US20120184687A1 - Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates - Google Patents

Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates Download PDF

Info

Publication number
US20120184687A1
US20120184687A1 US13/097,707 US201113097707A US2012184687A1 US 20120184687 A1 US20120184687 A1 US 20120184687A1 US 201113097707 A US201113097707 A US 201113097707A US 2012184687 A1 US2012184687 A1 US 2012184687A1
Authority
US
United States
Prior art keywords
mole
chdm
tmcd
dl
acid residues
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/097,707
Inventor
Wesley Raymond Hale
Gary Michael Stack
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US201161433337P priority Critical
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Priority to US13/097,707 priority patent/US20120184687A1/en
Assigned to EASTMAN CHEMICAL COMPANY reassignment EASTMAN CHEMICAL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: STACK, GARY MICHAEL, HALE, WESLEY RAYMOND
Publication of US20120184687A1 publication Critical patent/US20120184687A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015Biocides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition 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
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/18Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition 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
    • C08L2666/54Inorganic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Abstract

The clear blends of this invention are unique compositions of matter and are prepared by blending polyesters prepared from terephthalic acid, 40 to 5 mole % 2,2,4,4-tetramethy-1,3-cyclobutanediol and 60 to 95 mole % 1,4-cyclohexanedimethanol with a copolyestercarbonate comprising a bisphenol A diol component and 50-90 mole % isophthalic acid and 0-60 mole % terephthalic acid and 0 to 60 mole % carbonic acid. The composition of the blend includes up to about 95 weight % the copolyestercarbonate. These blends have a combination of clarity and toughness making the materials particularly useful in engineering molding plastics and packaging.

