EP0497902A1 - Compositions de moulage a base de poly(1,4-cyclohexylene dimethylene terephtalate) - Google Patents

Compositions de moulage a base de poly(1,4-cyclohexylene dimethylene terephtalate)

Info

Publication number
EP0497902A1
EP0497902A1 EP90917330A EP90917330A EP0497902A1 EP 0497902 A1 EP0497902 A1 EP 0497902A1 EP 90917330 A EP90917330 A EP 90917330A EP 90917330 A EP90917330 A EP 90917330A EP 0497902 A1 EP0497902 A1 EP 0497902A1
Authority
EP
European Patent Office
Prior art keywords
polyester
pps
weight
mol
repeat units
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.)
Withdrawn
Application number
EP90917330A
Other languages
German (de)
English (en)
Inventor
Larry Allen Minnick
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 Kodak Co
Original Assignee
Eastman Kodak 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 Kodak Co filed Critical Eastman Kodak Co
Publication of EP0497902A1 publication Critical patent/EP0497902A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention relates to reinforced poly(l,4-cyclohexylene dimethylene terephthalate) (PCT) molding compositions having improved thermo-oxidative stability.
  • Polyesters have been used as engineering plastics for mechanical parts of various machines, electrical equipment and parts of motor cars.
  • engineering plastics are provided with fire-proof properties, i.e., flame retardancy, in addition to well-balanced ordinary physical and chemical properties.
  • fire-proof properties i.e., flame retardancy
  • Such properties are indispensable in thermoplastic polyesters in order to enlarge their use as engineering plastics, because they are normally used at temperatures higher than 100°C.
  • This invention concerns the discovery of reinforced molding compositions based on PCT or high melting crystalline copolymers of PCT with improved thermo- oxidative stability.
  • PPS polyphenylene sulfide
  • GFR reinforced
  • These materials have high strength, stiffness, and heat resistance properties. These materials find application as a molding plastic in the electronics industry as printed circuit boards, connectors, etc. These are applications that require the material to have high strength, stiffness, heat resistance, and continuous use temperature rating.
  • U.S. Patent 4,140,671 discloses mixtures of linear polyesters, polyphenylene sulfide powder, flame retardants, fiber glass and talc to reduce the warpage of the polyester. No indication of improved long-term oven stability is made. Further, the PPS is present in the form of a filler, rather than as a melt blend, as ⁇ in the present invention.
  • U.S. Patent 4,689,365 discloses blends of poly(butylene terephthalate) (PBT) and pol (ethylene terephthalate) (PET) with polyphenylene sulfide of a specified melt flow, which provide materials with an improved heat deflection temperature. No disclosure of polyesters other .than PBT and PET is made.
  • polyester molding compositions containing a reinforcing material and polyphenylene sulfide as a thermo-oxidative stabilizer, the polyester containing repeat units from terephthalic acid and 1,4-cyclohexane- dimethanol. More particularly, the present invention provides reinforced polyester molding compositions having improved physical properties comprising
  • the polyester portion of the molding compositions of the present invention is prepared by conventional polycondensation procedures well known in the art.
  • the polyester poly(1,4- ⁇ yclohexylene dimethylene terephthalate), contains repeat units from a dicarboxylic acid component and a glycol component.
  • the dicarboxylic acid component a total of 100 mol %, is at least 90 mol % terephthalic acid and the glycol component, a total of 100 mol %, is at least 90 mol % 1,4-cyclohexanedimethanol.
  • the dicarboxylic acid component may contain up to 10 mol % of other conventional aromatic, aliphatic or alicyclic dicarboxylic acids such as isophthalic acid, naphthalenedi ⁇ arboxylic acid, cyclohexane-dicarboxylic acid, succinic acid, sebacic acid, adipic acid, glutaric acid, azelaic acid and the like.
  • the glycol component may contain up to 10 mol % of other conventional aliphatic or alicyclic glycols such as diethylene glycol, triethylene glycol, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and the like.
  • the polyesters can be prepared by direct condensation of terephthalic acid with 1,4-cy ⁇ lohexane- dimethanol or ester interchange using dimethyl terephthalate.
  • the essential components of the polyester e.g., terephthalic acid or dimethyl terephthalate and 1,4-cyclohexanedimethanol are ⁇ commercially available.
  • the polyesters and copolyesters described above should have an I.V. (inherent viscosity) of from 0.5 to 1.0.
  • the polyester and the PPS have melting temperatures close to each other so that the two can be melt blended without degradation of either.
  • the melting temperature of the polyester is 295°C and the melting temperature of PPS is 285°C.
  • PPS is used mostly as a filler and is not melt blended with the polyester.
  • the blend of polyester and PPS is homogeneous.
  • the improved polyester resin composition of this invention includes a reinforcing material.
  • a preferred reinforcing filler is glass fibers which may be introduced into the composition as chopped glass fibers or continuous glass fiber rovings in amounts of 10-50% by weight of the composition.
  • Other reinforcing materials such as metal fibers, graphite fibers, aramid fibers, glass beads, aluminum silicate, asbestos, mica, talc and the like may be used in combination with, or in place of the glass fibers .
  • any of the types of glass fibers generally known and/or used in the art are useful in the present invention.
  • Typical types are those described in British Patent No. 1,111,012, U.S. Patent No. 3,368,995 and German Auslegeschrift No. 2,042,447.
  • the average length of useful fibers covers a wide range, for example, 1/16 to 2 inches (0.159 cm to 5 cm).
  • the presently preferred glass fibers have an average length of 1/16 to 1/4 inch (0.159 cm to 0.64 cm).
  • Glass filaments made of calcium- luminum-boron silicate glass, which is relatively free from sodium carbonate, are preferably used. Glass of this type is known as "E” glass; however, where the electrical properties of the reinforced polyesters are not important, other glasses can also be used, for example the glass with a low sodium carbonate content which is known as "C” glass.
  • the diameters of the filaments can be in the range from 0.003 to 0.018 mm, but this is not critical for the present invention.
  • the blends of this invention may contain additives commonly employed with polyester resins, such as colorants, mold release agents, tougheners, nucleating agents, crystallization aids, plasticizers, ultraviolet light and heat stabilizers and the like.
  • Materials such as Irganox 1010 stabilizer and/or eston 619 stabilizer in amounts of up to 2%, preferably 0.1-05% by weight of the composition, are preferred.
  • the molding compositions according to this invention include at least one conventional flame retardant such as a halogenated organic compound, an antimony compound, or the like.
  • the blends of this invention are prepared by blending the components together by any convenient means to obtain an intimate blend.
  • Compounding temperatures must be at least the melting point of the PCT.
  • the polyester can be mixed dry in any suitable blender or tumbler with the other components and the mixture melt-extruded.
  • the extrudate can be chopped.
  • the reinforcing material can be omitted initially and added after the first melt extrusion, and the resulting mixture can then be melt extruded.
  • the product is especially suitable as an injection molding material for producing molded articles .
  • a series of blends of PCT with 30% glass fiber are prepared containing 0, 5, 10, 20, and 30% PPS based on the weight of the polyester. These formulations are then melt blended by extrusion compounding using the 1.5 inch single screw extruder at 300°C. The resulting formulations are then molded into 1/8 inch tensile and flexural test bars using an injection molding machine. Mechanical properties are determined on these test bars (see Table 1) .
  • the GFR PCT formulations containing PPS maintain excellent heat deflection temperature with only minimal loss of strength properties (tensile, flexural, Izod impact) .
  • the flammability properties of these formulations are improved as shown by the increasing oxygen index with increasing PPS concentration.
  • Thermo- oxidative stability is determined on these formulations by heating the tensile bars in a forced air oven at 180°C for 0-2352 hours and measuring the retained tensile strength (see Table 2) .
  • the retained tensile strength increases as the PPS concentration increases in the GFR PCT blends, which represents improved thermo-oxidative stability.
  • the blends contain conventional amounts of Be ⁇ zoflex S312 crystallization enhancer and Weston 619 and Irganox 1010 stabilizers Ryton P4 polyphenylene sulfide is used.
  • Oxygen Index is defined as the minimum concentration of oxygen in an oxygen and nitrogen mixture that will support combustion of a material in a candle-like configuration (ASTM designation D2863-77). Unless otherwise specified, all parts, percentages, ratios, etc., are by weight. Weight of reinforcing glass fibers and nucleating agents(s) are based on total composition weight.

