CN105778509A - Environment-friendly rubber composition and self-lubricating rubber sealing element prepared from same - Google Patents
Environment-friendly rubber composition and self-lubricating rubber sealing element prepared from same Download PDFInfo
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- CN105778509A CN105778509A CN201610217794.6A CN201610217794A CN105778509A CN 105778509 A CN105778509 A CN 105778509A CN 201610217794 A CN201610217794 A CN 201610217794A CN 105778509 A CN105778509 A CN 105778509A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses an environment-friendly rubber composition. The composition is at least prepared from, by weight, 100 parts of rubber basic material, 10-40 parts of silicone oil, 10-60 parts of filler, 1-5 parts of crosslinking agent, 1-10 parts of structure controlling agent, 0.1-1.5 parts of lubricant and 1-3 parts of component A. The rubber basic material at least comprises silicone rubber. The filler is hyperbranched polysiloxane modified silicon dioxide nanosheets containing an epoxy group. The component A has the structure of R1-R2-R1, wherein R1 is branched alkyl acid graft modified silicon dioxide nanospheres, branched alkyl acid at least comprises one carboxyl group, the number of carbon atoms of the carboxyl group is 3 to 20, and R2 is a polyimide and siloxane copolymer chain segment. The invention, on the other hand, further comprises a waterproof surface processing method and a self-lubricating rubber sealing element.
Description
Technical field
The present invention relates to a kind of environment-friendly rubber compositions, specifically the present invention relates to the group of environment-friendly rubber compositions
Become, the processing method of water-proof surface and use self-lubricating rubber seal prepared by this environment-friendly rubber compositions.
Background technology
Vehicle wiper is the safety component on the forward and backward window and illuminator of automobile wind shield glass, its work
It is to remove the ice of glass surface, snow, rainwater and earth dust etc. as purpose, to obtain the visual field clearly, improves
The safety of running car.The quality of Wiper blade directly affects grooming effect, thus affects security performance, the most right
Its performance requirement is the highest.
Wiper blade rubbers sealing joint strip is often placed in ratio in relatively rugged environment, such as under being exposed to the sun in summer, winter
Sleet sky.At sleet all over the world, wiper blade rubbers sealing joint strip often occurs that hardening cannot blow rain, snow smoothly；
During swinging, there will be the jumping of " chuckleing " situation such as scrape.Further, automobile driving during,
The dust on vehicle glass surface needs extra erasing.
Vehicle wiper rubber seal strip be mainly composed of rubber, such rubber typically all contains fluorine element,
The rubber of fluorinated has the most hydrophobic, oleophobic, corrosion-resistant a, acid rain resistance, but the rubber of fluorinated
Low temperature resistant and radiation resistance is poor, and the material of fluorinated is easily to environment.
Hence it is highly desirable to by developing one and scraping that water is effective, weatherability, high-low temperature resistant, corrosion-resistant and
The environment-friendly rubber compositions the most fluorine-containing in film and self-lubricating rubber seal prepared therefrom.
Summary of the invention
In order to solve the problems referred to above, the present invention provides environment-friendly rubber compositions, in parts by weight, at least includes:
Described rubber base material includes at least silicone rubber；
Described filler is the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxide group；
Described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；Described R2For polyimide-siloxane
Copolymer segment.
As one preferred embodiment, described rubber base material also includes acrylate rubber, chlorosulfonation
In polyethylene, chlorinated polyethylene, polyether rubber, polyurethane rubber, epoxy propane rubber any one or several
The mixing planted.
As one preferred embodiment, described silicone oil at least includes phenyl methyl silicone oil and alkyl-silicone oil, institute
The weight ratio stating phenyl methyl silicone oil and alkyl-silicone oil is 1:0.01～0.1.
As one preferred embodiment, described rubber base material also include fluorubber, fluorocarbon rubber, third
Olefin(e) acid ester rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polyether rubber, polyurethane rubber, expoxy propane rubber
Any one or a few mixing in glue.
As one preferred embodiment, described silicone oil at least includes phenyl methyl silicone oil and alkyl-silicone oil, institute
The weight ratio stating phenyl methyl silicone oil and alkyl-silicone oil is 1:0.01～0.1.
As one preferred embodiment, the described hyperbranched polyorganosiloxane improved silica containing epoxide group
Nanometer sheet, the weight ratio of the described hyperbranched polyorganosiloxane containing epoxide group and silica nanometer sheet be (2～
15): 1.
As one preferred embodiment, the thickness of described silica nanometer sheet is 0.8～3nm.
As one preferred embodiment, in described component A, the acid of described branched alkyl is received with silicon dioxide
The weight ratio of rice ball is (1～10): 1.
As one preferred embodiment, the structural formula of described branched alkyl acid is:
As one preferred embodiment, described rubber composition also includes the sulfonation of 0.1～2 weight portions
Polybenzimidazoles.
Another aspect of the present invention provides the processing method of a kind of water-proof surface: at least comprise the following steps:
(1) matrix material is provided；
(2) substrate material surface coating rubber compositions；
Described rubber composition, in parts by weight, at least includes:
Described rubber base material includes at least silicone rubber；
Described filler is the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxide group；
Described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；Described R2For polyimide-siloxane
Copolymer segment.
Another aspect of the present invention provides self-lubricating rubber seal prepared by a kind of above-mentioned environment-friendly rubber compositions
Part.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
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 has and the present invention
The identical implication that one skilled in the art are generally understood that.When there is contradiction, with in this specification
Definition is as the criterion.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ",
" include ", " 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 this kind of compositions, step, method, goods or device institute can be included
Intrinsic key element.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If wanted for right
In asking, this phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe,
But except relative customary impurities.In phrase " Consists of " occurs in the clause of claim main body
When being rather than immediately following after theme, it is only limited to the key element described in this clause；Other key element is not arranged
In addition in the described claim as entirety.
Equivalent, concentration or other value or parameter with scope, preferred scope or a series of upper limit preferred value and
During the Range Representation that lower preferable values limits, this is appreciated that and specifically discloses by any range limit or excellent
All scopes that arbitrary pairing of choosing value and any range lower limit or preferred value is formed, regardless of whether whether this scope
Separately disclose.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 "
Deng.When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end value
All integers within the range and mark.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or
Person's " any one " refers to that the item described thereafter or event may or may not occur, and this description includes
The situation that the situation of event generation and event do not occur.
Approximation 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 repairing of the change of relevant basic function
Positive part.Accordingly, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this
Exact numerical.In some example, approximation term likely corresponds to measure the precision of the instrument of numerical value.In this Shen
Please be in specification and claims, scope limits and can combine and/or exchange, if not stated otherwise this
A little scopes include all subranges contained therebetween.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or component
Quantitative requirement (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one
Or at least one, and the key element of singulative or component also include plural form, unless the obvious purport of described quantity
Refer to singulative.
" polymer " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.General
Term " polymer " " comprise term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerization at least two different monomers.Generic term " copolymerization
Body " include term " copolymer " (it is typically in order to refer to the polymer prepared by two kinds of different monomers) and term " three
Membered copolymer " (it is typically in order to refer to the polymer prepared by three kinds of different monomers).It also comprises by polymerization four
Or more kinds of monomer and the polymer that manufactures." blend " means that two or more polymer passes through physics
Or the method for chemistry jointly mix and the polymer that formed.
