WO1997009366A1 - Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties - Google Patents

Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties Download PDF

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Publication number
WO1997009366A1
WO1997009366A1 PCT/US1996/013759 US9613759W WO9709366A1 WO 1997009366 A1 WO1997009366 A1 WO 1997009366A1 US 9613759 W US9613759 W US 9613759W WO 9709366 A1 WO9709366 A1 WO 9709366A1
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WIPO (PCT)
Prior art keywords
acid
copolyester
mol
glycol
aliphatic dicarboxylic
Prior art date
Application number
PCT/US1996/013759
Other languages
French (fr)
Inventor
Larry Allen Minnick
Original Assignee
Eastman Chemical Company
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 Company filed Critical Eastman Chemical Company
Priority to EP96929750A priority Critical patent/EP0847411B1/en
Priority to DE69602276T priority patent/DE69602276T2/en
Priority to JP9511253A priority patent/JPH11512455A/en
Publication of WO1997009366A1 publication Critical patent/WO1997009366A1/en

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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
    • 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
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]

Definitions

  • PET is currently useful for the fabrication of injection molded vacuum blood tubes.
  • PET has good gas barrier properties and as a result blood tubes prepared from the resin have adequate retention of vacuum for selected applications.
  • improved gas barrier properties are desirable to extend the shelf life of these tubes in selected applications.
  • Copolyesters of polyethylene terephthalate (PET) , naphthalenedicarboxylic acid and at least one aliphatic dicarboxylic acid have been found to possess improved gas barrier properties relative to PET. Surprisingly these copolyesters also maintain the heat resistance and impact properties of PET.
  • Blood tubes for the medical industry have traditionally been prepared from glass.
  • plastic tubes are now being prepared from injection molded resins such as PET. These tubes are prepared and maintained under reduced pressure to allow for a convenient method for the sampling of blood. Because of the need to maintain reduced pressure in these tubes, there is a need for resins that will provide improved barrier properties relative to PET and therefore, give the extended shelf—life needed in selected applications.
  • Poly(ethylene—2,6—naphthalenedicarboxylate) (PEN) displays improved barrier properties relative to PET.
  • this resin is quite expensive and due to the increased melting point and melt viscosity requires very high processing temperatures relative to PET.
  • U.S. Patent 4,401,805 describes PET copolyesters containing 1—45 mol % of aliphatic dicarboxylic acids containing 3 to 8 carbon atoms which are reported to have good barrier properties. However, the addition of only aliphatic dicarboxylic acids lowers the heat resistance properties of the resultant polyester relative to those of PET. The addition of aromatic dicarboxylic acids other than terephthalic acid is not disclosed.
  • the present invention provides novel copolyesters derived from acid components comprising 45 to 85 mol % terephthalic acid; 10 to 40 mol % of at least one naphthalenedicarboxylic acid and 5 to 15 mol % of at least one aliphatic dicarboxylic acid having 2 to 8 carbon atoms and glycol component comprising ethylene glycol. Injection molded, blow molded and extruded articles made therefrom are also disclosed.
  • said copolyesters comprise 60 to 75 mole % terephthalic acid; 20 to 30 mole % of at least one naphthalenedicarboxylic acid and 5 to 10 mole % of said at least one aliphatic dicarboxylic acid.
  • the naphthalenedicarboxylic acid isomer is selected from 1,4-, 1,5-, 2,6-, 2,7-, 1,2-, 1,3-, 1,7-, 1,8-, 2,3—, 2,4—, 2,5-, and 2,8—naphthalenedicarboxylic acid isomers. Mixtures of the various isomers may also be used.
  • the isomer(s) chosen may be added to the reaction as either an acid or an ester.
  • the naphthalenedicarboxylic acid is 2,6—naphthalene ⁇ dicarboxylic acid isomer.
