WO2018121034A1 - 一种包含全氟聚醚活性成分的组合物 - Google Patents

一种包含全氟聚醚活性成分的组合物 Download PDF

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WO2018121034A1
WO2018121034A1 PCT/CN2017/108604 CN2017108604W WO2018121034A1 WO 2018121034 A1 WO2018121034 A1 WO 2018121034A1 CN 2017108604 W CN2017108604 W CN 2017108604W WO 2018121034 A1 WO2018121034 A1 WO 2018121034A1
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perfluoropolyether
pfpe
group
active ingredient
och
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PCT/CN2017/108604
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English (en)
French (fr)
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裴金东
李建
郦聪
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裴金东
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

Definitions

  • the invention belongs to the technical field of antifouling treatment of hard substrate surface, in particular to a composition comprising a perfluoropolyether active ingredient.
  • Perfluoropolyether active ingredients are commonly used to protect substrates from water, oil and stain.
  • transparent optical devices such as mobile phone glass screens
  • touch-type electronic display devices are often in contact with fingers, and are easily contaminated by fingerprints, sweat, oil, etc., after the surface of the device is treated with perfluoropolyether active ingredients, the dirt is not It can also be easily removed in the case of using a solvent, avoiding damage to the display device by using a solvent, and maintaining the visual perception of the display device.
  • the patent CN1284105 discloses an antifouling coating composition for an antireflection surface.
  • Patent CN101501046 discloses a novel perfluoropolyether siloxane composition
  • the patent CN102666759 discloses an optical substrate. Surface treatment composition.
  • the perfluoropolyether active ingredient usually needs to be dissolved or dispersed in a fluid medium for surface treatment applications, which involves a material serving as an active ingredient carrier, diluent, dispersion medium or solvent (hereinafter collectively referred to as a dispersion medium).
  • a dispersion medium should promote the transfer, delivery of the active ingredient in the intended use without affecting the action of the active ingredient; or at least promote the transfer, delivery of at least one active ingredient, and not adversely affect the action of the active ingredient.
  • the environmental properties of the dispersion medium material are of increasing interest as these dispersion media will volatilize into the atmosphere.
  • dispersion media materials with an ozone depletion potential (ODP) of zero and a small global warming potential (GWP).
  • ODP ozone depletion potential
  • GWP global warming potential
  • materials useful as dispersion media preferably also have inertness, low toxicity, and low flammability relative to one or more active ingredients.
  • the coating layer for depositing the perfluoropolyether active component by a coating method requires a dispersion medium, such as perfluorocarbons (for example, perfluorohexane, perfluoroheptane, and perfluorooctane), A fluorine-modified aromatic hydrocarbon solvent (for example, bis-trifluorotoluene), a partially fluorinated hydrocarbon solvent (for example, 2H, 3H-perfluoropentane), hydrofluoroether, and the like.
  • a very dilute solution of the active ingredient dissolved in a fluorinated dispersion medium is applied to the substrate to produce a very thin active ingredient coating layer. Therefore, a large amount of solvent is released into the atmosphere.
  • most of the above solvents have an ozone depletion potential (ODP) of not zero and a large global warming potential (GWP).
  • ODP ozone depletion potential
  • GWP global warming potential
  • Perfluorobutyl methyl ether (7100) and perfluorobutyl ether (7200) have an ozone depletion potential (ODP) of 0 and a small global warming potential (GWP), making them ideal for perfluoropolyether active ingredients.
  • ODP ozone depletion potential
  • GWP global warming potential
  • perfluorobutyl methyl ether and perfluorobutyl ethyl ether have low surface tension and low viscosity, and are easy to form a uniform spread on the surface of the substrate to be treated; and also have the advantages of low latent heat of evaporation and short drying time, thereby avoiding long solvent. Time retention may cause damage to the substrate; it is non-flammable and is an environmentally friendly solvent that has little effect on the environment.
  • perfluorobutyl methyl ether and perfluorobutyl ethyl ether are prepared by an electrolytic fluorination process, and the production process is complicated and more waste is generated in the preparation process. Therefore, its cost is high and production environmental protection pressure is high. In view of this, there is an urgent need to find alternative solvents that are easy to produce, produce no or little waste during production, and are low in cost.
  • the present invention aims to solve the above technical problems existing in the prior art, and provides a composition comprising a perfluoropolyether active component, which uses tetrafluoroethylene-derived hydrofluoroether as a dispersion medium, has zero ozone layer destruction coefficient, and has a global greenhouse effect.
  • the coefficient is also very low, and has almost no adverse effect on the environment; tetrafluoroethylene-derived hydrofluoroether is easy to produce, and the production cost is low, thereby greatly reducing the cost of the composition; compared with the perfluorobutyl methyl ether prepared by electrolytic fluorination, The waste produced by the production of tetrafluoroethylene-derived hydrofluoroether is less; in addition, the tetrafluoroethylene-derived hydrofluoroether has no adverse effect on the action of the perfluoropolyether active ingredient.
  • composition comprising a perfluoropolyether active ingredient, characterized in that the composition comprises:
  • composition may also optionally be added with one or more of tetrafluoroethylene-derived hydrogen fluoride
  • Other active and/or inactive additive components of the ether may also comprise other cosolvents which are miscible with the tetrafluoroethylene derived hydrofluoroether.
  • tetrafluoroethylene-derived hydrofluoroether is obtained by addition reaction of tetrafluoroethylene and monohydric alcohol.
  • the tetrafluoroethylene-derived hydrofluoroether is selected from the group consisting of HFE-347 (CF 3 CH 2 OCF 2 CF 2 H), HFE-494n (CH 3 CH 2 CH 2 OCF 2 CF 2 H), and HFE-458 (HCF 2 CF).
