WO1991008254A1 - Polymeres thermoplastiques avec additifs de fluorocarbone disperses - Google Patents

Polymeres thermoplastiques avec additifs de fluorocarbone disperses Download PDF

Info

Publication number
WO1991008254A1
WO1991008254A1 PCT/US1990/005928 US9005928W WO9108254A1 WO 1991008254 A1 WO1991008254 A1 WO 1991008254A1 US 9005928 W US9005928 W US 9005928W WO 9108254 A1 WO9108254 A1 WO 9108254A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorocarbon
additive
composition according
perfluorocarbon
polymer
Prior art date
Application number
PCT/US1990/005928
Other languages
English (en)
Inventor
Robert E. Sterling
Eugene P. Goldberg
Original Assignee
Res Development Corporation
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 Res Development Corporation filed Critical Res Development Corporation
Publication of WO1991008254A1 publication Critical patent/WO1991008254A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine

Definitions

  • the present invention relates to thermoplastic polymers modified with certain fluorocarbon additives. Description of the Prior Art it has recently been proposed to modify thermoplastic polymers by incorporating therein various oils, gums, etc.
  • U.S. Patent No. 3,485,787 discloses that certain block coploly ers may be extended by incorporating mineral oil therein.
  • U.S. Patent No. 3,485,787 discloses that certain block coploly ers may be extended by incorporating mineral oil therein.
  • 3,830,767 teaches that bleeding of the extending oil from the block copolymer may be prevented by incorporating a petroleum hydrocarbon wax therein.
  • U.S. Patent No. 4,123,409 relates to block copolymers having thermoplastic terminal blocks and an elastomeric intermediate block.
  • the patent discloses blending with the copolymer a high molecular weight oil which is compatible with the elastomeric block portion of the copolymer.
  • the oil employed is a mineral oil.
  • the elastomeric block is a polysiloxane, a silicone oil is blended therewith.
  • U.S. Patent No. 3,034,509 discloses the addition of silicone oil to polyethylene for use as surgical tubing.
  • U.S. Patent No. 4,386,179 discloses the dispersion of a polysiloxane throughout an elastomeric thermoplastic hydrocarbon block copolymer.
  • Japanese Patent No. 60104161 describes an anti-friction composite material comprising a resin and more than 1%, by weight, of a fluorocarbon oil which have been injected molded together in a manner such that the oil exudes onto the molded surfaces of the resin due to poor compatibility of the oil with the resin and differences in viscosity between the resin and oil to produce an anti-friction surface.
  • thermoplastic polymer compositions having properties and characteristics heretofore unattainable.
  • the present invention provides a composition of matter formed by melt-blending a thermoplastic polymer and from about 0.01% to less than 1%, by weight, of a fluorocarbon additive selected from the group consisting of a fluorocarbon oil, a fluorocarbon gum, a fluorocarbon grease and mixtures thereof, the fluorocarbon additive having a lower surface energy than that of the polymer; the melt-blending resulting in a substantially homogenous admixture of the polymer and the fluorocarbon additive; the admixture, upon cooling, resulting in a solid composition wherein the concentration of fluorocarbon additive is lower in the bulk polymer and higher at the surfaces thereof, i.e., is a gradient through a cross-section of the solid composition from a lower value in the interior or bulk thereof to a higher value at the surfaces thereof.
  • a fluorocarbon additive selected from the group consisting of a fluorocarbon oil, a fluorocarbon gum, a fluorocarbon grease and mixtures thereof, the fluor
