WO2018001028A1 - 包覆型氟聚合物颗粒及包含其的聚合物共混物和聚合物组合物 - Google Patents

包覆型氟聚合物颗粒及包含其的聚合物共混物和聚合物组合物 Download PDF

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WO2018001028A1
WO2018001028A1 PCT/CN2017/086637 CN2017086637W WO2018001028A1 WO 2018001028 A1 WO2018001028 A1 WO 2018001028A1 CN 2017086637 W CN2017086637 W CN 2017086637W WO 2018001028 A1 WO2018001028 A1 WO 2018001028A1
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fluoropolymer
polymer
group
siloxane
poly
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PCT/CN2017/086637
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English (en)
French (fr)
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王胜广
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王胜广
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Priority to CN202110055089.1A priority Critical patent/CN112876791B/zh
Priority to CN202110054192.4A priority patent/CN112876790B/zh
Priority to CN202110054193.9A priority patent/CN112852080B/zh
Priority to CN201780040806.5A priority patent/CN109689773B/zh
Publication of WO2018001028A1 publication Critical patent/WO2018001028A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the present invention generally relates to the field of polymer processing.
  • the present invention relates to coated fluoropolymer particles, polymer blends and polymer compositions comprising the same, and methods of making same.
  • a fluoropolymer represented by a tetrafluoroethylene derivative-based polymer (herein referred to as a tetrafluoroethylene polymer) generally has excellent high and low temperature resistance, non-stick properties, corrosion resistance, and flame retardancy.
  • Etc. has been widely used in chemical, textile, electrical and electronic, medical, mechanical and other fields.
  • Tetrafluoroethylene polymer has been used as an additive to wear-resistant lubricants and anti-drip agents in polymer materials.
  • these polymers especially tetrafluoroethylene polymers as flame retardants.
  • the anti-drip agent of the polymer composition causes poor appearance of extrusion, injection molding, blow molding and the like, and the mechanical properties of the product are seriously degraded. Obviously, these problems are due to the tetrafluoroethylene polymer in the polymer composition. Caused by poor dispersion.
  • Patent EP-AD, 166, 187 adopts coprecipitation method to obtain acrylonitrile-butadiene-styrene modified polytetrafluoroethylene powder, which has the disadvantage of high self-adhesiveness, when the content of polytetrafluoroethylene reaches 25% by weight, the powder The free flowability is poor and its dispersion properties in the polymer composition are not improved.
  • Patent CN1,147,269A discloses an anti-drip agent which is excellent in dripping resistance, workability and release properties.
  • the anti-drip agent core is a fibril-forming high-molecular-weight polytetrafluoroethylene
  • the shell portion is a non-fibril-forming low-molecular-weight polytetrafluoroethylene, but the coated polytetrafluoroethylene has a complicated preparation process and a shell
  • the part is soft, is easy to bond by external force, has poor free-flowing property, and its dispersibility in the polymer composition has not been fundamentally improved.
  • Patented CN1, 125, 096C prepared a novel coated tetrafluoroethylene polymer particle by free radical emulsion polymerization.
  • the coating material is selected from the group consisting of polystyrene, poly- ⁇ -methylstyrene, styrene-acrylonitrile copolymer, ⁇ -methylstyrene-acrylonitrile copolymer, and acrylonitrile-butadiene-styrene copolymer. And a mixture thereof, the coated tetrafluoroethylene polymer particles are currently widely used in the market except for pure powder of tetrafluoroethylene polymer.
  • the dispersibility in the polymer composition is deteriorated, the mechanical properties of the polymer composition are seriously deteriorated, and the surface of the molded article is defective.
  • the coating material used has poor thermal stability and flame retardancy.
  • the patent CN102286157A alone uses an acid as a catalyst, and needs to be repeatedly extracted and washed with an organic solvent such as toluene or xylene, and finally the solvent is distilled off.
  • the process is complicated, time-consuming, complicated in post-processing, uneconomical, and due to the low content of Q-links in the MQ silicone resin used for coating materials, it is easy to form super particle agglomerates, and the heat resistance is poor, and the amount of addition is small. When it is higher, its dispersibility in the polymer composition is deteriorated, and the molded article is defective.
  • Patent CN103849092A uses fluoropolymer powder or its condensed powder as raw material to mix with silane, so that silane penetrates into the gap between fluoropolymers, and silane is polymerized in situ for 4-16 hours, and finally heated to boiling to remove water.
  • the sieve is dried at a high temperature, and a composite fine powder having a particle diameter of 0.1 ⁇ m to 15 ⁇ m is obtained by a gas jet powder.
  • the product obtained by the method contains a large amount of super particle agglomerates, cannot be directly used, and needs to be subjected to jet pulverization and forced depolymerization to obtain a composite fine powder of the above particle size, and when the fluoropolymer is a fluoropolymer having strong fiber forming ability.
  • the treatment method of forced detachment of jet pulverization causes the fluoropolymer to be pre-fibrillated, and the dispersibility of the fluoropolymer anti-drip agent in the polymer composition cannot be solved.
  • the technical problem to be solved by the present invention is to overcome the shortcomings of the prior art fluoropolymer particles in terms of thermal stability, flame retardancy to carbon, and especially dispersibility.
  • a coated fluoropolymer particle which is free-flowing and which is composed of a fluoropolymer whose surface is completely or partially coated with a silicone polymer, selected from (i Preparation of methods), (ii), (iii), (iv):
  • emulsion hydrolysis-condensation polymerization method using water or water-organic solvent as a dispersion medium, using a basic compound as a catalyst, in the presence of a fluoropolymer, emulsion hydrolyzing-condensing a silicon compound, followed by solid-liquid separation and drying
  • the silicon compound is selected from the group consisting of a compound having a hydrolyzable group attached to a silicon atom, a hydrolyzate thereof, a partial hydrolyzate-condensate, and a mixture thereof;
  • Precipitation hydrolysis-condensation polymerization method using a water-organic solvent as a dispersion medium, using a basic compound as a catalyst, precipitating a hydrolyzed-condensed polymerized silicon compound in the presence of a fluoropolymer, and then performing solid-liquid separation and drying, wherein
  • the silicon compound is selected from the group consisting of a compound having a hydrolyzable group attached to a silicon atom, a hydrolyzate thereof, a partial hydrolyzate-condensate, and a mixture thereof;
  • emulsion condensation polymerization method a polysiloxane having at least two Si-OH groups in one molecule and a silicon compound having at least three hydrolyzable groups bonded to a silicon atom in one molecule, a hydrolyzate, a partial hydrolyzate-condensate, and a mixture thereof, or an organic hydrogenated (poly)siloxane having at least three hydrogen atoms bonded to a silicon atom in one molecule as a crosslinking agent, followed by emulsification in a fluoropolymer In the presence of a catalyst, cross-linking the cured polysiloxane with a crosslinking agent, and then performing solid-liquid separation and drying; or
  • hydrosilylation method an organic (poly)siloxane having at least two monovalent olefinic unsaturated groups in one molecule and at least two hydrogen atoms bonded to a silicon atom in one molecule (abbreviation)
  • a hydrosilylation catalyst is added in the presence of a fluoropolymer to crosslink and cure the organic (poly)siloxane and organic hydrogenation (poly) a siloxane, which is then subjected to solid-liquid separation drying, wherein at least three of the monovalent olefinic unsaturated group and the hydrogen atom bonded to the silicon atom are present in the molecule,
  • the silicone polymer is a polymer having a crosslinked structure
  • the weight ratio of the fluoropolymer to the silicone polymer in the coated fluoropolymer particles is from 95:5 to 5:95.
  • a polymer blend which is a free-flowing powder comprising the above coated fluoropolymer particles and silicone polymer particles.
  • a method of preparing the above polymer blend comprising:
  • an organic (poly)siloxane having at least two monovalent olefinic unsaturated groups in one molecule and at least two hydrogen atoms bonded to a silicon atom in one molecule (abbreviated as Si-H group)
  • a hydrosilylation catalyst is added in the presence of a fluoropolymer to crosslink and cure the organic (poly)siloxane and the organic hydrogenated (poly)siloxane, wherein At least one of a monovalent olefinic unsaturated group and a hydrogen atom bonded to a silicon atom exists in the molecule;
  • an article obtained by extrusion molding, injection molding or blow molding of the polymer blend is provided.
  • a polymer composition comprising a polymer matrix, The coated fluoropolymer particles or polymer blends described above are dispersed therein.
  • an article obtained by extrusion molding, injection molding or blow molding of the polymer composition is provided.
  • coated fluoropolymer particles and the polymer blend of the present invention have good dispersibility, thermal stability and flame retardant carbon formation, and when added as an additive to a polymer to form a polymer composition, the polymer is not significantly caused. The mechanical properties of the composition decreased.
  • Figure 1 is a scanning electron microscope of a sample of a polymer blend prepared in Example 1 of the present invention.
  • Example 2 is a scanning electron microscope of a sample of a polymer blend prepared in Example 2 of the present invention.
  • Example 3 is a scanning electron microscope of a sample of a polymer blend prepared in Example 4 of the present invention.
  • Example 4 is a scanning electron microscope of a sample of a polymer blend prepared in Example 5 of the present invention.
  • Figure 5 is a scanning electron microscope of a sample of a polymer blend prepared in Example 6 of the present invention.
  • Figure 6 is a scanning electron microscope of a polytetrafluoroethylene dispersion used in Examples 1, 2, 3, and 6 of the present invention.
  • coated fluoropolymer particles of the present invention are free-flowing and consist of a fluoropolymer whose surface is completely or partially coated with a silicone polymer.
  • Suitable fluoropolymers include homopolymers and copolymers comprising repeating units derived from one or more fluorinated alpha-olefin monomers.
  • the fluorinated alpha-olefin monomer i.e., an alpha-olefin monomer containing at least one fluorine atom substituent.
  • Suitable fluorinated alpha-olefin homopolymers include, for example, polytetrafluoroethylene, polyhexafluoropropylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene.
  • Suitable fluorinated alpha-olefin copolymers comprise copolymers comprising repeating units derived from two or more fluorinated alpha-olefin copolymers, such as tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoro Ethylene-bias a fluoroethylene copolymer, and a copolymer comprising a repeating unit derived from one or more fluorinated monomers and a non-fluorinated one or more copolymerizable with the fluorinated monomer
  • a repeating unit derived from an ethylenically unsaturated monomer for example, a tetrafluoroethylene-ethylene copolymer, a tetrafluoroethylene-ethylene-propylene copolymer.
  • Suitable non-fluorinated ethylenically unsaturated monomers include, but are not limited to, alpha-olefin monomers such as ethylene, propylene, etc., such as methyl methacrylate, butyl acrylate (meth)acrylic monomers, such as cyclohexyl.
  • alpha-olefin monomers such as ethylene, propylene, etc.
  • methyl methacrylate such as methyl methacrylate
  • butyl acrylate (meth)acrylic monomers such as cyclohexyl.
  • Vinyl ethers such as vinyl ether, ethyl vinyl ether, and n-butyl vinyl ether, and vinyl esters such as vinyl acetate and vinyl versatate.
  • a suitable fluoropolymer may be fibrillated or not fibrillated, and it is preferred in the present invention to be fibrillated.
  • the fluoropolymer is preferably a tetrafluoroethylene polymer.
  • the tetrafluoroethylene polymers that can be used are: polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, tetrafluoroethylene-fluoroethylene copolymer, tetrafluoroethylene-perfluoro An alkyl vinyl ether copolymer and a copolymer of tetrafluoroethylene and other copolymerizable ethylenically unsaturated monomers.
  • the fluoropolymer is further preferably polytetrafluoroethylene (PTFE).
  • the standard specific gravity of the polytetrafluoroethylene (“SSG", which is determined according to ASTM D4894 or ASTM D4895) is not limited, and is usually 2.230 or less, preferably 2.130 to 2.220, more preferably 2.140 to 2.200. The smaller the specific gravity, the higher the molecular weight.
  • primary particles and/or secondary particle agglomerates of a fluoropolymer having a suitable particle diameter can be selected depending on different reaction conditions, the kind of the silicon compound to be used, the preparation method, and the like.
  • the weight ratio of the fluoropolymer to the silicone polymer in the coated fluoropolymer particles is preferably from 95:5 to 5:95, more preferably from 80:20 to 20:80, most preferably from 60:40 to 60:40.
  • the silicone polymer is a polymer having a crosslinked structure, and may be a homopolymer, a copolymer, and a mixture thereof, and may also be, for example, a silicone resin, a condensation type silicone rubber, and an addition type silicone rubber, and a mixture thereof.
  • the silicone polymer may be a first type of silicone polymer prepared by emulsion hydrolysis-condensation or precipitation hydrolysis-condensation polymerization, which has a main chain Si-O chain link and a branched structure T-type structure. a unit in which a tetrafunctional link SiO 2 (Q), a trifunctional link RSiO 3/2 (T), a difunctional link R 2 SiO(D), a monofunctional link R 3 SiO 1 relative to the main chain
  • the proportion of /2 (M) is preferably:
  • the ratio of the sum of the SiO 2 (Q) and RSiO 3/2 (T) links is 70 to 100% by mol, and further preferably the RSiO 3/2 (T) chain is 70% to 100% by mol.
  • the sum of R 2 SiO(D) and R 3 SiO 1/2 (M) is preferably not more than 30% by mol, further preferably not more than 20% by mol, most preferably not more than 10% by mol, and preferably SiO 2 (Q)
  • the sum of R 2 SiO(D) and R 3 SiO 1/2 (M) is not more than 30% by mol, further preferably not more than 20% by mol.
  • Each R is independently a monovalent organic group.
  • each R is independently of each other a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, for example, having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 a linear, branched or cyclic alkyl group of carbon atoms; a linear or branched alkenyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms; optionally The above alkyl-substituted aryl group such as phenyl, naphthyl; the above-mentioned alkyl group optionally substituted by an aryl group such as a phenyl group; a part or all of a hydrogen atom bonded to a carbon atom of these groups is passed through a halogen atom (fluorine, Chlorine, bromine, iodine) and/or propyleneoxy, methacryloxy, epoxy, g
  • R is a methyl group, a phenyl group or a vinyl group, more preferably 50% by mol or more is a methyl group or a phenyl group, and most preferably 50% by mol or more is a methyl group.
  • various functional silicone polymers can be prepared depending on the R group, such as: phenyl, amino, epoxy, sulfonyl, sulfonate, alkenyl, propylene.
  • R group such as: phenyl, amino, epoxy, sulfonyl, sulfonate, alkenyl, propylene.
  • silicone polymers consisting of basic links such as T, TQ, TQD, TQM, TD, TM, TDM or QTDM, and mixtures thereof, which can be formed by T-links.
  • Polymers, TQ, TD, TM, TQD, TQM, TDM and TQDM and other basic chain forming copolymers examples include, but are not limited to: polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane , polyvinyl siloxane, polychloromethyl siloxane, polychloroethyl siloxane, polymethyl ethyl siloxane, polymethyl phenyl siloxane, polymethyl vinyl siloxane , polyphenylvinylsiloxane, polyethylphenylsiloxane, polyethylvinylsiloxane, polymethylphenyl(vinyl)siloxane, polymethylethyl (phenyl) (vinyl)siloxane, polychloromethylmethyl(ethyl)(phenyl)siloxane, polymethylaminopropylsiloxane
  • substitution of other metal or non-metal atoms for the silicon atom in the basic skeleton of the above silicone polymer may constitute a modification of the silicone polymer, and the modification may be any co-hydrolysis with the silicon compound described above.
  • - Condensed compounds including but not limited to: titanic acid, metal titanate, titanium chloride, titanium alkoxide, boric acid ester, and the like.
  • the proportion of the other metal or non-metal atom is preferably not more than 30% by mol, further preferably not more than 10% by mol, most preferably not more than 5% by mol.
  • the silicone polymer may also be a silicone polymer prepared by emulsion condensation polymerization, and the silicon compound used comprises: an organopolysiloxane (A) and a crosslinking agent (B), that is, a polysiloxane ( A) and the crosslinking agent (B) are emulsified, and a condensation catalyst (C) is added in the presence of a fluoropolymer, cross-linked and solidified, and then solid-liquid separation and drying.
  • an organopolysiloxane (A) and a crosslinking agent (B) that is, a polysiloxane ( A) and the crosslinking agent (B) are emulsified
  • a condensation catalyst (C) is added in the presence of a fluoropolymer, cross-linked and solidified, and then solid-liquid separation and drying.
  • the organopolysiloxane (A) comprises: at least two Si-OH groups in one molecule.
  • the crosslinking agent (B) is selected from the group consisting of a silicon compound having at least three hydrolyzable groups attached to a silicon atom in one molecule or a hydrolyzate thereof, a partial hydrolysis-condensate, and at least three molecules in one molecule
  • the condensation catalyst (C) is used for accelerating crosslinking curing of the organopolysiloxane (A) and the crosslinking agent (B) to obtain coated fluoropolymer particles.
  • the silicone polymer may also be a silicone polymer having a hydrosilylation reaction by a monovalent aliphatic unsaturation group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom ( a crosslinked structure formed by a hydrosilylation reaction) and having a cured product comprising a linear organosiloxane block represented by the formula -(R 1 2 SiO 2/2 ) n - wherein n
  • the positive integer is not particularly limited, and is preferably a positive integer of 5 to 5,000, and each of R 1 is a monovalent organic group independent of each other, and R 1 has the same definition as described above for R.
  • a silicon compound used in a silicone polymer prepared by a hydrosilylation method which comprises an organic (poly)siloxane and an organic hydrogenated (poly)siloxane, that is, comprises: An organic (poly)siloxane having at least two monovalent olefinic unsaturated groups in the molecule and an organic hydrogenation having at least two hydrogen atoms bonded to a silicon atom in one molecule (abbreviated as Si-H group)
  • the polysiloxane preferably at least one of a monovalent olefinically unsaturated group and at least one of hydrogen atoms bonded to a silicon atom exists in the molecule.
  • the particle size and morphology of the coated fluoropolymer particles are not particularly limited, and generally the volume average particle diameter is from 0.01 ⁇ m to 700 ⁇ m, preferably from 0.1 ⁇ m to 300 ⁇ m, further preferably from 0.1 ⁇ m to 100 ⁇ m, most preferably 0.1.
  • Mm-50 ⁇ m which may be a primary particle having a volume average particle diameter of 0.01 ⁇ m to 100 ⁇ m, or a secondary particle agglomerate having a volume average particle diameter of 0.1 ⁇ m to 700 ⁇ m formed by aggregation of primary particles, and a detailed preparation method thereof will be Described in the text.
  • the polymer blend of the present invention is a free-flowing powder comprising the coated fluoropolymer particles of the present invention and silicone polymer particles.
  • the proportion of fluoropolymer in the polymer blend can vary over a wide range, typically from 0.01% to 95% by weight, preferably from 1% to 80% by weight, based on the total weight of the polymer blend, further preferably 10% to 70% by weight, most preferably 30 to 70% by weight.
  • the polymer blend consists of coated fluoropolymer particles and silicone polymer particles, wherein the fluoropolymer is from 0.01% to 95% by weight, based on the total weight of the polymer blend, preferably It is from 1% to 80% by weight, further preferably from 10% to 70% by weight, most preferably from 30% to 70% by weight.
  • a portion of the silicone polymer is present as a coating of fluoropolymer particles, with the remainder being in the form of free silicone polymer particles.
  • the silicone polymer has a crosslinked structure and may be a homopolymer, a copolymer, and a mixture thereof, and may also be, for example, a silicone resin, a condensation type silicone rubber, an addition type silicone rubber, and a mixture thereof.
  • the silicone polymer when the inventors developed the functional silicone polymer, it was found that when a fluoropolymer is introduced, the silicone polymer can coat the fluoropolymer well, and at the same time impart more functions to the fluoropolymer, such as heat stabilization.
