EP1025151A1 - Article resistant a l'eau fabrique a partir d'un polymere thermodurcissable et d'un additif fluorocarbone - Google Patents

Article resistant a l'eau fabrique a partir d'un polymere thermodurcissable et d'un additif fluorocarbone

Info

Publication number
EP1025151A1
EP1025151A1 EP98955216A EP98955216A EP1025151A1 EP 1025151 A1 EP1025151 A1 EP 1025151A1 EP 98955216 A EP98955216 A EP 98955216A EP 98955216 A EP98955216 A EP 98955216A EP 1025151 A1 EP1025151 A1 EP 1025151A1
Authority
EP
European Patent Office
Prior art keywords
fluorocarbon
polymer
article
wear resistant
thermosetting polymer
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Withdrawn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
EP98955216A
Other languages
German (de)
English (en)
Inventor
Benjamin F. Du Pont
Leonard Edward Raymond Kosinski
Michael William Duch
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and 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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1025151A1 publication Critical patent/EP1025151A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • This invention relates to a wear resistant article comprising a thermosetting polymer-fluorocarbon composition and to a method for making said article.
  • U.S. Patent No. 5,061,759 relates to rubber compositions vulcanizable by 15 means of peroxides and containing processing-coadjuvating additives which are perfluoropolyethers in amounts ranging from 0.5 to 1 part by weight of the rubber composition.
  • the additives improve processability in extrusion and give better detachability of a vulcanized article from a molding die without adversely affecting the vulcanizing system or the properties of the vulcanized article.
  • the only articles 20 described in this patent are test pieces for evaluation of physical properties. There is no reference to wear resistance of the articles.
  • Japanese Patent Application Pub. No. 60-104161 describes an abrasion resistant molding material comprising a thermosetting resin or a thermoplastic resin with a fluorinated oil, preferably 1-10%, uniformly adhered to, impregnated or 25 dispersed jn the molding material.
  • Suitable fluorinated oils include perfluoropolyethers (such as, hexafluoropropylene oxide oligomers), and fluorocarbon oils (such as, tetrafluoroethylene oligomers).
  • the molding material is used to make more wear resistant sliding components for electrical contact switches, electromagnetic switches and the like.
  • 5,286,773 relate to a composition of matter formed by melt blending a thermoplastic polymer and from 0.01% to less than 1% of a fluorocarbon additive and to a method of forming the composition.
  • the fluorinated additive is a fluorocarbon oil, gum or grease including fluorinated hydrocarbons and fluorinated hydrocarbon polyether oils.
  • the compositions are said to enhance and accelerate molding and extrusion operations for films and fibers.
  • the basic bulk mechanical, physical and chemical properties of the thermoplastic polymers are retained or even enhanced. Due to the concentration of the fluorocarbon additive at the surface, articles made from the composition acquire fluorocarbon-like surface properties. There is no disclosure that the articles are wear resistant.
  • the composition is useful for medical products e.g., vascular grafts, mammary or ocular implants, electronic equipment, electro-optical or electro-mechanical components and as molds for precision parts for such devices.
  • thermoplastic composition which comprises mixtures of vinyl chloride polymers and chlorinated polyethylene and which contains up to 0.4% of finely divided fluoropolymers, such as polytetrafluoroethylene, polytrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride and fluorinated polyethers e.g., perfluorovinylpolyether.
  • fluoropolymers such as polytetrafluoroethylene, polytrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride and fluorinated polyethers e.g., perfluorovinylpolyether.
  • the composition has a markedly improved processability, particularly when shaped into articles by extrusion.
  • the use of such compositions for making shaped articles such slabs, tubes, and sheeting is described. There is no mention of such articles having improved wear resistance.
  • An object of the present invention is to make available articles which are useful in applications where minimum wear is required.
  • Articles made from thermosetting polymer-fluorocarbon compositions by the procedures of this invention are found to show improved wear resistance in a wide range of applications. Inco ⁇ oration of a fluorocarbon with the polymer greatly increases the longevity or permanence of the beneficial effect compared to surface treatment of the polymeric article with a fluorocarbon.
  • a wear resistant article can be made from a thermosetting polymer (or mixed thermosetting polymers) and about 0.01% to less than 1%, typically about 0.1% to less than 1%, bulk concentration by weight of an additive consisting of a fluorocarbon (or mixture of fluorocarbons), said fluorocarbon additive having a lower surface energy than that of said polymer and the concentration of said fluorocarbon being substantially higher at the surface of said article than the nominal bulk concentration.
  • wear resistant it is meant that the article will have a longer life in use compared to an article that is identical except for the absence of the fluorocarbon additive.