In order to solve the problems referred to above, the present invention provides a kind of environment-friendly rubber compositions, in parts by weight, at least
Including:
Described rubber base material includes at least silicone rubber；
Described filler is the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxide group；
Described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；Described R2For polyimide-siloxane
Copolymer segment.
Rubber base material:
Described rubber base material includes at least silicone rubber, and rubber base material can be merely silicone rubber, except
Can also include beyond silicone rubber acrylate rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polyether rubber,
Any one or a few mixing in polyurethane rubber, epoxy propane rubber.
In the present invention, the structural formula that described silicone rubber is had is:
In formula (1), end group can be-OH ,-Me (Me represents methyl) ,-CH=CH2Or long alkane
Base etc.；X, y, z are silica chain number (the also referred to as degree of polymerization)；R1、R2Can be-Me ,-Ph ,-CH=CH2,
-CH2CH2CN ,-halogen etc..
The degree of polymerization of above-mentioned silicone rubber preferably more than 100 (generally, 80～120000), more preferably 3000～
60000, particularly preferably 5000～30000, it is preferably, under room temperature (25 DEG C), not there is auto-flowability
So-called raw rubber shape (non-aqueous).If the degree of polymerization is too small, when making mixing material, it is possible to roller adhesion occurs
Etc. problem, roller workability reduces.Further, this degree of polymerization usually using toluene as developing solvent, as adopting
The weight average degree of polymerization analyzing the polystyrene standard conversion obtained with gel permeation chromatography (GPC) measures.
Work as R1、R2When being Me, described silicone rubber is dimethyl silicone rubber.
Work as R1For Me, R2During for Vi (vinyl), described silicone rubber is methyl vinyl silicone rubber, institute
Stating methyl vinyl silicone rubber, part methyl is replaced by vinyl, due to-CH=CH2Existence, it
Remaining under high/low temperature keep good viscoelasticity, time high temperature compressed, set deformation volume also to lack, lower temperature resistance and resistance to
Swellabilities etc. are preferable.In the present invention ,-MeViSiO-chain link is the 0.01%～1.0% of gross mass.
Work as R1For Vi, R2During for Ph, described silicone rubber is methyl phenyl silicone rubber.
Work as R1For CH2CH2CN、R2During for Vi, described silicone rubber is nitrile silicone rubber.
Above-mentioned silicone rubber can be used alone or two or more form of mixtures uses.
What described vinylsiloxane rubber can list has methyl vinyl silicone rubber, methyl phenyl vinyl silicon rubber
Glue etc..
Certainly, described vinylsiloxane rubber can also is that being total to of vinyl methyl siloxane/polydimethylsiloxane
Polymers, the polydimethylsiloxane of ethenyl blocking, the diphenyl siloxane/poly dimethyl silicon of ethenyl blocking
The copolymer of oxygen alkane, the copolymer of di-ethyl siloxane/polydimethylsiloxane of ethenyl blocking, vinyl
The PSI of end-blocking, the copolymer of vinyl methyl siloxane/dimethyl siloxane, trimethyl
The copolymer of dimethyl siloxane/vinyl methyl siloxane of siloxy end-blocking, trimethylsiloxy group block
Dimethyl siloxane/vinyl methyl siloxane/diphenylsiloxane copolymer etc..
In one embodiment, described rubber base material is the mixture of multiple silicone rubber, such as, 100
The rubber base material of weight portion, including dimethyl silicone rubber, 20～40 weight portions of 10～40 weight portions
Methyl vinyl silicone rubber, the methyl phenyl silicone rubber of surplus and the rubber of other kind.
In a preferred embodiment, described rubber base material also includes the acrylic acid of 1～15 weight portions
In ester rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polyether rubber, polyurethane rubber, epoxy propane rubber
Any one or a few mixing.
Although not containing fluorine element in the rubber base material of the present invention, but it hydrophobic can reach with oleophobic performance
The performance of fluorine-containing rubber.
Silicone oil:
In the present invention, described silicone oil at least includes phenyl methyl silicone oil, alkyl-silicone oil, and phenyl methyl silicone oil with
The weight ratio of alkyl-silicone oil is 1:0.01～0.1.
In the present invention, described phenyl methyl silicone oil refers to the part methyl in phenyl substituent methyl silicone oil.
The commercially available acquisition of described phenyl methyl silicone oil, it is also possible to be that those skilled in the art are by known method
Synthesis obtains.
In one embodiment, the preparation method of phenyl methyl silicone oil is as follows: add in three neck round bottom flask
100ml water and 40ml toluene, be slowly dropped into 0.33mol (CH when stirring2)2SiCl2, 0.038mol
Ph2SiCl2With 0.010mol (CH3)SiOSi(CH3)3Mixed liquor, controls system temperature less than 50 DEG C.After 5h
Stopped reaction, layering retains toluene phase and is washed to neutrality.Filtering, rotary evaporation is evaporated off toluene, 80 DEG C of vacuum
It is dried 2h, obtains colourless transparent liquid.
The molar fraction of described phenyl is 1～18%, preferably 7%～11%, more preferably 9%.
The mensuration mode of the molar fraction of heretofore described phenyl can use well known by persons skilled in the art
Any method measures.
The method using nuclear-magnetism in the present invention measures the content of toluene.Pass through1H NMR measures, in spectrogram
Low field 7.7～7.4ppm is the signal peak of phenyl ring 1H, and the signal that High-Field 0.1～0.4ppm is methyl 1H
Peak.From integration, methyl and the integral area ratio of phenyl in phenyl methyl silicone oil, such that it is able to draw methyl
Mol ratio with phenyl.
In the present invention, described alkyl-silicone oil is not particularly limited.
The commercially available acquisition of described alkyl-silicone oil, it is also possible to be that those skilled in the art are synthesized by known method
Obtaining, conventional having is following several: one is to be led to alpha-olefin by methylhydrochlorosilane or methyl hydrogen alkoxy silane
Cross hydrosilylation and prepare methyl chain alkyl chlorosilane or alkoxy silane, then obtain through hydrolysis-condensation reaction
Silicone intermediate, the most according to a conventional method catalytic equilibration；Two is by chain alkyl dimethyl dichlorosilane (DMCS) and three
Methyl silanol carries out cohydrolysis polycondensation reaction；Three to be that Methyl Hydrogen Polysiloxane Fluid directly carries out Si-H addition reaction with alpha-olefin anti-
Should.
In a preferred embodiment, what the preparation method of described alkyl-silicone oil can be enumerated has: alpha-olefin
Prepared by hydrosilylation with containing hydrogen silicone oil.
As one preferred embodiment, described phenyl methyl silicone oil is 1:0.07 with the weight ratio of alkyl-silicone oil.
In the present invention, it is also possible to add the silicone oil of other kind, the most aralkyl modified silicone oil, fluorinated alkyl change
Property silicone oil, Carboxyl Modified Polydimethylsiloxane, amino-modified silicone oil, hydroxyl modification silicone oil etc..
