[go: up one dir, main page]

WO2025116949A2 - Compositions de copolyester de cyclobutanediol ayant une résistance à la peinture, une résistance chimique et une résistance aux intempéries améliorées - Google Patents

Compositions de copolyester de cyclobutanediol ayant une résistance à la peinture, une résistance chimique et une résistance aux intempéries améliorées Download PDF

Info

Publication number
WO2025116949A2
WO2025116949A2 PCT/US2024/023765 US2024023765W WO2025116949A2 WO 2025116949 A2 WO2025116949 A2 WO 2025116949A2 US 2024023765 W US2024023765 W US 2024023765W WO 2025116949 A2 WO2025116949 A2 WO 2025116949A2
Authority
WO
WIPO (PCT)
Prior art keywords
mole
copolyester composition
copolyester
residues
composition according
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.)
Pending
Application number
PCT/US2024/023765
Other languages
English (en)
Other versions
WO2025116949A3 (fr
Inventor
Thomas Joseph Pecorini
Spencer Allen Gilliam
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
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of WO2025116949A2 publication Critical patent/WO2025116949A2/fr
Publication of WO2025116949A3 publication Critical patent/WO2025116949A3/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to the use of a combination of certain additives in a copolyester to improve the resistance to degradation of certain properties of the copolyester composition after exposure to certain paints, chemicals and/or exposure to sunlight. More specifically, the present invention relates to the use of combinations of certain impact modifiers in copolyesters to improve resistance to degradation of toughness (after exposure to certain paints, chemicals and/or exposure to sunlight), maintain a high heat deflection temperature, and provide good toughness when molded into thick sections.
  • Copolyesters containing cyclobutanediol residues have been commercialized that show outstanding toughness as measured by a notched Izod impact test, a standard method for measuring toughness.
  • these copolyesters can be caused to fail in a brittle manner under certain circumstances, such as when painted with certain paints, when exposed to certain chemicals, after exposure to sunlight, or when molded in thick sections.
  • a copolyester composition that comprises:
  • a diacid component comprising from 70 to 100 mole % residues of terephthalic acid, from 0 to 30 mole % residues of a modifying aromatic diacid having from 8 to 12 carbon atoms, and from 0 to 10 mole % residues of an aliphatic dicarboxylic acid;
  • a glycol component comprising from 45 to 95 mole % cyclohexanedimethanol (CHDM) residues from 5 to 65 mole % 2,2,4,4-tetramethylcyclobutane-1 ,3-diol (TMCD) residues, and from 0 to 10 mole% of a modifying glycol having 2 to 20 carbon atoms; wherein the inherent viscosity of the copolyester is from 0.5 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C, wherein the weight % is based on the weight of the copolyester, and wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the glycol component is 100 mole %; and
  • an impact modifier component that comprises a polymer or combination of polymers, said polymer or polymers comprising ethylene (E), alkyl acrylate (AA) and glycidyl (meth)acrylate (GMA and/or GA) groups wherein the weight ratio of alkyl acrylate to glycidyl (meth)acrylate is from about 3.0:1 to about 9.0:1 ; wherein the copolyester composition has a heat deflection temperature (HDT) of at least 75C; and wherein the copolyester composition has a notched Izod impact strength of 600 Joules/m or greater, or 700 Joules/m or greater, measured according to ASTM D256.
  • an impact modifier component that comprises a polymer or combination of polymers, said polymer or polymers comprising ethylene (E), alkyl acrylate (AA) and glycidyl (meth)acrylate (GMA and/or GA) groups wherein the weight ratio of alkyl acrylate to
  • the ethylene, alkyl acrylate, glycidyl (meth)acrylate containing impact modifier component is present in an amount from 5 to less than 20 wt%, or 5 to 15 wt%, or 5 to 14 wt%, or 5 to 13 wt%, or 5 to 12 wt%, or 5 to 11 wt%, or 5 to 10 wt%, or 5 to 9 wt%, or 5 to 8 wt%, or 5 to 7 wt%, of the copolyester composition.
  • the impact modifier component is present in an amount from 5 to 10 wt%, or 5 to 9 wt%, or 5 to 8 wt%, or 5 to 7 wt%, of the copolyester composition, and the ratio of alkyl acrylate to glycidyl (meth)acrylate in the ethylene, alkyl acrylate, glycidyl (meth)acrylate impact modifier component is from about 3.0:1 to about 9.0:1 , or about 4.0:1 to about 8.0:1 , or about 5.0:1 to about 7.0:1 , or about 3.0:1 to about 6.0:1 .
  • the AA group is a radical formed from a compound having the structure: wherein Ri is an alkyl group with 1 -8 carbon atoms, preferably 1 -4 carbon atoms, more preferably 1 -2 carbon atoms, and most preferably 1 carbon atom, and
  • R 2 is H, CH 3 or C 2 H 5 , preferably H or CH 3 , and most preferably H.
  • the AA group is a radical formed from methyl acrylate.
  • the GMA and/or GA (also designated as "G(M)A”) group is a radical of glycidyl methacrylate (GMA) or glycidyl acrylate (GA).
  • GMA and/or GA group is a radical of glycidyl methacrylate (GMA).
  • the impact modifier comprises a terpolymer of ethylene, alkyl acrylate, and glycidyl methacrylate (E-AA-GMA).
  • the impact modifier is a terpolymer of ethylene, alkyl acrylate, and glycidyl methacrylate (E-AA-GMA).
  • the E-AA-GMA terpolymer is a terpolymer of ethylene, methyl acrylate, and glycidyl methacrylate (E-MA- GMA).
  • the ethylene, alkyl acrylate, glycidyl methacrylate impact modifier component is obtained by blending a terpolymer of ethylene, alkyl acrylate and glycidyl methacrylate (E-AA-GMA) with a copolymer of ethylene and alkyl acrylate (E-AA).
  • E-AA-GMA terpolymer of ethylene, alkyl acrylate and glycidyl methacrylate
  • E-MA-GMA terpolymer of ethylene, methyl acrylate and glycidyl methacrylate
  • the E-AA-GMA terpolymer contains 10 to 40 wt%, or 14 to 34 wt%, or 16 to 32 wt%, or 18 to 30 wt%, or 20 to 28 wt%, or 22 to 26 wt% of alkyl acrylate, e.g., methyl acrylate, content.
  • the E-AA-GMA terpolymer contains 1 to 25 wt%, or 2 to 20 wt%, or 2 to 18 wt%, or 2 to 16 wt%, or 2 to 14 wt%, or 4 to 12 wt%, or 6 to 10 wt%, glycidyl methacrylate content.
  • the E-AA copolymer contains 10 to 40 wt%, or 14 to 34 wt%, or 16 to 32 wt%, or 18 to 30 wt%, or 20 to 28 wt%, or 22 to 26 wt% of alkyl acrylate, e.g., methyl acrylate, content.
  • the ethylene, alkyl acrylate, glycidyl methacrylate impact modifier component is present in an amount from 5 to 10 wt%, or 5 to 9 wt%, or 5 to 8 wt%, or 5 to 7 wt%, of the copolyester composition, and the weight ratio of E-AA-GMA terpolymer to E-AA copolymer is 0.7 to 2.0:1 , or 0.7 to 1.5:1 , or 0.7 to 1.1 :1 , or 0.8 to 2.0:1 , or 0.8 to 1 .5:1 , or 0.8 to 1.1 :1 , or 0.9 to 2.0:1 , or 0.9 to 1 .5:1 , or 0.9 to 1 .1 :1 .
  • the impact modifier component does not contain a core shell impact modifier.
  • the copolyester composition does contain a core shell impact modifier.
  • the glycol component comprises from 60 to 95 mole % cyclohexanedimethanol residues and from 5 to 40 mole % of 2, 2,4,4- tetramethylcyclobutane-1 ,3-diol residues. In certain embodiments, the glycol component comprises from 70 to 95 mole % cyclohexanedimethanol residues and from 5 to 30, or 10 to 30, or 15 to 30, or 20 to 30, or 15 to 25 mole % of 2,2,4,4-tetramethylcyclobutane-1 ,3-diol residues.
  • the inherent viscosity of the copolyester is from 0.55 to 0.85, or 0.55 to 0.65, or 0.60 to 0.70, or 0.65 to 0.80, or 0.65 to 0.75 dL/g.
  • the copolyester composition further comprises a chain extender.
  • the chain extender comprises a multifunctional epoxide chain extender.
  • the copolyester composition has a notched Izod impact strength of at least 700, or 725, or 750, or 775, or 800, or 825, or 850 Joules/m or greater measured according to ASTM D256. In one embodiment, the copolyester composition exhibits 100% ductile behavior when tested according to ASTM D256.