  • the properties of the fluoropolymer in the polymer composition are greatly improved by the properties of the fluoropolymer.
  • the free silicone polymer particles may have an irregular morphology such as a spherical shape or a sheet shape, preferably a spherical shape, and the volume average particle diameter thereof is preferably from 0.01 ⁇ m to 100 ⁇ m, further preferably from 0.1 ⁇ m to 50 ⁇ m, and most preferably from 0.1 ⁇ m to 30 ⁇ m.
  • the method for preparing a polymer blend of the present invention may comprise using a silicon compound under a basic catalyst, especially a water-soluble basic catalyst, in water or a water-organic solvent, particularly a water-alcohol system, in the presence of a fluoropolymer.
  • a dispersion medium emulsion polymerization (herein referred to as emulsion hydrolysis-condensation polymerization) is carried out to obtain a polymer blend precipitate, gel or dispersion (also referred to as emulsion, suspension emulsion or suspension, the same below), and solidified. After the liquid is separated and dried, a polymer blend in the form of a free-flowing powder is obtained.
  • the method for preparing a polymer blend of the present invention may also comprise, in the presence of a fluoropolymer, a silicon compound under a basic catalyst, especially a water-soluble basic catalyst, with a water-organic solvent, particularly water-alcohol.
  • the dispersion medium is subjected to precipitation polymerization (herein referred to as precipitation hydrolysis-condensation polymerization) to obtain a polymer blend precipitate, a gel or a dispersion, which is subjected to solid-liquid separation and drying to obtain a polymer blend in a free-flowing powder form. Things.
  • the method for preparing a polymer blend of the present invention may comprise a polysiloxane having at least two Si-OH groups in one molecule and a hydrolyzable group having at least three atoms bonded to a silicon atom in one molecule.
  • a compound, a hydrolyzate thereof, a partial hydrolyzate-condensate, and a mixture thereof, or an organic hydrogenated (poly)siloxane having at least three hydrogen atoms bonded to a silicon atom in one molecule is emulsified as a crosslinking agent,
  • a condensation catalyst is added to crosslink the cured polysiloxane with a crosslinking agent to obtain a dispersion of the polymer blend, which is subjected to solid-liquid separation and drying to obtain a polymer in a free-flowing powder form.
  • the method for preparing a polymer blend of the present invention may comprise an organic (poly)siloxane having at least two monovalent olefinic unsaturated groups in one molecule and at least two hydrogens bonded to silicon atoms in one molecule.
  • a hydrosilylation catalyst is added in the presence of a fluoropolymer to crosslink and cure the organic (poly)siloxane and organic a hydrogenated (poly)siloxane in which at least three of a monovalent olefinic unsaturated group and a hydrogen atom bonded to a silicon atom are present in the molecule to obtain a dispersion of the polymer blend, After solid-liquid separation and drying, a polymer blend in the form of a free-flowing powder is obtained.
  • coated fluoropolymer particles described above can be further isolated from the polymer blend.
  • the use form of the fluoropolymer (herein referred to as the fluoropolymer before the preparation of the coated fluoropolymer particles of the present invention) is not limited.
  • the fluoropolymer may be a single type of fluoropolymer fine powder particles and a dispersion thereof, or may be a fine powder particle of a blend of two or more fluoropolymers and a dispersion thereof.
  • the fine powder particles of the single type of fluoropolymer are conventionally known fluoropolymers, and the dispersion thereof may be a commercially available dispersion having a solid content (the dispersion generally contains 2 to 10% by weight of the surface).
  • the active agent and a certain amount of ammonia water are not particularly limited, and the solid content is 30%, 50%, 60%, etc., and may be a fluoropolymer polymerization dispersion obtained by an aqueous phase polymerization method.
  • the liquid may not be subjected to a concentration step, such as without concentration to a solids content of 30%, 50%, 60%, and the like.
  • the fine powder particles of the blend of the fluoropolymer or the dispersion thereof can be obtained by mixing a single type of fluoropolymer fine powder particles or a dispersion thereof.
  • the fluoropolymer may also be a conventionally known coated fluoropolymer fine powder particle, and the dispersion may be a dispersion in which it is previously dispersed in water and/or an organic solvent, or may be a coating type.
  • the fluoropolymer is preferably a mixed type of fluoropolymer fine powder particles and a dispersion thereof, further preferably a single type of fluoropolymer particles and a dispersion thereof, more preferably polytetrafluoroethylene particles and a dispersion thereof, and most preferably capable of fibrils Polytetrafluoroethylene particles and dispersions thereof.
  • the polymer blend of the present invention is prepared by emulsion hydrolysis-condensation polymerization or precipitation hydrolysis-condensation polymerization of a silicon compound, for example, simply by using a silicon compound under a basic catalyst condition in the presence of a fluoropolymer
  • the water or water-organic solvent acts as a dispersion medium for emulsion hydrolysis-condensation polymerization or precipitation hydrolysis-condensation polymerization.
  • Both emulsion hydrolysis-condensation polymerization or precipitation hydrolysis-condensation polymerization of various silicon compounds can be used to prepare coated fluoropolymers, such as batch, semi-continuous or continuous polymerization.
  • the fluoropolymer can be added at the beginning, that is, before any emulsion hydrolysis-condensation polymerization or precipitation hydrolysis-condensation polymerization reaction, or during the reaction, usually before 90% by weight or more of the hydrolysis and condensation reaction of the silicon compound.
  • Into the reaction medium that is, before any emulsion hydrolysis-condensation polymerization or precipitation hydrolysis-condensation polymerization reaction, or during the reaction, usually before 90% by weight or more of the hydrolysis and condensation reaction of the silicon compound.
  • the silicon compound used in the emulsion hydrolysis-condensation polymerization method or the precipitation hydrolysis-condensation polymerization method is any a hydrolyzable group-attached compound of a silicon atom, a hydrolyzate thereof, a partial hydrolyzate-condensate or a mixture thereof, wherein the hydrolyzable group bonded to Si may, but not limited to, an alkoxy group or an acyloxy group.
  • a silyl group preferably an alkoxy group having 1 to 6 carbon atoms, a hydrosilyl group, a silyl halide group, further preferably an alkoxy group, most preferably a methoxy group. Ethoxy.
  • the composition, structure, and the like of the silicon compound are not particularly limited, and the silicon compound may be exemplified by, but not limited to, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, silicon tetrachloride, Chloropropyltrichlorosilane, chloropropyltrimethoxysilane, chloropropylmethyldichlorosilane, chloropropylmethyldimethoxysilane, chloromethyltrichlorosilane, chloromethyltrimethoxysilane, Chloromethylmethyldichlorosilane, chloromethyldimethylchlorosilane, dichloromethyltrichlorosilane, triethylchlorosilane, n-dodecyltrichlorosilane, octylmethyldichlorosilane, Vinyltrichlorosilane, vinyldimethylchlorosilane, vinylmethyl
  • the polymer blend of the invention is preferably prepared using a mixture of silanes, preferably comprising:
  • RSiX 3 (T) 0.1-100% mol, more preferably 50-100% mol,
  • RSiX 3 (T) which provides a crosslinked structure by RSiX 3 (T) or RSiX 3 (T) and SiX 4 (Q), and preferably the sum of RSiX 3 (T) and SiX 4 (Q)
  • the ratio is 70-100% mol, and further preferably RSiX 3 (T) is 70-100% mol.
  • R 2 SiX 2 (D) and R 3 SiX 1 (M) is preferably not more than 30% by mol, further preferably not more than 20% by mol, most preferably not more than 10% by mol, and preferably SiX 4 (Q),
  • the sum of R 2 SiX 2 (D) and R 3 SiX 1 (M) is not more than 30% by mol, further preferably not more than 20% by mol.
  • R is the same as described above, and preferably 50% by mole or more of R is a methyl group, a phenyl group, a vinyl group, more preferably 50% by mole or more is a methyl group or a phenyl group, and most preferably 50% by mole or more is a methyl group.
  • X represents a halogen atom such as chlorine, or represents a hydrolyzable group such as an alkoxy group, an acyloxy group or the like, and more preferably an alkoxy group.
  • the above mole percentage is based on the total moles of the silane mixture (the amount of each monomer in the product can be estimated by measuring the amount of remaining monomers in the mixture, such as gas phase, liquid chromatography, mass spectrometry, nuclear magnetic, etc., and by assuming silane Compound complete hydrolysis-condensation estimation).
  • SiX 4 (Q) content the higher the SiX 4 (Q) content, the more the coating material of the obtained fluoropolymer is biased toward the inorganic compound (SiO 2 ), and the polymer blend also has higher thermal stability and carbon formation. performance.
  • a water-organic solvent is required as a dispersion medium, and preferably a water-alcohol is a dispersion medium, otherwise SiX 4 (Q) is easily hydrolyzed, It causes more free hydrolyzate and partial hydrolysis-condensate, which affects the coating of the fluoropolymer.
  • the amount of the R 3 SiX 1 (M) compound to be added should not be too high, otherwise the super particle agglomerates are easily formed.
  • the R 2 SiX 2 (D) compound provides a linear structure, and can be widely used for controlling the particle size, structural properties, and the like of the polymer blend of the present invention, and the content thereof cannot be too high, otherwise the product yield is liable to be lowered. Produces super particle agglomerates.
  • the polymer blend prepared by the emulsion hydrolysis-condensation polymerization method or the precipitation hydrolysis-condensation polymerization method is allowed to contain a portion of the silicon-bonded unhydrolyzed and/or uncondensed group, for example, but not It is limited to: alkoxy group, acyloxy group, hydrosilyl group, silyl group, silyl group, silanol group and the like, and the content thereof is preferably such that the free fluidity of the polymer blend is not affected.
  • the present invention prepares a polymer blend containing coated fluoropolymer particles by an emulsion hydrolysis-condensation polymerization method or a precipitation hydrolysis-condensation polymerization method, and the reaction temperature is not particularly limited, but is preferably 0 to 95 ° C, further preferably 5-80 ° C, more preferably 10-70 ° C.
  • the reaction time including the feeding time There is also no particular limitation, and it may be several minutes, several hours, or several days, preferably 1-10 hours.
  • the emulsion blending-condensation polymerization method or the precipitation hydrolysis-condensation polymerization method for preparing a polymer blend containing coated fluoropolymer particles must be carried out in the presence of water, and the minimum amount is sufficient to satisfy the hydrolysis of the silicon compound in the emulsion-
  • the amount required in the condensation polymerization or precipitation hydrolysis-condensation polymerization may be, and an excess amount of water is preferred.
  • the present invention uses water or a water-organic solvent as a reaction medium.
  • the present invention is defined as emulsion hydrolysis-condensation polymerization and precipitation hydrolysis-condensation polymerization, respectively, depending on the ratio of the reaction medium and the reaction medium, the form of the fluoropolymer raw material used, and whether or not the surfactant is used.
  • the invention is defined as emulsion hydrolysis-condensation polymerization; when water is used as a dispersion medium, and powder particles containing a fluoropolymer and a surfactant are used as raw materials, the invention is defined as emulsion hydrolysis-condensation polymerization; water is used as a dispersion medium to contain The powder particles of the fluoropolymer are raw materials, and the water and the fluoropolymer-containing powder particles are separated into two phases without adding a surfactant, but the added silicon compound is rapidly combined with the hydrophobic fluoropolymer-containing powder particles.
  • the hydrolysis reaction then takes place to produce a hydrophilic group which acts like a surfactant to disperse the fluoropolymer-containing powder particles in an aqueous dispersion medium.
  • the invention is still defined as emulsion hydrolysis-condensation polymerization.
  • the water-organic solvent is used as the dispersion medium.
  • the water-soluble organic solvent is preferably a dispersion medium, and the ratio of water to organic solvent can be varied within a wide range.
  • the ratio of water to organic solvent is such that the silicon compound is completely dissolved in the dispersion medium, in the presence of the fluoropolymer, after the hydrolysis/condensation reaction of the silicon compound, a highly crosslinked silicone polymer is produced and precipitates to form a precipitate.
  • a gel or dispersion is defined as a precipitation hydrolysis-condensation polymerization (which does not require a surfactant for the system, and when a surfactant is included, is a special case of precipitation polymerization, conventionally referred to as dispersion polymerization).
  • the precipitation hydrolysis-condensation polymerization of the present invention can be further described as a dispersion hydrolysis-condensation polymerization;
  • the proportion of water and organic solvent is such that the silicon compound is not completely dissolved in the dispersion medium, that is, water is the main dispersion medium, the polymerization method is the same as the emulsion hydrolysis-condensation polymerization described above, and the present invention is defined as emulsion hydrolysis-condensation polymerization.
  • the present invention is not limited to the type of water, and may be deionized water.
  • Mineral water, tap water, or the like is preferably water having a conductivity of not more than 1000 ⁇ S/m, further preferably water having a conductivity of not more than 200 ⁇ S/m, and most preferably water having a conductivity of not more than 100 ⁇ S/m.
  • the organic solvent is not particularly limited, and may or may not be added depending on the reaction system. If added, a water-soluble organic solvent is preferred, and examples thereof include, but are not limited to, methanol, ethanol, isopropanol, n-butanol, and acetone.
  • the organic solvent is an alcoholic organic solvent, and particularly when the alkoxysilane is used as a raw material, the hydrolyzate is an alcoholic organic solvent, which is a by-product of the reaction process and a good solvent for the silicon compound.
  • the reaction rate and the like can be controlled, and an organic solvent insoluble in water can be selected instead of an organic solvent dissolved in water, such as benzene, toluene, xylene, dichloromethane, or the like. It should be specially pointed out that when the polymer blend is prepared by the precipitation hydrolysis-condensation polymerization method, the ratio of the organic solvent is high.
  • the viscosity of the system may suddenly rise and occasionally cause condensation. Phenomenon, but as the hydrolysis-condensation reaction of the silicon compound proceeds, the viscosity of the system gradually decreases, eventually forming a precipitate, gel or dispersion of the polymer blend.
  • the amount thereof is sufficient for suspending the fluoropolymer, and preferably the weight ratio of the fluoropolymer to water is from 1.66 to 0.001, further preferably from 0.50 to 0.01, most Preferably, it is 0.30:0.05. If the ratio is too high, the fluoropolymer cannot be suspended, and super particle agglomerates are easily formed.
  • the ratio is too low, which may lead to prolonged reaction time, product yield, product performance degradation, etc.; when water-organic solvent
  • the amount thereof is sufficient for suspending the fluoropolymer, and preferably the weight ratio of the fluoropolymer to the water-organic solvent is in the range of 1.66 to 0.001, further preferably 0.50 to 0.01, most preferably 0.30:0.05. If the ratio is too high, the fluoropolymer cannot be suspended, and the super particle agglomerates are easily formed. The ratio is too low, which may lead to defects such as prolonged reaction time, product yield, and product performance degradation. Among them, the ratio of water-organic solvent is not.
  • the ratio of the two can be varied within a wide range.
  • the amount of water is sufficient to satisfy the silicon compound in the emulsion hydrolysis-condensation polymerization or precipitation hydrolysis-condensation polymerization process.
  • a surfactant preferably a surfactant
  • the active agent is not particularly limited and is preferably used in an amount of from 0.01 to 20% by weight based on the total amount of the dispersion, more preferably from 0.1 to 10% by weight.
  • the type of the surfactant is not particularly limited, and may be an anionic, cationic, zwitterionic or nonionic surfactant.
  • the surfactant may be selected according to the type of the dispersion medium or the type of the silicon compound, and may be used alone.
  • nonionic and anionic surfactants such as: dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, cetyltrimethylammonium bromide, Octadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium bromide, alkylphenol ethoxylate (OP) series including OP-6, OP-7, OP-8, OP- 9, OP-10, OP-13, OP-15, OP-18, OP-20, etc., polyoxyethylene sorbitol (TW) series including TW-20, TW-21, TW-40, TW- 80, TW-85, etc., the fatty alcohol polyoxyethylene ether (O) series includes AEO-8, AEO-10, AEO-15, AEO-30, etc., and mixtures thereof, and further preferably a nonionic surfactant.
  • OP alkylphenol ethoxylate
  • TW polyoxyethylene sorbitol
  • a hydrolysis-condensation catalyst for example, an acid or a base as a hydrolysis-condensation catalyst of a silicon compound.
  • an acidic catalyst sulfuric acid, alkylsulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, pyrophosphoric acid, boric acid, chlorosilane or the like can be exemplified.
  • an alkali metal a hydroxide, an alkali metal alkoxide, a silicon alkoxide, a quaternary ammonium base, a quaternary phosphonium base, a silanol quaternary ammonium salt, a silanol quaternary phosphonium salt, and an alkali metal organic compound.
  • Ammonia organic amines, carbonates, carbon Acid hydrogen salt and the like.
  • the particle size of the primary particles of the coated fluoropolymer and the aggregates thereof are controlled at a level that can be widely applied in the market, such as agglomerate particle size not higher than 500 ⁇ m, preferably not more than 100 ⁇ m, more preferably not more than 50 ⁇ m, most preferably not more than 30 ⁇ m. This object is achieved by the method of the invention.
  • the basic compound is selected as a catalyst for emulsion hydrolysis-condensation polymerization and precipitation hydrolysis-condensation polymerization, and further preferably a water-soluble basic catalyst for basifying water or a water-organic solvent dispersion medium, such as potassium hydroxide,
  • a water-soluble basic catalyst for basifying water or a water-organic solvent dispersion medium, such as potassium hydroxide
  • An alkali metal hydroxide such as sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, an alkali metal carbonate such as potassium carbonate or sodium carbonate, ethylamine, propylamine, butylamine, dimethylamine or trimethylamine.
  • Amine compounds such as triethylamine, silicon alkoxide, quaternary ammonium base, quaternary phosphonium base, silanol quaternary ammonium salt, silanol quaternary phosphonium salt and alkali metal organic compound, ammonia.
  • the present invention is preferably an ammonia which is soluble in water, has high catalytic activity and is volatile, and is easily removed from the product, further preferably aqueous ammonia, and most preferably ammonia containing 25-30% by weight of ammonia.
  • the basic pH of the emulsion hydrolysis-condensation polymerization and the precipitation hydrolysis-condensation polymerization system is not particularly limited, and is preferably 9-13, further preferably 10-12.
  • the alkalinity of the reaction system is too weak, which prolongs the hydrolysis and condensation time of the silicon compound and the product yield, and the reaction time is prolonged, which sometimes leads to the hydrolysis of the silicon compound and the partial hydrolysis-condensation of the different fluoropolymer coating layers. Inter-bonding, resulting in super-particle polymer blend agglomerates; too strong alkalinity, easy to cause uneven coating of fluoropolymer, formation of more free particles not used to coat fluoropolymer, and easy to produce Amorphous agglomerates.
  • the hydrolyzate, partial hydrolyzate-condensate of the silicon compound, and mixtures thereof can be used to prepare the polymer blend of the present invention, for example, by subjecting the silicon compound to hydrolysis reaction and partial hydrolysis under acidic conditions.
  • the condensation reaction (the degree of the condensation reaction is preferably such that it does not affect the dispersion property of the final polymer blend, which can be determined by a conventional experiment), and then is added to the above-mentioned alkaline dispersion medium containing a fluoropolymer to carry out a hydrolysis-condensation reaction.
  • any means capable of increasing the condensation reaction of the silicon compound such as adjusting the pH, increasing the temperature, etc., can be used.
  • the present invention is prepared by emulsion hydrolysis-condensation polymerization method and precipitation hydrolysis-condensation polymerization method.
  • the polymer blend of the fluoropolymer particles has no limitation on the order of addition and the manner of addition of the raw materials, and can be, for example, simply prepared by mixing a fluoropolymer, a surfactant, water, an organic solvent and a catalyst. Together, and adding a silicon compound under stirring, the silicon compound is subjected to emulsion hydrolysis-condensation or precipitation hydrolysis-condensation reaction in the presence of a fluoropolymer to obtain a polymerization containing a fluoropolymer wholly or partially coated with the silicone polymer.