The inventors discovered that, by phenyl methyl silicone oil and alkyl-silicone oil with the use of, there is preferable hydrophobicity,
Be conducive to complete wetting and sprawl, now can reduce the surface tension of hydrophobic membrane and glass interface, improve hydrophobic
Adhesiveness between film and glass and the hydrophobicity of hydrophobic membrane, increase the service life of hydrophobic membrane.Coordinate simultaneously and make
By hyperbranched polyorganosiloxane improved silica nanometer sheet so that though the feelings that this rubber composition moistens at glass
Under condition, it is also possible to form hydrophobic protecting film.
Filler:
In the present invention, described filler is hyperbranched polyorganosiloxane improved silica nanometer sheet.
Described hyperbranched polyorganosiloxane is the hyperbranched polyorganosiloxane containing epoxy radicals.
In one embodiment, the preparation method of the described hyperbranched polyorganosiloxane containing epoxy radicals is as follows:
By distilled water and 5～10 parts of trialkoxy silane mix homogeneously containing epoxy radicals of 10～20 weight portions,
It is slowly added dropwise 0.001～0.005 part of catalyst under agitation；Under the temperature conditions of 40～60 DEG C
React 3～7 hours, after precipitate washing, vacuum drying, obtain a kind of hyperbranched poly containing epoxy radicals
Siloxanes.
Described catalyst be hydrochloric acid, sulphuric acid, p-methyl benzenesulfonic acid, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide,
Any one in sodium hydroxide, potassium hydroxide.
In the present invention, any method synthesis that silica nanometer sheet can be known to those skilled in the art
Obtain, it is possible to commercially available acquisition.
The preparation method of described silica nanometer sheet is with " Graphene template prepares ultra-thin silica nanometer
Sheet ", 2012,57 (22) .2062～2065.
(1) specifically comprise the following steps that graphene oxide is dissolved in N,N-dimethylformamide (DMF) ultrasonic
1h.Add 3-(isobutene. acyl-oxygen) propyl trimethoxy silicane (MPS) monomer, finally protect at nitrogen and connect
Azodiisobutyronitrile (AIBN) initiator is added under continuous stirring.This reacts on and reacts a timing in 65 DEG C of oil bath pans
After between, centrifugal, dry, product is placed in heat treatment 10h at 700 DEG C, obtains silica nanometer sheet.
In the present invention, described hyperbranched polyorganosiloxane improved silica nanometer sheet is: silica nanometer sheet warp
Cross the first silicon-containing compound modified, then react with the hyperbranched polyorganosiloxane containing epoxide group.
Described first silicon-containing compound has following structure: YRnSiX3-n；
Wherein n=0～3, X are in chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group
Any one；R be carbon number be the chain alkyl of 5～15；Y at least contains an amino.
That can enumerate has: 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, β-aminoethyl-γ-
Aminopropyl trimethoxysilane, gamma-aminopropyl-triethoxy-silane, aminopropyl end-blocking polydimethylsiloxane, α,
The polydimethylsiloxane of ω-two aminopropyl end-blocking, α, ω-bis-(2-amino-ethyl) polydimethylsiloxane, α,
ω-bis-(3-aminopropyl) polydimethylsiloxane, α, ω-bis-(4-aminophenyl) polydimethylsiloxane, α, ω-
Double (4-amino-3-aminomethyl phenyl) polydimethylsiloxane, α, ω-bis-(3-aminopropyl) polydiphenylsiloxane,
Any one in α, ω-bis-(4-aminobutyl) polydimethylsiloxane.
In a preferred embodiment, silica nanometer sheet is through β-aminoethyl-γ-aminopropyl trimethoxy
The concrete preparation process of base silane modification is as follows:
After the β-aminoethyl-γ-aminopropyltrimethoxysilane of 2～8 weight portions is diluted by ethanol in proper amount, add
Enter the silica nanometer sheet of 10 weight portions, be dried 2～5h removing ethanol at 35 DEG C.Again at 70～85 DEG C
Heating in vacuum 2～3h removes absorption water, completes condensation reaction, obtains improved silica nanometer sheet.
In one embodiment, the described hyperbranched polyorganosiloxane containing epoxy radicals and silica nanometer sheet
Weight ratio is (2～15): 1.
In one embodiment, the preparation process of described hyperbranched polyorganosiloxane improved silica nanometer sheet is such as
Under: hyperbranched polyorganosiloxane obtained above is dissolved in ethanol solution, adds DIPEA,
After mixing 0.5～3 hour, add silane coupler modified silica nanometer sheet, at 20～40 DEG C, instead
Answer 0.5～3h, obtain the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals.
Inventors herein have recognized that, when the silicon dioxide that filler is conventional is replaced by silica nanometer sheet, make
Obtain the life of rubber composition, and there is preferable weather resistance.The present inventor guesses that possible reason is,
The silicone hydroxyl of the silica surface physical and chemical adsorption to rubber molecule, produces certain cross-linked structure, and then
Make rubber hardening.In the present invention, silicon dioxide is changed into silica nanometer sheet, and titanium dioxide from particle
Silicon nanometer sheet is modified through the hyperbranched polyorganosiloxane containing epoxide group.On the one hand, hyperbranched polyorganosiloxane can be
The surface of silica nanometer sheet forms layer protective layer, and the siliconoxygen bond in hyperbranched polyorganosiloxane has preferably
Compliance, is freely rotatable, and i.e. forms, at silica nanometer sheet, the protecting film that a sheaf space conformation is variable, has
The content controlling silicone hydroxyl of effect, the hyperbranched polyorganosiloxane on the other hand formed, it is also possible to play certain enhancing
Effect, its potentiation silicon dioxide to be less than.Hyperbranched polyorganosiloxane improved silica nanometer sheet is equivalent to
Strengthening a little with silica nanometer sheet for core, hyperbranched polyorganosiloxane is two grades and strengthens point, defines enhancing slow
Rush structure so that this rubber composition, not only there is intensity, also there is toughness, be highly suitable for making windscreen wiper
Device.Meanwhile, modified flaky silicon dioxide and glass can produce stronger adhesion, enhance service life,
And there is extraordinary hydrophobic effect.
Cross-linking agent:
Common cross-linking agent is organic peroxide: cumyl peroxide, benzoyl peroxide, di-t-butyl
Peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5 di-t-butyl hexane peroxide.
Preferred 2,5-dimethyl-2,5 di-t-butyl hexane peroxide in the present invention.
Antistructurizing agent:
Constitution controller is the preparation for control structure, it is possible to control structure, and structuring is that white carbon is filled out
Fill silicon rubber body and tie up in processing and storage, due to the surface activity hydroxyl of the white carbon physics to silicone rubber molecule
Chemisorbed and the sizing material that produces is hardening, plasticity declines, gradually lose back mixing and the phenomenon of process industrial art performance.
The auxiliary agent being intended to eliminate silicone rubber-white carbon architecture phenomenon is referred to as constitution controller or resistive connection structure agent.
