CN102164976A - Fluorosilicones and surface treatment agent - Google Patents

Fluorosilicones and surface treatment agent Download PDF

Info

Publication number
CN102164976A
CN102164976A CN2009801360656A CN200980136065A CN102164976A CN 102164976 A CN102164976 A CN 102164976A CN 2009801360656 A CN2009801360656 A CN 2009801360656A CN 200980136065 A CN200980136065 A CN 200980136065A CN 102164976 A CN102164976 A CN 102164976A
Authority
CN
China
Prior art keywords
monomer
group
atom
organopolysiloxane
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2009801360656A
Other languages
Chinese (zh)
Inventor
山本育男
桝谷哲也
榎本孝司
宫原正弘
南晋一
彼得·谢舍尔·胡佩费尔德
阿夫里尔·E·舍其诺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Dow Silicones Corp
Original Assignee
Daikin Industries Ltd
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd, Dow Corning Corp filed Critical Daikin Industries Ltd
Publication of CN102164976A publication Critical patent/CN102164976A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • 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
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
    • 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
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A surface treatment agent, which can impart the excellent water- and oil-repellency, soil resistance and feeling to the substrate, is obtained from a fluorine-containing polymer which contains: (A) a monomer which comprises; (a) a fluorine-containing monomer of the formula: CH2=C(-X)-C(=O)-Y-Z-Rf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 8 to 12 carbon atoms, and (B) at least one functional organopolysiloxane selected from the group consisting of a mercapto-functional organopolysiloxane, a vinyl-functional organopolysiloxane, a (meth)acrylamide-functional organopolysiloxane and a meth(acrylate) functional organopolysiloxane.