  • the precipitate, gel or dispersion of the blend is subjected to solid-liquid separation, such as filtration, and dried to obtain a free-flowing powder.
  • the emulsion condensation polymerization method of the present invention can be carried out simply by emulsifying a polysiloxane (A) and a crosslinking agent (B) with a surfactant and water in the presence of a fluoropolymer, and then adding a condensation catalyst ( C), after the crosslinking is cured, a dispersion of the polymer blend containing the fluoropolymer is obtained, and after solid-liquid separation and drying, a free-flowing powder is obtained.
  • A polysiloxane
  • B crosslinking agent
  • C condensation catalyst
  • the polysiloxane (A) contains at least two Si-OH groups in one molecule thereof, and its position is not particularly limited, but an organic group which is bonded to a Si atom at the end of the molecular chain is preferable. It may be a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms as described for R.
  • the molecular structure of the organopolysiloxane (A) is not particularly limited and may be a linear structure, a linear structure having a partial branch, a branched structure or a network.
  • the viscosity (25 ° C) of the organopolysiloxane (A) is not particularly limited, and is preferably 5-1,000,000 mPa ⁇ s, further preferably 5 to 50,000 mPa ⁇ s, most preferably 5 to 1,000 mPa ⁇ s, and the viscosity may not be too high. Otherwise it is more difficult to emulsify in water.
  • the crosslinking agent (B) cures the organopolysiloxane (A) by crosslinking by condensation with a Si-OH group.
  • a suitable crosslinking agent (B) comprises: a silane compound having at least three hydrolyzable groups bonded to a silicon atom in one molecule or a hydrolyzate thereof, a partial hydrolyzate-condensate, and at least three in one molecule An organic hydrogenated (poly)siloxane of a hydrogen atom to which a silicon atom is bonded, and a mixture thereof.
  • the hydrolyzable group attached to the silicon atom in the silane compound used as the crosslinking agent (B) comprises: an alkoxy group, a ketoximino group, an acyloxy group, a hydrosilyl group, etc., a crosslinking agent (B)
  • the intermediate silicon atom may also be bonded to an organic group, which may be a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms as described for R.
  • the crosslinking agent (B) may, for example, be an alkoxysilane such as methyltrimethoxysilane, ethyltrimethoxysilane, trimethoxysilane, tetramethoxysilane or tetraethoxysilane.
  • an aryl alkoxysilane such as phenyltrimethoxysilane; an alkenyl alkoxysilane such as vinyltrimethoxysilane; 3-aminopropyltrimethoxysilane, bis(trimethoxysilylpropyl)amine , 3-(2-aminoethylamino)propyltrimethoxysilane, diethylenetriaminepropyltrimethoxysilane, anilinemethyltrimethoxysilane, cyclohexylaminopropyltrimethoxysilane, diethyl Aminoalkoxysilane such as aminomethyltriethoxysilane; propylpropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, bis(triethoxysilylpropyl) Sulfur-containing alkoxysilanes such as disulfides; halogenated alkyl alkoxysilanes such
  • a partial hydrolyzate-condensate of the alkoxysilane compound and the silane compound is preferred, and a mixture of the partial hydrolyzate-condensate of the silane compound and the silane compound is most preferred as the crosslinking agent (B).
  • the molecular structure of the crosslinking agent (B) is not particularly limited, and may be a linear structure, a linear structure having a partial branch, a branched structure, a network structure, and a cyclic structure. Mention may be made, for example, a trimethylsiloxy-terminated methylhydrogenpolysiloxane, a copolymer of trimethylsiloxy-terminated dimethylsiloxane-methylhydrogensiloxane, dimethylhydrogen a copolymer of siloxy-terminated dimethylsiloxane-methylhydrogensiloxane, a cyclic methylhydrogensiloxane, and a part or all of a methyl group are an alkyl group such as an ethyl group, a propyl group, or a phenyl group. An alkenyl-substituted organopolysiloxane such as an aryl group or a vinyl group.
  • the amount of the crosslinking agent (B) to be used is not particularly limited, and is usually from 0.1 to 60% by weight, preferably from 0.1 to 30% by weight, still more preferably from 1 to 20% by weight based on the organopolysiloxane (A). weight. If the amount is too small, it is insufficient to crosslink the cured organopolysiloxane (A). If the amount is too large, it can be prepared according to the emulsion hydrolysis-condensation or precipitation hydrolysis-condensation method described in the present invention.
  • R 2 SiO (D) and R 3 SiO 1/2 (M) structured silane compounds may be selectively added, but Not limited to: dimethyl methoxy silane, methyl phenyl dimethoxy silane, methyl vinyl dimethoxy silane, trimethyl methoxy silane, vinyl dimethyl methoxy silane, 3 -methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- Glycidyloxypropylmethyldimethoxysilane or the like, and hydrolyzates thereof, partial hydrolyzate-condensates thereof.
  • the amount of addition thereof is not limited, and may be added as needed or not, to ensure that the organopolysiloxane (A) and the crosslinking agent (B) can be suitably cured, preferably with respect to the organopolysiloxane (A). More than 10% by weight, further preferably not more than 5% by weight.
  • the emulsification conditions are not particularly limited, and it is preferably emulsified by an emulsification disperser, and examples thereof include, but are not limited to, a homogenizer or a high-speed rotary centrifugal atomizer, a homomixer or a similar high-speed rotary shear mixer. , homogenizer or similar high pressure jet emulsification disperser, colloid mill, ultrasonic emulsifier, etc.
  • the kind of the surfactant to be used is not particularly limited, and examples thereof include cationic, anionic, nonionic and amphiphilic surfactants, and further preferred are anionic surfactants and nonionic surfactants, which have been previously described.
  • the relevant description of the surfactant will not be described again.
  • the amount thereof is not particularly limited, and is preferably 0.01 to 20% by weight (relative to the entire emulsion system), further preferably 0.1 to 10% by weight. If the amount is too small, the preparation process is high, the amount is too large, and the post-treatment is troublesome and Product performance has an impact.
  • a condensation catalyst (C) to accelerate condensation condensation curing of the organopolysiloxane (A) and the crosslinking agent (B) to obtain a polymer blend comprising a fluoropolymer.
  • the condensation catalyst (C) used comprises: a metal salt of an organic acid such as stannous octoate, tin oleate, zirconium octoate, magnesium octoate or tin octylate; ethyl titanate, titanic acid Titanate esters such as isopropyl ester, n-butyl titanate, t-butyl titanate, polyalkoxy titanate, and the like; dibutyltin dilaurate, di-n-octyltin dilaurate, etc.
  • the dialkyltin dicarboxylate preferably an organic acid metal salt, is further preferably an organic acid tin salt of not more than 10 carbon atoms.
  • the manner and order of addition are not limited, and it is preferably added after emulsifying the organopolysiloxane (A), the crosslinking agent (B), the fluoropolymer, the surfactant, and water.
  • the form of the condensation catalyst (C) after emulsification with a surfactant and water is preferably not particularly limited.
  • the average particle diameter of the condensation catalyst (C) in the emulsion is preferably not more than 30 ⁇ m, and most preferably not more than 10 ⁇ m.
  • the surfactant described above can be used for the emulsification of the condensation catalyst, and is preferably added in an amount of from 0.01 to 1000% by weight based on the weight of the condensation catalyst (C).
  • the organic solvent for dilution may be an alcohol such as methanol, ethanol, isopropanol or n-butanol; or a ketone solvent such as acetone or the like, preferably a lower alcohol having a carbon number of not more than 4.
  • the amount of the condensation catalyst (C) to be used is not particularly limited, and is an amount sufficient to cause a suitable condensation crosslinking curing of the organopolysiloxane (A) and the crosslinking agent (B), preferably 0.01 to 30% by weight (relative to organic polymerization).
  • the total weight of the siloxane (A) and the crosslinking agent (B), further preferably from 0.1 to 10% by weight, is too small to make the organopolysiloxane (A) and the crosslinking agent ( B) Cross-linking curing, the product is sticky, affecting the free flow of the polymer blend containing fluoropolymer; too much dosage, the reaction is not easy to control, and has an impact on product performance.
  • the manner of adding the fluoropolymer is not limited, and the condensation of the silicon compound can be usually carried out at the beginning, that is, before the start of any condensation crosslinking curing reaction, or during the reaction, usually at 90% by weight or more.
  • the crosslinking reaction is added to the reaction medium before the curing reaction. It may be emulsified together with the organopolysiloxane (A) and the crosslinking agent (B), or may be added after the emulsification of the organopolysiloxane (A) and the crosslinking agent (B).
  • the reaction temperature is not particularly limited, but is preferably from 1 to 80 ° C, further preferably from 4 to 70 ° C.
  • the condensation crosslinked cured silicone polymer prepared by the method is partially used for coating a fluoropolymer, and a part is used as a particle of a discrete silicone polymer (usually ranging from several hundred nanometers to several tens of micrometers), and the crosslinking is cured.
  • the silicone polymer not only improves the impact properties of the organic resin in the organic resin, but also improves the anti-adhesion, smoothness and flame retardancy.
  • Another method of preparing the polymer blends of the present invention is a hydrosilylation process (also referred to as hydrosilylation) of a silicon compound, particularly an organosilicon compound, by hydrogen atoms bonded to silicon atoms.
  • hydrosilylation also referred to as hydrosilylation
  • the silicone polymer prepared by the hydrosilylation method of an organosilicon compound preferably comprises a hardened substance having the formula -(R 1 2 SiO 2/2 ) n -
  • n is a positive integer, and is not particularly limited, and is preferably a positive integer of 5 to 5,000, each of R 1 being a monovalent organic group independent of each other, and the monovalent organic group is preferably the one described above for R A substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 1 to 30.
  • An organosilicon compound used in the preparation of a silicone polymer by hydrosilylation comprising an organic (poly)siloxane and an organic hydrogenated (poly)siloxane, comprising: an average composition of R 2 a SiO (4-a)/ 2 in one molecule represented by having at least two monovalent olefinic unsaturated group of the organo (poly) siloxanes, and the average composition of R 3 b SiO (4-b ) molecule / 2 represented by having at least two An organic hydrogenated (poly)siloxane bonded to a hydrogen atom of a silicon atom (abbreviated as Si-H group), but preferably at least one of a monovalent olefinic unsaturated group and a hydrogen atom bonded to a silicon atom There are at least three of these molecules.
  • the ratio of the number of moles of the Si-H group to the monovalent olefinically unsaturated group bonded to the silicon atom is preferably 0.01: 1 to 50:1, further preferably 0.1:1 to 20:1, more preferably 0.5:1 to 10:1.
  • the R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms as described above for R.
  • the subscript a is a positive number satisfying 0 ⁇ a ⁇ 3, preferably a positive number satisfying 0.01 ⁇ a ⁇ 3, further preferably a positive number satisfying 0.1 ⁇ a ⁇ 2.5, and the average formula is R 2 a SiO (4-a)
  • the organic (poly)siloxane of /2 must have at least 2 silicon-bonded monovalent olefinically unsaturated groups per molecule, and further have a olefinic unsaturated group other than the olefinic unsaturated group in R 2 a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 1 to 30, a monovalent olefinic unsaturated group, which may be exemplified by, but not limited to, a vinyl group, an allyl group, a propenyl group, a butenyl group
  • Alkenyl, heptenyl and the like are preferably vinyl in the industry.
  • the position of the monovalent olefinic unsaturated group in the organic (poly)siloxane is not particularly limited, and it may be bonded at the side hanging position, at the end position, or at both positions.
  • Said R 3 is selected from H, substituted or unsubstituted monovalent hydrocarbon radicals having from 1 to 30 carbon atoms, for example having from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, more preferably from 1 to 6 carbons a linear, branched or cyclic alkyl group of an atom; an aryl group optionally substituted by the above alkyl group such as a phenyl group, a naphthyl group; an alkyl group optionally substituted by an aryl group such as a phenyl group; a carbon atom of these groups
  • a part or all of the hydrogen atoms bonded above pass through a halogen atom (fluorine, chlorine, bromine, iodine) and/or a propyleneoxy group, a methacryloxy group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, a fluorenyl group.
  • amino, sulfonic acid, nitro, amine substituted including but not limited to: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, An alkyl group such as undecyl or dodecyl, an aryl group such as phenyl, tolyl, xylyl or naphthyl, an aralkyl group such as benzyl or phenethyl, cyclopentyl, cyclohexyl or cycloheptyl. Equivalent cycloalkyl.
  • the subscript b is a positive number satisfying 0 ⁇ b ⁇ 3, preferably a positive number satisfying 0.01 ⁇ b ⁇ 3, further preferably a positive number satisfying 0.1 ⁇ b ⁇ 2.5, and the average formula is R 3 b SiO (4-b)
  • the organic hydrogenated (poly)siloxane of /2 must have at least 2 Si-H groups per molecule, and also have a substituted or unsubstituted carbon number of 1 to 30 other than H in R 3 Monovalent hydrocarbon group.
  • the position of the Si-H group in the organic hydrogenated (poly)siloxane is not particularly limited, and may be bonded at the side of the side, at the end, or at both positions. Further, it is preferred that 50% by mole or more of the monovalent hydrocarbon group having 1 to 30 carbon atoms which are substituted or unsubstituted in R 3 is a methyl group.
  • organosilicon compounds composed of an organic (poly)siloxane and an organic hydrogenated (poly)siloxane
  • silicon-bonded monovalent olefinically unsaturated groups and organic hydrogenation in an organic (poly)siloxane At least one of the Si-H groups in the (poly)siloxane has at least 3 in its molecule, and if any one does not exist in at least 3 of its molecules, the resulting polymer blend becomes sticky, Reduce its dispersibility in polymer compositions can.
  • the molecular weight of the organic (poly)siloxane and the organic hydrogenated (poly)siloxane is not particularly limited, but it is recommended to have a kinematic viscosity at 25 ° C of 100,000 mm 2 /s or less, more preferably 50,000 mm 2 . Kinematic viscosity below /s.
  • the structure of the organic (poly)siloxane and the organic hydrogenated (poly)siloxane is not particularly limited, and may be linear, cyclic, branched or three-dimensional, and is preferably linear.
  • a polymer blend in which a silicone polymer is wholly or partially coated with a fluoropolymer by a hydrosilylation method of an organosilicon compound can be obtained, for example, simply by: organic (poly) siloxane Alkane and organic hydrogenated (poly)siloxane, fluoropolymer, surfactant, water are emulsified to obtain a mixed emulsion, and then mixed into a hydrosilylation catalyst, maintained at a certain temperature and time, and added to form a polymer blend emulsion after vulcanization. Finally, the polymer blend powder is obtained by solid-liquid separation and drying.
  • the hydrosilylation catalyst used is mainly used for accelerating the curing of the mixture of the organic (poly)siloxane and the organohydrogenated (poly)siloxane, and may be any well-known hydrosilylation catalyst such as platinum.
  • the manner of adding the hydrosilylation catalyst is not limited, and the hydrosilylation catalyst may be added to the organic (poly)siloxane and the organic hydrogenated (poly)siloxane mixture and the fluoropolymer emulsion; or may be dissolved in advance.
  • an organic (poly)siloxane and an organic hydrogenated (poly)siloxane mixture may also be pre-dissolved in a solvent and then added to the above emulsion or mixture; in addition of the hydrosilylation catalyst to the organic (poly) silicon oxide
  • the hydrosilylation reaction does not occur before the end of the emulsification step, for example, cooling the mixture to a low temperature of, for example, 5 ° C or lower, adding an appropriate amount of a hydrosilylation catalyst inhibitor, etc. Means reduce the incidence of hydrosilylation reactions.
  • the hydrosilylation reaction of the organic (poly)siloxane and the organic hydrogenated (poly)siloxane mixture can be carried out at normal temperature, and may be carried out under heating at less than 100 ° C in the case where the reaction is not completed.
  • the amount of the hydrosilylation catalyst to be added is not particularly limited, provided that the amount ensures that the mixture of the organic (poly)siloxane and the organic hydrogenated (poly)siloxane is suitably cured, per Millions (ppm) of a hydrosilylation catalyst having a composition of an organo(poly)siloxane and an organohydrogenated (poly)siloxane as described above in an amount of as little as 0.001 part by weight of an elemental platinum group metal to the present invention In the reaction system, it is preferably 0.1 ppm to 1000 ppm, further preferably 0.5 ppm to 100 ppm, and more preferably 1 ppm to 50 ppm.
  • any suitable hydrosilylation catalyst inhibitor may be added, which may be a well-known hydrosilylation catalyst inhibitor, for example, but not limited to: 2-methyl-3 Alkyne inhibitors such as butyne-2-ol, 1-ethynyl-2-cyclohexanol (see US Pat. No. 3,445,420); olefinic siloxanes (see US Pat. No. 3,989,667) and the like.
  • the surfactant to be used is not particularly limited, and may or may not be added depending on the specific preparation process. It may be an anionic, cationic, two-ionic or nonionic surfactant.
  • the addition of a surfactant can improve the stability of the dispersion emulsion of the reaction system and contribute to the improvement of the regularity of the polymer blend particles, further preferably nonionic.
  • the type of surfactant which has been described in the foregoing, will not be described again.
  • the amount of the surfactant to be used is not particularly limited, and is preferably 0.01 to 20% by weight based on the total amount of the dispersion, and further preferably 0.1 to 10% by weight.
  • the emulsification conditions are not particularly limited, and it is preferably emulsified by an emulsification disperser, which has been described in the foregoing and will not be described again.
  • the hydrosilylation reaction of the silicon compound can be usually carried out at the beginning, that is, before any hydrosilylation reaction is started, or during the reaction, usually at 90% by weight or more. Previously added to the reaction medium.
  • any component in the form of a filler may be incorporated, which may be
  • the inorganic filler may also be an organic filler.
  • the amount to be added there is no limitation on the amount to be added, and it can be determined by routine experimentation as needed.
  • the metal oxide powder or the silicone resin powder is used for recoating.
  • a sol of a metal oxide or a hydrolyzable-condensed silane compound is added to a dispersion of a polymer blend comprising a fluoropolymer to coat the polymer blend; it may also be artificial or mechanical Method
  • the metal oxide powder or the condensation product of the hydrolyzable silane compound is coated onto the polymer blend.
  • the next step is solid-liquid separation and drying, so that A polymer blend comprising fluoropolymer particles having a surface wholly or partially coated with a silicone polymer is obtained. Therefore, the polymer blend powder particles can be obtained by removing moisture, an organic solvent or the like from the precipitate, the gel or the dispersion, or by washing, if necessary, by heating, centrifugation, filtration, decantation or the like.
  • the dried polymer blend is not suitable for treatment by forced pulverization such as grinding or jet milling, which may cause premature fibrillation of the fluoropolymer.
  • the polymer blend prepared by the invention may contain a large number of small particle size primary particles and medium particle size secondary particle agglomerates, or may be a polymer blend having a particle size of 100 ⁇ m or less.
  • the silicone polymer used in the polymer blend of the present invention is partially coated with a fluoropolymer coating material, a portion of which is present in a free form, and the free silicone polymer and the coated silicone polymer are used in practical applications. It can be used as a processing aid for polymer compositions, such as anti-wear agents, opening agents, toughening agents, and the like.
  • the polymer blend of the present invention exhibits better flame retardancy even when the particle size of the aggregate is close to the particle size of the commercially available coated fluoropolymer due to the presence of the free silicone polymer. And mechanical properties, especially better dispersion properties.
  • Articles of the present invention can be obtained by directly extruding, injection molding, blow molding or molding the polymer blends described herein.