Consisting of with the organo-silicon compound of active group, anti-structuring function is preferential and white owing to active group
The hydroxyl effect of carbon blacksurface, is allowed to passivation and reaches anti-structuring purpose.Principal item includes hydroxyl silane
Compounds (such as hydroxy silicon oil, diphenyl silanediol etc.), oxyalkylsiloxane compounds are (as alkoxyl is low
Molecular silicone etc.), silazane compounds (such as hexamethyldisilazane, ring-type three silazane etc.) and containing
Borosiloxane compounds etc..
Lubricant:
Heretofore described lubricant is divided into in-lubricant and external lubricant two kinds.
In-lubricant is before processing, and in dispensing, addition and component have the lubricant of certain compatibility；
External lubricant is to form thin film layer at the finished surface made；
According to chemical composition, conventional lubricant is divided into: fitter acids and its ester class, fatty acid amide, metal soap,
Hydro carbons, alcohols, compounded lubricant class, inorganic lubricant.
Heretofore described lubricant is preferably inorganic lubricant, such as Pulvis Talci, mica powder, potter's clay, sticks in vain
Soil, calcium stearate, graphite etc..
Component A:
In the present invention, described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；
Described R2For polyimide-siloxane copolymer segment.
In a preferred embodiment, the structural formula of described branched alkyl acid is:
In the present invention, described " polyimide-siloxane copolymer segment " refers to polyimide preformed polymer and contains
The product that siloxane prepolymer copolymerization obtains.
In one embodiment, described polyimide-siloxane copolymer is by carboxy blocking polyimides pre-polymerization
Thing with containing diaminourea siloxanes 1:(0.98 in molar ratio～1) copolymerization obtains.
In one embodiment, described carboxy blocking polyimide preformed polymer by diacid and diamidogen is in molar ratio
1:(0.88～0.95).
In one embodiment, described polyimide-siloxane copolymer preparation method is as follows:
(1) preparation of carboxy blocking polyimide preformed polymer:
Diacid, appropriate metacresol and the triethylamine of 1 mole is added, in inertia in the there-necked flask being completely dried
Stir under gas shield, after diacid is completely dissolved, add the diamidogen of 0.88～0.95 mole and appropriate urging
Agent, after being stirred at room temperature about 20～40min, is heated to about 70～90 DEG C, reaction about 3～5h, then
At about 170～180 DEG C, react about 4～5h；After reaction terminates, it is down to room temperature, solution is poured in methanol,
There is Precipitation；After filtering after removing solvent with methanol cyclic washing, dry at about 40 DEG C in vacuum drying oven
About 20～40h, obtain carboxy blocking polyimide preformed polymer.
(2) preparation of polyimide-siloxane copolymer
In the there-necked flask being completely dried add 1 mole above-mentioned carboxy blocking polyimide preformed polymer and
Appropriate metacresol, stirs under inert gas shielding, after carboxy blocking polyimide preformed polymer is completely dissolved,
Add the diaminourea siloxanes of 0.98～1 mole and appropriate catalyst, after being stirred at room temperature about 30min,
It is heated to about 75～85 DEG C, reacts about 3.5～4.5h, then at about 175～185 DEG C, react about 3.5～4.5h；
After reaction terminates, it is down to room temperature, solution is poured in methanol, has Precipitation；Remove with methanol cyclic washing
Filter after solvent, then with after hydrochloric acid proton exchange 24h of 1mol/L, with deionized water cyclic washing 3 times
And in vacuum drying oven, at about 50 DEG C, dry about 22～24h, obtain polyimide-siloxane copolymer.
In one embodiment, what described diacid can be enumerated has: described aromatic diacid monomer is selected from: right
Phthalic acid, p-phthalic acid methyl ester, phthalic acid, adipic acid, FDCA, 2,6-pyridine
Dioctyl phthalate, 4-(4,5-diphenyl-imidazole base)-1,2-dibenzoic acid, FDCA methyl ester, 2,6-
One in naphthalenedicarboxylic acid methyl ester, phenylmalonic acid or a combination thereof.These compounds can be used alone, or with
Being applied in combination of two or more difference compound.
In one embodiment, what described diamidogen can be enumerated has: 4,4 '-diaminodiphenyl-methane, o-,
M-and p-phenylenediamine, double [4-(3-amino-benzene oxygen) phenyl] sulfone, 2,4 di amino toluene, 2,5-diaminourea
Toluene, 2,4-diaminourea dimethylbenzene, 3,6-diaminourea durene, 2,2 '-dimethyl-4,4 '-benzidine,
2,2 '-diethyl-4,4 '-benzidine, 2,2 '-dimethoxy-4 ', 4 '-benzidine, 2,2 '-diethyl
Epoxide-4,4 '-benzidine, 4，4′-diaminodipohenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-diamino
Base sulfobenzide., 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminourea benzophenone, 3,3 '-diaminourea benzophenone,
1,3-double (3-amino-benzene oxygen) benzene, 1, double (4-amino-benzene oxygen) benzene of 3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene,
4,4 '-bis-(4-amino-benzene oxygen) biphenyl, double [4-(4-amino-benzene oxygen) phenyl] sulfone, 2, double [4-(the 4-aminobenzene of 2-
Epoxide) phenyl] propane etc..These compounds can be used alone, or the group with two or more difference compound
Close and use.
In one embodiment, described diaminourea siloxanes is selected from: 1,3-double (3-aminopropyls)-1,1,3,
3-tetramethyl disiloxane, 1, double (the 4-aminobutyl)-1 of 3-, 1,3,3-tetramethyl disiloxane, double (4-ammonia
Phenoxyl) dimethylsilane, and 1, double (the 4-amino-benzene oxygen)-1 of 3-, in 1,3,3-tetramethyl disiloxane
Any one or more.
In the present invention, described " branched alkyl acid graft modification hydroxy compounds ", refer to containing branched structure
Alkyl graft modification hydroxy compounds.
The acid of described branched alkyl is (1～10) with the weight ratio of silica nanosphere: 1；Preferably, branched alkane
Base acid is (4～8) with the weight ratio of silica nanosphere: 1；It is further preferred that branched alkyl acid and dioxy
The weight ratio of SiClx nanosphere is 5:1.
The preparation process of described branched alkyl acid graft modified silicon dioxide nanosphere is as follows:
By the silica nanosphere of 1 weight portion 150ml reflux in toluene 24 hours, add 1～10
The branched alkyl acid of weight portion, reacts 5～24 hours under 40～60 degrees Celsius, then by modified titanium dioxide
Silicon, centrifugal 30 minutes, is dried under 80 degrees Celsius, obtains alkyl group acid graft modified silicon dioxide nanosphere.
In the present invention, described branched alkyl acid at least contains a carboxyl, and the carbon number of described alkyl is
3～20.
