a polymer blend comprising:
• the invention relates to a polymer blend comprising:
• the invention relates to a polymer blend comprising:
• One of the objectives of this invention is to provide blends of high molecular weight polyesters comprising units of terephthalic acid, 2,2,4,4-tetramethy-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol with copolyestercarbonates useful as molding plastics, fibers and films.
• a second objective of this invention is to provide blends useful as molding plastics, fibers, and films having excellent clarity.
• a third objective of this invention is to provide molding plastics, fibers, and films having good heat resistance.
• a fourth object of this invention is to provide a polymer blend that is miscible and clear with excellent thermal properties.
• This invention relates to clear miscible blends of a aliphatic-aromatic copolyester of terephthalic acid, 2,2,4,4, tetramethyl-1,3 cyclobutanediol and 1,4 cyclohexanedimethanol with a copolyestercarbonate of bisphenol A diol, and isophthalic acid, terephthalic acid, and carbonic acid.
• Conventional blends of two polymers are not clear and typically show two glass transition temperatures.
• the compatible blends of this invention on the other hand, have excellent clarity indicating miscibility and exhibit one glass transition temperature and have excellent heat resistance.
• a clear polymer blend comprising:
• the copolyesters useful in the polymer blends of the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25° C.: 0.45 to 1.2 dL/g; 0.45 to 1.1 dL/g; 0.45 to 1 dL/g; 0.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90 dL/g; 0.45 to 0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 to less than 0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to less than 0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to 0.45 to 0.45 to 0.
• the diacids useful in the present invention may comprise from about 65 to 100 mole percent, preferably 80 to 100 mole percent, more preferably, 85 to 100 mole percent, even more preferably, 90 to 100 mole percent, and further 95 to 100 mole percent, of dicarboxylic acids selected from the group consisting of terephthalic acid residues, isophthalic acids, or mixtures thereof.
• the polyester may comprise about 70 to about 100 mole % of diacid residues from terephthalic acid and 0 to about 30 mole % diacid residues from isophthalic acid (in one embodiment, about 0.1 to 30 mole percent isophthalic acid.
• Copolyesters of the polymer blends of the invention also may further comprise from about 0 to about 30 mole percent, preferably 0 to 10 mole percent, and more preferably, 0.1 to 10 mole percent of the residues of one or more modifying diacids containing about 2 to about 20 carbon atoms (not terephthalic acid and/or isophthalic acid).
• modifying diacids containing about 2 to about 20 carbon atoms include but are not limited to aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids.
• modifying dicarboxylic acids include, but are not limited to, one or more of succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, azelaic acid, dimer acid, sulfoisophthalic acid. Additional examples of modifying diacids are fumaric, maleic, itaconic, 1,3-cyclohexanedicarboxylic, diglycolic, 2,5-norbornanedicarboxyclic, phthalic acid, diphenic, 4,4′-oxydibenzoic, and 4,4′-sulfonyldibenzoic.
• modifying dicarboxylic acid residues include but are not limited to naphthalenedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Any of the various isomers of naphthalenedicarboxylic acid or mixtures of isomers may be used, but the 1,4-, 1,5-, 2,6-, and 2,7-isomers are preferred. Cycloaliphatic dicarboxylic acids such as, for example, 1,4-cyclohexanedicarboxylic acid may be present at the pure cis or trans isomer or as a mixture of cis and trans isomers.
• the molar ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary from the pure form of each and mixtures thereof.
• the molar percentages for cis and/or trans 2,2,4,4,-tetramethyl-1,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30 mole % trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30 mole % cis; or 50 to 70 mole % cis and 50 to 30 mole % trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % %
• the molar ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary within the range of 50/50 to 0/100, for example, between 40/60 to 20/80.
• the cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example, a cis/trans ratio of 60:40 to 40:60 or a cis/trans ratio of 70:30 to 30:70.