  • the aliphatic dicarboxylic acid is preferably selected from oxalic, succinic, malonic, glutaric, adipic, 1,4—cyclohexanediearboxylic acid and the like. More preferably the aliphatic dicarboxylic acid is selected from succinic, glutaric and adipic acid, and most preferably is succinic acid.
  • the copolyesters are readily prepared by either batch or continuous polycondensation processes well known to those skilled in the art.
  • the dicarboxylic acid moieties may be derived from the acids or their lower alkyl esters, such as the dimethyl esters.
  • Useful copolyesters will have inherent viscosity (IV) values of 0.4 to 1.1.
  • Typical catalysts which may be used in the polymerization of these copolyesters include the titanium alkoxides, dibutyl tin laurate, combinations of zinc, manganese, or magnesium acetates or benzoates with antimony oxide or antimony triacetate.
  • diols examples include propylene glycol; diethylene glycol; 1,2—propylene glycol; 2,4—dimethyl-2—ethyl—hexane- 1,3-diol; 2,2,4—trimethyl—1,3—pentanediol; 2,2-dimethy1— 1,3—propanediol; 2—ethyl—2—butyl—1,3—propanediol; 2,2—diethyl—1,3—propanediol; 2—methyl—2—propyl— 1,3—propanediol; 2—ethyl—2—isobutyl—1,3—propanediol; 1,3—butanediol; 1,4—butanediol; 1,5—pentaned
  • compositions of the present invention have excellent barrier properties and are readily processable at temperature ranges similar to PET.
  • copolyesters can be injection molded into blood tubes, serum vials, laboratory bottles and the like at temperatures ranging from 250°C to 280°C.
  • the copolyesters may also be formed into a variety of other articles such as containers, films and sheets by well known molding techniques such as injection molding, extrusion blow molding, extrusion molding and extrusion stretch molding.
  • the heat deflection temperature and other elevated temperature properties of these copolyesters are at least equal to PET.
  • copolyesters of the present invention are clear. Clarity is essential in several applications, including blood tubes.
  • composition of the present invention Small amounts of other ingredients may be added to the composition of the present invention to enhance their performance properties.
  • lubricants stabilizers, antioxidants, ultraviolet light absorbing agents, mold release agents, metal deactivators, zeolites, fillers, and the like can be used so long as they do not hinder the present invention from accomplishing the objective.
  • Examples were extruded into thin film (nominally 10 mil) using a 3/4 inch Killion single screw extruder for use in permeability testing. These materials were also molded into tensile and flexural bars using a Toyo 90 injection molding machine for use in mechanical property testing. Inherent viscosity (I.V.) was measured at 25°C using 0.5 gram of polyester per 100 ml of a solvent consisting of 60 wt% phenol and 40 wt% tetrachloroethane.
  • I.V. Inherent viscosity
  • Polyesters of terephthalic acid (T) , 2,6— naphthalenedicarboxylic acid (N) , succinic acid (S) and ethylene glycol (EG) as listed in Table 1 were prepared via polycondensation as follows. An excess of ethylene glycol was reacted with the listed acid components at about 200 to 220°C to remove water and methanol from the reaction mixture. The dimethylester of terephthalic acid and naphthlenedicarboxylic acid were used. Succinic acid was used in its acid form. Polymerization was conducted under reduced pressure at 285°C.
  • the properties of the resultant polyesters were measures as follows: I.V.s (described above), oxygen transmission rates (ASTM D3985) , toughness (tensile elongation to break — ASTM D638) and heat of deflection termperatures (HDTs — ASTM D648) and are shown in Table 2, below.

Abstract

Disclosed are terpolymers having improved barrier properties and tensile strength relative to PET comprising copolyesters derived from acid components comprising 45 to 85 mol % terephthalic acid; 10 to 40 mol % of at least one naphthalenedicarboxylic acid and 5 to 15 mol % of at least one aliphatic dicarboxylic acid having 1 to 6 carbon atoms and glycol component comprising ethylene glycol. The copolyesters of the present invention may be formed into a variety of articles such as blood tubes, serum vials, containers, films and sheeting.