  • the copolyester composition has a notched Charpy impact strength of 400, or 500, or 600 Joules/m or greater measured using a 1 /z” thick bar according to ASTM D61 10.
  • the copolyester composition has a notched charpy impact strength of 400, or 500, or 600 Joules/m or greater using a W thick bar aged in an oven for 72 hours at 80C measured according to ASTM D61 10.
  • an article that comprises a copolyester composition according to one or more of the embodiments, or a combination of any of the embodiments, described herein.
  • the article is in the form of a film, sheet, molded part, or profile.
  • the present invention provides a copolyester composition that comprises a cyclobutanediol copolyester and an impact modifier component that comprises a polymer or combination of polymers, the polymer or polymers comprising ethylene, alkyl acrylate, e.g., methyl acrylate, and glycidyl (meth)acrylate, in which the copolyester composition exhibits resistance to degradation of certain properties of the copolyester composition after exposure to certain paints, chemicals, sunlight, or when molded in thick sections.
  • the resistance to degradation of certain properties of the copolyester composition is resistance to embrittlement, or where the copolyester composition maintains toughness (or impact resistance) after exposure to the certain chemicals or sunlight.
  • the copolyester composition has a heat deflection temperature (HDT) of at least 75C, using a 3.2mm thick injection molded bar and a 1 .8 MPa applied stress.
  • the copolyester composition has a notched Izod impact strength of 600 Joules/m or greater, or 700 Joules/m or greater, measured according to ASTM D256.
  • the invention is directed to copolyester compositions having a combination of good toughness, relatively high HDT, good flow during molding (i.e., a viscosity that permits good flow during molding, e.g., in thin molds), and that resist or avoid embrittlement after exposure to certain chemicals, e.g., acrylic paint or canola oil, or UV light (or sunlight), articles made therefrom, and methods of making the compositions and articles.
  • certain chemicals e.g., acrylic paint or canola oil, or UV light (or sunlight
  • the present invention involves the use of certain classes of impact modifiers to improve or retain good impact properties while avoiding embrittlement after exposure to certain chemicals, e.g., acrylic paint or canola oil, or UV light (or sunlight).
  • the impact modifier component comprises a polymer or polymers comprising ethylene, alkyl acrylate and glycidyl (meth)acrylate.
  • the copolyester composition possesses a notched Izod impact strength which is greater than about 600 Joules/m, or 650, or 700, or 750, or 800, or 850 Joules/m or greater, according to ASTM D256 while avoiding embrittlement after exposure to certain chemicals or UV light.
  • the copolyester composition contains the impact modifier component in an amount from 5 to 20, or 5 to 15, or 5 to 10 wt%, based on the total weight of the copolyester composition.
  • the weight ratio of alkyl acrylate to glycidyl (meth)acrylate, or AA:G(M)A, in the ethylene, alkyl acrylate, glycidyl (meth)acrylate impact modifier component is in a range from about 2.0:1 to about 10.0:1 , or from about 2.0:1 to about 9.0:1 , or from about 2.0:1 to about 8.0:1 , or from about 2.0:1 to about 7.0:1 , or from about 2.0:1 to about 6.0:1 , or from about 3.0:1 to about 10.0:1 , or from about 3.0:1 to about 9.0:1 , or from about 3.0:1 to about 8.0:1 , or from about 3.0:1 to about 7.0:1 , or from about 3.0:1 to about 6.0:1 , or from about 4.0:1 to about 10.0:1 , or from about 4.0:1 to about 9.0:1 , or from about 4.0:1 to about 10.0:1
  • the weight ratio of alkyl acrylate to glycidyl (meth)acrylate, or AA:G(M)A, in the ethylene, alkyl acrylate, glycidyl (meth)acrylate impact modifier component is in a range from about 2.0:1 to about 10.0:1 , or from about 3.0:1 to about 9.0:1 , or from about 3.0:1 to about 6.0:1.
  • the impact modifier component comprises ethylene, methyl acrylate, glycidyl methacrylate and the weight ratio of methyl acrylate to glycidyl methacrylate (MA:GMA) is in a range from about 2.0:1 to about 10.0:1 , or from about 3.0:1 to about 9.0:1 , or from about 3.0:1 to about 6.0:1 .
  • the ethylene, alkyl acrylate, glycidyl methacrylate impact modifier component is obtained by blending a terpolymer of ethylene, alkyl acrylate and glycidyl methacrylate (E-AA-GMA) with a copolymer of ethylene and methyl acrylate (E-AA).
  • the E-AA-G(M)A and E-AA can be present in a weight ratio of E-AA-G(M)A:E-AA in a range from 0.1 to 2.5:1 , or 0.2 to 2.5:1 , or 0.3 to 2.5:1 , or 0.4 to 2.5:1 , or 0.5 to 2.5:1 , or 0.6 to 2.5:1 , or 0.7 to 2.5:1 , or 0.8 to 2.5:1 , or 0.9 to 2.5:1 , or 1 to 2.5:1 , or 0.1 to 2:1 , or 0.2 to 2:1 , or 0.3 to 2:1 , or 0.4 to 2:1 , or 0.5 to 2:1 , or 0.6 to 2:1 , or 0.7 to 2:1 , or 0.8 to 2:1 , or 0.9 to 2:1 , or 1 to 2:1 , or 0.1 to 1 .5:1 , or 0.2 to 1 .5:1 , or 0.3 to 1 .5:1 , or 0.4 to 1.5:1 , or 0.5 to
  • the copolyester composition contains terpolymer of E-AA-G(M)A and copolymer of E-AA in a combined amount from 5 to 8 wt%, based on the total weight of the copolyester composition, and the E-AA-G(M)A and E-AA can be present in a weight ratio of E-AA-G(M)A:E-AA in a range from 0.5 to 2.5:1 , or 0.6 to 2.5:1 , or 0.7 to 2.5:1 , or 0.8 to 2.5:1 , or 0.9 to 2.5:1 , or 1 to 2.5:1 , or 0.5 to 2:1 , or 0.6 to 2:1 , or 0.7 to 2:1 , or 0.8 to 2:1 , or 0.9 to 2:1 , or 1 to 2:1 , or 0.5 to 1 .5:1 , or 0.6 to 1 .5:1 , or 0.7 to 1 .5:1 , or 0.8 to 1 .5:1 , or
  • the copolyester composition comprises the impact modifier component in amounts sufficient to provide compositions that reduce or avoid embrittlement after exposure to certain chemicals or UV light.
  • the copolyester compositions pass the impact tests after exposure to acylic enamel paint and/or canola oil, when tested as described below in the Examples section, with three replicates showing no breaking.
  • the copolyester compositions have an impact resistance of at least 40, or at least 45, or at least 50, or at least 55, or at least 60 kJ/m2 after exposure to a Xenon Arc for 168 hrs according to ASTM D6395, as described more fully below in the Examples section.
  • the alkyl acrylate can comprise an alkyl group with 1 -8 carbon atoms, preferably 1 -4 carbon atoms, more preferably 1 to 2 carbon atoms, and most preferably 1 carbon atom.
  • the alkyl acrylate can comprise methyl acrylate, ethyl acrylate or butyl acrylate.
  • the alkyl acrylate is methyl acrylate.
  • the copolyester composition has an HDT of at least 75°C, or at least 77°C or at least 79°C, determined according to ASTM D648 using a 3.2mm thick injection molded bar and a 1 .82 MPa applied stress.
  • the copolyester composition has a viscosity of less than 4000, or less than 3950, or less than 3900, or less than 3875, or less than 3850 poise, measured at 280C according to ASTM D4440 using a Rheometrics Dynamic Analyzer (RDA II) using parallel plate at a shear rate of 400 rad/s.
  • RDA II Rheometrics Dynamic Analyzer
  • the copolyester composition has a viscosity in a range from 3000 to 4000, or 3000 to 3950, or 3000 to 3900, or 3000 to 3875, or 3000 to 3850, or 3100 to 4000, or 3100 to 3950, or 3100 to 3900, or 3100 to 3875, or 3100 to 3850, or 3200 to 4000, or 3200 to 3950, or 3200 to 3900, or 3200 to 3875, or 3200 to 3850, or 3300 to 4000, or 3300 to 3950, or 3300 to 3900, or 3300 to 3875, or 3300 to 3850, or 3400 to 4000, or 3400 to 3950, or 3400 to 3900, or 3400 to 3875, or 3400 to 3850, or 3500 to 4000, or 3500 to 3950, or 3500 to 3900, or 3500 to 3875, or 3500 to 3850 poise, measured at 280C according to ASTM D4440 using a Rheometrics Dynamic
  • the copolyester composition has a flexural modulus of at least 1250, or at least 1300, or at least 1350, or at least 1400, or at least 1450 MPa, measured according to ASTM D790 Procedure A at a crosshead movement speed of 1.27 mm/minute using a 3.2mm thick injection molded bar conditioned for 48 hrs at 23C and 50%RH prior to testing.