In a preferred embodiment, the structural formula of described branched alkyl acid is:
R1-R2-R1Preparation method:
The R of 1 mole is added in the there-necked flask being completely dried2With the R of 2 moles1, add catalyst,
At 30～60 DEG C, react about 3～10h, reaction terminate after, be down to room temperature, product through filter, washing,
After precipitation, obtain R1-R2-R1。
The present inventor is found surprisingly that, after adding component A in the present invention, branched alkyl acid contains more first
Base, in the continuing on of windscreen wiper, with " umbrella " structure distribution on interface, beneficially complete wetting and
Sprawl, now can reduce the surface tension of hydrophobic membrane and glass interface, improve gluing between hydrophobic membrane and glass
Attached property and the hydrophobicity of hydrophobic membrane, increase the service life of hydrophobic membrane.
Although the rubber in the present invention does not contains fluorine element, but its hydrophobic performance can reach fluorine-containing rubber institute
The performance having.
Sulfonate polybenzimidazole:
In the present invention, described " sulfonate polybenzimidazole " refers to the material in polybenzimidazoles containing sulfonate radical.
In the present invention, described " sulfonate polybenzimidazole " both can be directly polybenzimidazoles to be carried out sulfonating reaction,
Can also be to use sulfonated monomer polymerization to obtain sulfonate polybenzimidazole.
In the present invention, described sulfonate polybenzimidazole is by sulfonation diacid monomer, non-sulfonated diacid monomer and tetramine
Monomer (0.05～0.25) in molar ratio: (0.75～0.95): 1 copolymerization obtains.
In a preferred embodiment, described sulfonation diacid monomer, non-sulfonated diacid monomer and tetramine list
Body 0.15:0.85:1 in molar ratio.
In one embodiment, described sulfonation diacid monomer is selected from: between 2-sulfonic acid p-phthalic acid, 4-sulfonic acid
Phthalic acid, 4,6-disulfonic acid base M-phthalic acid, 2-sulfonic acid isophthalic two hydrobromic acid, 4-sulfonic acid isophthalic dihydro bromine
Acid, 4,6-disulfonic acid base isophthalic two hydrobromic acid, 2-sulfonic group adipic acid, 3-sulfonic group adipic acid, 2-sulfonic group are pungent
Any one or more in diacid and 3-sulfonic group suberic acid；
Preferably, described sulfonation diacid selected from 2-sulfonic acid p-phthalic acid, 4-sulfonic acid M-phthalic acid, 4,6-bis-
Any one or more in sulfonic group M-phthalic acid；It is highly preferred that described sulfonation diacid is that 2-sulfonic acid is to benzene
Dioctyl phthalate.
In one embodiment, described diacid selected from isophthalic acid, terephthalic acids, 4,4 '-biphenyl dicarboxylic acid,
Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, diphenic acid (2,2 '-diphenyl dicarboxylic acid), phenyl indane dicarboxylic acid, 1,6-naphthalenedicarboxylic acid,
NDA, 4,4 '-diphenyl ether dioctyl phthalate and 4, any one in 4 '-diphenylsulfide dioctyl phthalate
Plant or multiple；Preferably, described diacid selected from isophthalic acid, terephthalic acids, 4,4 '-biphenyl dicarboxylic acid, 1,
Any one or more in 4-naphthalenedicarboxylic acid；It is highly preferred that described diacid is terephthalic acids.
In one embodiment, described tetramine is selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino hexichol
Ether, 3,3', 4,4'-bis-amido diphenyl sulphone (DPS), 3,3', 4,4'-bis-aminobenzophenone, 3,3', 4,4'-bis-amido hexichol first,
In 3,3', 4,4'-bis-amido diphenyl sulfide, 1,2,4,5-tetra-amido benzene or 1,2,5,6-tetra-amido naphthalene any one or many
Kind；Preferably, described tetramine be selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino diphenyl ether, 3,3', 4,4'-
Two amido diphenyl sulphone (DPS)s, the 3,3', 4,4'-bis-any one or more in aminobenzophenone；It is highly preferred that it is described
Tetramine is DAB.
In one embodiment, described sulfonate polybenzimidazole synthetic method is as follows:
The polyphosphoric acids of weighing certain mass, in three-neck flask, connects gas access, drying tube, gas outlet
And mechanical agitator, be passed through noble gas, after 3-5min, add the tetramine of 1 mole, described polyphosphoric acids with
The ratio of tetramine is 180g/10mmol, after tetramine is uniformly dispersed being dissolved in polyphosphoric acids, add 0.1～
The sulfonation diacid of 0.2 mole and the diacid of 0.8～0.9 mole, add phosphorus pentoxide afterwards to strengthen instead
Answer the absorption of product water, start simultaneously at stirring and heat up, be warming up to 200 DEG C, react 20h at such a temperature；Treat
After temperature of reaction system is cooled to 150 DEG C, pouring in deionized water, cyclic washing removes polyphosphoric acids；Afterwards
Product is poured into stirring 24h in the sodium hydrate aqueous solution that mass fraction is 7%-10%, uses deionized water afterwards
Cyclic washing removes sodium hydroxide, is dried by products therefrom sulfonate polybenzimidazole in vacuum drying oven at 60 DEG C
Standby.
After polybenzimidazoles is sulfonated in the present invention, after controlling sulfonation degree, the adhesiveness with glass can be improved
While, and there is the strongest hydrophobicity simultaneously.
Pigment:
According to the demand of color can be added that can buy on various market, be suitable for adding organic silicon rubber
In pigment.Its consumption can be come according to the general knowledge of oneself and the requirement to color by those of ordinary skill in the art
Determine.
Additive:
As long as the effect of the present invention is unaffected, so that it may other additives different types of to be mixed in the group of the present invention
In compound, the example of described additive has: the reinforcer in addition to fine silica, such as pyrolitic oxidation
Titanium；Non-reinforcing fillers, such as silica flour, crystalline silica, kieselguhr, asbestos, aluminosilicate, oxidation
Zinc and calcium carbonate；Hydrosilylation controlling agent such as nitrogen-containing compound, acetylenic compound, phosphorus compound, nitration
Compound, carboxylate/ester, tin compound, mercury compound, acetylenic compound such as ethynylcyclohexanol, and sulfur
Compound；Heat-resistant agent such as ferrum oxide and cerium oxide；Slip agent, cross-linking agent, packing material, ultra-violet absorption
Agent, plasticizer, coloring agent, antistatic additive, heat stabilizer, antioxidant, light stabilizer, fire retardant,
Lubricant, antioxidant, age resistor, reaction promoter, reaction suppressor, resin etc..Phenol antioxidant,
The various antioxidant such as Phosphorus antioxidant；Benzophenones UV absorbent, Benzotriazole Ultraviolet Stabilizer,
The various UV absorbent such as benzoate UV absorbent；Bisamide class dispersant, paraffin class dispersant,
The various dispersants such as organic metal salt dispersant；Pulvis Talci, Muscovitum, clay, calcium carbonate, aluminium hydroxide,
Magnesium hydroxide, barium sulfate, glass fibre, carbon fiber, silicon dioxide, calcium silicates, potassium titanate, wollastonite etc.
Various inorganic fillers.
Another aspect provides the processing method of a kind of water-proof surface: at least comprise the following steps:
(1) matrix material is provided；
(2) substrate material surface coating rubber compositions；
Described rubber composition, in parts by weight, at least includes:
Described rubber base material includes at least silicone rubber；
Described filler is the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxide group；
Described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；Described R2For polyimide-siloxane
Copolymer segment.