  • a further embodiment of the invention comprises a method of forming a composition of matter - 3 - comprising a thermoplastic polymer and from about 0.01% to less than about 1%, by weight, of a fluoro ⁇ carbon additive selected from the group consisting of a fluorocarbon oil, a fluorocarbon gum and mixtures thereof, the fluorocarbon additive having a lower surface energy than that of the polymer, the method comprising melt-blending, preferably in an efficient compounding blender, the polymer and the fluorocarbon additive at a temperature above the glass transition temperature or softening point of the polymer but below that having a deleterious effect on the polymer and the fluorocarbon additive and for a time sufficient to produce a substantially homogenous admixture of polymer and fluorocarbon additive, followed by cooling the admixture to produce a solid composition wherein the concentration of fluorocarbon additive through a cross-section of solid composition is lower in the polymer bulk thereof and higher at the surfaces thereof, i.e., is a gradient
  • thermo ⁇ plastic polymers when efficiently melt-blended with less than 1%, by weight, of a fluorocarbon oil, gum or mixture thereof such that the fluorocarbon additive is homogenously distributed throughout the melt, yield, upon cooling, solid compositions which, because of the differences in thermodynamic compatibility and surface energy between the fluorocarbon additive and the polymer, have higher concentrations of the additive at the surface than throughout the interior thereof.
  • concentration of fluoro ⁇ carbon additive is a gradient through a cross-section from a lower value at the center thereof to a higher value at the surfaces
  • concentration is not intended to suggest that the concentration varies uniformly from the center of the composition to the surface. Although this may be the case with respect to some combinations of polymer and additive, typi ⁇ cally, a much higher concentration of the additive is at the surfaces of the composition with a much smaller amount in the interior or bulk of the polymer.
  • the high concentrations of fluorocarbon additive at the surfaces provide compositions having the advantages of fluorocarbon-like surface properties, i.e., greater hydrophobicity, lower surface energy, non-adherent surface characteristics, more chemically inert, lower friction, smoother, etc.
  • the presence of the fluorocarbon additive enhances molding operations since it reduces "sticking" of the composition to the mold surfaces and enhances mold release.
  • the additive will, because of the lubricant properties thereof, permit higher speed processing of extruded objects, i.e., films, fibers and other objects formed therefrom and with smoother surfaces; with the added benefits of shorter injection molding cycles and higher extrusion rates.
  • the fluorocarbon surfaces are especially advantageous since they exhibit superior bioco patibility in contact with tissue - 5 - surfaces, cells, physiological fluids and blood as compared with most thermoplastic polymers.
  • compositions of this invention are therefore particularly advantageous for such applica- tions as blood and fluid handling, medical tubing; vascular grafts, mammary implants, joint and tendon prostheses, ocular implants, and the like.
  • Fibers prepared from compositions of the invention possess superior surface smoothness and uniformity and handling properties for weaving as well as different textures and "feel” because of the surface properties imparted by the fluorocarbon additives.
  • the compositions and methods of the invention are advantageous and more economical in the manufacture of fibers since the high concentration of fluorocarbon additive at the surfaces of the fiber facilitates high-speed processing with less damage to dies, shuttles and weaving equipment to produce more uniform, smooth melt spun fibers.
  • the basic bulk mechanical, physical and chemical properties of the thermoplastic polymer employed are retained or even enhanced for the compositions of the present invention but acquire the fluorocarbon surface properties of the additive due to the above-noted gradient concentration of the fluorocarbon additive through a cross-section of the composition from a lower value in the bulk to a higher value at the surface.
  • the lower concentrations of fluorocarbon additive in the interior portion of the thermoplastic can also advantageously modify the bulk mechanical, physical and chemical properties of the polymer, however, particularly with respect to the classes of thermoplastic polymers discussed hereinbelow.