  • the wear resistant article may also contain conventional compounding additives such as fillers, reinforcing agents colorants and the like.
  • a valuable property of an article of this invention is that its wear resistant character extends throughout its useful life.
  • this invention relates to a method for making a wear resistant article which consists of mixing a thermosetting polymer, a fluorocarbon and other compounding additives and producing the desired shape by an appropriate procedure such as molding or extrusion.
  • a wear resistant article of this invention comprises a thermosetting polymer, or mixed thermosetting polymers, and an additive consisting of fluorocarbon or mixture of fluorocarbons, the proportion of the latter ranging from about 0.01% to less than 1%, typically from about 0.1%, to less than 1% bulk concentration by weight of the amount of polymer, said fluorocarbon additive having a lower surface energy than that of said polymer and the concentration of said fluorocarbon being substantially higher at the surface of said article than the nominal bulk concentration.
  • the wear resistant article may also contain conventional compounding additives such as fillers, reinforcing agents, colorants and the like.
  • a valuable property of an article of this invention is that its wear resistant character is retained throughout its useful life.
  • This invention also relates to a method for inco ⁇ orating a thermosetting polymer with a fluorocarbon and other compounding additives and for forming a wear resistant article of this invention from such a composition.
  • gasket includes (1) articles inserted between two relatively hard surfaces to cushion their contact, and (2) articles that contact against a hard surface to form a seal, such as weather-stripping or lubricant seals; and the term “blade” includes articles that move across a hard surface to remove a substance, such as windshield wipers and squeegees.
  • Preferred wear resistant articles of this invention are stationary or moving parts which are in sliding contact with stationary or moving surfaces, such as wear pads, windshield wiper blades, conveyer line sections, engine drive belts, gears, contact switches, magnetic switches, luggage straps and buckles, footwear (particularly footwear for athletic pu ⁇ oses), window hardware components, seals between flanges such as gaskets for engines, for lines that carry gases or liquids, for pumps, for reaction vessels and the like, seal caps and boots for lubricated joints, wire harness connectors, spark plug caps, oriented bumpers, bumper suspensions, tail light assemblies, parts for domestic and commercial appliances.
  • stationary or moving surfaces such as wear pads, windshield wiper blades, conveyer line sections, engine drive belts, gears, contact switches, magnetic switches, luggage straps and buckles, footwear (particularly footwear for athletic pu ⁇ oses), window hardware components, seals between flanges such as gaskets for engines, for lines that carry gases or liquids, for pumps, for reaction vessels and the like, seal caps and boots for lubricated joints, wire
  • the wear resistant articles of this invention are suitable in applications where some flexibility, and the maintenance of a high level of performance when exposed to adverse conditions over extended periods, are desirable. They meet these requirements when they are used as sealing elements or as items for aesthetic or functional pu ⁇ oses.
  • a particular advantage of the wear resistant articles of this invention derives from compounding the fluorocarbon material and thermosetting polymer components prior to fabrication of the desired shape. Migration of the fluorocarbon towards the surface of the article occurs during the fabrication step so that the concentration of fluorocarbon is much greater at the surface than the nominal bulk concentration.
  • the high concentration of fluorocarbon additive near the surface gives rise to fluorocarbon-like surface properties such as, lower friction, hydrophobicity, chemical inertness and non-adherent surfaces. These properties are often beneficial and in particular the extent to which wear occurs is considerably decreased and it can be virtually eliminated in many situations.
  • An important additional benefit which derives from mixing the fluorocarbon component with the thermosetting polymer and other additives prior to or during fabrication is the greater longevity of performance compares with that obtained with post applied surface coatings.
  • Thermosetting polymer resins are used in the compositions from which the wear resistant articles of this invention are made.
  • Thermosetting resins are converted to infusible material during the fabrication process and thus the finished product is no longer susceptible to molten reprocessing without severe property losses.
  • Both hard and soft categories of thermosetting resins are useful to make compositions suitable for fabricating the wear resistant articles of this invention.
  • hard polymer resins can be classified as having a Rockwell R scale hardness in the range of from about 50 to about 115, as measured by ASTM method D-785-89.
  • Soft polymer resins are those having a Durometer Shore A scale hardness in the range of from about 10 to about 90, as measured by ASTM method D-2240-91.