• the trans-cyclohexanedimethanol can be present in an amount of 60 to 80 mole % and the cis-cyclohexanedimethanol can be present in an amount of 20 to 40 mole % wherein the total percentages of cis-cyclohexanedimethanol and trans-cyclohexanedimethanol is equal to 100 mole %.
• the trans-cyclohexanedimethanol can be present in an amount of 60 mole % and the cis-cyclohexanedimethanol can be present in an amount of 40 mole %. In particular embodiments, the trans-cyclohexanedimethanol can be present in an amount of 70 mole % and the cis-cyclohexanedimethanol can be present in an amount of 30 mole %. Any of 1,1-, 1,2-, 1,3-, 1,4-isomers of cyclohexanedimethanol or mixtures thereof may be present in the glycol component of this invention.
• glycol portion of these aliphatic-aromatic copolyesters may contain up to 30 mol % or up to 10 mole %, up to 5 mol % of another glycol containing 2 to 16 carbon atoms.
• suitable glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or p-xylene glycol.
• the polymers may also be modified with polyethylene glycols or polytetramethylene glycols.
• esters of the dicarboxylic acids useful in this invention include the dimethyl, dipropyl, diisopropyl, dibutyl, diphenyl etc.
• the glycol component for the copolyester useful in blends of the invention include but are not limited to at least one of the following combinations of ranges: 5 to 99 mole % TMCD and 1 to 95 mole % CHDM; 5 to 95 mole % TMCD and 5 to 95 mole % CHDM; 5 to 90 mole % TMCD and 10 to 95 mole % CHDM; 5 to 85 mole % TMCD and 15 to 95 mole % CHDM; 5 to 80 mole % TMCD and 20 to 95 mole % CHDM, 5 to 75 mole % TMCD and 25 to 95 mole % CHDM; 5 to 70 mole % TMCD and 30 to 95 mole % CHDM; 5 to 65 mole % TMCD and 35 to 95 mole % CHDM; 5 to 60 mole % TMCD and 40 to 95 mole % CHDM; 5 to 55 mole % TMCD and 45 to 95 mole % CHDM; and 5 to
• the glycol component for the copolyester useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 5 to less than 50 mole % TMCD and greater than 50 to 95 mole % CHDM; 5 to 45 mole % TMCD and 55 to 95 mole % CHDM; 5 to 40 mole % TMCD and 60 to 95 mole % CHDM; 5 to 35 mole % TMCD and 65 to 95 mole % CHDM; 5 to less than 35 mole % TMCD and greater than 65 to 95 mole % CHDM; 5 to 30 mole % TMCD and 70 to 95 mole % CHDM; 5 to 25 mole % TMCD and 75 to 95 mole % CHDM; 5 to 20 mole % TMCD and 80 to 95 mole % CHDM; 5 to 15 mole % TMCD and 85 to 95 mole % CHDM; 5 to 10 mole % TMCD and 90 to
• the glycol component for the copolyesters useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 10 to 99 mole % TMCD and 1 to 90 mole % CHDM; 10 to 95 mole % TMCD and 5 to 90 mole % CHDM; 10 to 90 mole % TMCD and 10 to 90 mole % CHDM; 10 to 85 mole % TMCD and 15 to 90 mole % CHDM; 10 to 80 mole % TMCD and 20 to 90 mole % CHDM; 10 to 75 mole % TMCD and 25 to 90 mole % CHDM; 10 to 70 mole % TMCD and 30 to 90 mole % CHDM; 10 to 65 mole % TMCD and 35 to 90 mole % CHDM; 10 to 60 mole % TMCD and 40 to 90 mole % CHDM; 10 to 55 mole % TMCD and 45 to 90 mole % CHDM;