  • compositions of the invention are unique advantages associated with the compositions of the invention. That if cut into plural sections, the fluorocarbon additive in the interior will migrate to the new surfaces formed by the cutting operation.
  • polymers may be utilized in the practice of the invention. Preferred among the suitable polymers are:
  • Polyolefins such as polyethylene, polypropylene, etc. are advantageously and preferably employed in the practice of the invention because fluorocarbon surface properties are achieved at very low overall fluorocarbon additive concentrations. For example, using only 0.5 wt% of a 450 centistoke vis ⁇ cosity perfluoropolypropylene oxide fluorocarbon oil in low density polyethylene, a surface composition of 21 atomic % fluorine is achieved as shown by XPS analysis.
  • This surface is characterized by an increase in hydrophobicity (water contact angle changed from 61" for polyethylene to 94 * for the fluorocarbon modified composition) and a decrease in surface energy (from 40.6 dynes/cm for polyethylene to 28.1 dynes/cm for the fluorocarbon modified poly ⁇ ethylene); indicative of the significantly altered surface properties achieved using only 0.5 wt% of fluorocarbon additive.
  • An improvement in mechanical properties, greater ductility, is also achieved using the fluorocarbon additive.
  • Tensile elongation changes from 840% for polyethylene to 1100% with 0.1% F-additive and 1500% with 0.3% F-additive. The energy required for extrusion (torque) is also substantially reduced.
  • Olefin copolymers and block copolymers such as ethylene-propylene, and styrene- olefin block copolymers such as styrene-butadiene, styrene-butadiene-styrene, and styrene-ethylene/- butylene-styrene- and styrene graft copolymers such as styrene-butadiene-acrylonitrile (ABS) are another class of preferred polymers for the practice of the invention.
  • ABS styrene-butadiene-acrylonitrile
  • styrene-ethylene/butylene-styrene block copolymer results in greatly improved mechanical properties; from 825 psi tensile strength for S-E/B-S to 1600 psi with only 0.1 wt% additive.
  • ABS graft polymers i.e., Cycolac
  • F-additive yielding 5 atomic % surface fluorine and an increase in hydrophobicity to 96 * contact angle from 73 * with 0.8 wt% F-additive.
  • Polyether and polyamide polymers and block copolymers such as a polyether-polyamide are a third class of preferred polymers for use in the practice of the invention.
  • Mechanical, surface, and processing properties here too are improved by low concentrations of F-additive.
  • improved tensile strength and ductility as shown by an increase in tensile strength from 4030 psi to 4850 psi and an increase in % elongation from 1110% to 1490% with 0.1 wt% F-additive.
  • Polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), aromatic terephthalates and isophthates, and polycarbonates and polyurethanes such as those with aromatic or aliphatic isocyanate derived polymers with polyether or polyester soft segments are also significantly improved by low concentrations of F-additive.
  • PBT exhibits improved extrusion and molding properties as well as fluorocarbon surface properties; i.e., 5.3 atomic % surface fluorine with 0.5% additive.
  • Bisphenol polycarbonate with 0.5 wt% F-additive, has improved tensile strength (7410 to 7930 psi), increased hydrophobicity (contact angle from 78 * to 97 * ), and exhibits 32 atomic % surface fluorine. - 8 -
  • V Other vinyl polymers also exhibit enhanced properties and fluorocarbon surfaces using the additives of this invention.
  • Such polymers include acrylic and methacrylic polymers, i.e., polyraethylmethacrylate, polymethylacrylate, poly- butylmethacrylate, etc., and polyvinyl chloride, and various aromatic vinyl polymers, i.e., polystyrene.
  • fluorocarbon additives having a surface energy substantially lower than that of the polymer with which it is compounded in order to ensure the high surface fluorine concentration described above.