  • Thermosetting hard and soft polymer resins which are suitable for making of the wear resistant articles of the present invention, include, but are not necessarily limited to: allyl molding compounds, bis-maleimides, epoxy resins, phenolic resins, polyesters, ethylene-propylene-diene te ⁇ olymers (e.g., EPDM rubber), polyimides, ionomers (e.g., Surlyn®), polyurethanes, segmented polyurea/urethanes, silicones and urea-melamine formaldehyde resins.
  • Thermosetting resins are also meant to include thermoplastic resins which have been cross-linked to a high enough degree such that molten reprocessing is no longer possible without severe property losses.
  • thermoplastic and thermosetting polymers such as EPDM rubber “alloys” with polypropylene (Santoprene®) and with PVC (Alcryn®) are also suitable for making the wear resistant articles of this invention.
  • Articles comprising foamed polymer-fluorocarbon compositions are also within the purview of this invention.
  • the polymer resins used in the wear resistant articles of this invention may also contain one or more of the following conventional resin compounding ingredients, such as but are not necessarily limited to: organic or inorganic fillers, reinforcing agents, colorants, thermal stabilizers, antioxidants, antiozonants, antistatic agents, antimicrobial agents, plasticizers, lubricants, antifogging agents, coupling agents, flame retardants, foaming agents, fragrances, heat stabilizers, impact modifiers, mold release agents, titanates, ultraviolet stabilizers, thermally conductive fillers, electrically conductive fillers, curing agents, cross-linking agents catalysts, and the like.
  • conventional resin compounding ingredients such as but are not necessarily limited to: organic or inorganic fillers, reinforcing agents, colorants, thermal stabilizers, antioxidants, antiozonants, antistatic agents, antimicrobial agents, plasticizers, lubricants, antifogging agents, coupling agents, flame retardants, foaming agents, fragrances, heat stabilizers, impact modifiers,
  • Suitable fluorocarbon additives are oils, gums or greases comprising fluorinated hydrocarbons or fluorinated hydrocarbonpolyethers having six or more carbon atoms, including linear, branched and cyclic compounds.
  • suitable compositions are perfluoroalkylpolyethers, ( e.g.
  • Krytox® Fomblin®, Demnum® and Aflunox® perfluoropolyethylene oxide, perfluoropolypropylene oxide, polytetrafluoroethylene (Teflon®), perfluoropolyethylene-polypropylene, perfluoropolybutadiene, polyvinylidene fluoride perfluorocarbons and fluorohydrocarbons including ethers containing functional group(s) such as but not limited to alcohols, amines, amides, esters, nitriles, thiols, acids, acid halides, including chlorine , bromine and iodine.
  • functional group(s) such as but not limited to alcohols, amines, amides, esters, nitriles, thiols, acids, acid halides, including chlorine , bromine and iodine.
  • Higher molecular weight homologous linear and branched fluorohydrocarbons and fluorinated cyclic hydrocarbons may also be used, as well as partially fluorinated additives, such as those more than 50% fluorinated, preferably more than 75% fluorinated.
  • partially fluorinated additives such as those more than 50% fluorinated, preferably more than 75% fluorinated.
  • polychlorotrifluoroethylenes, polytetrafluoroexetanes, or other highly fluorinated compounds may be selected.
  • Fluorocarbon or mixed fluorocarbon additives compounded with thermosetting polymer resins preferably have a surface energy substantially lower than that of the polymers. This leads to migration of the fluorocarbon to the surface of the wear resistant article during the fabrication process. Generally it is preferred that a fluorocarbon have a surface energy at least 5 dynes/cm lower than the surface energy of the polymer with which it is compounded.
  • the amount of fluorocarbon which may be compounded with a polymeric material is in the range of about 0.01% to less than 1%, typically from about 0.1% to less than 1%, bulk concentration on a weight basis.
  • the beneficial effects of the fluorocarbon additive are evident at the lowest end of the range, due to the concentration at the surface being much higher than the nominal bulk concentration.
  • concentration of fluorocarbon in a surface layer 10 nm thick is respectively about 35% and about 88%. It is preferred that at least 0.1% of fluorocarbon be used in many of the shaped articles of the invention in order to obtain a desirable level of performance in most applications.
  • the optimum amount of fluorocarbon additive will vary with the selected polymer, processing conditions, and intended use, and is readily determined by routine experimentation.
  • the relationship between the surface concentration and the nominal bulk loading of a fluorocarbon additive in a polymer is ascertained by determining the former by conducting the ESCA analytical procedure on test specimens, "poker chips", compounded with different levels of perfluoroalkylpolyether oil, (Krytox®).
  • This procedure which quantitatively analyzed the atomic concentration of elements in a surface layer 5 to 10 nanometers (nm) thick, is calibrated by applying a film of Krytox® oil to a glass slide and determining the level of fluorine in the film. This amount of fluorine, about 65wt%, corresponds to 100% coverage, with Krytox® oil.
  • the level of Krytox® oil in the surface layer is ascertained.
  • the data given in Table 1 are from a series of samples in which the Krytox® additive ranged from about 0.1 wt% to about 1.0 wt%.