Description

PET COPOLYESTERS CONTAINING SUCCINIC AND
NAPHTHALENEDICARBOXYLIC ACID MOIETIES
HAVING IMPROVED BARRIER PROPERTIES
PET is currently useful for the fabrication of injection molded vacuum blood tubes. PET has good gas barrier properties and as a result blood tubes prepared from the resin have adequate retention of vacuum for selected applications. However, improved gas barrier properties are desirable to extend the shelf life of these tubes in selected applications. Copolyesters of polyethylene terephthalate (PET) , naphthalenedicarboxylic acid and at least one aliphatic dicarboxylic acid have been found to possess improved gas barrier properties relative to PET. Surprisingly these copolyesters also maintain the heat resistance and impact properties of PET.
Background of the Invention Blood tubes for the medical industry have traditionally been prepared from glass. In recent years, the possibility of infectious disease being spread by contact with blood from broken tubes has caused the medical industry to increasingly depend on plastic tubes. Tubes are now being prepared from injection molded resins such as PET. These tubes are prepared and maintained under reduced pressure to allow for a convenient method for the sampling of blood. Because of the need to maintain reduced pressure in these tubes, there is a need for resins that will provide improved barrier properties relative to PET and therefore, give the extended shelf—life needed in selected applications.
Poly(ethylene—2,6—naphthalenedicarboxylate) (PEN) displays improved barrier properties relative to PET. However, this resin is quite expensive and due to the increased melting point and melt viscosity requires very high processing temperatures relative to PET.
U.S. Patent 4,401,805 describes PET copolyesters containing 1—45 mol % of aliphatic dicarboxylic acids containing 3 to 8 carbon atoms which are reported to have good barrier properties. However, the addition of only aliphatic dicarboxylic acids lowers the heat resistance properties of the resultant polyester relative to those of PET. The addition of aromatic dicarboxylic acids other than terephthalic acid is not disclosed.
Research Disclosure No. 36009 (April, 1994) describes PET copolyesters containing either 10—50 mol % isophthaiic acid, or 10—30 mol % of either succinic acid, glutaric acid, adipic acid, or mixtures of these aliphatic acids. These copolyesters are reported to be useful for the preparation of blood tubes.
Research Disclosure No. 36903 (January, 1995) discloses PET copolyesters containing glutarate, succinate, adipate or mixutures thereof that are reported to have improved shelf—life in blood tubes. Terpolymers of PET, isophthaiic and naphthalenedicarboxylic acids are also disclosed. Research Disclosure No. 29484 (October, 1988) discloses various PEN copolyesters.
Description of the Invention
The present invention provides novel copolyesters derived from acid components comprising 45 to 85 mol % terephthalic acid; 10 to 40 mol % of at least one naphthalenedicarboxylic acid and 5 to 15 mol % of at least one aliphatic dicarboxylic acid having 2 to 8 carbon atoms and glycol component comprising ethylene glycol. Injection molded, blow molded and extruded articles made therefrom are also disclosed. Preferably said copolyesters comprise 60 to 75 mole % terephthalic acid; 20 to 30 mole % of at least one naphthalenedicarboxylic acid and 5 to 10 mole % of said at least one aliphatic dicarboxylic acid.
The naphthalenedicarboxylic acid isomer is selected from 1,4-, 1,5-, 2,6-, 2,7-, 1,2-, 1,3-, 1,7-, 1,8-, 2,3—, 2,4—, 2,5-, and 2,8—naphthalenedicarboxylic acid isomers. Mixtures of the various isomers may also be used. The isomer(s) chosen may be added to the reaction as either an acid or an ester. Preferably, the naphthalenedicarboxylic acid is 2,6—naphthalene¬ dicarboxylic acid isomer.
The aliphatic dicarboxylic acid is preferably selected from oxalic, succinic, malonic, glutaric, adipic, 1,4—cyclohexanediearboxylic acid and the like. More preferably the aliphatic dicarboxylic acid is selected from succinic, glutaric and adipic acid, and most preferably is succinic acid. The copolyesters are readily prepared by either batch or continuous polycondensation processes well known to those skilled in the art. The dicarboxylic acid moieties may be derived from the acids or their lower alkyl esters, such as the dimethyl esters. Useful copolyesters will have inherent viscosity (IV) values of 0.4 to 1.1.