In the present invention, what described matrix material can be enumerated has simple glass, safety glass, plastics, vehicle window glass
Glass, sun-shielding glass.
The self-lubricating rubber that yet another aspect of the present invention provides a kind of above-mentioned environment-friendly rubber compositions to prepare is close
Sealing.Described preparation method is mill or banbury carries out mixing.The present invention uses mill mixing: double
Roller mill mixer roller speed ratio is with (1.2～1.4): 1 is advisable.Roller must be connected with cooling water, and melting temperature preferably exists
Less than 40 DEG C.Start roll spacing less (1～5mm) time mixing, then incrementally increase.Charging and operation order:
Rubber (-constitution controller-reinforcing filler-heat resistance accessory-coloring agent-thin logical 5 times-blanking.Mixing time is
20～40min.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example
It is served only for that the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, this field
Some nonessential improvement and adjustment that professional and technical personnel makes according to the content of the invention described above, still fall within this
The protection domain of invention.
It addition, illustrate without other, raw materials used is all commercially available.
Rubber base material:
A1: dimethyl silicone rubber, KF96, originates in SHIN-ETSU HANTOTAI's chemistry；
A2: methyl vinyl silicone rubber, is purchased from Zhejiang Heng Ye organosilicon company limited；
A3: methyl phenyl vinyl silicone rubber, is purchased from Hangzhou Hong Xing bloc trade company limited；
The dimethyl silicone rubber of A4:15 weight portion, the methyl vinyl silicone rubber of 30 weight portions, 40 weight portions
Methyl phenyl silicone rubber, the polyurethane rubber of 15 weight portions.
Silicone oil
B1: phenyl methyl silicone oil, alkyl-silicone oil (phenyl methyl silicone oil is 1:0.01 with the weight ratio of alkyl-silicone oil)
Phenyl methyl silicone oil is purchased from Beijing Chemical Co., Ltd. of Hua Weirui section；
Alkyl-silicone oil, product type: LX0701, it is purchased from Solenognathus rising sun Chemical Co., Ltd.；
B2: phenyl methyl silicone oil, alkyl-silicone oil (phenyl methyl silicone oil is 1:0.07 with the weight ratio of alkyl-silicone oil)
Phenyl methyl silicone oil is purchased from Beijing Chemical Co., Ltd. of Hua Weirui section；
Alkyl-silicone oil, product type: LX0701, it is purchased from Solenognathus rising sun Chemical Co., Ltd.；
B3: phenyl methyl silicone oil, alkyl-silicone oil (phenyl methyl silicone oil is 1:0.1 with the weight ratio of alkyl-silicone oil)
Phenyl methyl silicone oil is purchased from Beijing Chemical Co., Ltd. of Hua Weirui section；
Alkyl-silicone oil, product type: LX0701, it is purchased from Solenognathus rising sun Chemical Co., Ltd.；
B4: phenyl methyl silicone oil
Phenyl methyl silicone oil is purchased from Beijing Chemical Co., Ltd. of Hua Weirui section；
B5: alkyl-silicone oil
Alkyl-silicone oil, product type: LX0701, it is purchased from Solenognathus rising sun Chemical Co., Ltd.；
B6: phenyl methyl silicone oil, alkyl-silicone oil (phenyl methyl silicone oil is 1:1 with the weight ratio of alkyl-silicone oil)
Phenyl methyl silicone oil is purchased from Beijing Chemical Co., Ltd. of Hua Weirui section；
Alkyl-silicone oil, product type: LX0701, it is purchased from Solenognathus rising sun Chemical Co., Ltd.；
Filler:
C1: the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals
Preparation method: by distilled water and 5 parts of trialkoxy silane mix homogeneously containing epoxy radicals of 10 weight portions
Hyperbranched polyorganosiloxane containing epoxy radicals, it is slowly added dropwise 0.001 weight portion catalysis under agitation
Agent hydrochloric acid；React 5 hours under the temperature conditions of 40 DEG C, after precipitate washing, vacuum drying, obtain
Hyperbranched polyorganosiloxane containing epoxy radicals.
The preparation method of silica nanometer sheet: the graphene oxide of 10 weight portions is dissolved in N, N-dimethyl
In Methanamide, add 50 weight portion 3-(isobutene. acyl-oxygen) propyl trimethoxy silicane monomer, then lead to nitrogen
Gas, under agitation adds initiator；At 65 DEG C after water-bath 36h, centrifugal, dry, product is placed in 700 DEG C
Lower heat treatment 10h, obtains silica nanometer sheet, and the thickness of silica nanometer sheet is 0.8nm.
The preparation method of silane coupler modified silica nanometer sheet:
After the β-aminoethyl-γ-aminopropyltrimethoxysilane of 1 weight portion is diluted by ethanol in proper amount, add
The silica nanometer sheet of 10 weight portions, removes ethanol at 35 DEG C of dry 5h.Again 70 DEG C of heating in vacuum 2h
Remove absorption water, complete condensation reaction, obtain improved silica nanometer sheet.
The preparation method of the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals: obtain above-mentioned
The hyperbranched polyorganosiloxane of 2 weight portions be dissolved in ethanol solution, add DIPEA, mix
After 0.5 hour, add the improved silica nanometer sheet of 1 weight portion, at 20 DEG C, react 3h,
To hyperbranched polyorganosiloxane improved silica nanometer sheet.
C2: the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals
The same C1 of preparation method of the hyperbranched polyorganosiloxane containing epoxy radicals；
The same C1 of preparation method of silica nanometer sheet, the thickness of silica nanometer sheet is 3nm；
The preparation method of silane coupler modified silica nanometer sheet:
After being diluted by ethanol in proper amount by the 3-aminopropyl triethoxysilane of 5 weight portions, add 10 weight portions
Silica nanometer sheet, removes ethanol at 35 DEG C of dry 5h.Absorption is removed again 85 DEG C of heating in vacuum 2h
Water, complete condensation reaction, obtain improved silica nanometer sheet.
The preparation method of the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals: obtain above-mentioned
The hyperbranched polyorganosiloxane of 15 weight portions be dissolved in ethanol solution, add DIPEA, mix
After 3 hours, add the improved silica nanometer sheet of 1 weight portion, at 40 DEG C, react 3h, obtain
Hyperbranched polyorganosiloxane improved silica nanometer sheet.
C3: the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals
The same C1 of preparation method of the hyperbranched polyorganosiloxane containing epoxy radicals；
The same C1 of preparation method of silica nanometer sheet, the thickness of silica nanometer sheet is 2nm；
The preparation method of silane coupler modified silica nanometer sheet:
After being diluted by ethanol in proper amount by the 3-aminopropyl triethoxysilane of 10 weight portions, add 10 weight portions
Silica nanometer sheet, removes ethanol at 35 DEG C of dry 5h.Absorption is removed again 85 DEG C of heating in vacuum 2h
Water, complete condensation reaction, obtain improved silica nanometer sheet.