  • extrusion, injection molding, blow molding or molding processes for preparing articles are well known in the art, and those skilled in the art will readily determine the specific molding process and process parameters based on the various indexes of the polymer blend and the intended use of the article. This will not be repeated.
  • the article may be, for example, a sheet, a sleeve, a rod, a plate, a gasket, a component.
  • the polymer composition of the present invention comprises a polymer matrix in which the coated fluoropolymer particles or polymer blends of the present invention are dispersed.
  • polystyrene especially high impact polystyrene, polyamide such as nylon 6, nylon 66, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butyl Diene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer/polycarbonate blend, polystyrene/polyphenylene ether blend, thermoplastic polystyrene/ethylene terephthalates, polyacrylate such as polymethyl acrylate, polymethacrylate such as polymethyl methacrylate, polyphenylene ether, polysulfone, polycarbonate Ester, polystyrene, especially high impact polystyrene, polyamide such as nylon 6, nylon 66, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylon
  • the polymer composition of the invention preferably further comprises a flame retardant, i.e. a polymer composition which is preferably a flame retardant.
  • a flame retardant is not particularly limited, and any known flame retardant system for a polymer composition can be used.
  • the flame retardant used in the polymer composition may be used singly or in combination, for example, a combination of a halogenated aromatic compound, particularly a brominated compound and cerium oxide, has a synergistic flame retardant effect.
  • any conventional additives such as a pigment, a UV stabilizer, an antioxidant, a heat stabilizer, a reinforcing filler, a chain extender, a colorant, a toughening agent and the like may be added to the polymer composition.
  • the polymer composition can be prepared by mixing the components by any known method. Typically, there are two different mixing steps: premixing and melt mixing. In the premixing step, the dry components are mixed together. The premixing is generally carried out using a tumbler mixer or a ribbon blender, and if desired, the premix can also be prepared using a high shear mixer. After premixing, it is usually melt mixed. Further, the components of the raw materials may be directly added to the feed portion of the melt mixing device without undergoing a premixing step. In melt mixing, the components of the polymer composition are typically melt blended in a single screw or twin screw extruder, extruded by standard techniques and cut into molded articles, such as conventional granules, pellets, and the like. The composition is then molded in any equipment conventionally used for molding, such as a Newbury type injection molding machine, a Van Dorn type injection molding machine.
  • Fluoropolymers have been used as anti-drip agents, anti-wear agents, etc. in flame retardant polymer compositions, and the coated fluoropolymer particles, polymer blends of the present invention have been shown to increase polymer compositions In particular, the flame retardancy of the flame retardant polymer composition is particularly useful.
  • the polymer composition of the present invention is preferably a flame retardant polymer composition.
  • the flame retardant polymer composition has improved processability, dispersion properties, flame retardancy and mechanical properties.
  • the coated fluoropolymer particles and the polymer blend of the invention not only improve the processing and dispersing properties, mechanical properties and apparent properties of the fluoropolymer in the polymer composition, but also because of the large amount of silicone polymer
  • the presence of Si atoms also has good flame retardant carbon formation. Even if the fluoropolymer is in a higher content in the polymer composition, the coated fluoropolymer and the polymer blend of the present invention are easily dispersed in the polymer matrix, so that the surface of the product is free from defects and can be Other excellent properties of the polymer composition are maintained.
  • the amount of the coated fluoropolymer particles and the polymer blend is such that the weight content of the fluoropolymer in the polymer composition is preferably from 0.01 to 30%, further preferably 0.1. -10%, more preferably 0.1-6%.
  • the particle size of the product is measured by a laser diffraction type particle size analyzer (Shimadzu SALD-2300) and a scanning electron microscope (ZEISS EVO18, the number of samples is not less than 100), and the melt index test is performed in accordance with the ASTM D1238 standard.
  • the cantilever notched impact strength test was carried out in accordance with ASTM D256.
  • the tensile strength and elongation at break tests were carried out in accordance with ASTM D638.
  • the flexural strength test was carried out in accordance with ASTM D790.
  • the combustion test was carried out in accordance with the method specified in UL 94.
  • the reaction washing and filtration, drying was carried out in a 105 ° C hot cycle blast drying oven to obtain 120 g of a polymer blend white powder having a polytetrafluoroethylene content of about 50% by weight and a water content of 0.3% by weight.
  • the sample was subjected to a laser diffraction type particle size analyzer and a scanning electron microscope test. As shown in Fig. 1, the obtained polymer blend was composed of primary particles and secondary particle agglomerates, and the average particle diameter thereof was 0.23 ⁇ m and 13 ⁇ m, respectively.
  • a mixture solution of 150 g of ethanol, 1 g of OP-10, 50 g of water and 61 g of methyltrimethoxysilane was added to the reaction vessel, and after stirring at room temperature, 50 g of a polytetrafluoroethylene dispersion having a solid content of 60% was added (primary The particle size is 0.2 ⁇ m, SSG is 2.175) and 12.5g is 28% ammonia water. After about 1min, the system begins to appear solid suspension. After stirring for 15min at room temperature, the temperature is raised to 50°C. After constant temperature for 2h, the reaction is terminated. After washing and filtering.
  • Drying was carried out in a hot cycle blast drying oven at 105 ° C to obtain 60 g of a polymer blend white powder having a polytetrafluoroethylene content of about 50% by weight and a water content of 0.3% by weight.
  • the sample was subjected to a laser diffraction type particle size analyzer and a scanning electron microscope test.
  • the obtained polymer blend was mainly composed of secondary particle agglomerates, and its average particle diameter was 61 ⁇ m.
  • a mixed solution of 75 g of ethanol, 25 g of water, and 61 g of methyltrimethoxysilane was added to the reaction vessel, and some acetic acid was added to adjust the pH to 4, and the mixture was stirred at room temperature for 3 hours to obtain a hydrolyzate containing methyltrimethoxysilane and partially hydrolyzed.
  • a mixed solution of a condensate which is added to a solution of 50 g of a polytetrafluoroethylene dispersion having a solid content of 60% (primary particle diameter of 0.2 ⁇ m, SSG of 2.175), 1 g of OP-10, 150 g of water, and 25 g of ammonia water.
  • Polymer blend free flowing powder Sampling was carried out by laser diffraction particle size analyzer and scanning electron microscopy. As shown in Fig. 3, the obtained polymer blend was composed of primary particles and secondary particle agglomerates, and the average particle diameter was 3 ⁇ m (polymerization by free organosilicon). Mainly), 388 ⁇ m.
  • the sample was subjected to laser diffraction particle size analyzer measurement and scanning electron microscopy.
  • the obtained polymer blend powder had a primary average particle diameter of 12 ⁇ m (mainly free silicone polymer), and the average secondary aggregate was average.
  • the particle size was 398 ⁇ m.
  • the particle size of the fluoropolymer-containing polymer blend prepared by the above emulsion hydrolysis-condensation polymerization, precipitation hydrolysis-condensation polymerization, emulsion condensation polymerization and hydrosilylation method can be controlled not only within 500 ⁇ m but also at 100 ⁇ m. Within the range of 20 ⁇ m or less, the aggregates are prepared at one time, and do not require any forced depolymerization of the polymer blend such as grinding or jet milling. Further, according to the scanning electron micrograph (see Figs. 1-5), the polymer blend of the present invention contains substantially no fiber filaments, i.e., the product is not advanced in fiberization, and has a core-shell structure.
  • the viscosity of the reaction system increased, and the solid suspension began to appear.
  • the temperature was raised to 50 ° C, and then the stirring was continued for 2 hours, and the obtained polymer blend was obtained.
  • the dispersion was washed, filtered under reduced pressure, and then dried in a hot cycle blast oven at 105 ° C to obtain 72.1 g of a polymer blend having a polytetrafluoroethylene content of about 50% by weight and a white content of 0.3% by weight. powder.
  • the sample was subjected to a laser diffraction type particle size analyzer and a scanning electron microscope test. As shown in Fig. 5, the obtained polymer blend was composed of primary particles and secondary particle agglomerates, and the average particle diameter thereof was 0.26 ⁇ m and 11 ⁇ m, respectively.