  • HFE-347 CF 3 CH 2 OCF 2 CF 2 H
  • HFE-494n CH 3 CH 2 CH 2 OCF 2 CF 2 H
  • HFE-458 HFE 2 CF
  • tetrafluoroethylene-derived hydrofluoroether is preferably HFE-347 (CF 3 CH 2 OCF 2 CF 2 H).
  • perfluoropolyether active component containing both the perfluoropolyether group and the reactive group can be represented by the formula (1) or the formula (2):
  • PFPE 1 is a monovalent perfluoropolyether group
  • PFPE 2 is a divalent perfluoropolyether
  • N and K are divalent organic groups
  • I is a s+1 valence organic group or a covalent bond
  • M is m+n-valent organic group
  • R is a C 1-4 alkyl group
  • m, n, s are positive integers; when m and n are integers greater than or equal to 2, it means a perfluoropolymer having a comb structure ether.
  • x is a positive integer
  • y, z is a positive integer greater than or equal to 2; may also be selected from PFPE 1 -CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , PFPE 1 -(OH)(CH 2 CH 2 CH One of 2 Si(OCH 3 ) 3 ) 2 and the like.
  • the perfluoropolyether active component of the formula (2) containing both the perfluoropolyether group and the reactive group is selected from ((H 3 CO) 3 SiCH 2 CH 2 CH 2 ) 2 NOC-PFPE 2 -CON (CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) 2 .
  • composition comprising the perfluoropolyether active ingredient of the present invention uses tetrafluoroethylene-derived hydrofluoroether as a dispersion medium, has a zero ozone layer destruction coefficient, and has a low global greenhouse effect coefficient, and has almost no adverse effect on the environment;
  • composition containing the perfluoropolyether active ingredient of the present invention uses tetrafluoroethylene-derived hydrofluoroether as a dispersion medium, and the tetrafluoroethylene-derived hydrofluoroether has excellent solubility in active ingredients, and tetrafluoroethylene-derived hydrofluoroether is easy to produce.
  • the production cost is low, which also greatly reduces the cost of the composition;
  • the waste produced by the tetrafluoroethylene-derived hydrofluoroether in the composition containing the perfluoropolyether active ingredient of the present invention has less waste, that is, the raw material production is also safe and environmentally friendly;
  • the present invention provides a composition comprising a perfluoropolyether active ingredient, comprising: at least one a perfluoropolyether active component having a perfluoropolyether group and a reactive group, wherein the perfluoropolyether active component having a comb structure accounts for 0.2% or more of the total mass of the active component; at least one tetrafluoroethylene-derived hydrogen fluoride An ether in an amount sufficient to dissolve or disperse the active ingredient.
  • Tetrafluoroethylene-derived hydrofluoroether has a low surface tension and viscosity comparable to perfluorobutyl ethyl ether, and is also easy to form a uniform spread on the surface of the substrate to be treated; it also has the advantages of low latent heat of evaporation and short drying time, which can be avoided.
  • the long-term retention of the solvent may cause damage to the substrate; its non-flammable, ozone layer damage coefficient is 0, the global warming effect coefficient is very low, and it is also an environmentally friendly solvent that has almost no adverse effect on the environment.
  • the perfluoropolyether active ingredient comprising a comb structure contains a perfluoropolyether group, which is easy to migrate to the surface of the coating during curing, imparting excellent antifouling properties to the coating; the comb type perfluoropolyether has a higher The siloxane group with more molecular weight and quantity has stronger binding ability to the substrate, further improving the wear resistance and anti-fouling durability of the coating; comb-type perfluoropolyether and other perfluoropolyethers are easier to work with each other. A uniform coating film is formed.
  • composition may also optionally add one or more other active and/or inactive additive components which are soluble in the tetrafluoroethylene-derived hydrofluoroether, and have certain effects on improving the lubricating hand feeling and coating hardness of the combined coating. Regulatory effect.
  • the tetrafluoroethylene-derived hydrofluoroether of the present invention is obtained by an addition reaction of tetrafluoroethylene with a monohydric alcohol.
  • the specific reaction formula is as follows:
  • the monohydric alcohol HO-R can be exemplified by CH 3 OH, CF 3 CH 2 OH, CH 3 CH 2 OH, CH 3 CH 2 CH 2 OH, CH 3 CH(OH)CH 3 , CH 3 OCH 2 CH 2 OH, CH 3 CH 2 CH 2 CH 2 OH, (CH 3 ) 2 CH 2 CH 2 OH, m-CH 3 -C 6 H 4 -OH, C 6 H 5 -CH 2 OH, HCF 2 CF 2 CH 2 OH, etc. .
  • tetrafluoroethylene-derived hydrofluoroether HFE-254 (CH 3 OCF 2 CF 2 H), HFE-347 (CF 3 CH 2 O CF 2 CF 2 H), HFE-374 (CH 3 CH) can be prepared.
  • HFE-494n (CH 3 CH 2 CH 2 OCF 2 CF 2 H), HFE-494i ((CH 3 ) 2 CHOCF 2 CF 2 H), HFE-494e2 (CH 3 OCH 2 CH 2 OCF 2 CF 2 H), HF E-5114n (CH 3 (CH 2 ) 3 OCF 2 CF 2 H), HFE-5114i ((CH 3 ) 2 CHCH 2 OCF 2 CF 2 H), HFE-894m (m) -CH 3 C 6 H 4 OCF 2 CF 2 H), HFE-894Bz (C 6 H 5 CH 2 OCF 2 CF 2 H), HFE-458 (H CF 2 CF 2 CH 2 OCF 2 CF 2 H) or the like.
  • HFE-347, HFE-494n and HFE-458 are preferable; and among them, HFE-347 is more preferable.
  • tetrafluoroethylene-derived hydrofluoroether produces less waste during production, and environmental protection pressure is small, which is from production to use. The ideal solvent for environmental protection.