Description

    FIELD OF THE INVENTION
  • 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.
  • BACKGROUND OF THE INVENTION
  • Clear blends of two polymers are rare. Blends of polyesters containing % 2,2,4,4-tetramethy-1,3-cyclobutanediol with copolyestercarbonates provide clear blends.
  • SUMMARY OF THE INVENTION
  • These and other objects are achieved by 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 %.
  • In one embodiment, the invention relates to a polymer blend comprising:
    • (A) about 5% to about 95% by weight of at least one polyester (A) which comprises:
      • (a) a dicarboxylic acid component comprising:
        • i) 70 to 100 mole % of terephthalic acid residues;
        • ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and
        • iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
      • (b) a glycol component comprising:
        • i) 15 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
        • ii) 60 to 85 mole % of 1,4-cyclohexanedimethanol residues,
      • wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and
    • (B) about 95% to about 5% by weight of at least one polymer (B) comprising a copolyestercarbonate of bisphenol A diol, and isophthalic acid, terephthalic acid, and carbonic acid;
      wherein said percentages are based on the total weight of the polymer blend.
  • In another embodiment, the invention relates to a polymer blend comprising:
    • (A) about 5% to about 95% by weight of at least one polyester (A) which comprises:
      • (a) a dicarboxylic acid component comprising:
        • i) 70 to 100 mole % of terephthalic acid residues;
        • ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and
        • iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
      • (b) a glycol component comprising:
        • i) 15 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
        • ii) 60 to 85 mole % of 1,4-cyclohexanedimethanol residues,
      • wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and
    • (B) about 95% to about 5% by weight of at least one polymer (B) comprising a copolyestercarbonate of bisphenol A diol, and 50 to 90 mole % isophthalic acid, 0 to 60 mole % terephthalic acid, and 0 to 60 mole % carbonic acid;
      • wherein said acid percentages of polymer (B) are based on a total of 100 mole % of acid units; and
        wherein said weight percentages of polymers in the blend are based on the total weight of the polymer blend.
  • In yet another embodiment, the invention relates to a polymer blend comprising:
    • (A) about 5% to about 95% by weight of at least one polyester (A) which comprises:
      • (a) a dicarboxylic acid component comprising:
        • i) 70 to 100 mole % of terephthalic acid residues;
        • ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and
        • iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
      • (b) a glycol component comprising:
        • i) 20 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
        • ii) 60 to 80 mole % of 1,4-cyclohexanedimethanol residues,
      • wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and
    • (B) about 95% to about 5% by weight of at least one polymer (B) comprising a copolyestercarbonate of bisphenol A diol, and 35 to 50 mole % isophthalic acid residues, 1 to 10 mole % terephthalic acid residues, and 40 to 60 mole % carbonic acid residues;
      • wherein said acid percentages of polymer (B) are based on a total of 100 mole % of acid units; and
        wherein said weight percentages of polymers in the blend are based on the total weight of the polymer blend.
  • 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.
  • DETAILED DESCRIPTION
  • 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.
  • According to the present invention, therefore, is provided a clear polymer blend comprising:
  • (1) 5-95 weight % of a copolyester having repeat units from terephthalic acid, 2,2,4,4, tetramethyl-1,3 cyclobutanediol (trans or cis or mixtures thereof) and 1,4 cyclohexanedimethanol(CHDM) (trans or cis or mixtures thereof) wherein the CHDM content is between 60 to 95 mole % of the total glycol component.
  • (2) 5-95 weight % of a copolyestercarbonate of bisphenol A diol, and isophthalic acid, terephthalic acid, and carbonic acid.
  • For embodiments of the invention, 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 0.65 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1.1 dL/g; 0.50 to 1 dL/g; 0.50 to less than 1 dL/g; 0.50 to 0.98 dL/g; 0.50 to 0.95 dL/g; 0.50 to 0.90 dL/g; 0.50 to 0.85 dL/g; 0.50 to 0.80 dL/g; 0.50 to 0.75 dL/g; 0.50 to less than 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g; 0.50 to less than 0.70 dL/g; 0.50 to 0.68 dL/g; 0.50 to less than 0.68 dL/g; 0.50 to 0.65 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1.1 dL/g; 0.55 to 1 dL/g; 0.55 to less than 1 dL/g; 0.55 to 0.98 dL/g; 0.55 to 0.95 dL/g; 0.55 to 0.90 dL/g; 0.55 to 0.85 dL/g; 0.55 to 0.80 dL/g; 0.55 to 0.75 dL/g; 0.55 to less than 0.75 dL/g; 0.55 to 0.72 dL/g; 0.55 to 0.70 dL/g; 0.55 to less than 0.70 dL/g; 0.55 to 0.68 dL/g; 0.55 to less than 0.68 dL/g; 0.55 to 0.67 dL/g; 0.55 to 0.65 dL/g; 0.58 to 1.2 dL/g; 0.58 to 1.1 dL/g; 0.58 to 1 dL/g; 0.58 to less than 1 dL/g; 0.58 to 0.98 dL/g; 0.58 to 0.95 dL/g; 0.58 to 0.90 dL/g; 0.58 to 0.85 dL/g; 0.58 to 0.80 dL/g; 0.58 to 0.75 dL/g; 0.58 to less than 0.75 dL/g; 0.58 to 0.72 dL/g; 0.58 to 0.70 dL/g; 0.58 to less than 0.70 dL/g; 0.58 to 0.68 dL/g; 0.58 to less than 0.68 dL/g; 0.58 to 0.65 dL/g; 0.60 to 1.2 dL/g; 0.60 to 1.1 dL/g; 0.60 to 1 dL/g; 0.60 to less than 1 dL/g; 0.60 to 0.98 dL/g; 0.60 to 0.95 dL/g; 0.60 to 0.90 dL/g; 0.60 to 0.85 dL/g; 0.60 to 0.80 dL/g; 0.60 to 0.75 dL/g; 0.60 to less than 0.75 dL/g; 0.60 to 0.72 dL/g; 0.60 to 0.70 dL/g; 0.60 to less than 0.70 dL/g; 0.60 to 0.68 dL/g; 0.60 to less than 0.68 dL/g; 0.60 to 0.65 dL/g; 0.60 to 0.64 dL/g; 0.61 to 0.68 dL/g; 0.64 to 0.65 dL/g; 0.65 to 1.2 dL/g; 0.65 to 1.1 dL/g; 0.65 to 1 dL/g; 0.65 to less than 1 dL/g; 0.65 to 0.98 dL/g; 0.65 to 0.95 dL/g; 0.65 to 0.90 dL/g; 0.65 to 0.85 dL/g; 0.65 to 0.80 dL/g; 0.65 to 0.75 dL/g; 0.65 to less than 0.75 dL/g; 0.65 to 0.72 dL/g; 0.65 to 0.70 dL/g; 0.65 to less than 0.70 dL/g; 0.68 to 1.2 dL/g; 0.68 to 1.1 dL/g; 0.68 to 1 dL/g; 0.68 to less than 1 dL/g; 0.68 to 0.98 dL/g; 0.68 to 0.95 dL/g; 0.68 to 0.90 dL/g; 0.68 to 0.85 dL/g; 0.68 to 0.80 dL/g; 0.68 to 0.75 dL/g; 0.68 to less than 0.75 dL/g; 0.68 to 0.72 dL/g; 0.69 to 0.75 dL/g; 0.76 dL/g to 1.2 dL/g; 0.76 dL/g to 1.1 dL/g; 0.76 dL/g to 1 dL/g; 0.76 dL/g to less than 1 dL/g; 0.76 dL/g to 0.98dL/g; 0.76 dL/g to 0.95 dL/g; 0.76 dL/g to 0.90 dL/g 0.80 dL/g to 1.2 dL/g; 0.80 dL/g to 1.1 dL/g; 0.80 dL/g to 1 dL/g; 0.80 dL/g to less than 1 dL/g; 0.80 dL/g to 1.2 dL/g; 0.80 dL/g to 0.98dL/g; 0.80 dL/g to 0.95 dL/g; 0.80 dL/g to 0.90 dL/g.