  • Example 6 In addition to replacing 60 g of the polytetrafluoroethylene dispersion having a solid content of 60% by weight with 90 g, the preparation process was as in Example 6, obtaining 90.2 g of a polymer having a polytetrafluoroethylene content of about 60% by weight and a content of 0.3% by weight or less. Blend white powder. The sample was subjected to a laser diffraction particle size analyzer and a scanning electron microscope test, and the obtained polymer blend was composed of primary particles and secondary particle agglomerates, and the average particle diameter thereof was 0.25 ⁇ m and 13 ⁇ m, respectively.
  • Example 6 In addition to replacing 60 g of the polytetrafluoroethylene dispersion having a solid content of 60% by weight with 40 g, the preparation process was as in Example 6, obtaining 60.2 g of a polymer having a polytetrafluoroethylene content of about 40% by weight and a content of 0.3% by weight or less. Blend white powder. The sample was subjected to a laser diffraction particle size analyzer and a scanning electron microscope test, and the obtained polymer blend was composed of primary particles and secondary particle agglomerates, and the average particle diameter thereof was 0.3 ⁇ m and 9 ⁇ m, respectively.
  • the present invention produced polymer blends containing functional groups such as phenyl groups, amino groups, and the like having different fluoropolymer contents.
  • Example 2 In addition to removing the polytetrafluoroethylene dispersion having a solid content of 60% by weight, the preparation process was as in Example 1, and finally 60 g of a silicone polymer having a water content of 0.3% by weight or less was obtained.
  • the preparation process was the same as in Example 4 except that the polytetrafluoroethylene powder was not added, and finally 443 g was obtained.
  • the preparation process was the same as in Example 5 except that the polytetrafluoroethylene powder was not added, and finally 469 g of a silicone polymer having a water content of 0.5% by weight or less was obtained.
  • reaction liquid was introduced into a separating funnel to separate the layers, the water layer was partitioned, the oil layer was washed with water until neutral, and dried by distillation.
  • 49.7 g of a white powdery solid was obtained, wherein the polytetrafluoroethylene content was 60%, which was agglomerated white microspheres, and the average particle diameter was 0.42 mm, wherein the M/Q ratio of the obtained MQ silicone resin was 0.61.
  • the polymer blend was added in an amount such that the content of PTFE in the total amount of the components of the composition system was 0.4% by weight.
  • the twin-screw extruder used has a length to diameter ratio of 40 and has precise temperature control and vacuum exhaust equipment. The screw speed is 100-700 rpm, and the extrusion working temperature is: 230°C-260 in one zone. °C, two zones 230 ° C -270 ° C, three zones 230 ° C -270 ° C, four zones 240 ° C -280 ° C, residence time 1-2 minutes.
  • OSP silicone polymer
  • the introduction of the silicone polymer coating material greatly improves the dispersion property of the fluoropolymer in the polymer composition.
  • the silicone polymer-coated fluoropolymer prepared by polymerizing a silane with an acid as a catalyst alone is inferior to the polymer mixture of the present invention in dispersibility, processability, and flame retardancy in the polymer composition.
  • the aggregate size of the polymer blend and the pre-fibrillation of the fluoropolymer in the polymer blend have a significant effect on its dispersion and processing properties in the polymer composition, ultimately on the polymer combination.
  • the flame retardant and mechanical properties of the material have an effect. It will be apparent that the polymer blends of the present invention have better dispersion and processing properties in the polymer composition, and the resulting polymer composition has Better mechanical properties and flame retardant properties.
  • the increase in the molecular weight of the polycarbonate can significantly improve the mechanical properties and flame retardancy of the polymer composition.
  • the increased amount of polymer blend of the present invention can significantly increase the flame retardant properties of the polymer composition such that the polymer composition still has better surface topography and mechanical properties.

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Abstract

包覆型氟聚合物颗粒、包含其的聚合物共混物和聚合物组合物及其制备方法。所述包覆型氟聚合物颗粒为可自由流动的且由表面被有机硅聚合物完全或部分地包覆的氟聚合物组成。该包覆型氟聚合物颗粒具有良好分散性、热稳定性和阻燃成炭性，可广泛用于化工、石油、纺织、电子电气、医疗、机械等领域。

Description

包覆型氟聚合物颗粒及包含其的聚合物共混物和聚合物组合物 技术领域
本发明总地来说涉及聚合物加工领域。具体地讲，本发明涉及包覆型氟聚合物颗粒、包含其的聚合物共混物和聚合物组合物及其制备方法。
背景技术
目前，以基于四氟乙烯衍生物的聚合物(本文简称为四氟乙烯聚合物)为代表的氟聚合物，一般具有优良的耐高低温性能、不粘性能、抗腐蚀性能、及阻燃性能等，已在化工、纺织、电子电气、医疗、机械等领域获得了广泛应用。四氟乙烯聚合物作为添加助剂已被用来作为聚合物材料中的耐磨润滑剂及抗滴落剂，但是，使用这些聚合物存在几个问题，尤其是四氟乙烯聚合物作为阻燃聚合物组合物的抗滴落剂，会造成挤出、注塑，吹塑等产品的表观形貌差，产品力学性能下降严重，显然，这些问题是由于四氟乙烯聚合物在聚合物组合物中的不良分散造成的。
为弥补上述缺点，提高四氟乙烯聚合物在聚合物组合物中的分散性，人们对四氟乙烯聚合物进行了大量的研究和技术改进。
专利EP-A-D,166,187采用共沉淀的方法得到丙烯腈-丁二烯-苯乙烯改性的聚四氟乙烯粉末，其缺点是自粘性高，当聚四氟乙烯含量达到25％重量时，粉末自由流动性差，其在聚合物组合物中的分散性能没有得到改善。
专利CN1，147,269A公开了一种抗滴落性能、作业性能及脱模性能优良的防滴剂。该防滴剂芯部为原纤维形成性的高分子量聚四氟乙烯，壳部为非原纤维形成性的低分子量聚四氟乙烯，但该包覆型聚四氟乙烯制备工艺复杂，且壳部较柔软，受外力作用易粘结，自由流动性差，其在聚合物组合物中的分散性仍没有得到根本改善。
专利CN1，125,096C采用自由基乳液聚合的方法制备了一种新型包覆型四氟乙烯聚合物颗粒。其包覆材料选自：聚苯乙烯、聚α-甲基苯乙烯、苯乙烯-丙烯腈共聚物、α-甲基苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物和它们的混合物，该包覆型四氟乙烯聚合物颗粒是目前市场上除四氟乙烯聚合物纯粉外广泛使用的产品类型。但是在较高添加量的情况下，其在聚合物组合物中的分散性变差，聚合物组合物力学性能下降严重，且成型制品表面有缺陷。此外，其所用包覆材料热稳定性及阻燃成炭性差。
专利CN102286157A单独以酸为催化剂，需要用甲苯、二甲苯等有机溶剂反复萃取和洗涤，最后蒸馏去除溶剂。其工艺复杂，耗时长，后处理繁琐，不经济，并且由于用于包覆材料的MQ硅树脂中Q链节含量较低，易形成超级粒子凝聚体，且耐热性能较差，且添加量较高时，其在聚合物组合物中的分散性变差，成型制品有缺陷。
专利CN103849092A以含氟聚合物粉末或其凝聚态粉末为原料与硅烷混合，使硅烷渗透至氟聚合物的空隙之间，使硅烷原位聚合反应4-16小时，最后升温至沸腾除水，经过筛高温干燥，经气流粉粹得到高档涂料用粒径为0.1μm-15μm的复合微粉。该方法所得产品含有较多的超级粒子凝聚体，无法直接使用，需要经过气流粉碎强制解聚才能得到所述粒径的复合微粉，并且当含氟聚合物为成纤能力强的氟聚合物时，气流粉碎强制解聚的处理方法会导致氟聚合物提前纤维化，无法解决氟聚合物抗滴落剂在聚合物组合物中的分散性。
目前本领域仍对具有热稳定性和阻燃成炭性，特别是良好分散性的氟聚合物颗粒存在需求。
发明内容
本发明所要解决的技术问题是克服现有技术氟聚合物颗粒在热稳定性、阻燃成碳性、特别是分散性方面的缺点。
本发明所要解决的技术问题通过以下技术方案得以解决：
根据本发明的第一方面，提供一种包覆型氟聚合物颗粒，其为可自由流动的且由表面被有机硅聚合物完全或部分地包覆的氟聚合物组成，由选自(i)、(ii)、(iii)、(iv)的方法制备：
(i)乳液水解-缩合聚合法：以水或水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，乳液水解-缩合聚合硅化合物，然后进行固液分离干燥，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
(ii)沉淀水解-缩合聚合法：以水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，沉淀水解-缩合聚合硅化合物，然后进行固液分离干燥，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
(iii)乳液缩合聚合法：使一分子中至少含有两个Si-OH基团的聚硅氧烷与以一分子中至少含有三个与硅原子相连接的可水解基团的硅化合物、其水解物、部分水解-缩合物以及它们的混合物，或以一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷为交联剂乳化后，在氟聚合物的存在下，加入缩 合催化剂，交联固化聚硅氧烷与交联剂，然后进行固液分离干燥；或
(iv)氢化硅烷化法：将一分子中具有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及一分子中具有至少2个键合在硅原子的氢原子(简述为Si-H基)的有机氢化(聚)硅氧烷乳化后，在氟聚合物的存在下，加入氢化硅烷化催化剂，交联固化所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷，然后进行固液分离干燥，其中一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个，
所述有机硅聚合物为具有交联结构的聚合物，
所述包覆型氟聚合物颗粒中氟聚合物与有机硅聚合物的重量比例为95∶5-5∶95。
根据本发明的第二方面，提供一种聚合物共混物，其是可自由流动的粉末，其包含上述包覆型氟聚合物颗粒以及有机硅聚合物颗粒。
根据本发明的第三方面，提供一种制备上述聚合物共混物的方法，其包括：
(1)进行选自(i)、(ii)、(iii)、(iv)的步骤：
(i)以水或水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，乳液水解-缩合聚合硅化合物，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
(ii)以水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，沉淀水解-缩合聚合硅化合物，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
(iii)使一分子中至少含有两个Si-OH基团的聚硅氧烷与以一分子中至少含有三个与硅原子相连接的可水解基团的硅化合物、其水解物、部分水解-缩合物以及它们的混合物，或以一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷为交联剂乳化后，在氟聚合物的存在下，加入缩合催化剂，缩合交联固化聚硅氧烷与交联剂；或
(iv)将一分子中具有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及一分子中具有至少2个键合在硅原子的氢原子(简述为Si-H基)的有机氢化(聚)硅氧烷乳化后，在氟聚合物的存在下，加入氢化硅烷化催化剂，交联固化所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷，其中一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个；和
(2)进行固液分离干燥，从而得到能自由流动的粉末形式的聚合物共混物。
根据本发明的第四方面，提供通过将所述聚合物共混物挤塑、注塑或吹塑等得到的制品。
根据本发明的第五方面，提供一种聚合物组合物，其包含一种聚合物基体， 其中分散有上述包覆型氟聚合物颗粒或聚合物共混物。
根据本发明的第六方面，提供通过将所述聚合物组合物挤塑、注塑或吹塑等得到的制品。
本发明的包覆型氟聚合物颗粒以及聚合物共混物具有良好分散性、热稳定性和阻燃成炭性，作为添加剂加入聚合物中形成聚合物组合物时，不会明显导致聚合物组合物力学性能下降。
附图说明
下面结合附图对本发明进行说明，其中：
图1是本发明实施例1所制备的聚合物共混物样品的扫描电镜。
图2是本发明实施例2所制备的聚合物共混物样品的扫描电镜。
图3是本发明实施例4所制备的聚合物共混物样品的扫描电镜。
图4是本发明实施例5所制备的聚合物共混物样品的扫描电镜。
图5是本发明实施例6所制备的聚合物共混物样品的扫描电镜。
图6是本发明实施例1、2、3、6中所用聚四氟乙烯分散液的扫描电镜。
具体实施方案
以下对本发明的技术方案进行详细描述。
包覆型氟聚合物颗粒
本发明的包覆型氟聚合物颗粒，为可自由流动的，其由表面被有机硅聚合物完全或部分地包覆的氟聚合物组成。
适宜的氟聚合物包括均聚物和共聚物，所述氟聚合物包含衍生自一种或多种氟化α-烯烃单体的重复单元。
所述氟化α-烯烃单体，即，含有至少一个氟原子取代基的α-烯烃单体。适宜的氟化α-烯烃单体有：例如CF2＝CF2、CHF＝CF2、CH2＝CF2、CH2＝CHF、CClF＝CF2、CCl2＝CF2、CClF＝CClF、CHF＝CCl2、CH2＝CClF和CCl2＝CClF等氟乙烯，例如，CF3CF＝CF2、CF3CF＝CHF、CF3CH＝CF2、CF3CH＝CH2、CF3CF＝CHF、CHF2CH＝CHF和CF3CH＝CH2等氟丙烯。适宜的氟聚合物及制备这些氟聚合物的方法是熟知的，参见例如美国专利3,671,487、美国专利3,723,373、美国专利3,383,092。
适宜的氟化α-烯烃均聚物包含，比如聚四氟乙烯、聚六氟丙烯、聚偏氟乙烯、聚氟乙烯、聚三氟氯乙烯。
适宜的氟化α-烯烃共聚物包含这样的共聚物，其含有由两种或更多种氟化α-烯烃共聚物衍生的重复单元，比如，四氟乙烯-六氟丙烯共聚物、四氟乙烯-偏 氟乙烯共聚物，以及包含这样的共聚物，其含有由一种或更多种氟化单体衍生的重复单元以及由一种或更多种能够与所述氟化单体共聚的非氟化烯类不饱和单体衍生的重复单元，比如，四氟乙烯-乙烯共聚物、四氟乙烯-乙烯-丙烯共聚物。适宜的非氟化烯类不饱和单体包括但不限于：比如乙烯、丙烯等α-烯烃单体，比如甲基丙烯酸甲酯、丙烯酸丁酯等(甲基)丙烯酸类单体、比如环己基乙烯基醚、乙基乙烯基醚、正丁基乙烯基醚等乙烯基醚类、比如乙酸乙烯酯、叔碳酸乙烯酯等乙烯酯类。
适宜的氟聚合物，可以是能够原纤维化的，也可以是不能够原纤维化的，本发明优选的是能够原纤维化的。
所述氟聚合物优选四氟乙烯聚合物。可以使用的四氟乙烯聚合物有：聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、四氟乙烯-偏氟乙烯共聚物、四氟乙烯-氟乙烯共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物以及四氟乙烯与其它可共聚的烯类不饱和单体的共聚物。这些聚合物都是众所周知的，在Schildknecht所著的“Vinyl and related polymers(乙烯基单体和相关聚合物)”(John Wiley&Sons，Inc.，New York，1952，第484-494页)和Woll所著的“Fluoropolymers(含氟聚合物)”(Wiley-Interscience，Johy Wiley&Sons，Inc.，NewYork，1972)中都有详述。
所述氟聚合物，进一步优选聚四氟乙烯(PTFE)。
对聚四氟乙烯的标准比重(Standard Specific Gravity，简称“SSG”，根据ASTM D4894或ASTM D4895标准测定)没有任何的限定，通常为2.230以下，优选2.130-2.220，更优选2.140-2.200，该标准比重越小，表示分子量越高。上述标准比重为2.140-2.200的PTFE的数均分子量按式“log10(数均分子量)＝31.83-11.58×(标准比重))”计算约为2×106-1×107。
