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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/0286—Chemical after-treatment
  • C08G75/029—Modification with organic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
  • C08L23/283—Iso-olefin halogenated homopolymers or copolymers

Definitions

• the invention relates to the field of chemistry and relates to polyphenylene sulfide (per) fluoropolymer Matehalien, for example, as tribomaterials for z.
• polyphenylene sulfide (per) fluoropolymer Matehalien for example, as tribomaterials for z.
• Polyphenylene sulfides (PPS) as high performance materials are offered commercially modified with various fillers and reinforcing agents.
• these fillers and reinforcing materials are physically incorporated into the prior art PPS polymer matrix.
• the materials with special tribological properties include the (per) fluoropolymers such.
• the polytetrafluoroethylene (PTFE) and the FEP are examples of fluoropolymers.
• PTFE polytetrafluoroethylene
• FEP fluoropolymers
• chemical activation of PTFE with (1.) sodium amide in liquid ammonia and (2.) with organometallic compounds in aprotic inert solvents is achieved.
• the object of the present invention is to provide polyphenylene sulfide (per) fluoropolymer materials which have improved tribological behavior and a simple and inexpensive process for their preparation and use.
• the polyphenylene sulfide (per) fluoropolymer materials according to the invention consist of a polyphenylene sulfide polymer matrix (PPS polymer matrix) material prepared by melt modification with modified (per) fluoropolymers dispersed therein (poly) dispersed, wherein the modification the (per) fluoropolymer is realized with functional groups, and the modified (per) fluoropolymer particles bound via chemical couplings with the PPS polymer matrix, the chemical couplings during the melt modification by reaction with existing functional, reactive Groups of (per) fluoropolymers and / or with functional groups formed during the melt modification of persistent (persistent) perfluorocarbon (peroxy) radicals of the (per) fluoropolymers and / or with functional (re) active groups formed during the melt modification the (per) fluoropolymers have taken place.
• PPS polymer matrix polymer matrix
• the (per) fluoropolymers are chemically coupled via thioether and / or thiolester bond (s) with the PPS polymer matrix
• linear and / or branched polymers are present as PPS matrix.
• polytetrafluoroethylene and / or poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) and / or poly (ethylene-co-tetrafluoroethylene) (ETFE) and / or polychlorotrifluoroethylene (PCTFE) and / or poly (tetrafluoroethylene-co-perfluoroalkylvinylether) (TFA or PFA).
• the chemically coupled (per) fluoropolymers acting as nucleating agent / nucleating agent are finely distributed in the PPS polymer matrix.
• Polyphenylene sulfide (PPS) having thiol and / or thiolate groups with one or more modified (per) fluoropolymer (micro / nano) powders are used in the process of making polyphenylene sulfide (per) fluoropolymer materials of the present invention - or multi-stage in melt compounded reactive, wherein Further thermoplastic or thermosetting (high-performance) polymers and / or fillers and / or reinforcing agents and / or additives may be added.
• modified (per) fluoropolymer powders having olefinically unsaturated groups and / or with carboxylic acid groups and / or carboxylates and / or carboxylic acid halide groups, even more advantageously with perfluoroalkylene groups or the Carbon
• modified (per) fluoropolymer powders with persistent perfluorocarbon (peroxy) radicals are used, even more advantageously modified (per) fluoropolymer powders with persistent (persistent) perfluorocarbon (peroxy) radicals are used have been prepared by radiation-chemical modification of (per) fluoropolymer (micro / nano) powder particles under the influence of oxygen.
• modified (per) fluoropolymer (micro / nano) powder polytetrafluoroethylene (PTFE) and / or poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) and / or poly (ethylene-co-tetrafluoroethylene) ( ETFE) and / or polychlorotrifluoroethylene (PCTFE) and / or poly (tetrafluoroethylene-co- perfluoroalkylvinylether) (TFA or PFA) are used, wherein advantageously as a modified (per) fluoropolymer (micro / nano) powder blasting chemically mined PTFE and is still advantageously used under the influence of oxygen radiation chemically mined PTFE.
• PTFE polytetrafluoroethylene
• FEP tetrafluoroethylene-co-hexafluoropropylene
• ETFE ethylene-co-tetrafluoroethylene
• PCTFE polychlorotriflu
• a PTFE degraded with at least 20 kGy, even more advantageously with at least 100 kGy and modified PTFE, is used as radiation-degraded PTFE. It is also advantageous if a thermally / thermomechanically modified (per) fluoropolymer (micro / nano) powder particle is used as the modified (per) fluoropolymer (micro / nano) powder.
• PPS polymers having a small number of thiol and / or thiolate groups in relation to thiol- and / or thiolate-rich PPS polymers of 99: 1 to 1:99 are used.
• PPS polymers with ⁇ 1% thiol groups are used at the PPS chain ends as PPS polymers with a low proportion of thiol and / or thiolate groups.
• PPS polymers with> 1% thiol groups are used at the PPS chain ends as PPS polymers with a high proportion of thiol and / or thiolate groups.
• thermoplastic or thermosetting (high-performance) polymers and / or fillers and / or reinforcing substances are added before or during or after the reactive compounding.
• the reactive compounding is carried out in a melt mixer and / or in a kneader and / or a twin-screw or multi-screw extruder and / or in a planetary roller extruder. It is also advantageous if the reactive compounding is carried out at melt processing temperatures of at least or above the melt temperature of the PPS material.
• the reactive compounding is at
• the modified (per) fluoropolymer (micro / nano) powder is added to the melt during compounding at one or more metering points.
