CN105802366A - Coating composition and water-based polytetrafluoroethylene windshield wiper coating prepared from same - Google Patents

Coating composition and water-based polytetrafluoroethylene windshield wiper coating prepared from same Download PDF

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CN105802366A
CN105802366A CN201610218563.7A CN201610218563A CN105802366A CN 105802366 A CN105802366 A CN 105802366A CN 201610218563 A CN201610218563 A CN 201610218563A CN 105802366 A CN105802366 A CN 105802366A
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methyl
sulfonation
hyperbranched
compositions described
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CN105802366B (en
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方六月
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Ye new material technology (Shanghai) Co., Ltd.
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Beijing Kairuijiecheng New Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00—Polymer mixtures characterised by other features
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Abstract

The invention provides coating composition. The coating composition at least comprises raw materials of polytetrafluoroethylene, adhesive resin, modified acrylic resin, a compatibilizer, water and a tackifier in parts by weight, wherein modified acrylic resin is organosilicon modified acrylic resin.

Description

The aqueous politef rain brush coating of coating composition and preparation thereof
Technical field
This patent relates to rubber coating field, is specifically related to C09D133.
Background technology
Rubber has heatproof, wear-resisting, ageing-resistant, corrosion-resistant or resistance to wet goods performance because of it, mainly for the manufacture of automobile tire, adhesive tape, sebific duct, rubber overshoes, cable, sealing article, druggist rubber sundrier, adhesive, latex product, vehicle fuel tank cap O etc..But the mechanical performance of rubber is poor, in use, it is necessary at surface-coated one coating of rubber, with use wear-resisting, lubrication.Conventional rubber coating mainly has acrylic resin, polyurethane resin etc..
Politef, PTFE, also known as King, there is lubrication, wear-resisting, viscous, anticorrosion, the performance such as high temperature resistant, thus be frequently used for rubber coating field.But owing to politef is full symmetric and unbranched linear macromolecule, in politef, carbon, two kinds of elements of fluorine combine with covalent bond.Meanwhile, carbon-fluorine bond is extremely firm, and its bond energy reaches 460.2Kj/mol, and its molecule is stable.Therefore it is poor with the affinity of rubber.Politef is high temperature resistant simultaneously, and the solidification temperature of its coating is significantly high, and conventional rubber there will be carbonization at 260 DEG C.Simultaneously because rubber is the material that a kind of inertia is very strong, conventional curing coating is difficult to obtain good adhesion on its surface.
For the problems referred to above, need now the politef rubber coating of a kind of low-temperature curable badly, for instance can solidify at about 150 DEG C.
Summary of the invention
For the problems referred to above, the present invention provides the politef rubber coating of a kind of low-temperature curable, and described coating has good adhesive force, the oil resistivity of excellence, anti-wear performance and greasy property, can realize the solidification of politef at 130-150 DEG C simultaneously.
The present invention provides a kind of rubber coating compositions, by weight, at least includes:
Described acrylic resin modified for organosilicon modified crylic acid resin；
The structural formula of described viscosifier is as follows: R1-R2-R3-R4-R5；
Wherein, R1、R5Group is hydrophobic group, R2、R4Group is hydrophilic radical, R3Group is polymethylene, polyoxyethylene and polyoxypropylene.
As a kind of embodiment, described R1And R5Group contains fluorine element.
As a kind of embodiment, described R1And R5Group is the perfluoroalkyl of 2-6 selected from carbon number.
As a kind of embodiment, described R1And R5Group is selected from perfluoro butyl, perfluoropentyl, perfluoro hexyl.
As a kind of embodiment, the monomer preparing described acrylic resin at least includes alkyl acrylate, alkyl methacrylate, and the weight ratio of alkyl acrylate and alkyl methacrylate is (1～3): (4～1).
As a kind of embodiment, the structural formula of described organosilicon is as follows:
RSi(OR1)3(1)
In formula, R1Represent the organic group in alkoxyl, for instance, it is possible to enumerate methyl, ethyl, propyl group or phenyl.Any one group represented by R expression (1-1), formula (1-2).
CH2=C (R2)-COO-(CH2)P(1-1)
CH2=C (R3)(1-2)
In these formulas, R2And R3Representing hydrogen or methyl respectively, p represents the integer of 1～6.
As a kind of embodiment, also include hyperbranched sulfonation Nomex-silane copolymer, and the weight ratio of hyperbranched sulfonation Nomex and silane is (2～6): 1.
As a kind of embodiment, described hyperbranched sulfonation Nomex is by sulfonation triamine, triamine and dianhydride (0.1～0.3) in molar ratio: (0.7～0.9): (1～1.3) prepares
A kind of method using compositions described above, it is used as the surface coating of rubber molding product.
Another aspect of the present invention provides a kind of rubber molding product, and rubber surface has been carried out coating by above-mentioned compositions by it.
Detailed description of the invention
Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood present disclosure.Unless otherwise defined, all technology used herein and scientific terminology have the identical implication being generally understood that with one skilled in the art of the present invention.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ", " having ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, comprise the compositions of listed elements, step, method, goods or device and be not necessarily solely those key elements, but other not expressly listed key element or the intrinsic key element of this kind of compositions, step, method, goods or device can be included.
Conjunction " by ... composition " get rid of any key element, step or component do not pointed out.If in claim, this phrase will make claim be closed so that it is does not comprise the material except the material of those descriptions, but except relative customary impurities.When phrase " by ... composition " occurs in and is rather than immediately following after theme in the clause of claim main body, it is only limited to the key element described in this clause；Other key element is not excluded outside the described claim as entirety.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that and specifically discloses all scopes formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, regardless of whether whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end value and all integers within the scope of this and mark.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or " any one " refer to that the item described thereafter or event can occur or do not occur, and this description includes situation and the situation that do not occur of event that event occurs.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this particular number, also includes close to this quantity acceptable without causing the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term likely corresponds to measure the precision of the instrument of numerical value.In present specification and claims, scope limits and can combine and/or exchange, without additionally illustrating that these scopes include all subranges contained therebetween.
Additionally, indefinite article " one " before key element of the present invention or component and " one " quantitative requirement (i.e. occurrence number) unrestriction to key element or component.Therefore " one " or " one " should be read as and include one or at least one, and the key element of singulative or component also include plural form, unless the obvious purport of described quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.Generic term " polymer " comprises term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means by being polymerized polymer prepared by least two different monomers.Generic term " copolymer " includes term " copolymer " (it is generally in order to refer to the polymer prepared by two kinds of different monomers) and term " terpolymer " (it is generally in order to refer to the polymer prepared by three kinds of different monomers).It also comprises the polymer manufactured by polymerization four or more kinds of monomer." blend " mean two or more polymer by physics or the method for chemistry jointly mix and the polymer that formed.
The present invention provides a kind of rubber coating compositions, by weight, at least includes:
Described acrylic resin modified for organosilicon modified crylic acid resin；
The structural formula of described viscosifier is as follows: R1-R2-R3-R4-R5；
Wherein, R1、R5Group is hydrophobic group, R2、R4Group is hydrophilic radical, R3Group is polymethylene, polyoxyethylene and polyoxypropylene.
Politef:
Term used in this application " politef " refers to the polymer comprising tetrafluoroethylene monomer unit.
Term used in this application " tetrafluoroethylene monomer " includes having chemical formula CF2=CF2Tetrafluoroethene.
In one embodiment, it is possible to the melt viscosity for the politef of the application is 700,000 below Pa s, it is preferred to 55-65 ten thousand Pa s.