在本发明中，可根据不同的反应条件、所用硅化合物的种类及制备方法等，选择合适粒径的氟聚合物的初级粒子和/或次级粒子凝聚体。包覆型氟聚合物颗粒中氟聚合物与有机硅聚合物的重量比例优选95∶5-5∶95，更优选80∶20-20∶80，最优选60∶40-60∶40。
所述有机硅聚合物是具有交联结构的聚合物，可以是均聚物、共聚物以及它们的混合物，也可以是比如：硅树脂、缩合型硅橡胶及加成型硅橡胶以及它们的混合物。
所述有机硅聚合物可以是采用乳液水解-缩合或沉淀水解-缩合聚合法制备的具有以下特征的第一类有机硅聚合物：含有主链Si-O链节且含有支链结构T型结构单元，其中相对主链而言，四官能链节SiO2(Q)，三官能链节RSiO3/2(T)，二官能链节R2SiO(D)，单官能链节R3SiO1/2(M)所占比例优选为：
SiO2(Q)：0-70％mol，更优选0-20％mol，
RSiO3/2(T)：0.1-100％mol，更优选50-100％mol，
R2SiO(D)：0-30％mol，更优选0-10％mol，
R3SiO1/2(M)：0-30％mol，更优选0-10％mol，
其中，SiO2(Q)和RSiO3/2(T)链节的总和所占比例为70-100％mol，进一步优选RSiO3/2(T)链节为70％-100％mol。此外，R2SiO(D)及R3SiO1/2(M)的总和优选不超过30％mol，进一步优选不超过20％mol，最优选不超过10％mol，并且优选SiO2(Q)、R2SiO(D)及R3SiO1/2(M)的总和不超过30％mol，进一步优选不超过20％mol。各R彼此独立地为一价有机基团。
优选地，各R彼此独立地为经取代或未经取代的碳数为1-30的一价烃基，例如具有1-12个碳原子，优选1-8个碳原子，更优选1-6个碳原子的直链、支链或环状烷基；具有2-10个碳原子，优选2-8个碳原子，更优选2-6个碳原子的直链或支链烯基；任选被上述烷基取代的芳基如苯基、萘基；任选被芳基如苯基取代的上述烷基；这些基团的碳原子上键合的一部分或全部的氢原子经卤素原子(氟、氯、溴、碘)和/或丙烯氧基、甲基丙烯酰氧基、环氧基、缩水甘油氧基、羧基、羟基、巯基、氨基、磺酸基、硝基、胺基取代，包括但不限于：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基等烷基，苯基、甲苯基、二甲苯基、萘基等芳基，苄基、苯乙基等芳烷基，乙烯基、烯丙基、丙烯基、丁烯基、己烯基、庚烯基等烯基，环戊基、环己基、环庚基等环烷基等。优选R中50％mol以上为甲基、苯基、乙烯基，进一步优选50％mol以上为甲基、苯基，最优选50％mol以上为甲基。
在本发明中，根据R基团的不同，可制备出各种功能性包覆用有机硅聚合物，比如：含有苯基、氨基、环氧基、巯基、磺酸基、链烯基、丙烯氧基及上述其它各种官能基团等。
可以提及的第一类有机硅聚合物有：由T，TQ，TQD，TQM，TD，TM，TDM或QTDM等基本链节组成的有机硅聚合物及它们的混合物，可由T链节形成均聚物，TQ，TD，TM，TQD，TQM，TDM及TQDM等基本链节形成共聚物，实例包括但不限于：聚甲基硅氧烷、聚乙基硅氧烷、聚苯基硅氧烷、聚乙烯基硅氧烷、聚氯甲基硅氧烷、聚氯乙基硅氧烷、聚甲基乙基硅氧烷、聚甲基苯基硅氧烷、聚甲基乙烯基硅氧烷、聚苯基乙烯基硅氧烷、聚乙基苯基硅氧烷、聚乙基乙烯基硅氧烷、聚甲基苯基(乙烯基)硅氧烷、聚甲基乙基(苯基)(乙烯基)硅氧烷、聚氯甲基甲基(乙基)(苯基)硅氧烷、聚甲基氨丙基硅氧烷、聚甲基苯基(氨丙基)硅氧烷、聚甲基巯丙基硅氧烷、聚甲基苯基(巯丙基)硅氧烷、聚甲基缩水甘油醚氧基丙基硅氧烷、聚甲基苯基(缩水甘油醚氧基丙基)硅氧烷、聚甲基(丙烯酰氧基丙基)硅氧烷、聚甲基苯基(丙烯酰氧基丙基)硅氧烷等。
此外，可针对上述有机硅聚合物的基本骨架中的硅原子进行其它金属或非金属原子的取代，构成对有机硅聚合物的改性，改性物为任何可以与前面所述硅化合物共水解-缩合的化合物，包括但不限于：钛酸、钛酸金属盐、氯化钛、烷氧基钛、硼酸酯等。所述其它金属或非金属原子所占比例优选不超过30％mol，进一步优选不超过10％mol，最优选不超过5％mol。
所述有机硅聚合物还可以是由乳液缩合聚合法制备的有机硅聚合物，所使用硅化合物包含：有机聚硅氧烷(A)及交联剂(B)，即由聚硅氧烷(A)和交联剂(B)经乳化后，在氟聚合物的存在下，加入缩合催化剂(C)，交联固化后经固液分离干燥得到。
所述有机聚硅氧烷(A)包含：一分子中至少含有两个Si-OH基团。所述交联剂(B)选自：一分子中至少含有三个与硅原子相连接的可水解基团的硅化合物或其水解物、部分水解-缩合物，及一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷。所述缩合催化剂(C)，用于加速有机聚硅氧烷(A)与交联剂(B)的交联固化，得到包覆型氟聚合物颗粒。
所述有机硅聚合物还可以是具有以下特征的有机硅聚合物：具有通过键合在硅原子上的一价脂肪族不饱和基与键合在硅原子上的氢原子的氢化硅烷化反应(也可称为硅氢加成反应)而形成的交联结构并且具有包含式-(R1 2SiO2/2)n-所表示的线性有机硅氧烷嵌段的硬化物，其中式中n为正整数，对其没有特别的限制，优选为5～5,000的正整数，各R1为彼此独立的一价有机基团，在此R1具有前面针对R所述相同的定义。
由氢化硅烷化法(也可称为乳液氢化硅烷化法)制备有机硅聚合物中所用的硅化合物，其包含有机(聚)硅氧烷与有机氢化(聚)硅氧烷，即包含：一分子中具有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及一分子中具有至少2个键合在硅原子的氢原子(简述为Si-H基)的有机氢化(聚)硅氧烷，优选一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个。
本发明中，对包覆型氟聚合物颗粒的粒径和形貌没有特别的限制，一般体积平均粒径为0.01μm-700μm，优选0.1μm-300μm，进一步优选0.1μm-100μm，最优选0.1μm-50μm，其可以是体积平均粒径为0.01μm-100μm的初级粒子，也可以是由初级粒子聚集形成的体积平均粒径为0.1μm-700μm次级粒子凝聚体，其详细制备方法将在下文中描述。
聚合物共混物
本发明的聚合物共混物，是可自由流动的粉末，其包含本发明所述的包覆型氟聚合物颗粒以及有机硅聚合物颗粒。
氟聚合物在所述聚合物共混物中的比例可以在很宽的范围变化，通常为聚合物共混物总重量的0.01％-95％重量，优选为1％-80％重量，进一步优选10％-70％重量，最优选30-70％重量。
在一个实施方案中，所述聚合物共混物由包覆型氟聚合物颗粒和有机硅聚合物颗粒组成，其中氟聚合物为聚合物共混物总重量的0.01％-95％重量，优选为1％-80％重量，进一步优选10％-70％重量，最优选30-70％重量。有机硅聚合物的一部分以氟聚合物颗粒的包覆物的形式存在，其余以游离的有机硅聚合物颗粒形式存在。所述有机硅聚合物，具有交联结构，可以是均聚物、共聚物以及它们的混合物，也可以是例如：硅树脂、缩合型硅橡胶、加成型硅橡胶以及它们的混合物。
本发明人在开发所述功能性有机硅聚合物时，发现引入氟聚合物时，有机硅聚合物能很好包覆氟聚合物，同时又能赋予氟聚合物更多的功能，比如热稳定性、增韧性能、阻燃成碳性，特别是大大提高了氟聚合物在聚合物组合物中的分散性能。
在本发明中，对聚合物共混物的粒径及形貌没有特别的限制。其中游离的有机硅聚合物颗粒可以是球形或者片状等不规则形貌，优选为球形，其体积平均粒径优选0.01μm-100μm，进一步优选0.1μm-50μm，最优选0.1μm-30μm。
制备聚合物共混物的方法
本发明制备聚合物共混物的方法可以包括在氟聚合物的存在下，使硅化合物在碱性催化剂，尤其是水溶性碱性催化剂下，以水或水-有机溶剂特别是水-醇体系作为分散介质，进行乳液聚合(本文称为乳液水解-缩合聚合)，得到聚合物共混物沉淀、凝胶或分散液(也可称为乳液、悬浮乳液或悬浮液，下同)，经固液分离干燥后，得到能自由流动的粉末形式的聚合物共混物。
本发明制备聚合物共混物的方法也可以包括在氟聚合物的存在下，使硅化合物在碱性催化剂，尤其是水溶性碱性催化剂下，以水-有机溶剂，特别是水-醇为分散介质，进行沉淀聚合(本文称为沉淀水解-缩合聚合)，得到聚合物共混物沉淀、凝胶或分散液，经固液分离干燥后，得到能自由流动的粉末形式的聚合物共混物。
本发明制备聚合物共混物的方法可以包括使一分子中至少含有两个Si-OH基团的聚硅氧烷与以一分子中至少含有三个与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物，或以一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷为交联剂乳化后，在氟聚合物的存在下，加入缩合催化剂，交联固化聚硅氧烷与交联剂，得到聚合物共混物的分散液，经固液分离干燥后，得到能自由流动的粉末形式的聚合物共混物。
本发明制备聚合物共混物的方法可以包括将一分子中具有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及一分子中具有至少2个键合在硅原子的氢原子(简述为Si-H基)的有机氢化(聚)硅氧烷乳化后，在氟聚合物的存在下，加入氢化硅烷化催化剂，交联固化所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷，其中一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个，得到聚合物共混物的分散液，经固液分离干燥后，得到能自由流动的粉末形式的聚合物共混物。
进一步地可以从聚合物共混物中分离出前面所述的包覆型氟聚合物颗粒。
本发明中，对氟聚合物(这里是指用于制备本发明包覆型氟聚合物颗粒之前的氟聚合物)的使用形态没有限制。
氟聚合物可以是单一类型的氟聚合物细粉颗粒及其分散液、也可以是两种或更多种氟聚合物的共混物的细粉颗粒及其分散液。所述单一类型的氟聚合物的细粉颗粒为已有的公知的氟聚合物，其分散液可以是市售的具有一定固含量的分散液(该分散液一般含有2-10％重量的表面活性剂及一定量的氨水)，对固含量没有特别的限定，比如固含量为30％、50％、60％等，也可以是由水相聚合法得到的氟聚合物聚合分散液，该聚合分散液可无需经过浓缩步骤，比如无需浓缩至固含量为30％、50％、60％等。所述氟聚合物的共混物的细粉颗粒或其分散液可以通过混合单一类型的氟聚合物细粉颗粒或其分散液获得。
所述氟聚合物还可以是已有的公知的包覆型氟聚合物细粉颗粒，其分散液可以是其预先分散在水和/或有机溶剂中的分散液，也可以是指包覆型氟聚合物在其制备过程中的悬浮乳液。
氟聚合物优选为混合类型的氟聚合物细粉颗粒及其分散液，进一步优选单一类型的氟聚合物颗粒及其分散液，更优选聚四氟乙烯颗粒及其分散液，最优选能够原纤维化的聚四氟乙烯颗粒及其分散液。
本领域技术人员容易根据最终要求确定所用氟聚合物的形态、粒径及分子量。
由硅化合物的乳液水解-缩合聚合或沉淀水解-缩合聚合反应制备本发明的聚合物共混物，例如可以简单的通过在氟聚合物的存在下，使硅化合物在碱性催化剂条件下，以水或水-有机溶剂特别是水-醇体系作为分散介质，进行乳液水解-缩合聚合或沉淀水解-缩合聚合。各种硅化合物的乳液水解-缩合聚合法或沉淀水解-缩合聚合法都可以用来制备包覆型氟聚合物，例如间歇、半连续或连续聚合法。氟聚合物可在一开始，即在任何乳液水解-缩合聚合反应或沉淀水解-缩合聚合反应开始之前，或在反应期间，通常是在90％重量或更多的硅化合物水解-缩合反应之前加入到反应介质中。
乳液水解-缩合聚合法或沉淀水解-缩合聚合法所用硅化合物为任何具有与 硅原子相连接的可水解基团的化合物、其水解产物、部分水解-缩合物或它们的混合物，其中与Si键合的可水解基团，可以列举但不限于：烷氧基、酰氧基、硅氢基、硅氮基、酮肟基、硅卤基等，优选具有1-6个碳原子的烷氧基、硅氢基、硅卤基，进一步优选烷氧基，最优选甲氧基、乙氧基。对所述硅化合物的组分、结构等没有任何的限制，所述硅化合物可以列举但不限于：甲基三氯硅烷、二甲基二氯硅烷、三甲基氯硅烷、四氯化硅、氯丙基三氯硅烷、氯丙基三甲氧基硅烷、氯丙基甲基二氯硅烷、氯丙基甲基二甲氧基硅烷、氯甲基三氯硅烷、氯甲基三甲氧基硅烷、氯甲基甲基二氯硅烷、氯甲基二甲基氯硅烷、二氯甲基三氯硅烷、三乙基氯硅烷、n-十二烷基三氯硅烷、辛基甲基二氯硅烷、乙烯基三氯硅烷、乙烯基二甲基氯硅烷、乙烯基甲基二氯硅烷、苯基三氯硅烷、二苯基二氯硅烷、三苯基氯硅烷、甲基二苯基氯硅烷、三甲基氟硅烷、(3，3，3-三氟丙基)甲基二氯硅烷、三甲基溴硅烷、三甲基碘硅烷及类似含卤硅烷(卤素为氟、氯、溴、碘，优选氯)、四甲氧基硅烷、四乙氧基硅烷及类似硅酸酯，硅酸钠及类似金属硅酸盐，三乙氧基硅烷、甲基二乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲基二甲氧基硅烷、乙基三甲氧基硅烷、丙基三甲氧基硅烷、苯基三甲氧基硅烷、甲基苯基二甲氧基硅烷、三甲基甲氧基硅烷及类似烷氧基硅烷，甲基三丁酮肟基硅烷、乙烯基三丁酮肟基硅烷、甲基乙烯基二丁酮肟基硅烷及类似酮肟基硅烷，甲基三乙酰氧基硅烷、乙烯基三乙酰氧基硅烷、乙基三乙酰氧基硅烷及类似酰氧基硅烷，三甲氧基硅烷、三甲基硅烷、甲基二甲氧基硅烷、二甲基甲氧基硅烷及类似含Si-H基硅烷、2，4，6，8-四甲基环四硅氧烷、1，1，3，3-四甲基二硅氧烷、三甲基硅封端的聚甲基氢硅氧烷、三甲基硅封端的二甲基硅氧烷-甲基氢硅氧烷共聚物及类似含Si-H基硅氧烷、六甲基二硅氮烷及类似硅氮烷、3-氨丙基三甲氧基硅烷、双(三甲氧基硅基丙基)胺、3-氨丙基甲基二乙氧基硅烷、3-(2-氨基乙基氨基)丙基三甲氧基硅烷、二乙烯三胺基丙基三甲氧基硅烷、二乙烯三胺基丙基甲基二甲氧基硅烷、苯胺甲基三甲氧基硅烷、环己胺基丙基三甲氧硅烷、二乙氨基甲基三乙氧基硅烷及类似氨基硅烷、巯丙基三甲氧基硅烷、巯丙基甲基二甲氧基硅烷、双(三乙氧基硅基丙基)四硫化物、双(三乙氧基硅基丙基)二硫化物及类似含硫硅烷、3-硫氰基丙基三乙氧基硅烷及类似硫氰基硅烷、3-脲丙基三甲氧基硅烷及类似脲基硅烷、3-异氰酸酯基丙基三甲氧基硅烷及类似异氰酸酯基硅烷，3-缩水甘油醚氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基甲基二甲氧基硅烷、2-(3，4-环氧环己烷)乙基三甲氧基硅烷及类似环氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷及类似丙烯酰氧基硅烷、苯基三乙氧基硅烷、二苯基二甲氧基硅烷、甲基苯基二乙氧基硅烷及类似苯基硅烷、乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、 乙烯基二甲基甲氧基硅烷及类似乙烯基硅烷，及它们的水解产物、部分水解-缩合物以及它们的混合物。
优选使用硅烷混合物制备本发明的聚合物共混物，所述硅烷混合物优选包含：
SiX4(Q)：0-70％mol，更优选0-20％mol，
RSiX3(T)：0.1-100％mol，更优选50-100％mol，
R2SiX2(D)：0-30％mol，更优选0-10％mol，
R3SiX1(M)：0-30％mol，更优选0-10％mol，
其中，必须含有RSiX3(T)，由RSiX3(T)或RSiX3(T)和SiX4(Q)提供交联结构，且优选RSiX3(T)与SiX4(Q)的总和所占比例为70-100％mol，进一步优选RSiX3(T)为70-100％mol。此外，R2SiX2(D)及R3SiX1(M)的总和优选不超过30％mol，进一步优选不超过20％mol，最优选不超过10％mol，并且优选SiX4(Q)、R2SiX2(D)及R3SiX1(M)的总和不超过30％mol，进一步优选不超过20％mol。
R的定义与上文所述相同，优选R中50％mol以上为甲基、苯基、乙烯基，进一步优选50％mol以上为甲基、苯基，最优选50％mol以上为甲基。
X表示一种卤素原子比如氯，或者表示一种可水解基团，比如烷氧基、酰氧基等，进一步优选烷氧基。
以上摩尔百分比基于硅烷混合物的总摩尔数(可以通过测试混合物中剩余单体的量，推算产品中各个链节的含量，比如采用气相、液相色谱、质谱、核磁等手段，还可以通过假设硅烷化合物完全水解-缩合估算)。
需要指出的是，当SiX4(Q)含量越高，所得氟聚合物的包覆材料越偏向无机化合物(SiO2)的性能，聚合物共混物也具有更高的热稳定性能及成碳性能。一般情况下，当SiX4(Q)含量较高，比如超过50％mol时，需要用水-有机溶剂为分散介质，优选水-醇类为分散介质，否则由于SiX4(Q)极易水解，导致较多的游离的水解物及部分水解-缩合物，影响对氟聚合物的包覆。R3SiX1(M)化合物的添加量不能过高，否则易形成超级粒子凝聚体。此外，R2SiX2(D)化合物提供线型结构，可广泛用于控制本发明的聚合物共混物的粒径、结构性能等，其含量不能过高，否则易导致产品收率下降、产生超级粒子凝聚体。
此外，由乳液水解-缩合聚合法或沉淀水解-缩合聚合法制备的聚合物共混物中允许含有部分与硅键合的未水解和/或未缩合的基团存在，例如可以举出但不限于：烷氧基、酰氧基、硅氢基、硅氮基、硅卤基、硅羟基等，其含量以不影响聚合物共混物的自由流动性为宜。
本发明通过乳液水解-缩合聚合法或沉淀水解-缩合聚合法制备包含包覆型氟聚合物颗粒的聚合物共混物，对反应温度没有特别的限制，优选为0-95℃，进一步优选为5-80℃，更优选10-70℃。同时，对包括加料时间在内的反应时间 也没有特别的限制，可以是数分钟、数小时，也可以是数天，优选1-10h。
乳液水解-缩合聚合法或沉淀水解-缩合聚合法制备包含包覆型氟聚合物颗粒的聚合物共混物，必须在有水的条件下才能进行，其最少量足以满足硅化合物在乳液水解-缩合聚合或沉淀水解-缩合聚合过程中所需要的量即可，优选过量的水。
本发明以水或水-有机溶剂为反应介质。根据反应介质及反应介质比例的不同、所用氟聚合物原料形态的不同及表面活性剂的是否使用等，本发明分别定义为乳液水解-缩合聚合及沉淀水解-缩合聚合。
以水为分散介质，以氟聚合物分散液(通常氟聚合物分散液中含有表面活性剂，比如2-10％重量，市售氟聚合物通常是4-8％重量范围)为原料时，本发明定义为乳液水解-缩合聚合；以水为分散介质，以含有氟聚合物的粉末颗粒及表面活性剂为原料时，本发明定义为乳液水解-缩合聚合；以水为分散介质，以含有氟聚合物的粉末颗粒为原料，在不添加表面活性剂的情况下，水与含有氟聚合物的粉末颗粒分为两相，但加入的硅化合物与疏水的含有氟聚合物的粉末颗粒迅速结合后发生水解反应，产生亲水基团，起到类似表面活性剂的作用，使含有氟聚合物的粉末颗粒分散在水分散介质中，本发明仍定义为乳液水解-缩合聚合。
以水-有机溶剂为分散介质，本发明优选水-水溶性有机溶剂为分散介质，由于水、有机溶剂的比例可以在很宽的范围内变化。当水、有机溶剂的比例使得硅化合物完全溶于分散介质中时，在氟聚合物的存在下，硅化合物发生水解-缩合反应后，产生高度交联的有机硅聚合物而沉淀出来形成沉淀、凝胶或者分散液，本发明定义为沉淀水解-缩合聚合(其对体系是否含有表面活性剂没有要求，当含有表面活性剂时，是沉淀聚合的一种特殊情形，传统上称为分散聚合)，正如前文所述，硅化合物在发生水解反应后，会产生亲水基团，起到类似表面活性剂的作用，本发明的沉淀水解-缩合聚合，可进一步说是分散水解-缩合聚合；当水、有机溶剂的比例使得硅化合物不能完全溶于分散介质时即以水为主要分散介质时，其聚合方法与前文所述乳液水解-缩合聚合相同，本发明定义为乳液水解-缩合聚合。
本发明对水的种类没有限制，可以是去离子水。矿物质水、自来水等，优选电导率不超过1000μS/m的水，进一步优选电导率不超过200μS/m的水，最优选电导率不超过100μS/m的水。对有机溶剂没有特别的限制，根据反应体系的不同，可选择添加或不添加，若添加，则优选水溶性有机溶剂，可以列举但不限于：甲醇、乙醇、异丙醇、正丁醇、丙酮等，进一步优选有机溶剂为醇类有机溶剂，特别是由烷氧基硅烷为原料时，其水解物为醇类有机溶剂，其既是反应过程的副产物，又是硅化合物的良溶剂。有时根据不同的目的，比如控制最终产品的粒径、 控制反应速度等，可以选择不溶于水的有机溶剂代替溶于水的有机溶剂，比如苯、甲苯、二甲苯、二氯甲烷等。需要特别指出的是，以沉淀水解-缩合聚合法制备聚合物共混物时，由于有机溶剂比例较高，此时选择加入氟聚合物分散液时，有时体系粘度会骤然升高，偶尔产生凝聚现象，但会随着硅化合物的水解-缩合反应的进行，体系粘度会逐渐下降，最终形成聚合物共混物的沉淀、凝胶或分散液。
在本发明中，当以水为分散介质时，原则上，其量足以用于悬浮氟聚合物即可，优选氟聚合物与水的重量比范围为1.66-0.001，进一步优选0.50-0.01，最优选0.30∶0.05，比例过高，则不能悬浮氟聚合物，极易生成超级粒子凝聚体，比例过低，易导致反应时间延长及产品收率、产品性能下降等缺陷；当以水-有机溶剂为分散介质时，原则上，其量足以用于悬浮氟聚合物即可，优选氟聚合物与水-有机溶剂的重量比范围为1.66-0.001，进一步优选0.50-0.01，最优选0.30∶0.05，比例过高，则不能悬浮氟聚合物，且极易生成超级粒子凝聚体，比例过低，易导致反应时间延长、产品收率、产品性能下降等缺陷，其中，对水-有机溶剂的比例没有特别的限定，两者比例可以在很宽的范围内变化，原则上，水的量足以满足硅化合物在乳液水解-缩合聚合或沉淀水解-缩合聚合过程中所需要的量即可，优选过量的水。
通过乳液水解-缩合聚合法或沉淀水解-缩合聚合法制备包含包覆型氟聚合物颗粒的聚合物共混物，根据需要可以添加或不添加表面活性剂，优选添加表面活性剂，对所用表面活性剂没有特别的限制，其用量优选为0.01-20％重量(相对分散液的总重量)，更优选0.1-10％重量。对表面活性剂的种类也没有特别的限制，可以是阴离子、阳离子、两性离子及非离子表面活性剂，可根据不同的分散介质、硅化合物的种类等选择合适的表面活性剂种类，可单独使用，也可以组合使用，优选非离子及阴离子表面活性剂，比如：十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十六烷基三甲基溴化铵、十八烷基三甲基氯化铵、十二烷基二甲基苄基溴化铵、烷基酚聚氧乙烯醚(OP)系列包括OP-6、OP-7、OP-8、OP-9、OP-10、OP-13、OP-15、OP-18、OP-20等、聚氧乙烯失水山梨糖醇(TW)系列包括TW-20、TW-21、TW-40、TW-80、TW-85等、脂肪醇聚氧乙烯醚(O)系列包括AEO-8、AEO-10、AEO-15、AEO-30等，以及它们的混合物，进一步优选非离子型表面活性剂。