  • the copolyester composition has a flexural modulus in a range from 1250 to 1600, or 1250 to 1550, or 1300 to 1600, or 1300 to 1550, or 1350 to 1600, or 1350 to 1550, or 1400 to 1600, or 1400 to 1550, or 1450 to 1600, or 1400 to 1550 MPa, measured according to ASTM D790 Procedure A at a crosshead movement speed of 1.27 mm/minute using a 3.2mm thick injection molded bar conditioned for 48 hrs at 23C and 50%RH prior to testing.
  • the copolyester composition has a notched Izod impact strength of at least 700, or 725, or 750, or 775, or 800, or 825, or 850 Joules/m or greater measured according to ASTM D256 Test Method A using a 3.2mm thick injection molded bar, machine notched with a 0.25mm radius notch and then conditioned for 48 hrs at 23C and 50%RH after notching and prior to testing, and per the ASTM method, the hammer weight was 2.7 Joules or 13.6 Joules, depending on the inherent brittleness of the sample.
  • the copolyester composition has a notched Izod impact strength in a range from 700 to 1000, or 700 to 950, or 700 to 900, or 725 to 1000, or 725 to 950, or 725 to 900, or 750 to 1000, or 750 to 950, or 750 to 900, or 775 to 1000, or 775 to 950, or 775 to 900, or 800 to 1000, or 800 to 950, or 800 to 900, or 825 to 1000, or 825 to 950, or 825 to 900, or 850 to 1000, or 850 to 950, or 850 to 900 Joules/m measured according to ASTM D256 Test Method A using a 3.2mm thick injection molded bar, machine notched with a 0.25mm radius notch and then conditioned for 48 hrs at 23C and 50%RH after notching and prior to testing, and per the ASTM method, the hammer weight was 2.7 Joules or 13.6 Joules, depending on the inherent bri
  • the copolyester composition has a Charpy impact strength of at least 400, or at least 450, or at least 500, or at least 550, or at least 600, or at least 650 J/m, measured according to ASTM D6110 using a 12.7mm thick injection molded bar cut down to 63mm in length and machine notched with either a 0.10mm or 0.25mm radius notch conditioned for 48 hrs at 23C and 50%RH after notching and prior to testing, using a span of 51 mm and a hammer weight of 15 Joules.
  • the copolyester composition has a Charpy impact strength in a range of 400 to 800, or 400 to 750, or 450 to 800, or 450 to 750, or 500 to 800, or 500 to 750, or 550 to 800, or 550 to 750, or 600 to 800, or 600 to 750, or 625 to 800, or 625 to 750, or 650 to 800, or 650 to 750 J/m, measured according to ASTM D6110 using a 12.7mm thick injection molded bar cut down to 63mm in length and machine notched with either a 0.10mm or 0.25mm radius notch conditioned for 72 hrs at 80C and 50%RH after notching and prior to testing, using a span of 51 mm and a hammer weight of 15 Joules.
  • the E-MA-GMA terpolymer has a methyl acrylate (MA) content in a range from 14 to 34, or 16 to 32, or 18 to 30, or 20 to 28, or 22 to 26, or 23 to 25 wt%, measured by FTIR, based on the weight of the E-MA-GMA terpolymer.
  • the E-MA-GMA terpolymer has a glycidal methacrylate (GMA) content in a range from 2 to 14, or 2 to 6, or 4 to 12, or 6 to 10, or 7 to 9 wt%, measured by FTIR, based on the weight of the E- MA-GMA terpolymer.
  • the E-BA-GMA terpolymer has a butyl acrylate (BA) content in a range from 14 to 34, or 16 to 32, or 18 to 30, or 20 to 28, or 22 to 26, or 23 to 25 wt%, measured by FTIR, based on the weight of the E- BA-GMA terpolymer.
  • the E-BA-GMA terpolymer has a glycidal methacrylate (GMA) content in a range from 2 to 14, or 2 to 6, or 4 to 12, or 6 to 10, or 7 to 9 wt%, measured by FTIR, based on the weight of the E-BA-GMA terpolymer.
  • the E-MA copolymer has a methyl acrylate (MA) content in a range from 14 to 34, or 16 to 32, or 18 to 30, or 20 to 28, or 22 to 26, or 23 to 25 wt%, measured by FTIR, based on the weight of the E-MA copolymer.
  • MA methyl acrylate
  • the E-MA copolymer can be a commercially available product, such as LOTRYL® 24MA07T or 24MA02T or 24MA02 or 24MA005 or 20MA08 or 18MA02 or 29MA03T or 29MA03 or 28MA07 (from SK Corporation).
  • the E-BA copolymer can be a commercially available product, such as LOTRYL® 28BA175 or 28BA175T or 30BA02 or 35BA40 (from SK Corporation).
  • the impact modifier component comprises at least one additional impact modifier.
  • additional impact modifiers that can be included in the impact modifier component, in certain embodiments, include, core-shell polymers with cores comprised of rubbery polymers and shells comprised of styrene copolymers.
  • Examples of additional impact modifiers that can be used include, but are not limited to, ethylene/propylene terpolymers; 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.
  • Modiper® 4300 and Modiper® 4400 available from Nippon Oil & Fat Corporation; Kane Ace® M300, available from Kaneka Americas Holding, Inc.; Kane Ace® B564, available from Kaneka Americas Holding, Inc.; Kane Ace® ECO 1000, available from Kaneka Americas Holding, Inc.
  • Copolyesters useful in the present invention comprise residues of an aromatic diacid and residues of two or more glycols.
  • copolyester is intended to include “polyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds.
  • the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols.
  • diacid or “dicarboxylic acid” include multifunctional acids, such as branching agents.
  • glycol as used in this application includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds.
  • the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid
  • the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone.
  • reduce as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer.
  • the term “repeating unit,” as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group.
  • the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
  • dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester.
  • terephthalic acid is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
  • modifying aromatic diacid means an aromatic dicarboxylic acid other than terephthalic acid.
  • modifying glycol means a glycol other than cyclohexanedimethanol (CHDM) or 2, 2,4,4- tetramethylcyclobutane-1 ,3-diol (TMCD).
  • terephthalic acid may be used as the starting material.
  • dimethyl terephthalate may be used as the starting material.
  • mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or as an intermediate material.
  • the copolyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the copolyester polymer as their corresponding residues.
  • the copolyesters of the present invention therefore, can contain substantially equal molar proportions of acid residues (100 mole%) and diol (and/or multifunctional hydroxyl compounds) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%.
  • the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
  • a copolyester containing 30 mole% isophthalic acid means the copolyester contains 30 mole% isophthalic acid residues out of a total of 100 mole% acid residues. Thus, there are 30 moles of isophthalic acid residues among every 100 moles of acid residues.
  • a copolyester containing 30 mole% 1 ,4- cyclohexanedimethanol means the copolyester contains 30 mole% 1 ,4-cyclohexanedimethanol residues out of a total of 100 mole% diol residues. Thus, there are 30 moles of 1 ,4- cyclohexanedimethanol residues among every 100 moles of diol residues.
  • the copolyesters comprise 70 to 100 mole% of terephthalic acid (TPA).
  • the copolyesters comprise 80 to 100 mole% TPA, or 90 to 100 mole % TPA or 95 to 100 mole % TPA or 100 mole % TPA.
  • terephthalic acid and “dimethyl terephthalate” are used interchangeably herein.
  • the dicarboxylic acid component of the copolyester useful in the invention can comprise up to 30 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole %, or up to 1 mole % of one or more modifying aromatic dicarboxylic acids.
  • Yet another embodiment contains 0 mole % modifying aromatic dicarboxylic acids.
  • modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 30 mole %, 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole.
  • modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para-oriented, or symmetrical.
  • modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1 ,4-, 1 ,5-, 2,6-, 2,7- naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and esters thereof.
  • the modifying aromatic dicarboxylic acid is isophthalic acid.
  • the carboxylic acid component of the copolyesters useful in the invention can be further modified with up to 10 mole %, such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids. Certain embodiments can also comprise 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying aliphatic dicarboxylic acids.
  • Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids.
  • the amount of one or more modifying aliphatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 10 mole % and from 0.1 to 10 mole %.
  • the total mole % of the dicarboxylic acid component is 100 mole%.
  • esters of terephthalic acid and the other modifying dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids.
  • Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters.
  • the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
  • the copolyesters useful in the copolyesters compositions of the invention can comprise from 0 to 10 mole %, for example, from 0.01 to 5 mole %, from 0.01 to 1 mole %, from 0.05 to 5 mole %, from 0.05 to 1 mole %, or from 0.1 to 0.7 mole %, based the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
  • the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polyester.
  • the copolyester(s) useful in the invention can thus be linear or branched.
  • branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
  • multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
  • the polyester composition comprises at least one polyester, which comprises:
  • 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
  • the glycol component for the polyesters can include but is not limited to at least one of the following combinations of ranges: 5 to less than 55 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and greater than 45 up to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to less than 50 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and greater than 50 up to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to less than 45 mole % 2, 2,4,4- tetramethyl-1 ,3-cyclobutanediol and greater than 55 up to 95 mole % 1 ,4- cyclohexanedimethanol; 5 to less than 40 mole % 2, 2, 4, 4-tetramethyl-1 ,3- cyclobutanediol and greater than 60 up to 95 mole % 1
  • the glycol component of the polyester portion of the polyester composition can contain 25 mole % or less of one or more modifying glycols which are not 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol or 1 ,4-cyclohexanedimethanol; in one embodiment, the polyesters useful in the invention may contain less than 15 mole % of one or more modifying glycols. In another embodiment, the polyesters can contain 10 mole % or less of one or more modifying glycols. In another embodiment, the polyesters can contain 5 mole % or less of one or more modifying glycols. In another embodiment, the polyesters can contain 3 mole % or less of one or more modifying glycols.
  • the mole % of the isomers of 2, 2,4,4- tetramethyl-1 ,3-cyclobutanediol in certain polyesters is from 30 to 70 mole % of cis-2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol or from 30 to 70 mole % of trans-
  • 2.2.4.4-tetramethyl-1 ,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1 ,3- cyclobutanediol is equal to a total of 100 mole %.
  • the polyesters can be amorphous or semi-crystalline. In one aspect, certain polyesters can have a relatively low crystallinity. Certain polyesters can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • the Tg of the polyesters can be at least one of the following ranges: 100 to 200° C.; 100 to 190° C.; 100 to 180° C.; 100 to 170° C.; 100 to 160° C.; 100 to 155° C.; 100 to 150° C.; 100 to 145° C.; 100 to
  • the glass transition temperature (Tg) of the polyesters can be determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20° C./min.
  • the polyesters can have an HDT in at least one of the following ranges: 70 to 120° C.; 70 to 110° C.; 70 to 100° C.; 70 to 95° C.; 70 to 90° C.; 72 to 120° C.; 72 to 110° C.; 72 to 100° C.; 72 to 95° C.; 72 to 90° C.; 75 to 120° C.; 75 to 110° C.; 75 to 100° C.; 75 to 95° C.; 75 to 90° C.; 76 to 120° C.; 76 to 110° C.; 76 to 100° C.; 76 to 95° C.; 76 to 90° C.; 77 to 120° C.; 77 to 110° C.; 77 to 100° C.; 77 to 95° C.; 77 to 90° C.; 78 to 120° C.; 78 to 110° C.; 78 to 100° C.; 78 to 95° C.; 78 to 90° C.; 79 to 120
  • the polyesters may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.: 0.10 to 1 .2 dL/g; 0.10 to 1 .1 dL/g; 0.10 to 1 dL/g; 0.10 to less than 1 dL/g; 0.10 to 0.98 dL/g; 0.10 to 0.95 dL/g; 0.10 to 0.90 dL/g; 0.10 to 0.85 dL/g; 0.10 to 0.80 dL/g; 0.10 to 0.75 dL/g; 0.10 to less than 0.75 dL/g; 0.10 to 0.72 dL/g; 0.10 to 0.70 dL/g; 0.10 to less than 0.70 dL/g; 0.10 to 0.68 dL/g; 0.10 to less than 0.68 dL/g
  • the polyesters may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 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; 0.45 to 1 .2 d
  • the polyester compositions can possess at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that the polyester compositions can possess at least one of the Tg ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that the polyester compositions can possess at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
  • the molar ratio of cis/trans 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol can vary from the pure form of each or 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% trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30% cis or 50 to 70 mole % cis and 50 to 30% 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
  • polyester portion of the polyester compositions can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include those disclosed in U.S. Published Application 2006/0287484, the contents of which is incorporated herein by reference.
  • the polyester can be prepared by a method that includes reacting one or more dicarboxylic acids (or derivative thereof) with one or more glycols under conditions to provide the polyester including, but are not limited to, the steps of reacting one or more dicarboxylic acids (or derivative thereof) with one or more glycols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
  • the polyester composition can be a polymer blend, wherein the blend comprises: (a) 5 to 95 wt % of at least one of the polyesters described herein; and (b) 5 to 95 wt % of at least one additional polymer component.
  • polymer components include, but are not limited to, nylon, polyesters different from those described herein, e.g., polyethylene or polybutylene terephthalate (PET or PBT), polyamides such as ZYTEL® from DuPont; polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers such as GP-35 ABS (from Ineos-Styrolution), 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);
  • the blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
  • the polycarbonate is not present in the polyester composition.
  • the polyester compositions useful in the invention also contemplate the exclusion of polycarbonate as well as the inclusion of polycarbonate.
  • the additional polymer component is present in an amount 5 to 25, or 5 to 20, or 5 to 15, or 5 to 10 wt%, based on the total weight of the polyester composition.
  • the copolyester composition may further comprise one or more additional additives chosen from colorants, dyes, mold release agents, flame retardants, plasticizers, processing aids, rheology modifiers, nucleating agents, antioxidants, light stabilizers, fillers, and reinforcing materials.