• the glycol component for the copolyester useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 15 to 99 mole % TMCD and 1 to 85 mole % CHDM; 15 to 95 mole % TMCD and 5 to 85 mole % CHDM; 15 to 90 mole % TMCD and 10 to 85 mole % CHDM; 15 to 85 mole % TMCD and 15 to 85 mole % CHDM; 15 to 80 mole % TMCD and 20 to 85 mole % CHDM; 15 to 75 mole % TMCD and 25 to 85 mole % CHDM; 15 to 70 mole % TMCD and 30 to 85 mole % CHDM; 15 to 65 mole % TMCD and 35 to 85 mole % CHDM; 15 to 60 mole % TMCD and 40 to 85 mole % CHDM; 15 to 55 mole % TMCD and 45 to 85 mole % CHDM;
• the glycol component for the copolyester useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 20 to 99 mole % TMCD and 1 to 80 mole % CHDM; 20 to 95 mole % TMCD and 5 to 80 mole % CHDM; 20 to 90 mole % TMCD and 10 to 80 mole % CHDM; 20 to 85 mole % TMCD and 15 to 80 mole % CHDM; 20 to 80 mole % TMCD and 20 to 80 mole % CHDM; 20 to 75 mole % TMCD and 25 to 80 mole % CHDM; 20 to 70 mole % TMCD and 30 to 80 mole % CHDM; 20 to 65 mole % TMCD and 35 to 80 mole % CHDM; 20 to 60 mole % TMCD and 40 to 80 mole % CHDM; 20 to 55 mole % TMCD and 45 to 80 mole % CHDM;
• the glycol component for the copolyesters useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 25 to 99 mole % TMCD and 1 to 75 mole % CHDM; 25 to 95 mole % TMCD and 5 to 75 mole % CHDM; 25 to 90 mole % TMCD and 10 to 75 mole % CHDM; 25 to 85 mole % TMCD and 15 to 75 mole % CHDM; 25 to 80 mole % TMCD and 20 to 75 mole % CHDM; 25 to 75 mole % TMCD and 25 to 75 mole % CHDM; 25 to 70 mole % TMCD and 30 to 75 mole % CHDM; 25 to 65 mole % TMCD and 35 to 75 mole % CHDM; 25 to 60 mole % TMCD and 40 to 75 mole % CHDM; 25 to 55 mole % TMCD and 45 to 75 mole % CHDM;
• the glycol component for the copolyester useful in the blends of the invention include but are not limited to at least one of the following combinations of ranges: 30 to 99 mole % TMCD and 1 to 70 mole % CHDM; 30 to 95 mole % TMCD and 5 to 70 mole % CHDM; 30 to 90 mole % TMCD and 10 to 70 mole % CHDM; 30 to 85 mole % TMCD and 15 to 70 mole % CHDM; 30 to 80 mole % TMCD and 20 to 70 mole % CHDM; 30 to 75 mole % TMCD and 25 to 70 mole % CHDM; 30 to 70 mole % TMCD and 30 to 70 mole % CHDM; 30 to 65 mole % TMCD and 35 to 70 mole % CHDM; 30 to 60 mole % TMCD and 40 to 70 mole % CHDM; 30 to 55 mole % TMCD and 45 to 70 mole % CHDM; 30 to
• the glycol component for the copolyesters useful in the blends of the invention include but are not limited to at least one of the following combinations of ranges: 35 to 99 mole % TMCD and 1 to 65 mole % CHDM; 35 to 95 mole % TMCD and 5 to 65 mole % CHDM; 35 to 90 mole % TMCD and 10 to 65 mole % CHDM; 35 to 85 mole % TMCD and 15 to 65 mole % CHDM; 35 to 80 mole % TMCD and 20 to 65 mole % CHDM; 35 to 75 mole % TMCD and 25 to 65 mole % CHDM; 35 to 70 mole % TMCD and 30 to 65 mole % CHDM; 35 to 65 mole % TMCD and 35 to 65 mole % CHDM; 35 to 60 mole % TMCD and 40 to 65 mole % CHDM; 35 to 55 mole % TMCD and 45 to 65 mole % CHDM; 35 to