  • the level of Krytox® is clearly much higher in the surface layer than in the bulk of the sample.
  • the degree to which fluorocarbon surface enrichment occurs depends upon the particular polymer and fluorocarbon components of a composition and the procedure used to mix them and fabricate an article of this invention.
  • thermosetting polymer-fluorocarbon composition At some point during fabrication of a wear resistant article comprising a thermosetting polymer-fluorocarbon composition, the thermosetting polymer- fluorocarbon composition must be processed as a liquid.
  • the fluorocarbon is completely or to a large degree immiscible with the polymer and other components. Sufficient mixing must be provided to disperse the fluorocarbon throughout the polymer-fluorocarbon composition.
  • the fluorocarbon wets the processing equipment surfaces because of its low surface tension.
  • Processing a thermosetting polymer-fluorocarbon composition from the liquid state to a solid article should include an essentially non-turbulent (i.e., not well mixed) flow field and adequate quench time to allow the fluorocarbon enriched surface layer to develop. Antithetically, if the liquid state were in a highly turbulent (i.e., well mixed) flow field and instantaneously quenched to the solid state considerably less fluorocarbon surface enrichment would occur.
  • thermosetting polymer-fluorocarbon composition contains other additives which remain as solids when the polymer-fluorocarbon composition is being processed as a liquid
  • these solid ingredients should be wetted with molten polymer or molten composition ingredients other than the fluorocarbon prior to addition of the fluorocarbon. Otherwise, the fluorocarbon having a very low surface tension would wet the solid additive surfaces resulting in decreased fluorocarbon surface enrichment for the thermosetting polymer-fluorocarbon phase.
  • Thermosetting polymer-fluorocarbon compositions can be made via two different routes: 1) Involves molten processing of additives and fluorocarbons with an already formed polymer with simultaneous or subsequent curing (i.e., cross-linking) to affect its thermoset character;
  • thermosetting polymer-fluorocarbon Involves contacting monomer, additive and fluorocarbon to form the thermosetting polymer directly; the fluorocarbon will need to be well mixed in the reactants as they contact each other, to form the enriched surface layer as the thermoset polymerization occurs. In either case, it is unlikely that the fluorocarbon will interfere with polymerization or curing reactions.
  • some of the possible (but not inclusive) processing methods are: 1) dry mixing a polymer powder, a plasticizer, and other additives so as to wet the ingredients which remain solid during the molten processing, adding the fluorocarbon last to the dry blend, and feeding to a molten mixing device;
  • Liquid injection of the fluorocarbon into a molten mixing device is the preferred manner of adding fluorocarbon to the polymer-fluorocarbon composition.
  • Some examples of molten mixing devices which can be used to mix the polymer-fluorocarbon composition are continuos mixers, extruders, kneaders and injection molding machines.
  • thermosetting polymer When the thermosetting polymer is directly formed from the reactants, the fluorocarbon will need to be well mixed in with the reactants as they contact each other, and will need to form the enriched surface layer as the thermoset polymerization occurs.
  • Thermosetting polymer-fluorocarbon articles the concentration of said fluorocarbon being in the range from about 0.01% to less than 1% bulk concentration by weight can be formed by a number of established fabrication processes.
  • the fabrication process will usually be determined by cost effectiveness, for example the elimination of topical application labor costs, and/or the need to fit existing process equipment.
  • the fabrication process used to make the thermosetting polymer- fluorocarbon article will determine the nature of the polymer and fluorocarbon feedstocks to the process. If the fabrication process involves little or no mixing, e.g., compression molding, then a pre-compounded polymer-fluorocarbon composition would best serve as the feedstock. However, if the fabrication process employs a molten mixing device with sufficient mixing, the process feeds could be a post-compounded polymer-fluorocarbon composition, polymer with fluorocarbon liquid injection, or blends of polymer and a pre-compounded polymer-fluorocarbon composition.
  • thermosetting polymer-fluorocarbon article is comprised of a polymer foam
  • the maximum outer surface enrichment by the fluorocarbon will be obtained if the fluorocarbon surface enrichment largely occurs prior to the foam expansion and freezing step.
  • the foamed polymer-fluorocarbon composition is processed molten as an expanded foam the fluorocarbon, due to its low surface tension, would enrich the surfaces of the interior foam cells decreasing enrichment of the outer surface of the article.
  • thermosetting polymer-fluorocarbon article fabrication processes include, but are not limited to: extrusion, injection molding, injection blow molding, extrusion blow molding, calendaring, pultrusion, reactive injection molding, and reactive extrusion.
  • thermosetting polymer-fluorocarbon article shapes that can be fabricated include, but are not limited to: fibers, rods, tubes, films, sheets, profiles and intricately shaped parts.