  • Suitable fluorocarbon oils, gums and greases include fluorinated hydrocarbons and fluorinated hydrocarbon-polyether oils, i.e., Aflunox" and Krytox" oils and greases, including such oils, gums and greases as perfluoropolyethylene- oxide, perfluoropolypropylene oxide, polytetrafluoro- ethylene oligomers, perfluoropolyethylene-propylene, perfluoropolybutadiene oligomers, polyvinylidene fluoride oligomers and their copolymers and perfluoro- hydrocarbon oils such as perfluorocyclohexane, perfluorohexane, perfluorodocedane and higher molecular weight homologous linear or branched perfluorohydrocarbons, and perfluorinated cyclic hydrocarbons.
  • fluorinated hydrocarbons and fluorinated hydrocarbon-polyether oils i.e., Aflunox" and
  • the preferred fluorocarbon oils, gums and greases of this invention are characterized by having viscosities in the range of 20 to more than 50,000 centistokes at 20 * C, and the preferred fluorocarbon greases useful in this invention are characterized by having consistencies (as determined by ASTM D-217) in the range of NLGI grades 0 to 6.
  • Preferred greases include those made by mixing or blending fluoro- polyether oils with perfluorhydrocarbons, such as - 9 - those prepared from mixtures of Krytox" fluoroether oils with Vydax" fluorotelomers.
  • the fluorocarbon additive have a lower surface energy, by more than about 5 dynes/cm, as compared with the polymer with which it is compounded. It is a particularly advantageous feature of the present invention that extremely small amounts of fluorocarbon additive may be incorporated in the thermoplastic polymer to achieve the highly unusual and desirable properties associated with the compositions of the invention.
  • the method of the invention for compounding the polymer and fluorocarbon additive enables the use of such small amounts.
  • the melt-blending step results in a homogenous admixture of the ingredients, one is able to obtain, upon cooling the melt, a solid composition having the above-described gradient concentration.
  • the product will comprise a composition wherein a sub- stantial amount of unmixed free fluorocarbon additive simply coats the surface of the polymer. Because of the incompatibility of the F-additive and the differ ⁇ ence in surface energies between the polymers and the fluorocarbon additive, the latter will not readily diffuse into and penetrate the polymer to any appreci ⁇ able extent.
  • a melt-blending apparatus which ensures homogenous mixing of the ingredients is required. It has been found that a twin-screw compounding blender/extruder is particularly advantageous and is therefore preferred for carrying out the method of the invention.
  • Any suitable temperature which is below the decomposition temperature of either the polymer or additive but above the softening point of the polymer and which ensures homogenous admixing of the ingredients may be employed.
  • small particle sizes e.g., pellets or powders
  • This ensures efficient wetting of the polymer particle surface prior to melt-blending thereby ensuring efficient dispersion of the additive throughout the polymer.
  • the fluorocarbon additive is pre-mixed with a fraction of pelletized polymer and the thus wetted fraction or pre-mix is then admixed with the remainder of the polymer and subsequently melt-blended in an efficient high shear compounding extruder such as a twin screw compounding extruder-blender.
  • a major improvement in melt processing for homogeneously blended compositions of this invention is achieved by the incorporation of ⁇ 1 wt% of the fluorocarbon additive.
  • less torque or pressure is required for many compositions as compared to the normal thermoplastic polymer.
  • a reduction in extrusion torque from 3700 meter-grams to 1950 meter-grams is achieved for low density polyethylene containing only 0.5 wt% fluorocarbon oil.
  • the invention is illustrated by the following non-limiting examples in which all percentages are by weight except as otherwise indicated.