The melt viscosity of described politef is according to using flow velocity set tester method to record.
The polymerization of described politef is not particularly limited, it is possible to adopt any method well known by persons skilled in the art to prepare, including emulsion synthetic method and suspension polymerisation etc..
It is commercially available for may be used for the politef of the application.
Politef is full symmetric and unbranched linear macromolecule, and in politef, carbon, two kinds of elements of fluorine combine with covalent bond, and polyethylene is then combined by hydrocarbon two kinds of elements.In politef, fluorine atom instead of the hydrogen atom in polyethylene, owing to fluorine atom radius is significantly greater than hydrogen atom radius, make politef not to become the interatomic Van der Waals force of key more than polyethylene, having bigger repulsive force, this just causes carbon carbon bond to be gradually torqued into the spiral phenomenon of poly-four degree of ethylene by the plane of polyethylene, wide-spread tortuous conformation.This spiral phenomenon is just enclosed in politef by the protective layer defining a close fluoro completely outside the carbon chain backbone of chemical attack, and this main polymer chain being is by the invasion and attack of extraneous any reagent.Meanwhile, carbon-fluorine bond is extremely firm, and its bond energy reaches 460.2kJ/mol, high many more than carbon-hydrogen link (410kJ/mol) and carbon-carbon bond (372kJ/mol), and owing to the chemical bond energy of molecule is more high, its molecule is more stable.The structures shape of politef politef has a higher chemical stability, broad use temperature range, not stickiness, excellent lubricity, resistance to ag(e)ing and heat stability.But also due to the architectural feature of politef, the solidification temperature of teflon coating is higher, politef is non-polar polymer simultaneously, it is impossible to carry out crosslinking curing.Simultaneously in coating, due to the molecular structure reason of politef, the affinity of politef and resin is poor, the phenomenon of layering easily occurs.
Heretofore described politef is the emulsion that polytetrafluoroethylgranule granule is prepared from, described polytetrafluoroethylgranule granule be sized to 0.1-0.3 μm.
Acrylic resin modified:
Heretofore described acrylic resin modified acrylic resin modified for organic silicon monomer.
In the Si-O key of described organic silicon monomer, Rotation energy barrier is low, and key rotates easily, and surface can be little, and molecular volume is big so that organosilicon material has the thermostability of excellence, non-oxidizability.
Wherein, the structural formula of described organosilicon is
RSi(OR1)3(1)
In formula, R1Represent the organic group in alkoxyl, for instance, it is possible to enumerate methyl, ethyl, propyl group or phenyl.Any one group represented by R expression (1-1), formula (1-2).
CH2=C (R2)-COO-(CH2)P(1-1)
CH2=C (R3)(1-2)
In these formulas, R2And R3Representing hydrogen or methyl respectively, p represents the integer of 1～6.
As the functional group that formula (1-1) represents, it is possible to enumerate methacryloxyalkyl.As the siloxanes containing this group, for example, it is possible to enumerate Beta-methyl acryloyl-oxyethyl dimethoxymethylsilane, γ-methacryloxypropyl methoxyl group dimethylsilane, γ-methacryloxypropyl dimethoxymethylsilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl ethyoxyl diethylsilane, γ-methacryloxypropyl diethoxy silane, δ-methacryloxy butyl diethoxy silane.
As the siloxanes with the functional group that formula (1-2) represents, as vinyltrimethoxy silane, VTES can be enumerated.
As a kind of optimal way, the weight ratio of described organic silicon monomer and acrylic monomers is (0.2～0.4): 1, it is more preferable to for 0.25:1.
Acrylic resin refers to by the resin of acrylic compounds and methyl acrylic ester and other vinyl monomer copolymerizations.Conventional acrylic resin is prepared by three class monomers: hard monomer, soft monomer and function monomer.The vitrification point of described hard monomer is high, gives hardness of film, hot strength, cohesiveness and wearability；Soft monomer gives the certain pliability of film, extensibility and durability.The introducing of function monomer is introduced into functional group, gives the cross-linking reaction that polymer is certain, plays crosslinked action.
In the present invention, the monomer preparing described acrylic resin at least includes alkyl acrylate, alkyl methacrylate, and the carbon chain length of described alkyl acrylate is C1-C8, and the carbon chain length of described alkyl methacrylate is C1-C4.
As a kind of embodiment, described alkyl acrylate can enumerate acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, 2-EHA, n-octyl.
In the present invention, described alkyl acrylate is preferably the alkyl acrylate that vitrification point is relatively low, for instance n-butyl acrylate.
As a kind of embodiment, described alkyl methacrylate can enumerate methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate therein one or more.
When acrylic resin has various of monomer copolymerization to form, it is possible to synthesize the acrylic resin with particular glass temperature by the kind and percentage ratio shared in the copolymer adjusting monomer.Wherein, described vitrification point is that high polymer is changed into the temperature of glassy state by elastomeric state, has reacted the condition changed between high polymer elasticity and fragility.Acrylic resin belongs to typical copolymer, and its vitrification point can be calculated by Fox formula:
1 T = Σ i = 1 n W i T g i
The vitrification point of the mass ratio of every kind of monomer i and homopolymer thereof in Wi, Tgi respectively copolymer in above formula.The methacrylate difference from acrylic ester monomer is, methacrylate has methyl to exist at alpha-position, disturb the rotary motion of carbon-carbon skeletal chain, it it is typical unsymmetric structure, it can make the molecule of copolymer polarity occur, therefore the vitrification point of polymethacrylates is higher, brittle temperature and hot strength are bigger.Adding methacrylate and can improve the physical and mechanical properties of film, therefore methacrylate polymers is harder than acrylate polymer, and resistance to ag(e)ing is better.
The weight ratio of alkyl acrylate of the present invention and alkyl methacrylate is (1～3): (4～1), it is preferred to (2～3): (2～1).
In the present invention, described acrylic resin modified structure is preferably the less acrylic resin of side chain.
Acrylic resin modified preparation method can adopt any method well known by persons skilled in the art to prepare.Conventional method is condensation methods, radical polymerization and Si-H addition reaction method.Preferred radical polymerization in the present invention.
Radical polymerization is combined into and causes with free radical, makes the ever-increasing polyreaction of propagating radical, also known as radical polymerization.Raolical polymerizable, by opening the double bond in monomer molecule, in the intermolecular additive reaction being repeated repeatedly, couples together many monomers, forms macromole.The most frequently used method producing free radical is the decomposes of initiator, it is also possible to produce free radical by methods such as heating, ultraviolet irradiation, high-energy irradiation, electrolysis and plasma initiations.
As polymerization initiator, it is possible to enumerate peroxidating system polymerization initiator, azo system polymerization initiator etc..
As peroxidating system polymerization initiator, it is possible to enumerate the organic peroxides such as such as peroxycarbonates, ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester.
As azo system polymerization initiator, it is possible to enumerate such as 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2, the azo-compound such as 2 '-azo-bis-iso-dimethyl.
Binder resin:
Heretofore described binder resin can be binder resin well known by persons skilled in the art, for instance can be acrylic acid series polymeric compounds, improved polyalkene, epoxy resin, polyamidoimide, polyurethane resin, amino resins etc..
Acrylic acid series polymeric compounds: acrylic acid series polymeric compounds obtains by making the monomer reaction comprising acrylate and the acrylate containing functional group containing functional group.
nullAcrylate is alkyl methacrylate and/or alkyl acrylate，Specifically can enumerate (methyl) acrylic acid methyl ester.、(methyl) ethyl acrylate、(methyl) propyl acrylate、(methyl) isopropyl acrylate、(methyl) butyl acrylate、(methyl) Isobutyl 2-propenoate、(methyl) sec-butyl acrylate、(methyl) tert-butyl acrylate、(methyl) amyl acrylate、(methyl) isoamyl acrylate、(methyl) Hexyl 2-propenoate、(methyl) heptylacrylate、(methyl) 1-Octyl acrylate、(methyl) acrylic acid-2-ethyl caproite、(methyl) Isooctyl acrylate monomer、(methyl) acrylic acid ester in the ninth of the ten Heavenly Stems、(methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems、(methyl) decyl acrylate、(methyl) isodecyl acrylate、(methyl) acrylic acid undecyl ester、(methyl) dodecylacrylate、(methyl) tridecyl acrylate、(methyl) acrylic acid myristyl ester、(methyl) acrylic acid pentadecyl ester、(methyl) aliphatic acrylate、(methyl) acrylic acid heptadecyl ester、(methyl) octadecyl acrylate、(methyl) acrylic acid nonadecyl ester、Alkyl (methyl) acrylate etc. of the carbon numbers 1～20 (C1-20) such as (methyl) acrylic acid eicosyl ester.
As acrylate, it may be preferred to enumerate (methyl) acrylic acid C2-14 Arrcostab, more preferably enumerate (methyl) acrylic acid C4-9 Arrcostab.
Acrylate may be used singly or in combination of two or more.The combination that can preferably enumerate different types of (methyl) acrylic acid C4-9 Arrcostab uses, the combination that can more preferably enumerate (methyl) acrylic acid C4-6 Arrcostab and (methyl) acrylic acid C7-9 Arrcostab uses, and the combination that specifically can enumerate (methyl) butyl acrylate and (methyl) acrylic acid-2-ethyl caproite uses.
It addition, in order to introduce the crosslinking points for making monomer heat cross-linking, (methyl) acrylate containing functional group is involved in the composition.By by the acrylic ester polymerization containing functional group, it is possible to realize improving the bonding force with adherend.
As the acrylate containing functional group, it is possible to enumerate the acrylate of such as hydroxyl, containing sulfonic acrylate, the acrylate containing amino, the acrylate etc. containing glycidyl.
Vinyl monomer as hydroxyl, it is possible to enumerate such as (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-3-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, (methyl) acrylic acid own ester of-6-hydroxyl, (methyl) acrylic acid-8-hydroxyl monooctyl ester, (methyl) acrylic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid-12-hydroxylauric base ester, (methyl) acrylic acid (4-hydroxymethylcyclohexyl) methyl ester etc..
As containing sulfonic acrylate, it is possible to enumerate such as (methyl) acrylic acid sulphur propyl ester etc..
As the acrylate containing amino, it is possible to enumerate such as (methyl) dimethylaminoethyl acrylate, (methyl) tbutylaminoethylacrylate etc..
As the acrylate containing glycidyl, it is possible to enumerate such as (methyl) glycidyl acrylate etc..
As the acrylate containing functional group, it may be preferred to enumerate the acrylate of hydroxyl, it is possible to more preferably enumerate (methyl) acrylic acid-2-hydroxyl ethyl ester.
These acrylate containing functional group may be used singly or in combination of two or more.
It addition, relative to monomer, the mixing ratio of the acrylate containing functional group is such as 0.01～5 mass %, it is preferable that 0.03～3 mass %.
If the mixing ratio of the acrylate containing functional group exceedes the above-mentioned upper limit, then there is cohesiveness and become too high, heat conductivity adhesive resin composition the bonding force of the heat conductivity bonding sheet formed becomes insufficient situation.On the other hand, if not enough above-mentioned lower limit, then there is cohesiveness and decline, retentivity becomes insufficient situation.
Additionally, in order to improve the various characteristics such as such as cohesiveness, as required, can also contain in monomer can with the co-polymerized monomer of acrylic ester copolymer.
As co-polymerized monomer, such as (methyl) acrylic acid can be enumerated, itaconic acid, maleic acid, .beta.-methylacrylic acid, the carboxylic monomer such as maleic anhydride or its anhydride, such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxy (methyl) acrylamide, the monomer of the amide-containings such as N-butoxymethyl (methyl) acrylamide, the vinyl esters such as such as vinyl acetate, such as styrene, the aromatic ethenyl compounds such as vinyltoluene, such as (methyl) acrylonitrile, such as N-(methyl) acryloyl morpholine, such as NVP etc..
As co-polymerized monomer, it may be preferred to enumerate carboxylic monomer, it is possible to more preferably enumerate (methyl) acrylic acid.
These co-polymerized monomers may be used singly or in combination of two or more.
Relative to monomer, the mixing ratio of co-polymerized monomer is preferably 0.5～10 mass %, more preferably 1～5 mass %.
For making monomer reaction, the monomer comprising such as acrylate, the acrylate containing functional group and co-polymerized monomer as required is made to be polymerized.
Further, as by the method for polymerizing monomer components, it is possible to enumerate the known polymerizations such as such as polymerisation in solution, polymerisation in bulk, emulsion polymerization, various radical polymerizations, it may be preferred to enumerate polymerisation in solution.
In polymerisation in solution, coordinating monomer component to prepare monomer solution in a solvent, then heating monomer solution coordinates polymerization initiator simultaneously.
As solvent, it is possible to enumerate the organic solvents such as ether series solvent such as such as the aromatic series series solvent such as toluene, benzene, dimethylbenzene, such as ethyl acetate.
Solvent can be used alone or combine use.
Relative to monomer component 100 mass parts, the mixing ratio of solvent is such as 10～1000 mass parts, it is preferable that 50～500 mass parts.
As polymerization initiator, it is possible to enumerate peroxidating system polymerization initiator, azo system polymerization initiator etc..
As peroxidating system polymerization initiator, it is possible to enumerate the organic peroxides such as such as peroxycarbonates, ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester.
As azo system polymerization initiator, it is possible to enumerate such as 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2, the azo-compound such as 2 '-azo-bis-iso-dimethyl.
As polymerization initiator, it may be preferred to enumerate azo system polymerization initiator.
Relative to monomer 100 mass parts, the mixing ratio of polymerization initiator is such as 0.01～5 mass parts, it is preferable that 0.05～3 mass parts.
Heating-up temperature is such as 50～80 DEG C, and heat time heating time is such as 1～24 hour.
By above-mentioned polymerisation in solution by polymerizing monomer components, obtain the acrylic polymer solution containing acrylic acid series polymeric compounds.
For the viscosity of acrylic polymer solution, for instance be 0.1～100Pa s at 30 DEG C, it is preferable that 0.5～50Pa s.
If the viscosity of monomer mixture is unsatisfactory for above-mentioned scope, then formability or processability become insufficient sometimes.
If the mixing ratio of acrylic acid series polymeric compounds is unsatisfactory for above-mentioned scope, then cohesiveness, bonding force become insufficient sometimes.
The preferred 8000-10000 of weight average molecular weight of the acrylic polymer prepared.Weight average molecular weight is based on gel permeation chromatography (hreinafter referred to as " GPC ".) measure and carry out the value after polystyrene conversion.The condition determination of GPC adopts the condition test that this area is conventional, for instance, following mode can be adopted to test and to obtain.
Post: following post is connected in series and uses.
" TSKgelG5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer)；Column temperature: 40 DEG C；Eluent: oxolane (THF)；Flow velocity: 1.0mL/ minute；Injection rate: 100 μ L (tetrahydrofuran solution of sample solution concentration 4mg/mL)；Standard specimen: use following monodisperse polystyrene, makes standard curve.
Improved polyalkene: the polyolefin (A) used by the present invention is obtained by the olefinic polymerization of ethylene with at least one in the alpha-olefin that carbon number is 3～20 or more than a kind.
Specifically, except ethylene, carbon number be 3～20 alpha-olefin can enumerate propylene, 1-butylene, 2-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4, 4-dimethyl-1-amylene, 4-methyl isophthalic acid-hexene, 4, 4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, the alkene such as 1-eicosylene, can individually or Several combinations use above-mentioned single polymers or copolymer.
Wherein, polyolefin (A) is preferably single polymers or the copolymer of the alkene containing a kind or more than a kind in ethylene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene.
Wherein, polyolefin (A) be more preferably containing ethylene single-polymer (A-1) or ethylene and selected from carbon number be 3～20 alpha-olefin in the copolymer (A-2) of at least one.The present invention is particularly preferably propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene with the alpha-olefin of ethylene copolymer.
Epoxy resin: there is the epoxy resin of at least 2 epoxy radicals in 1 molecule, it is possible to use such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring epoxy resins,
As a kind of optimal way, epoxy resin of the present invention preferably has the epoxide equivalent being typically less than 300, it is more preferable to epoxide equivalent is 160-260.
In the present invention, the quality of described " epoxide equivalent " resin referred to relative to epoxy amount 1g equivalent, it is possible to measure as follows according to JISK7236:
Carrying out sample dissolution with chloroform and acetic acid, add solution 10ml in this lysate, described solution is the solution being dissolved in 400ml by tetraethyl-ammonium bromide 100g, using crystal violet as indicator and with perchloric acid acetum titration, is calculated by following formula.
Epoxide equivalent (g/eq)=1000 × m/ (c × v)
M: sample solid sub-prime amount (g),
C: the concentration of the perchloric acid acetic acid of volumetric solution,
V: titer.
Polyamidoimide: the polyamide-imide resin of the present invention is not particularly limited, as long as it is the polymer in the molecule with amido link and imide bond, for instance this polyamide-imide resin can be polymerized in the solvent with urea key by the trivalent carboxylic acid derivates making diisocyanate cpd with have anhydride group and prepare.
Compatilizer:
In system, very low in conjunction with enthalpy between polymer and polymer, so being difficult to compatible or reaching completely uniform mixed effect between polymer.Therefore, usually need to add in system to increase the compatilizer of the compatibility between incompatible two-phase polymer.
As a kind of embodiment, described compatilizer such as has water-miscible organic solvent, low molecular weight monomers.
As water-miscible organic solvent, it is possible to enumerate acetone, butanone, propylene glycol, dipropylene glycol methyl ether, dipropylene glycol, tripropylene glycol, ethanol etc.
As a kind of embodiment, described compatilizer can also is that surfactant.
Described surfactant can be anion surfactant: higher fatty acid salt, sulfonate, sulfate, fatty acyl-peptide condensation substance and phosphate ester salt；
Suitable anion surfactant includes: alkali alkyl sulfate such as sodium lauryl sulphate or lauryl sulphate acid potassium；Alkylsurfuric acid ammonium such as ammonium lauryl sulfate；The alkali metal salt of Brij-35 sodium sulfate, sodium sulfonate and sulfonated olefins；Alkyl sulfate enters the ammonium salt of sulfonated olefins；Soap such as sodium laurate, triethanolamine oleate or rosin acid triethanolamine；The alkali metal sulfates of alkylaryl sulfonates such as dodecylbenzene sodium sulfonate or alkaline phenol ethoxy；Senior alkyl naphthalene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product.
Described surfactant can be cationic surfactant: amine salt cationic surfactant and quaternary ammonium salt cationic surfactant；
Described surfactant can be amphoteric surfactant: amino acid type amphoteric surface active agent, betaine type amphoteric surfac-tant, imidazoline type amphoteric surfactant and amine oxide.
Described surfactant can be nonionic surfactant: polyethylene glycol type nonionic surfactant, polyol-based non-ionic surfactant；
Suitable nonionic surfactant includes polyoxyethylene ether, polyoxyethylene propylidene alkyl ether, polyoxyethylene phenyl ether and polyoxyethylene fatty acid ester.Particularly with stability preferably polyoxyethylene ether, polyoxyethylene propylidene alkyl ether and polyoxyethylene phenyl ether.Suitable example includes polyoxyethylene Octyl Ether, polyoxyethylene nonyl ethers, polyoxyethylene certain herbaceous plants with big flowers base ether, polyoxyethylene propylidene certain herbaceous plants with big flowers base ether, polyoxyethylenelauryl ether, polyoxyethylene propylidene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene propylidene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether and polyoxyethylene styrenated phenyl ether.
Described surfactant can be specific type surfactant: fluorine surfactant, silicon surface active agent, amino acid-based surfactant, high molecular surfactant and biosurfactant.
As a kind of optimal way, described surfactant can be Polyethylene Glycol, polyoxyethylene lauryl ether, isomery ten polyoxyethylenated alcohol, Heptadecyl alcohol polyethenoxy ether carboxylate.
Viscosifier:
The structural formula of heretofore described viscosifier is as follows:
R1-R2-R3-R4-R5
Wherein, R1、R5Group is hydrophobic group, R2、R4Group is hydrophilic radical, R3Group is linking group, the one in polymethylene, polyoxyethylene and polyoxypropylene.
Described hydrophobic group can be selected from pure carbochain, ester group, amide groups, fluoro-containing group etc., and the present invention is preferably fluoro-containing group.
Described fluoro-containing group refers to that protium on hydrocarbon group is by the replaced group of fluorine element, for instance: the carbon in alkane, alkene is replaced by fluorine element.Such as, the protium on butane is replaced by fluorine element, has perfluorinated butane, 3-pentafluorobutane, 1,1,1,2-tetrafluoro butane etc..The quantity of described replacement protium is not specifically limited, it is possible to be the whole protiums on alkane, alkene, it is also possible to be one, two or three protiums.
The preferred carbon number of heretofore described fluoro-containing group is the perfluoroalkyl of 2-6.
Described hydrophilic radical can be any hydrophilic radical well known by persons skilled in the art.Such as: hydroxy-acid group, sulfonic acid group, fatty polyol, phosphate group, sulfate group, amine salt type group and quaternary group.
In the present invention, it may be preferable to for sulfonic acid group, quaternary ammonium salt group.
Such as, when fluorine-containing hydrophobic group is perfluor polyoxypropylene, described hydrophilic group is quaternary ammonium salt, described R3Group is carbon number is the alkylidene of 6.
Described preparation method is as follows:
Hyperbranched sulfonation Nomex-silane copolymer:
Term of the present invention " silane-modified hyperbranched sulfonated polyimide " is prepared by the raw material including epoxy type silane coupler and amino-terminated hyperbranched sulfonated polyimide.
In one embodiment, the preparation method of described silane-modified hyperbranched sulfonated polyimide includes:
(1) preparation of amino-terminated hyperbranched sulfonated polyimide
In dry three-necked bottle, it is sequentially added into the organic good solvent of the triamine of 0.8mmol, the sulfonation triamine of 0.2mmol, the dianhydride of 1～1.3mmol, 2mmol benzoic acid, 0.5～3mL isoquinolin and 10～500mL.Logical nitrogen protection, after 0.1～10h, is warming up to 100～160 DEG C of reaction 1～4h, then heats to 180 DEG C～220 DEG C reaction 2～20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 30～80 DEG C of dry 2～10h obtain amino-terminated hyperbranched sulfonated polyimide；
(2) preparation of hyperbranched sulfonation Nomex-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched sulfonated polyimide 10 parts; epoxy type silane coupler KH-5601～30 part and appropriate good solvent; after stirring 5～50min under inert gas shielding; heat after reacting 0.1～10h to 60～100 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, at 20 DEG C～80 DEG C, dry 1h～24h, obtain silane-modified super-branched polyimide；
As a kind of embodiment, described hyperbranched sulfonated polyimide is by sulfonation triamine, triamine and dianhydride (0.1～0.3) in molar ratio: (0.7～0.9): (1～1.3) prepares, it is preferred to 0.2:0.8:1.1.
As a kind of embodiment, the weight ratio of described hyperbranched sulfonation Nomex and silane is (2～6): 1, it is preferred to 3:1.
In one embodiment, the described triamine any one or two kinds in 2,4,6-triamido pyridines and three (4-aminophenyl) amine；Preferably, described triamine is 2,4,6-triamido pyridines.
In one embodiment, described sulfonation triamine is selected from the sulfonated products of above-mentioned 2,4,6-triamido pyridines and the sulfonated products of three (4-aminophenyl) amine.
In one embodiment, described dianhydride selected from pyromellitic dianhydride, 3,4,9,10-tetracarboxylic anhydrides, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, the pungent-7-alkene-2 of dicyclo [2.2.2], 3,5,6-tetracarboxylic dianhydrides, 3,3', 4,4'-benzophenone tetracarboxylic dianhydrides, Isosorbide-5-Nitrae, in 5,8-naphthalenetetracarbacidic acidic dianhydrides any one or multiple；Preferably, described dianhydride is selected from 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and pungent-7-alkene-2 of dicyclo [2.2.2], any one or two kinds in 3,5,6-tetracarboxylic dianhydrides；It is highly preferred that described dianhydride is 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids.
Additive:
Do not affecting on the basis of the invention, the addition of agent can be added as required.Additive may be, but not limited to, one or more in light stabilizer, viscosity agent, delustering agent etc..Specifically, light stabilizer as used herein can be hindered amine light stabilizer.Light stabilizer may be, but not limited to, and selects free decanedioic acid double; two-(2,2,6,6-tetramethyl-4-piperidyls) ester (Tinuvin770), decanedioic acid be double; two-[N-methyl-2,2,6,6-pentamethyl-4-piperidyls) ester and four (2,2,6,6-tetramethyl-4-piperidyl-1,2,3,4-butane) tetrabasic ester composition group in one or more.Additionally, viscosity agent may be, but not limited to, select one or both or the more mixture of two kinds in the group of free polyurethanes (urethane esters) and acrylic compounds viscosity agent composition.Delustering agent as used herein can for changing the gloss on surface after forming coat film.Delustering agent may be, but not limited to, type siloxane delustering agent etc..
Wetting dispersing agent is the silicone additive that can improve surface sliding characteristic (slippingproperty), and the surface tension of coating composition can be reduced to increase the spreadability of compositions, and contact area can be increased to improve the bond properties to contact surface.The capillary reduction of coating composition is possible to prevent the contingent shrinkage cavity (cratering) when paint film is dry and the generation can swiped on surface by improving the slip characteristic on coating composition surface to suppress.Additionally, when slip characteristic improves, the scratch resistance of compositions and stain resistance can improve, it is possible to be easily performed washing, and adhesive resistance can improve.
Firming agent is the isocyanate prepolymer can in molecular end with multiple isocyanate groups (-NCO), and can in conjunction with to PEPA, alkyd polyol, acrylic polyhydric alcohol etc., to form the crosslinked coating film including amino-formate bond, thus improving the physical characteristic of coating composition.More specifically, firming agent can to include the form supply of diisocyanate, and the type of diisocyanate that firming agent includes can be classified as aromatic diisocyanate and aliphatic diisocyanate.The example of aromatic diisocyanate includes toluene di-isocyanate(TDI) (TDI), methylenediphenyl diisocyanates (MDI), XDI (XDI), naphthalene diisocyanate (NDI) etc., wherein, isocyanate groups is bonded directly to phenyl ring, and the example of aromatic diisocyanate includes isophorone diisocyanate (IPD), hexamethylene diisocyanate (HDI) etc..
Prepared by coating:
The preparation method that present invention also offers this coating composition, weighs each component by weight, and step is as follows:
The preparation of politef: politef, solvent are added in vessel, disperse 20～40min with high speed dispersor under the rotating speed of 1000～2000rpm, grind, controls fineness and is not more than 0.5 μm；
Prepared by coating: be added dropwise to binder resin, acrylic resin modified, compatilizer, viscosifier, light stabilizer, antiwear assistant, levelling agent in ground politef, 30～90min is disperseed at 1000～1800rpm with high speed dispersor, mix homogeneously, is eventually adding partial solvent and adjusts viscosity to 60～90s.
Painting method:
The present invention also provides for painting method, and its step containing the coating composition being coated with the invention described above on substrate surface forms.
Substrate surface as the coating composition that can be coated with the present invention, it does not have limit especially, comprises raw material metal face and its surface treatment face of such as ferrum, aluminum, zinc etc.；The raw material face of concrete, mortar, slabstone, timber, plastics, stone material etc. and its surface treatment face；And then on these raw material faces and surface treatment face arrange old coating film face etc..
As a kind of optimal way, the substrate surface that can be coated with the coating composition of the present invention is rubber, and described rubber is not particularly limited, and comprises such as silicone rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers, nitrile rubber, neoprene etc. or natural rubber.
Play present composition effect and be applicable not only to the formed products of above-mentioned rubber, the seal members such as such as O, oil sealing, packing ring, barrier film, valve, also it is used in the rubber components such as the rubber rollers of used in copy machines, rubber strip, industrial rubber hose, rubber strip, wiper, weather strip for automobile, stripping chute, is efficiently used for their anti-bonding, low friction, wet goods anti-wear, anti-.
The compositions of the present invention also applies to easily produce dirt, damage, oil tank sealing cover etc..
This coating can utilize general method to carry out, for instance can be coated with bristle, spray, roller coat, trowelling, various coater coatings etc. carry out, and can also be coated with coating and/or painting coating as required on the film formed in being coated with.Middle painting coating and painting coating are not particularly limited, the coating of organic solvent known per se or aqueous can be used, it is possible to enumerate the coating of such as epoxy resin, acrylic resin system, polyurethane resin system, acrylic rubber system, organic siliconresin system, fluororesin system.
Politef, due to the speciality of its molecular structure, just can only solidify under ability high temperature.But present inventor is found surprisingly that, described coating composition can solidify at 150 DEG C.Simultaneously present inventor is found surprisingly that, and after acrylic resin modified in the present invention, viscosifier and politef carry out pretreatment at lower than 130 DEG C, the cured film of formation is very fine and close, has very strong oil resistance simultaneously, has very strong adhesive force with rubber.This possible reason is because described viscosifier and will not evaporate when more than 100 DEG C, when simultaneously they are at lower than 130 DEG C, molecular chain structure becomes very soft, very strong affinity is now had with politef, therefore, passing below the pretreatment at 130 DEG C of temperature, the film of the rubber coating compositions of the politef of the present invention is very fine and close.
By the examples below the present invention is specifically described.Be necessary it is pointed out here that be; following example are served only for that the invention will be further described; it is not intended that limiting the scope of the invention; some nonessential improvement and adjustment that professional and technical personnel in the field makes according to the content of the invention described above, still fall within protection scope of the present invention.
It addition, illustrate without other, raw materials used is all commercially available.
A1: politef (PTFE)
The trade mark of described politef is AD-911, is purchased from Japan AGC.
B1: binder resin (acrylic resin)
The trade mark of described acrylic resin is PB9788, is purchased from Shanghai weathercock chemistry Science and Technology Ltd.；
B2: binder resin (amino resins)
The trade mark of described amino resins is CYMEL-325, is purchased from U.S.'s cyanogen special；
B3: binder resin (polyurethane resin)
Described polyurethane resin trade mark 786L, is purchased from Dongguan City Huang river Samsung plastic material company.
C1: acrylic resin modified (acrylic resin)
The trade mark of described acrylic resin is PB9788, is purchased from Shanghai weathercock chemistry Science and Technology Ltd.；
C2: acrylic resin modified (organosilicon modified crylic acid resin, and the weight ratio of organosilicon and acrylic resin is 0.25:1, the structural formula of described organosilicon is CH2=CHSi (OCH3)3)
Described acrylic resin is prepared by (methyl) acrylic acid methyl ester. of 40wt% and the butyl acrylate of 60wt%.
Preparation method: (1) raw material mixes: by above-mentioned 0.25 weight portion organosilicon and the acrylic resin of 1 weight portion, 2,2 '-azodiisobutyronitrile, tert-dodecyl mercaptan mix homogeneously by a certain percentage, prepare monomer mixture, the consumption that makes of described tert-dodecyl mercaptan is 0.1wt%, described 2, the consumption that makes of 2 '-azodiisobutyronitrile is 0.1wt%；
(2) polyreaction: adding a certain amount of toluene in reaction vessel, heating, to reflux state, maintains the reflux for state, and at the uniform velocity drips monomer mixture in reaction vessel, dropwised in 3 hours, then regulates reaction mass to 70 DEG C, and is incubated 1 hour；
(3) post processing: using the method for normal pressure and decompression distillation that solvent is evaporated off, material is poured in aluminum dish while hot, cooling, obtains the organosilicon modified crylic acid resin of the present invention.
C3: acrylic resin modified (organosilicon modified crylic acid resin, and the weight ratio of organosilicon and acrylic resin is 0.4:1, the structural formula of described organosilicon is CH2=CH-COOCH2Si(OCH3)3)
Described acrylic resin is prepared by (methyl) acrylic acid methyl ester. of 40wt% and the butyl acrylate of 60wt%.
Preparation method: (1) raw material mixes: by above-mentioned 0.4 weight portion organosilicon and the acrylic resin of 1 weight portion, 2,2 '-azodiisobutyronitrile, tert-dodecyl mercaptan mix homogeneously by a certain percentage, prepare monomer mixture, the consumption that makes of described tert-dodecyl mercaptan is 0.1wt%, described 2, the consumption that makes of 2 '-azodiisobutyronitrile is 0.1wt%；
(2) polyreaction: adding a certain amount of toluene in reaction vessel, heating, to reflux state, maintains the reflux for state, and at the uniform velocity drips monomer mixture in reaction vessel, dropwised in 3 hours, then regulates reaction mass to 70 DEG C, and is incubated 1 hour；
(3) post processing: using the method for normal pressure and decompression distillation that solvent is evaporated off, material is poured in aluminum dish while hot, cooling, obtains the organosilicon modified crylic acid resin of the present invention.
C4: acrylic resin modified (organosilicon modified crylic acid resin, and the weight ratio of organosilicon and acrylic resin is 0.5:1, the structural formula of described organosilicon is CH2=CHSi (OCH3)3)
Described acrylic resin is prepared by (methyl) acrylic acid methyl ester. of 40wt% and the butyl acrylate of 60wt%.
Preparation method: (1) raw material mixes: by above-mentioned 0.5 weight portion organosilicon and the acrylic resin of 1 weight portion, 2,2 '-azodiisobutyronitrile, tert-dodecyl mercaptan mix homogeneously by a certain percentage, prepare monomer mixture, the consumption that makes of described tert-dodecyl mercaptan is 0.1wt%, described 2, the consumption that makes of 2 '-azodiisobutyronitrile is 0.1wt%；
(2) polyreaction: adding a certain amount of toluene in reaction vessel, heating, to reflux state, maintains the reflux for state, and at the uniform velocity drips monomer mixture in reaction vessel, dropwised in 3 hours, then regulates reaction mass to 70 DEG C, and is incubated 1 hour；
(3) post processing: using the method for normal pressure and decompression distillation that solvent is evaporated off, material is poured in aluminum dish while hot, cooling, obtains the organosilicon modified crylic acid resin of the present invention.
C5: acrylic resin modified (organosilicon modified crylic acid resin, and the weight ratio of organosilicon and acrylic resin is 0.1:1, the structural formula of described organosilicon is CH2=CHSi (OCH3)3)
Described acrylic resin is prepared by (methyl) acrylic acid methyl ester. of 40wt% and the butyl acrylate of 60wt%.
Preparation method: (1) raw material mixes: by above-mentioned 0.1 weight portion organosilicon and the acrylic resin of 1 weight portion, 2,2 '-azodiisobutyronitrile, tert-dodecyl mercaptan mix homogeneously by a certain percentage, prepare monomer mixture, the consumption that makes of described tert-dodecyl mercaptan is 0.1wt%, described 2, the consumption that makes of 2 '-azodiisobutyronitrile is 0.1wt%；
(2) polyreaction: adding a certain amount of toluene in reaction vessel, heating, to reflux state, maintains the reflux for state, and at the uniform velocity drips monomer mixture in reaction vessel, dropwised in 3 hours, then regulates reaction mass to 70 DEG C, and is incubated 1 hour；
(3) post processing: using the method for normal pressure and decompression distillation that solvent is evaporated off, material is poured in aluminum dish while hot, cooling, obtains the organosilicon modified crylic acid resin of the present invention.
D1: (weight ratio of hyperbranched sulfonation Nomex and silane is 2:1 to hyperbranched sulfonation Nomex-silane copolymer, and hyperbranched sulfonation Nomex is prepared by sulfonation triamine, triamine and dianhydride 0.1:0.9:1 in molar ratio.)
Preparation method: the preparation of (1) amino-terminated hyperbranched sulfonated polyimide
In dry three-necked bottle, it is sequentially added into the dimethyl sulfoxide of sulfonation three (4-aminophenyl) amine of 0.1mmol, three (4-aminophenyl) amine of 0.9mmol, the pyromellitic dianhydride of 1mmol, 2mmol benzoic acid, 2mL isoquinolin and 200mL.Logical nitrogen protection, after 5h, is warming up to 140 DEG C of reaction 4h, then heats to 180 DEG C of reaction 20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 50 DEG C of dry 10h obtain amino-terminated hyperbranched polyimides；
(2) hyperbranched sulfonation Nomex-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched polyimides 10 weight portion; epoxy type silane coupler KH-5605 weight portion and dimethyl sulfoxide; after stirring 20min under inert gas shielding; heat after reacting 5h to 80 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide；
D2: hyperbranched sulfonation Nomex-silane copolymer (weight ratio of hyperbranched sulfonation Nomex and silane is 6:1, and hyperbranched sulfonation Nomex is prepared by sulfonation triamine, triamine and dianhydride 0.1:0.9:1 in molar ratio)
Preparation method: the preparation of (1) amino-terminated hyperbranched sulfonated polyimide
In dry three-necked bottle, it is sequentially added into the dimethyl sulfoxide of sulfonation three (4-aminophenyl) amine of 0.1mmol, three (4-aminophenyl) amine of 0.9mmol and the pyromellitic dianhydride of 1mmol, 2mmol benzoic acid, 2mL isoquinolin and 200mL.Logical nitrogen protection, after 5h, is warming up to 140 DEG C of reaction 4h, then heats to 180 DEG C of reaction 20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 50 DEG C of dry 10h obtain amino-terminated hyperbranched polyimides；
(2) hyperbranched sulfonation Nomex-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched polyimides 6 weight portion; epoxy type silane coupler KH-5601 weight portion and dimethyl sulfoxide; after stirring 20min under inert gas shielding; heat after reacting 5h to 80 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide；
D3: hyperbranched sulfonation Nomex-silane copolymer (weight ratio of hyperbranched sulfonation Nomex and silane is 3.5:1, and hyperbranched sulfonation Nomex is prepared by sulfonation triamine, triamine and dianhydride 0.1:0.9:1 in molar ratio)
Preparation method: the preparation of (1) amino-terminated hyperbranched sulfonated polyimide
In dry three-necked bottle, it is sequentially added into the dimethyl sulfoxide of sulfonation three (4-aminophenyl) amine of 0.1mmol, three (4-aminophenyl) amine of 0.9mmol and the pyromellitic dianhydride of 1mmol, 2mmol benzoic acid, 2mL isoquinolin and 200mL.Logical nitrogen protection, after 5h, is warming up to 140 DEG C of reaction 4h, then heats to 180 DEG C of reaction 20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 50 DEG C of dry 10h obtain amino-terminated hyperbranched polyimides；
(2) hyperbranched sulfonation Nomex-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched polyimides 7 weight portion; epoxy type silane coupler KH-5602 weight portion and dimethyl sulfoxide; after stirring 20min under inert gas shielding; heat after reacting 5h to 80 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide；
D4: hyperbranched sulfonation Nomex-silane copolymer (weight ratio of hyperbranched sulfonation Nomex and silane is 3.5:1, and hyperbranched sulfonation Nomex is prepared by sulfonation triamine, triamine and dianhydride 0.2:0.8:1 in molar ratio)
(1) preparation of amino-terminated hyperbranched sulfonated polyimide
In dry three-necked bottle, it is sequentially added into the dimethyl sulfoxide of sulfonation three (4-aminophenyl) amine of 0.2mmol, three (4-aminophenyl) amine of 0.8mmol and the pyromellitic dianhydride of 1mmol, 2mmol benzoic acid, 2mL isoquinolin and 200mL.Logical nitrogen protection, after 5h, is warming up to 140 DEG C of reaction 4h, then heats to 180 DEG C of reaction 20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 50 DEG C of dry 10h obtain amino-terminated hyperbranched polyimides；
(2) hyperbranched sulfonation Nomex-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched polyimides 3.5 weight portion; epoxy type silane coupler KH-5601 weight portion and dimethyl sulfoxide; after stirring 20min under inert gas shielding; heat after reacting 5h to 80 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide；
D5: hyperbranched sulfonation Nomex-silane copolymer (weight ratio of hyperbranched sulfonation Nomex and silane is 3.5:1, and hyperbranched sulfonation Nomex is prepared by sulfonation triamine, triamine and dianhydride 0.3:0.7:1.1 in molar ratio)
(1) preparation of amino-terminated hyperbranched sulfonated polyimide
In dry three-necked bottle, it is sequentially added into the dimethyl sulfoxide that dianhydride is pyromellitic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and 200mL of sulfonation 2,4, the 6-triamido pyridine of 0.3mmol, 2,4, the 6-triamido pyridines of 0.7mmol, 1.1mmol.Logical nitrogen protection, after 5h, is warming up to 140 DEG C of reaction 4h, then heats to 180 DEG C of reaction 20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 50 DEG C of dry 10h obtain amino-terminated hyperbranched polyimides；
(2) hyperbranched sulfonation Nomex-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched polyimides 7 weight portion; epoxy type silane coupler KH-5602 weight portion and dimethyl sulfoxide; after stirring 20min under inert gas shielding; heat after reacting 5h to 80 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide；
D6: Hyperbranched Aromatic Polyamides-silane copolymer (weight ratio of hyperbranched sulfonation Nomex and silane is 3.5:1, and hyperbranched sulfonation Nomex is prepared by triamine and dianhydride 1:1.1 in molar ratio)
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, it is sequentially added into the dimethyl sulfoxide that dianhydride is pyromellitic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and 200mL of 2,4, the 6-triamido pyridines of 1mmol, 1.1mmol.Logical nitrogen protection, after 5h, is warming up to 140 DEG C of reaction 4h, then heats to 180 DEG C of reaction 20h.Reaction is down to room temperature and pours in methanol by reaction solution, precipitating out a large amount of solid after terminating.After this solids with methanol cyclic washing, sucking filtration and by the solid collected in vacuum drying oven, 50 DEG C of dry 10h obtain amino-terminated hyperbranched polyimides；
(2) Hyperbranched Aromatic Polyamides-silane copolymer
The there-necked flask being completely dried adds amino-terminated hyperbranched polyimides 7 weight portion; epoxy type silane coupler KH-5602 weight portion and dimethyl sulfoxide; after stirring 20min under inert gas shielding; heat after reacting 5h to 80 DEG C; it is down to room temperature; solution is poured in methanol, has Precipitation；After filtering after removing solvent with methanol cyclic washing, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide；
E1: compatilizer (dodecylbenzene sodium sulfonate) anion form is lived
The trade mark: P60, supplier is Guangzhou Zou Yang Chemical Co., Ltd.；
E2: compatilizer (isomery ten polyoxyethylenated alcohol) nonionic table is lived
Described isomery ten polyoxyethylenated alcohol uses E1006, and supplier is Hai'an petro-chemical corporation.
E3: compatilizer (Heptadecyl alcohol polyethenoxy ether carboxylate) nonionic table is lived
Described Heptadecyl alcohol polyethenoxy ether carboxylate uses AEO-9, and supplier creates Chemical Co., Ltd. for Guangzhou.
F1: (structural formula is R to viscosifier1-R2-R3-R4-R5, R1For long-chain carbon, R2Sulfonic acid group, without R3-R5Group), described viscosifier are n-hexadecyl sodium sulfonate, model: 70, and manufacturer is Zhengzhou Guan Da chemical products company limited；
F2: (structural formula is R to viscosifier1-R2-R3-R4-R5, R1For fluoro-containing group, R2Quaternary ammonium salt group, without R3-R5Group), described viscosifier are perfluoro capryl quaternary ammonium salt, and synthesis step is as follows:
F3: (structural formula is R to viscosifier1-R2-R3-R4-R5, R1=R5For the long-chain carbon that carbon number is 8, R2=R4For quaternary ammonium salt group, R3It is the Long carbon chain of 6 for carbon number), the synthesis step of described viscosifier is as follows:
No. CAS of described N, N-dimethyl n octylame is 7378-99-6.
F4: (structural formula is R to viscosifier1-R2-R3-R4-R5, R1=R5For fluoro-containing group, R2=R4For quaternary ammonium salt group, R3For Long carbon chain), the synthesis step of described viscosifier is as follows:
F5: (structural formula is R to viscosifier1-R2-R3-R4-R5, R1=R5For fluoro-containing group, R2=R4For quaternary ammonium salt group, R3Group for containing phenyl ring), described preparation process such as F4, except hexamethylene diamine is replaced with 2,2'(1,4-phenylene) diethylamine, described 2,2'(1,4-phenylene) No. CAS of diethylamine be 7423-50-9, is purchased from the two days biochemical company limiteies in Wuhan, Hubei.
G1: water
Described water is the distilled water that second distillation is crossed.
Table 1 embodiment is arranged
Performance test:
1, coating appearance adopts GB9278-1988 standard testing；
2, film property stability is respectively adopted HG/T2458-1993 standard testing；
3, resistance to surface abrasion: using surface wear testing machine with No. 6 canvas of loading of 1Kgf, the surface of each sheet material after shaping to be rubbed, measuring until producing the number of times of cut.And, it is evaluated with following benchmark.
More than zero: 5000 time
More than △: 2000 times～lower than 5000 times
×: lower than 2000 times；
4, oil resistivity evaluation: the ratio face of each sheet material after forming is coated with Adeps Bovis seu Bubali with 2cm radius, after placing 5 days, removes Adeps Bovis seu Bubali under 80 DEG C of atmosphere.And, by gridiron pattern cellophane tape, the coated side of Adeps Bovis seu Bubali is carried out disbonded test, is evaluated with following benchmark:
Zero: good
×: bad
5, adaptation evaluation: coated by coating composition on sheet material, makes its hot air drying at 130 DEG C at 5 minutes, 250 DEG C 60 minutes, and making dried thickness is 15 ± 5 μm, it is thus achieved that duplexer.According to the cross cut test using cellophane tape, thus evaluating the adaptation of the film of coating composition.Testing standard: JISK5600-5-6:1999.
When temperature (23 ± 2) DEG C, relative humidity (50 ± 5) %, on the film layer being made up of the coating composition of above-mentioned duplexer, form the 100mm of 10mm × 10mm in 1mm interval2Decussation cutting grid, the outward appearance of film of residual after visualization cellophane tape glass.
Zero: the situation that the number of grid remains completely；
△: the quantity residual of grid is the situation less than 100 and more than 80；
×: the quantity of grid only remains the situation less than 80；
6, cohesive evaluation: evaluation criterion: JIS-K5400
After the laminated polyester film obtained is placed in each condition of following (1)～(3), establishing criteria, the cutting guide rail excision that uses clearance gap to be 1mm is through is cut stricture of vagina by rete 100 lattice-shapeds reaching base film.Subsequently, transparent adhesive tape is glued on the facet being posted on lattice-shaped, carry out wiping with erasing rubber, thus so as to after adhering to completely, quickly peel off with the peel angle of 90 °, observe release surface subsequently, and by following standard, cohesive has been evaluated:
Adhesion test condition:
(1) normality cohesive: 23 DEG C/relative humidity 65%, 24 hours；
(2) moistening cohesive: 60 DEG C/relative humidity 90%, 100 hours；
(3) wet-heat resisting cohesive: 60 DEG C/relative humidity 90%, 300 hours；
Cohesive evaluation criterion:
◎: peel off area less than 5%
Zero: peel off area more than 5%, less than 15%
△: peel off area more than 15%, less than 20%
×: peel off area more than 20%.
7, petrol-resistance
By the polypropylene loop device of diameter 4cm at each coated surface, and then cover the lid having 5mm hole, and crimp, add the gasoline of 10ml with dropping pipette from this hole, use cellophane tape plugging hole.After at room temperature placing 4 hours, remove gasoline, the outward appearance of visual film, be carried out as follows evaluation.Shown in result:
Zero: without exception；
×: expand, it has been found that peel off.
In sum, it is known that, the coating composition of the present invention, compared with not containing sulfonated polyimide-silane copolymer acrylic resin modified, hyperbranched and viscosifier, has very strong oil resistant, antifriction, film property, cohesive and compactness.
Aforesaid example is merely illustrative, for explaining some features of inventive feature.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and embodiments as presented herein is only the explanation of embodiment of selection of combination according to all possible embodiment.Therefore, the selectional restriction of the example that the claim that the purpose of applicant is appended is not illustrated inventive feature.And the progress in science and technology will form the possible equivalent not being presently considered due to the inaccurate reason of language performance or son replacement, and these changes also should be interpreted to be covered by appended claim in the conceived case.

Claims (10)

1. a coating composition, by weight, at least includes:
Described acrylic resin modified for organosilicon modified crylic acid resin；
The structural formula of described viscosifier is as follows:
R1-R2-R3-R4-R5
Wherein, R1、R5Group is hydrophobic group, R2、R4Group is hydrophilic radical, R3Group is polymethylene, polyoxyethylene and polyoxypropylene.
2. the compositions described in claim 1, described R1And R5Group contains fluorine element.
3. the compositions described in claim 1, described R1And R5Group is the perfluoroalkyl of 2-6 selected from carbon number.
4. the compositions described in claim 1, described R1And R5Group is selected from perfluoro butyl, perfluoropentyl, perfluoro hexyl.
5. the compositions described in claim 1, the monomer preparing described acrylic resin at least includes alkyl acrylate, alkyl methacrylate, and the weight ratio of alkyl acrylate and alkyl methacrylate is (1～3): (4～1).
6. the compositions described in claim 1, the structural formula of described organosilicon is as follows:
RSi(OR1)3(1)
In formula, R1Represent the organic group in alkoxyl, for instance, it is possible to enumerate methyl, ethyl, propyl group or phenyl.Any one group represented by R expression (1-1), formula (1-2).
CH2=C (R2)-COO-(CH2)P(1-1)
CH2=C (R3)(1-2)
In these formulas, R2And R3Representing hydrogen or methyl respectively, p represents the integer of 1～6.
7. the compositions described in claim 1, also includes the hyperbranched sulfonation Nomex-silane copolymer of 1-10 weight portion, and the weight ratio of hyperbranched sulfonation Nomex and silane is (2～6): 1.
8. the compositions described in claim 7, described hyperbranched sulfonation Nomex is by sulfonation triamine, triamine and dianhydride (0.1～0.3) in molar ratio: (0.7～0.9): (1～1.3) prepares.
9. the compositions described in claim 1, it is used as the aqueous teflon coating of rubber molding product.
10. rubber molding product, surface has been carried out coating by the compositions described in claim 1～9 by it.
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CN108020444A (en) * 2017-11-17 2018-05-11 上海市城市排水监测站 A kind of water level is servo-actuated sampling system
CN110591551A (en) * 2019-08-20 2019-12-20 宁波喜尔美厨房用品有限公司 Preparation method of high-strength high-wear-resistance non-stick pan coating
CN114645488A (en) * 2022-02-16 2022-06-21 江阴宝柏包装有限公司 Paper-based recyclable composite material and preparation method thereof

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CN101824271A (en) * 2010-05-25 2010-09-08 吕相洋 Aqueous bi-component coating of vehicle rubber and plastic sealing strip and preparation method thereof
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CN108020444A (en) * 2017-11-17 2018-05-11 上海市城市排水监测站 A kind of water level is servo-actuated sampling system
CN110591551A (en) * 2019-08-20 2019-12-20 宁波喜尔美厨房用品有限公司 Preparation method of high-strength high-wear-resistance non-stick pan coating
CN114645488A (en) * 2022-02-16 2022-06-21 江阴宝柏包装有限公司 Paper-based recyclable composite material and preparation method thereof

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