Description

Fluorosilicone and surface treatment agent
The cross reference of related application
The application has the right of priority of No. the 61/096th, 930, the U. S. application submitted on September 15th, 2008, and its disclosure is incorporated this specification sheets into by quoting.
Technical field
The present invention relates to the fluorosilicone reaction product and the method for preparing fluorosilicone of functionalized organopolysiloxane and fluorochemical monomer.The fluorosilicone product is suitable for as matrix such as textiles, particularly fabrics, to give textiles oil repellent (oleophobic property).
Fluorosilicone reaction product (that is the polymkeric substance of fluorine-containing and silicon) can be used for the surface treatment agent of giving excellent water repellency, oil repellent, resistance to soiling and sense of touch as matrix such as textiless (that is the surface treatment agent of fluorine-containing and silicon).
Background technology
Fluorocarbon polymer is widely used in the textile industry, for fabric is given oleophobic property/oil repellent.For example, US-A-5247008 has described the finishing composition that is used for textiles, leather, paper and mineral substrate, and described finishing composition is the aqueous liquid dispersion of the multipolymer of perfluoroalkyl acrylate or perfluoroalkyl methacrylate, alkyl acrylate or alkyl methacrylate and acrylic-amino alkyl ester or amino alkyl methacrylate.
US-A-5068295 has described a kind of water-repellent oil-repellent agent, and described water-repellent oil-repellent agent comprises perfluoroalkyl acrylate or perfluoroalkyl methacrylate, contains the organopolysiloxane of vinyl and contains isocyanic ester or the multipolymer of the vinyl monomer of blocked isocyanate groups.
US-A-6582620 and US-A-5883185 have described a kind of used for textiles treatment compositions of giving the textiles water and oil repellant, and cohydrolysis and condensation that organoalkoxysilane, (B) that described treatment compositions has a fluoro-alkyl by (A) has amino organoalkoxysilane and (C) have an organopolysiloxane of alkoxysilyl obtain.
The mixture that US-A-5536304 has described the end capped polydimethylsiloxane of succinyl oxide and poly-(methacrylic acid fluoroalkyl ester) is applied to cotton, to provide oil repellent to fabric.
US-A-6472019 has described and has used the water-repellent oil-repellent agent that contains fluoropolymer and sulfation fatty acid cpds to handle textiles, and WO 2004/069935 and WO 2004/069955 have described the fluoropolymer of supplying with aqueous dispersions as textile treatment.
Use a main drawback of the described finishing composition of fluorocarbon polymer preparation to be that they have given coarse sense of touch for fabric face.Need to give fabric oleophobic property and oil repellent and can not give the textile treating agent of the coarse sense of touch of fabric face (the preferred while can be given the sense of touch that makes moderate progress than untreated fabric).
Up to the present, for to providing water and oil repellant and flexibility simultaneously, a kind ofly comprise the perfluoroalkyl that water and oil repellant is provided and provide the water and oil repellant composition of the silicone compounds of flexibility to be used widely as matrix such as textiless.See also for example JP-A-58-42682, JP-A-60-190408, JP-A-63-075082, JP-A-09-143877 and USP4070152.
For example, the method (for example JP-A-02-214791 and JP-A-03-231986) that has the multipolymer of a kind of use fluorinated acrylate monomer that is used for identical purpose and siloxanes acrylate monomer.But, this method has the problem of water and oil repellant reduction.
The problem to be solved in the present invention
The object of the present invention is to provide the water-repellent oil-repellent agent that contains fluorinated acrylate polymer, when using described water-repellent oil-repellent agent to handle matrix, it can give excellent water and oil repellant and resistance to soiling to matrix.
Summary of the invention
The present invention finds that above-mentioned purpose can realize that described polymkeric substance is formed and polymerization in the presence of functionalized organopolysiloxane by the monomer that comprises fluorochemical monomer by following polymkeric substance.
The invention provides a kind of fluoropolymer, described fluoropolymer comprises and comes from the monomeric repeating unit that comprises fluorochemical monomer, and wherein said fluoropolymer has (or coming from it) oxyalkylene segment that functionalized organopolysiloxane has.
The present invention also provides a kind of method of producing fluoropolymer, described fluoropolymer comprises and comes from the monomeric repeating unit that comprises fluorochemical monomer, and wherein said method is included in functionalized organopolysiloxane makes monomer polymerization so that described fluoropolymer to be provided under existing.
The invention provides a kind of fluoropolymer, described fluoropolymer comprises:
(A) monomer, described monomer comprises:
(a) fluorochemical monomer of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein, X is hydrogen atom, any monovalent organic radical group or halogen atom,
Y is-O-or-NH-,
Z is Direct Bonding or divalent organic group, and
Rf be have 8～12 carbon atoms fluoroalkyl and
(B) be selected from least a functionalized organopolysiloxane in the group of forming by hydrosulphonyl functionalized organopolysiloxane, vinyl-functional organopolysiloxane, the functionalized organopolysiloxane of (methyl) acrylamide and (methyl) acrylate functional organopolysiloxane.
The present invention also provides a kind of method of producing fluoropolymer, and described method comprises to be made:
(A) monomer, described monomer comprises:
(a) fluorochemical monomer of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein, X is hydrogen atom, any monovalent organic radical group or halogen atom,
Y is-O-or-NH-,
Z is Direct Bonding or divalent organic group, and
Rf is the fluoroalkyl with 8～12 carbon atoms,
In the presence of following material, carry out polymerization:
(B) be selected from least a functionalized organopolysiloxane in the group of forming by hydrosulphonyl functionalized organopolysiloxane, vinyl-functional organopolysiloxane, the functionalized organopolysiloxane of (methyl) acrylamide and (methyl) acrylate functional organopolysiloxane.
Fluoropolymer of the present invention (that is fluorosilicone product) can be used for providing oil repellent to various surfaces.When handling textiles, fluorosilicone of the present invention also can provide than conventional carbon fluorine class and refuse oil treatment more soft hand feeling or sense of touch.
The invention effect
According to the present invention, matrix after treatment, the water-repellent oil-repellent agent that contains fluorinated acrylate polymer can be given excellent water and oil repellant and resistance to soiling to matrix.When matrix was textiles, treated textiles had good sense of touch.
Embodiment
In the present invention, the monomer (A) that forms described fluoropolymer comprises:
(a) fluorochemical monomer,
(b) the no fluorine monomer that is different from cross-linkable monomer that exists alternatively and
(c) cross-linkable monomer that exists alternatively.
Fluoropolymer can be the homopolymer that is formed by a kind of monomer, also can be the multipolymer that is formed by at least two kinds of monomers.
Homopolymer has the repeating unit that comes from fluorochemical monomer (a).Multipolymer can have the repeating unit that comes from least two kinds of fluorochemical monomers (a), also can also have the repeating unit that comes from no fluorine monomer (b) and optional cross-linkable monomer (c) except that the repeating unit that comes from fluorochemical monomer (a).
Fluoropolymer can prepare by polymerization single polymerization monomer (A) in the presence of functionalized organopolysiloxane (B).
The fluoropolymer that constitutes surface treatment agent of the present invention comprises:
(a) fluorochemical monomer and
Optionally (b) be different from cross-linkable monomer no fluorine monomer and
Optional (c) cross-linkable monomer.
(A) monomer
(a) fluorochemical monomer
Component of the present invention (a) is the fluorochemical monomer of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein, X is hydrogen atom, any monovalent organic radical group or halogen atom,
Y is-O-or-NH-,
Z is Direct Bonding or divalent organic group, and
Rf is the fluoroalkyl with 8～12 carbon atoms.Z can be the straight or branched alkylidene group that for example has 1～20 carbon atom, suc as formula-(CH 2) x-group (wherein x is 1～10), formula-SO 2N (R 1) R 2-or formula-CON (R 1) R 2-group (R wherein 1Be alkyl and R with 1～10 carbon atom 2For having the straight or branched alkylidene group of 1～10 carbon atom), or formula-CH 2CH (OR 3) CH 2-group (R wherein 3Expression hydrogen atom or have the acyl group of 1～10 carbon atom is as formyl radical or ethanoyl), or formula-Ar-CH 2-group (wherein Ar is for having substituent arylidene alternatively), or-(CH 2) m-SO 2-(CH 2) n-Ji, or-(CH 2) m-S-(CH 2) n-Ji (wherein m is 1～10, and n is 0～10).X can be for example H, Me (methyl), Cl, Br, I, F, CN and/or CF 3
Fluorochemical monomer (a) is preferably the acrylate of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf (I)
Wherein, X is hydrogen atom, has straight or branched alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, a CFX of 1～21 carbon atom 1X 2Base (wherein, X 1And X 2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, have 1～21 carbon atom the straight or branched fluoroalkyl, have substituting group or do not have substituent benzyl, perhaps have substituting group or do not have substituent phenyl;
Y is-O-or-NH-;
Z is a Direct Bonding, have the aliphatic group of 1～10 carbon atom, aromatic series or alicyclic group with 6～18 carbon atoms ,-CH 2CH 2N (R 1) SO 2-Ji (R wherein 1For having the alkyl of 1～4 carbon atom) ,-CH 2CH (OZ 1) CH 2-Ji (Z wherein 1Be hydrogen atom or ethanoyl) ,-(CH 2) m-SO 2-(CH 2) n-Ji or-(CH 2) m-S-(CH 2) n-Ji (wherein m is 1～10, and n is 0～10); And
Rf is the straight or branched fluoroalkyl with 8～12 carbon atoms.
The α position of fluorochemical monomer can be substituted with halogen atom etc.Therefore, in formula (I), X can be straight or branched alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, the CFX with 2～21 carbon atoms 1X 2Base (X wherein 1And X 2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, have 1～21 carbon atom the straight or branched fluoroalkyl, have substituting group or do not have substituent benzyl, perhaps have substituting group or do not have substituent phenyl.
In formula (I), the Rf base is preferably perfluoroalkyl.The carbon number of Rf base is 8～12, for example is 8～10, particularly 8 or 10.
Z be preferably the aliphatic group with 1～10 carbon atom, aromatic series or alicyclic group with 6～18 carbon atoms ,-CH 2CH 2N (R 1) SO 2-Ji (R 1For having the alkyl of 1～4 carbon atom) ,-CH 2CH (OY 1) CH 2-Ji (Y 1Be hydrogen atom or ethanoyl) ,-(CH 2) m-SO 2-(CH 2) n-Ji or-(CH 2) m-S-(CH 2) n-Ji (wherein m is 1～10, and n is 0～10).Described aliphatic group is preferably alkylidene group (particularly carbon number is 1～4, for example 1 or 2).Described aromatic group and alicyclic group can have substituting group or not have substituting group.Described S or SO 2-Ji can be directly and the Rf base key close.
The limiting examples of fluorochemical monomer (a) is as follows:
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-O-C 6H 4-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2N(-CH 3)SO 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2N(-C 2H 5)SO 2-Rf
CH 2＝C(-H)-C(＝O)-O-CH 2CH(-OH)CH 2-Rf
CH 2＝C(-H)-C(＝O)-O-CH 2CH(-OCOCH 3)CH 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CH 3)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-NH-(CH 2) 3-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
Wherein Rf is the straight or branched fluoroalkyl with 8～12 carbon atoms.
(b) no fluorine monomer
Fluoropolymer can have the repeating unit that comes from no fluorine monomer (b).No fluorine monomer (b) is different from cross-linkable monomer (c).Monomer (b) is preferably the no fluorine monomer with carbon-carbon double bond.Monomer (b) is preferably floride-free vinyl monomer.No fluorine monomer (b) is generally the compound with a carbon-carbon double bond.The preferred embodiment of no fluorine monomer (b) comprising: for example, and ethene, vinyl-acetic ester, as vinyl halides such as vinylchlorid, as the inclined to one side halogenide of vinylidenes such as vinylidene chloride, vinyl cyanide, vinylbenzene, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.No fluorine monomer (b) is not limited to these examples.No fluorine monomer (b) can contain vinyl halide and/or vinylidene halide.