  • Base polymer was tumble mixed with 0.5 wt% - 12 - fluorocarbon oil (perfluoropolypropylene oxide, viscosity 450 centistokes at 20 * C) to insure uniform coating of the pellets which were then carefully introduced into the injection molding machine screw for molding under conditions used for the base polymer. It was found, however, that the polymer containing 0.5 wt% additive would not feed adequately for molding. Satisfactory molding could not be achieved despite testing a number of variations in screw speeds and other molding conditions. A similar result, inability to properly feed and mold the base polymer with additive was observed using only 0.25 wt% additive.
  • fluorocarbon oil perfluoropolypropylene oxide, viscosity 450 centistokes at 20 * C
  • compositions identified herein were prepared with dispersed perfluorocarbon oil (perfluoropoly ⁇ propylene oxide, 450 centistoke viscosity at 20 * C, Dupont KrytoxTM AX) in the following manner: The appropriate weight of the oil was added to about 100 grams of polymer pellets as a premix. This was then , added to 1-2 pound quantities of the polymer which was tumble mixed to uniformly distribute the premix pellets which had been wet with the fluorocarbon oil. In initial experiments, concentrations in the range 0.1 to 0.6% oil were used and the polymer-pellet premix appeared uniform.
  • dispersed perfluorocarbon oil perfluoropoly ⁇ propylene oxide, 450 centistoke viscosity at 20 * C, Dupont KrytoxTM AX
  • the oil-mixed pellets were fed into an HBI System 90 microprocessor controlled torque rheometer twin screw extruder (conical twin-screw, three-quarter-inch compounding blender/extruder, with a two-inch, heated strip-die head) to produce approximately 2-inch-wide film extrusions of approximately 0.06-inch thickness.
  • HBI System 90 microprocessor controlled torque rheometer twin screw extruder conical twin-screw, three-quarter-inch compounding blender/extruder, with a two-inch, heated strip-die head
  • Post-extrusion equipment involved chilling rolls in a 3-roll, take-up system.
  • the extruder-rheometer provided information during the compounding and extrusion for torque, temperature, head pressure, etc.
  • the extrusion blending was generally run at speeds of 20-50 RPM.
  • Polyproplyene (PP) was compounded with 0.1, 0.2 and 0.5 wt% oil. It, too, exhibited excellent blend homogeneity at all concentrations. Extrusion zone conditions were 370 to 440 * F at 25 RPM. For polypropylene, there was a surprisingly rapid reduction in torque from 4735 M-g for polypropylene to 1395 M-g with only 0.1% fluorocarbon oil.
  • SEBS Styrene-Ethylene/Butylene-Styrene TPE Block Copolymer
  • contact angle wettability using water and methylene iodide was measured to determine the changes in surface hydrophobicity and surface energy produced by the additive. This was done with a Rami-Harte goniometer using the method of Owens and Wendt.
  • the ductility of the polyethylene is enhanced significantly by low concentrations of the fluorocarbon additive.
  • the polar component decreases significantly and a smaller increase is noted in the dispersive component resulting in a significant decrease in the total surface energy, which is characteristic of a fluoro ⁇ carbon surface. - 17 -
  • the XPS results show much higher concentration of the fluorocarbon additive at the surface as compared to the overall amount added demonstrating the surpri- ingly large effect of small fluorocarbon concentra ⁇ tions in producing fluorocarbon surfaces.
  • the FTIR/ATR spectra show the emergence of a new peak at 1240 cm-1 corresponding to -CF2 ⁇ absorption, and its intensity increases as the amount of additive is increased.
  • the FTIR and XPS data correlate well.
  • the base polymer had poorer properties as compared to the polymer with additive. Ultimate tensile strength and elongation were surprisingly higher for the samples with additive. The mechanical properties did not appear to change significantly above the 0.1% level.
  • Example 1 The procedure of Example 1 was followed to prepare and test the following compositions containing 0.1% to 0.8% F-additive.
  • ABS Acrylonitrile-butadiene-styrene
  • the water contact angle increases (increasingly hydrophobic) as the amount of additive increases.