  • the polyester compositions and the polymer blend compositions may also contain (in addition to the component described herein) 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 other impact modifiers.
  • UV additives can be incorporated into the articles (e.g., ophthalmic product(s)) through addition to the bulk or in the hard coat.
  • the polyester compositions and the polymer blend compositions may contain fillers or reinforcing additives, such as glass (or other) fibers, in an amount from 1 to 45 wt%, or 1 to 40 wt%, or 1 to 35 wt%, or 1 to 30 wt%, or 5 to 45 wt%, or 5 to 40 wt%, or 5 to 35 wt%, or 5 to 30 wt%, or 10 to 45 wt%, or 10 to 40 wt%, or 10 to 35 wt%, or 10 to 30 wt%, or 15 to 45 wt%, or 15 to 40 wt%, or 15 to 35 wt%, or 15 to 30 wt%, or 20 to 45 wt%, or 20 to 40 wt%, or 20 to 35 wt%, or 20 to 30 wt%, based on the total composition.
  • fillers or reinforcing additives such as glass (or other) fibers
  • the polyester compositions and the polymer blend compositions may also contain (in addition to the components described herein and the fillers/reinforcing additives) from 0.01 to 25%, or 0.01 to 20%, or 0.01 to 15%, or 0.01 to 10% by weight of the overall composition other common additives, such as those discussed above.
  • the polyester compositions and the polymer blend compositions may also contain (in addition to the components described herein and the colorants) from 0.01 to 25%, or 0.01 to 20%, or 0.01 to 15%, or 0.01 to 10% by weight of the overall composition other common additives, such as those discussed above.
  • the polyester compositions and the polymer blend compositions may contain one or more antioxidants in an amount from 0.01 to 2 wt%, or 0.01 to 1 .5 wt%, or 0.01 to 1 wt%, or 0.01 to 0.75 wt%, or 0.01 to 0.5 wt%, or 0.01 to 0.4 wt%, or 0.01 to 0.3 wt%, based on the total composition.
  • antioxidants can include Irganox 1010, Irgafos 168, or combinations thereof.
  • the copolyester compositions of the present invention comprise a copolyester composition comprising any of the copolyesters described above and the impact modifier component.
  • the polyesters can comprise at least one chain extender.
  • Suitable chain extenders include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example, epoxylated novolacs, and phenoxy resins.
  • chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extenders can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion.
  • the amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired but is generally from 0.1 percent by weight to 10 percent by weight, such as from 0.1 to 5 percent by weight, based on the total weigh of the polyester.
  • Thermal stabilizers are compounds that stabilize polyesters during polyester manufacture and/or post polymerization, including, but not limited to, phosphorous compounds, including, but not limited to, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof.
  • the esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl.
  • the number of ester groups present in the particular phosphorous compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the thermal stabilizer used.
  • the term “thermal stabilizer” is intended to include the reaction product(s) thereof.
  • reaction product refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive. In embodiments, these can be present in the polyester compositions.
  • reinforcing materials may be useful in the polyester compositions.
  • 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 are glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • the invention relates to copolyester compositions comprising a copolyester produced by a process comprising:
  • step (II) heating the initial copolyester of step (I) at a temperature of 240 to 320°C for 1 to 4 hours;
  • Suitable catalysts for use in this process include, but are not limited to, organo-zinc or tin compounds.
  • organo-zinc or tin compounds include, but are not limited to, organo-zinc or tin compounds.
  • the use of this type of catalyst is well known in the art.
  • Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide.
  • Other catalysts may include, but are not limited to, those based on titanium, zinc, manganese, lithium, germanium, and cobalt.
  • Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to 10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 based on the catalyst metal and based on the weight of the final polymer.
  • the process can be carried out in either a batch or continuous process.
  • step (I) can be carried out until 50% by weight or more of the glycol has been reacted.
  • Step (I) may be carried out under pressure, ranging from atmospheric pressure to 100 psig.
  • reaction product as used in connection with any of the catalysts useful in the invention refers to any product of a polycondensation or esterification reaction with the catalyst and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
  • step (II) and step (III) can be conducted at the same time. These steps can be carried out by methods known in the art such as by placing the reaction mixture under a pressure ranging from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
  • the impact modifier component can be incorporated into the copolyester in a concentrate form by any conventional method for ultimate formation into an article.
  • the impact modifiers can be incorporated in a plastics compounding line such as a twin-screw compounding line to form a copolyester composition concentrate.
  • the pellets are then fed into the throat of the extruder and melted from 430°F to 520°F (221°C to 271 °C) to produce a viscous thermoplastic material.
  • the impact modifiers added together with a loss-in-weight feeder or added singly in a loss-in-weight feeder.
  • the rotation of the two screws disperses the impact modifiers into the copolyester.
  • the mixture is then extruded through a die to produce multiple strands.
  • the strands are fed through a water trough to cool the pellets.
  • the strands Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the impact modifiers can be incorporated into a plastics compounding line such as a two-rotor continuous compounding mixer (such as a Farrell Continuous Mixer) to form a copolyester composition concentrate.
  • a plastics compounding line such as a two-rotor continuous compounding mixer (such as a Farrell Continuous Mixer) to form a copolyester composition concentrate.
  • copolyester pellets are dried for 4 to 6 hours at 150°F to 190°F (65.6°C to 87.8°C) to reduce moisture.
  • the copolyester pellets and the impact modifers are fed into the throat of the continuous mixer and melted into a homogenous mixture at 430°F to 520°F (221 °C to 271 ° C).
  • the output rate of the mixer is controlled by varying the area of a discharge orifice.
  • the melt can be sliced off into ‘loaves’ and fed to a two-roll mill or the throat of a single screw extruder.
  • the melt covers one of the rolls to form a sheet of the concentrate which is cut into strips which are fed to the throat of a single screw extruder.
  • the mixture is then extruded through a die to produce multiple strands.
  • the strands are fed through a water trough to cool the pellets. Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the mixture is extruded through a die to produce multiple strands.
  • the strands can be fed through a water trough to cool the pellets. Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the impact modifiers can be incorporated in a high- intensity mixer such a Banbury® batch type mixer to form a copolyester composition concentrate.
  • the copolyester pellets can be dried for 4 to 6 hours at 150°F to 190°F (65.6°C to 87.8°C) to reduce moisture.
  • the copolyester pellets and the impact modifiers are charged into a high-intensity mixer and a ram lowered to compress the pellet/impact modifiers mixture into the mixing chamber. Two rotating mixer blades melt the pellets and disperse the impact modifiers into the melt. When the desired temperature is reached, a door is opened in the bottom of the mixer and the mixture is dropped onto a two-roll mill.