No fluorine monomer (b) can be (methyl) acrylate with alkyl.The carbonatoms of alkyl can be 1～30, for example 6～30, for example 10～30.For example, no fluorine monomer (b) can be the acrylate of following general formula:
CH 2＝CA 1COOA 2
Wherein, A 1Be hydrogen atom, methyl or the halogen atom except that fluorine atom (for example, chlorine atom, bromine atoms and iodine atom), and
A 2For by C nH 2n+1(n=1～30) represented alkyl.
(c) cross-linkable monomer
Fluoropolymer can contain the repeating unit that comes from cross-linkable monomer (c).Cross-linkable monomer (c) can be the floride-free vinyl monomer with at least two reactive groups and/or carbon-carbon double bond.Cross-linkable monomer (c) can be the compound with at least two carbon-carbon double bonds, perhaps has the compound of at least one carbon-carbon double bond and at least one reactive group.The example of reactive group comprises hydroxyl, epoxy group(ing), chloromethyl, end capped isocyanate group, amino and carboxyl.
The example of cross-linkable monomer (c) comprises diacetone-acryloamide(DAA), (methyl) acrylamide, N-methylol-acrylamide, (methyl) vinylformic acid hydroxyl methyl esters, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 3-chloro-2-hydroxypropyl acrylate, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, divinyl, isoprene, chloroprene, (methyl) vinylformic acid glyceryl ester and (methyl) glycidyl acrylate, cross-linkable monomer is not limited to these examples.
Can improve various character alternatively with the copolymerization of monomer (b) and/or monomer (c), for example solvability, hardness and the sense of touch in the cleaning weather resistance of water repellency and resistance to soiling, described water repellency and resistance to soiling and washing resistance, the solvent.
In fluoropolymer, with respect to 100 weight part fluorochemical monomers (a), the amount of no fluorine monomer (b) can be 0.1 weight part～100 weight parts, for example is 0.1 weight part～50 weight parts, and
The amount of cross-linkable monomer (c) can be 50 weight parts at the most, for example is 20 weight parts, particularly 0.1 weight part～15 weight parts at the most.
Above-mentioned weight part is all for 100 weight part fluorochemical monomers (a).
Monomer (A) can polymerization in the presence of organopolysiloxane (B).The example of the olefinic unsaturated comonomer that comprises in the monomer (A) comprises: have the alkyl acrylate or the alkyl methacrylate of 1～30 carbon atom in the alkyl, as butyl acrylate, ethyl propenoate, methyl acrylate, methyl methacrylate or butyl methacrylate etc.Alkyl acrylate or alkyl methacrylate can be used for regulating by the second-order transition temperature (Tg) of monomer (A) with the polymerisate that reaction obtained of organopolysiloxane (B); For example, have 4～20, particularly the acrylate of the chain alkyl of 8～20 carbon atoms (as octadecyl acrylate or stearyl methacrylate, Octyl acrylate, 2-EHA or dodecyl acrylate or methacrylic dodecyl gallate) can be used for forming have low Tg than the softish polymkeric substance.Can improve various character with the multipolymer of alkyl acrylate or alkyl methacrylate monomer, for example water and oil repellant and release dirt, described water and oil repellant and release cleaning weather resistance, washing resistance and the wear resistance of dirt, solvability, hardness and sense of touch (feel) in the solvent.Other acrylate of available or methacrylate co-monomers comprise: macrogol ester acrylate or methacrylic ester, polypropylene glycol acrylate or methacrylic ester, methoxy poly (ethylene glycol) acrylate or methacrylic ester and methoxyl group polypropylene glycol acrylate or methacrylic ester.Other olefinic unsaturated comonomers of available comprise vinylchlorid, vinylidene chloride, vinylbenzene, vinyl cyanide, methacrylonitrile, ethene, vinyl alkyl ethers, isoprene or vinyl ester (as vinyl-acetic ester or vinyl propionate base ester).Can use the olefinic unsaturated comonomer that contains following functional group,, can give such as higher substantivity character such as (substantivity) textiles and other matrix with other functional group reactionses though described functional group does not react with amino.The example of described functional group is hydroxyl, amino and amido, the example that contains their olefinic unsaturated comonomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, vinylformic acid 3-chloro-2-hydroxypropyl acrylate or methacrylic acid 3-chloro-2-hydroxypropyl acrylate, vinylformic acid N, N-dimethylamino ethyl ester or methacrylic acid N, N-dimethylamino ethyl ester and vinylformic acid diethylamino ethyl ester or diethyl aminoethyl methacrylate.
(B) functionalized organopolysiloxane
Functionalized organopolysiloxane is hydrosulphonyl functionalized organopolysiloxane, vinyl-functional organopolysiloxane, the functionalized organopolysiloxane of (methyl) acrylamide, (methyl) acrylate functional polysiloxane or its mixture.Functionalized organopolysiloxane (B) serves as chain-transfer agent.By polyreaction, functionalized organopolysiloxane (B) is by functionalized organic group and fluoropolymer bonding.
Composition of the present invention (B) can be hydrosulphonyl functionalized organopolysiloxane,, has the organopolysiloxane that is present in the hydrosulphonyl functionalized organic group in the molecule that is." hydrosulphonyl functionalized organic group " as used in this specification is any organic group that contains sulphur atom, as-(CH 2) n-SH (n is 0～10, particularly 1～5 number).The siloxanes (B) that contains sulfydryl (promptly, hydrosulphonyl functionalized organopolysiloxane (B)) for (for example having at least one, 1～500, particularly 1～50, especially 2～40) sulfydryl and the silicone compounds that contains the oxyalkylene segment of two above siloxane bonds.
Composition of the present invention (B) can be the vinyl-functional organopolysiloxane,, has the organopolysiloxane of the vinyl-functional organic group that is present in the molecule that is." vinyl-functional organic group " as used in this specification is to contain-CH=CH 2The group of base, as-(CH 2) n-CH=CH 2(n is 0～10, particularly 1～5 number) etc.Contain vinylsiloxane (B) (promptly, vinyl-functional organopolysiloxane (B)) for (for example having at least one, 1～500, particularly 1～50, especially 2～40) vinyl and the silicone compounds that contains the oxyalkylene segment of two above siloxane bonds.
Composition of the present invention (B) can be the functionalized organopolysiloxane of (methyl) acrylamide,, has the organopolysiloxane of the functionalized organic group of (methyl) acrylamide that is present in the molecule that is.Term " (methyl) acrylamide " refers to acrylamide or Methacrylamide." the functionalized organic group of (methyl) acrylamide " as used in this specification be contain-NH-C (=O)-CQ=CH 2The group of base, as-(CH 2) n-NH-C (=O)-CQ=CH 2(wherein, Q is hydrogen atom or methyl, and n is 0～10, particularly 1～5 number) etc.The siloxanes (B) that contains (methyl) acrylamido (promptly, the functionalized organopolysiloxane of (methyl) acrylamide (B)) for (for example having at least one, 1～500, particularly 1～50, especially 2～40) (methyl) acrylamido and the silicone compounds that contains the oxyalkylene segment of two above siloxane bonds.
Composition of the present invention (B) can be (methyl) acrylate functional organopolysiloxane,, has the organopolysiloxane of (methyl) acrylate functional organic group that is present in the molecule that is.Term " (methyl) acrylate " refers to acrylate or methacrylic ester." (methyl) acrylate functional organic group " as used in this specification is to contain-Q-O-C (=O) CX=CH 2Group, wherein Q is divalent organic group, for example C 1-20Alkyl is (as C 1-10Alkylidene group etc.), and X be Me or H.Contain (methyl) acrylate-based siloxanes (B) (promptly, (methyl) acrylate functional organopolysiloxane (B)) for (for example having at least one, 1～500, particularly 1～50, especially 2～40) (methyl) is acrylate-based and contain the silicone compounds of the oxyalkylene segment of two above siloxane bonds.
Organopolysiloxane is known in the art, usually by general formula R nSiO (4-n)/2Expression, wherein said organopolysiloxane can comprise " M " (monofunctional) siloxy units (R of any amount 3SiO 0.5), " D " (difunctional) siloxy units (R 2SiO), " T " (trifunctional) siloxy units (RSiO 1.5) or " Q " siloxy units (SiO 2), wherein R is any monovalent organic radical group independently.Thereby these siloxy units can make up in every way and form ring-type, straight or branched structure.The physics of the polymer architecture that is obtained and chemical property can be different.For example, organopolysiloxane can be volatility or low viscosity fluid, high viscosity fluid/rubber cement, elastomerics or rubber and resin.R is any monovalent organic radical group independently, and alternatively, R is the alkyl that contains 1～30 carbon, and alternatively, R is the alkyl that contains 1～30 carbon atom, and perhaps alternatively, R is a methyl.
The organopolysiloxane that can be used as the composition (B) among the present invention is characterised in that, at formula R nSiO (4-n)/2In at least one R group be sulfydryl, vinyl, (methyl) acrylamide or methyl (acrylate) base, perhaps alternatively, at least one R group is to have one to be organo-functional group in sulfydryl, vinyl, (methyl) acrylamide or methyl (acrylate) base and the R group, perhaps alternatively, there is one to be the organo-functional group that also contains sulfydryl, vinyl, (methyl) acrylamide or methyl (acrylate) base in the R group.Organo-functional group and sulfydryl, vinyl, (methyl) acrylamide or methyl (acrylate) functional group may reside on the substituent siloxy units of any R of having, that is, they may reside on any M, D or the T unit.Usually, organo-functional group and sulfydryl, vinyl, (methyl) acrylamide or methyl (acrylate) base exist as the R substituting group on the D siloxy units.
" organo-functional group " as used in this specification is meant the organic group that contains any amount carbon atom, but described group contains the atom outside at least one de-carbon and the hydrogen.The representative example of described organo-functional group comprises amino, amido, sulfonamido, quaternary ammonium group, ether, epoxy group(ing), phenolic group, ester group, carboxyl, ketone group, haloalkyl and aryl, and these are several examples wherein.Alternatively, organo-functional group is the aminofunctional organic group.
When organic functional group was the aminofunctional organic group, the aminofunctional organic group was expressed as R in the formula of this specification sheets N, and shown in the group with following formula :-R 1NHR 2,-R 1NR 2 2Or-R 1NHR 1NHR 2, wherein, each R 1Be bivalent hydrocarbon radical independently with at least 2 carbon atoms, and R 2The alkyl that maybe can have 1～10 carbon atom for hydrogen.Each R 1Be generally alkylidene group with 2～20 carbon atoms.R 1Shown in following group, for example :-CH 2CH 2-,-CH 2CH 2CH 2-,-CH 2CHCH 3-,-CH 2CH 2CH 2CH 2-,-CH 2CH (CH 3) CH 2-,-CH 2CH 2CH 2CH 2CH 2-,-CH 2CH 2CH 2CH 2CH 2CH 2-,-CH 2CH 2CH (CH 3CH 3) CH 2CH 2CH 2-,-CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-and-CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-.Alkyl R 2As above-mentioned be those groups shown in the R.Work as R 2During for alkyl, it typically is methyl.
Some examples of suitable aminofunctional alkyl are:
-CH 2CH 2NH 2,-CH 2CH 2CH 2NH 2,-CH 2CHCH 3NH ,-CH 2CH 2CH 2CH 2NH 2,-CH 2CH 2CH 2CH 2CH 2NH 2,-CH 2CH 2CH 2CH 2CH 2CH 2NH 2,-CH 2CH 2NHCH 3,-CH 2CH 2CH 2NHCH 3,-CH 2(CH 3) CHCH 2NHCH 3,-CH 2CH 2CH 2CH 2NHCH 3,-CH 2CH 2NHCH 2CH 2NH 2,-CH 2CH 2CH 2NHCH 2CH 2CH 2NH 2,-CH 2CH 2CH 2CH 2NHCH 2CH 2CH 2CH 2NH 2,-CH 2CH 2NHCH 2CH 2NHCH 3,-CH 2CH 2CH 2NHCH 2CH 2CH 2NHCH 3,-CH 2CH 2CH 2CH 2NHCH 2CH 2CH 2CH 2NHCH 3With-CH 2CH 2NHCH 2CH 2NHCH 2CH 2CH 2CH 3Usually, amido functional group is-CH 2CH 2CH 2NH 2