  • 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. For example, 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). Examples of modifying diacids containing about 2 to about 20 carbon atoms that may be used include but are not limited to aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Specific examples of 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. Other examples of 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.
  • For the copolyesters of the present invention, 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. In certain embodiments, 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 % cis and less than 30 mole % trans; wherein the total mole percentages for cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mole %. In an additional embodiment, 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. In another embodiment, 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 %. In particular embodiments, 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.
  • The 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. Examples of 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. Examples of esters of the dicarboxylic acids useful in this invention include the dimethyl, dipropyl, diisopropyl, dibutyl, diphenyl etc.
  • In other aspects of the invention, 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 50 mole % TMCD and 50 to 95 mole % CHDM.
  • In other aspects of the invention, 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 95 mole % CHDM; greater than 5 to less than 10 mole % TMCD and less than 90 to greater than 95 mole % CHDM; 5.5 mole % to 9.5 mole % TMCD and 94.5 mole % to 90.5 mole % CHDM; and 6 to 9 mole % TMCD and 94 to 91 mole % CHDM.
  • In other aspects of the invention, 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; 10 to 50 mole % TMCD and 50 to 90 mole % CHDM; 10 to less than 50 mole % TMCD and greater than 50 to 90 mole % CHDM; 10 to 45 mole % TMCD and 55 to 90 mole % CHDM; 10 to 40 mole % TMCD and 60 to 90 mole % CHDM; 10 to 35 mole % TMCD and 65 to 90 mole % CHDM; 10 to less than 35 mole % TMCD and greater than 65 to 90% CHDM; 10 to 30 mole % TMCD and 70 to 90 mole % CHDM; 10 to 25 mole % TMCD and 75 to 90 mole % CHDM; 10 to 20 mole % TMCD and 80 to 90 mole % CHDM; and 10 to 15 mole % TMCD and 85 to 90 mole % CHDM.
  • In other aspects of the invention, 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; 15 to 50 mole % TMCD and 50 to 85 mole % CHDM; 15 to less than 50 mole % TMCD and greater than 50 to 85 mole % CHDM; 15 to 45 mole % TMCD and 55 to 85 mole % CHDM; 15 to 40 mole % TMCD and 60 to 85 mole % CHDM; 15 to 35 mole % TMCD and 65 to 85 mole % CHDM; 15 to 30 mole % TMCD and 70 to 85 mole % CHDM; 15 to 25 mole % TMCD and 75 to 85 mole % CHDM; and 15 to 24 mole % TMCD and 76 to 85 mole % CHDM.
  • In other aspects of the invention, 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; 20 to 50 mole % TMCD and 50 to 80 mole % CHDM; 20 to less than 50 mole % TMCD and greater than 50 to 80 mole % CHDM; 20 to 45 mole % TMCD and 55 to 80 mole % CHDM; 20 to 40 mole % TMCD and 60 to 80 mole % CHDM; 20 to 35 mole % TMCD and 65 to 80 mole % CHDM; 20 to 30 mole % TMCD and 70 to 80 mole % CHDM; and 20 to 25 mole % TMCD and 75 to 80 mole % CHDM.
  • In other aspects of the invention, 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; 25 to 50 mole % TMCD and 50 to 75 mole % CHDM; 25 to less than 50 mole % TMCD and greater than 50 to 75 mole % CHDM; 25 to 45 mole % TMCD and 55 to 75 mole % CHDM; 25 to 40 mole % TMCD and 60 to 75 mole % CHDM; 25 to 35 mole % TMCD and 65 to 75 mole % CHDM; and 25 to 30 mole % TMCD and 70 to 75 mole % CHDM.
  • In other aspects of the invention, 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 50 mole % TMCD and 50 to 70 mole % CHDM; 30 to less than 50 mole % TMCD and greater than 50 to 70 mole % CHDM; 30 to 45 mole % TMCD and 55 to 70 mole % CHDM; 30 to 40 mole % TMCD and 60 to 70 mole % CHDM; 30 to 35 mole % TMCD and 65 to 70 mole % CHDM; 31 to 35 mole % TMCD and 65 to 69 mole % CHDM.
  • In other aspects of the invention, 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 50 mole % TMCD and 50 to 65 mole % CHDM; 35 to less than 50 mole % TMCD and greater than 50 to 65 mole % CHDM; 35 to 45 mole % TMCD and 55 to 65 mole % CHDM; 35 to 40 mole % TMCD and 60 to 65 mole % CHDM.
  • In other aspects of the invention, 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; 40 to 55 mole % TMCD and 45 to 60 mole % CHDM; 40 to less than 50 mole % TMCD and greater than 50 to 60 mole % CHDM; 40 to 50 mole % TMCD and 50 to 60 mole % CHDM; and 40 to 45 mole % TMCD and 55 to 60 mole % CHDM.
  • In other aspects of the invention, 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 than 45 to 55 mole % TMCD and 45 to less than 55 mole % CHDM; 45 to 55 mole % TMCD and 45 to 55 mole % CHDM; and 45 to 50 mole % TMCD and 50 to 60 mole % CHDM.
  • In other aspects of the invention, 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.
  • In other aspects of the invention, 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.
  • In other aspects of the invention, 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. Examples of 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. In one embodiment, 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.
  • The 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. The term “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. The term “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. The term “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. Alternatively, 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. For example, when preparing the polyester by means of an ester interchange reaction, i.e., from the ester form of the dicarboxylic acid components, 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. for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 414 kPa gauge (60 pounds per square inch, “psig”). Preferably, 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). Thereafter, 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. to about 350° C., preferably about 250° C. to about 310° C. and, most preferably, about 260° C. to about 290° C. for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained. 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. The 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. 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.
  • To ensure that the reaction of the diol component and dicarboxylic acid component by an ester interchange reaction is driven to completion, it is sometimes desirable to employ about 1.05 to about 2.5 moles of diol component to one mole dicarboxylic acid component. Persons of skill in the art will understand, however, that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.