  • a ribbon from the two-roll mill can then be fed to a single screw extruder.
  • the mixture is then extruded through a die to produce multiple strands.
  • the strands can be fed through a water trough to cool the pellets. Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the present invention includes plastic articles comprising the copolyester compositions.
  • the plastic articles may be made by processes comprising, but not limited to, extrusion of the copolyester composition to produce a continuous flat sheet or profile or injection molding to create discrete articles or calendering to produce a continuous film or sheet or additive manufacturing of a powder or filament to produce a three-dimensional shape.
  • Films and/or sheets useful in the present invention can be of any thickness which would be apparent to one of ordinary skill in the art.
  • the films(s) of the invention have a thickness of less than 30 mils or less than 20 mils or less than 10 mils or less than 5 mils.
  • the sheets of the invention have a thickness of greater than 30 mils.
  • the sheets of the invention have a thickness of from 30 mils to 100 mils or from 30 mils to 200 mils or from 30 mils to 500 mils.
  • the invention further relates to the films and/or sheets comprising the polyester compositions of the invention.
  • the methods of forming the polyesters into films and/or sheets are well known in the art.
  • films and/or sheets of the invention include, but are not limited to, extruded films and/or sheets, calendered films and/or sheets, compression molded films and/or sheets, injection molded films or sheets, and solution casted films and/or sheets.
  • Methods of making film and/or sheet include but are not limited to extrusion, calendering, extrusion molding, compression molding, and solution casting. These films or sheets may be made or subjected to further processing such as orientation (uniaxial or biaxial), heat setting, surface treatment, etc.
  • the invention comprises a flat sheet or profile.
  • the sheet or profile is prepared by extruding the copolyester composition to produce a flat sheet or profile.
  • pellets of the copolyester composition are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours and are then fed to either a single screw extruder, a twin-screw extruder, or a conical twin screw extruder.
  • the copolyester composition pellets are conveyed and compressed by the screw(s) down the extruder barrel to melt the pellets and discharge the melt from the end of the extruder.
  • the melt is fed through a screening device to remove debris and/or a melt pump to reduce pressure variations caused by the extruder.
  • the melt is then fed through a die to create a continuous flat sheet or into a profile die to create a continuous shape.
  • the melt is extruded onto a series of metal rolls, typically three, to cool the melt and impart a finish onto the sheet.
  • the flat sheet is then conveyed in a continuous sheet for a distance or period of time sufficient to cool the sheet.
  • the sheet is then trimmed to the desired width and then either rolled up into a roll or sheared or sawed into sheet form of desired dimensions.
  • a flat sheet can also be formed into a shaped article through mechanical means to form a desired shaped article and then cooled either by spraying with water, by conveying through a water trough or by blowing air on the shaped article. The article then sawed or sheared to the desired length.
  • the die In the case of a profile die, the die is designed to produce the desired shape of the profile. After exiting the die, the profile is then cooled either by spraying with water, by conveying through a water trough or by blowing air on the profile. The profile is then sawed or sheared to the desired length.
  • the fiber can be pulled out of the extrusion die spinnerets to the desired fiber diameter and crystallized for physical property enhancement.
  • Another embodiment of the invention comprises mixing neat copolyester pellets with a concentrate of impact modifiers and then extruding the copolyester composition.
  • the impact modifier concentrate can be compounded as a pellet.
  • the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours before extrusion.
  • the pellets are dried after being blended in a low-intensity mixer such as a ribbon blender, a tumbler, or conical screw blender.
  • the pellets are then fed to an extruder including, but not limited to, a single screw extruder, a twin-screw extruder, or a conical twin screw extruder.
  • the pellets are conveyed and compressed by the screw(s) down the extruder barrel to melt the pellets and discharge the melt from the end of the extruder.
  • the melt is typically fed through a screening device to remove debris and/or a melt pump to reduce pressure variations caused by the extruder.
  • the melt is then fed through a die to create a continuous flat sheet or into a profile die to create a continuous shape.
  • the melt is extruded onto a series of metal rolls, typically three, to cool the melt and impart a finish onto the sheet.
  • the flat sheet is then conveyed in a continuous sheet for a distance or period of time sufficient to cool the sheet.
  • a flat sheet can also be formed into a shape through mechanical means to form a desired shape and then cooled either by spraying with water, through a water trough or by blowing air on the shaped article. It can then be sawed or sheared to the desired length.
  • the film may be produced and wound into a roll.
  • the die is designed to produce the desired shape of the article. After exiting the die, the profile can then be cooled either by spraying with water, through a water trough or by blowing air on the profile. It can then be sawed or sheared to the desired length.
  • the fiber In the case of a fiber, the fiber can be pulled out of the extrusion die spinnerets to the desired fiber diameter and crystallized for physical property enhancement.
  • the pellets are conveyed and compressed by the screw(s) down the extruder barrel to melt the pellets and discharge the melt from the end of the extruder.
  • the melt can be fed through a screening device to remove debris and/or a melt pump to reduce pressure variations caused by the extruder.
  • the melt can then be fed through a die to create a continuous flat sheet or into a profile die to create a continuous shape.
  • the melt is extruded onto a series of metal rolls, typically three, to cool the melt and impart a finish onto the sheet.
  • the flat sheet is then conveyed in a continuous sheet to cool the sheet. It can then be trimmed to the desired width and then either rolled up into a roll or sheared or sawed into sheet form.
  • the fiber can be pulled out of the extrusion die spinnerets to the desired fiber diameter and crystallized for physical property enhancement.
  • Another embodiment can comprise extruding fully compounded pellets of the copolyester composition, comprising the copolyester and impact modifiers, to produce an injection molded article.
  • the pellets are dried at 150° F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours to dry the pellets which are then fed to an injection molding machine.
  • a gate is opened at the end of the extruder and the melted plastic is pumped by the screw into a heated mold to form an article of the desired shape.
  • a coolant is pumped through the mold to cool it and the melted plastic. Once the plastic has solidified, the mold is opened and the article is removed from the mold.
  • Another embodiment can comprise mixing neat copolyester pellets with a concentrate of the impact modifiers and with or without short or long strand glass fiber to form the copolyester composition and then molding the copolyester composition to produce an injection molded article.
  • the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours and are then fed to an injection molding machine.