  • the tetrafluoroethylene-derived hydrofluoroether has no adverse effect on the action of the perfluoropolyether active ingredient.
  • perfluoropolyether active ingredient containing both a perfluoropolyether group and a reactive group in the present invention may be represented by formula (1) or formula (2)
  • PFPE 1 is a monovalent perfluoropolyether group
  • PFPE 2 is a divalent perfluoropolyether
  • N and K are divalent organic groups
  • I is a s+1 valence organic group or a covalent bond
  • M is m+n-valent organic group
  • R is a C 1-4 alkyl group
  • m, n, s are positive integers; when m and n are integers greater than or equal to 2, it means a perfluoropolymer having a comb structure ether.
  • CH 2 CHCH 2 Si(OCH 3 ) 3
  • CH 2 CH Si(OCH 2 CH 3 ) 3
  • the perfluoropolyether active ingredient containing a perfluoropolyether group and a reactive group in the formula (1) can be exemplified as follows: PFPE 1 -CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , PFPE 1 -CON(CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) 2 , PFPE 1 -CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , PFPE 1 -CH 2 OCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3 , PFPE 1 -CH 2 OCH 2 CH 2 CH 2 Si(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 , PFPE 1 -CH 2 OCH 2 CH 2 CH 2 Si(CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) 3 , PFPE 1 -CONHCH(CH 2 OCONHCH 2 CH 2 OOCCH 2 CH 2 N(CH 2 CH 2
  • the perfluoropolyether active ingredient of the formula (2) containing both a perfluoropolyether group and a reactive group can be enumerated as follows: (H 3 CO) 3 SiCH 2 CH 2 CH 2 NHOC-PFPE 2 -CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , ((H 3 CO) 3 SiCH 2 CH 2 CH 2 ) 2 NOC-PFPE 2 -CON(CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) 2 , (H 3 CO 3 SiCH 2 CH 2 CH 2 OCH 2 -PFPE 2 -CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 .
  • PFPE 1 is a monovalent perfluoropolyether group, which may be enumerated as follows: F(CF(CF 3 )CF 2 O) k CF(CF 3 )-, F(CF(CF 3 )CF 2 O) k CF 2 CF 2 -, CF 3 O(CF 2 CF 2 O) k CF 2 -, CF 3 O(CF 2 O) l (CF 2 CF 2 O) k CF 2 -, etc., wherein k and l are 1 to An integer of 50.
  • PFPE 2 is a divalent perfluoropolyether group, which may be enumerated as follows: -CF(CF 3 )O(CF(CF 3 )CF 2 O) k CF(CF 3 )-, -CF 2 CF 2 ( CF(CF 3 )CF 2 O) k CF 2 CF 2 -, -CF 2 O(CF 2 CF 2 O) k CF 2 -, -CF 2 O(CF 2 O) l (CF 2 CF 2 O) k CF 2 -etc, wherein k, l are integers from 1 to 50.
  • active and/or inactive additive components which are soluble in the tetrafluoroethylene-derived hydrofluoroether in the present invention are as follows: ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyl Trimethoxysilane, isopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, F(CF(CF 3 )CF 2 O) k CF 2 CF 3 (wherein k is 10 to 60) or the like may be one of them, or a mixture of two or more. Among them, one of orthosilicate, methyltrimethoxysilane and perfluoropolyether oil or a mixture thereof is preferred.
  • the raw materials used in the present invention are commercially available or prepared as follows:
  • CH 2 C(CH 3 )COOCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 ;
  • Y1 diisopropyl peroxydicarbonate
  • Dispersing medium HFE-347;
  • Each of the parts in Table 1 is a part by mass; X in X/Y means the number of parts of the dispersion medium, and Y means the number of parts of the perfluoropolyether active ingredient. Stability refers to the phenomenon that no stratification or precipitation occurs at room temperature for one month.
  • the dispersion medium was replaced with perfluorobutyl methyl ether (7100) using the same perfluoropolyether active ingredient formulation as in Examples 1, 4, and 6.
  • Examples 1 to 6 were diluted to a concentration of 0.1% with HFE-345, and the comparative example was diluted to 0 with 7100. At a concentration of 1%, the dilution was sprayed on a glass screen of a mobile phone and cured at 160 ° C for 0.5 h to form an antifouling coating.
  • the anti-fouling mobile phone glass screen was subjected to a contact angle test of deionized water (W) and white mineral oil (O) using a contact angle meter. The determination was performed 5 times in parallel and averaged. The larger the contact angle, the smaller the surface energy. The results are shown in Table 2.
  • Oily pen test Draw a line on the glass screen of the mobile phone with an oil-based pen, and then carefully observe the change of the ink mark and evaluate it with the following criteria:
  • the composition containing the perfluoropolyether active ingredient of the present invention does not adversely affect the performance of the perfluoropolyether active ingredient after using HFE-347 as a dispersion medium.
  • composition containing the perfluoropolyether active ingredient of the present invention uses tetrafluoroethylene-derived hydrofluoroether as a dispersion medium, has a zero ozone layer destruction coefficient, and has a low global greenhouse effect coefficient, and has almost no adverse effect on the environment.
  • composition containing the perfluoropolyether active ingredient of the present invention uses tetrafluoroethylene-derived hydrofluoroether as a dispersion medium, and the production cost is greatly reduced.
  • the waste produced by the tetrafluoroethylene-derived hydrofluoroether in the composition containing the perfluoropolyether active ingredient of the present invention is less, that is, the raw material production is also safe and environmentally friendly.