• modified (per) fluoropolymer (micro / nano) powder is used as a mixture of unmodified and modified (per) fluoropolymers.
• polyphenylene sulfide (per) fluoropolymer materials takes place as a compact substance and / or as additive / constituent of slide bearings and / or in oleophobic and / or hydrophobic or thus equipped partial or compact materials and / or in molded parts and / or as Surface modification component in (sliding) films or as a coating and / or in (lubricious) films and / or as a blend component and / or as an additive.
• the polyphenylene sulfide (per) fluoropolymer materials are used for further processing into a thermoplastic melt and / or to a reactive mass and / or to a dispersion.
• the present invention makes it possible to provide chemically coupled polyphenylene sulfide (per) fluoropolymer materials via a melt reactive reaction having a stable processing morphology and a finely dispersed (per) fluoropolymer component in the PPS matrix component, which may be added to Components can be processed, the sliding friction values comparable to the PTFE and have low wear coefficients. As a result, such components achieve a longer service life.
• the compounds according to the invention of PPS and (per) fluoropolymer are obtained by reactive conversion in, for example, a melt mixer.
• the modified (per) fluoropolymer component is not only homogeneously distributed in the PPS matrix, but it is compatibilized with the PPS matrix component by chemical coupling, i. chemically coupled. This leads to the advantageous properties of the materials according to the invention.
• Detection of the chemical coupling is carried out via the separation of the unbound PPS matrix component from the insoluble (per) fluoropolymer component, according to the invention no longer the pure (per) fluoropolymer is obtained, but a (per) fluoropolymer product containing surface-chemically coupled and post-separation modified PPS polymer chains.
• Reactive groups on the PPS are the thiol and / or thiolate groups of the linear or branched PPS polymers, which are preferably present as end groups.
• the reactive groups in the (per) fluoropolymer are olefinically unsaturated double bonds which are capable of addition with the thiol and / or thiolate groups in the PPS.
• the melt processing conditions can be adjusted to form such elimination / elimination reactions as to form reactive olefinic double bonds in the (per) fluoropolymer component.
• hydrogen halide and preferably hydrogen fluoride is split off and / or existing carboxylic acid groups react with elimination of CO 2 and simultaneous or subsequent elimination of hydrogen fluoride and thus in-situ reactive coupling centers are formed.
• Another coupling reaction is the reaction of the thiol and / or thiolate groups on the PPS with carbonyl fluoride groups on the (per) fluoropolymer, e.g. B. during radiation modification z. B. with electron and / or gamma rays in the presence of oxygen.
• Such persistent / long-lasting perfluoro (peroxy) radical centers in the (per) fluorine polymer have arisen during the polymerization reaction of the (per) fluoropolymer or can also be additionally produced by radiation-chemical and / or plasma-chemical modification of (per) fluoropolymers.
• the (per) fluoropolymer particles are compatibilized via chemical bonds with the PPS matrix, i. H. compatible.
• the (per) fluoropolymer (micro / nano) powder can either be melted together with the PPS component or added directly to the PPS melt.
• the materials according to the invention are formed directly in the melt reaction, it being advantageous to obtain directly further processable materials.
• the reactive reaction in the melt is carried out at PPS processing temperatures.
• PPS processing temperatures To prepare the materials according to the invention, all PPS materials can be used in pure form and / or filled and / or reinforced. Likewise, further polymers can be added. These materials may be used as the starting mixture and / or added during melt processing and / or in a subsequent step, for example, glazing.
• the production process can be realized as a one-step or multi-step process.
• the materials produced can be used as a compact substance and / or as an additive / constituent of plain bearings and / or in oleophobic and / or hydrophobic or thus equipped part or compact materials and / or in moldings and / or as a surface modification component, for example in sliding films or films and / or be used as a coating and / or as a blend component and / or as an additive, for example, in bonded coatings.
• the invention will be explained in more detail below with reference to several exemplary embodiments.
• twin-screw extruder ZSK30 (Werner & Pfleiderer)
• X kg / h of PPS Formtron, Ticona
• Y kg / h of PTFE see Table 1
• the twin-screw extruder is operated with the temperature profile listed below and a speed of 200 rpm.
• the melt strand is granulated after Wasserbadkühlung.
• the resulting material is further processed by injection molding into semi-finished products and test specimens, from which the test specimens were prepared and on which the following properties were determined.
• Processing temperature 290- 330 - 330 - 330 - 300 - 280 - D: 270 ° C
• the tribological properties of the PPS + PTFE-cg materials have a sliding friction behavior similar to PTFE. Compared to the pure PPS, a reduction of the wear values to 27 to 30% with the addition of 20% by mass of PTFE and to 18 to 21% with the addition of 30% by mass of PTFE is found.

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• 2007
  • 2007-08-13 DE DE102007038929A patent/DE102007038929B4/de not_active Expired - Fee Related
• 2008
  • 2008-08-08 JP JP2010520547A patent/JP2010535922A/ja active Pending
  • 2008-08-08 EP EP08802981.4A patent/EP2178981B1/de active Active
  • 2008-08-08 WO PCT/EP2008/060467 patent/WO2009021922A1/de not_active Ceased
  • 2008-08-08 CN CN200880103398A patent/CN101784611A/zh active Pending
  • 2008-08-08 US US12/673,362 patent/US20110040017A1/en not_active Abandoned

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