Hydrosulphonyl functionalized organic group is expressed as R in the formula of this specification sheets S, and shown in the group with following formula :-R 1SR 2, R wherein 1And R 2Respectively for as defined above.Mercapto functional group is shown below :-CH 2CH 2CH 2SH ,-CH 2CHCH 3SH ,-CH 2CH 2CH 2CH 2SH ,-CH 2CH 2CH 2CH 2CH 2SH ,-CH 2CH 2CH 2CH 2CH 2CH 2SH ,-CH 2CH 2SCH 3Usually, mercapto functional group is-CH 2CH 2CH 2SH.
The vinyl-functional organic group is expressed as R in the formula of this specification sheets VThe vinyl-functional organic group is shown below :-CH=CH 2,-CH 2CH 2CH 2-CH=CH 2,-CH 2CHCH 3-CH=CH 2,-CH 2CH 2CH 2CH 2-CH=CH 2,-CH 2CH 2CH 2CH 2CH 2-CH=CH 2,-CH 2CH 2CH 2CH 2CH 2CH 2-CH=CH 2Usually, vinyl-functional is-CH=CH 2
The functionalized organic group of (methyl) acrylamide is expressed as R in the formula of this specification sheets AM, and shown in the group with following formula :-R 1-NH-C (=O)-CQ=CH 2Group (wherein, R 1For having the bivalent hydrocarbon radical of at least 2 carbon atoms, and Q is hydrogen atom or methyl).(methyl) acrylamide functional group is shown below :-CH 2CH 2CH 2-NH-C (=O)-CH=CH 2,-CH 2CH 2CH 2-NH-C (=O)-C (CH 3)=CH 2,-CH 2CHCH 3-NH-C (=O)-CH=CH 2,-CH 2CHCH 3-NH-C (=O)-C (CH 3)=CH 2,-CH 2CH 2CH 2CH 2-NH-C (=O)-C (CH 3)=CH 2,-CH 2CH 2CH 2CH 2-NH-C (=O)-C (CH 3)=CH 2Usually, (methyl) acrylamide functional group is-CH 2CH 2CH 2-NH-C (=O)-C (CH 3)=CH 2
(methyl) acrylate functional organic group is expressed as R in the formula of this specification sheets MA, and shown in the group with following formula :-R 1-O-C (=O)-CQ=CH 2Group (wherein, R 1For having the bivalent hydrocarbon radical of at least 2 carbon atoms, and Q is hydrogen atom or methyl).(methyl) acrylamide functional group is shown below :-CH 2CH 2CH 2-O-C (=O)-CH=CH 2,-CH 2CH 2CH 2-O-C (=O)-C (CH 3)=CH 2,-CH 2CHCH 3-O-C (=O)-CH=CH 2,-CH 2CHCH 3-O-C (=O)-C (CH 3)=CH 2,-CH 2CH 2CH 2CH 2-O-C (=O)-C (CH 3)=CH 2,-CH 2CH 2CH 2CH 2-O-C (=O)-C (CH 3)=CH 2Usually, (methyl) acrylate-functional groups is-CH 2CH 2CH 2-O-C (=O)-C (CH 3)=CH 2
In a preferred implementation, functionalized organopolysiloxane (being appointed as B ') comprises the siloxy units with following average formula:
(R 2SiO) a(RR NSiO) b(RR FOSiO) c
Wherein: a is 0～4000, is 1～1000 alternatively, is 2～400 alternatively,
B is 0～1000, is 1～100 alternatively, is 2～50 alternatively,
C is 1～1000, is 2～100 alternatively, is 3～50 alternatively;
R is any monovalent organic radical group independently,
Alternatively, R is the hydrocarbon that contains 1～30 carbon atom,
Alternatively, R is the univalent alkyl that contains 1～12 carbon, or
Alternatively, R is a methyl;
R NBe monovalence aminofunctional organic group as defined above,
R FORespectively be the hydrosulphonyl functionalized organic group (R of monovalence as defined above S), monovalence vinyl-functional organic group (R V), the functionalized organic group (R of monovalence (methyl) acrylamide AM) or monovalence (methyl) acrylate functional organic group (R MA).
R NBase can be R F, R wherein FCan be monovalence organo-functional group, for example hydroxyl, amino, amido, sulfonamido, quaternary ammonium group, ether, epoxy group(ing), phenolic group, ester group, carboxyl, ketone group, haloalkyl and aryl as defined above.For example, functionalized organopolysiloxane can comprise the siloxy units with following average formula:
(R 2SiO) a(RR FSiO) b(RR FOSiO) c
Wherein, group and subscript (that is, a, b and c) are with defined above identical.R FOGroup is the hydrosulphonyl functionalized organic group (R of monovalence S), monovalence vinyl-functional organic group (R V), the functionalized organic group (R of monovalence (methyl) acrylamide AM) or monovalence (methyl) acrylate functional organic group (R MA).
Organopolysiloxane (B ') can be with hydrogen atom end-blocking (forming silanol group) on the terminal siloxy units of terpolymer, also can be to contain alkyl-blocked (the forming alkoxyl group on the terminal siloxy units of terpolymer) of 1～30 carbon atom.When using alkyl, alkyl can be the straight or branched alkyl that contains 1～30 carbon atom, and alternatively, alkyl can be the chain alkyl with 4～20 (being 8～20 alternatively) carbon atoms, for example stearyl etc.Alternatively, organopolysiloxane can be with the trimethyl silyl end-blocking.
The organopolysiloxane of this preferred implementation (B ') can for example represent by following average formula:
Figure BDA0000050383680000141
Wherein: a is 0～4000, is 1～1000 alternatively, is 2～400 alternatively,
B is 0～1000, is 1～100 alternatively, is 2～50 alternatively,
C is 1～1000, is 2～100 alternatively, is 3～50 alternatively;
And R ' is H, have the alkyl or the Me of 1～40 carbon atom 3Si.
The amino-mercapto functional organopolysiloxane terpolymer of this preferred implementation (B ') can be by being used for preparing the organopolysiloxane terpolymer that contains amino and/or mercapto functional group any known technology of this area prepare.Usually, organopolysiloxane (B ') is by the aminofunctional organoalkoxysilane shown in following general reaction formula, hydrosulphonyl functionalized silane monomer with have alkoxyl group or the polycondensation of the organopolysiloxane of silanol end group prepares.
Figure BDA0000050383680000151
The condensation of organopolysiloxane is being known in the art, and comes catalysis by adding as highly basic such as alkali metal hydroxide or tin compounds usually.Alternatively, can adopt the copolymerization of functionalized cyclosiloxane.
The polysiloxane (B) that contains vinyl has for example following formula:
Figure BDA0000050383680000152
Wherein, R 1Be methyl, methoxyl group, phenyl or hydroxyl,
R 2Be methyl, methoxyl group, phenyl or hydroxyl,
R 3Be methyl, methoxyl group, phenyl or hydroxyl,
R ' is hydrogen atom, have the alkyl or the Me of 1～40 carbon atom 3Si or H,
B is the divalent saturated hydrocarbon base with 1～10 carbon atom that can separate with one or two ehter bond,
C is hydroxyl, amino, amido, sulfonamido, quaternary ammonium group, ether, epoxy group(ing), phenolic group, ester group, carboxyl, ketone group, haloalkyl or aryl,
A, b and c are the integer of expression repeating unit quantity, and a is 1～4000, for example 2～2000, and b is 0～1000, is preferably 1～800, c is 0～1000, is preferably 1～800.
The example of polysiloxane (B) that contains vinyl is as follows.
Figure BDA0000050383680000153
Wherein, as R 1Identical with definition above Deng group with following target definition.
The C of functional group is preferably amino (that is, the siloxanes (B) that contains vinyl is the vinyl aminosiloxane) especially.Amino have significantly improve with the other materials that constitutes makeup and with the effect of the affinity of human body skin.
The organopolysiloxane of above-mentioned preferred implementation (B ') can represent by for example following average formula:
Figure BDA0000050383680000161
Wherein: a is 0～4000, is 1～1000 alternatively, is 2～400 alternatively,
B is 0～1000, is 1～100 alternatively, is 2～50 alternatively,
C is 1～1000, is 2～100 alternatively, is 3～50 alternatively;
And R ' is H, have the alkyl or the Me of 1～40 carbon atom 3Si.
The vinyl aminofunctional organopolysiloxane terpolymer of this preferred implementation (B ') can be by being used for preparing the organopolysiloxane terpolymer that contains amino and/or vinyl-functional any known technology of this area prepare.Usually, for example shown in following general reaction formula, organopolysiloxane (B ') by in the presence of end-capping reagent (as hexamethyldisiloxane), making aminofunctional organoalkoxysilane, 2,4,6,8-tetramethyl--2,4,6,8-tetrem thiazolinyl cyclotetrasiloxane, octamethylcyclotetrasiloxane equilibrium polymerization (equilibration polymerization) and prepare.
Figure BDA0000050383680000162
The organopolysiloxane of balance preparation is being known in the art, and comes catalysis by adding as strong acid such as alkali metal hydroxide or sulfonic acid or highly basic usually.Alternatively, can adopt the copolymerization of functionalized organoalkoxysilane and silanol stopped polydimethylsiloxane.
Usually, the functionalized organopolysiloxane of (methyl) acrylamide can be by preparing aminofunctional organopolysiloxane and the reaction of (methyl) acrylic anhydride.In reaction, amino (NH 2) be converted into (methyl) acrylamido ((NH-C (=O)-CQ=CH 2(wherein Q is hydrogen atom or methyl)).For example, the functionalized organopolysiloxane of (methyl) acrylamide can have ≡ Si-(CH 2) n-NH-C (=O)-CQ=CH 2Base (wherein, Q is hydrogen atom or methyl, and n is 0～10, particularly 1～5 number).
Usually, (methyl) acrylate functional organopolysiloxane can be by preparing functionalized organopolysiloxane of carbinol (carbinol) and the reaction of (methyl) acrylic anhydride.In reaction, utilize the carbinol functionalized silicone, former alcohol radical (OH) be converted into (methyl) acrylate-based ((O-C (=O)-CQ=CH 2(wherein Q is hydrogen atom or methyl)).For example, methacrylate functionalized organopolysiloxane can have ≡ Si-(CH 2) n-O-C (=O)-CQ=CH 2Base (wherein, Q is hydrogen atom or methyl, and n is 0～10, particularly 1～5 number).
The weight-average molecular weight of fluoropolymer can be 2,000～5,000,000, particularly 3,000～5,000,000, especially 10,000～1,000,000.The weight-average molecular weight of fluoropolymer (according to polystyrene conversion) can be passed through GPC (gel permeation chromatography) and determine.
In fluoropolymer, repeating unit can be in and be different from the position shown in this chemical formula, and fluoropolymer can be unregulated polymer or segmented copolymer.
Fluoropolymer of the present invention can be produced by mass polymerization, solution polymerization and letex polymerization.
In mass polymerization, adopt following method, wherein, in the mixture of monomer and functionalized organopolysiloxane, feed nitrogen, add polymerization starter then, and stir the mixture a few hours (2 hours～15 hours) are so that its polymerization in 30 ℃～80 ℃ scopes.The example of polymerization starter comprises Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, lauroyl peroxide, Cumene Hydroperoxide 80, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester and di-isopropyl peroxydicarbonate.With respect to 100 weight parts monomers, the consumption of polymerization starter can be 0.01 weight part～20 weight parts, for example 0.01 weight part～10 weight parts.
In solution polymerization, the mixture of monomer and functionalized organopolysiloxane is dissolved in the suitable organic solvent, and described material may be dissolved in the described solvent and is inert for described solvent, then with to aforementioned similar mode polymerization.The example of organic solvent comprises varsol, esters solvent, ketones solvent, alcoholic solvent, type siloxane solvent and contains fluorous solvent.Organic solvent is inert and solubilized monomer for monomer, the example comprises acetone, chloroform, HCHC225, Virahol, pentane, hexane, heptane, octane, hexanaphthene, benzene,toluene,xylene, sherwood oil, tetrahydrofuran (THF), 1,4-dioxane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butylacetate, 1,1,2,2-tetrachloroethane, 1, trieline, tetrachloroethylene, C2Cl4F2 and Refrigerant R 113.With respect to 100 weight parts monomers total amounts, the consumption of organic solvent can be 50 weight parts～2,000 weight parts, for example 50 weight parts～1,000 weight part.
In solution polymerization, can use following method: in the presence of polymerization starter, monomer is dissolved in the organic solvent, uses nitrogen replacement atmosphere, in heating (for example 30 ℃～120 ℃ temperature), stirred the mixture 1 hour～10 hours.
In letex polymerization, in water, after the emulsification, carry out polymerization in the same manner as described above at the mixture that uses suitable emulsifying agent with monomer and functionalized organopolysiloxane.In some combinations of monomer (a)～(c) and functionalized organopolysiloxane, monomer and the consistency of functionalized organopolysiloxane in water cause copolymerization relatively poor than missionary society.In this case, adopt suitable solubility promoter such as adding as two pure and mild alcohol and/or low molecular weight monomers method with the consistency of raising mixture.Hydrophobic group in the emulsifying agent that uses in the letex polymerization can be any in hydrocarbon type, siliceous type and the fluorine-containing type.Ionic as for hydrophilic radical can be used any nonionic hydrophilic radical, anionic hydrophilic group, cationic hydrophilic groups and both sexes hydrophilic radical.As the letex polymerization polymerization starter, for example (for example can use water soluble starter, benzoyl peroxide, lauroyl peroxide, t-butylperoxyl benzoate, 1-hydroxy-cyclohexyl hydroperoxide, peroxidation 3-carboxyl propionyl, acetyl peroxide, azo diisobutyl amidine dihydrochloride, Diisopropyl azodicarboxylate, sodium peroxide, Potassium Persulphate and ammonium persulphate) and oil-soluble initiator (for example, Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, lauroyl peroxide, Cumene Hydroperoxide 80, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester and di-isopropyl peroxydicarbonate).With respect to 100 weight parts monomers, the consumption of polymerization starter can be 0.01 weight part～10 weight parts.