  • In the preparation of polyester by direct esterification, i.e., from the acid form of the dicarboxylic acid component, 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. to about 280° C., more preferably ranging from about 220° C. to about 270° C. This low molecular weight polymer may then be polymerized by a polycondensation reaction. Examples of the 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.
  • The compositions of this invention are prepared by any conventional mixing methods. For example, 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.
  • It should, of course be obvious to those skilled in the art that other additives may be included in the present compositions. These 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. Suitable examples of the 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(ester-carbonates); polycarbonates such as LEXAN® (a polycarbonate from General Electric); polysulfones; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures of any of the foregoing polymers.
  • 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. For example, in one embodiment, 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.
  • In addition, 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. Examples of 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. In one embodiment, the reinforcing materials include glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • In one embodiment, 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.
  • This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
  • EXAMPLES
  • 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). The miscibility of the blends was determined by the presence of a single glass transition and clarity of molded bars.
  • Example 1
  • 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.
  • The aliphatic-aromatic copolyester was dried at 90° C. and the copolyestercarbonate was dried at 120° C. 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.
  • TABLE 1
    UNITS
    % Aliphatic-aromatic polyester % 100 90 80 70 50 30 0
    % Copolyester carbonate % 0 10 20 30 50 70 100
    Heat Deflection Temperature 264 Psi (deg C.) 82 89 95 99 112 122 143
    Tensile Strength MPa 44 46 49 52 56 61 65
    Tensile Break Elongation % 141 147 93 98 76 64 88
    Flexural Modulus MPa 1427 1485 1571 1624 1725 1842 1948
    Flexural Strength MPa 59 63 67 70 77 85 93
    DSC Tg (Second Cycle) ° C. 109 114 118 123 132 145 163
    Visual Clarity CLEAR CLEAR CLEAR CLEAR CLEAR CLEAR CLEAR
  • Example 2
  • 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.
  • The aliphatic-aromatic copolyester was dried at 90° C. and the copolyestercarbonate was dried at 120° C. 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.
  • TABLE 2
    UNITS
    % Aliphatic-aromatic polyester % 100 90 80 70 50 30 0
    % Copolyester carbonate % 0 10 20 30 50 70 100
    Heat Deflection Temperature 264 Psi (deg C.) 82 86 96 101 117 129 151
    Tensile Strength MPa 44 46 50 52 58 63 69
    Tensile Break Elongation % 141 131 110 106 77 83 33
    Flexural Modulus MPa 1427 1545 1721 1616 1537 1789 1904
    Flexural Strength MPa 59 63 79 73 68 86 95
    DSC Tg (Second Cycle) ° C. 109 112 119 124 139 151 176
    Visual Clarity CLEAR CLEAR CLEAR CLEAR CLEAR CLEAR CLEAR
  • Example 3
  • 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.
  • The aliphatic-aromatic copolyester was dried at 90° C. and the polyarylate was dried at 120° C. 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.
  • TABLE 3
    UNITS
    % Aliphatic-aromatic polyester % 100 90 80 70 50 30 0
    % Polyarylate % 0 10 20 30 50 70 100
    Heat Deflection Temperature 264 Psi (deg C.) 82 90 98 105 118 133 163
    Tensile Strength MPa 44 47 51 54 59 64 70
    Tensile Break Elongation % 141 133 109 104 61 33 18
    Flexural Modulus MPa 1427 1407 1455 1555 1667 1682 1787
    Flexural Strength MPa 59 64 69 75 83 84 91
    DSC Tg (Second Cycle) ° C. 109 116 121 131 142 163 190
    Visual Clarity CLEAR CLEAR CLEAR CLEAR CLEAR CLEAR CLEAR
  • Counter Example 1
  • 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.
  • The aliphatic-aromatic copolyester was dried at 90° C. and the copolyestercarbonate was dried at 120° C. 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 immiscibility of these blends is indicated by their haziness. Two Tg's are observed in the 50/50 blend which also indicates immiscibility. It is likely that the minor component in the other blends also has a second Tg which was too weak to be detected by DSC.
  • TABLE 4
    UNITS
    % Aliphatic-aromatic polyester % 100 90 80 70 50 30 0
    % Copolyester carbonate % 0 10 20 30 50 70 100
    Heat Deflection Temperature 264 Psi (deg C.) 105 104 112 114 12 128 143
    Tensile Strength MPa 48 49 52 54 58 61 65
    Tensile Break Elongation % 90 99 63 66 49 76 88
    Flexural Modulus MPa 1500 1561 1613 1677 1740 1865 1948
    Flexural Strength MPa 66 66 70 73 80 85 93
    DSC Tg (Second Cycle) ° C. 133 135 137 140 140 156 163
    155
    Visual Clarity CLEAR CLEAR HAZY HAZY HAZY HAZY CLEAR
  • Counter Example 2
  • 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.
  • The aliphatic-aromatic copolyester was dried at 90° C. and the copolyestercarbonate was dried at 120° C. 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 immiscibility of these blends is indicated by their opacity. In this example two Tg's are observed over a wider composition range which also indicates immiscibility.
  • TABLE 5
    UNITS
    % Aliphatic-aromatic polyester % 100 90 80 70 50 30 0
    % Copolyester carbonate % 0 10 20 30 50 70 100
    Heat Deflection Temperature 264 Psi (deg C.) 105 108 113 116 129 136 151
    Tensile Strength MPa 48 49 52 54 59 63 69
    Tensile Break Elongation % 90 82 82 70 61 68 33
    Flexural Modulus MPa 1500 1556 1575 1617 1732 1857 1904
    Flexural Strength MPa 66 71 74 76 82 87 95
    DSC Tg (Second Cycle) ° C. 133 135 136 139 139 170 176
    168 167 166
    Visual Clarity CLEAR OPAQUE OPAQUE OPAQUE OPAQUE OPAQUE CLEAR
  • Counter Example 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 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.
  • The aliphatic-aromatic copolyester was dried at 90° C. and the polyarylate was dried at 120° C. 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.
  • In this example, clarity is obtained over part of the composition range and only one Tg is observed. This blend system appears to be on the borderline of forming a clear miscible blend.
  • TABLE 6
    UNITS
    % Aliphatic-aromatic polyester % 100 90 80 70 50 30 0
    % Polyarylate % 0 10 20 30 50 70 100
    Heat Deflection Temperature 264 Psi (deg C.) 106 113 114 119 132 140 163
    Tensile Strength MPa 48 50 52 56 60 65 70
    Tensile Break Elongation % 59 82 67 39 23 26 18
    Flexural Modulus MPa 1433 1480 1592 1592 1790 1787 1787
    Flexural Strength MPa 66 66 68 77 90 91 91
    DSC Tg (Second Cycle) ° C. 131 137 140 142 154 169 190
    Visual Clarity CLEAR OPAQUE OPAQUE HAZY CLEAR CLEAR CLEAR
  • The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (6)