Typical catalysts which may be used in the polymerization of these copolyesters include the titanium alkoxides, dibutyl tin laurate, combinations of zinc, manganese, or magnesium acetates or benzoates with antimony oxide or antimony triacetate.
In general, up to 20 mol % of other aliphatic and aromatic diols can be used to prepare the polyesters as long as 80 mol % is ethylene glycol. Examples of such diols include propylene glycol; diethylene glycol; 1,2—propylene glycol; 2,4—dimethyl-2—ethyl—hexane- 1,3-diol; 2,2,4—trimethyl—1,3—pentanediol; 2,2-dimethy1— 1,3—propanediol; 2—ethyl—2—butyl—1,3—propanediol; 2,2—diethyl—1,3—propanediol; 2—methyl—2—propyl— 1,3—propanediol; 2—ethyl—2—isobutyl—1,3—propanediol; 1,3—butanediol; 1,4—butanediol; 1,5—pentanediol; 1,6—hexanediol; 2,2,4—trimethyl—1,6—hexanediol, 1,2—cyclohexanedimethanol; 1,3—cyclohexanedimethanol; 2,2,4,4—tetramethyl—1,3—cyclobutanediol; 0-, m-, and p—xylylene diols; 4,4'—sulfonyldiphenol;
4,4'—oxydiphenol; 4,4'—isopropylidenediphenol; and 2,5'—naphthalenediol.
The compositions of the present invention have excellent barrier properties and are readily processable at temperature ranges similar to PET. For example, such copolyesters can be injection molded into blood tubes, serum vials, laboratory bottles and the like at temperatures ranging from 250°C to 280°C. The copolyesters may also be formed into a variety of other articles such as containers, films and sheets by well known molding techniques such as injection molding, extrusion blow molding, extrusion molding and extrusion stretch molding. The heat deflection temperature and other elevated temperature properties of these copolyesters are at least equal to PET.
Moreover, the copolyesters of the present invention are clear. Clarity is essential in several applications, including blood tubes.
Small amounts of other ingredients may be added to the composition of the present invention to enhance their performance properties. For example, lubricants, stabilizers, antioxidants, ultraviolet light absorbing agents, mold release agents, metal deactivators, zeolites, fillers, and the like can be used so long as they do not hinder the present invention from accomplishing the objective.
Examples The polyesters and copolyesters made in the
Examples were extruded into thin film (nominally 10 mil) using a 3/4 inch Killion single screw extruder for use in permeability testing. These materials were also molded into tensile and flexural bars using a Toyo 90 injection molding machine for use in mechanical property testing. Inherent viscosity (I.V.) was measured at 25°C using 0.5 gram of polyester per 100 ml of a solvent consisting of 60 wt% phenol and 40 wt% tetrachloroethane.
Examples 1—5
Polyesters of terephthalic acid (T) , 2,6— naphthalenedicarboxylic acid (N) , succinic acid (S) and ethylene glycol (EG) as listed in Table 1 were prepared via polycondensation as follows. An excess of ethylene glycol was reacted with the listed acid components at about 200 to 220°C to remove water and methanol from the reaction mixture. The dimethylester of terephthalic acid and naphthlenedicarboxylic acid were used. Succinic acid was used in its acid form. Polymerization was conducted under reduced pressure at 285°C.
Table 1
EX. # mole % T mole % N mole % S mole % EG
1 100 — — 100
2 50 50 — 100
3 85 — 15 100
4 75 20 5 100
5 60 25 15 100 The properties of the resultant polyesters were measures as follows: I.V.s (described above), oxygen transmission rates (ASTM D3985) , toughness (tensile elongation to break — ASTM D638) and heat of deflection termperatures (HDTs — ASTM D648) and are shown in Table 2, below.
Table 2
Ex # IV Permeabilty % tensile HDT (C @ (cc- elong. to 66/264 mil/100in2— break psi) 24hr—atm)
1 0.56 12.6 95 70/63
2 0.61 6.9 8 86/73
3 0.55 7 257 56/51
4 0.66 8.3 258 73/65
5 0.72 6.6 86 63/60
These examples show that the gas barrier properties of PET can be improved significantly by the addition of the combination of succinic and 2,6—naphthalene¬ dicarboxylic acids. Surprisingly, these improvements can be obtained without the detrimental effects of lowered toughness and increased melt viscosity that is obtained in PET containing only 2,6-naphthalene- dicarboxylic acid (>50 mol %) . Also, these improvements can be obtained without the detrimental effects of lowered HDT that is obtained in PET containing only succinic acid.