• the glycol component for the copolyester useful in the blends of the invention include but are not limited to at least one of the following combinations of ranges: 40.1 to 100 mole % TMCD and 1 to 59.9 mole % CHDM 40 to 99 mole % TMCD and 1 to 60 mole % CHDM; 40 to 95 mole % TMCD and 5 to 60 mole % CHDM; 40 to 90 mole % TMCD and 10 to 60 mole % CHDM; 40 to 85 mole % TMCD and 15 to 60 mole % CHDM; 40 to 80 mole % TMCD and 20 to 60 mole % CHDM; 40 to 75 mole % TMCD and 25 to 60 mole % CHDM; 40 to 70 mole % TMCD and 30 to 60 mole % CHDM; 40 to 65 mole % TMCD and 35 to 60 mole % CHDM; 40 to 60 mole % TMCD and 40 to 60 mole % CHDM
• the glycol component for the copolyesters useful in the blends of the invention include but are not limited to at least one of the following combinations of ranges: 45 to 100 mole % TMCD and 0 to 55 mole % CHDM; 45 to 99 mole % TMCD and 1 to 55 mole % CHDM; 45 to 95 mole % TMCD and 5 to 55 mole % CHDM; 45 to 90 mole % TMCD and 10 to 55 mole % CHDM; 45 to 85 mole % TMCD and 15 to 55 mole % CHDM; 45 to 80 mole % TMCD and 20 to 55 mole % CHDM; 45 to 75 mole % TMCD and 25 to 55 mole % CHDM; 45 to 70 mole % TMCD and 30 to 55 mole % CHDM; 45 to 65 mole % TMCD and 35 to 55 mole % CHDM; 45 to 60 mole % TMCD and 40 to 55 mole % CHDM; greater
• the glycol component for the copolyesters useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 55 to 99 mole % TMCD and 1 to 45 mole % CHDM; 55 to 95 mole % TMCD and 5 to 45 mole % CHDM; 55 to 90 mole % TMCD and 10 to 45 mole % CHDM; 55 to 85 mole % TMCD and 15 to 45 mole % CHDM; 55 to 80 mole % TMCD and 20 to 45 mole % CHDM; 55 to 75 mole % TMCD and 25 to 45 mole % CHDM; 55 to 70 mole % TMCD and 30 to 45 mole % CHDM; 55 to 65 mole % TMCD and 35 to 45 mole % CHDM; and 55 to 60 mole % TMCD and 40 to 45 mole % CHDM.
• the glycol component for the copolyesters useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 60 to 99 mole % TMCD and 1 to 40 mole % CHDM; 60 to 95 mole % TMCD and 5 to 40 mole % CHDM; 60 to 90 mole % TMCD and 10 to 40 mole % CHDM; 60 to 85 mole % TMCD and 15 to 40 mole % CHDM; 60 to 80 mole % TMCD and 20 to 40 mole % CHDM; 60 to 75 mole % TMCD and 25 to 40 mole % CHDM; and 60 to 70 mole % TMCD and 30 to 40 mole % CHDM.
• the glycol component for the polyesters useful in the polymer blends of the invention include but are not limited to at least one of the following combinations of ranges: 65 to 99 mole % TMCD and 1 to 35 mole % CHDM; 65 to 95 mole % TMCD and 5 to 35 mole % CHDM; 65 to 90 mole % TMCD and 10 to 35 mole % CHDM; 65 to 85 mole % TMCD and 15 to 35 mole % CHDM; 65 to 80 mole % TMCD and 20 to 35 mole % CHDM; 65 to 75 mole % TMCD and 25 to 35 mole % CHDM; and 65 to 70 mole % TMCD and 30 to 35 mole % CHDM.