  • a gate is opened at the end of the extruder and the melted plastic is pumped by the screw into a heated mold to form an article of the desired shape.
  • a coolant is pumped through the mold to cool it and the melted plastic. Once the plastic has solidified, the mold is opened and the article is removed from the mold.
  • Another embodiment can comprise mixing neat copolyester pellets with a concentrate of impact modifiers to form the copolyester composition and then calendering the copolyester composition to produce a film product.
  • Calendering is a well-known process of forming a film or sheet through successive co-rotating parallel rollers.
  • the pellets may not need to be pre-dried if the processing temperatures are low enough (e.g., 350°F to 400°F; 177°C to 204°C). In such a case, degradation and hydrolysis of the polyester may not occur in a significant amount.
  • the copolyester and impact modifer composition may be melted by using a high intensity mixer or extruder, including but not limited to, Buss Ko-kneader, a planetary gear extruder, Farrell continuous mixer, a twin- screw extruder, or a Banbury® type mixer.
  • the melt is then conveyed to the calender.
  • a calender typically consists essentially of a system of three or more large diameter heated rollers which convert high viscosity plastic into a film or sheet.
  • the flat sheet or film is conveyed in a continuous web to cool the sheet. It can then be trimmed to the desired width and then either rolled up into a roll or sheared or sawed into sheet form.
  • the copolyester composition may be prepared by mixing or blending a concentrate of the impact modifiers and copolyester
  • the copolyester composition may alternatively be prepared by blending the impact modifiers directly with the copolyester, using any of the mixing or blending processed previously described for making the copolyester composition by blending the impact modifier concentrate and the copolyester.
  • Impact modifiers may be mixed or blended with the copolyester simultaneously or sequentially.
  • articles comprising any of the copolyester compositions can include articles or components of articles configured for use or otherwise useful in any application where chemical resistance and impact resistance properties are beneficial, for example in one or more of the following applications: medical device housings or components, housings for electronic devices or peripherals, personal electronic device components, television or monitor housings or components, power tool housings or components, power adapter housings or components, home automation device components, gaming device housings or components, building and construction materials and components, furnishing and home decoration components, wiring and connector housings or components, and automotive structural or decorative components.
  • J is Joules
  • J/m is Joules per meter
  • kJ is kilojoules
  • kJ/m 2 is kilojoules per square meter
  • MPa is megapascal
  • weight % is weight percent
  • CS is core-shell
  • IM impact modifier
  • TPA is terephthalic acid
  • TMCD 2,2,4,4-tetramethylcyclobutane-1 ,3-diol
  • 1 ,4-CHDM is 1 ,4-cyclohexanedimethanol.
  • Table 1 The materials used in testing are listed in Table 1.
  • Copolyester compositions were prepared by compounding on a Coperion ZSK-26mm co-rotating twin screw extruder. Prior to blending and compounding, TX1500HF pellets were dried for 6 hrs in 88°C desiccated air, Makrolon 2207 polycarbonate was dried for 6 hrs in 110°C desiccated air,
  • Terluran GP-35 ABS was dried for 6 hrs in 82°C desiccated air, and impact modifiers were not dried. Materials were fed into the extruder at the prescribed ratios using loss-in-weight gravimetric feeders. Barrel temperatures of 260- 275°C were used. [00119] Extruded strands were pelletized via a water bath/cutter or underwater pelletizer system, achieving an appropriate pellet size/shape for further processing. The formulations prepared are shown in Table 2 below.
  • copolyester compositions were molded into parts/pieces for testing via an injection molding process using a Toyo 90 ton injection molding machine. Prior to molding, pellets of compounded materials were dried 6 hrs in 88 C desiccated air, and then test parts/pieces were molded under the following conditions: barrel temperatures ranged from 265-275°C with water-cooled mold temperatures ranging from 35-45°C. Test bars were molded at thicknesses of 3.2 mm (for notched Izod, HDT, flexural modulus and chemical/weathering testing) and 12.5 mm (for Charpy impact testing). Testing was performed on the Example materials and controls as described herein and the results are shown below in Table 3.
  • Standard Izod testing (1/8”) Standard notched Izod testing was performed according to ASTM D256 Test Method A using a 3.2mm thick injection molded bar, machine notched with a 0.25mm radius notch. Per the ASTM method, the hammer weight was 2.7 Joules or 13.6 Joules, depending on the inherent brittleness of the samples. Samples were conditioned for 48 hrs at 23C and 50%RH after notching and prior to testing. Impact resistance values are reported in units of Joules per meter of thickness (J/m).
  • Charpy testing (1/2”) with and without aging: Charpy testing was performed according to ASTM D6110 using a 12.7mm thick injection molded bar cut down to 63mm in length and machine notched with either a 0.10mm or 0.25mm radius notch. The span was 51 mm. The hammer weight was 15 Joules. Samples were conditioned for 48 hrs at 23C and 50%RH after notching and prior to testing. One set of testing was performed on the as- molded bars, and another set was performed after ageing bars in an oven for 72 hours at 80C. Impact resistance values are reported in units of Joules per meter of thickness (J/m).
  • HDT The heat deflection temperature (HDT) was determined according to ASTM D648 using a 3.2mm thick injection molded bar and a 1 .82 MPa applied stress. Samples were conditioned for 48 hrs at 23C and 50%RH after notching and prior to testing.
  • Flexural modulus Flexural tangent modulus of elasticity was measured according to ASTM D790 Procedure A at a crosshead movement speed of 1 .27 mm/minute using a 3.2mm thick injection molded bar. Samples were conditioned for 48 hrs at 23C and 50%RH prior to testing.
  • Melt viscosity Melt viscosity as a function of frequency was measured at 280C according to ASTM D4440 using a Rheometrics Dynamic Analyzer (RDA II) using parallel plate. The frequency ranged between 1 and 400 rad/sec. Values obtained at 280C and a frequency of 400 rad/sec, in units of Poise, are reported in table 3 below.
  • IV Inherent viscosity (IV) was determined according to ASTM D4603 in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25C.
  • compositions with a certain combination of the E-MA-GMA and E-MA additives had improved resistance to embrittlement as a result of paint, canola oil and UV exposure, while maintaining adequate viscosity, HDT, flexural modulus, Izod impact and Charpy impact, compared to the other materials tested.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne une composition de copolyester comprenant un composant du type agent antichoc qui comprend un polymère ou des polymères contenant de l'éthylène, de l'acrylate d'alkyle et du (méth)acrylate de glycidyle (E-AA-G(M)A), et qui a une résistance chimique et/ou une résistance aux UV améliorées tout en conservant des propriétés thermiques et antichoc y compris lorsqu'elle est moulée sous forme de sections épaisses, des procédés de fabrication de la composition de copolyester et des articles fabriqués à partir de la composition de copolyester.
PCT/US2024/023765 2023-04-21 2024-04-10 Compositions de copolyester de cyclobutanediol ayant une résistance à la peinture, une résistance chimique et une résistance aux intempéries améliorées Pending WO2025116949A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363497461P 2023-04-21 2023-04-21
US63/497,461 2023-04-21