The preparation method of the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxy radicals: obtain above-mentioned
The hyperbranched polyorganosiloxane of 10 weight portions is dissolved in ethanol solution, adds DIPEA, mixes 3
After hour, add the improved silica nanometer sheet of 1 weight portion, at 40 DEG C, react 3h, surpassed
Branched polysiloxane improved silica nanometer sheet.
C4: silica nanosphere, model: KL-5000；It is purchased from Cologne, Dongguan City, Guangdong Province Chemical trade.
C5: silica nanometer sheet, the same C1 of preparation method of silica nanometer sheet；
C6: silica nanometer sheet is only through aminosilane coupling agent modifying
C7: polysiloxane-modified silica nanometer sheet；
The concrete same C3 of preparation process, difference is, polysiloxanes is linear chain structure.
Cross-linking agent:
D1:2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, model: 101XL45, manufacturer: Shanghai
Sen Di Chemical Co., Ltd.；
Constitution controller:
E1: hydroxy silicon oil, model: QLS-203M, producer: Wuxi City Quan Li Chemical Co., Ltd.；
Lubricant:
F1: calcium stearate, model: HB-02, manufacturer: Hangzhou Mao Lai Chemical Co., Ltd.；
Component A:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；
Described R2For polyimide-siloxane copolymer segment.
G1:R1-R2-R1
R2Preparation method: the preparation of (1) carboxy blocking polyimide preformed polymer:
P-phthalic acid, appropriate metacresol and the triethylamine of 1 mole is added in the there-necked flask being completely dried,
Stir under inert gas shielding, after p-phthalic acid is completely dissolved, add the 4 of 0.95 mole, 4 '-diamino
Base diphenyl methane and catalyst, after being stirred at room temperature about 40min, be heated to about 80 DEG C, and reaction is about
5h, then at about 180 DEG C, react about 4h；After reaction terminates, it is down to room temperature, solution is poured in methanol,
There is Precipitation；After filtering after removing solvent with methanol cyclic washing, dry at about 40 DEG C in vacuum drying oven
About 30h, obtains carboxy blocking polyimide preformed polymer.
(2) preparation of polyimide-siloxane copolymer
In the there-necked flask being completely dried add 1 mole above-mentioned carboxy blocking polyimide preformed polymer and
Appropriate metacresol, stirs under inert gas shielding, after carboxy blocking polyimide preformed polymer is completely dissolved,
Add diaminourea siloxanes and the catalyst of 1 mole, after being stirred at room temperature about 30min, be heated to about 85 DEG C,
React about 4.5h, then at about 175 DEG C, react about 3.5h；After reaction terminates, it is down to room temperature, solution is fallen
Enter in methanol, have Precipitation；Filter after removing solvent with methanol cyclic washing, then with the salt of 1mol/L
After acid proton exchange 24h, dry about at about 50 DEG C with deionized water cyclic washing 3 times and in vacuum drying oven
24h, obtains polyimide-siloxane copolymer.
The preparation method of branched alkyl acid graft modified silicon dioxide nanosphere: the silicon dioxide of 1 weight portion is received
Rice ball, 150ml reflux in toluene 24 hours, adds the isostearic acid of 1 weight portion, anti-under 40 degrees Celsius
Answer 24 hours, then by modified silicon dioxide, centrifugal 30 minutes, be dried under 80 degrees Celsius, obtain chain
Alkyl acid graft modified silicon dioxide nanosphere.
The structural formula of isostearic acid is:
R1-R2-R1Preparation method:
The R of 1 mole is added in the there-necked flask being completely dried2With the R of 2 moles1, add catalyst,
At 60 DEG C, react about 5h, after reaction terminates, be down to room temperature, product after filtering, wash, precipitating,
Obtain R1-R2-R1。
G2:R1-R2-R1, the same G1 of preparation method, its difference is, the acid of described branched alkyl and silicon dioxide
The weight ratio of nanosphere is 5:1.
G3:R1-R2-R1, the same G1 of preparation method, its difference is, the acid of described branched alkyl and silicon dioxide
The weight ratio of nanosphere is 10:1.
G4:R1, the same G1 of preparation method.
G5:R2, the same G1 of preparation method.
G6: straight chained alkyl acid improved silica nanosphere, the same G1 of preparation method, its difference is, straight chain
Alkyl acid is straight chain octadecanoic acid.
Sulfonate polybenzimidazole
H1: the polyphosphoric acids of weighing certain mass, in three-neck flask, connects gas access, drying tube, gas
Outlet and mechanical agitator, be passed through noble gas, adds 3,3', 4, the 4'-tetramino diphenyl ether of 1 mole after 5min,
Described polyphosphoric acids and 3,3', the ratio of 4,4'-tetramino diphenyl ether is 200g/10mmol, when 3,3', 4,4'-tetra-ammonia
After yl diphenyl ether is uniformly dispersed being dissolved in polyphosphoric acids, add the 2-sulfonic acid p-phthalic acid of 0.1 mole with
And the terephthalic acids of 0.9 mole, add phosphorus pentoxide afterwards to strengthen the absorption to reaction product water, simultaneously
Start stirring to heat up, be warming up to 200 DEG C, react 20h at such a temperature；Question response system temperature is cooled to 150 DEG C
After, to pour in deionized water, cyclic washing removes polyphosphoric acids；It is 10% that product is poured into mass fraction afterwards
Sodium hydrate aqueous solution in stir 24h, afterwards with deionized water cyclic washing remove sodium hydroxide, by gained
Product sulfonate polybenzimidazole dry for standby at 60 DEG C in vacuum drying oven.
H2: polybenzimidazoles, is purchased from Qun Xu plastic material company limited.
The preparation method of the wiper blade rubbers bar of environment-friendly rubber compositions: two-roll mill roller speed ratio is with 1.2:
1, roller must be connected with cooling water, feeding operation order: rubber base material-constitution controller-reinforcement and filler
Agent-heat resistance accessory-coloring agent-thin logical 5 times-blanking, mixing time is 40min, obtains wiper blade rubbers bar,
Test standby.
Table 1 embodiment is arranged
Table 2 comparative example is arranged
Performance test:
One, waterproofing tests
The self-lubricating rubber seal (wiper) being made up of environment-friendly rubber compositions, testing standard is with reference to JIS
D5710, wiper is dry brush 5 minutes on glass for vehicle window, the most again by water with the speed of 500 cc/min
Degree is injected on windshield uniformly, if vibration substantially and operates unstable, this test suspends.
Test evaluation criteria is as follows:
1, the performance that the contact portion of whole is hydrophobic/good；
2, the contact portion of at least 50% hydrophobic/slightly degraded performance；
3, contact portion less than 50% hydrophobic/degraded performance.
Embodiment test result such as table 3, comparative example test result such as table 4.
Table 3 embodiment water resistance is tested
Table 4 comparative example water resistance is tested
This test process does not occur wiper vibration, jumps brush and the jiggly phenomenon of windscreen wiper.
Two, contact angle test: by the rain brush of the present invention dry brush 5 minutes on glass for vehicle window before test, uses GB/T
24368-2009 carries out water contact angle test, again tests contact angle after 60 days.Embodiment test knot
Fruit is such as table 5, comparative example test result such as table 6.