• the copolyesters in the present invention comprise from about 0 to about 10 or 0.01 to about 10 weight percent (wt %), or from about 0.05 to about 5 weight percent, or from about 0.01 to 1 weight percent, or 0.1 to 0.7 weight percent, based on the total weight of the polyester, of one or more residues of a branching monomer having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
• branching monomers include, but are not limited to, multifunctional acids or glycols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
• the branching monomer residues comprise about 0.1 to about 0.7 mole percent of one or more residues of: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, or trimesic acid.
• the branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176.
• polyesters present in the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, the appropriate diol or diol mixtures, and optionally branching monomers using typical polycondensation reaction conditions. They may be made by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors.
• continuous as used herein means a process wherein reactants are introduced and products withdrawn simultaneously in an uninterrupted manner. By “continuous” it is meant that the process is substantially or completely continuous in operation in contrast to a “batch” process.
• Continuous is not meant in any way to prohibit normal interruptions in the continuity of the process due to, for example, start-up, reactor maintenance, or scheduled shut down periods.
• batch process as used herein means a process wherein all the reactants are added to the reactor and then processed according to a predetermined course of reaction during which no material is fed or removed into the reactor.
• semicontinuous means a process where some of the reactants are charged at the beginning of the process and the remaining reactants are fed continuously as the reaction progresses.
• a semicontinuous process may also include a process similar to a batch process in which all the reactants are added at the beginning of the process except that one or more of the products are removed continuously as the reaction progresses.
• the polyesters included in the present invention are prepared by procedures known to persons skilled in the art.
• the reaction of the diol, dicarboxylic acid, and optional branching monomer components may be carried out using conventional polyester polymerization conditions.
• the reaction process may comprise two steps. In the first step, the diol component and the dicarboxylic acid component, such as, for example, dimethyl terephthalate, are reacted at elevated temperatures, typically, about 150° C. to about 250° C.
• the temperature for the ester interchange reaction ranges from about 180° C. to about 230° C. for about 1 to about 4 hours while the preferred pressure ranges from about 103 kPa gauge (15 psig) to about 276 kPa gauge (40 psig).
• the reaction product is heated under higher temperatures and under reduced pressure to form the polyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system.
• This second step, or polycondensation step is continued under higher vacuum and a temperature which generally ranges from about 230° C.
• the polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture.
• reaction rates of both stages are increased by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
• catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
• a three-stage manufacturing procedure similar to that described in U.S. Pat. No. 5,290,631, may also be used, particularly when a mixed monomer feed of acids and esters is employed.
• polyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components and the branching monomer component.
• the reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight polyester product having an average degree of polymerization of from about 1.4 to about 10.
• the temperatures employed during the direct esterification reaction typically range from about 180° C.
• catalyst materials that may be used in the synthesis of the polyesters utilized in the present invention may include but are not limited to tin, titanium, manganese, zinc, cobalt, antimony, gallium, lithium, calcium, silicon and germanium. Such catalyst systems are described in U.S. Pat. Nos. 3,907,754, 3,962,189, 4,010,145, 4,356,299, 5,017,680, 5,668,243 and 5,681,918, herein incorporated by reference in their entirety.
• the amount of catalytic metal used may range from about 5 to 100 ppm but the use of catalyst concentrations of about 5 to about 35 ppm titanium is preferred in order to provide polyesters having good color, thermal stability and electrical properties.
• Phosphorus compounds frequently are used in combination with the catalyst metals and any of the phosphorus compounds normally used in making polyesters may be used. Up to about 100 ppm phosphorus typically may be used.
• Polyestercarbonate resins which are suitable for use in the present invention are known in the art and are generally commercially available. These polyestercarbonates may be prepared by a variety of conventional and well known processes which include melt polymerization, interfacial polymerization, etc. Suitable processes for preparing the polycarbonates of the present invention are described in any of the following Patent Cooperation Treaty Publications: WO 01/18104 A1 (Shakhnovich et al., 3/15/2001); 01/32741 A1, (Davis et al. 5/10/2001) 01/32742 A1, (Banach et al. 5/10/2001); and 01/32743 A1 (Banach et al. 5/10/2001).