Publications (2)

Publication Number Publication Date
WO2025116949A2 true WO2025116949A2 (fr) 2025-06-05
WO2025116949A3 WO2025116949A3 (fr) 2025-10-09

Family

ID=95375336

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/023765 Pending WO2025116949A2 (fr) 2023-04-21 2024-04-10 Compositions de copolyester de cyclobutanediol ayant une résistance à la peinture, une résistance chimique et une résistance aux intempéries améliorées

Country Status (1)

Country Link
WO (1) WO2025116949A2 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772405A (en) 1972-02-02 1973-11-13 Eastman Kodak Co Process for preparing aromatic diester containing copolyesters and products obtained thereby
US5654347A (en) 1993-10-04 1997-08-05 Eastman Chemical Company Concentrates for improving polyester compositions and method of making same
US5696176A (en) 1995-09-22 1997-12-09 Eastman Chemical Company Foamable polyester compositions having a low level of unreacted branching agent
US20060287484A1 (en) 2005-06-17 2006-12-21 Crawford Emmett D Opththalmic devices comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002509565A (ja) * 1996-12-19 2002-03-26 イーストマン ケミカル カンパニー 流動性が改良された靱性強化ポリエステル
WO2000015717A1 (fr) * 1998-09-14 2000-03-23 Eastman Chemical Company Compositions de polyester renfermant un agent antichoc
KR101881930B1 (ko) * 2014-06-23 2018-07-26 사빅 글로벌 테크놀러지스 비.브이. 결합강도가 개선된 충전제 보강 열가소성 조성물
US12404400B2 (en) * 2019-05-10 2025-09-02 Eastman Chemical Company Blends of copolyesters having recycled content and high heat resistance
CN115943183A (zh) * 2020-06-16 2023-04-07 乐高公司 由聚合聚酯材料制成的玩具建造元件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772405A (en) 1972-02-02 1973-11-13 Eastman Kodak Co Process for preparing aromatic diester containing copolyesters and products obtained thereby
US5654347A (en) 1993-10-04 1997-08-05 Eastman Chemical Company Concentrates for improving polyester compositions and method of making same
US5696176A (en) 1995-09-22 1997-12-09 Eastman Chemical Company Foamable polyester compositions having a low level of unreacted branching agent
US20060287484A1 (en) 2005-06-17 2006-12-21 Crawford Emmett D Opththalmic devices comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

Also Published As

Publication number Publication date
WO2025116949A3 (fr) 2025-10-09

Similar Documents

Publication Publication Date Title
EP2814871B1 (fr) Articles semi-cristallins transparents dotés d'une résistance améliorée à la chaleur
KR101238995B1 (ko) 사이클로뷰테인다이올을 포함하고 고유 점도와 적절한 유리 전이 온도의 특정 조합을 갖는 폴리에스터 조성물을 포함하는 필름 및/또는 시트
US20190194448A1 (en) Flame retardant copolyester compositions
EP2611867B1 (fr) Compositions de copolyester retardatrices de flammes
WO2023178548A1 (fr) Compositions de copolyester ignifuges
US20120322951A1 (en) Clear blends of aliphatic-aromatic polyesters and aliphatic polyesters
EP4103644B1 (fr) Compositions de copolyester ignifuges
EP4103647A1 (fr) Compositions de copolyester ignifuges non halogénées
WO2025116949A2 (fr) Compositions de copolyester de cyclobutanediol ayant une résistance à la peinture, une résistance chimique et une résistance aux intempéries améliorées
EP4514895A1 (fr) Compositions de copolyester ignifuges
EP3894472A1 (fr) Compositions de copolyester, de polycarbonate et de polychlorure de vinyle et articles fabriqués à l'aide de ces compositions
EP4380995B1 (fr) Compositions de copolyester ignifuges
WO2024158786A1 (fr) Compositions de copolyester ignifuges
WO2025111838A1 (fr) Compositions de copolyester ignifuges à module élevé
WO2021257370A1 (fr) Compositions de polychlorure de vinyle, de polycarbonate et de copolyester et articles fabriqués à l'aide de ces compositions
JP2004300377A (ja) ポリトリメチレンテレフタレート樹脂組成物