为加快和促进硅化合物的水解-缩合反应，需加入水解-缩合催化剂，例如以酸或碱作硅化合物的水解-缩合催化剂。作为酸性催化剂的实例，可以例举的是硫酸、烷基磺酸、盐酸、硝酸、磷酸、焦磷酸、硼酸、氯硅烷等。作为碱性催化剂，可以列举的是：碱金属、氢氧化物、碱金属醇盐、硅醇盐、季铵碱、季磷碱、硅醇季铵盐、硅醇季磷盐及碱金属有机化合物、氨水、有机胺、碳酸盐、碳 酸氢盐等。
经过研究发现，单独以酸作为硅烷化合物的水解-缩合催化剂时，得到的一般是低交联度的聚硅氧烷树脂，其含有大量未完全缩合的基团，需要通过升温、加入固化剂等方法提高交联度，这在氟聚合物的存在下，易形成超级粒子凝聚体(通常几百微米到几毫米不等)，如果要得到小粒径的聚合物共混物，需要物理方法强制解聚，难免会对氟聚合物的结构和性能产生影响，特别是可原纤维化的氟聚合物树脂时，会使其提前纤维化。
本发明的一个目的是：在氟聚合物的存在下，使硅化合物较快形成高度交联的三维网状有机硅聚合物包覆材料，从而与氟聚合物一起形成沉淀、凝胶或者分散液，并尽可能的降低包覆材料之间的粘结反应，将包覆型氟聚合物的初级粒子及其凝聚体的粒径控制在可以广泛市场应用的水平，比如凝聚体粒径不高于500μm，优选不高于100μm，更优选不高于50μm，最优选不高于30μm。此目的通过本发明的方法得以实现。
本发明中，选择碱性化合物为乳液水解-缩合聚合及沉淀水解-缩合聚合反应的催化剂，进一步优选水溶性碱性催化剂，使水或水-有机溶剂分散介质碱化，比如：氢氧化钾、氢氧化钠等碱金属氢氧化物，氢氧化钙、氢氧化镁等碱土金属氢氧化物，碳酸钾、碳酸钠等碱金属碳酸盐，乙胺、丙胺、丁胺、二甲胺、三甲胺、三乙胺等胺类化合物，硅醇盐，季铵碱，季磷碱，硅醇季铵盐，硅醇季磷盐及碱金属有机化合物，氨类。本发明优选氨类，因其溶于水、催化活性高及易挥发，且易从产物中去除，进一步优选氨水，最优选含氨25-30％重量的氨水。对乳液水解-缩合聚合及沉淀水解-缩合聚合反应体系的碱性PH值没有特别的限制，优选9-13，进一步优选10-12。反应体系的碱性太弱，会延长硅化合物的水解和缩合时间及产品收率，反应时间的延长，有时会导致不同氟聚合物包覆层中硅化合物的水解物及部分水解-缩合物之间的粘结，产生超级粒子聚合物共混物凝聚体；碱性过强，易造成包覆氟聚合物不均匀、形成较多游离的未用于包覆氟聚合物的粒子，且易产生无定形凝聚物。
如前文所述，硅化合物的水解物、部分水解-缩合物以及它们的混合物可用于制备本发明的聚合物共混物，例如：先在酸性条件下，使硅化合物发生水解反应及部分水解-缩合反应(缩合反应的程度以不影响最终聚合物共混物的分散性能为宜，可以通过常规实验确定)，然后加入到含有氟聚合物的上述碱性分散介质中进行水解-缩合反应。在本发明中，硅化合物的缩合反应是否完全，直接影响聚合物共混物的自由流动性能，可以使用任何能够提高硅化合物的缩合反应的手段，比如调节PH值、提高温度等。
本发明中，由乳液水解-缩合聚合法及沉淀水解-缩合聚合法制备包含包覆型 氟聚合物颗粒的聚合物共混物，对原料的加入顺序和加入方式没有任何的限制，例如可以简单地使用以下方法制备得到：将氟聚合物、表面活性剂、水、有机溶剂及催化剂混合在一起，并在搅拌下加入硅化合物，使得硅化合物在氟聚合物存在下进行乳液水解-缩合或者沉淀水解-缩合反应，得到含有由有机硅聚合物全部或部分包覆的氟聚合物的聚合物共混物沉淀、凝胶或分散液，经固液分离如过滤处理后，干燥得到可自由流动的粉末。
本发明的乳液缩合聚合法可以简单地通过如下进行：在氟聚合物的存在下，聚硅氧烷(A)和交联剂(B)用表面活性剂和水进行乳化后，加入缩合催化剂(C)，交联固化后得到含有氟聚合物的聚合物共混物的分散液，经固液分离干燥后，得到可自由流动的粉末。
聚硅氧烷(A)在其一分子中至少含有两个Si-OH基团，对其所在位置没有特别的限定，但优选在分子链的末端，与Si原子相连接的有机基团，其可以是针对R所述的取代或未经取代的碳数为1-30的一价烃基。对有机聚硅氧烷(A)的分子结构没有特别的限制，可以是线性结构、带有部分支链的线性结构、支链结构或网状结构。对有机聚硅氧烷(A)的粘度(25℃)没有特别的限制，优选5-1,000,000mPa·s，进一步优选5-50,000mPa·s，最优选5-1,000mPa·s，粘度不能过高，否则较难在水中乳化。
交联剂(B)通过与Si-OH基团之间的缩合交联固化有机聚硅氧烷(A)。合适的交联剂(B)包含：一分子中至少含有三个与硅原子相连接的可水解基团的硅烷化合物或其水解物、部分水解-缩合物，及一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷，以及它们的混合物。其中，用作交联剂(B)的硅烷化合物中与硅原子相连接的可水解基团，包含：烷氧基、酮肟基、酰氧基、硅氢基等，交联剂(B)中硅原子还可以连接有有机基团，其可以是针对R所述的取代或未经取代的碳数为1-30的一价烃基。
本发明中，交联剂(B)可以列举的有：甲基三甲氧基硅烷、乙基三甲氧基硅烷、三甲氧基硅烷、四甲氧基硅烷、四乙氧基硅烷等烷氧基硅烷、苯基三甲氧基硅烷等芳基烷氧基硅烷；乙烯基三甲氧硅烷等链烯基烷氧基硅烷；3-氨丙基三甲氧基硅烷、双(三甲氧基硅基丙基)胺、3-(2-氨基乙基氨基)丙基三甲氧基硅烷、二乙烯三胺基丙基三甲氧基硅烷、苯胺甲基三甲氧基硅烷、环己胺基丙基三甲氧硅烷、二乙氨基甲基三乙氧基硅烷等含氨基烷氧基硅烷；巯丙基三甲氧基硅烷、双(三乙氧基硅基丙基)四硫化物、双(三乙氧基硅基丙基)二硫化物等含硫烷氧基硅烷；氯甲基三甲氧基硅烷、3-氯丙基三甲氧基硅烷等卤代烷基烷氧基硅烷；甲基三丁酮肟基硅烷、乙烯基三丁酮肟基硅烷、四丁酮肟基硅烷等酮肟基硅烷；甲基三乙酰氧基硅烷、乙烯基三乙酰氧基硅烷、乙基三乙酰氧基硅烷、四乙酰氧基硅 烷等酰氧基硅烷等T及Q型硅烷化合物，以及它们的水解物、部分水解-缩合物及混合物。优选烷氧基硅烷化合物及硅烷化合物的部分水解-缩合物，最优选所述硅烷化合物及硅烷化合物的部分水解-缩合物的混合物作为交联剂(B)。
对交联剂(B)的分子结构没有特别的限定，可以是线性结构、带有部分支链的线性结构、支状结构、网状结构及环状结构等。可以列举的有：三甲基硅氧基封端甲基氢聚硅氧烷、三甲基硅氧基封端的二甲基硅氧烷-甲基氢硅氧烷的共聚物、二甲基氢硅氧基封端的二甲基硅氧烷-甲基氢硅氧烷的共聚物、环状甲基氢硅氧烷及部分或全部甲基基团被乙基、丙基等烷基、苯基等芳基或乙烯基等链烯基取代的有机聚硅氧烷。
对交联剂(B)的用量没有特别的限制，其用量一般是：相对有机聚硅氧烷(A)0.1-60％的重量，优选0.1-30％的重量，进一步优选1-20％的重量。用量太少，则不足以交联固化有机聚硅氧烷(A)，用量太多，则可以按照本发明前文所述的乳液水解-缩合或沉淀水解-缩合法制备。
有时为控制交联固化反应、控制产品的结构性能等，可以选择性的加入其它组分，比如：R2SiO(D)和R3SiO1/2(M)结构的硅烷化合物，可以列举但不限于：二甲基甲氧基硅烷、甲基苯基二甲氧基硅烷、甲基乙烯基二甲氧基硅烷、三甲基甲氧基硅烷、乙烯基二甲基甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲基甲氧基硅烷、3-巯丙基甲基二甲氧基硅烷、3-缩水甘油醚氧基丙基甲基二甲氧基硅烷等，以及它们的水解物、部分水解-缩合物。对其添加量没有限定，可以根据需要添加或不添加，以确保有机聚硅氧烷(A)及交联剂(B)能够合适的固化为宜，优选相对有机聚硅氧烷(A)不超过10％的重量，进一步优选不超过5％的重量。
本发明中，对乳化条件没有特别的限制，优选乳化分散机进行乳化，可以列举但不限于：均质分散机或类似高速旋转离心放射式搅拌机、均质混合机或类似高速旋转剪切式搅拌机、均质搅拌机或类似高压喷射式乳化分散机、胶体磨机、超声波乳化机等。
本发明中，对所用表面活性剂的种类没有特别的限制，比如阳离子、阴离子、非离子型及两亲性表面活性剂，进一步优选阴离子表面活性剂及非离子型表面活性剂，前文中已有表面活性剂相关描述，不再赘述。对其添加量没有特别的限制，优选0.01-20％重量(相对整个乳液体系)，进一步优选0.1-10％重量，用量过少，则对制备工艺要求高，用量过多，后处理麻烦及对产品性能有影响。
本发明中，需要加入缩合催化剂(C)，加速有机聚硅氧烷(A)与交联剂(B)的缩合交联固化，得到包含氟聚合物的聚合共混物。所用缩合催化剂(C)，包含：辛酸亚锡、油酸锡、辛酸锆、辛酸镁、辛酸锡等有机酸的金属盐；钛酸乙酯、钛酸 异丙酯、钛酸正丁酯、钛酸叔丁酯、多烷氧基钛酸酯等钛酸酯及其螯合物；二丁基二月桂酸锡、二正辛基二月桂酸锡等二烷基锡的二羧酸盐，优选有机酸金属盐，进一步优选不超过10个碳原子的有机酸锡盐。对其添加方式及顺序没有限制，优选在有机聚硅氧烷(A)、交联剂(B)、氟聚合物、表面活性剂及水乳化后加入。对其加入时的形态没有限制，优选用表面活性剂及水进行乳化后的缩合催化剂(C)，进一步优选缩合催化剂(C)在乳液中的平均粒径不超过30μm，最优选不超过10μm。前文所述表面活性剂可用于缩合催化剂的乳化，其添加量优选0.01-1000％重量(相对缩合催化剂(C)重量)。稀释用有机溶剂可以是醇类，比如：甲醇、乙醇、异丙醇及正丁醇等；也可以是酮类溶剂，比如丙酮等，优选碳原子数不超过4的低碳醇。对缩合催化剂(C)的用量没有特别的限制，其量要足以使得有机聚硅氧烷(A)与交联剂(B)适宜的缩合交联固化，优选0.01-30％重量(相对有机聚硅氧烷(A)与交联剂(B)的总重量)，进一步优选0.1-10％的重量，用量过少，则不足以使所述有机聚硅氧烷(A)与交联剂(B)交联固化，产品有粘性，影响含有氟聚合物的聚合物共混物的自由流动性；用量过多，反应不易控制，对产品性能有影响。
本发明中，对氟聚合物的加入方式没有任何的限制，可在一开始，即在任何缩合交联固化反应开始之前，或在反应期间，通常是在90％重量或更多的硅化合物缩合交联固化反应之前加入到反应介质中。其可以与有机聚硅氧烷(A)及交联剂(B)一起乳化；也可以在有机聚硅氧烷(A)及交联剂(B)乳化后加入。此外，对反应温度没有特别的限制，优选1-80℃，进一步优选4-70℃。
由此法制备的缩合交联固化有机硅聚合物，一部分用于包覆氟聚合物，一部分作为离散的有机硅聚合物的粒子(通常几百纳米到几十微米不等)，此交联固化有机硅聚合物在有机树脂中不但可以提高有机树脂的冲击性能，还可以提高抗粘着性、爽滑性及阻燃性能等。
另一种制备本发明聚合物共混物的方法是硅化合物，特别是有机硅化合物的氢化硅烷化法(也称作硅氢加成法)，即通过键合在硅原子上的氢原子与键合在硅原子上的一价脂肪族不饱和基的加成反应，得到具有交联结构的有机硅聚合物。
由有机硅化合物的氢化硅烷化法(也可称为乳液氢化硅烷化法)制备的有机硅聚合物以包含如下硬化物为宜，所述硬化物具有式-(R1 2SiO2/2)n-所表示的线性有机硅氧烷嵌段。式中n为正整数，对其没有特别的限制，优选为5-5,000的正整数，各R1为彼此独立的一价有机基团，一价有机基团优选为前面针对R所述的经取代或未经取代的碳数为1-30的一价烃基。
由氢化硅烷化法制备有机硅聚合物中所用的有机硅化合物，包含有机(聚)硅氧烷与有机氢化(聚)硅氧烷，即包含：平均组成R2 aSiO(4-a)/2所表示的一分子中具 有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及平均组成R3 bSiO(4-b)/2所表示的一分子中具有至少2个键合在硅原子的氢原子(简述为Si-H基)的有机氢化(聚)硅氧烷，但是优选一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个。此外，所述有机(聚)硅氧烷与有机氢化(聚)硅氧烷中，Si-H基与键合在硅原子上的一价烯烃性不饱和基的摩尔数之比优选为0.01∶1-50∶1，进一步优选为0.1∶1-20∶1，更优选为0.5∶1-10∶1。
所述R2为前面针对R所述的取代或未经取代的碳数为1-30的一价烃基。下标a为满足0＜a≤3的正数，优选满足0.01≤a≤3的正数，进一步优选满足0.1≤a≤2.5的正数，并且平均式为R2 aSiO(4-a)/2的有机(聚)硅氧烷的每一分子中必须具有至少2个与硅键合的一价烯烃性不饱和基，且还具有R2中所述除烯烃性不饱和基以外的经取代或未经取代的碳数为1-30的一价烃基，一价烯烃性不饱和基，可以列举但不限于：乙烯基、烯丙基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基等，工业上优选乙烯基。此外，对一价烯烃性不饱和基在有机(聚)硅氧烷中的位置没有特别的限制，其可以在侧挂的位置、在末端的位置或在这两个位置键合。
所述R3选自H、经取代或未经取代的碳数为1-30的一价烃基，例如具有1-12个碳原子，优选1-8个碳原子，更优选1-6个碳原子的直链、支链或环状烷基；任选被上述烷基取代的芳基如苯基、萘基；任选被芳基如苯基取代的上述烷基；这些基团的碳原子上键合的一部分或全部的氢原子经卤素原子(氟、氯、溴、碘)和/或丙烯氧基、甲基丙烯酰氧基、环氧基、缩水甘油氧基、羧基、羟基、巯基、氨基、磺酸基、硝基、胺基取代，包括可以列举但不限于：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基等烷基，苯基、甲苯基、二甲苯基、萘基等芳基，苄基、苯乙基等芳烷基，环戊基、环己基、环庚基等环烷基。下标b为满足0＜b≤3的正数，优选满足0.01≤b≤3的正数，进一步优选满足0.1≤b≤2.5的正数，并且平均式为R3 bSiO(4-b)/2的有机氢化(聚)硅氧烷每一分子中必须具有至少2个Si-H基，且还具有R3中所述除H以外的经取代或未经取代的碳数为1-30的一价烃基。对Si-H基在有机氢化(聚)硅氧烷中的位置没有特别的限制，可以在侧挂的位置、在末端的位置或在这两个位置键合。此外，优选R3中经取代或未经取代的碳数为1-30的一价烃基中50％摩尔以上为甲基。
由有机(聚)硅氧烷及有机氢化(聚)硅氧烷组成的有机硅化合物中，优选的是有机(聚)硅氧烷中与硅键合的一价烯烃性不饱和基与有机氢化(聚)硅氧烷中的Si-H基至少其一在其分子中存在至少3个，若任何一个均不在其分子中存在至少3个，则所得的聚合物共混物变得有粘性，降低其在聚合物组合物中的分散性 能。
在本发明中，对有机(聚)硅氧烷及有机氢化(聚)硅氧烷的分子量没有特别的限制，但推荐25℃下具有100,000mm2/s以下的运动粘度，更优选50,000mm2/s以下的运动粘度。此外，对所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷的结构没有特别的限制，可以为直链状、环状、分支状或三维结构，优选直链状。
在本发明中，由有机硅化合物的氢化硅烷化法制备有机硅聚合物全部或部分包覆氟聚合物的聚合物共混物，例如可以简单的通过以下方法得到：将有机(聚)硅氧烷及有机氢化(聚)硅氧烷、氟聚合物、表面活性剂、水经乳化得到混合乳液，然后混入氢化硅烷化催化剂，保持一定温度和时间，加成硫化后得到聚合物共混物乳液，最后经固液分离干燥后得到聚合物共混物粉末。
在本发明中，所用氢化硅烷化催化剂主要用于加速所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷组成的混合物固化，可以是任何众所周知的氢化硅烷化催化剂，例如铂类催化剂、铑类催化剂、铱类催化剂、钯类催化剂或钌类催化剂，优选铂类催化剂，比如：铂细粉，铂黑，氯化铂，氯化铂酸及氯化铂酸盐，醇改性的氯铂酸，铂-烯烃络合物，铂-链烯基硅氧烷络合物，铂-羰基络合物等。
此外，对氢化硅烷化催化剂的添加方式没有任何的限制，氢化硅烷化催化剂可以添加到有机(聚)硅氧烷及有机氢化(聚)硅氧烷混合物和氟聚合物乳液中；也可以预先溶解在有机(聚)硅氧烷及有机氢化(聚)硅氧烷混合物中；也可以预先溶解在溶剂中后添加到上述乳液或混合物中；在将氢化硅烷化催化剂加入到有机(聚)硅氧烷及有机氢化(聚)硅氧烷混合物前，以在乳化工序结束之前不发生氢化硅烷化反应为宜，比如将混合物冷却到例如5℃以下的低温、加入适量的氢化硅烷化催化剂抑制剂等手段降低氢化硅烷化反应发生的几率。有机(聚)硅氧烷及有机氢化(聚)硅氧烷混合物的氢化硅烷化反应可以在常温下进行，在反应未完成下，也可以在低于100℃的加热下进行。
在本发明中，对氢化硅烷化催化剂的加入量没有特别的限制，条件是这一用量确保由有机(聚)硅氧烷与有机氢化(聚)硅氧烷组成的混合物适宜地固化，以每百万份(ppm)上述在有机(聚)硅氧烷及有机氢化(聚)硅氧烷组成的混合物计，可将用量小至0.001重量份元素铂族金属的氢化硅烷化催化剂加入到本发明的反应体系中，优选0.1ppm-1000ppm，进一步优选0.5ppm-100ppm，更优选1ppm-50ppm。此外，为更好的控制氢化硅烷化反应，可以添加任何合适的氢化硅烷化催化剂抑制剂，其可以是众所周知的氢化硅烷化催化剂抑制剂，例如可以举出但不限于：2-甲基-3-丁炔-2-醇、1-乙炔基-2-环己醇等炔类抑制剂(参见US3,445,420)；烯属硅氧烷(参见US3,989,667)等。
在本发明中，通过有机硅化合物的氢化硅烷化法制备聚合物共混物的过程中， 对所用表面活性剂没有特别的限定，根据具体的制备工艺可选择添加或不添加。可以是阴离子、阳离子、两离子型或非离子表面活性剂，表面活性剂的加入能够提高反应体系分散乳液的稳定性，且有助于提高聚合物共混物粒子的规整性，进一步优选非离子型表面活性剂，前文中已有相关描述，不再赘述。对表面活性剂的用量没有特别的限制，其用量优选为0.01-20％重量(相对分散液的总重量)，进一步优选为0.1-10％重量。
根据本发明，通过有机硅化合物的氢化硅烷化法制备聚合物共混物的过程中，对乳化条件没有特别的限制，优选乳化分散机进行乳化，前文中已有相关描述，不再赘述。此外，对氟聚合物的加入方式没有任何的限制，可在一开始，即在任何氢化硅烷化反应开始之前，或在反应期间，通常是在90％重量或更多的硅化合物氢化硅烷化反应之前加入到反应介质中。
在本发明的一些实施方案中，有时为了改进聚合物共混物的某些性能，比如进一步提高其分散性能、增强机械性能、改进制备工艺等，可以掺入填料形式的任意组分，可以是无机填料，也可以是有机填料。对其加入量没有任何的限制，可以根据需要通过常规实验确定。有时，为进一步提高包含包覆型氟聚合物的聚合物共混物在聚合物组合物中的分散性能，采用金属氧化物的粉末或硅树脂粉末进行再次包覆。比如，将金属氧化物的溶胶或可水解-缩合反应的硅烷化合物加入到包含氟聚合物的聚合物共混物的分散液中对聚合物共混物进行包覆；也可以用人工或机械的方法将金属氧化物粉末或可水解硅烷化合物的缩合产物对所述聚合物共混物进行包覆。
根据本发明，乳液水解-缩合聚合、沉淀水解-缩合聚合、乳液缩合聚合、氢化硅烷化反应结束后得到聚合物共混物的沉淀、凝胶或分散液，下一步就是固液分离干燥，以便得到包含表面被有机硅聚合物全部或部分包覆的氟聚合物颗粒的聚合物共混物。因此，可以通过从该沉淀、凝胶或分散液中除去水分、有机溶剂等得到聚合物共混物粉末颗粒，也可以通过采用加热、离心、过滤、倾析或其它方法，视需要随后洗涤，比如除酸、碱、表面活性剂等，然后经过在常压或减压下热干燥、喷洒分散液到热空气流中或者通过使用加热介质得到本发明的聚合物共混物粉末颗粒，如所用氟聚合物为可原纤维化的，则干燥后的聚合物共混物不适宜用研磨、气流粉碎等强制粉碎的方法处理，否则会导致氟聚合物提前纤维化。
经过实验研究发现，本发明所制备的聚合物共混物可以为含有大量的小粒径初级粒子及中粒径次级粒子凝聚体，也可以为粒径为100μm以内的聚合物共混物凝聚体、甚至粒径为20μm以内的聚合物共混物凝聚体，而市面上所售粉末型氟聚合物及包覆型氟聚合物抗滴落剂一般以凝聚体的形式存在，且粒径一般在300μm以上，通常500μm左右，这是造成其添加量不能过高、分散能力不佳 的直接原因。此外，当市售包覆型氟聚合物添加量较高时，比如超过0.5％重量，其分散性能下降严重，严重影响聚合物组合物基材的机械性能及阻燃性能。
本发明的聚合物共混物中所用有机硅聚合物一部分以氟聚合物的包覆材料存在，一部分以游离的形式存在，游离的有机硅聚合物及包覆用有机硅聚合物在实际应用中，可以作为聚合物组合物加工助剂，比如耐磨剂、开口剂、增韧剂等。本发明的聚合物共混物，即使在凝聚体粒径接近市售的包覆型氟聚合物的粒径时，由于有游离的有机硅聚合物存在，也能表现出更好的阻燃性能及机械性能，特别是更好的分散性能。
制品
本发明的制品可以通过直接将本发明所述的聚合物共混物挤塑、注塑、吹塑或模压等得到。
制备制品的挤塑、注塑、吹塑或模压工艺是本领域中所熟知，本领域技术人员容易根据聚合物共混物的各项指标及制品的预期用途确定具体的成型工艺、工艺参数，在此不进行赘述。
所述制品可以为例如：片、套管、棒、板、垫片、零部件。
聚合物组合物
本发明的聚合物组合物包含一种聚合物基体，其中分散有本发明所述的包覆型氟聚合物颗粒或聚合物共混物。
所述聚合物基体可以提及的有：乙烯基聚合物如聚氯乙烯、聚乙烯醇、聚乙酸乙烯酯，聚链烯烃如聚乙烯、聚丙烯，聚对苯二甲酸亚烷基酯如聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯，聚丙烯酸酯如聚丙烯酸甲酯，聚甲基丙烯酸酯如聚甲基丙烯酸甲酯，聚苯醚，聚砜，聚碳酸酯，聚苯乙烯、尤其是高冲击强度聚苯乙烯，聚酰胺如尼龙6、尼龙66，聚酰亚胺，苯乙烯-丙烯腈共聚物，苯乙烯-丁二烯共聚物，丙烯腈-丁二烯-苯乙烯共聚物，丙烯腈-丁二烯-苯乙烯共聚物/聚碳酸酯共混物，聚苯乙烯/聚苯醚共混物，热塑性聚酯/聚碳酸酯共混物如对苯二甲酸丁二醇酯/聚碳酸酯共混物，硅橡胶，以及它们的混合物。
本发明的聚合物组合物优选还含有阻燃剂，即优选是阻燃的聚合物组合物。对于阻燃剂没有特别的限制，可以使用任何已知的聚合物组合物用阻燃剂体系。聚合物组合物所用阻燃剂可单一使用，也可以组合使用，比如将卤代芳族化合物、特别是溴化化合物和氧化锑的组合使用，具有协同阻燃的效果。
根据本发明，聚合物组合物中可以加入任何常规的添加剂，比如：颜料、UV稳定剂、抗氧剂、热稳定剂、增强填料、扩链剂、着色剂、增韧剂等。
所述聚合物组合物的制备方法，可以是通过任意已知的方法将组分混合。通常，有两个不同的混合步骤：预混和熔融混合。在预混这一步骤中，将干组分混合在一起。所述预混一般采用转鼓混合机或带状掺和机进行的，如需要，也可使用高剪切混合机制备该预混物。预混之后，通常是熔融混合。此外，可以不经过预混步骤，将原料中各组分直接添加到熔融混合装置的进料部分中。在熔融混合中，一般将聚合物组合物各组分在单螺杆或双螺杆挤出机中熔融混和，以标准技术挤出并切成模制物，比如，常规的颗粒、团粒等。然后将组合物在常规用于模制的任意设备，比如Newbury型注塑机、Van Dorn型注塑机中进行模制。