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)

Abstract

Composition de matière formée par mélange en fusion d'un polymère thermoplastique et de 0,01 % à moins de 1 % en poids d'une huile, d'une gomme ou de graisse de fluorocarbone, l'additif ayant une énergie superficielle inférieure à celle du polymère, de sorte que la concentration de l'additif de fluorocarbone dans une coupe transversale du mélange obtenu est inférieure à l'intérieur et supérieure sur les surfaces.
PCT/US1990/005928 1989-12-06 1990-10-22 Polymeres thermoplastiques avec additifs de fluorocarbone disperses WO1991008254A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44667589A 1989-12-06 1989-12-06
US446,675 1989-12-06

Publications (1)

Publication Number Publication Date
WO1991008254A1 true WO1991008254A1 (fr) 1991-06-13

Family

ID=23773459

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/005928 WO1991008254A1 (fr) 1989-12-06 1990-10-22 Polymeres thermoplastiques avec additifs de fluorocarbone disperses

Country Status (5)

Country Link
EP (1) EP0504152A4 (fr)
JP (1) JP2631911B2 (fr)
AU (1) AU6618290A (fr)
CA (1) CA2029404A1 (fr)
WO (1) WO1991008254A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04372653A (ja) * 1991-06-24 1992-12-25 Central Glass Co Ltd 熱可塑性ウレタン樹脂組成物
US5482765A (en) * 1994-04-05 1996-01-09 Kimberly-Clark Corporation Nonwoven fabric laminate with enhanced barrier properties
US5688157A (en) * 1994-04-05 1997-11-18 Kimberly-Clark Worldwide, Inc. Nonwoven fabric laminate with enhanced barrier properties
US5939341A (en) * 1994-06-08 1999-08-17 Kimberly-Clark Worldwide, Inc. Nonwoven fabric laminate
US6380289B1 (en) 1993-06-28 2002-04-30 3M Innovative Properties Company Thermoplastic composition comprising fluoroaliphatic radical-containing surface-modifying additive
US6541558B1 (en) * 1996-10-09 2003-04-01 Res Development Corporation Thermoplastic polymers with dispersed fluorocarbon additives
WO2008065164A1 (fr) * 2006-11-30 2008-06-05 Solvay Solexis S.P.A. Additifs d'halopolymères
EP2135982A3 (fr) * 2008-06-18 2010-05-26 Teijin Monofilament Germany Gmbh Monofilaments modifiés à l'aide de perfluoropolyéthers
EP3795636A1 (fr) * 2019-09-20 2021-03-24 SABIC Global Technologies B.V. Utilisation de polyéthers perfluorés pour la modification de copolymères de polycarbonate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126358A (en) * 1964-03-24 Polypropylene
US3956000A (en) * 1972-07-21 1976-05-11 Hoechst Aktiengesellschaft Fluorocarbon waxes and process for producing them
US4146524A (en) * 1977-12-02 1979-03-27 General Electric Company Polycarbonate compositions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2510625A1 (de) * 1974-03-29 1975-10-02 Crinospital Spa Polyvinylchlorid enthaltende zubereitung
JPS5719781A (en) * 1980-07-11 1982-02-02 Canon Kk Electronic geography learning machine
JPS60104161A (ja) * 1983-11-10 1985-06-08 Fuji Electric Co Ltd 耐摩耗性成形材料
CA1309544C (fr) * 1986-02-25 1992-10-27 Jerold C. Rosenfeld Compositions stabilisees de polyester aromatique
US4855360A (en) * 1988-04-15 1989-08-08 Minnesota Mining And Manufacturing Company Extrudable thermoplastic hydrocarbon polymer composition
JP2623318B2 (ja) * 1988-11-10 1997-06-25 日本ユニカー株式会社 熱収縮性フイルムの製造方法
JPH02140261A (ja) * 1988-11-18 1990-05-29 Kanegafuchi Chem Ind Co Ltd 成形用粒状組成物
JPH02250208A (ja) * 1989-03-23 1990-10-08 Fujikura Ltd 絶縁電線