• the polyestercarbonates which are used in the present invention are derived from Bisphenol A, isophthalic acid, terephthalic acid, and carbonic acid.
• a commercial aromatic polyester product line is sold by General Electric under the trade name Lexan 4000 series.
• the acid portion of the aromatic polyester may contain from 0 to 50 mole % carbonic acid, 0 to 60 mole % terephthalic acid and from 50 to 95 mole % isophthalic acid.
• the inherent viscosity of the polyestercarbonate can vary from about 0.3 dL/gram to about 0.7 dl/gram, but preferably should be in the range from 0.5-0.6 dL/gram.
• compositions of this invention are prepared by any conventional mixing methods.
• a preferred method comprises mixing the aliphatic-aromatic and copolyestercarbonate in powder or granular form in an extruder and extruding the mixture into strands, chopping the strands into pellets and molding the pellets into the desired article.
• additives include plasticizers, pigments flame retardant additives, reinforcing agents such as glass fibers, stabilizers, processing aids, impact modifiers, etc.
• the blends of the invention may comprise additional polymeric components.
• additional polymeric components include, but are not limited to, nylon; polyesters different than those described herein; polyamides such as ZYTEL® from DuPont; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methylmethacrylate); acrylic copolymers; poly(ether-imides) such as ULTEM® (a poly(ether-imide) from General Electric); polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)/polystyrene blends such as NORYL 1000® (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resins from General Electric); polyphenylene sulfides; polyphenylene sulfide/sulfones; poly(esters)
• All polymer blends (also intended to encompass the word “mixtures”) of the invention can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
• the compositions of this invention are prepared by any conventional mixing methods.
• the blending method comprises mixing the aliphatic-aromatic and aliphatic polyester in powder or granular form in an extruder and extruding the mixture into strands, chopping the strands into pellets and molding the pellets into the desired article.
• the polyester blends of the invention may also contain from 0.01 to 25% by weight of the overall composition common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
• typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymeric impact modifiers, and various acrylic core/shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition
• Reinforcing materials may be useful in the polymer blends of this invention.
• the reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.
• the reinforcing materials include glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
• the copolyesters useful in the invention as well as the blends of the invention can be visually clear.
• the term “visually clear” is defined herein as an appreciable absence of cloudiness, haziness, and/or muddiness, when inspected visually. Notched Izod impact strength, as described in ASTM D256, is a common method of measuring toughness.
• the inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.
• the glass transition temperatures were determined using a TA 2920 differential scanning calorimeter (DSC) at a scan rate of 20° C.
• the composition of the neat resins was determined by proton nuclear magnetic resonance spectroscopy (NMR).
• NMR proton nuclear magnetic resonance spectroscopy
• the aliphatic-aromatic copolyester used contained terephthalic acid, 25.1 mol % 2,2,4,4, tetramethyl-1,3 cyclobutanediol (50.4 mol % cis isomer), 74.9% cyclohexanedimethanol.
• the inherent viscosity was measured to be 0.66.
• the copolyestercarbonate used consisted of bisphenol A diol, 51.6 mol % carbonic acid, 44.6 mol % isophthalic acid, and 3.7 mol % terephthalic acid. The inherent viscosity was measured to be 0.56.
• Blends were prepared in a 19 mm Leistritz twin screw extruder. The polyesters were premixed by tumble blending and fed into the extruder and the extruded strand was pelletized. The pellets were injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%. Processing temperatures used were in the range of 270° C. to 300° C. The compositions and properties of the blends are shown in Table 1.
• Heat deflection temperature at 264 psi, was determined according to ASTM D648. Flexural modulus and flexural strength were determined according to ASTM D790. Tensile properties were determined according to ASTM D638.
• the aliphatic-aromatic copolyester used contained terephthalic acid, 25.1 mol % 2,2,4,4, tetramethyl-1,3 cyclobutanediol (50.1% cis isomer), 74.9% cyclohexanedimethanol. The inherent viscosity was measured to be 0.66.