Claims

CLAIMSWE CLAIM
1. A copolyester derived from acid components comprising 45 to 85 mol % terephthalic acid; 10 to
40 mol % of at least one naphthalenedicarboxylic acid and 5 to 15 mol % of at least one aliphatic dicarboxylic acid having 2 to 8 carbon atoms and glycol component comprising ethylene glycol. 2. The copolyester of claim 1 wherein said acid components comprise 60 to 75 mole % terephthalic acid; 20 to 30 mole % of at least one naphthalenedicarboxylic acid and 5 to 10 mole % of said at least one aliphatic dicarboxylic acid. 3. The copolyester of claim 1 wherein said naphthalenedicarboxylic acid is selected from the group consisting of 1,4—, 1,5—, 2,6—, 2,7—, 1,2—, 1,3—, 1,7—, 1,8—,
2,
3—, 2,4—, 2,5—, 2,8—naphthalenedicarboxylic acid and mixtures thereof. 4. The copolyester of claim 1 wherein said aliphatic dicarboxylic acid is selected from the group consisting of succinic acid, malonic acid, glutaric acid, adipic acid and 1,
4—cyclohexanediearboxylic acid.
5. The copolyester of claim 4 wherein said aliphatic dicarboxylic acid is selected from the group consisting of oxalic, succinic, glutaric and adipic acid.
6. The copolyester of claim 4 wherein said aliphatic dicarboxylic acid is succinic acid.
7. The copolyesters of claim 1 wherein said glycol component further comprises up to 20 mol % of at least one second glycol.
8. The copolyester of claim 7 wherein said second glycol is selected from the group consisting of propylene glycol; diethylene glycol; 1,2—propylene glycol; 2,4-dimethyl-2—ethyl—hexane—1,3-diol;
2,2,4—trimethyl—1,3—pentanediol; 2,2—dimethyl—
1,3—propanediol; 2—ethyl—2—butyl—1,3—propanediol;
2,2—diethyl-1,3—propanediol; 2—methyl—2—propyl— l,3—propanediol; 2—ethyl—2—isobutyl—1,3-propanediol;
1,3—butanediol; 1,4—butanediol; 1,5—pentanediol;
1,6—hexanediol; 2,2,4—trimethyl—1,6—hexanediol,
1,2—cyclohexanedimethanol; 1,3—cyclohexanedimethanol;
2,2,4,4-tetramethyl-l,3-cyclobutanediol; 0-, m-, and p-xylylene diols; 4,4'—sulfonyldiphenol;
4,4'-oxydiphenol; 4,4'-isopropylidenediphenol; and
2,5'—naphthalenediol.
9. A formed article made from the copolyester of claims 1 through 8.
10. The article of claim 9 wherein said article is selected from the group consisting of blood tubes, serum vials, laboratory bottles, containers, films and sheeting.
PCT/US1996/013759 1995-09-01 1996-08-27 Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties WO1997009366A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96929750A EP0847411B1 (en) 1995-09-01 1996-08-27 Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties
DE69602276T DE69602276T2 (en) 1995-09-01 1996-08-27 PET COPOLYESTER CONTAINS UNITS OF SUCCINTERY AND NAPHTHALENE DICARBONIC ACID WITH IMPROVED GAS-TIGHTNESS
JP9511253A JPH11512455A (en) 1995-09-01 1996-08-27 PET copolyester containing succinic acid and naphthalenedicarboxylic acid moieties with improved barrier properties

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/522,882 US5506014A (en) 1995-09-01 1995-09-01 Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties
US08/522,882 1995-09-01

Publications (1)

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US (1) US5506014A (en)
EP (1) EP0847411B1 (en)
JP (1) JPH11512455A (en)
DE (1) DE69602276T2 (en)
WO (1) WO1997009366A1 (en)

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US5506014A (en) 1996-04-09
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DE69602276T2 (en) 1999-09-30
EP0847411B1 (en) 1999-04-28
MX9801576A (en) 1998-07-31

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