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126358A (en) * 1964-03-24 Polypropylene
US3956000A (en) * 1972-07-21 1976-05-11 Hoechst Aktiengesellschaft Fluorocarbon waxes and process for producing them
US4146524A (en) * 1977-12-02 1979-03-27 General Electric Company Polycarbonate compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0504152A4 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04372653A (ja) * 1991-06-24 1992-12-25 Central Glass Co Ltd 熱可塑性ウレタン樹脂組成物
US6380289B1 (en) 1993-06-28 2002-04-30 3M Innovative Properties Company Thermoplastic composition comprising fluoroaliphatic radical-containing surface-modifying additive
US5482765A (en) * 1994-04-05 1996-01-09 Kimberly-Clark Corporation Nonwoven fabric laminate with enhanced barrier properties
US5688157A (en) * 1994-04-05 1997-11-18 Kimberly-Clark Worldwide, Inc. Nonwoven fabric laminate with enhanced barrier properties
US5939341A (en) * 1994-06-08 1999-08-17 Kimberly-Clark Worldwide, Inc. Nonwoven fabric laminate
US6541558B1 (en) * 1996-10-09 2003-04-01 Res Development Corporation Thermoplastic polymers with dispersed fluorocarbon additives
WO2008065164A1 (fr) * 2006-11-30 2008-06-05 Solvay Solexis S.P.A. Additifs d'halopolymères
US20090326154A1 (en) * 2006-11-30 2009-12-31 Solvay Solexis S.P.A. Additives for Halopolymers
CN101595179B (zh) * 2006-11-30 2011-12-07 索维索莱克西斯公开有限公司 用于卤代聚合物的添加剂
US8217119B2 (en) * 2006-11-30 2012-07-10 Solvay Solexis S.P.A. Additives for halopolymers
EP2135982A3 (fr) * 2008-06-18 2010-05-26 Teijin Monofilament Germany Gmbh Monofilaments modifiés à l'aide de perfluoropolyéthers
EP3795636A1 (fr) * 2019-09-20 2021-03-24 SABIC Global Technologies B.V. Utilisation de polyéthers perfluorés pour la modification de copolymères de polycarbonate
WO2021053622A1 (fr) * 2019-09-20 2021-03-25 Shpp Global Technologies B.V. Utilisation de polyéthers perfluorés pour la modification de copolymères de polycarbonate
CN114585687A (zh) * 2019-09-20 2022-06-03 高新特殊工程塑料全球技术有限公司 全氟化聚醚用于聚碳酸酯共聚物的改性的用途

Also Published As

Publication number Publication date
CA2029404A1 (fr) 1991-06-07
EP0504152A4 (en) 1993-06-23
EP0504152A1 (fr) 1992-09-23
JPH05504581A (ja) 1993-07-15
AU6618290A (en) 1991-06-26
JP2631911B2 (ja) 1997-07-16

Similar Documents

Publication Publication Date Title
US5286773A (en) Thermoplastic polymers with dispersed fluorocarbon additives
EP0051933B1 (fr) Compositions de PTFE contenant des polymères formant une masse fondue anisòtropique
US5912291A (en) Thermoplastic polymers with polyfluoroalkylsiloxane modified surfaces
US5306772A (en) Polyacetal resin composition and its molded article
IE43418B1 (en) Blend of thermoplastic polymers including block radial polymers of the butadiene-styrene type
JPH08506373A (ja) 掻傷耐性を有する重合体組成物
WO1991008254A1 (fr) Polymeres thermoplastiques avec additifs de fluorocarbone disperses
DE10330287A1 (de) Organopolysiloxangranulat
JP3177984B2 (ja) 少なくとも一種類のカプセル化された成核剤を含有するポリオキシメチレン組成物
US4423192A (en) Lubricated thermoplastic compositions of polyvinylidene fluoride
JPH06287406A (ja) ポリアセタール樹脂組成物および摺動部材
US5435925A (en) Polyethylene lubricant-dispensing compositions
US6087430A (en) Thermoplastic polymers with dispersed fluorocarbon additives
JP3592845B2 (ja) 熱可塑性有機樹脂とオルガノポリシロキサンからなるマスターバッチの製造方法
CN114350071A (zh) 一种高均匀度聚丙烯改性母粒及其制备方法
JP3081610B1 (ja) 自己潤滑性ポリアセタール樹脂組成物
SU1558932A1 (ru) Антифрикционна полимерна композици и способ ее получени
JPH06287405A (ja) ポリアセタール樹脂組成物および摺動部材
US6794438B2 (en) Thermoset polymers with dispersed fluorocarbon additives
EP0709431A2 (fr) Compositions de polyacétal autolubrifiantes
Raveverma et al. Mechanical behaviour and compatibility analysis of thermoplastic polyurethane/polycaprolactone-based new fused deposition modelling filament composite
JPS63179965A (ja) 摺動材用組成物
JPH10330500A (ja) 木目模様を有する板状樹脂成形品の製造方法
US20060194911A1 (en) Thermoset polymers with dispersed fluorocarbon additives
KR790001326B1 (ko) 수지 조성물

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1990916144

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1990916144

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1990916144

Country of ref document: EP