In letex polymerization, can use following method: in the presence of polymerization starter and emulsifying agent in water emulsified monomer, use nitrogen replacement atmosphere, for example in the temperature of 30 ℃～120 ℃ (for example 50 ℃～80 ℃), in stirring polymerization down 1 hour～10 hours.
When monomer is incomplete when compatible, preferably in these monomers, add to make its fully compatible compatibilizing agent (for example water-miscible organic solvent and low molecular weight monomers).By adding compatibilizing agent, can improve emulsifying property and polymerizability.
The example of water-miscible organic solvent comprises acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.With respect to 100 weight parts waters, the consumption of water-miscible organic solvent can be 1 weight part～50 weight parts, for example 10 weight parts～40 weight parts.The example of low molecular weight monomers is methyl methacrylate, methyl propenoic acid glycidyl base ester, methacrylic acid 2,2, the 2-trifluoro ethyl ester.With respect to the monomer total amount of 100 weight parts, the consumption of low molecular weight monomers can be 1 weight part～50 weight parts, for example 10 weight parts～40 weight parts.
For emulsifying agent, can use as various emulsifying agents such as anionic emulsifier, cationic emulsifier and nonionic emulsifying agents, its consumption is 0.5 weight part～20 weight parts with respect to 100 weight parts monomers.The emulsifying agent that uses in the letex polymerization can have hydrophobic group (it can be hydrocarbon, siloxanes or fluorochemicals) and hydrophilic radical (it can be nonionic, anionic property, cationic or amphoteric).For obtain simultaneously emulsion stability and to skin safety, the combination of preferred anionic emulsifying agent and nonionic emulsifying agent.With respect to the total amount of anionic emulsifier and nonionic emulsifying agent, the amount of anionic emulsifier is 5 weight %～80 weight %, is preferably 10 weight %～60 weight %.Preferably, anionic emulsifier is polyxyethylated (preferred C 1～C 30Alkyl) ether sulfate, nonionic emulsifying agent are lipid acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, polyoxyethylene hardened castor oil and/or polyoxyethylene fatty acid sorbitol ester.
For obtaining to have the high polymers solids content and have very fine, stable particulate aqueous polymer dispersion, it is desirable to by use can apply strong shearing can emulsifying device (for example, high-pressure homogenizer and ultrasonic homogenizer) mixture of monomer and functionalized organopolysiloxane is dispersed in the water with the fine granular of preparation mixture, carry out polymerization then.
The fluorosilicone reaction product of monomer (A) and organopolysiloxane (B) can prepare by any reaction method of described monomeric polymeric that carries out well known in the art.Preferably, can the method according to this invention prepare fluorosilicone, described method comprises:
I) by polyreaction, preferred Raolical polymerizable, make
(A) monomer, described monomer comprises the fluorochemical monomer shown in the following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein, X is hydrogen atom, any monovalent organic radical group or halogen atom,
Y is-O-or-NH-,
Z is Direct Bonding or divalent organic group, and
Rf is the fluoroalkyl with 8～12 carbon atoms,
{。##.##1},
(B) functionalized organopolysiloxane
There is reaction down.
Composition in the described method (A) and (B) are with mentioned above identical.
Described method can also be carried out in the presence of polar organic solvent.Polar organic solvent can be one or more alcohol, ketone or the ester solvent that is selected from butanols, the trimethyl carbinol, Virahol, butyl cellosolve, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, butylacetate or the ethyl acetate, and/or reaches wherein one or more mixture as aromatic hydrocarbon such as dimethylbenzene, toluene or trimethylbenzenes.
The initiator of Raolical polymerizable can be any compound that is used to cause free radical reaction well known in the art, for example organo-peroxide or azo-compound.Representational limiting examples is: as Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) azo-compounds such as (AIVN), as superoxide such as benzoyl peroxides.Polymerization temperature is generally 50 ℃～120 ℃.
Alternatively, can use following emulsion polymerization technology to obtain polymeric reaction product, in described technology, with all the components polymerization in the presence of water, tensio-active agent and polymerization starter.
The fluorosilicone reaction product can contain the monomer (A) and the organopolysiloxane (B) of various ratios, its by composition (A) and (B) separately amount control.Fluorosilicone can contain the monomer (A) of 5 weight %～99.9 weight %, preferred 10 weight %～95 weight % and the organopolysiloxane (B) of 0.1 weight %～95 weight %, preferred 5 weight %～90 weight %, and condition is that (A) and weight % summation (B) are 100%.Have at high proportion that the fluorosilicone product of organopolysiloxane can provide higher substantivity to fibre substrate, or provide better pleasant softness for treated material.Having at high proportion, the polymerisate of fluorochemical monomer can provide maximum hydrophobicity and oleophobic property.
The fluorosilicone reaction product obtains as solution usually.Can be by evaporating solvent with its separation.When using as oil-repellent agent, requiring the fluorosilicone reaction product usually is liquid form, and the solution that obtains by reaction can be diluted as the solution that is fit to be applied to textiles usually.Alternatively, the fluorosilicone reaction product can be diluted in different used for textiles solvents, for example dilutes in the high boiling point polar organic solvent.Alternatively, the fluorosilicone reaction product can be by mixing and emulsification with water and emulsifying agent (as cats product and/or nonionic or anion surfactant).Can be emulsified in emulsification or polymerisate solution (optionally remove and desolvate) separate fluorine siloxane reaction product before.If polymerisate obtains by letex polymerization, then use the emulsion of dilution as required usually, and need not the separation of polymeric product.
The solution of fluorosilicone reaction product or emulsion can be applied to as fibre substrates such as textiless by any currently known methods that uses the liquid treatment textiles.The concentration of fluorosilicone reaction product in being applied to the solution of textiles is for example 0.5 weight %～20 weight %, alternatively, can be 1 weight %～5 weight %.When textiles is fabric, fabric can be immersed in the described solution, also can use described solution to fill or the sprinkling fabric.Treated textiles is dried, and preferably heats at for example 100 ℃～200 ℃, to strengthen its oil repellent.
Alternatively, can pass through washing process,, the fluorosilicone reaction product is applied to textiles as in laundry applications or dry-cleaning process.
Processed textiles is generally fabric, comprises the fabric and the carpet of braiding, knitting and supatex fabric, clothing form, but also can be fiber, yarn or middle textile product (as sliver or rove).Textile material can be as cotton or hair wait natural fiber, as viscose rayon or sky regenerated fibers such as (lyocell) or as synthon such as polyester, polymeric amide or acrylic fibers, also can be fibre blend, as the mixture of natural fiber and synthon.Polymerisate of the present invention is being given as effective especially aspect cellulosic fibre oleophobic properties such as cotton or artificial silk and the oil repellent.Method of the present invention is also given textiles hydrophobicity and water repellency usually.The fabric treating of using polymerisate of the present invention to carry out can be given the fabric oil repellent, also can give simultaneously than untreated fabric and obtain improvement on the sense of touch, also can give than the fabric that uses known fluoropolymer textile treating agent to handle and obtain improvement on the sense of touch.
Alternatively, fibre substrate also can be a leather.The different steps that polymerisate can be handled at leather is applied to leather with the form of the aqueous solution or emulsion, for example in wet type end treatment process or on leather in the photoreduction process, to give leather hydrophobic and oleophobic property.
Alternatively, fibre substrate also can be a paper.Polymerisate can be applied to the premolding paper, perhaps is applied to each stage of papermaking, for example in the paper dryer process.
Surface treatment agent of the present invention is preferably solution, emulsion or aerosol form.Surface treatment agent comprises fluoropolymer and medium (particularly liquid medium, for example organic solvent and/or water) usually.The concentration of fluoropolymer in surface treatment agent can be 0.1 weight %～50 weight % for example.
Surface treatment agent can be applied to matrix to be processed by known program.Can carry out using of surface treatment agent by immersing, spray and being coated with.Usually, with an organic solvent or water dilution surface treatment agent, make its surface that adheres to matrix by known program (as dip-coating, spraying and foam coating), and dry.In case of necessity, treatment solution is used with suitable linking agent, solidify then.Also can in surface treatment agent, add mothproofing agent, tenderizer, biocide, fire retardant, static inhibitor, coating fixing agent, anti-creasing agent etc.With respect to treatment solution, can be 0.01 weight %～10 weight % (particularly for dip-coating) with the concentration of fluorochemicals in the treatment solution that matrix contacts, for example be 0.05 weight %～10 weight % (particularly for spraying).
Preferably, the matrix of using surface treatment agent of the present invention (for example water-repellent oil-repellent agent) to handle is textiles.Textiles comprises various examples.The example of textiles comprises: the natural fiber in animal or plant source, as cotton, fiber crops, hair and silk; Synthon are as polymeric amide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; Semi-synthetic fibre is as artificial silk and rhodia; Inorganic fibre is as glass fibre, carbon fiber and fibrous magnesium silicate; Mixture with these fibers.
Textiles can be for as any forms such as fiber, yarn and fabrics.
Term " processing " is meant by dipping, sprinkling or coating etc. treatment application in matrix.By handling, can be penetrated into matrix inside as the fluoropolymer of the activeconstituents of treatment agent, perhaps can stick on the stromal surface.
Embodiment
Following preparation example and embodiment further describe the present invention, but should not think that they limit the scope of the invention.Unless point out in addition, otherwise all umbers among the embodiment and per-cent all are based on weight, and all measuring results are all in about 23 ℃ of acquisitions.
Spray water repellency test (JIS-L-1092)
Spray the water repellency test according to JIS-L-1092.The spray water repellency is by water repellency numbering expression (as shown in following table 1).
Using volume is the glass funnel of 250ml at least and the nozzle that can spray 250ml water in 20 seconds～30 seconds.Sample stent is that diameter is the through metal of 15cm.Prepare the test specimen of three chip sizes, and described sheet material is installed on the test specimen maintenance support, so that sheet material does not have gauffer for about 20cm * 20cm.The center of spray thrower is arranged on the top at sheet material center.Flood chamber warm water (250mL) in glass funnel, and be sprayed on the test specimen sheet (continuing 25 seconds～30 seconds times).To keep support to take off from pedestal, one side catch the face down that makes that keeps support, and use hard thing to impact the other side gently.To keep support to be further rotated 180 °, and repeat same program so that unnecessary water droplet drippage.Moistening test specimen and the moistening reference standard thing that is rated 0,50,70,80,90 and 100 fen by the relatively poor order to the water repellency excellence of water repellency are compared.The result is available from the mean value of three measurements.