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)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Video Image Reproduction Devices For Color Tv Systems (AREA)

Abstract

Est décrit du poly(1,4-cyclohexylène-dimethylène-terephthalate) renforcé, contenant 5 à 30 % en poids de sulfure de polyphénylène utilisé comme stabilisant thermo-oxydant.
EP90917330A 1989-10-26 1990-10-16 Compositions de moulage a base de poly(1,4-cyclohexylene dimethylene terephtalate) Withdrawn EP0497902A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42665689A 1989-10-26 1989-10-26
US426656 1989-10-26

Publications (1)

Publication Number Publication Date
EP0497902A1 true EP0497902A1 (fr) 1992-08-12

Family

ID=23691670

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90917330A Withdrawn EP0497902A1 (fr) 1989-10-26 1990-10-16 Compositions de moulage a base de poly(1,4-cyclohexylene dimethylene terephtalate)

Country Status (5)

Country Link
EP (1) EP0497902A1 (fr)
JP (1) JPH05501279A (fr)
KR (1) KR927003724A (fr)
CA (1) CA2065366A1 (fr)
WO (1) WO1991006603A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10292099A (ja) * 1997-04-21 1998-11-04 Teijin Ltd 樹脂組成物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284549A (en) * 1977-07-27 1981-08-18 Hooker Chemicals & Plastics Corp. Polymer blends with improved hydrolytic stability
US4251429A (en) * 1977-07-27 1981-02-17 Hooker Chemicals & Plastics Corp. Polymer blends with improved flame retardance
US4140671A (en) * 1977-12-30 1979-02-20 General Electric Company Warp-resistant flame-retarded reinforced thermoplastic compositions
NL8500905A (nl) * 1985-03-28 1986-10-16 Philips Nv Werkwijze voor het vervaardigen van een inrichting met een elektrische weerstandslaag en toepassing van de werkwijze.
US4689365A (en) * 1986-05-06 1987-08-25 Celanese Engineering Resins, Inc. High temperature resistant polyester compositions
JPS62296326A (ja) * 1986-06-16 1987-12-23 Hitachi Ltd 撮像管の静電偏向電極加工法
US4837254A (en) * 1988-03-02 1989-06-06 Eastman Kodak Company Poly(1,4-cyclohexylene dimethylene terephthalate) molding compositions
JP2707714B2 (ja) * 1989-04-25 1998-02-04 東レ株式会社 ポリフェニレンスルフィド樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9106603A1 *

Also Published As

Publication number Publication date
CA2065366A1 (fr) 1991-04-27
WO1991006603A1 (fr) 1991-05-16
KR927003724A (ko) 1992-12-18
JPH05501279A (ja) 1993-03-11

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