CN105694646B - Fluoro-containing composition for porous substrate surface treatment - Google Patents

Fluoro-containing composition for porous substrate surface treatment Download PDF

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CN105694646B
CN105694646B CN201610148371.3A CN201610148371A CN105694646B CN 105694646 B CN105694646 B CN 105694646B CN 201610148371 A CN201610148371 A CN 201610148371A CN 105694646 B CN105694646 B CN 105694646B
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fluoro
porous substrate
monomer
surface treatment
substrate surface
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CN105694646A (en
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裴金东
李建
郭雅飞
王树华
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QUZHOU FLUORIDE AND SILICON RESEARCH INSTITUTES
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QUZHOU FLUORIDE AND SILICON RESEARCH INSTITUTES
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/63—Additives non-macromolecular organic

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Abstract

The invention discloses the fluoro-containing compositions being surface-treated for porous substrate, include the fluoropolymer of (1) 20 mass parts of following component, for fluoropolymer by free-radical polymerized acquisition, fluoropolymer includes at least one --- Si (OR)3(wherein R is C to siloxane group1~4Alkyl group)；The polyisocyanate derivative of (2) 0.1~20 mass parts, polyisocyanate derivative have the siloxane group of formula (I)；The silicone compounds of (3) 0.1~10 mass parts, per molecule silicone compounds at least have there are two hydrolyzable groups；(4) organic solvent of above-mentioned (1), (2), (3) can be completely dissolved.Not only Water-proof and oil-proof and antifouling property are good for the composition, but also ideal with base material bonding effect, help to promote Water-proof and oil-proof, antifouling persistence, reduce usage amount, and use cost reduces.

Description

Fluoro-containing composition for porous substrate surface treatment
Technical field
The present invention relates to a kind of fluoro-containing compositions, the more particularly, to fluoro-containing composition of porous substrate surface treatment, belong to In surfacecti proteon processing technology field.
Background technology
Using containing fluoro-alkyl (Rf) compound porous substrate surface is handled, can assign its surface waterproofing, Grease proofing and antifouling effect.Such as R will be carriedfThe acrylate of base is coated on cement or stone material and forms protective film, with RfBase Phosphate handles stone material, will include to contain RfBase monomer and the poly- silica system ethylene for accounting for polymer weight fractin 0.1%~1.9% The polymer that monomer is formed is used as inorganic agent, but there are still the problems of Water-proof and oil-proof and antifouling property deficiency for the above protective agent.
Patent CN01123552.7 discloses the fluorine including fluorochemical monomer, silicon-containing monomer, emulsion stability and other monomers Siliceous copolymer, the copolymer are used for the water and oil repellant processing of stone material.Patent 200380102163.0 discloses will be comprising fluorine-containing Substituted alkyl (RfBase) monomer and account for polymer weight fractin 2.0~6.0% silicon-containing monomer fluorine-silicon copolymer object, the copolymer It is used as masonry-treating agnet.Patent CN200980140046.0 discloses including fluorochemical monomer and is shown below：
The fluorine-silicon copolymer object of the silicone containing sulfydryl.Wherein R1、R2、R3Respectively methyl, methoxyl group, phenyl or hydroxyl；A, B is non- Divalent straight or straight chain that Wei be with 1~10 carbon atom include alkyl, do not have ehter bond in saturated hydrocarbyl or there are one being inserted into Or two ehter bonds；C is with amino, hydroxyl, epoxy group or carboxyl.The copolymer is used at the water and oil repellant of porous matrix Reason.It includes fluorochemical monomer and silicon-containing monomer that patent CN200980144765.X, which is disclosed using silane compound as reaction medium, Fluorine-silicon copolymer object is equally used for the water and oil repellant processing of porous matrix.
The porous substrate protective agent announced in patent documents above, Water-proof and oil-proof and antifouling property are preferable, but above-mentioned poly- The bonding force for closing object and base material is limited, so be easy gradually to lose effect in use.In addition, fluoropolymer higher price, user It is often desirable to can reach ideal effect using less dosage, to reduce cost.
Invention content
The purpose of the present invention is to provide the fluoro-containing composition being surface-treated for porous substrate, the composition is not only prevented Water, grease proofing and antifouling property are good, and ideal with base material bonding effect, help to be promoted Water-proof and oil-proof, antifouling lasting Property, usage amount is reduced, use cost reduces.
In order to solve the above-mentioned technical problem, it adopts the following technical scheme that：
A kind of fluoro-containing composition for porous substrate surface treatment, it is characterised in that including following component：
The fluoropolymer of (1) 20 mass parts, for fluoropolymer by free-radical polymerized acquisition, fluoropolymer includes two kinds of forms：1, fluorine Polymers includes at least one fluorochemical monomer and at least one non-fluorochemical monomer；2, fluoropolymer by copolymer and modifying agent adduction and At copolymer includes at least one fluorochemical monomer and at least one non-fluorochemical monomer；Fluoropolymer includes at least one following formula (I) table The siloxane group shown：
——Si(OR)3 (Ⅰ)
Wherein R is C1~4Alkyl group；
The polyisocyanate derivative of (2) 0.1~20 mass parts, polyisocyanate derivative have the siloxanes of formula (I) Group；
The silicone compounds of (3) 0.1~10 mass parts, per molecule silicone compounds at least have there are two hydrolyzable base Group；
(4) organic solvent of above-mentioned (1), (2), (3) can be completely dissolved.
It after it is preferred that, counts in parts by weight, the composition of fluoropolymer is as follows：
At least one of wherein non-fluorochemical monomer, functional additive or modifying agent contain the siloxane group of formula (I), and Parts by weight are more than 0.
After it is preferred that, fluorochemical monomer can use formula (II) or formula (III) to indicate：
CH2=C (R1)COO-Q-Rf (Ⅱ)
CH2=C (R1)-(COOCH2)m-CH2-NH-CO-Q-Rf (Ⅱ)
Wherein, R1For H or CH3, m is 1 or 0, and Q is bivalent organic group, RfFor Polyfluoroalkyl or perfluoropolyether group.