• the copolyestercarbonate used consisted of bisphenol A diol, 20 mol % carbonic acid, 74.2 mol % isophthalic acid, and 5.8 mol % terephthalic acid. The inherent viscosity was measured to be 0.57.
• Blends were prepared in a 19 mm Leistritz twin screw extruder. The polyesters were premixed by tumble blending and fed into the extruder and the extruded strand was palletized. The pellets were injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%. Processing temperatures used were in the range of 270° C. to 320° C. The compositions and properties of the blends are shown in Table 2.
• the aliphatic-aromatic copolyester used contained terephthalic acid, 25.1 mol % 2,2,4,4, tetramethyl-1,3 cyclobutanediol (50.4 mol % cis isomer), 74.9% cyclohexanedimethanol.
• the inherent viscosity was measured to be 0.66.
• the polyarylate Ardel U100 was used in this example. It contains bisphenol A diol, 50 mol % isophthalic acid, and 50 mol % terephthalic acid. The inherent viscosity was measured to be 0.64.
• Blends were prepared in a 19 mm Leistritz twin screw extruder. The polyesters were premixed by tumble blending and fed into the extruder and the extruded strand was pelletized. The pellets were injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%. Processing temperatures used were in the range of 270° C. to 340° C. The compositions and properties of the blends are shown in Table 3.
• the aliphatic-aromatic copolyester used contained terephthalic acid, 50.5 mol % 2,2,4,4, tetramethyl-1,3 cyclobutanediol (54.0 mol % cis isomer), 49.5 mol % cyclohexanedimethanol.
• the inherent viscosity was measured to be 0.58.
• the copolyestercarbonate used consisted of bisphenol A diol, 51.6mol % carbonic acid, 44.6 mol % isophthalic acid, and 3.7 mol % terephthalic acid. The inherent viscosity was measured to be 0.56.
• Blends were prepared in a 19 mm Leistritz twin screw extruder. The polyesters were premixed by tumble blending and fed into the extruder and the extruded strand was pellitized. The pellets were injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%. Processing temperatures used were in the range of 270° C. to 300° C. The compositions and properties of the blends are shown in Table 4.
• the aliphatic-aromatic copolyester used contained terephthalic acid, 50.5 mol % 2,2,4,4, tetramethyl-1,3 cyclobutanediol (54.0 mol % cis isomer), 49.5 mol % cyclohexanedimethanol.
• the inherent viscosity was measured to be 0.58.
• the copolyestercarbonate used consisted of bisphenol A diol, 20 mol % carbonic acid, 74.2 mol % isophthalic acid, and 5.8 mol % terephthalic acid. The inherent viscosity was measured to be 0.57.
• Blends were prepared in a 19 mm Leistritz twin screw extruder. The polyesters were premixed by tumble blending and fed into the extruder and the extruded strand was pelletized. The pellets were injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%. Processing temperatures used were in the range of 270° C. to 320° C. The compositions and properties of the blends are shown in Table 5.
• the aliphatic-aromatic copolyester used contained terephthalic acid, 50.5 mol % 2,2,4,4, tetramethyl-1,3 cyclobutanediol (54.0 mol % cis isomer), 49.5 mol % cyclohexanedimethanol.
• the inherent viscosity was measured to be 0.58.
• the polyarylate Ardel U100 was used in this example. It contains bisphenol A diol, 50 mol % isophthalic acid, and 50 mol % terephthalic acid. The inherent viscosity was measured to be 0.64.
• Blends were prepared in a 19 mm Leistritz twin screw extruder. The polyesters were premixed by tumble blending and fed into the extruder and the extruded strand was pelletized. The pellets were injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%. Processing temperatures used were in the range of 270° C. to 340° C. The compositions and properties of the blends are shown in Table 6.

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