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  • 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

La présente invention concerne un article résistant à l'usure, comprenant une composition de polymère fluorocarboné thermodurcissable et son procédé de fabrication.
EP98955216A 1997-10-31 1998-10-30 Article resistant a l'eau fabrique a partir d'un polymere thermodurcissable et d'un additif fluorocarbone Withdrawn EP1025151A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US6389597P 1997-10-31 1997-10-31
US63895P 1997-10-31
PCT/US1998/023114 WO1999023148A1 (fr) 1997-10-31 1998-10-30 Article resistant a l'eau fabrique a partir d'un polymere thermodurcissable et d'un additif fluorocarbone

Publications (1)

Publication Number Publication Date
EP1025151A1 true EP1025151A1 (fr) 2000-08-09

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Application Number Title Priority Date Filing Date
EP98955216A Withdrawn EP1025151A1 (fr) 1997-10-31 1998-10-30 Article resistant a l'eau fabrique a partir d'un polymere thermodurcissable et d'un additif fluorocarbone

Country Status (3)

Country Link
EP (1) EP1025151A1 (fr)
JP (1) JP2001521962A (fr)
WO (1) WO1999023148A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20010554A1 (it) 2001-03-16 2002-09-16 Ausimont Spa Additivi per resine idrogenate
CN102365331B (zh) 2009-03-27 2014-07-09 株式会社Adeka 塑料瓶的制造方法
US20180319982A1 (en) 2015-11-05 2018-11-08 Solvay Specialty Polymers Italy S.P.A. Method for the manufacture of (per)fluoropolyether modified polyamides and polyamides obtainable with such method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60104161A (ja) * 1983-11-10 1985-06-08 Fuji Electric Co Ltd 耐摩耗性成形材料
US5143963A (en) * 1989-12-06 1992-09-01 Res Development Corp. Thermoplastic polymers with dispersed fluorocarbon additives
JP3472050B2 (ja) * 1995-10-02 2003-12-02 大同メタル工業株式会社 湿式スラスト軸受用摺動部材

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9923148A1 *

Also Published As

Publication number Publication date
JP2001521962A (ja) 2001-11-13
WO1999023148A1 (fr) 1999-05-14

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