1. A polymer blend comprising:
(A) about 5% to about 95% by weight of at least one polyester (A) which comprises:
(i) a dicarboxylic acid component comprising:
a) 70 to 100 mole % of terephthalic acid residues;
b) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and
c) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
(ii) a glycol component comprising:
a) 15 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
b) 60 to 85 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and
(B) about 95% to about 5% by weight of at least one polymer (B) comprising a copolyestercarbonate of bisphenol A diol, and isophthalic acid residues, terephthalic acid residues, and carbonic acid residues;
wherein said weight percentages are based on the total weight of the polymer blend.
2. The blend of claim 1 wherein said polymer blend exhibits a single glass transition temperature.
3. The blend of claim 1 wherein said polymer blend is miscible.
4. The blend of claim 2 wherein said polymer blend is visually clear.
5. A polymer blend comprising:
(A) about 5% to about 95% by weight of at least one polyester (A) which comprises:
(1) a dicarboxylic acid component comprising:
a) 70 to 100 mole % of terephthalic acid residues;
b) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and
c) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
(2) a glycol component comprising:
a) 15 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
b) 60 to 85 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and
(B) about 95% to about 5% by weight of at least one polymer (B) comprising a copolyestercarbonate of bisphenol A diol, and 0 to 90 mole % isophthalic acid residues, 0 to 60 mole % terephthalic acid residues, and 0 to 60 mole % carbonic acid residues;
wherein said acid percentages of polymer (B) are based on a total of 100 mole % of acid units; and
wherein said weight percentages of polymers in the blend are based on the total weight of the polymer blend.
6. A polymer blend comprising:
(A) about 5% to about 95% by weight of at least one polyester (A) which comprises:
(1) a dicarboxylic acid component comprising:
a) 70 to 100 mole % of terephthalic acid residues;
b) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and
c) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
(2) a glycol component comprising:
a) 20 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
b) 60 to 80 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and
(B) about 95% to about 5% by weight of at least one polymer (B) comprising a copolyestercarbonate of bisphenol A diol, and 35 to 50 mole % isophthalic acid residues, 1 to 10 mole % terephthalic acid residues, and 40 to 60 mole % carbonic acid residues;
wherein said acid percentages of polymer (B) are based on a total of 100 mole % of acid units; and
wherein said weight percentages of polymers in the blend are based on the total weight of the polymer blend.
US13/097,707 2011-01-17 2011-04-29 Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates Abandoned US20120184687A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US201161433337P true 2011-01-17 2011-01-17
US13/097,707 US20120184687A1 (en) 2011-01-17 2011-04-29 Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US13/097,707 US20120184687A1 (en) 2011-01-17 2011-04-29 Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates

Publications (1)

Publication Number Publication Date
US20120184687A1 true US20120184687A1 (en) 2012-07-19

Family

ID=46491242

Family Applications (5)

Application Number Title Priority Date Filing Date
US13/097,707 Abandoned US20120184687A1 (en) 2011-01-17 2011-04-29 Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates
US13/097,701 Expired - Fee Related US8309624B2 (en) 2011-01-17 2011-04-29 Haze reduction for blends of aromatic-aliphatic polyesters and antimicrobial additives
US13/097,722 Abandoned US20120184668A1 (en) 2011-01-17 2011-04-29 Clear Ternary Blends of Polycarbonate with an Aliphatic Polyester and an Aromatic-Aliphatic Polyester
US13/097,696 Active 2031-05-18 US8633262B2 (en) 2011-01-17 2011-04-29 Haze reduction for blends of aromatic-aliphatic polyesters with aliphatic polyesters and antimicrobial additives
US13/097,715 Abandoned US20120184669A1 (en) 2011-01-17 2011-04-29 Miscible Blends Comprising Copolyesters of Aromatic Dicarboxylic Acid With CHDM and Either NPG or TMCD

Family Applications After (4)

Application Number Title Priority Date Filing Date
US13/097,701 Expired - Fee Related US8309624B2 (en) 2011-01-17 2011-04-29 Haze reduction for blends of aromatic-aliphatic polyesters and antimicrobial additives
US13/097,722 Abandoned US20120184668A1 (en) 2011-01-17 2011-04-29 Clear Ternary Blends of Polycarbonate with an Aliphatic Polyester and an Aromatic-Aliphatic Polyester
US13/097,696 Active 2031-05-18 US8633262B2 (en) 2011-01-17 2011-04-29 Haze reduction for blends of aromatic-aliphatic polyesters with aliphatic polyesters and antimicrobial additives
US13/097,715 Abandoned US20120184669A1 (en) 2011-01-17 2011-04-29 Miscible Blends Comprising Copolyesters of Aromatic Dicarboxylic Acid With CHDM and Either NPG or TMCD

Country Status (5)