After it is preferred that, fluorochemical monomer is
CH2=CHCOOCH2CH2NHCOOCH2CH2CF2CF2CF2CF2CF2CF3、
CH2=C (CH3)COOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3、
CH2=CHCOOCH2CH2CF2CF2CF2CF2CF2CF2CF2CF3、
CH2=C (CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3
One or both of mixture, wherein p average out to 5.3.
After it is preferred that, non-fluorochemical monomer is to contain-Si (OR)3The siloxanyl monomers of group contain C12~22The length of alkyl group Alkyl chain monomer, the monomer containing hydroxyl group, or mixtures thereof one kind in the monomer containing epoxy group, wherein R are C1~4 Alkyl group.
After it is preferred that, siloxanyl monomers are
CH2=CHCOOCH2CH2NHCOONHCH2CH2NHCH2CH2CH2Si(OCH3)3、
CH2=CHCH2Si(OCH3)3、
CH2=C (CH3)COOCH2CH2CH2Si(OCH3)3
In one kind；Long alkyl chain monomer is
CH2=CHCOO (CH2)17CH3、
CH2=C (CH3)COO(CH2)17CH3
In one kind；Monomer containing hydroxyl group is
CH2=C (CH3)COOCH2CH2OH、
CH2=CHCOOCH2CH2OH
In one kind；Monomer containing epoxy group is glycidyl methacrylate.
After it is preferred that, functional additive is 3- mercaptopropyl trimethoxysilanes (HSCH2CH2CH2Si(OCH3)3), dodecane Base mercaptan (HSCH2(CH2)10CH3), mercaptoethanol (HSCH2CH2OH one kind in)；Initiator is azobisisobutyronitrile；It is modified Agent is isocyanatopropyl triethoxysilane (OCNCH2CH2CH2Si(OC2H5)3), 3-aminopropyltriethoxysilane (NH2CH2CH2CH2Si(OC2H5)3), γ-glycidyl ether oxygen propyl trimethoxy silicane (CH2OCHCH2OCH2CH2CH2Si (OCH3)3) in one kind.
After it is preferred that, polyisocyanate derivative is polyisocyanates and amino silicone or sulfydryl siloxanes and optional Fluorine alcohol, non-fluorine alcohol addition product.
After it is preferred that, polyisocyanates is toluene di-isocyanate(TDI) (TDI) tripolymer, hexamethylene diisocyanate (HDI) Tripolymer；Amino silicone is 3- TSL 8330s (NH2CH2CH2CH2Si(OC2H5)3), N- β-aminoethyl- γ-aminopropyltrimethoxysilane (NH2CH2CH2NHCH2CH2CH2Si(OCH3)3)；Sulfydryl siloxanes is 3- mercapto propyl trimethoxies Base silane (HSCH2CH2CH2Si(OCH3)3)；Fluorine alcohol is perfluoro butyl ethyl alcohol (HOCH2CH2CF2CF2CF2CF3), perfluoro hexyl second Alcohol (HOCH2CH2CF2CF2CF2CF2CF2CF3)；Non-fluorine alcohol is octadecyl alcolol (HOCH2(CH2)16CH3)。
After it is preferred that, silicone compounds are tetraethyl orthosilicate, methyltrimethoxysilane, dimethyldimethoxysil,ne Or one kind in 1,2- bis- (triethoxy silicon substrate) ethane.
Due to the adoption of the above technical scheme, it has the advantages that：
The present invention is the fluoro-containing composition being surface-treated for porous substrate, the composition not only Water-proof and oil-proof and antifouling It is functional and ideal with base material bonding effect, help to promote Water-proof and oil-proof, antifouling persistence, reduces usage amount, Use cost reduces.Its specific advantageous effect shows as the following：
(1) fluoro-containing composition for porous substrate surface treatment of the invention, the three proofings effect such as Water-proof and oil-proof, antifouling It is good；
(2) fluoro-containing composition for porous substrate surface treatment of the invention, it is good with the bonding effect of base material, waterproof, Grease proofing, antifouling persistence is more excellent；
(3) fluoro-containing composition for porous substrate surface treatment of the invention, can show excellent under lower dosage Water-proof and oil-proof and antifouling property, i.e., dosage decline, so that use cost is reduced.
Specific implementation mode
The present invention is used for the fluoro-containing composition of porous substrate surface treatment,
(1) siloxane group in fluoropolymer therein can come from the monomer segments of silicone-containing group, can also come The functional additive of self-contained siloxane group could also be from the modifying agent of silicone-containing group.By free-radical polymerized straight The fluoropolymer containing siloxane group obtained, if also without using functional additive, it is required that in non-fluorochemical monomer Contain siloxanyl monomers；If using functional additive, and siloxanyl monomers are not contained in non-fluorochemical monomer, then require work( Energy property additive must contain siloxane group.It is poly- by fluorine made of free-radical polymerized obtained copolymer and modifying agent adduction Object, if not containing siloxanyl monomers in non-fluorochemical monomer, and is also free of siloxane group in functional additive, then requires to change It must contain siloxane group in property agent.
It counts in parts by weight, the composition of fluoropolymer is as follows：
(a), fluorochemical monomer can use formula (II) or/and formula (III) to indicate：
CH2=C (R1)COO-Q-Rf (Ⅱ)
CH2=C (R1)-(COOCH2)m-CH2-NH-CO-Q-Rf (Ⅲ)
Wherein, R1For H or CH3, m is 1 or 0.Q is bivalent organic group, such as (CH2)n(integer that n is 1~6), CH2CH2N (CH3)SO2、CH2CH2N(CH2CH3)SO2、 CH(CH3)CH2N(CH3)SO2、CH2CH2NH、N(CH3)CH2CH2NH etc..RfFor polyfluoro Alkyl or perfluoropolyether group：Such as C1~20Polyfluoroalkyl, preferably C3~8Polyfluoroalkyl (CF2)2CF3、 CF(CF3)2、(CF2)3CF3、CF2CF(CF3)2、C(CF3)3、(CF2)4H、(CF2)2CF(CF3)2、(CF2)5CF3、(CF2)7CF3Deng；Such as CF (CF3) [OCF2CF(CF3)]pOCF2CF2CF3、 CF2[OCF2CF2]pOCF3、C(O)CF(CF3)(OCF2CF(CF3))pOC3F7、 C(O)CF (OCF2CF2)pOCF3The perfluoropolyether of equal expressions, p average out to 1~20, preferably 4~10.
Fluorochemical monomer shown in formula (II) can be by (methyl) acrylic acid and corresponding polyfluoro alcohol (such as HOCH2CH2CF2CF2CF2CF3、HOCH2CH2N(CH3)SO2CF2CF2CF2CF3、 HOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3、 HOCH2CH2NHCOCF2[OCF2CF2]pOCF3Deng) or polyfluoro amine (such as HN (CH3)CH2CH2NHCOCF(CF3) [OCF2CF(CF3)]pOCF2CF2CF3Deng) through over-churning or amidation process acquisition, it can also be by (methyl) acrylates (such as CH2=CHCOONa) with corresponding polyfluoro iodide (ICH2CH2CF2CF2CF2CF3) obtained through taking off the esterification of salt compounded of iodine (such as NaI) .Fluorochemical monomer shown in formula (III) can pass through allyl isocyanate or isocyanates ethyl acrylate and corresponding polyfluoro Alcohol or polyfluoro amine are obtained through esterification or amidation process.
Fluorochemical monomer can be listed below：
CH2=CR1COOCH2CH2CF2CF2CF2CF3
CH2=CR1COOCH2CH2CF2CF2CF2CF2CF2CF2CF2CF3
CH2=CR1COOCH2CH2CF2CF(CF3)2
CH2=CR1COOCH2CH2C(CF3)3
CH2=CR1COOCH2CF2CF2CF3
CH2=CR1COOCH2CF2CF2CF2CF3
CH2=CR1COOCH2CF2CF2CF2CF2H
CH2=CR1COOCH2CF2CF2CF2CF2CF2CF3
CH2=CR1COOCH2CH2N(CH3)SO2CF2CF2CF2CF3
CH2=CR1COOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF3
CH2=CR1COOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF2CF2CF3
CH2=CR1COOCH(CH3)CH2N(CH3)SO2CF2CF2CF2CF3
CH2=CR1COOCH2CH2N(CH3)SO2CF(CF3)2
CH2=CR1COOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(p average out to 4~10)
CH2=CR1COOCH2CF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1COOCH2CH2NHCOCF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(p average out to 4~10)
CH2=CR1COOCH2CH2NHCOCF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1CON(CH3)CH2CH2NHCOCF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(p average out to 4~10)
CH2=CR1CON(CH3)CH2CH2NHCOCF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1CH2NHCOOCH2CH2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CH2CF2CF2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CH2CF2CF(CF3)2
CH2=CR1CH2NHCOOCH2CH2C(CF3)3
CH2=CR1CH2NHCOOCH2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CF2CF2CF2CF2H
CH2=CR1CH2NHCOOCH2CF2CF2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CH2N(CH3)SO2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH(CH3)CH2N(CH3)SO2CF2CF2CF2CF3
CH2=CR1CH2NHCOOCH2CH2N(CH3)SO2CF(CF3)2
CH2=CR1CH2NHCOOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(p average out to 4~10)
CH2=CR1CH2NHCOOCH2CF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1CH2NHCOOCH2CH2NHCOCF(CF3)[OCF2CF(CF3)]pOCF2CF2CF 3(p average out to 4~10)
CH2=CR1CH2NHCOOCH2CH2NHCOCF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1CH2NHCON(CH3)CH2CH2NHCOCF(CF3)[OCF2CF(CF3)]pOCF2 CF2CF3(p average out to 4 ~10)
CH2=CR1CH2NHCON(CH3)CH2CH2NHCOCF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1COOCH2CH2NHCOOCH2CH2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CH2CF2CF2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CH2CF2CF(CF3)2
CH2=CR1COOCH2CH2NHCOOCH2CH2C(CF3)3
CH2=CR1COOCH2CH2NHCOOCH2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CF2CF2CF2CF2H
CH2=CR1COOCH2CH2NHCOOCH2CF2CF2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CH2N(CH3)SO2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF2CF 2CF3
CH2=CR1COOCH2CH2NHCOOCH(CH3)CH2N(CH3)SO2CF2CF2CF2CF3
CH2=CR1COOCH2CH2NHCOOCH2CH2N(CH3)SO2CF(CF3)2
CH2=CR1COOCH2CH2NHCOOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(p average out to 4~10)
CH2=CR1COOCH2CH2NHCOOCH2CF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1COOCH2CH2NHCOOCH2CH2NHCOCF(CF3)[OCF2CF(CF3)]pOC F2CF2CF3(p average out to 4 ~10)
CH2=CR1COOCH2CH2NHCOOCH2CH2NHCOCF2[OCF2CF2]pOCF3(p average out to 4~10)
CH2=CR1COOCH2CH2NHCON(CH3)CH2CH2NHCOCF(CF3)[OCF2CF(CF3 )]pOCF2CF2CF3(p is flat It is 4~10)
CH2=CR1COOCH2CH2NHCON(CH3)CH2CH2NHCOCF2[OCF2CF2]pOCF3(p average out to 4~10)
Wherein, the above various middle R1For H or CH3.Fluorochemical monomer can be one such or several mixture.
Fluorochemical monomer is preferably
CH2=CHCOOCH2CH2NHCOOCH2CH2CF2CF2CF2CF2CF2CF3、
CH2=C (CH3)COOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3、
CH2=CHCOOCH2CH2CF2CF2CF2CF2CF2CF2CF2CF3、
CH2=C (CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3
One or both of mixture, wherein p average out to 5.3.
(b), non-fluorochemical monomer is to contain-Si (OR)3The siloxanyl monomers of group contain C12~22The long alkane of alkyl group Base chain monomer, the monomer containing hydroxyl group, or mixtures thereof one kind in the monomer containing epoxy group, wherein R are C1~4's Alkyl group.
Siloxanyl monomers can be listed below：
CH2=CHSi (OCnH2n+1)3(vinyl trialkyl oxysilane)
CH2=CHCH2Si(OCnH2n+1)3(anone silane)
CH2=CR2COOCH2CH2CH2Si(OCnH2n+1)3((methyl) acryloxy propyl trialkoxy silane)
CH2=CR2COOCH2CH2OCONHCH2CH2CH2Si(OCnH2n+1)3
CH2=CHCOOCH2CH2NHCOONHCH2CH2NHCH2CH2CH2Si(OCnH2n+1)3
CH2=CR2CH2OCONHCH2CH2CH2Si(OCnH2n+1)3
The above various middle R2For H or CH3, n be 1~5 integer.The compound containing carbamate can pass through phase above The hydroxyl or amino-compound answered are reacted with corresponding isocyanate compound to be obtained.
Siloxanyl monomers are preferably：
CH2=CHCOOCH2CH2NHCOONHCH2CH2NHCH2CH2CH2Si(OCH3)3、
CH2=CHCH2Si(OCH3)3、
CH2=C (CH3)COOCH2CH2CH2Si(OCH3)3
In one kind.
The long alkyl chain monomer is such as：CH2=CR3COO(CH2)11~21CH3、 CH2=CHCH2NHCOO(CH2)11~ 21CH3、CH2=CHCOOCH2CH2NHCOO(CH2)11~21CH3Deng.Wherein CH2=CR3COO(CH2)11~21CH3(methyl) can be passed through Acrylic acid is obtained with corresponding fatty alcohol through esterification；CH2=CHCH2NHCOO(CH2)11~21CH3Isocyanic acid alkene can be passed through Propyl ester is obtained with corresponding fatty alcohol through esterification；CH2=CHCOOCH2CH2NHCOO(CH2)11~21CH3Isocyanide can be passed through Acid esters ethyl acrylate is obtained with corresponding fatty alcohol through esterification.Long alkyl chain monomer can be listed below：
CH2=CR3COO(CH2)17CH3((methyl) octadecyl acrylate)
CH2=CR3COO(CH2)15CH3((methyl) Process Conditions of Cetane Acrylate)
CH2=CR3COO(CH2)13CH3((methyl) tetradecyl acrylate)
CH2=CR3COO(CH2)11CH3((methyl) dodecyl acrylate)
CH2=CHCH2NHCOO(CH2)17CH3(allyl amino formic acid octadecyl ester)
CH2=CHCH2NHCOO(CH2)15CH3(allyl amino formic acid hexadecyl ester)
CH2=CHCH2NHCOO(CH2)13CH3(14 ester of allyl amino formic acid)
CH2=CHCH2NHCOO(CH2)11CH3(allyl amino first dodecyl gallate)
CH2=CHCOOCH2CH2NHCOO(CH2)17CH3(propenoate Ethyl carbamic acid octadecyl ester)
CH2=CHCOOCH2CH2NHCOO(CH2)15CH3(propenoate Ethyl carbamic acid hexadecyl ester)
CH2=CHCOOCH2CH2NHCOO(CH2)13CH3(14 ester of propenoate Ethyl carbamic acid)
CH2=CHCOOCH2CH2NHCOO(CH2)21CH3(20 diester of propenoate Ethyl carbamic acid)
The above various middle R3For H or CH3。
Long alkyl chain monomer is preferably：
CH2=CHCOO (CH2)17CH3、
CH2=C (CH3)COO(CH2)17CH3
In one kind.
Monomer containing hydroxyl group is the monomer containing hydroxyl and carbon-carbon double bond simultaneously in same molecule, preferably：
CH2=C (CH3)COOCH2CH2OH、
CH2=CHCOOCH2CH2OH
In one kind.
The monomer containing epoxy group is preferably glycidyl methacrylate.
(c), functional additive is the compound of the tunable molecular weight containing mercapto groups, wherein preferably 3- mercaptos propyl Trimethoxy silane (HSCH2CH2CH2Si(OCH3)3), lauryl mercaptan (HSCH2(CH2)10CH3), mercaptoethanol (HSCH2CH2OH one kind in).
(d) initiator described in is azo or peroxide compound, wherein preferably azobisisobutyronitrile.
(e) modifying agent described in is siloxane compound, the isocyanide that can be reacted with hydroxyl or epoxy group or amino Ester compound etc., wherein preferably isocyanatopropyl triethoxysilane (OCNCH2CH2CH2Si(OC2H5)3), 3- aminopropans Ethyl triethoxy silicane alkane (NH2CH2CH2CH2Si(OC2H5)3), γ-glycidyl ether oxygen propyl trimethoxy silicane (CH2OCHCH2OCH2CH2CH2Si(OCH3)3) in one kind.
(2) polyisocyanate derivative therein is polyisocyanates and amino silicone or sulfydryl siloxanes and optional The addition product of fluorine alcohol, non-fluorine alcohol.
Polyisocyanates be toluene di-isocyanate(TDI) (TDI) tripolymer, hexamethylene diisocyanate (HDI) tripolymer, Benzhydryl vulcabond (MDI) tripolymer, isophorone diisocyanate (IPDI) tripolymer, 1,5- naphthalene diisocyanates (NDI) tripolymer, tetramethyl group diisocyanate (TMXDI) tripolymer, to phenyl diisocyanate (PPDI) tripolymer, two methylenes Base phenyl diisocyanate (XDI) tripolymer etc.；Wherein, preferably toluene di-isocyanate(TDI) (TDI) tripolymer, hexa-methylene two Isocyanates (HDI) tripolymer.
Amino silicone is 3- TSL 8330s (NH2CH2CH2CH2Si(OC2H5)3), N- β-aminoethyl- γ-aminopropyltrimethoxysilane (NH2CH2CH2NHCH2CH2CH2Si(OCH3)3)；
Sulfydryl siloxanes is 3- mercaptopropyl trimethoxysilanes (HSCH2CH2CH2Si(OCH3)3)。
Fluorine alcohol is perfluoroalkyl ethyl alcohol, preferably perfluoro butyl ethyl alcohol (HOCH2CH2CF2CF2CF2CF3), perfluoro hexyl Ethyl alcohol (HOCH2CH2CF2CF2CF2CF2CF2CF3)；The non-fluorine alcohol is the alkylol of C12~22, such as lauryl alcohol, hexadecanol, ten Eight alcohol, docosanol etc., wherein preferably octadecyl alcolol (HOCH2(CH2)16CH3)。
(3) wherein per molecule at least have there are two hydrolyzable groups silicone compounds such as：Methyl trialkoxysilane, Tetraalkoxysilane, dimethyldialkylammonium oxysilane, γ-chloropropyl trialkoxy silane, γ-aminopropyltrialkoxysilane, 1,2- bis- (triethoxy silicon substrate) ethane etc..Preferably tetraethyl orthosilicate, methyltrimethoxysilane, dimethylformamide dimethyl oxygroup One kind in silane or 1,2- bis- (triethoxy silicon substrate) ethane.
(4) organic solvent therein is without particular/special requirement, as long as can dissolve being total to containing carbamoyl of the present invention in principle Organic volatile solvents of silicon-fluorine polymer object all can be selected.Organic solvent can be ketone, esters, alcohols, ethers, hydro carbons, acyl Amine etc., ketone such as acetone, butanone, methyl isoamyl ketone, cyclohexanone etc., esters such as ethyl acetate, butyl acetate etc., alcohols such as second Alcohol, isopropanol, n-butanol, tert-butyl alcohol etc., ethers such as methyl ethyl ether, Anaesthetie Ether etc., hydro carbons for example hexane, octane, petroleum ether, 150# solvent naphthas, benzene,toluene,xylene etc., amides such as N, N --- dimethylformamide, N, N --- dimethylacetylamide Deng.One such or several mixture can be selected.
The fluoro-containing composition for porous substrate surface treatment of the present invention, when use, first have to be diluted to certain dense Degree, which is determined according to specific base material and using technique, usually 0.07%~2.5%；Suitable catalyst is added, Usually the 0.5 ‰ of composition non-solvent component dosage~5 ‰, and be uniformly mixed；Then use suitable method by composition Surface coated on base material can be realized by spraying, the suitable method of impregnating；Finally removed at a temperature of 20~200 DEG C Solvent is removed, and composition is made to cure to obtain protective coating.It is solid that the catalyst plays acceleration in the solidification process of composition Organic tin compound, organic titanium compound, acetylacetone metallic compound etc. can be selected, such as in the effect of change：Dibutyl two Tin laurate ((C11H23COO)2Sn(C4H9)2), dibutyltin diacetate ((CH3COO)2Sn(C4H9)2), dibutyl two (12 Alkyl sulfide) tin ((C12H25S)2Sn(C4H9)2), dibutyl maleic acid tin ((OOC CH2CH2COO)Sn(C4H9)2), stannous octoate ((C7H15COO)2Sn), tetra-n-butyl titanate (Ti (O (CH2)3CH3)4), tetraisopropyl titanate (Ti (OCH (CH3)2)4), metatitanic acid Four tert-butyl esters (Ti (OC (CH3)3)4), two (levulinic ketone group) metatitanic acid diisopropyl ester ((CH3COCH=C (CH3)O)2 Ti(OCH (CH3)2)2), bis- (levulinic ketone group) isobutoxy isopropoxy titanate esters ((CH3COCH=C (CH3)O)2Ti(OCH(CH3)2) (OCH2CH(CH3)2)), bis- (levulinic ketone group) ethyoxyl isopropoxy titanate esters ((CH3COCH=C (CH3)O)2Ti (OCH2CH3)(OCH(CH3)2)), aluminium acetylacetonate (Al (CH3COCH=C (CH3)O)3) etc., wherein more preferable dibutyl tin Cinnamic acid tin, dibutyltin diacetate, tetraisopropyl titanate, two (levulinic ketone group) metatitanic acid diisopropyl ester, aluminium acetylacetonates etc..
With reference to specific embodiment, the invention will be further described：
The raw materials used in the present invention is commercially available or is prepared, specific as follows：
D1：CH2=CHCOOCH2CH2NCO
D2：CH2=C (CH3)COOH
C1：HOCH2CH2CF2CF2CF2CF3
C2：HOCH2CH2CF2CF2CF2CF2CF2CF3
C3：HOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3, (p average out to 5.3)
C4：HOCH2(CH2)16CH3
F1：CH2=CHCOOCH2CH2CF2CF2CF2CF2CF2CF2CF2CF3
F2：CH2=C (CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3
S1：CH2=CHCH2Si(OCH3)3
S2：CH2=C (CH3)COOCH2CH2CH2Si(OCH3)3
M1：CH2=CHCOO (CH2)17CH3
M2：CH2=C (CH3)COO(CH2)17CH3
Q1：CH2=C (CH3)COOCH2CH2OH
Q2：CH2=CHCOOCH2CH2OH
H1：CH2=C (CH3)COOCH2CH2OCH2(glycidyl methacrylate)
G1：HSCH2CH2CH2Si(OCH3)3
G2：HSCH2(CH2)10CH3(lauryl mercaptan)
G3：HSCH2CH2OH
Y1：Azobisisobutyronitrile
B1：OCNCH2CH2CH2Si(OC2H5)3
B2：NH2CH2CH2CH2Si(OC2H5)3
B3：CH2OCHCH2OCH2CH2CH2Si(OCH3)3(γ-glycidyl ether oxygen propyl trimethoxy silicane)
B4：NH2CH2CH2NHCH2CH2CH2Si(OCH3)3
T1：HDI trimer
T2：TDI tripolymers
The preparation method of which part raw material is as follows：
Synthesis example 1
Monomer CH2=CHCOOCH2CH2NHCOOCH2CH2CF2CF2CF2CF2CF2CF3Synthesis --- F3
364g is added in tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser The D1 of 141g (1mol) is added dropwise under the C2 of (1mol), room temperature and stirring condition, 30min is added dropwise, adds a small amount of to benzene Diphenol polymerization inhibitor, after be heated to 80 DEG C reaction 8h, obtain light yellow clear liquid.Infrared analysis shows isocyanate groups Absorption peak completely disappears.
Synthesis example 2
Monomer CH2=C (CH3)COOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3Synthesis, p indicates to repeat single The number of member, p average out to 5.3 --- F4
1196g is added in tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser D2, appropriate water entrainer and a small amount of hydroquinone polymerization inhibitor of C3, the 95g (1.1mol) of (1mol) and a small amount of Catalyzed by p-Toluenesulfonic Acid Agent is warming up to 120 DEG C of progress esterifications under stiring, until when the water in separator is close to theoretical value, esterification finishes. Then it is gone out water entrainer and unreacted methacrylic acid by air-distillation and vacuum distillation, then is urged by washing away respectively Agent and polymerization inhibitor, vacuum drying obtain target product.
Synthesis example 3
Monomer CH2=CHCOOCH2CH2NHCOONHCH2CH2NHCH2CH2CH2Si(OCH3)3Synthesis --- S3
222g is added in tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser The D1 of 141g (1mol) is added dropwise under the B4 of (1mol), room temperature and stirring condition, 30min is added dropwise, adds a small amount of to benzene Diphenol (be purchased from Nanjing Xin Huayuan Chemical Co., Ltd.s) polymerization inhibitor, after be heated to 80 DEG C of reaction 8h, obtain light yellow clear Liquid.Infrared analysis shows that isocyanate groups absorption peak completely disappears.
The synthesis of fluoropolymer is as follows：
Synthesis example 4 (fluoropolymer solution --- PF1)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 75g F1, 25g S1,1g G2,0.8g Y1 and 400g ethyl acetate.Reaction bulb is replaced 3 times with nitrogen, then heats to 80 DEG C of reaction 4h, Obtain fluoropolymer solution --- the PF1 that active ingredient is 20%.
Synthesis example 5 (fluoropolymer solution --- PF2)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 50g F2, 10g S2,40g M1,0.1g Y1 and 400g butyl acetates.Reaction bulb is replaced 3 times with nitrogen, then heats to 70 DEG C of reaction 6h, Obtain fluoropolymer solution --- the PF2 that active ingredient is 20%.
Synthesis example 6 (fluoropolymer solution --- PF3)
70g F3,5g are added in tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser S1,25g M2,0.5g G2,0.4g Y1 and 400g butyl acetates.Reaction bulb is replaced 3 times with nitrogen, then heats to 70 DEG C instead Answer 6h to get fluoropolymer solution --- the PF3 for being 20% to active ingredient.
Synthesis example 7 (fluoropolymer solution --- PF4)
65g F4,3g are added in tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser S2,32g M1,3g Y1 and 400g butyl acetates.Reaction bulb with nitrogen replace 3 times, then heat to 60 DEG C reaction 10h to get Fluoropolymer solution --- the PF4 for being 20% to active ingredient.
Synthesis example 8 (fluoropolymer solution --- PF5)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 60g F1, 40g M2,2.5g G1,2g Y1 and 400g butyl acetates.Reaction bulb is replaced 3 times with nitrogen, then heats to 85 DEG C of reaction 3h, Obtain fluoropolymer solution --- the PF5 that active ingredient is 20%.
Synthesis example 9 (fluoropolymer solution --- PF6)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 55g F2, 30g M1,5.2g Q1,1.5g Y1 and 400g ethyl acetate.Reaction bulb is replaced 3 times with nitrogen, then heats to 75 DEG C of reactions 5h.Then 35 DEG C are cooled to, 9.8g B1 are added dropwise in 10min, then is warming up to 85 DEG C of reaction 3h and is to get to active ingredient 20% fluoropolymer solution --- PF6.
Synthesis example 10 (fluoropolymer solution --- PF7)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 62g F1, 28g M2,4g Q2,0.4g G3,1.1g Y1 and 400g ethyl acetate.Reaction bulb is replaced 3 times with nitrogen, then heats to 75 DEG C reaction 5h.Then 35 DEG C are cooled to, 6g B1 are added dropwise in 10min, then be warming up to 85 DEG C reaction 3h to get to effectively at It is divided into 20% fluoropolymer solution --- PF7.
Synthesis example 11 (fluoropolymer solution --- PF8)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 57g F2, 28g M1,5.9g H1,0.8g Y1 and 400g ethyl acetate.Reaction bulb is replaced 3 times with nitrogen, then heats to 75 DEG C of reactions 5h.Then 35 DEG C are cooled to, 9.1g B2 are added dropwise in 10min, then is warming up to 60 DEG C of reaction 3h and is to get to active ingredient 20% fluoropolymer solution --- PF8.
Synthesis example 12 (fluoropolymer solution --- PF9)
In tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 60g F1, 12.1g S3,20g M2,0.65g G2,0.5g Y1 and 400g ethyl acetate.Reaction bulb is replaced 3 times with nitrogen, is then heated to 75 DEG C of reaction 5h.Then 35 DEG C are cooled to, 7.9g B3 are added dropwise in 10min, then is warming up to 60 DEG C of reaction 3h to get to having Imitate fluoropolymer solution --- the PF9 that ingredient is 20%.
Synthesis example 13 (fluoropolymer solution --- PF10)
60g F3,7g are added in tetra- mouthfuls of reaction flasks of the 1L for being equipped with blender, constant temperature oil bath, thermometer and condenser F4,7g S2,26g M2,1g G1,0.8g Y1 and 400g butyl acetates.Reactor is replaced 3 times with nitrogen, then heats to 75 DEG C reaction 5h to get to active ingredient be 20% fluoropolymer solution --- PF10.
The synthesis of polyisocyanate derivative is as follows：
Synthesis example 14 (polyisocyanate derivative solution --- N1)
560g is added (about in tetra- mouthfuls of reaction flasks of the 2L for being equipped with blender, constant temperature oil bath, thermometer and condenser T1 1mol), stirring are warming up to 45 DEG C, the B2 of 552g (about 2.5mol) are added dropwise in 30 minutes；85 DEG C are then raised temperature to, instead 3h is answered, cool down and is diluted with ethyl acetate, solution --- the N1 that polyisocyanate derivative active ingredient is 20% is obtained.
Synthesis example 15 (polyisocyanate derivative solution --- N2)
560g is added (about in tetra- mouthfuls of reaction flasks of the 2L for being equipped with blender, constant temperature oil bath, thermometer and condenser T1 1mol), stirring are warming up to 45 DEG C, the B4 of 444g (about 2mol) are added dropwise in 30 minutes, then raise temperature to 85 DEG C, reaction 1h；Be cooled to 50 DEG C again, the C1 of 264g (about 1mol) be added dropwise in 15min, after be warming up to 85 DEG C, react 3h.Cool down and is used in combination Ethyl acetate dilutes, and obtains solution --- the N2 that polyisocyanate derivative active ingredient is 20%.
Synthesis example 16 (polyisocyanate derivative solution --- N3)
870g is added (about in tetra- mouthfuls of reaction flasks of the 2L for being equipped with blender, constant temperature oil bath, thermometer and condenser T2 1mol), stirring are warming up to 45 DEG C, the G1 of 392g (about 2mol) are added dropwise in 30 minutes, then raise temperature to 85 DEG C, reaction 1h；Above-mentioned product is added dropwise to the mixed liquor of the C4 of the C2 and 135g (about 0.5mol) of 182g (about 0.5mol) in 30min In, and keep the temperature the reaction was continued 2h.Cool down and diluted with ethyl acetate, it is 20% to obtain polyisocyanate derivative active ingredient Solution --- N3.
Synthesis example 17 (polyisocyanate derivative solution --- N4)
870g is added (about in tetra- mouthfuls of reaction flasks of the 2L for being equipped with blender, constant temperature oil bath, thermometer and condenser T2 1mol), stirring are warming up to 45 DEG C, the B4 of 400g (about 1.8mol) are added dropwise in 30 minutes, then raises temperature to 85 DEG C, instead Answer 1h；Above-mentioned product is added dropwise to the mixed liquor of the C4 of the C2 and 54g (about 0.2mol) of 291g (about 0.8mol) in 30min In, and keep the temperature the reaction was continued 2h.Cool down and diluted with ethyl acetate, it is 20% to obtain polyisocyanate derivative active ingredient Solution --- N4.
Synthesis example 18 (polyisocyanate derivative solution --- N5)
560g is added (about in tetra- mouthfuls of reaction flasks of the 2L for being equipped with blender, constant temperature oil bath, thermometer and condenser T1 1mol), stirring are warming up to 45 DEG C, the B2 of 442g (about 2mol) are added dropwise in 30 minutes, then raise temperature to 85 DEG C, reaction 1h；Above-mentioned product is added dropwise in 30min in the mixed liquor of the C4 of 243g (about 0.9mol), and keeps the temperature the reaction was continued 2h.Drop Wen Bingyong ethyl acetates dilute, and obtain solution --- the N5 that polyisocyanate derivative active ingredient is 20%.
Examples 1 to 20
At least have being equipped with blender vial and sequentially adding fluoropolymer solution, polyisocyanate derivative and per molecule There are two the silicone compounds of hydrolyzable groups, then it is diluted with petroleum ether to active constituent content as 20% to get to originally The fluoro-containing composition for porous substrate surface treatment of invention, specific proportioning refer to table 1.
Comparative example 1~4
The same embodiment of preparation method, specific formula refer to table 1.
Table 1 is used for the fluoro-containing composition formula table of porous substrate surface treatment
Note：A-- tetraethyl orthosilicates, b-- methyltrimethoxysilane, c-- dimethyldimethoxysil,nes, d--1,2- Two (triethoxy silicon substrate) ethane.
Base material treatment method：
The fluoro-containing composition for porous substrate surface treatment that above-described embodiment 1~20 and comparative example 1~4 obtain is used Solvent petroleum ether is diluted to 0.09~1% mass concentration, adds and accounts for fluoro-containing composition non-solvent component mass fraction 2 ‰ Acid dibutyl tin catalyst is coated on various porous substrate surfaces, removes solvent at room temperature after mixing, and after Continuous placement makes composition cure to obtain protective coating for 24 hours.
Performance test methods
(1) contact angle is tested
The contact angle that processed base material is carried out deionized water (W) and white mineral oil (O) with contact angle instrument is tested. Parallel determination 5 times, is averaged.
(2) resistant is tested
Pollutant is placed on processed and untreated base material, placement wipes drop with paper handkerchief afterwards for 24 hours.According to stain The depth and range of scatter size carry out resistance to soiling evaluation：
1=stains are deep, oil droplet diffusion range is larger
2=stains depth, oil droplet diffusion range are small or without diffusion
3=moderates stain, oil droplet diffusion range are small
The slight stains of 4=, oil droplet are without diffusion
5=free from smutting, oil droplet are without diffusion
(3) the antifouling persistence test of waterproof and oilproof
Processed base material is carried out with abrasion test instrument (load 250g) to 500 turns of wear test, the base after abrasion Material carries out the test of contact angle and resistance to soiling again.With contact angle variation before and after wear test less than 10%, resistance to soiling change of rank It is qualification no more than 2.
The resistance to soiling for the concrete substrate that the compositions-treated of table 2 1% is crossed is tested
Edible oil Soy sauce It is laughable Fruit juice Coffee Ink
Embodiment 1 5 5 5 5 5 5
Embodiment 2 5 4 5 5 5 5
Embodiment 3 5 5 5 5 5 5
Embodiment 4 5 5 5 5 5 5
Embodiment 5 5 5 5 5 5 5
Embodiment 6 5 5 5 5 5 5
Embodiment 7 5 5 5 5 5 5
Embodiment 8 5 5 5 5 5 5
Embodiment 9 5 5 5 5 5 5
Embodiment 10 5 5 5 4 5 5
Embodiment 11 5 5 5 5 5 5
Embodiment 12 5 5 5 5 5 5
Embodiment 13 5 5 5 5 5 5
Embodiment 14 5 5 5 5 5 5
Embodiment 15 5 5 5 5 5 5
Embodiment 16 5 5 5 5 5 5
Embodiment 17 5 5 5 5 5 5
Embodiment 18 5 5 5 5 5 5
Embodiment 19 5 5 5 5 5 5
Embodiment 20 5 5 5 5 5 5
The contact angle for the lime stone base material that the compositions-treated of table 3 0.4% is crossed is tested
The soil resistance for the lime stone base material that the compositions-treated of table 4 0.4% is crossed is tested
The contact angle and soil resistance for the marble base material that the compositions-treated of table 5 0.09% is crossed are tested
It these are only specific embodiments of the present invention, but the technical characteristic of the present invention is not limited thereto.It is any with this hair Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made ground simple change, etc. With replacement or modification etc., all it is covered by among protection scope of the present invention.

Claims (10)

1. the fluoro-containing composition for porous substrate surface treatment, it is characterised in that including following component：
The fluoropolymer of (1) 20 mass parts, for fluoropolymer by free-radical polymerized acquisition, fluoropolymer includes two kinds of forms：1, fluoropolymer Include at least one fluorochemical monomer and at least one non-fluorochemical monomer；2, fluoropolymer is formed by copolymer and modifying agent adduction, Copolymer includes at least one fluorochemical monomer and at least one non-fluorochemical monomer；Fluoropolymer includes that at least one following formula (I) indicates Siloxane group：
——Si(OR)3 (Ⅰ)
Wherein R is C1~4Alkyl group；
The polyisocyanate derivative of (2) 0.1~20 mass parts, polyisocyanate derivative have the siloxane group of formula (I)；
The silicone compounds of (3) 0.1~10 mass parts, per molecule silicone compounds at least have there are two hydrolyzable groups；
(4) organic solvent of above-mentioned (1), (2), (3) can be completely dissolved.
2. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 1, it is characterised in that：In parts by weight Meter, the composition of fluoropolymer are as follows：
At least one of wherein non-fluorochemical monomer, functional additive or modifying agent contain the siloxane group of formula (I), and weight Number is more than 0.
3. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 1, it is characterised in that：Fluorochemical monomer can To be indicated with formula (II) or formula (III)：
CH2=C (R1)COO-Q-Rf (Ⅱ)
CH2=C (R1)-(COOCH2)m-CH2-NH-CO-Q-Rf (Ⅲ)
Wherein, R1For H or CH3, m is 1 or 0, and Q is bivalent organic group, RfFor Polyfluoroalkyl or perfluoropolyether group.
4. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 3, it is characterised in that：Fluorochemical monomer is
CH2=CHCOOCH2CH2NHCOOCH2CH2CF2CF2CF2CF2CF2CF3、
CH2=C (CH3)COOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3、
CH2=CHCOOCH2CH2CF2CF2CF2CF2CF2CF2CF2CF3、
CH2=C (CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3
One or both of mixture, wherein p average out to 5.3.
5. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 1, it is characterised in that：Non- fluorochemical monomer To contain-Si (OR)3The siloxanyl monomers of group contain C12~22The long alkyl chain monomer of alkyl group contains hydroxyl group Or mixtures thereof one kind in monomer, the monomer containing epoxy group, wherein R are C1~4Alkyl group.
6. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 5, it is characterised in that：Siloxanyl monomers For
CH2=CHCOOCH2CH2NHCOONHCH2CH2NHCH2CH2CH2Si(OCH3)3、
CH2=CHCH2Si(OCH3)3、
CH2=C (CH3)COOCH2CH2CH2Si(OCH3)3
In one kind；Long alkyl chain monomer is
CH2=CHCOO (CH2)17CH3、
CH2=C (CH3)COO(CH2)17CH3
In one kind；Monomer containing hydroxyl group is
CH2=C (CH3)COOCH2CH2OH、
CH2=CHCOOCH2CH2OH
In one kind；The monomer containing epoxy group is glycidyl methacrylate.
7. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 2, it is characterised in that：Functionality addition Agent is one kind in 3- mercaptopropyl trimethoxysilanes, lauryl mercaptan, mercaptoethanol；The initiator is that azo two is different Butyronitrile；The modifying agent is isocyanatopropyl triethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidol One kind in ether oxygen propyl trimethoxy silicane.
8. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 1, it is characterised in that：Polyisocyanates Derivative is the addition product of polyisocyanates and amino silicone or sulfydryl siloxanes and optional fluorine alcohol, non-fluorine alcohol.
9. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 8, it is characterised in that：Polyisocyanates For toluene diisocyanate trimer, hexamethylene diisocyanate trimer；Amino silicone is 3- aminopropyl trimethoxies Base silane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane；Sulfydryl siloxanes is 3- mercaptopropyl trimethoxysilanes；Fluorine alcohol For perfluoro butyl ethyl alcohol, perfluoro hexyl ethyl alcohol；Non-fluorine alcohol is octadecyl alcolol.
10. being used for the fluoro-containing composition of porous substrate surface treatment according to claim 1, it is characterised in that：Siliconization Conjunction object is tetraethyl orthosilicate, methyltrimethoxysilane, dimethyldimethoxysil,ne or 1,2- bis- (triethoxy silicon substrate) One kind in ethane.
CN201610148371.3A 2016-03-15 2016-03-15 Fluoro-containing composition for porous substrate surface treatment Active CN105694646B (en)

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