Table 1
Oil repellent test (according to AATCC testing method 118-1992)
It is that 21 ℃, humidity are in 65% the controlled thermohygrostat at least 4 hours that treated fabric is stored in temperature.Use also in the test fluid (as shown in table 3) of 21 ℃ of storages.In temperature is that 21 ℃, humidity are to test in 65% the air-conditioned room.By micropipet 5 test fluid gently are dropped on the fabric, one amount is 50 μ L.If leave standstill after 30 seconds and still remain with 4 or 5 on the fabric, then test fluid is by test.Oil repellent is by dividing value representation by the maximum of test fluid of test.Oil repellent is be evaluated as 9 grades, they by relatively poor rank to excellent level other in proper order for do not pass through, 1,2,3,4,5,6,7 and 8.
Table 2 oil repellent test fluid
Figure BDA0000050383680000231
The washing resistance of water and oil repellant
According to JIS L-0217-103 method, repetitive scrubbing ten times, 20 times or 30 times is estimated water and oil repellant (HL10, HL20 or HL30) then.HL0 is meant the evaluation of carrying out after the not washing.
Sense of touch
Before washing, estimate the sense of touch of treated fabric.According to following standard, determine sense of touch by touching with hand.
Excellent: significantly more soft than untreated fabric
Very good: more soft than untreated fabric
Well: have identical flexibility with untreated fabric
Difference: harder than untreated fabric
Synthesizing of amino mercapto functionalized silicone:
Siloxanes A
In three mouthfuls of round-bottomed flasks that are equipped with prolong, overhead type agitator and thermopair, add the first silanol stopped polydimethylsiloxane (323g, about 900), the second silanol stopped polydimethylsiloxane (380g, Mn: about 300), sulfydryl propyl group methyl dimethoxysilane (230g), aminopropyl methyldiethoxysilane (27g), trimethylethoxysilane (42g), hydrated barta (0.62g) and sodium orthophosphate (0.25g) Mn:.This reaction mixture is heated to 75 ℃, and kept 3 hours in this temperature.Removed volatile matter in 4 hours in 75 ℃ of decompressions (200 millibars) then, to obtain the amino mercapto siloxanes.
Described in the physics of amino mercapto siloxanes and textural property such as the following table:
Table 3
Preparation example 1
In the autoclave of 1L, add CF 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOCH=CH 2(mean value of n=2.0) (17FA and 21FA) (184g), stearyl acrylate base ester (StA) (23.1g), N hydroxymethyl acrylamide (NMA) (6.4g), methacrylic acid 3-chloro-2 hydroxy propyl esters (CHPMA) (1.5g), amino mercapto siloxanes (siloxanes A) (28.4g), pure water (500g), tripropylene glycol (79.4g), alkyl trimethyl ammonium chloride (3.7g), single palmitinic acid sorbitan ester (4.5g), polyoxyethylene oleyl ether (4.5g) and polyoxyethylene lauryl ether (18.0g), and 60 ℃ under stirring by ultrasonic emulsification 15 minutes.After using the atmosphere in the nitrogen replacement autoclave, inject vinylchlorid (VCM) (67g).Then, add 2,2 '-two (2-amidine propane) dihydrochlorides (3.6g) of azo, and reacted 5 hours at 60 ℃, obtain having the aqueous liquid dispersion of the polymkeric substance of following formula:
Figure BDA0000050383680000241
R v＝C8F17CH2CH2-，C10F21CH2CH2-，C18H37
Wherein, x, y and z are 3: 22: 70 number for making unitary mol ratio, and (a+b), c and the d number that equals 66: 25: 9 for the weight ratio that makes (17FA+21FA): VCM: StA.In following formula, come from N hydroxymethyl acrylamide and be omitted, because N hydroxymethyl acrylamide (the repeating unit total amount with respect to 17FA, 21FA, VCM, StA, NMA and CHPMA is 2 weight %) and the amount of methacrylic acid 3-chloro-2-hydroxy-propyl ester (is 0.5 weight % with respect to the repeating unit total amount) in polymkeric substance are seldom with the repeating unit that is derived from methacrylic acid 3-chloro-2-hydroxy propyl ester.This chemical formula shows, amine (Si-CH 2CH 2CH 2NH 2) formed Michael (Michael) affixture of (methyl) acrylate, i.e. Si-CH 2CH 2CH 2NH-CH 2CH 2C (=O) O-R v(R wherein vBe CF 3CF 2-(CF 2CF 2) n-CH 2CH 2-Ji or stearyl), but this amine also may not form the Michael addition thing of this (methyl) acrylate.
Preparation example 2
In the autoclave of 1L, add CF 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(mean value of n=3.2) (17FA and 21FA) (184g), stearyl acrylate ester (StA) (23.1g), N hydroxymethyl acrylamide (6.4g), methacrylic acid 3-chloro-2 hydroxy propyl esters (1.5g), amino mercapto siloxanes (siloxanes A) (14.2g), pure water (500g), tripropylene glycol (79.4g), alkyl trimethyl ammonium chloride (3.7g), single palmitinic acid sorbitan ester (4.5g), polyoxyethylene oleyl ether (4.5g) and polyoxyethylene lauryl ether (18.0g), and 60 ℃ under stirring by ultrasonic emulsification 15 minutes.After using the atmosphere in the nitrogen replacement autoclave, inject vinylchlorid (VCM) (67g).Then, add 2,2 '-two (2-amidine propane) dihydrochlorides (3.6g) of azo, and reacted 5 hours at 60 ℃, obtain having the aqueous liquid dispersion of the polymkeric substance of following formula:
Figure BDA0000050383680000251
R v＝C8F17CH2CH2-，C10F21CH2CH2-，C18H37
Wherein, x, y and z are 3: 22: 70 number for making unitary mol ratio, and (a+b), c and the d number that equals 66: 25: 9 for the weight ratio that makes (17FA+21FA): VCM: StA.In following formula, the repeating unit that comes from N hydroxymethyl acrylamide and methacrylic acid 3-chloro-2-hydroxy propyl ester is omitted, because N hydroxymethyl acrylamide (the repeating unit total amount with respect to 17FA, 21FA, VCM, StA, NMA and CHPMA is 2 weight %) and the amount of methacrylic acid 3-chloro-2-hydroxy-propyl ester (is 0.5 weight % with respect to the repeating unit total amount) in polymkeric substance are seldom.This chemical formula shows, amine (Si-CH 2CH 2CH 2NH 2) formed the Michael addition thing of (methyl) acrylate, i.e. Si-CH 2CH 2CH 2NH-CH 2C (R ') HC (=O) O-R v(R wherein vBe CF 3CF 2-(CF 2CF 2) n-CH 2CH 2-Ji, stearyl or 3-chloro-2 hydroxypropyls, and R ' is hydrogen atom or methyl), but this amine also may not form the Michael addition thing of this (methyl) acrylate.
Comparative preparation example 1
In the autoclave of 1L, add CF 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(mean value of n=3.2) (17FA and 21FA) (204g), stearyl acrylate base ester (StA) (25.6g), N hydroxymethyl acrylamide (6.4g), methacrylic acid 3-chloro-2-hydroxy propyl ester (1.5g), pure water (486g), tripropylene glycol (88g), alkyl trimethyl ammonium chloride (3.4g), sorbitan monopalmitate (4.6g), polyoxyethylene oleyl ether (4.9g) and polyoxyethylene lauryl ether (20.0g), and 60 ℃ under stirring by ultrasonic emulsification 15 minutes.After using the atmosphere in the nitrogen replacement autoclave, inject vinylchlorid (VCM) (67g).Then, add 2,2 '-two (2-amidine propane) dihydrochlorides (2.2g) of azo, and reacted 5 hours at 60 ℃, obtain having the aqueous liquid dispersion of the polymkeric substance of following formula:
Figure BDA0000050383680000261
Wherein, (a+b), c and the d number that equals 66: 25: 9 for the weight ratio that makes (17FA+21FA): VCM: StA.In following formula, the repeating unit that comes from N hydroxymethyl acrylamide and methacrylic acid 3-chloro-2-hydroxy propyl ester is omitted, because N hydroxymethyl acrylamide (the repeating unit total amount with respect to 17FA, 21FA, VCM, StA, NMA and CHPMA is 2 weight %) and the amount of methacrylic acid 3-chloro-2-hydroxy-propyl ester (is 0.5 weight % with respect to the repeating unit total amount) in polymkeric substance are seldom.
Comparative preparation example 2
In the flask of 300cc, add CF 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (Cl)=CH 2(mean value of n=1.0) (9FClA) (33g), stearyl acrylate ester (StA) (18g), N hydroxymethyl acrylamide (11g), methacrylic acid 3-chloro-2 hydroxy propyl esters (0.53g), amino mercapto siloxanes (siloxanes A) (2.5g), pure water (66.1g), tripropylene glycol (14.4g), acetate (0.11g), polyoxy alkyl oxide (0.7g), polyoxyethylene mono lauric acid dehydration sorbitol ester (2.8g) and stearyl trimethyl ammonium chloride (2.1g), and 60 ℃ under stirring by ultrasonic emulsification 15 minutes.After the atmosphere of using the nitrogen replacement flask, add 2,2 '-two (2-amidine propane) dihydrochlorides (0.3g) of azo, and reacted 3 hours at 60 ℃, obtain having the aqueous liquid dispersion of the polymkeric substance of following formula:
Figure BDA0000050383680000262
Wherein, x, y and z are 3: 22: 70 number for making unitary mol ratio, and a and the c number that equals 66: 34 for the weight ratio that makes 9FClA: StA.In following formula, the repeating unit that comes from N hydroxymethyl acrylamide and methacrylic acid 3-chloro-2-hydroxy propyl ester is omitted, because N hydroxymethyl acrylamide (the repeating unit total amount with respect to 9FClA, StA, NMA and CHPMA is 2 weight %) and the amount of methacrylic acid 3-chloro-2-hydroxy propyl ester (is 0.5 weight % with respect to the repeating unit total amount) in polymkeric substance are seldom.This chemical formula shows, amine (Si-CH 2CH 2CH 2NH 2) formed the Michael addition thing of (methyl) acrylate, i.e. Si-CH 2CH 2CH 2NH-CH 2C (R ') HC (=O) O-R v(R wherein vBe CF 3CF 2-(CF 2CF 2) n-CH 2CH 2-Ji, stearyl or 3-chloro-2 hydroxypropyls, and R ' is hydrogen atom, methyl or chlorine atom), but this amine also may not form the Michael addition thing of this (methyl) acrylate.
Comparative preparation example 3
In comparative preparation example 2, add amino modified silicone oil (having following formula) in the prepared aqueous liquid dispersion (15g) (by Dow Corning ﹠amp; Toray silicone Co., the SF8417 that Ltd. makes) (0.23g), and stir 1 hour to obtain aqueous liquid dispersion.
Figure BDA0000050383680000271
Comparative preparation example 4
In comparative preparation example 2, add amino modified silicone oil in the prepared aqueous liquid dispersion (15g) (by DowCorning ﹠amp; Toray Silicone Co., the SF8417 that Ltd. makes) (0.46g), and stir 1 hour to obtain aqueous liquid dispersion.
Embodiment 1
Use the prepared waterborne liquid (4.8g) of pure water dilution preparation example 1, with preparation test fluid (100g).(510mm * 205mm) immerse this test fluid makes it pass through rolling machine, and handles 2 minutes in pin tenter in 160 ℃ with a slice nylon test fabric.Cut this test fabric then so that three three/a slices (size that has 170mm * 205mm separately) to be provided.Three three/a slice fabrics are respectively applied for do not wash, wash ten times and wash 20 times.Fabric is sprayed water repellency test, oil repellent test and sense of touch test.In the above described manner, ((510mm * 205mm) repeats identical program for 510mm * 205mm) and the cotton test fabric of a slice to a slice PET test fabric.The result is as shown in table 4.
Embodiment 2
With the prepared polymkeric substance of the mode Processing of Preparation example identical 2, spray water repellency test, oil repellent test and sense of touch test then with embodiment 1.The result is as shown in table 4.
Comparative example 1
Handle the prepared polymkeric substance of comparative preparation example 1 in the mode identical, spray water repellency test, oil repellent test and sense of touch test then with embodiment 1.The result is as shown in table 5.
Comparative example 2
Handle the prepared polymkeric substance of comparative preparation example 2 in the mode identical, spray water repellency test, oil repellent test and sense of touch test then with embodiment 1.The result is as shown in table 5.
Comparative example 3
Handle the prepared polymkeric substance of comparative preparation example 3 in the mode identical, spray water repellency test, oil repellent test and sense of touch test then with embodiment 1.The result is as shown in table 5.
Comparative example 4
Handle the prepared polymkeric substance of comparative preparation example 4 in the mode identical, spray water repellency test, oil repellent test and sense of touch test then with embodiment 1.The result is as shown in table 5.
Table 4
Figure BDA0000050383680000281
Table 5
Figure BDA0000050383680000291