Country Link
US (5) US20120184687A1 (en)
EP (2) EP2665774B1 (en)
JP (2) JP6027028B2 (en)
CN (2) CN103282435B (en)
WO (2) WO2012099764A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100249293A1 (en) * 2009-03-27 2010-09-30 Eastman Chemical Company Polyester blends
US9273206B2 (en) 2012-07-09 2016-03-01 Eastman Chemical Company Ternary blends of terephthalate or isophthalate polyesters containing EG, CHDM and TMCD
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US9982125B2 (en) 2012-02-16 2018-05-29 Eastman Chemical Company Clear semi-crystalline articles with improved heat resistance

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201429105A (en) * 2013-01-04 2014-07-16 Primax Electronics Ltd Wireless charging transferring device
US9353029B2 (en) 2013-03-14 2016-05-31 Honeywell International, Inc. Fluorination process and reactor
TWI495680B (en) * 2013-11-07 2015-08-11 Ind Tech Res Inst Polyester composition, electronic device, and method of forming film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043322A (en) * 1996-12-28 2000-03-28 Eastman Chemical Company Clear polycarbonate and polyester blends
US20080033088A1 (en) * 2004-11-05 2008-02-07 Eastman Chemical Company Blends of polyesters with modified polycarbonates

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63175117A (en) 1987-01-08 1988-07-19 Hagiwara Giken:Kk Antimicrobial fibrous structural material
US5180585A (en) 1991-08-09 1993-01-19 E. I. Du Pont De Nemours And Company Antimicrobial compositions, process for preparing the same and use
US5372864A (en) 1993-09-03 1994-12-13 Eastman Chemical Company Toners for polyesters
IL110514D0 (en) 1993-10-04 1994-10-21 Eastman Chem Co Concentrates for improving polyester compositions and a method for preparing such compositions
US5480926A (en) 1995-04-28 1996-01-02 Eastman Chemical Company Blends of ultraviolet absorbers and polyesters
US5696176A (en) 1995-09-22 1997-12-09 Eastman Chemical Company Foamable polyester compositions having a low level of unreacted branching agent
US5783307A (en) 1996-11-04 1998-07-21 Eastman Chemical Company UV stabilized multi-layer structures with detectable UV protective layers and a method of detection
US6352783B1 (en) 1999-12-13 2002-03-05 Eastman Kodak Company Copolyester containing 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and an ultraviolet light absorbing compound and articles made therefrom
US20050079372A1 (en) * 2003-10-09 2005-04-14 Schmal Michael D. Polyester films and methods for making the same
GB0414333D0 (en) * 2004-06-25 2004-07-28 Dupont Teijin Films Us Ltd Polymeric film
US8071695B2 (en) * 2004-11-12 2011-12-06 Eastman Chemical Company Polyeste blends with improved stress whitening for film and sheet applications
US7582690B2 (en) * 2004-11-19 2009-09-01 Eastman Chemical Company Stabilized aliphatic polyester compositions
US7955533B2 (en) * 2005-03-02 2011-06-07 Eastman Chemical Company Process for the preparation of transparent shaped articles
US7955674B2 (en) * 2005-03-02 2011-06-07 Eastman Chemical Company Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7906610B2 (en) 2005-06-17 2011-03-15 Eastman Chemical Company Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7425590B2 (en) * 2005-07-12 2008-09-16 Eastman Chemical Company Transparent two phase polyester-polycarbonate compositions
JP4294621B2 (en) * 2005-07-27 2009-07-15 バンドー化学株式会社 Polyester resin sheet
MX2009003369A (en) * 2006-10-27 2009-04-14 Eastman Chem Co Polyester compositions which comprise cyclobutanediol, ethylene glycol, titanium, and phosphorus with improved color and manufacturing processes therefor.
WO2008140705A1 (en) * 2007-05-10 2008-11-20 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
EP1950036A4 (en) * 2005-11-15 2008-11-19 Toray Industries Matte multilayer polyester film
DE102007003662A1 (en) * 2007-01-18 2008-07-24 Rebac Gmbh Antimicrobial polyester molding composition, useful e.g. for producing fibers, films or shaped articles, contains monovalent copper and aromatic, aliphatic and/or cycloaliphatic polyester(s)
JP4978246B2 (en) * 2007-03-09 2012-07-18 三菱エンジニアリングプラスチックス株式会社 Resin composition and a resin molded article
WO2008064750A2 (en) 2007-10-24 2008-06-05 Polytech & Net Gmbh Antimicrobial resin materials and method of manufacturing the same
KR20100087171A (en) * 2007-11-21 2010-08-03 이스트만 케미칼 컴파니 Plastic baby bottles, other blow molded articles, and processes for their manufacture
US20090304762A1 (en) 2008-06-05 2009-12-10 Bayer Materialscience Llc Antimicrobial thermoplastic molding composition
US20100099828A1 (en) * 2008-10-21 2010-04-22 Eastman Chemical Company Clear Binary Blends of Aliphatic Polyesters and Aliphatic-Aromatic Polyesters
US20100159176A1 (en) * 2008-12-18 2010-06-24 Eastman Chemical Company Miscible blends of terephthalate polyesters containing 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethylcyclobutane-1,3-diol
WO2010143317A1 (en) * 2009-06-12 2010-12-16 互応化学工業株式会社 Antibacterial composition, antibacterial polyester fiber, and process for production of antibacterial polyester fiber
JP5498198B2 (en) * 2010-02-23 2014-05-21 日華化学株式会社 Resin antibacterial and resin molding using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043322A (en) * 1996-12-28 2000-03-28 Eastman Chemical Company Clear polycarbonate and polyester blends
US20080033088A1 (en) * 2004-11-05 2008-02-07 Eastman Chemical Company Blends of polyesters with modified polycarbonates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US10017606B2 (en) 2005-11-22 2018-07-10 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US20100249293A1 (en) * 2009-03-27 2010-09-30 Eastman Chemical Company Polyester blends
US9062197B2 (en) 2009-03-27 2015-06-23 Eastman Chemical Company Polyester blends
US9982125B2 (en) 2012-02-16 2018-05-29 Eastman Chemical Company Clear semi-crystalline articles with improved heat resistance
US9273206B2 (en) 2012-07-09 2016-03-01 Eastman Chemical Company Ternary blends of terephthalate or isophthalate polyesters containing EG, CHDM and TMCD