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Abstract

公开了一种包含全氟聚醚活性成分的组合物，该组合物包括：(1)至少一种同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分，其中具有梳型结构的全氟聚醚活性成分占活性成分总质量的0.2％以上；(2)至少一种四氟乙烯衍生氢氟醚，其量足以溶解或分散(1)中的活性成分。该组合物还可以选择性的添加一种或多种可溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分，也可以包含可与四氟乙烯衍生氢氟醚互溶的其它共溶剂。该组合物可用于基材表面处理，尤其是硬质基材如光学玻璃、陶瓷等，具有优异的防污功能；四氟乙烯衍生氢氟醚对活性成分溶解性能优良，且合成中几乎无三废产生，安全环保。

Description

一种包含全氟聚醚活性成分的组合物 技术领域
本发明属于硬质基材表面防污处理技术领域，具体涉及一种包含全氟聚醚活性成分的组合物。
背景技术
全氟聚醚活性成分常用来对基材进行防护处理，以获得防水、防油和防污的特性。例如触摸式电子显示器件的透明光学器件(如手机玻璃屏等)，经常与手指接触，容易被指纹、汗水、油污等污染，器件表面经过全氟聚醚活性成分防护处理后，污物在不使用溶剂的情况下也能方便去除，避免了使用溶剂对显示器件可能造成的损坏，保持了显示器件的视感。例如专利CN1284105公布了一种用于防反射表面的防污涂层组合物，专利CN101501046公布了一种新型全氟聚醚硅氧烷的组合物，专利CN102666759公布了一种用于光学基材的表面处理组合物。
但全氟聚醚活性成分通常需要溶解或分散在流体介质中才能进行表面处理应用，这就涉及到充当活性成分载体、稀释剂、分散介质或溶剂的材料(下文统称分散介质)。该分散介质应该能促进活性成分在预期使用中的转移、传送，并不影响活性成分的作用；或至少应该能促进至少一种活性成分的转移、传送，并且不对活性成分的作用产生负面影响。当使用时，由于这些分散介质将挥发进入大气中，因此分散介质材料的环境特性变得日益受到关注。在过十几年间，大量的努力致力于开发对臭氧损耗潜势(ODP)为0且对全球变暖潜势(GWP)较小的分散介质材料。除有要考虑有利于环境特性外，用做分散介质的材料还优选具有相对于一种或多种活性成分的惰性、低毒性和低可燃性。
通过涂布的方法来沉积全氟聚醚活性组分的涂布层需要分散介质，可选的分散介质如全氟化碳(例如全氟己烷、全氟庚烷和全氟辛烷)、氟改性的芳族烃溶剂(例如双-三氟甲苯)、部分氟化的烃溶剂(例如2H，3H-全氟戊烷)和氢氟醚等。典型地，将溶解于氟化分散介质中的活性成分的非常稀的溶液涂布到基材上以产生非常薄的活性成分涂料层。因此，大量的溶剂释放到大气环境中。然而，大部上述溶剂分对臭氧损耗潜势(ODP)不为0，对全球变暖潜势(GWP)较大。
全氟丁基甲醚(7100)和全氟丁基乙醚(7200)臭氧损耗潜势(ODP)为0，对全球变暖潜势(GWP)较小，因此被认定为全氟聚醚活性成分的理想分散介质，专利CN1284105、CN101501046和CN102666759等均采用7100为分散介质。其次，全氟丁基甲基醚和全氟丁基乙基醚表面张力低、粘度低，容易在被处理基材表面形成均匀铺展；而且还具有蒸发潜热低、干燥时间短的优点，避免了溶剂长时间保留可能对基材产生的破坏；其不可燃，是一种对环境几无影响的环保型溶剂。然而，全氟丁基甲基醚和全氟丁基乙基醚采用电解氟化工艺制备，生产工艺复杂、制备过程中会产生较多废弃物。因而其成本高、生产环保压力大。鉴于此，急需寻找易于生产、生产过程中不产生或少产生废弃物、且成本低的替代溶剂。
发明内容
本发明目的在于解决现有技术中存在的上述技术问题，提供一种包含全氟聚醚活性成分的组合物，以四氟乙烯衍生氢氟醚为分散介质，臭氧层破坏系数为零，地球温室效应系数也很低，对环境几乎无不良影响；四氟乙烯衍生氢氟醚易于生产，生产成本低，从而也大大降低了组合物的成本；与电解氟化制备的全氟丁基甲基醚相比，四氟乙烯衍生氢氟醚生产过程中产生的废弃物较少；另外，四氟乙烯衍生氢氟醚对全氟聚醚活性成分的作用无不良影响。
为了解决上述技术问题，本发明采用如下技术方案：
一种包含全氟聚醚活性成分的组合物，其特征在于该组合物包括：
(1)至少一种同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分，其中具有梳型结构的全氟聚醚活性成分占活性成分总质量的0.2％以上；
(2)至少一种四氟乙烯衍生氢氟醚，其量足以溶解或分散(1)中的活性成分；该组合物还可以选择性地添加一种或多种溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分，也可以包含可与四氟乙烯衍生氢氟醚互溶的其它共溶剂。
进一步，四氟乙烯衍生氢氟醚由四氟乙烯与一元醇经加成反应获得。
进一步，四氟乙烯衍生氢氟醚选自HFE-347(CF3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2H)和HFE-458(HCF2CF2CH2OCF2CF2H)中的一种。
进一步，四氟乙烯衍生氢氟醚优选为HFE-347(CF3CH2OCF2CF2H)。
进一步，同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分可以用式(1)或式(2)表示：
(PFPE1-N)m-M-(K-Si(OR)3)n         式(1)，
((RO)3Si-K)s-I-PFPE2-I-(K-Si(OR)3)s      式(2)；
其中，PFPE1为一价全氟聚醚基团，PFPE2为二价全氟聚醚，N和K为二价有机基团，I为s+1价有机基团或共价键，M为m+n价有机基团，R为C1～4的烷基，m、n、s为正整数；当m、n均为大于等于2的整数时，即表示具有梳型结构的全氟聚醚。
进一步，式(1)中同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分可以由单体CH2＝CR1-A-PFPE1和CH2＝CR2-B-Si(OR′)3经自由基共聚获得或由(CH3)3SiO(Si(CH3)2O)x(Si(CH3)H)y+zSi(CH3)3分别与y摩尔的单体CH2＝CHCH2OCH2PFPE1和z摩尔的单体CH2＝CH-E-Si(OR′)3经硅氢加成获得，其中R1、R2和R3为H或CH3，R′为C1～4的烷基，A、D为二价有机基团，B、E为共价键或二价有机基团，PFPE1为一价全氟聚醚基团，x为正整数，y、z为大于等于2 的正整数；也可以选自PFPE1-CH2OCH2CH2CH2Si(OCH3)3、PFPE1-(OH)(CH2CH2CH2Si(OCH3)3)2等中的一种。
进一步，单体CH2＝CR1-A-PFPE1选自CH2＝CHCH2OCH2PFPE1和CH2＝C(CH3)COOCH2PFPE1中的一种，单体CH2＝CR2-B-Si(OR′)3选自CH2＝CHCH2Si(OCH3)3和CH2＝C(CH3)COO CH2CH2CH2Si(OCH2CH3)3中的一种；单体CH2＝CH-E-Si(OR′)3选自CH2＝CHCH2Si(OCH3)3；其中PFPE1为一价全氟聚醚基团。
进一步，式(2)中同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分选自((H3CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2CH2Si(OCH3)3)2。
进一步，可溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分原硅酸乙酯、甲基三甲氧基硅烷和全氟聚醚油中的一种或其混合物。
本发明由于采用了上述技术方案，具有以下有益效果：
1)本发明的包含全氟聚醚活性成分的组合物以四氟乙烯衍生氢氟醚为分散介质，臭氧层破坏系数为零，地球温室效应系数也很低，对环境几乎无不良影响；
2)本发明的包含全氟聚醚活性成分的组合物以四氟乙烯衍生氢氟醚为分散介质，四氟乙烯衍生氢氟醚对活性成分溶解性能优良，四氟乙烯衍生氢氟醚易于生产，生产成本低，从而也大大降低了组合物的成本；
3)本发明的包含全氟聚醚活性成分的组合物中的四氟乙烯衍生氢氟醚生产过程中产生的废弃物较少，即原料生产也具有安全环保的特点；
4)本发明的包含全氟聚醚活性成分的组合物其中的分散介质四氟乙烯衍生氢氟醚对全氟聚醚活性成分的作用无不良影响，组合物防水、防油和防污性能优良，可用于基材表面处理，尤其是硬质基材如光学玻璃、陶瓷等。
具体实施方式
本发明提供一种包含全氟聚醚活性成分的组合物，包括：至少一种同时含有 全氟聚醚基团和反应活性基团的全氟聚醚活性成分，其中具有梳型结构的全氟聚醚活性成分占活性成分总质量的0.2％以上；至少一种四氟乙烯衍生氢氟醚，其量足以溶解或分散活性成分。四氟乙烯衍生氢氟醚具有可比拟全氟丁基乙基醚的低表面张力和粘度，同样容易在被处理基材表面形成均匀铺展；也具有蒸发潜热低、干燥时间短的优点，可以避免溶剂长时间保留可能对基材产生的破坏；其不可燃、臭氧层破坏系数为0、地球温室效应系数很低，同样是一种对环境几乎无不良影响的环保型溶剂。包含具有梳型结构的全氟聚醚活性成分含有全氟聚醚基团，其在固化过程中易于向涂层表面迁移，赋予涂层优良的防污性能；梳型全氟聚醚具有较高分子量和数量较多的硅氧烷基基团，与基材结合力强，进一步提高了涂层耐磨性和防污持久性；梳型全氟聚醚和其它全氟聚醚相互配合更容易形成均匀涂膜。该组合物还可以选择性的添加一种或多种可溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分，对于改善组合涂层的润滑手感、涂膜硬度等具有一定的调节作用。
本发明的四氟乙烯衍生氢氟醚由四氟乙烯与一元醇经加成反应获得。具体反应式如下：
Figure PCTCN2017108604-appb-000001
一元醇HO-R可列举如下：CH3OH、CF3CH2OH、CH3CH2OH、CH3CH2CH2OH、CH3CH(OH)CH3、CH3OCH2CH2OH、CH3CH2CH2CH2OH、(CH3)2CH2CH2OH、m-CH3-C6H4-OH、C6H5-CH2OH、HCF2CF2CH2OH等。由上述一元醇可以制备得到四氟乙烯衍生氢氟醚HFE-254(CH3OCF2CF2H)、HFE-347(CF3CH2O CF2CF2H)、HFE-374(CH3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2H)、HFE-494i((CH3)2CHOCF2CF2H)、HFE-494e2(CH3OCH2CH2OCF2CF2H)、HF E-5114n(CH3(CH2)3OCF2CF2H)、HFE-5114i((CH3)2CHCH2OCF2CF2H)、HFE- 894m(m-CH3C6H4OCF2CF2H)、HFE-894Bz(C6H5CH2OCF2CF2H)、HFE-458(H CF2CF2CH2OCF2CF2H)等。其中优选为HFE-347、HFE-494n和HFE-458中的一种；其中更优选为HFE-347。与通过电解氟化法制备的全氟丁基甲醚或全氟丁基乙醚相比，四氟乙烯衍生氢氟醚生产过程中产生废弃物较少，生产环保压力小，是一种从生产到使用均环保的理想溶剂。另外，四氟乙烯衍生氢氟醚对全氟聚醚活性成分的作用无不良影响。
本发明中同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分可以用式(1)或式(2)表示
(PFPE1-N)m-M-(K-Si(OR)3)n           式(1)，
((RO)3Si-K)s-I-PFPE2-I-(K-Si(OR)3)s       式(2)。
其中，PFPE1为一价全氟聚醚基团，PFPE2为二价全氟聚醚，N和K为二价有机基团，I为s+1价有机基团或共价键，M为m+n价有机基团，R为C1～4的烷基，m、n、s为正整数；当m、n均为大于等于2的整数时，即表示具有梳型结构的全氟聚醚。
式(1)中同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分可以由单体CH2＝CR1-A-PFPE1、CH2＝CR2-B-Si(OR′)3和CH2＝CR3-D-N(R′)2经自由基共聚获得或由(CH3)3SiO(Si(CH3)2O)x(Si(CH3)H)y+zSi(CH3)3分别与y摩尔的单体CH2＝CHCH2OCH2PFPE1和z摩尔的单体CH2＝CH-E-Si(OR′)3经硅氢加成获得，其中R1、R2和R3为H或CH3，R′为C1～4的烷基，A、D为二价有机基团，B、E为共价键或二价有机基团，PFPE1为一价全氟聚醚基团，x为正整数，y、z为大于等于2的正整数；也可以选自PFPE1-CH2OCH2CH2CH2Si(OCH3)3、PFPE1-(OH)(CH2CH2CH2Si(OCH3)3)2等中的一种。
本发明中单体CH2＝CR1-A-PFPE1选自CH2＝CHCH2OCH2PFPE1、CH2＝CHCO OCH2PFPE1和CH2＝C(CH3)COOCH2PFPE1中的一种。CH2＝CHCH2OCH2PFPE1可以通过HOCH2PFPE1与CH2＝CH CH2Br醚化反应获得，CH2＝CHCOOCH2PFPE1和CH2＝C(CH3)COOCH2PFPE1可以通过HOCH2PFPE1与CH2＝CHCOOH或CH2＝C(CH3)COOH酯化反应获得。
本发明中单体CH2＝CR2-B-Si(OR)3可列举如下：CH2＝CHSi(OCH3)3、CH2＝CHSi(OC2H5)3、CH2＝CH CH2Si(OCH3)3、CH2＝CHCH2Si(OC2H5)3、CH2＝CHCOO(CH2)3Si(OCH3)3、CH2＝CHCOO(CH2)3Si(OC2H5)3、CH2＝CH(CH3)COO(CH2)3Si(OCH3)3、CH2＝CH(CH3)COO(CH2)3Si(OC2H5)3等，可以是其中一种，也可以是两种及以上的混合物。其中优选为CH2＝CHCH2Si(OCH3)3、CH2＝CH Si(OCH2CH3)3和CH2＝C(CH3)COOCH2CH2CH2Si(OCH2CH3)3中的一种。
本发明中单体CH2＝CR3-D-N(R′)2可列举如下：CH2＝CHCH2N(CH3)2、CH2＝CHCH2N(C2H5)2、CH2＝CHCH2N(C3H8)2、CH2＝C(CH3)COOCH2CH2N(CH3)2、CH2＝C(CH3)COOCH2CH2N(C2H5)2、CH2＝CHCOOCH2CH2N(CH3)2、CH2＝CHCOOCH2CH2N(C2H5)2等，可以是其中一种，也可以是两种及以上的混合物。其中优选为CH2＝C(CH3)COOCH2CH2N(CH3)2和CH2＝CHCH2N(CH3)2中的一种。
本发明中单体CH2＝CH-E-Si(OR′)3选自CH2＝CHCH2Si(OCH3)3和CH2＝CHSi(OCH2CH3)3中的一种；其中PFPE1为一价全氟聚醚基团。
式(1)中含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分可列举如下：PFPE1-CONHCH2CH2CH2Si(OCH3)3、PFPE1-CON(CH2CH2CH2Si(OCH3)3)2、PFPE1-CH2OCH2CH2CH2Si(OCH3)3、PFPE1-CH2OCH2CH2CH2Si(OC2H5)3、PFPE1-CH2OCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2Si(OCH3)3、PFPE1-CH2OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3、PFPE1-CONHCH(CH2OCONHCH2CH2OOCCH2CH2N(CH2CH2CH2Si(OCH3)3)2)2、PFPE1-CH2OCH2CH2CH2Si(CH3)O(Si(CH3)(CH2 CH2CH2Si(OCH3)3)O)2Si(CH3)(CH2CH2CH2Si(OCH3)3)O及梳型结构的全氟聚醚。
式(2)中同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分可列举如下：(H3CO)3SiCH2CH2CH2NHOC-PFPE2-CONHCH2CH2CH2Si(OCH3)3、((H3CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2CH2Si(OCH3)3)2、(H3CO)3SiCH2CH2CH2OCH2-PFPE2-CH2OCH2CH2CH2Si(OCH3)3。
本发明中PFPE1为一价全氟聚醚基团，可列举如下：F(CF(CF3)CF2O)kCF(CF3)-、F(CF(CF3)CF2O)kCF2CF2-、CF3O(CF2CF2O)kCF2-、CF3O(CF2O)l(CF2CF2O)kCF2-等，其中k、l为1至50的整数。
本发明中PFPE2为二价全氟聚醚基团，可以列举如下：-CF(CF3)O(CF(CF3)CF2O)kCF(CF3)-、-CF2CF2(CF(CF3)CF2O)kCF2CF2-、-CF2O(CF2CF2O)kCF2-、-CF2O(CF2O)l(CF2CF2O)kCF2-等，其中k、l为1至50的整数。
本发明中可溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分可列举如下：原硅酸乙酯、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、异丙基三甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-缩水甘油醚氧丙基三乙氧基硅烷、F(CF(CF3)CF2O)k CF2CF3(其中k为10～60)等，可以是其中一种，也可以是两种及以上的混合物。其中优选原硅酸乙酯、甲基三甲氧基硅烷和全氟聚醚油中的一种或其混合物。
本发明所用原料均可市售或制备得到，具体如下：
A1：CH2＝CHCH2Br；
A2：CH2＝C(CH3)COOH；
C1：H3COOCCF(CF3)[OCF2CF(CF3)]30OCF2CF2CF3；
C2：H3COOCCF2O(CF2O)12.3(CF2CF2O)13CF2COOCH3；
C3：F(CF(CF3)CF2O)34CF2CF3；
C4：HOCH2CF(CF3)[OCF2CF(CF3)]30OCF2CF2CF3(由C1通过NaBH4还原 制备)；
S1：CH2＝CHCH2Si(OCH3)3；
S2：CH2＝C(CH3)COOCH2CH2CH2Si(OCH2CH3)3；
S3：Si(OC2H5)4；
S4：CH3Si(OCH3)3；
S5：NH(CH2CH2CH2Si(OCH3)3)2；
S6：(CH3)3SiO(Si(CH3)2O)35(Si(CH3)H)10Si(CH3)3；
S7：HSiCl3；
Y1：过氧化二碳酸二异丙酯；
分散介质：HFE-347；
合成例1(单体CH2＝CHCH2OCH2PFPE1的合成——F1)
在装配有回流冷凝管和恒压漏斗的三口烧瓶装置中，加入500gC4和1500ml HFC-347，在氮气保护下加入20％NaOH溶液80g作为催化剂，后加入60g A1，回流反应6小时，用水洗涤，减压蒸馏除去溶剂和残留的水，得到510gF1。
合成例2(单体CH2＝C(CH3)COOCH2PFPE1的合成——F2)
在装配有搅拌器、恒温油浴、温度计和冷凝器的四口反应烧瓶中加入1000g的C1、45g的A2、适量带水剂及少量对苯二酚阻聚剂和少量对甲苯磺酸催化剂，在搅拌下升温至120℃进行酯化反应，至水分离器中的水接近理论值时，酯化反应完毕。然后通过常压蒸馏和减压蒸馏分别出去带水剂和未反应的A2，再通过水洗出去催化剂和阻聚剂，真空干燥得到1005gF2。
合成例3(梳型全氟聚醚E1的合成)
在装配有搅拌器、恒温油浴、温度计和冷凝器的四口反应烧瓶中加入50gF1、6.5gS1、0.5gY1和85g HFC-347，搅拌升温至回流温度，反应15h，红外分析双键吸收峰消失，再加入适量HFC-347，调节有效成分至25％，得到梳型全氟聚醚E1的25％溶液。
合成例4(梳型全氟聚醚E2的合成)
在装配有搅拌器、恒温油浴、温度计和冷凝器的四口反应烧瓶中加入50gF2、10gS2、0.5gY1和90g HFC-347，搅拌升温至回流温度，反应15h，红外分析双键吸收峰消失，再加入适量HFC-347，调节有效成分至25％，得到梳型全氟聚醚E2的25％溶液。
合成例5(梳型全氟聚醚E3的合成)
在装配有回流冷凝管和恒压漏斗的三口烧瓶装置，向恒压漏斗中加入20gS6和20ml HFC-347，向三口瓶中加入30gF1、5gS1和70ml HFC-347，搅拌混合均匀，加入氯铂酸催化剂0.3g，加热至回流温度，开始缓慢滴加S8溶液，30分钟滴完，反应15h，红外检测双键吸收峰消失，再加入适量HFC-347，调节有效成分至25％，得到梳型全氟聚醚E5的25％溶液。
合成例6(全氟聚醚硅氧烷PFPE1-CH2OCH2CH2CH2Si(OCH3)3的合成——D1)
参照专利CN103551075A合成例1中的方法，由F1与S7硅氢加成，在经过醇解制备，然后加入适量HFC-347调节有效成分至25％，得到D1的25％溶液。
合成例7(全氟聚醚硅氧烷PFPE1-C(OH)(CH2CH2CH2Si(OCH3)3)2的合成——D2)
参照专利CN104945610A合成例1中的方法由C1与烯丙基溴化镁反应制备，然后加入适量HFC-347调节有效成分至25％，得到D2的25％溶液。
合成例8(全氟聚醚硅氧烷((H3CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2C H2Si(OCH3)3)2的合成——D3)
通过摩尔比为1:2的C2与S5的酰胺化反应制备。反应在氮气保护下进行，85℃反应5h。产物中加入适量的HFC-347，调节有效成分至25％，得到D3的25％溶液。
实施例1～6
定量称取各组分，并加入烧瓶中，搅拌均匀即获得本发明的包含全氟聚醚活性成分的组合物。具体配方详见表1。
Figure PCTCN2017108604-appb-000002
表1
表1中均为质量份数；X/Y中的X指分散介质的份数，Y指全氟聚醚活性成分的份数。稳定性是指常温静置1个月无分层、沉淀等现象发生。
对比例
采用与实施例1、4、6相同的全氟聚醚活性成分配方，将分散介质用全氟丁基甲基醚(7100)替代。
基材处理
将实施例1～6用HFE-345稀释到0.1％的浓度，将对比例用7100稀释到0. 1％的浓度，将稀释液喷涂在在手机玻璃屏上，并于160℃下固化0.5h，形成防污涂层。
测试方法
1、接触角测试
将经过防污处理的手机玻璃屏用接触角测定仪进行去离子水(W)和白矿物油(O)的接触角测试。平行测定5次，取平均值。接触角越大，表面能越小，结果详见表2。
2、防污性能评价
油性笔测试：用油性笔在手机玻璃屏涂膜上画一条线，然后仔细观察油墨痕迹变化，并以下面标准加以评价：
E：油墨快速收缩，
F：油墨部分收缩，
NG：油墨基本不收缩，
结果详见表2。
3、污物易去除性评价