Claims (26)

1. fluoropolymer, described fluoropolymer comprises:
(A) monomer, described monomer comprises:
(a) fluorochemical monomer of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein, X is hydrogen atom, any monovalent organic radical group or halogen atom,
Y is-O-or-NH-,
Z is Direct Bonding or divalent organic group, and
Rf be have 8～12 carbon atoms fluoroalkyl and
(B) be selected from least a functionalized organopolysiloxane in the group of forming by hydrosulphonyl functionalized organopolysiloxane, vinyl-functional organopolysiloxane, the functionalized organopolysiloxane of (methyl) acrylamide and (methyl) acrylate functional organopolysiloxane.
2. fluoropolymer as claimed in claim 1, wherein, described fluorochemical monomer (a) is the acrylate of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf (I)
Wherein, X is hydrogen atom, has straight or branched alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, a CFX of 1～21 carbon atom 1X 2Base (wherein, X 1And X 2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, have 1～21 carbon atom the straight or branched fluoroalkyl, have substituting group or do not have substituent benzyl, perhaps have substituting group or do not have substituent phenyl;
Y is-O-or-NH-;
Z is Direct Bonding, have the aliphatic group of 1～10 carbon atom, have the aromatic series of 6～18 carbon atoms or alicyclic group ,-CH 2CH 2N (R 1) SO 2-Ji (R wherein 1For having the alkyl of 1～4 carbon atom) ,-CH 2CH (OZ 1) CH 2-Ji (Z wherein 1Be hydrogen atom or ethanoyl) ,-(CH 2) m-SO 2-(CH 2) n-Ji or-(CH 2) m-S-(CH 2) n-Ji (wherein m is 1～10, and n is 0～10); And
Rf is the straight or branched fluoroalkyl with 8～12 carbon atoms.
3. fluoropolymer as claimed in claim 1, wherein, described functionalized organopolysiloxane (B) is the aminofunctional organopolysiloxane, described aminofunctional organopolysiloxane comprises the siloxy units with following average formula:
(R 2SiO) a(RR NSiO) b(RR FOSiO) c
Wherein, a is 0～4000, and b is 1～1000, and c is 1～1000,
R is any monovalent organic radical group independently,
R NBe monovalence aminofunctional organic group, and
R FORespectively be the hydrosulphonyl functionalized organic group (R of monovalence S), monovalence vinyl-functional organic group (R V), the functionalized organic group (R of monovalence (methyl) acrylamide AM) or monovalence (methyl) acrylate functional organic group (R MA).
4. fluoropolymer as claimed in claim 3, wherein, the functionalized organopolysiloxane of described amino mercapto has average formula:
Figure FDA0000050383670000021
Wherein, a is 0～4000, and b is 0～1000, and c is 1～1000, and R ' is H, has the alkyl or a Me of 1～40 carbon atom 3Si.
5. fluoropolymer as claimed in claim 4, wherein said vinyl aminofunctional organopolysiloxane has average formula:
Figure FDA0000050383670000022
Wherein, a is 0～4000, and b is 0～1000, and c is 1～1000, and R ' is H, has the alkyl or a Me of 1～40 carbon atom 3Si.
6. fluoropolymer as claimed in claim 1, wherein said monomer (A) also comprises except that described fluorochemical monomer (a):
(b) not the monomer of contain fluorine atoms and
(c) cross-linkable monomer that exists alternatively.
7. fluoropolymer as claimed in claim 6, wherein said no fluorine monomer (b) is the acrylate of following general formula:
CH 2＝CA 1COOA 2
A wherein 1Be hydrogen atom, methyl or the halogen atom except that fluorine atom, and
A 2For by C nH 2n+1(n=1～30) represented alkyl.
8. fluoropolymer as claimed in claim 6, wherein said cross-linkable monomer (c) is no fluorine monomer, described no fluorine monomer has at least two parts that are selected from reactive group and carbon-carbon double bond.
9. fluoropolymer as claimed in claim 6, wherein said cross-linkable monomer (c) is not fluorine-containing.
10. fluoropolymer as claimed in claim 1, wherein said X are chlorine.
11. a method of producing fluoropolymer, described method comprises to be made:
(A) monomer, described monomer comprises:
(a) fluorochemical monomer of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein, X is hydrogen atom, any monovalent organic radical group or halogen atom,
Y is-O-or-NH-,
Z is Direct Bonding or divalent organic group, and
Rf is the fluoroalkyl with 8～12 carbon atoms,
In the presence of following material, carry out polymerization:
(B) be selected from least a functionalized organopolysiloxane in the group of forming by hydrosulphonyl functionalized organopolysiloxane, vinyl-functional organopolysiloxane, the functionalized organopolysiloxane of (methyl) acrylamide and the functionalized organopolysiloxane of methyl (acrylate).
12. method as claimed in claim 11, wherein said fluorochemical monomer (a) is the acrylate of following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf (I)
Wherein, X is hydrogen atom, has straight or branched alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, a CFX of 1～21 carbon atom 1X 2Base (wherein, X 1And X 2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, have 1～21 carbon atom the straight or branched fluoroalkyl, have substituting group or do not have substituent benzyl, perhaps have substituting group or do not have substituent phenyl;
Y is-O-or-NH-;
Z is Direct Bonding, have the aliphatic group of 1～10 carbon atom, have the aromatic series of 6～18 carbon atoms or alicyclic group ,-CH 2CH 2N (R 1) SO 2-Ji (R wherein 1For having the alkyl of 1～4 carbon atom) ,-CH 2CH (OZ 1) CH 2-Ji (Z wherein 1Be hydrogen atom or ethanoyl) ,-(CH 2) m-SO 2-(CH 2) n-Ji or-(CH 2) m-S-(CH 2) n-Ji (wherein m is 1～10, and n is 0～10); And
Rf is the straight or branched fluoroalkyl with 8～12 carbon atoms.
13. method as claimed in claim 11, wherein said functionalized organopolysiloxane (B) is the aminofunctional organopolysiloxane, and described aminofunctional organopolysiloxane comprises the siloxy units with following average formula:
(R 2SiO) a(RR NSiO) b(RR FOSiO) c
Wherein, a is 0～4000, and b is 0～1000, and c is 1～1000,
R is any monovalent organic radical group independently,
R NBe monovalence aminofunctional organic group, and
R FORespectively be the hydrosulphonyl functionalized organic group (R of monovalence S), monovalence vinyl-functional organic group (R V), the functionalized organic group (R of monovalence (methyl) acrylamide AM) or monovalence (methyl) acrylate functional organic group (R MA).
14. method as claimed in claim 13, wherein said amino-mercapto functional organopolysiloxane has following average formula:
Figure FDA0000050383670000041
Wherein, a is 0～4000, and b is 0～1000, and c is 1～1000, and R ' is H, has the alkyl or a Me of 1～40 carbon atom 3Si.
15. method as claimed in claim 13, wherein said vinyl aminofunctional organopolysiloxane has following average formula:
Figure FDA0000050383670000042
Wherein, a is 0～4000, and b is 0～1000, and c is 1～1000, and R ' is H, has the alkyl or a Me of 1～40 carbon atom 3Si.
16. method as claimed in claim 11, wherein said monomer (A) also comprises except that described fluorochemical monomer (a):
(b) not the monomer of contain fluorine atoms and
(c) cross-linkable monomer that exists alternatively.
17. method as claimed in claim 16, wherein said no fluorine monomer (b) is the acrylate of following general formula:
CH 2＝CA 1COOA 2
Wherein, A 1Be hydrogen atom, methyl or the halogen atom except that fluorine atom (for example, chlorine atom, bromine atoms and iodine atom), and
A 2For by C nH 2n+1(n=1～30) represented alkyl.
18. method as claimed in claim 16, wherein said cross-linkable monomer (c) is no fluorine monomer, and described no fluorine monomer has at least two reactive groups and/or carbon-carbon double bond.
19. method as claimed in claim 16, wherein said cross-linkable monomer (c) is not fluorine-containing.
20. method as claimed in claim 16, wherein said X is a chlorine.
21. as each described method in the claim 11～20, wherein in described method, use 5 weight %～99.9 weight % described monomer (A) and
0.1 the described functionalized organopolysiloxane (B) of weight %～95 weight %,
Condition is that (A) and summation (B) equal 100%.
22. fluoropolymer according to each described method preparation in the claim 11～21.
23. a surface treatment agent, described surface treatment agent comprise as claim 1 or 22 described fluoropolymers.
24. surface treatment agent as claimed in claim 23, described surface treatment agent also comprises liquid medium.
25. method of using claim 23 or 24 described surface treatment agents to handle matrix.
26. textiles that uses claim 23 or 24 described surface treatment agents to handle.
CN2009801360656A 2008-09-15 2009-09-11 Fluorosilicones and surface treatment agent Pending CN102164976A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US9693008P 2008-09-15 2008-09-15
US61/096,930 2008-09-15
PCT/JP2009/066316 WO2010030041A1 (en) 2008-09-15 2009-09-11 Fluorosilicones and surface treatment agent

Publications (1)

Publication Number Publication Date
CN102164976A true CN102164976A (en) 2011-08-24

Family

ID=41320084

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009801360656A Pending CN102164976A (en) 2008-09-15 2009-09-11 Fluorosilicones and surface treatment agent

Country Status (4)

Country Link
JP (1) JP5680529B2 (en)
CN (1) CN102164976A (en)
TW (1) TW201016732A (en)
WO (1) WO2010030041A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103306139A (en) * 2013-07-10 2013-09-18 苏州市相城区开来化工有限公司 Environment-friendly fluorinated polysiloxane waterproof agent
CN109942762A (en) * 2019-02-21 2019-06-28 上海普信高分子材料有限公司 A kind of preparation method of the surface treating agent with flame retardant property
CN111825840A (en) * 2020-06-23 2020-10-27 湖北航天化学技术研究所 Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method
CN112646062A (en) * 2020-12-18 2021-04-13 浙江理工大学 Preparation method and application of temperature response type fabric finishing agent
CN113529242A (en) * 2021-07-29 2021-10-22 吉祥三宝高科纺织有限公司 Method for preparing anti-cutting gloves by using carbon fiber composite material

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2607627C (en) * 2005-05-09 2010-12-14 Daikin Industries, Ltd. Fluorosilicones and fluorine- and silicon-containing surface treatment agent
CN102159605B (en) * 2008-09-15 2014-01-08 大金工业株式会社 Aqueous polymer dispersion composition and surface treatment agent
US9677220B2 (en) 2009-11-20 2017-06-13 Daikin Industries, Ltd. Fluoropolymers and treatment agent
WO2011062294A1 (en) 2009-11-20 2011-05-26 Daikin Industries, Ltd. Fluoropolymers and surface treatment agent
JP2011201981A (en) * 2010-03-25 2011-10-13 Daikin Industries Ltd Water-repelling, oil-repelling dispersion and method for producing the same
WO2011122442A1 (en) * 2010-03-30 2011-10-06 ダイキン工業株式会社 Water- and oil-repellents using α-chloroacrylate
WO2014208424A1 (en) 2013-06-28 2014-12-31 ダイキン工業株式会社 Surface treatment agent
CN110894267B (en) * 2019-11-27 2022-03-04 东莞东阳光科研发有限公司 Fluorine-silicon graft copolymer, surface treating agent and application

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5068295A (en) * 1989-02-15 1991-11-26 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Water and oil repellants
US7776982B2 (en) * 2003-06-09 2010-08-17 Daikin Industries, Ltd. Silicon-containing fluorochemical surface-treating agent
JP5047949B2 (en) * 2005-05-09 2012-10-10 ダウ・コーニング・コーポレイション Amino mercapto functional organopolysiloxane
CA2607627C (en) * 2005-05-09 2010-12-14 Daikin Industries, Ltd. Fluorosilicones and fluorine- and silicon-containing surface treatment agent
CN101517018B (en) * 2006-07-27 2014-01-08 陶氏康宁公司 Greaseproof paper
WO2009084705A1 (en) * 2007-12-27 2009-07-09 Daikin Industries, Ltd. Cosmetic comprising silicone-containing fluoroacrylate polymer
JP5398723B2 (en) * 2008-02-06 2014-01-29 ダイキン工業株式会社 Fluorosilicone and fluorine-containing silicon-containing surface treatment agent
WO2009119423A1 (en) * 2008-03-28 2009-10-01 Daikin Industries, Ltd. Polymer for leather treatment and leather treatment agent
EP2265758B1 (en) * 2008-03-31 2013-05-29 Daikin Industries, Ltd. Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103306139A (en) * 2013-07-10 2013-09-18 苏州市相城区开来化工有限公司 Environment-friendly fluorinated polysiloxane waterproof agent
CN109942762A (en) * 2019-02-21 2019-06-28 上海普信高分子材料有限公司 A kind of preparation method of the surface treating agent with flame retardant property
CN109942762B (en) * 2019-02-21 2021-10-22 上海普信高分子材料有限公司 Preparation method of surface treating agent with flame retardant property
CN111825840A (en) * 2020-06-23 2020-10-27 湖北航天化学技术研究所 Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method
CN111825840B (en) * 2020-06-23 2022-04-22 湖北航天化学技术研究所 Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method
CN112646062A (en) * 2020-12-18 2021-04-13 浙江理工大学 Preparation method and application of temperature response type fabric finishing agent
CN113529242A (en) * 2021-07-29 2021-10-22 吉祥三宝高科纺织有限公司 Method for preparing anti-cutting gloves by using carbon fiber composite material

Also Published As

Publication number Publication date
WO2010030041A1 (en) 2010-03-18
JP2012503030A (en) 2012-02-02
TW201016732A (en) 2010-05-01
JP5680529B2 (en) 2015-03-04

Similar Documents

Publication Publication Date Title
CN102159605B (en) Aqueous polymer dispersion composition and surface treatment agent
CN101939347B (en) Fluorosilicones and fluorine- and silicon-containing surface treatment agent
CN101981248B (en) Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent
CN102159606B (en) Fluorosilicone polymers and surface treatment agent
CN102164976A (en) Fluorosilicones and surface treatment agent
EP1899392B1 (en) Fluorosilicones and fluorine- and silicon-containing surface treatment agent
CN101171274B (en) Fluorosilicones and fluorine- and silicon-containing surface treatment agent
WO2011062292A1 (en) Fluoropolymers and treatment agent
CN102666970B (en) Fluoropolymers and surface treatment agent
CN100497419C (en) Polymeric reaction products from substituted adminosiloxanes
JP2007522266A (en) Polymer products useful as oil repellents
MX2007014071A (en) Fluorosilicones and fluorine- and silicon-containing surface treatment agent.

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20110824