Also Published As

Publication number Publication date
JP2014503032A (en) 2014-02-06
EP2665768B1 (en) 2015-01-07
JP5917564B2 (en) 2016-05-18
CN103314045A (en) 2013-09-18
US8633262B2 (en) 2014-01-21
WO2012099764A1 (en) 2012-07-26
CN103282435A (en) 2013-09-04
WO2012099766A1 (en) 2012-07-26
JP6027028B2 (en) 2016-11-16
US8309624B2 (en) 2012-11-13
US20120184669A1 (en) 2012-07-19
JP2014503031A (en) 2014-02-06
US20120184643A1 (en) 2012-07-19
CN103314045B (en) 2016-02-03
CN103282435B (en) 2016-04-20
US20120184668A1 (en) 2012-07-19
EP2665774A1 (en) 2013-11-27
EP2665774B1 (en) 2014-12-31
US20120184641A1 (en) 2012-07-19
EP2665768A1 (en) 2013-11-27

Similar Documents

Publication Publication Date Title
EP1891138B1 (en) Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
JP2581505B2 (en) The modified polyethylene terephthalate
US3778410A (en) Process for preparing a final copolyester by reacting a starting polyester with an acyloxy aromatic carboxylic acid
US5942585A (en) Polycarbonate and polyester blends
EP1560869B1 (en) Method for making isosorbide containing polyesters
US6011124A (en) Blends of bisphenol a polycarbonate and polyesters
US5510448A (en) Copolyestercarbonate composition derived from dihydricphenol, carbonate precursor and alpha omega-dicarboxylic acid
JP3383311B2 (en) High impact product obtained from polyester blends
US6037424A (en) Clear blends of polycarbonates and polyesters
US5955565A (en) Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol
US4619976A (en) Blends of copolyesters and polycarbonate
US6043322A (en) Clear polycarbonate and polyester blends
CN1931894B (en) Ester-modified dicarboxylate polymers
US6005059A (en) Clear polycarbonate and polyester blends
US9676903B2 (en) Polyester resin and method for preparing the same
US6245844B1 (en) Nucleating agent for polyesters
US20080009574A1 (en) Polyamide-Polyester Polymer Blends and Methods of Making the Same
KR101971677B1 (en) Polyester compositions containing furandicarboxylic acid or an ester thereof and cyclohexanedimethanol
US6723768B2 (en) Polyester/polycarbonate blends with reduced yellowness
EP0879265B1 (en) Polyester/polyesteramide blends
EP2480589B1 (en) Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof
WO1997009366A1 (en) Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties
US6350822B1 (en) Modified polyesters
JP2006514703A (en) Polycarbonate / polyester copolymer blends, as well as a process for their preparation
JP2008518083A (en) New copolyester composition having improved low temperature impact strength

Legal Events

Date Code Title Description
AS Assignment

Owner name: EASTMAN CHEMICAL COMPANY, TENNESSEE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HALE, WESLEY RAYMOND;STACK, GARY MICHAEL;SIGNING DATES FROM 20110506 TO 20110714;REEL/FRAME:026598/0116

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION