CN105838160B - Coating composition and its lubricating and wear-resisting polytetrafluoroethylene (PTFE) rubber coating of preparation - Google Patents

Coating composition and its lubricating and wear-resisting polytetrafluoroethylene (PTFE) rubber coating of preparation Download PDF

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CN105838160B
CN105838160B CN201610217791.2A CN201610217791A CN105838160B CN 105838160 B CN105838160 B CN 105838160B CN 201610217791 A CN201610217791 A CN 201610217791A CN 105838160 B CN105838160 B CN 105838160B
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methyl
acid
ptfe
organosilicon
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CN105838160A (en
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方六月
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Yechong New Material Technology Shanghai Co ltd
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Ye New Material Technology (shanghai) 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to a kind of coating composition, by weight, at least include：The polytetrafluoroethylene (PTFE) 15 20 of 15 20 weight portions, the binder resin of 6 13 weight portions, the acrylic resin modified of 15 weight portions, the compatilizer of 25 40 weight portions, the water of 100 weight portions；Wherein it is described it is acrylic resin modified be organosilicon, organic fluorin modified crylic acid resin.

Description

Coating composition and its lubricating and wear-resisting polytetrafluoroethylene (PTFE) rubber coating of preparation
Technical field
This patent is related to rubber coating field, is specifically related to C09D133.
Background technology
Silicon rubber has elastic good, good weatherability, the advantages of non-aging, is applied to every field, for example：Electronics, electricity O-ring on the button of device product, fuel tank cap or engine etc..But the mechanical performance of silicon rubber is poor, as oil During O-ring on case lid or engine, it is necessary to coat a coating on the surface of silicon rubber, to wear-resisting, lubrication, oil resistant it With.
Polytetrafluoroethylene (PTFE), also known as King, with lubrication, it is wear-resisting, do not stick, the performance such as anti-corrosion, high temperature resistant, thus through conventional In rubber coating field, but it is 385-425 DEG C because the solidification temperature of teflon coating is higher, and some conventional Rubber can be carbonized at 260 DEG C or so, and this defect seriously limits application of the polytetrafluoroethylene (PTFE) in rubber coating field.
Regarding to the issue above, a kind of polytetrafluoroethylene (PTFE) rubber coating of low-temperature curable is needed badly now, such as on 150 DEG C of left sides It is right to solidify.Simultaneously because silicon rubber is a kind of very strong material of inertia, conventional curing coating is difficult to be obtained on its surface Obtain good adhesion.
The content of the invention
Regarding to the issue above, the present invention provides a kind of polytetrafluoroethylene (PTFE) rubber coating of low-temperature curable, the coating tool There is good adhesive force, excellent oil resistivity, anti-wear performance and greasy property, while polytetrafluoro can be realized at 130-150 DEG C The solidification of ethene.
The present invention provides a kind of rubber coating composition of low-temperature curable polytetrafluoroethylene (PTFE), by weight, at least wraps Include：
It is described it is acrylic resin modified be organosilicon, organic fluorin modified crylic acid resin.
Used as a kind of implementation method, the weight ratio of the organosilicon, Organic fluoride and acrylic resin is (0.2~0.4)： (0.05~0.1)：1.
Used as a kind of implementation method, the structural formula of the organosilicon is as follows：
RSi(OR1)3 (1)
In formula, R1The organic group in alkoxy is represented, for example, methyl, ethyl, propyl group or phenyl can be enumerated.R is represented Any one group represented by formula (1-1), formula (1-2).
CH2=C (R2)-COO-(CH2)P (1-1)
CH2=C (R3) (1-2)
In these formulas, R2And R3Hydrogen or methyl are represented respectively, and p represents 1~6 integer.
Used as a kind of implementation method, the structural formula of the Organic fluoride is as follows：
Wherein, R1、R2、R3And R4Selected from one or more in fluorine, hydrogen, carboxyl, hydroxyl, epoxy radicals, and R1、R2、R3And R4 In at least one be fluorine.
Used as a kind of implementation method, the composition also includes sulfonated polyimide-silane copolymer.
Used as a kind of implementation method, the sulfonated polyimide is by amino-terminated sulfonated polyimide prepolymer and epoxy silicon Alkane is prepared.
As a kind of implementation method, the sulfonated polyimide by sulfonated diamine, diamines and dianhydride in molar ratio (0.1~ 0.5)：(0.9~0.5)：(0.75~0.98) prepares.
Used as a kind of implementation method, the weight ratio of the sulfonated polyimide and epoxy silane is (5~10)：1.
A kind of method using composition described above, its surface coating for being used as rubber molding product.
Another aspect of the present invention provides a kind of rubber molding product, and it is applied with above-mentioned composition to rubber surface Layer.
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " including ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, and can be including not expressly listed other key elements or This kind of composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this Phrase will make claim be closed, it is not included the material in addition to the material that those are described, but relative normal Except rule impurity.When phrase " Consists of " is appeared in be rather than immediately following after theme in the clause of claim main body, It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open During 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 number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end Value and all integers and fraction within the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise.It is " optional " or " any It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific Quantity, also including the acceptable part without cause the amendment of the change of related basic function close to the quantity.Phase Answer, a numerical value is modified with " about ", " about " etc., mean the invention is not restricted to the exact numerical.In some examples, approximately Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by the identical or different type that is polymerized.Generic term " polymer " includes term " homopolymers ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer prepared by least two different monomers that are polymerized.Generic term " EVA " includes (its is general with term " terpolymer " for term " copolymer " (it is typically used to refer to the polymer prepared by two kinds of different monomers) It is used to refer to the polymer prepared by three kinds of different monomers).Its polymerization for also being manufactured comprising monomer is planted by polymerization four or more Thing." blend " means the polymerization that two or more polymer is mixed and formed jointly by physics or chemistry method Thing.
The present invention provides a kind of rubber coating composition of low-temperature curable polytetrafluoroethylene (PTFE), by weight, at least wraps Include：
It is described it is acrylic resin modified be organosilicon, organic fluorin modified crylic acid resin.
Polytetrafluoroethylene (PTFE)：
Term " polytetrafluoroethylene (PTFE) " used in this application refers to the polymer comprising tetrafluoroethylene monomer unit.
Term " tetrafluoroethylene monomer " used in this application includes thering is chemical formula CF2=CF2Tetrafluoroethene.
In one embodiment, can be used for the melt viscosity of the polytetrafluoroethylene (PTFE) of the application for 700,000 below Pas, The preferably Pas of 55-65 ten thousand.
The melt viscosity of the polytetrafluoroethylene (PTFE) is measured according to using flow velocity set tester method.
The polymerization of the polytetrafluoroethylene (PTFE) is not particularly limited, and can use well known by persons skilled in the art any Prepared by method, including the emulsion synthetic method and suspension polymerisation etc..
The polytetrafluoroethylene (PTFE) that can be used for the application is commercially available.
Polytetrafluoroethylene (PTFE) is full symmetric and unbranched linear macromolecule, carbon, two kinds of elements of fluorine in polytetrafluoroethylene (PTFE) It is combined with covalent bond, and polyethylene is combined by hydrocarbon two kinds of elements.In polytetrafluoroethylene (PTFE), fluorine atom instead of poly- second Hydrogen atom in alkene, because fluorine atom radius is significantly greater than hydrogen atom radius so that non-bonding is interatomic in polytetrafluoroethylene (PTFE) Van der Waals force is more than polyethylene, there is larger repulsive force, and this just causes plane, wide-spread song of the carbon carbon bond by polyethylene Folding conformation is torqued into the spiral phenomenon of poly- four degree of ethene gradually.The spiral phenomenon is just enclosed in polytetrafluoroethylene (PTFE) by chemical attack Carbon chain backbone outside form a closely protective layer for fluoro completely, the main polymer chain that this is is by extraneous any reagent Invasion and attack.Meanwhile, carbon-fluorine bond is extremely firm, and its bond energy reaches 460.2kJ/mol, more than carbon-hydrogen link (410kJ/mol) and carbon-carbon bond (372kJ/mol) high many, because the chemical bond energy of molecule is higher, its molecule is more stable.The structures shape of polytetrafluoroethylene (PTFE) Polytetrafluoroethylene (PTFE) has a chemical stability higher, broad temperature in use scope, not stickiness, excellent lubricity, ageing-resistant Property and heat endurance.But also due to the architectural feature of polytetrafluoroethylene (PTFE), the solidification temperature of teflon coating is higher, together When polytetrafluoroethylene (PTFE) be non-polar polymer, it is impossible to carry out crosslinking curing.Simultaneously in coating, due to the molecule of polytetrafluoroethylene (PTFE) The compatibility of reasons in structure, polytetrafluoroethylene (PTFE) and resin is poor, the phenomenon for layering easily occur.
The emulsion that heretofore described polytetrafluoroethylene (PTFE) is prepared from for polytetrafluoroethylgranule granule, the polytetrafluoroethylene (PTFE) The size of particle is 0.1-0.3 μm.
It is acrylic resin modified：
It is heretofore described it is acrylic resin modified be organic silicon monomer, the monomer modified acrylic resin of Organic fluoride.
Rotation energy barrier is low in the Si-O keys of the organic silicon monomer, and key rotation is easy, and surface can be small, and molecular volume is big, makes Obtaining organosilicon material has excellent heat resistance, inoxidizability.
Wherein, the structural formula of the organosilicon is
RSi(OR1)3 (1)
In formula, R1The organic group in alkoxy is represented, for example, methyl, ethyl, propyl group or phenyl can be enumerated.R is represented Any one group represented by formula (1-1), formula (1-2).
CH2=C (R2)-COO-(CH2)P (1-1)
CH2=C (R3) (1-2)
In these formulas, R2And R3Hydrogen or methyl are represented respectively, and p represents 1~6 integer.
As the functional group that formula (1-1) is represented, methacryloxyalkyl can be enumerated.As the silicon containing the group Oxygen alkane, for example, Beta-methyl acryloyl-oxyethyl dimethoxymethylsilane, γ-methacryloxypropyl can be enumerated Methoxyl group dimethylsilane, γ-methacryloxypropyl dimethoxymethylsilane, γ-methacryloxypropyl Trimethoxy silane, γ-methacryloxypropyl ethyoxyl diethylsilane, γ-methacryloxypropyl diethyl TMOS, δ-methacryloxy butyl diethoxy silane.
As the siloxanes of the functional group represented with formula (1-2), vinyltrimethoxy silane, ethene can be such as enumerated Ethyl triethoxy silicane alkane.
Organic fluoride
Organic fluoride has low surface tension, therefore with performances such as good water-fast dirty and resistance to greasy dirts.The electricity of fluorine element Negativity is maximum, and atomic radius very little, only 0.064nm, with minimum polarizability.And on fluorine atom substitution c h bond H, forms C-F keys, and key is extremely short and bond energy is up to greatly 460kJ/mol, and in fluorinated acrylate polymer, fluorine-containing group is located at resin On side chain, after film forming, shielding protection is played a part of to main chain and interior molecules.Again because the radius ratio hydrogen atom of fluorine atom It is bigger but all smaller than other atomic radiuses, carbon-carbon skeletal chain can tightly be encased, play a protective role.
The structural formula of heretofore described Organic fluoride is as follows：
Wherein, R1、R2、R3And R4Selected from one or more in fluorine, hydrogen, carboxyl, hydroxyl, epoxy radicals, and R1、R2、R3And R4 In at least one be fluorine.
Work as R1-R4Only one of which is fluorine, and when remaining is hydrogen, the Organic fluoride is a PVF.Accordingly, with the increasing of fluorine Plus, the reduction of hydrogen, the Organic fluoride is difluoroethylene, vinylidene, tetrafluoroethene.
Work as R1-R4In have three fluorine, remaining be methanol-based when, the Organic fluoride is
Work as R1-R4In when having two fluorine, by that analogy, two of which fluorine can be on same carbon for the structure, it is also possible to On two carbon respectively.
Used as a kind of preferred embodiment, the weight ratio of the organic silicon monomer, organic fluorine monomer and acrylic monomers is (0.2 ~0.4)：(0.05~0.1)：1, more preferably 0.3：0.08：1.
Acrylic resin refers to the resin synthesized by 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 vitrifying of the hard monomer Temperature is high, assigns hardness of film, tensile strength, cohesive force and wearability；Soft monomer gives the certain pliability of film, extensibility And durability.The introducing of function monomer is to introduce functional group, assigns polymer certain crosslinking reactivity, plays crosslinked action.
In the present invention, the monomer for preparing the acrylic resin at least includes alkyl acrylate, methacrylate Ester, and the alkyl acrylate a length of C1-C8 of carbochain, a length of C1-C4 of carbochain of the alkyl methacrylate.
Used as a kind of embodiment, the alkyl acrylate can enumerate methyl acrylate, ethyl acrylate, acrylic acid third Ester, butyl acrylate, 2-EHA, n-octyl.
In the present invention, the alkyl acrylate is preferably the relatively low alkyl acrylate of glass transition temperature, such as propylene Sour N-butyl.
Used as a kind of implementation method, the alkyl methacrylate can enumerate methyl methacrylate, metering system Acetoacetic ester, propyl methacrylate and one or more therein of butyl methacrylate.
When acrylic resin has various of monomer copolymerization to form, can be by adjusting the species of monomer and shared in the copolymer Percentage synthesize the acrylic resin with particular glass temperature.Wherein, the glass transition temperature is high polymer by height The temperature that state is changed into glassy state is played, the condition changed between high polymer elasticity and fragility has been reacted.Acrylic resin belongs to allusion quotation The copolymer of type, its glass transition temperature can be calculated with Fox formula：
Wi, Tgi are respectively the mass ratio of every kind of monomer i in copolymer and its glass transition temperature of homopolymers in above formula.First Base acrylate is that methacrylate, with the presence of methyl, disturbs carbon-to-carbon in alpha-position with the difference of acrylic ester monomer The rotary motion of main chain, is typical unsymmetric structure, and it can make the molecule of copolymer polarity occur, therefore polymethylacrylic acid The glass transition temperature of ester is higher, and brittle temperature and tensile strength are larger.Adding methacrylate can improve the physics of film Mechanical performance, therefore methacrylate polymers are harder than acrylate polymer, resistance to ag(e)ing is more preferable.
The weight ratio of alkyl acrylate of the present invention and alkyl methacrylate is (1~3):(4~1), preferably It is (2~3):(2~1).
In the present invention, the acrylic resin modified structure is preferably the less acrylic resin of side chain.
Acrylic resin modified preparation method can be prepared using any method well known by persons skilled in the art Obtain.Conventional method is condensation methods, radical polymerization and hydrosilation method.Preferred radical polymerization in the present invention.
Radical polymerization is combined into and is triggered with free radical, makes the ever-increasing polymerisation of propagating radical, also known as free radical Polymerization.Raolical polymerizable, by opening the double bond in monomer molecule, in the intermolecular addition reaction for carrying out repeatedly, Many monomers are coupled together, macromolecular is formed.The method of the most frequently used generation free radical is being thermally decomposed for initiator, also may be used Free radical is produced with methods such as heating, ultraviolet irradiation, high-energy irradiation, electrolysis and plasma initiations.
As polymerization initiator, peroxide system polymerization initiator, azo system polymerization initiator etc. can be enumerated.
As peroxide system polymerization initiator, such as peroxycarbonates, ketone peroxide, peroxidating contracting can be enumerated The organic peroxides such as ketone, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester.
As azo system polymerization initiator, such as 2,2 '-azodiisobutyronitrile, 2, (the 2- methyl of 2 '-azo two can be enumerated Butyronitrile), 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 example, can be propylene Sour based polymer, improved polyalkene, epoxy resin, polyamidoimide, polyurethane resin, amino resins etc..
Acrylic acid series polymeric compounds：Acrylic acid series polymeric compounds are by making comprising acrylate and containing functional group containing functional group Acrylate monomer reaction and obtain.
Acrylate is alkyl methacrylate and/or alkyl acrylate, can specifically enumerate (methyl) acrylic acid Methyl esters, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (first Base) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) propylene Acid -2- Octyl Nitrites, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid last of the ten Heavenly stems ester, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (first Base) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) propylene Sour cetyl ester, (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate, (methyl) acrylic acid nonadecane Alkyl (methyl) acrylate of carbon number 1~20 (C1-20) such as base ester, (methyl) acrylic acid eicosane base ester etc..
As acrylate, it may be preferred to enumerate (methyl) acrylic acid C2-14 Arrcostabs, more preferably enumerate (methyl) propylene Sour C4-9 Arrcostabs.
Acrylate may be used singly or in combination of two or more.Can preferably enumerate different types of (methyl) third Being applied in combination for olefin(e) acid C4-9 Arrcostabs, can more preferably enumerate (methyl) acrylic acid C4-6 Arrcostabs and (methyl) acrylic acid Being applied in combination for C7-9 Arrcostabs, can specifically enumerate (methyl) butyl acrylate with (methyl) acrylic acid-2-ethyl caproite It is applied in combination.
In addition, in order to introduce the crosslinking points for making monomer heat cross-linking, (methyl) acrylate containing functional group is wrapped Containing in the composition.By that by the acrylic ester polymerization containing functional group, can realize improving the bonding force with adherend.
As the acrylate containing functional group, the acrylate of such as hydroxyl can be enumerated, containing sulfonic propylene Acid esters, the acrylate containing amino, the acrylate containing glycidyl etc..
As the vinyl monomer of hydroxyl, such as (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) propylene can be enumerated Acid -3- hydroxypropyl acrylates, (methyl) acrylic acid -4- hydroxy butyl esters, the own ester of (methyl) acrylic acid -6- hydroxyls, (methyl) acrylic acid -8- hydroxyls are pungent Ester, (methyl) acrylic acid -10- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid -12- hydroxylaurics base ester, (methyl) acrylic acid (4- methylols Cyclohexyl) methyl esters etc..
As such as (methyl) acrylic acid sulphur propyl ester etc. containing sulfonic acrylate, can be enumerated.
As the acrylate containing amino, such as (methyl) dimethylaminoethyl acrylate, (methyl) propylene can be enumerated Sour t-butylaminoethyl etc..
As the acrylate containing glycidyl, such as (methyl) glycidyl acrylate etc. can be enumerated.
As the acrylate containing functional group, it may be preferred to enumerate the acrylate of hydroxyl, (first can be more preferably enumerated Base) acrylic acid -2- hydroxyl ethyl esters.
These acrylate containing functional group may be used singly or in combination of two or more.
In addition, relative to monomer, the mixing ratio of the acrylate containing functional group is, for example, 0.01~5 mass %, preferably 0.03~3 mass %.
If the mixing ratio of the acrylate containing functional group exceedes the above-mentioned upper limit, there is cohesiveness becomes too high, by leading The bonding force of the thermal conductivity bonding sheet that hot adhesive resin composition is formed becomes insufficient situation.On the other hand, if not enough , then there is cohesiveness decline in above-mentioned lower limit, confining force becomes insufficient situation.
Additionally, in order to improve the various characteristics such as such as cohesiveness, as needed, can also contain in monomer can be with third The co-polymerized monomer of olefin(e) acid ester copolymerization.
As co-polymerized monomer, such as (methyl) acrylic acid, itaconic acid, maleic acid, crotonic acid, maleic anhydride can be enumerated Etc. carboxylic monomer or its acid anhydrides, such as (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N- methylols The amide containings such as (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide The aromatic vinyl such as the vinyl esters such as the monomer of base, such as vinyl acetate, such as styrene, vinyltoluene is closed Thing, 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, (methyl) acrylic acid can be more preferably enumerated.
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, make comprising such as acrylate, the acrylate containing functional group and copolymerization as needed The monomer of property monomer is polymerized.
Also, as by the method for polymerizing monomer components, can enumerate such as polymerisation in solution, polymerisation in bulk, emulsion polymerization, The known polymerization such as various radical polymerizations, it may be preferred to enumerate polymerisation in solution.
In polymerisation in solution, coordinate monomer component to prepare monomer solution in a solvent, then heat monomer solution and match somebody with somebody simultaneously Close polymerization initiator.
As solvent, such as ether system such as the fragrant family such as toluene, benzene, dimethylbenzene solvent, such as ethyl acetate can be enumerated The organic solvents such as solvent.
Solvent can be used alone or be applied in combination.
Relative to the mass parts of monomer component 100, the mixing ratio of solvent is, for example, 10~1000 mass parts, preferably 50~ 500 mass parts.
As polymerization initiator, peroxide system polymerization initiator, azo system polymerization initiator etc. can be enumerated.
As peroxide system polymerization initiator, such as peroxycarbonates, ketone peroxide, peroxidating contracting can be enumerated The organic peroxides such as ketone, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester.
As azo system polymerization initiator, such as 2,2 '-azodiisobutyronitrile, 2, (the 2- methyl of 2 '-azo two can be enumerated Butyronitrile), 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 the mass parts of monomer 100, the mixing ratio of polymerization initiator is, for example, 0.01~5 mass parts, preferably 0.05 ~3 mass parts.
Heating-up temperature is, for example, 50~80 DEG C, and the heat time is, for example, 1~24 hour.
By above-mentioned polymerisation in solution by polymerizing monomer components, the acrylic polymeric containing acrylic acid series polymeric compounds is obtained Thing solution.
For the viscosity of acrylic polymer solution, for example 30 DEG C be 0.1~100Pas, preferably 0.5~ 50Pa·s。
If the viscosity of monomer mixture is unsatisfactory for above range, formability or processability become insufficient sometimes.
If the mixing ratio of acrylic acid series polymeric compounds is unsatisfactory for above range, cohesiveness, bonding force become not fill sometimes Point.
The preferred 8000-10000 of weight average molecular weight of the acrylic polymer for preparing.Weight average molecular weight is based on solidifying Glue penetration chromatography is (hreinafter referred to as " GPC ".) determine and carry out the value after polystyrene conversion.The condition determination of GPC is used The conventional condition test in this area, for example, can be tested by the way of following obtaining.
Post：Following posts are connected in series and are used.
" 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℃；Eluent：Tetrahydrofuran (THF)；Flow velocity：1.0mL/ points Clock；Injection rate：100 μ L (tetrahydrofuran solution of sample solution concentration 4mg/mL)；Standard specimen：Use following monodisperse polystyrenes Alkene, makes standard curve.
Improved polyalkene：Polyolefin (A) used by the present invention by ethene be selected from carbon number 3~20 alpha-olefin in At least a kind or more than a kind olefinic polymerization and obtain.
Specifically, in addition to ethene, carbon number is that 3~20 alpha-olefin can enumerate propylene, 1- butylene, 2- fourths Alkene, 1- amylenes, 3-methyl-1-butene, 1- hexenes, 4-methyl-1-pentene, 3- Methyl-1-pentenes, 3- ethyl -1- amylenes, 4,4- Dimethyl -1- amylenes, 4- methyl isophthalic acids-hexene, 4,4- dimethyl -1- hexenes, 4- ethyl -1- hexenes, 3- ethyl -1- hexenes, 1- The alkene such as octene, 1- decene, 1- dodecylenes, tetradecene, cetene, 1- vaccenic acids, 1- eicosylenes, can be with Independent or Several combinations use above-mentioned single polymers or copolymer.
Wherein, polyolefin (A) is preferably containing selected from ethene, propylene, 1- butylene, 4-methyl-1-pentene, 1- hexenes, 1- 1 kind or single polymers or copolymer of more than a kind of alkene in octene.
Wherein, polyolefin (A) is more preferably containing ethylene single-polymer (A-1) or ethene and is 3~20 selected from carbon number Alpha-olefin at least a kind of copolymer (A-2).In the present invention propylene, 1- are particularly preferably with the alpha-olefin of ethylene copolymer Butylene, 4-methyl-1-pentene, 1- hexenes, 1- octenes.
Epoxy resin：There are at least 2 epoxy resin of epoxy radicals in 1 molecule, it is possible to use such as bisphenol type epoxy Resin, bisphenol f type epoxy resin, bisphenol-A D-ring oxygen tree fat,
Used as a kind of preferred embodiment, epoxy resin of the present invention preferably has typically less than 300 epoxide equivalent, more It is preferred that epoxide equivalent is 160-260.
In the present invention, described " epoxide equivalent " refers to the quality of the resin relative to epoxy amount 1g equivalents, can basis JISK7236 is determined as follows：
With chloroform and acetic acid come sample dissolution, solution 10ml is added in the lysate, the solution is by bromination tetrem Ammonium 100g is dissolved in the solution in 400ml, is titrated as indicator and with perchloric acid acetum using crystal violet, under Formula is calculated.
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 titrating solution,
v：Titer.
Polyamidoimide：Polyamide-imide resin of the invention is not particularly limited, as long as it is have in the molecule There is the polymer of amido link and imide bond, for example the polyamide-imide resin can be by making diisocyanate chemical combination Thing and the trivalent carboxylic acid derivates with anhydride group are polymerized and are obtained in the solvent with urea bond.
Compatilizer：
In system, the combination enthalpy between polymer and polymer is very low, so being difficult compatible between polymer or reaching The mixed effect of substantially uniformity.Therefore, usually needing in system addition increases compatibility between incompatible two-phase polymer Compatilizer.
Used as a kind of implementation method, the compatilizer for example has water-miscible organic solvent, low molecular weight monomers.
As water-miscible organic solvent, acetone, MEK, propane diols, dipropylene glycol methyl ether, a contracting can be enumerated DPG, tripropylene glycol, ethanol etc.
Used as a kind of implementation method, the compatilizer can also be surfactant.
The surfactant can be anion surfactant：Higher fatty acid salt, sulfonate, sulfate, fat Acyl-peptide condensation product and phosphate ester salt；
Suitable anion surfactant includes：Alkali alkyl sulfate such as lauryl sodium sulfate or dodecyl Potassium sulfate；Alkylsurfuric acid ammonium such as ammonium lauryl sulfate；Brij-35 sodium sulphate, sodium sulfonate and sulfonated olefins Alkali metal salt；Alkyl sulfate enters the ammonium salt of sulfonated olefins；Soap such as sodium laurate, triethanolamine oleate or rosin acid three Monoethanolamine；The alkali metal sulfates of alkylaryl sulfonates such as neopelex or alkaline phenol ethoxy；Senior alkane Base naphthalene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product.
The surfactant can be cationic surfactant：Amine salt cationic surfactant and quaternary Cationic surfactant；
The surfactant can be amphoteric surfactant：Amino acid type amphoteric surfactant, betaine type two Property surfactant, imidazoline type amphoteric surfactant and amine oxide.
The surfactant can be nonionic surface active agent：It is polyethylene glycol type nonionic surfactant, many First alcohol type nonionic surfactant；
Suitable nonionic surface active agent include polyoxyethylene ether, polyoxyethylene propylidene alkyl ether, Polyoxyethylene phenyl ether and polyoxyethylene fatty acid ester.Particularly with for stability be preferably polyoxyethylene Alkyl 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, polyoxyethylene month Osmanthus base ether, polyoxyethylene propylidene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene propylidene tridecyl Ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl group Phenyl ether, polyoxyethylene nonylplenyl ether and polyoxyethylene styrenated phenyl ether.
The surfactant can be specific type surfactant：Fluorine surfactant, silicon surface active agent, amino Acid is surfactant, high molecular surfactant and biosurfactant.
Used as a kind of preferred embodiment, the surfactant can be polyethylene glycol, ethoxylated dodecyl alcohol, isomery ten Alcohol APEO, heptadecanol polyethenoxy ether carboxylate.
Sulfonated polyimide-silane copolymer：
Sulfonated polyimide-the silane copolymer is coupled by amino-terminated sulfonated polyimide prepolymer and epoxy silane Agent is prepared.
In one embodiment, the weight ratio of the sulfonated polyimide and epoxy silane is (5~10)：1.
In one embodiment, the amino-terminated sulfonated polyimide prepolymer by comprising mol ratio for (0.1~ 0.5)：(0.9~0.5)：The raw material of the sulfonated diamine, diamines and dianhydride of (0.75~0.98) is prepared；
Its preparation method is：
0.1~0.5 mole of sulfonated diamine, 0.9~0.5 diamines is added in the there-necked flask being completely dried, in right amount Metacresol and triethylamine, stir under inert gas shielding, after sulfonated diamine is completely dissolved, add 0.8~0.98 mole Dianhydride and 2.0~4.0 moles of catalyst, after about 30min is stirred at room temperature, are heated to about 75~85 DEG C, and reaction about 3.5~ 4.5h, then at about 175~185 DEG C, react about 3.5~4.5h；After reaction terminates, room temperature is down to, solution is poured into methyl alcohol, There is Precipitation；After being filtered after methyl alcohol cyclic washing removal solvent, about 22~24h is dried at about 50 DEG C in vacuum drying oven, Obtain final product amino-terminated polyimide preformed polymer.
In one embodiment, the sulfonated diamine be selected from 4,4 '-diamino-diphenyl -2,2 '-disulfonic acid, 4,4 ' - Diaminourea -3,3 '-dimethyl diphenyl methane -2,2 '-disulfonic acid, 4,4 '-diaminourea -2,2 ', 3,3 '-dimethyl diphenyl methane - 2,2 '-disulfonic acid, 4,4 '-diaminourea -2,2 '-dimethyl diphenyl -2,2 '-disulfonic acid, 4,4 '-diaminourea -3,3 '-dimethyl connection Benzene -2,2 '-disulfonic acid, 4,4 '-benzidine -3,3 '-disulfonic acid, 2,6 '-diaminostilbene, 3,5- tri-methyl p-toluenesulfonates, 3, 5- diamino benzene sulfonic acids, 4,4 '-diaminodiphenyl ether -2,2 '-disulfonic acid, 3,4 '-diaminodiphenyl ether -2,3 '-disulfonic acid, 4, 4 '-diaminostilbene ", 3 " two phenoxy group benzene -5 "-sulfonic acid, 3,3 '-diaminostilbene ", 3 "-two phenoxy group benzene -5 "-sulfonic acid, 9,9 ' - Double (4- aminophenyls) fluorenes -2,7 '-disulfonic acid, 4,4 '-diaminourea -4 ", 4 " '-two aminophenoxy biphenyls -3 ", 3 " '-disulfonic acid, 4, 4 '-diaminourea -4 ", 4 " '-two phenoxy groups-diphenyl isopropyl alkane -5 ", 5 " '-disulfonic acid or 4,4 '-diaminostilbenes ", 4 "-hexichol Epoxide-benzene -2 "-sulfonic acid, 2,2 '-bis- (4- sulfonic benzos epoxide) biphenyl sulfonated diamines, 3,3 '-bis- (4- sulfonic benzos epoxides) connection In benzene sulfonated diamine any one or more；Preferably, the sulfonated diamine is 3,3 '-bis- (phenoxy group) biphenyl sulfonated diamines.
In one embodiment, the diamines can select the corresponding diamines product of sulfonated diamine.
In one embodiment, the dianhydride is selected from pyromellitic dianhydride, 3, and 4,9,10- perylene tetracarboxylic acid acid anhydrides, 4,4 '- (hexafluoro isopropyl alkene) two anhydride phthalic acids, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone Any one or more in tetracarboxylic acid dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride；Preferably, the dianhydride is Isosorbide-5-Nitrae, 5,8- naphthalenes Tetracarboxylic acid dianhydride.
The preparation of silane-modified super-branched polyimide：Added in the there-necked flask being completely dried amino-terminated hyperbranched 10 parts of polyimides, 1~30 part of epoxy type silane coupler KH-560 and appropriate good solvent, stir under inert gas shielding After mixing 5~50min, after being heated to 60~100 DEG C of 0.1~10h of reaction, room temperature is down to, solution is poured into methyl alcohol, there is precipitation to analyse Go out；After being filtered after methyl alcohol cyclic washing removal solvent, 1h~24h is dried at 20 DEG C~80 DEG C in vacuum drying oven, obtain final product silicon Alkane modified ultra-branching polyimides.
Additive：
On the basis of the invention is not influenceed, the addition of agent can be as needed added.Additive can be, But it is not limited to, one or more in light stabilizer, viscosity agent, delustering agent etc..Specifically, light stabilization as used herein Agent can be hindered amine light stabilizer.Light stabilizer may be, but not limited to, selected from by decanedioic acid pair-(2,2,6,6- tetramethyls Base -4- piperidyls) ester (Tinuvin 770), decanedioic acid be double-[N- methyl -2,2,6,6- pentamethyl -4- piperidyls) ester and four One or more in the group of (2,2,6,6- tetramethyl -4- piperidyl -1,2,3,4- butane) tetrabasic ester composition.Additionally, viscous Degree agent may be, but not limited to, selected from the group being made up of polyurethanes (urethane esters) and acrylic compounds viscosity agent One or two or more two kinds mixture.Delustering agent as used herein can be after coat film be formed for changing Become the gloss on surface.Delustering agent may be, but not limited to, type siloxane delustering agent etc..
Wetting dispersing agent can be the silicone additive for improving surface sliding characteristic (slipping property), and And the surface tension of coating composition can be reduced to increase the spreadability of composition, and contact area can be increased to improve To the bond properties of contact surface.The reduction of the surface tension of coating composition can be prevented may be occurred when paint film is dried Shrinkage cavity (cratering), and can be suppressed by improving the slip characteristic on coating composition surface on surface scrape Generation.Additionally, when slip characteristic improves, the scratch resistance and stain resistance of composition can be improved, can be easy Ground performs washing, and adhesive resistance can be improved.
Curing agent is the isocyanate prepolymer that can have multiple isocyanate groups (- NCO) in molecular end, and PEPA, alkyd polyol, propylene polylol etc. can be bound to, include that the crosslinking of amino-formate bond is applied to be formed Material film, so as to improve the physical characteristic of coating composition.More specifically, curing agent can be supplied in the form of including diisocyanate Should, and the type of diisocyanate that curing agent includes can be classified as aromatic diisocyanate and the isocyanide of aliphatic two Acid esters.The example of aromatic diisocyanate includes toluene di-isocyanate(TDI) (TDI), methylenediphenyl diisocyanates (MDI), XDI (XDI), naphthalene diisocyanate (NDI) etc., wherein, isocyanate groups are bonded directly to benzene Ring, and the example of aromatic diisocyanate includes IPDI (IPD), hexamethylene diisocyanate (HDI) etc..
Painting method：
The present invention painting method is also provided, its contain on substrate surface coat the invention described above coating composition the step of Form.
As the substrate surface that can coat coating composition of the invention, it is not particularly limited, comprising such as iron, aluminium, zinc Deng raw material metal face and its surface treatment face；The former material charge level of concrete, mortar, slabstone, timber, plastics, stone material etc. and Its surface treatment face；And then the old coating film face set on these former material charge levels and surface treatment face etc..
As a kind of preferred embodiment, the substrate surface of coating composition of the invention can be coated for rubber, the rubber does not have Especially limit, comprising such as silicon 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, for example O-ring, oil sealing, packing ring, The seal members such as barrier film, valve, are also used in rubber rollers, rubber strip, industrial rubber hose, rubber strip, the cunning of used in copy machines Moving plate, weather strip for automobile, peel off the rubber components such as chute, be efficiently used for they anti-bonding, low friction, it is anti-wear, It is grease proofing etc..
Composition of the invention is also applied to easily produce dirt, damaged, oil tank sealing cover etc..
The coating can be carried out using general method, for example, can use bristle coating, spraying, roller coat, trowelling, various paintings Glassware coating etc. is carried out, and coating and/or painting coating are applied in can also being coated as needed on the film for being formed.Middle painting coating It is not particularly limited with painting coating, it is possible to use organic solvent or aqueous coating known per se, can be enumerated for example Epoxy resin, acrylic resin system, polyurethane resin system, acrylic rubber system, organic siliconresin system, the painting of fluororesin system Material.
Polytetrafluoroethylene (PTFE) can only can just solidify due to the speciality of its molecular structure under ability high temperature.But the present application People is found surprisingly that the coating composition can be solidified at 150 DEG C.While present inventor is found surprisingly that, After acrylic resin modified and polytetrafluoroethylene (PTFE) is pre-processed at less than 130 DEG C in the present invention, the cured film of formation is very Densification, while there is very strong oil resistance, and the adhesive force very strong with rubber oil.The reason for this is possible is because in the present invention Described acrylic resin modified at less than 130 DEG C, acrylic resin modified and polytetrafluoroethylene (PTFE) molecular chain structure is very soft, Simultaneously because the reason for the fluorine element on the structure of acrylic resin and surface, have very strong compatibility with polytetrafluoroethylene (PTFE), therefore, The pretreatment at a temperature of 130 DEG C is passed below, the film of the rubber coating composition of polytetrafluoroethylene (PTFE) of the invention is very fine and close.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some nonessential modifications and adaptations that content according to the invention described above is made, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
A1 polytetrafluoroethylene (PTFE) (PTFE)
The trade mark of the polytetrafluoroethylene (PTFE) is AD-911, is purchased from Japan AGC.
B1 binder resins (acrylic resin)
The trade mark of the acrylic resin is PB9788, is purchased from Shanghai weathercock chemistry Science and Technology Ltd.；
B2 binder resins (amino resins)
The trade mark of the amino resins is CYMEL-325, is purchased from U.S.'s cyanogen special；
B3 binder resins (polyurethane resin)
The 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 the acrylic resin is PB9788, is purchased from Shanghai weathercock chemistry Science and Technology Ltd.；
C2 acrylic resin modified (organosilicon modified crylic acid resin)
The structural formula of the organosilicon is CH2=CHSi (OCH3)3, and the organosilicon and acrylic resin weight ratio It is 0.2：1, the acrylic resin is prepared by (methyl) methyl acrylate of 40wt% and the butyl acrylate of 60wt%.
Preparation method：(1) raw material mixing：By above-mentioned 0.2 weight portion organosilicon and acrylic resin, 2 of 1 weight portion, 2 '- Azodiisobutyronitrile, tert-dodecyl mercaptan are well mixed by a certain percentage, and monomer mixture is obtained, the tert-dodecyl mercaptan Usage amount is 0.1wt%, described 2, the usage amount of 2 '-azodiisobutyronitrile is 0.1wt%；
(2) polymerisation：A certain amount of toluene is added in reaction vessel, reflux state is heated to, state is maintained the reflux for, and To monomer mixture is at the uniform velocity added dropwise in reaction vessel, then the completion of dropping in 3 hours adjusts reaction mass to 70 DEG C, and protect Temperature 1 hour；
(3) post-process：Solvent is evaporated off using the method for normal pressure and vacuum distillation, material is poured into aluminium dish while hot, cools down, i.e., Obtain organosilicon modified crylic acid resin of the invention.
C3 acrylic resin modified (organic fluorin modified crylic acid resin)
The Organic fluoride is perfluorobutadiene, and the weight ratio of the Organic fluoride and acrylic resin is 0.05：1.
Preparation method：(1) ethylene glycol monobutyl ether that parts by weight are 40 points is mixed and is added in reactor as solvent；
(2) reactor is warmed up to 95 DEG C, starts that mixture is added dropwise toward reactor, the mixture is 0.5 weight portion Perfluorobutadiene, the acrylic resin of the C2 of 10 weight portions is obtained by mixing, and the mixture was added dropwise to complete in 20 minutes；
(3) polymerisation is produced toward adding in reactor the benzoyl peroxide of 1 weight portion to trigger；
(4) after being warming up to 190 DEG C, vacuumize, the vacuum is -0.008mpa；
(5) nitrogen release is used, then 0.5mpa is forced into nitrogen, and organic fluorine richness is obtained in 190 DEG C of bottom discharges Acrylic resin；
Above-mentioned preparation process requirement is waterless operation.
C4 acrylic resin modified (organosilicon and organic fluorin modified crylic acid resin, and organosilicon, Organic fluoride and acrylic acid The weight ratio of resin is 0.2：0.05：1, the structural formula of the organosilicon is CH2=CHSi (OCH3)3, the structure of the Organic fluoride Formula is perfluoropropene, C3F6)
The acrylic resin is 3 by 2-ethyl hexyl acrylate and methacrylic acid -2- Octyl Nitrites by weight：1 is prepared into Arrive.
Preparation method：(1) organic fluorin modified crylic acid resin is prepared according to the preparation method in C3；
(2) organic fluorin modified crylic acid resin, organosilicon and the mixing of 0.1 weight portion azodiisobutyronitrile that will be prepared Uniformly, it is standby.During the toluene of 10 weight portions put into there-necked flask, 75 DEG C are heated to, above-mentioned mixing is uniformly added dropwise in 3h Solution, 1h is incubated after dripping off, and adds the azodiisobutyronitrile of 0.1 weight portion and the toluene of 3 weight portions, is incubated 8 hours.Plus such as 6 The dimethylbenzene of weight portion converts alkene, cooling, discharging, prepares gained organosilicon, organic fluorin modified crylic acid resin.
C5 acrylic resin modified (organosilicon and organic fluorin modified crylic acid resin, and organosilicon, Organic fluoride and acrylic acid The weight ratio of resin is 0.2：0.05：1, the structural formula of the organosilicon is CH2=CH-COOCH2Si(OCH3)3, it is described organic The structural formula of fluorine is perfluorobutadiene, C4F6)
Preparation method：Same C4.
C6 acrylic resin modified (organosilicon and organic fluorin modified crylic acid resin, and organosilicon, Organic fluoride and acrylic acid The weight ratio of resin is 0.4：0.1：1, the structural formula of the organosilicon is CH2=CHSi (OCH3)3, the structure of the Organic fluoride Formula is perfluoropropene, C3F6)
Preparation method：Same C4.
C7 acrylic resin modified (organosilicon and organic fluorin modified crylic acid resin, and organosilicon, Organic fluoride and acrylic acid The weight ratio of resin is 0.4：0.1：1, the structural formula of the organosilicon is CH2=CH-COOCH2Si(OCH3)3, the Organic fluoride Structural formula be perfluorobutadiene, C4F6)
Preparation method：Same C4.
C8 acrylic resin modified (organosilicon and organic fluorin modified crylic acid resin, and organosilicon, Organic fluoride and acrylic acid The weight ratio of resin is 0.5：0.5：1, the structural formula of the organosilicon is CH2=CH-COOCH2Si(OCH3)3, the Organic fluoride Structural formula be perfluorobutadiene, C4F6)
Preparation method：Same C4.
C9 acrylic resin modified (organosilicon and organic fluorin modified crylic acid resin, and organosilicon, Organic fluoride and acrylic acid The weight ratio of resin is 0.1：0.01：1, the structural formula of the organosilicon is CH2=CH-COOCH2Si(OCH3)3, it is described organic The structural formula of fluorine is perfluorobutadiene, C4F6)
Preparation method：Same C4.
D1：(amino-terminated sulfonated polyimide prepolymer is sulfonated polyimide-silane copolymer by comprising mol ratio 0.1：0.9：The raw material of 0.75 sulfonated diamine, diamines and dianhydride is prepared；The weight of sulfonated polyimide and epoxy silane Than being 5：1)
Preparation method：(1) 0.1 mole of 4,4 '-diamino-diphenyl -2 are added in the there-necked flask being completely dried, 2 '-disulfonic acid, the 4 of 0.9 mole, 4 '-diamino-diphenyl, 20 moles of cresols and 2.2 moles of triethylamine, in inert gas The lower stirring of protection, when 4,4 '-diamino-diphenyl -2, after 2 '-disulfonic acid is completely dissolved, adds 0.75 mole of Pyromellitic Acid Acid anhydride and 4.0 moles of benzoic acid, after about 30min is stirred at room temperature, are heated to about 75 DEG C, react about 3.5h, then at about 175 DEG C Under, react about 3.5h；After reaction terminates, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；Use methyl alcohol cyclic washing After being filtered after removal solvent, about 22h is dried at about 50 DEG C in vacuum drying oven, obtain final product amino-terminated polyimide preformed polymer.
(2) preparation of silane-modified super-branched polyimide：Added in the there-necked flask being completely dried amino-terminated super 10 parts of branched polyimide, 2 parts of epoxy type silane coupler KH-560 and appropriate solvent, 5 are stirred under inert gas shielding After~50min, after being heated to 70 DEG C of reaction 1h, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；With methyl alcohol repeatedly After being filtered after washing removal solvent, 12h is dried at 50 DEG C in vacuum drying oven, obtain final product sulfonated polyimide-silane copolymer.
D2：(amino-terminated sulfonated polyimide prepolymer is sulfonated polyimide-silane copolymer by comprising mol ratio 0.5：0.5：The raw material of 0.98 sulfonated diamine, diamines and dianhydride is prepared；The weight of sulfonated polyimide and epoxy silane Than being 8：1)
Preparation method：(1) in the there-necked flask being completely dried add 0.5 mole 9,9 '-bis- (4- aminophenyls) fluorenes- 2,7 '-disulfonic acid, the 9 of 0.5 mole, 9 '-bis- (4- aminophenyls) fluorenes, 20 moles of cresols and 2.2 moles of triethylamine, lazy Property gas shield under stir, when 9,9 '-bis- (4- aminophenyls) fluorenes -2, after 7 '-disulfonic acid is completely dissolved, add 0.98 mole Pyromellitic dianhydride and 4.0 moles of benzoic acid, after about 30min is stirred at room temperature, are heated to about 75 DEG C, react about 3.5h, Again at about 175 DEG C, about 3.5h is reacted；After reaction terminates, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；Use first After being filtered after alcohol cyclic washing removal solvent, about 22h is dried at about 50 DEG C in vacuum drying oven, obtain final product amino-terminated polyimides Prepolymer.
(2) preparation of silane-modified super-branched polyimide：Added in the there-necked flask being completely dried amino-terminated super 8 parts of branched polyimide, 1 part of epoxy type silane coupler KH-560 and appropriate solvent, stir under inert gas shielding After 30min, after being heated to 70 DEG C of reaction 1h, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；Washed repeatedly with methyl alcohol Wash removal solvent after filter after, dry 12h at 50 DEG C in vacuum drying oven, obtain final product sulfonated polyimide-silane copolymer.
D3：(amino-terminated sulfonated polyimide prepolymer is sulfonated polyimide-silane copolymer by comprising mol ratio 0.9：0.1：The raw material of 0.75 sulfonated diamine, diamines and dianhydride is prepared；The weight of sulfonated polyimide and epoxy silane Than being 5：1)
Preparation method：(1) 0.9 mole of 4,4 '-diaminostilbene is added in the there-necked flask being completely dried ", 3 " hexichol Epoxide benzene -5 "-sulfonic acid, 0.1 mole of 4,4 '-diaminostilbene ", 3 " two phenoxy group benzene, 20 moles of cresols and the three of 2.2 moles Ethamine, stirs, when 4,4 '-diaminostilbene under inert gas shielding ", after 3 " two phenoxy group benzene -5 "-sulfonic acid are completely dissolved, plus Enter 0.75 mole of pyromellitic dianhydride and 4.0 moles of benzoic acid, after about 30min is stirred at room temperature, be heated to about 75 DEG C, Reaction about 3.5h, then at about 175 DEG C, react about 3.5h；After reaction terminates, room temperature is down to, solution is poured into methyl alcohol, there is heavy Precipitation goes out；After being filtered after methyl alcohol cyclic washing removal solvent, about 22h is dried at about 50 DEG C in vacuum drying oven, obtain final product amino Capped polyimides prepolymer.
(2) preparation of silane-modified super-branched polyimide：Added in the there-necked flask being completely dried amino-terminated super 5 parts of branched polyimide, 1 part of epoxy type silane coupler KH-560 and appropriate solvent, stir under inert gas shielding After 30min, after being heated to 70 DEG C of reaction 1h, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；Washed repeatedly with methyl alcohol Wash removal solvent after filter after, dry 12h at 50 DEG C in vacuum drying oven, obtain final product sulfonated polyimide-silane copolymer.
D4：(amino-terminated sulfonated polyimide prepolymer is sulfonated polyimide-silane copolymer by comprising mol ratio 0.1：0.9：The raw material of 1.1 sulfonated diamine, diamines and dianhydride is prepared；The weight ratio of sulfonated polyimide and epoxy silane It is 10：1)
Preparation method：(1) 0.1 mole of 4,4 '-diaminourea -4 is added in the there-necked flask being completely dried ", 4 " '-two Aminophenoxy biphenyl -3 ", 3 " '-disulfonic acid, 0.9 mole of 4,4 '-diaminourea -4 ", 4 " '-two aminophenoxy biphenyls, 20 moles of first Phenol and 2.2 moles of triethylamine, stir, when 4,4 '-diaminourea -4 under inert gas shielding ", 4 " '-two aminophenoxy biphenyls - 3 ", after 3 " '-disulfonic acid is completely dissolved, 1.1 moles of pyromellitic dianhydride and 4.0 moles of benzoic acid is added, is stirred at room temperature After mixing about 30min, 75 DEG C are heated to about, react about 3.5h, then at about 175 DEG C, react about 3.5h；After reaction terminates, it is down to Room temperature, solution is poured into methyl alcohol, there is Precipitation；After being filtered after methyl alcohol cyclic washing removal solvent, in vacuum drying oven About 22h is dried at about 50 DEG C, amino-terminated polyimide preformed polymer is obtained final product.
(2) preparation of silane-modified super-branched polyimide：Added in the there-necked flask being completely dried amino-terminated super 10 parts of branched polyimide, 1 part of epoxy type silane coupler KH-560 and appropriate solvent, stir under inert gas shielding After 30min, after being heated to 70 DEG C of reaction 1h, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；Washed repeatedly with methyl alcohol Wash removal solvent after filter after, dry 12h at 50 DEG C in vacuum drying oven, obtain final product sulfonated polyimide-silane copolymer.
D5：(amino-terminated polyimide preformed polymer is 1 by comprising mol ratio to polyimides-silane copolymer：The two of 0.98 The raw material of amine and dianhydride is prepared；The weight ratio of polyimides and epoxy silane is 8：1)
Preparation method：(1) 1 mole of 4,4 '-diaminourea -4 is added in the there-necked flask being completely dried ", 4 " '-hexichol Epoxide biphenyl, 20 moles of cresols and 2.2 moles of triethylamine, stir, when 4,4 '-diaminourea -4 under inert gas shielding ", 4 " after '-two aminophenoxy biphenyls are completely dissolved, 0.98 mole of pyromellitic dianhydride and 4.0 moles of benzoic acid is added, in room temperature After lower stir about 30min, 75 DEG C are heated to about, react about 3.5h, then at about 175 DEG C, react about 3.5h；After reaction terminates, Room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；After being filtered after methyl alcohol cyclic washing removal solvent, dried in vacuum About 22h is dried at about 50 DEG C in case, amino-terminated polyimide preformed polymer is obtained final product.
(2) preparation of silane-modified super-branched polyimide：Added in the there-necked flask being completely dried amino-terminated super 8 parts of branched polyimide, 1 part of epoxy type silane coupler KH-560 and appropriate solvent, stir under inert gas shielding After 30min, after being heated to 70 DEG C of reaction 1h, room temperature is down to, solution is poured into methyl alcohol, there is Precipitation；Washed repeatedly with methyl alcohol Wash removal solvent after filter after, dry 12h at 50 DEG C in vacuum drying oven, obtain final product sulfonated polyimide-silane copolymer.
E1 compatilizers (ethoxylated dodecyl alcohol)
The ethoxylated dodecyl alcohol uses MOA-9, and supplier is Hai'an petro-chemical corporation.
E2 compatilizers (heterogeneous ten alcohol polyoxyethylene ether)
The heterogeneous ten alcohol polyoxyethylene ether uses E1006, and supplier is Hai'an petro-chemical corporation.
E3 compatilizers (heptadecanol polyethenoxy ether carboxylate)
The heptadecanol polyethenoxy ether carboxylate uses AEO-9, and supplier is wound Yue Chemical Co., Ltd. of Guang Zhou cities.
F1 water
The embodiment of table 1 is set
Performance test：
1st, coating appearance uses GB9278-1988 standard testings；
2nd, film forming stability is respectively adopted HG/T2458-1993 standard testings；
3rd, resistance to surface abrasion：Using surface wear testing machine with the loading of 1Kgf with No. 6 canvas to shaping after each The surface of material is rubbed, and determines the number of times until producing cut.And, evaluated with following benchmark.
○：More than 5000 times
△：More than 2000 times~be less than 5000 times
×：Less than 2000 times；
4th, oil resistivity evaluation：The ratio face of each sheet material after forming coats butter with 2cm radiuses, in 80 DEG C of atmosphere decentralizations After putting 5 days, butter are removed.And, disbonded test is carried out to the coated side of butter by gridiron pattern cellophane tape, with following base Standard is evaluated：
○：Well
×：It is bad
5th, adaptation evaluation：Coating composition is coated on sheet material, is made within 60 minutes 5 minutes at 130 DEG C, at 250 DEG C Its heated-air drying, makes dried thickness for 15 ± 5 μm, obtains layered product.According to using cellophane tape cross cut test, from And evaluate the adaptation of the film of coating composition.Testing standard：JIS K5600-5-6：1999.
Under conditions of temperature (23 ± 2) DEG C, relative humidity (50 ± 5) %, in the Coating material composition by above-mentioned layered product On the film layer that thing is constituted, 100mm in terms of forming 10mm × 10mm is spaced by 1mm2Right-angled intersection cutting grid, visually see Examine the outward appearance of the film remained after cellophane tape glass.
○：The situation that the number of grid is remained completely；
△：The quantity residual of grid is less than the situation of 100 and more than 80；
×：The quantity of grid only remains the situation less than 80；
6th, cohesive evaluation：Evaluation criterion：JIS-K5400
After the laminated polyester film that will be obtained is placed in each condition of following (1)~(3), establishing criteria uses clearance gap For the cutting guide rail excision insertion of 1mm cuts line by film layer and 100 lattice-shapeds for reaching base film.Then, will be transparent viscous Gum deposit band is pasted on the cut surface of lattice-shaped, is wiped with erasing rubber, so as to be allowed to after attachment completely, with 90 ° of stripping Digression degree is quickly peeled off, and then observes release surface, and cohesive is evaluated by following standards：
Adhesion test condition：
(1) normality cohesive：23 DEG C/relative humidity 65%, 24 hours；
(2) cohesive is moistened：60 DEG C/relative humidity 90%, 100 hours；
(3) moisture-proof Thermoadhesive：60 DEG C/relative humidity 90%, 300 hours；
Cohesive evaluation criterion：
◎：Peels off area is less than 5%
○：Peels off area more than 5%, less than 15%
△：Peels off area more than 15%, less than 20%
×：Peels off area is more than 20%.
7th, petrol-resistance
By the polypropylene loop device of diameter 4cm in each coated surface, and then the lid for being provided with 5mm holes is covered, and is crimped, The gasoline of 10ml is added from the hole with dropping pipet, cellophane tape plugging hole is used.After placing 4 hours at room temperature, vapour is removed Oil, the outward appearance of visual film is carried out as follows evaluation.Shown in result：
○：It is without exception；
×：Expansion, finds to peel off.
The performance test results of table 2
In sum, it is known that, coating composition of the invention with do not contain acrylic resin modified, sulfonated polyimide- Silane copolymer is compared, with very strong oil resistant, antifriction, film forming, cohesive and compactness.
Foregoing example is merely illustrative, some features for explaining feature of the invention.Appended claim The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment Combination selection implementation method explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim is covered.

Claims (5)

1. coating composition, by weight, at least includes：
It is described it is acrylic resin modified be organosilicon, organic fluorin modified crylic acid resin；
The weight ratio of the organosilicon, Organic fluoride and acrylic resin is (0.2~0.4)：(0.05~0.1)：1；
Sulfonated polyimide-the silane copolymer is prepared into by amino-terminated sulfonated polyimide prepolymer with epoxy silane Arrive, and the weight ratio of the amino-terminated sulfonated polyimide prepolymer and epoxy silane is (5~10)：1；
The amino-terminated sulfonated polyimide prepolymer is (0.1~0.5) by comprising mol ratio：(0.9~0.5)：(0.75~ 0.98) raw material of sulfonated diamine, diamines and dianhydride is prepared.
2. the composition described in claim 1, the structural formula of the organosilicon is as follows：
RSi(OR1)3 (1)
In formula, R1The organic group in alkoxy is represented, for example, methyl, ethyl, propyl group or phenyl can be enumerated;R expressions (1- 1), any one group represented by formula (1-2);
CH2=C (R2)-COO-(CH2)P (1-1)
CH2=C (R3) (1-2)
In these formulas, R2And R3Hydrogen or methyl are represented respectively, and p represents 1~6 integer.
3. the composition described in claim 1, the structural formula of the Organic fluoride is as follows：
Wherein, R1、R2、R3And R4Selected from one or more in fluorine, hydrogen, carboxyl, hydroxyl, epoxy radicals, and R1、R2、R3And R4In extremely Rare one is fluorine.
4. the composition described in claim 1, its lubricating and wear-resisting polytetrafluoroethylene (PTFE) rubber coating for being used as rubber molding product.
5. rubber molding product, it has carried out coating with any described composition of Claims 1 to 4 to surface.
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