配制质量分数为3％的红色油基染料，用手指沾取足够量后，将手指在手机玻璃屏涂膜上以1Kgf的力压保持5秒，然后对无尘布施加1Kgf的压力、并来回擦除指纹5次，以下面标准加以评价：
E：没有留下污点，
F：留有少数污点，
NG：留有多数污点，
结果详见表2。
Figure PCTCN2017108604-appb-000003
Figure PCTCN2017108604-appb-000004
表2
从表2可以看出，本发明的包含全氟聚醚活性成分的组合物在采用HFE-347为分散介质后，对全氟聚醚活性成分的性能无不良影响。
本发明具有以下有益效果：
1)本发明的包含全氟聚醚活性成分的组合物以四氟乙烯衍生氢氟醚为分散介质，臭氧层破坏系数为零，地球温室效应系数也很低，对环境几乎无不良影响。
2)本发明的包含全氟聚醚活性成分的组合物以四氟乙烯衍生氢氟醚为分散介质，生产成本大大降低。
3)本发明的包含全氟聚醚活性成分的组合物中的四氟乙烯衍生氢氟醚生产过程中产生的废弃物较少，即原料生产也具有安全环保的特点。
4)本发明的包含全氟聚醚活性成分的组合物其中的分散介质四氟乙烯衍生氢氟醚对全氟聚醚活性成分的作用无不良影响，组合物防水、防油和防污性能优良，可用于基材表面处理，尤其是硬质基材如光学玻璃、陶瓷等。
以上仅为本发明的具体实施例，但本发明的技术特征并不局限于此。任何以本发明为基础，为解决基本相同的技术问题，实现基本相同的技术效果，所作出的简单变化、等同替换或者修饰等，皆涵盖于本发明的保护范围之中。

Claims (9)

  1. 一种包含全氟聚醚活性成分的组合物，其特征在于该组合物包括：
    (1)至少一种同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分，其中具有梳型结构的全氟聚醚活性成分占活性成分总质量的0.2％以上；
    (2)至少一种四氟乙烯衍生氢氟醚，其量足以溶解或分散(1)中的活性成分；
    该组合物添加有一种或多种溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分，或者包含与四氟乙烯衍生氢氟醚互溶的其它共溶剂。
  2. 根据权利要求1所述的一种包含全氟聚醚活性成分的组合物，其特征在于：所述四氟乙烯衍生氢氟醚由四氟乙烯与一元醇经加成反应获得。
  3. 根据权利要求2所述的一种包含全氟聚醚活性成分的组合物，其特征在于：所述四氟乙烯衍生氢氟醚选自HFE-347(CF3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2H)和HFE-458(HCF2CF2CH2OCF2CF2H)中的一种。
  4. 根据权利要求3所述的一种包含全氟聚醚活性成分的组合物，其特征在于：所述四氟乙烯衍生氢氟醚优选为HFE-347(CF3CH2OCF2CF2H)。
  5. 根据权利要求1所述的一种包含全氟聚醚活性成分的组合物，其特征在于：所述同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分用式(1)或式(2)表示：
    (PFPE1-N)m-M-(K-Si(OR)3)n       式(1)，
    ((RO)3Si-K)s-I-PFPE2-I-(K-Si(OR)3)s     式(2)；
    其中，PFPE1为一价全氟聚醚基团，PFPE2为二价全氟聚醚，N和K为二价有机基团，I为s+1价有机基团或共价键，M为m+n价有机基团，R为C1～4的烷基，m、n、s为正整数；当m、n均为大于等于2的整数时，即表示具有梳型结构的全氟聚醚。
  6. 根据权利要求5所述的一种包含全氟聚醚活性成分的组合物，其特征在于：式(1)所述同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分由单体CH2＝CR1-A-PFPE1和CH2＝CR2-B-Si(OR′)3经自由基共聚获得或由(CH3)3SiO(Si(CH3)2O)x(Si(CH3)H)y+zSi(CH3)3分别与y摩尔的单体CH2＝CH CH2OCH2PFPE1和z摩尔的单体CH2＝CH-E-Si(OR′)3经硅氢加成获得，其中R1、R2和R3为H或CH3，R′为C1～4的烷基，A、D为二价有机基团，B、E为共价键或二价有机基团，PFPE1为一价全氟聚醚基团，x为正整数，y、z为大于等于2的正整数；或选自PFPE1-CH2OCH2CH2CH2Si(OCH3)3、PFPE1-C(OH)(CH2CH2CH2Si(OCH3)3)2中的一种。
  7. 根据权利要求6所述的一种包含全氟聚醚活性成分的组合物，其特征在于：单体CH2＝CR1-A-PFPE1选自CH2＝CHCH2OCH2PFPE1和CH2＝C(CH3)COOCH2PFPE1中的一种，单体CH2＝CR2-B-Si(OR′)3选自CH2＝CHCH2Si(OCH3)3和CH2＝C(CH3)COOCH2CH2CH2Si(OCH2CH3)3中的一种；单体CH2＝CH-E-Si(OR′)3选自CH2＝CH CH2Si(OCH3)3；其中PFPE1为一价全氟聚醚基团。
  8. 根据权利要求5所述的一种包含全氟聚醚活性成分的组合物，其特征在于：式(2)所述同时含有全氟聚醚基团和反应活性基团的全氟聚醚活性成分选自((H3CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2CH2Si(OCH3)3)2。
  9. 根据权利要求1所述的一种包含全氟聚醚活性成分的组合物，其特征在于：所述可溶解于四氟乙烯衍生氢氟醚的其它活性和/或非活性添加剂成分为原硅酸乙酯、甲基三甲氧基硅烷和全氟聚醚油中的一种或其混合物。
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