氟聚合物已被用来作为阻燃聚合物组合物中的抗滴落剂、耐磨剂等，本发明的包覆型氟聚合物颗粒、聚合物共混物被证明对于增加聚合物组合物，特别是阻燃性聚合物组合物的阻燃性是特别有用的。
本发明的聚合物组合物优选是阻燃性聚合物组合物。所述阻燃性聚合物组合物具有改进的加工性能、分散性能、阻燃性能及力学性能。
本发明的包覆型氟聚合物颗粒、聚合物共混物不但能改善氟聚合物在聚合物组合物中的加工分散性能、力学性能及成型制品表观性能，而且因为有机硅聚合物中大量Si原子的存在还具有良好的阻燃成炭性。即便氟聚合物在聚合物组合物中较高含量的情况下，本发明的包覆型氟聚合物、聚合物共混物也很容易分散在聚合物基体中，使得制品表面无缺陷，又能保持聚合物组合物的其它优异性能。
在本发明所述的聚合物组合物中，包覆型氟聚合物颗粒、聚合物共混物的量使得氟聚合物在聚合物组合物中的重量含量优选为0.01-30％，进一步优选0.1-10％，更优选0.1-6％。
实施例
现在参考以下具体实施例中对本发明进行详细说明。然而，本领域技术人员不难理解，此处的实施例仅仅用于示例目的，本发明的范围并不局限于此。
在本发明中，产品粒径由激光衍射式粒度分析测量仪(岛津SALD-2300)及扫面电镜(ZEISS EVO18，取样数不少于100个)测得，熔融指数试验按照ASTM D1238标准进行，悬臂梁缺口冲击强度试验按照ASTM D256标准进行，拉伸强度和断裂伸长率试验按照ASTM D638标准进行，弯曲强度试验按照ASTM D790标准进行，燃烧试验按照UL 94标准规定的方法进行。
实施例1
将800g水、4g OP-10、20g浓度为28％的氨水及100g固含量为60％的聚四氟乙烯分散液(初级粒径为0.2μm，SSG为2.175)加入到反应容器中，室温搅拌 均匀后，将121.6g甲基三甲氧基硅烷逐滴加入到反应容器中，约30min后滴入完毕，体系粘度增加且出现固体悬浮物，继续恒温搅拌30min后升温至50℃，搅拌2h后结束反应，洗涤过滤后，在105℃的热循环鼓风干燥箱中进行干燥，得到120g含水率0.3％wt以内的聚四氟乙烯含量约50％重量的聚合物共混物白色粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，如图1，所得聚合物共混物由初级粒子和次级粒子凝聚体组成，且其平均粒径分别为0.23μm、13μm。
实施例2
将150g乙醇、1g OP-10、50g水及61g甲基三甲氧基硅烷组成的混合物溶液加入到反应容器中，室温搅拌均匀后，加入50g固含量为60％的聚四氟乙烯分散液(初级粒径为0.2μm，SSG为2.175)及12.5g浓度为28％的氨水，约1min后体系开始出现固体悬浮物，继续室温搅拌15min后升温至50℃，恒温保持2h后结束反应，洗涤过滤后，在105℃的热循环鼓风干燥箱中进行干燥，得到60g含水率0.3％wt以内的聚四氟乙烯含量约50％重量的聚合物共混物白色粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，如图2，所得聚合物共混物主要由次级粒子凝聚体组成，且其平均粒径为61μm。
实施例3
将75g乙醇、25g水、61g甲基三甲氧基硅烷组成的混合溶液加入到反应容器中，加入若干醋酸调节PH为4，室温搅拌3h后得到含有甲基三甲氧基硅烷的水解物及部分水解-缩合物的混合溶液，将上述溶液加入到由50g固含量为60％的聚四氟乙烯分散液(初级粒径为0.2μm，SSG为2.175)、1g OP-10、150g水及25g氨水组成的混合分散液中，约1min后，体系出现类似固体悬浮物，继续室温搅拌15min后升温至50℃，恒温保持2h后结束反应，洗涤过滤后，在105℃的热循环鼓风干燥箱中进行干燥，得到60g含水率0.3％wt以内的聚四氟乙烯含量约50％重量的聚合物共混物白色粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，所得聚合物共混物主要由次级粒子凝聚体组成，且其平均粒径为66μm。
实施例4
将423g羟基封端的聚二甲基硅氧烷(羟基含量为9％重量)、53g分子式为(C2H5O)12Si5O4的正硅酸乙酯的部分水解-缩合物和25g甲基丙烯酰氧基丙基三甲氧基硅烷混合均匀后，使用均质机将该混合物在含有5g复合表面活性剂(OP-10及十二烷基苯磺酸钠的重量比为3∶2)的150g水中充分均质乳化，然后加入440g 聚四氟乙烯粉末(可原纤维化的，初级及凝聚体平均粒径分别为0.2μm、350μm，SSG为2.175)及含有10g上述复合表面活性剂的300g水，继续均质乳化均匀后，加入由5g辛酸亚锡、3g上述复合表面活性剂及100g水经乳化形成的粒径约5μm的乳液，继续均质均匀后加入800g水进行稀释，最后转移至装有搅拌器的反应容器中，室温搅拌一天后结束反应，在搅拌下，进行洗涤和过滤，最后经喷雾干燥后得到881g含水率0.5％wt以内含聚四氟乙烯约50％重量的聚合物共混物可自由流动粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，如图3，所得聚合物共混物由初级粒子和次级粒子凝聚体组成，且其平均粒径分别为3μm(以游离的有机硅聚合物为主)、388μm。
实施例5
将22.72g粘度为30mm2/s的三甲基甲硅烷氧基封端的二甲基硅氧烷-甲基氢硅氧烷共聚物(Si-H含量为0.34％重量)、450g粘度为600mm2/s的二甲基乙烯基甲硅烷氧基封端的二甲基聚硅氧烷(乙烯基含量为0.4％重量)加入到玻璃烧杯中(Si-H与乙烯基摩尔比例为1.16)，用均质混合机混合均匀。然后加入1g OP-10和120g水，用均质机乳化后，加入350g水得到O/W型白色乳液，继续均质乳化，加入9g上述表面活性剂、850g水及472.72g聚四氟乙烯粉末(可原纤维化的，初级及凝聚体平均粒径分别为0.2μm、350μm，SSG为2.175)，确认混合均匀后，将所得混合乳液转移至含有4g上述表面活性剂、780g水的反应容器中，搅拌下控制温度为25℃，并加入1.2g铂-二乙烯基四甲基二硅氧烷(Karstedt型催化剂)的甲苯溶液(铂金属含量为0.8％重量)和1g上述表面活性剂组成的混合溶解物，然后升温至70℃，继续搅拌6h后得到悬浮分散液，在搅拌下，同时过滤和洗涤，最后使用喷雾干燥器对所得分散液进行固液分离干燥，最终得到943.80g(含水率0.5％重量以内)聚四氟乙烯含量约50％重量的聚合物共混物粉末。取样进行激光衍射式粒度分析测量仪测试及扫描电镜测试，如图4，所得聚合物共混物粉末的初级平均粒径为12μm(以游离的有机硅聚合物为主)，次级凝聚体平均粒径为398μm。
通过以上乳液水解-缩合聚合、沉淀水解-缩合聚合、乳液缩合聚合及氢化硅烷化法制备的含有氟聚合物的聚合物共混物的凝聚体粒径不但可控制在500μm以内，还可以达到100μm以内，甚至20μm以内，该凝聚体均为一次制备而成，不需要任何的研磨、气流粉碎等强制解聚聚合物共混物。此外，根据扫描电镜图(参见图1-5)可知，本发明的聚合物共混物基本不含有纤维丝即产品没有提前纤维化，且具有核壳结构。
实施例6
将360g去离子水、40g无水乙醇、10g浓度为28％的氨水、1g OP-10、60g固含量为60％的聚四氟乙烯分散液(初级粒径为0.2μm，SSG为2.175)加入到反应容器中，调整体系温度为20℃，pH为11.8，在搅拌下，将含有64.8g甲基三甲氧基硅烷、3.1g苯基三甲氧基硅烷、4g氨丙基三乙氧基硅烷组成的混合物逐滴加入到反应容器中，30min内完成添加，此时反应体系粘度增加，开始出现固体悬浮物，继续搅拌30min后升温至50℃，然后继续搅拌2h后，将所得聚合物共混物的分散液洗涤、减压过滤、然后在105℃的热循环鼓风干燥箱中进行干燥，得到72.1g含水率0.3％wt以内的聚四氟乙烯含量约50％重量的聚合物共混物白色粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，如图5，所得聚合物共混物由初级粒子和次级粒子凝聚体组成，且其平均粒径分别为0.26μm、11μm。
实施例7
除了将固含量为60％重量的聚四氟乙烯分散液用量60g替换为90g，制备过程如同实施例6，得到90.2g含水率0.3％重量以内的聚四氟乙烯含量约60％重量的聚合物共混物白色粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，所得聚合物共混物由初级粒子和次级粒子凝聚体组成，且其平均粒径分别为0.25μm、13μm。
实施例8
除了将固含量为60％重量的聚四氟乙烯分散液用量60g替换为40g，制备过程如同实施例6，得到60.2g含水率0.3％重量以内的聚四氟乙烯含量约40％重量的聚合物共混物白色粉末。取样进行激光衍射式粒度分析测量仪及扫描电镜测试，所得聚合物共混物由初级粒子和次级粒子凝聚体组成，且其平均粒径分别为0.3μm、9μm。
通过实施例6-8，本发明制备了不同氟聚合物含量的含有苯基、氨基等官能团的聚合物共混物。
对比例1
除了去除固含量为60％重量的聚四氟乙烯分散液，制备过程如同实施例1，最终得到60g含水率0.3％重量以内的有机硅聚合物。
对比例2
除了不添加聚四氟乙烯粉末以外，制备过程如同实施例4，最终得到443g 含水率0.5％重量以内的有机硅聚合物。
对比例3
除了不添加聚四氟乙烯粉末以外，制备过程如同实施例5，最终得到469g含水率0.5％重量以内的有机硅聚合物。
对比例4
将800g水及100g固含量为60％的聚四氟乙烯分散液(初级粒径为0.2μm，SSG为2.175)加入到反应容器中，室温搅拌均匀后，加入稀盐酸调节PH为3，将121.6g甲基三甲氧基硅烷逐滴加入到反应容器中，约30min后滴入完毕，继续恒温搅拌30min后升温至50℃，搅拌2h后，体系粘度没什么变化，且仍为稳定的乳液体系，没有任何固体悬浮物生成，继续搅拌6h后，体系仍为稳定的乳液体系，后升温至沸腾，开始有颗粒物生成且呈粘性，很快凝聚成不规则形状超级粒子凝聚体，收集固体份后在105℃热循环鼓风干燥箱中干燥，得到119.5g含有约50％重量的聚四氟乙烯的聚合物混合物，且含有大量坚硬的超级粒子凝聚体，经气流粉碎后，产品为粉纤状，部分产品已提前纤维化(肉眼就可以判断)。
对比例5
在带有温度计、回流装置和搅拌装置的250ml三口烧瓶中加入7.4g1，3二乙烯基-1，1，3，3，-四甲基二硅氧烷，0.3ml的浓盐酸，3ml去离子水及6ml乙醇的混合液，然后开动搅拌，然后再1小时内滴加完50g聚四氟乙烯浓缩分散液(美国杜邦公司teflon 30J，固含量60％)。然后快速加入16g正硅酸甲酯水解缩合，水解1小时后，加入50ml甲苯萃取，1小时后将反应液导入分液漏斗中分层，将水层分区，油层水洗至中性，蒸馏干燥去除甲苯后得到白色粉末状固体49.7g，其中聚四氟乙烯含量60％，为凝聚体白色微球，平均粒径为0.42mm，其中所得MQ硅树脂中M/Q比值为0.61。
对比例6
在反应容器中加入1000g聚四氟乙烯粉末(可原纤维化的，初级及凝聚体平均粒径分别为0.2μm、350μm，SSG为2.175)，然后加入1400g甲基三甲氧基硅烷搅拌均匀，在加入0.003g盐酸作催化剂混合均匀，最后加入550g水，控制反应温度不超过45℃反应16小时。将上述混合液升温至沸腾出去水分，体系已产生大量超级粒子凝聚体，然后用100目滤布过滤得到湿粉，在250℃下烘干湿粉2小时后得到干粉1667g，聚合物共混物中聚四氟乙烯含量约为60％重量，聚合物共混物中含有大量的坚硬的超级粒子凝聚体。经气流粉碎强制解聚后，超级 粒子凝聚体被破碎成粉纤状，部分产品已提前纤维化(肉眼就能判断)。
实施例9
取实施例1、2、3、4、5、6、7、8样品各10g放入马弗炉中300℃灼烧5分钟几乎无失重、无变色、无气味；取市场上广泛使用的包覆型PTFE产品即AS(苯乙烯-丙烯腈共聚物)包覆的PTFE粉末(PTFE/AS重量比例为50/50)10g放入马弗炉中300℃灼烧5分钟有失重，且变色严重、有分解气味；取对比例4、5、6样品各10g放入马弗炉中300℃灼烧5分钟，对比例4、6几乎无失重、无变色、无气味，对比例5有较多失重。由此可见，本发明包含四氟乙烯聚合物的聚合物共混物与对比例4、6比AS包覆的PTFE及MQ硅树脂包覆的PTFE具有更好的热稳定性能。
实施例10-14和对比例7-13
在实施例10-14和对比例7-13中制备如表1所示的PC(来自SABIC)和本发明的聚合物共混物、有机硅聚合物、PTFE纯粉(可原纤维化的，初级粒径为0.2μm、凝聚体粒径为350μm，SSG为2.175)、自由基聚合的包覆型PTFE(来自SABIC IP的F449，PTFE/AS(苯乙烯-丙烯腈共聚物)＝50/50(重量比))、单独以酸为催化剂以乳液水解-缩合聚合法得到的聚合物共混物、MQ硅树脂包覆型PTFE或以酸为催化剂聚合硅烷得到的复合材料微粉的聚合物组合物。将相应组分经混合机混合后，观察混合情况，确认混合均匀后使用双螺杆挤出机挤出造粒，将所得粒料经注塑机注射成所需标准样条，最后进行相关标准测试。聚合物共混物的加入量使得PTFE在组合物体系组分总量中的含量为0.4％重量。所使用双螺杆挤出机，其长径比为40，并带有精准的温控和真空排气设备，螺杆转速在100-700转/分钟，挤出工作温度为：一区230℃-260℃，二区230℃-270℃，三区230℃-270℃，四区240℃-280℃，停留时间1-2分钟。
并对制备的聚合物组合物的分散性、力学性能以及阻燃性能进行表征，结果见表1。
表1
Figure PCTCN2017086637-appb-000001
Figure PCTCN2017086637-appb-000002
Figure PCTCN2017086637-appb-000003
注：OSP代表有机硅聚合物。有缺陷表示有较多明显的斑点、凹凸不平或纤维点等
根据表1测试结果可知，有机硅聚合物包覆材料的引入，大大提高了氟聚合物在聚合物组合物中的分散性能。但单独以酸为催化剂聚合硅烷制备的有机硅聚合物包覆型氟聚合物，无论在聚合物组合物中的分散性能、加工性能，还是阻燃性能都不及本发明的聚合物混合物。此外，聚合物共混物的凝聚体粒径及聚合物共混物中氟聚合物的提前纤维化，对其在聚合物组合物中的分散及加工性能有显著的影响，最终对聚合物组合物的阻燃及机械性能产生影响。显然，本发明的聚合物共混物在聚合物组合物中具有更好的分散及加工性能，所得聚合物组合物具 有更好的力学性能及阻燃性能。
实施例15-20和对比例14-18
在实施例15-20和对比例14-18中制备如表2所示的不同重均分子量的PC(聚碳酸酯，来自SABIC)和本发明的带有苯基、氨基基团的聚合物共混物、PTFE纯粉(可原纤维化的，初级粒径为0.2μm、凝聚体粒径为350μm、SSG为2.175)、自由基聚合的包覆型PTFE(来自SABIC IP的F449，PTFE/AS(苯乙烯-丙烯腈共聚物)＝50/50(重量比))、单独以酸为催化剂以乳液水解-缩合聚合法得到的聚合物共混物、MQ硅树脂包覆型PTFE、以酸为催化剂聚合硅烷得到的复合材料微粉的聚合物组合物。
表2
Figure PCTCN2017086637-appb-000004
Figure PCTCN2017086637-appb-000005
表中“-”表示未测试；有缺陷表示有较多明显的斑点、凹凸不平或纤维点等
根据表2测试结果可知，聚碳酸酯分子量的增加能明显提高聚合物组合物的机械性能和阻燃性能。此外，本发明的聚合物共混物的加入量的增加能够明显增加聚合物组合物的阻燃性能，使得聚合物组合物仍然具有较好的表观形貌及机械性能。
虽然已经展示和讨论了本发明的一些方面，但是本领域的技术人员应该意识到，可以在不背离本发明原理和精神的条件下对上述方面进行改变，因此本发明的范围将由权利要求以及等同的内容所限定。

Claims (11)

  1. 一种包覆型氟聚合物颗粒，其特征在于，其为可自由流动的且由表面被有机硅聚合物完全或部分地包覆的氟聚合物组成，其由选自(i)、(ii)、(iii)、(iv)的方法制备：
    (i)乳液水解-缩合聚合法：以水或水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，乳液水解-缩合聚合硅化合物，然后进行固液分离干燥，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
    (ii)沉淀水解-缩合聚合法：以水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，沉淀水解-缩合聚合硅化合物，然后进行固液分离干燥，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
    (iii)乳液缩合聚合法：使一分子中至少含有两个Si-OH基团的聚硅氧烷与以一分子中至少含有三个与硅原子相连接的可水解基团的硅化合物、其水解物、部分水解-缩合物以及它们的混合物，或以一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷为交联剂乳化后，在氟聚合物的存在下，加入缩合催化剂，交联固化聚硅氧烷与交联剂，然后进行固液分离干燥；或
    (iv)氢化硅烷化法：将一分子中具有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及一分子中具有至少2个键合在硅原子的氢原子(Si-H基)的有机氢化(聚)硅氧烷乳化后，在氟聚合物的存在下，加入氢化硅烷化催化剂，交联固化所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷，然后进行固液分离干燥，其中一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个，
    所述有机硅聚合物为具有交联结构的聚合物，
    所述包覆型氟聚合物颗粒中氟聚合物与有机硅聚合物的重量比例为95∶5-5∶95。
  2. 根据权利要求1所述的包覆型氟聚合物颗粒，其特征在于，由所述乳液水解-缩合聚合法或沉淀水解-缩合聚合法制备的包覆型氟聚合物颗粒中的有机硅聚合物含有主链Si-O链节，且含有支链结构RSiO3/2(T)结构单元，其中相对主链而言，四官能链节SiO2(Q)，三官能链节RSiO3/2(T)，二官能链节R2SiO(D)，单官能链节R3SiO1/2(M)所占比例为：
    SiO2(Q)：0-70％mol，更优选0-20％mol，
    RSiO3/2(T)：0.1-100％mol，更优选50-100％mol，
    R2SiO(D)：0-30％mol，更优选0-10％mol，
    R3SiO1/2(M)：0-30％mol，更优选0-10％mol，
    其中，SiO2(Q)和RSiO3/2(T)链节的总和所占比例为70-100％mol，各R彼此独立地为一价有机基团。
  3. 根据权利要求1所述的包覆型氟聚合物颗粒，其特征在于，由所述氢化硅烷化法制备的有机硅聚合物具有通过键合在硅原子上的一价脂肪族不饱和基与键合在硅原子上的氢原子的加成反应而形成的交联结构并且具有包含式-(R1 2SiO2/2)n-所表示的线性有机硅氧烷嵌段的硬化物，其中n为正整数，各R1为彼此独立的一价有机基团。
  4. 根据权利要求1至3中任一项所述的包覆型氟聚合物颗粒，其特征在于，所述氟聚合物选自包含衍生自一种或多种氟化α-烯烃单体的重复单元的均聚物、共聚物或其混合物。
  5. 根据权利要求2或3所述的包覆型氟聚合物颗粒，其特征在于，各R和R1彼此独立地为经取代或未经取代的碳数为1-30的一价烃基。
  6. 一种聚合物共混物，其是可自由流动的粉末，其特征在于，其包含权利要求1-5中任一项所述的包覆型氟聚合物颗粒以及有机硅聚合物颗粒。
  7. 根据权利要求6所述的聚合物共混物，其特征在于，氟聚合物的含量为所述聚合物共混物总重量的0.01-95％重量。
  8. 制备权利要求6或7的聚合物共混物的方法，其特征在于，其包括：
    (1)进行选自(i)、(ii)、(iii)、(iv)的步骤：
    (i)以水或水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，乳液水解-缩合聚合硅化合物，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
    (ii)以水-有机溶剂为分散介质，以碱性化合物为催化剂，在氟聚合物的存在下，沉淀水解-缩合聚合硅化合物，其中所述硅化合物选自具有与硅原子相连接的可水解基团的化合物、其水解物、部分水解-缩合物以及它们的混合物；
    (iii)使一分子中至少含有两个Si-OH基团的聚硅氧烷与以一分子中至少含有三个与硅原子相连接的可水解基团的硅化合物、其水解物、部分水解-缩合物以及它们的混合物，或以一分子中至少含有三个与硅原子相连接的氢原子的有机氢化(聚)硅氧烷为交联剂乳化后，在氟聚合物的存在下，加入缩合催化剂，交联固化聚硅氧烷与交联剂；或
    (iv)将一分子中具有至少2个一价烯烃性不饱和基的有机(聚)硅氧烷及一分子中具有至少2个键合在硅原子的氢原子(简述为Si-H基)的有机氢化(聚)硅氧烷乳化后，在氟聚合物的存在下，加入氢化硅烷化催化剂，交联固化所述有机(聚)硅氧烷及有机氢化(聚)硅氧烷，其中一价烯烃性不饱和基与键合在硅原子的氢原子的至少其一在所述分子中存在至少3个；和
    (2)进行固液分离干燥，从而得到能自由流动的粉末形式的聚合物共混物。
  9. 一种聚合物组合物，其特征在于，其包含一种聚合物基体，其中分散有权利要求1-5中任一项所述的包覆型氟聚合物颗粒或权利要求6-7的聚合物共混物。
  10. 根据权利要求9所述的聚合物组合物，其特征在于，所述聚合物基体选自：聚碳酸酯、聚苯醚、聚对苯二甲酸亚烷基酯、乙烯基聚合物、聚链烯烃、聚丙烯酸酯、聚甲基丙烯酸酯、聚苯乙烯、高冲击强度聚苯乙烯、聚砜、聚酰胺、聚酰亚胺、苯乙烯-丙烯腈共聚物、苯乙烯-丁二烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、硅橡胶及其共混物。
  11. 根据权利要求9或10所述的聚合物组合物，其特征在于，所述包覆型氟聚合物颗粒或聚合物共混物的量使得氟聚合物在聚合物组合物中的重量含量为0.01-30％。
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