Table 5 embodiment contact angle is tested
Table 6 comparative example contact angle is tested
In sum, by embodiments above and comparative example it can be seen that work as the wiper being used for self-lubricating rubber
Form one layer of hydrophobic membrane on the surface of glass for vehicle window, the contact angle of this hydrophobic membrane may be up to 160, and uses 60
After it, contact angle still may be up to 158, and this hydrophobic membrane has the strongest hydrophobicity and has longer service life,
So glass with waterproof layer makes raindrop be easy to be dispersed, the available good visual field, it is to avoid windscreen wiper
The noise of device and vibration.Additionally, the environment-friendly rubber compositions of the present invention does not contains and is easily caused environmental pollution
Fluorine element, has energy-conserving and environment-protective, thus provides beneficial effects of the present invention.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended right
Require to be intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only according to all
The explanation of the embodiment of the selection of the combination of possible embodiment.Therefore, the purpose of applicant is appended power
Profit requires the selectional restriction of example inventive feature not being described.And progressive in science and technology will be formed by
The possible equivalent or the son that are not presently considered in the inaccurate reason of language performance are replaced, and these become
Change and also should be interpreted in the conceived case to be covered by appended claim.
Claims (10)
1. environment-friendly rubber compositions, in parts by weight, at least includes:
Described rubber base material includes at least silicone rubber；
Described filler is the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxide group；
Described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；Described R2For polyimide-siloxane
Copolymer segment.
2. environment-friendly rubber compositions as claimed in claim 1, it is characterised in that described rubber base material
Also include acrylate rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polyether rubber, polyurethane rubber, ring
Any one or a few mixing in Ethylene Oxide rubber.
3. environment-friendly rubber compositions as claimed in claim 1, it is characterised in that described silicone oil at least includes
Phenyl methyl silicone oil and alkyl-silicone oil, the weight ratio of described phenyl methyl silicone oil and alkyl-silicone oil be 1:0.01～
0.1。
4. as claimed in claim 1 environment-friendly rubber compositions, it is characterised in that described containing epoxide group
Hyperbranched polyorganosiloxane improved silica nanometer sheet, described hyperbranched polyorganosiloxane containing epoxide group and dioxy
The weight ratio of SiClx nanometer sheet is (2～15): 1.
5. environment-friendly rubber compositions as claimed in claim 1, it is characterised in that described silica nanometer
The thickness of sheet is 0.8～3nm.
6. environment-friendly rubber compositions as claimed in claim 1, it is characterised in that in described component A, institute
The weight ratio stating branched alkyl acid and silica nanosphere is (1～10): 1.
7. environment-friendly rubber compositions as claimed in claim 1, it is characterised in that the acid of described branched alkyl
Structural formula is:
8. environment-friendly rubber compositions as claimed in claim 1, it is characterised in that environment-friendly rubber compositions
In also include the sulfonate polybenzimidazole of 0.1～2 weight portions.
9. the processing method of a water-proof surface: at least comprise the following steps:
(1) matrix material is provided；
(2) substrate material surface coating rubber compositions；
Described rubber composition, in parts by weight, at least includes:
Described rubber base material includes at least silicone rubber；
Described filler is the hyperbranched polyorganosiloxane improved silica nanometer sheet containing epoxide group；
Described component A has a following structure:
R1-R2-R1；
Wherein, described R1For branched alkyl acid graft modified silicon dioxide nanosphere, described branched alkyl acid is extremely
Containing a carboxyl less, the carbon number of described alkyl is 3～20；Described R2For polyimide-siloxane
Copolymer segment.
10. use self-lubricating rubber prepared by the environment-friendly rubber compositions described in any one of claim 1～8
Sealing member.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189245A (en) * | 2016-08-23 | 2016-12-07 | 杨子妹 | A kind of windscreen wiper anti tear resistance to deformation silastic material |
| CN106189263A (en) * | 2016-08-23 | 2016-12-07 | 杨子妹 | A kind of windscreen wiper lubricating and wear-resisting silastic material |
| CN106349701A (en) * | 2016-08-23 | 2017-01-25 | 杨子妹 | High-intensity wear-resistant silicon rubber material for windscreen wiper |
| CN106633426A (en) * | 2016-11-14 | 2017-05-10 | 芜湖天鸿汽车零部件有限公司 | Wiper bar of windscreen wiper and preparation method of wiper bar |
| CN106818253A (en) * | 2017-02-15 | 2017-06-13 | 佛山市秸和科技有限公司 | A kind of garden saw |
| CN107793851A (en) * | 2017-11-06 | 2018-03-13 | 贵州大学 | A kind of use for electronic products Nano waterproof paint |
| CN107884426A (en) * | 2017-12-26 | 2018-04-06 | 上海够得实业有限公司 | A kind of Novel button detection device |
| CN108219668A (en) * | 2018-01-12 | 2018-06-29 | 邯郸市富奥新材料有限公司 | A kind of polysiloxanes coatings on railway bracket and preparation method thereof |
| CN108410180A (en) * | 2018-04-24 | 2018-08-17 | 山东东都新材料科技有限公司 | A kind of environment-friendly type silica gel sebific duct and preparation method thereof |
| CN112452687A (en) * | 2020-11-18 | 2021-03-09 | 李英南 | Bendable light and thin toughened glass and preparation method thereof |
| CN112513196A (en) * | 2018-07-30 | 2021-03-16 | 3M创新有限公司 | Transparent elastomeric nanocomposite blends |
| CN114644885A (en) * | 2020-12-17 | 2022-06-21 | 中国石油化工股份有限公司 | Coating liquid composition for film-coated rubber plug, method for preparing coating liquid through esterification reaction, coating liquid, film-coated rubber plug and preparation method of film-coated rubber plug |
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| CN101824220A (en) * | 2010-04-14 | 2010-09-08 | 吴江朗科化纤有限公司 | Self-moistening type organic silicon rubber material and preparation method thereof |
| CN102504548A (en) * | 2011-11-29 | 2012-06-20 | 桂林裕天新材料有限公司 | Rubber material for windscreen wipers, preparation method thereof and process for producing windscreen wiper from the rubber material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189245A (en) * | 2016-08-23 | 2016-12-07 | 杨子妹 | A kind of windscreen wiper anti tear resistance to deformation silastic material |
| CN106189263A (en) * | 2016-08-23 | 2016-12-07 | 杨子妹 | A kind of windscreen wiper lubricating and wear-resisting silastic material |
| CN106349701A (en) * | 2016-08-23 | 2017-01-25 | 杨子妹 | High-intensity wear-resistant silicon rubber material for windscreen wiper |
| CN106633426A (en) * | 2016-11-14 | 2017-05-10 | 芜湖天鸿汽车零部件有限公司 | Wiper bar of windscreen wiper and preparation method of wiper bar |
| CN106818253A (en) * | 2017-02-15 | 2017-06-13 | 佛山市秸和科技有限公司 | A kind of garden saw |
| CN107793851A (en) * | 2017-11-06 | 2018-03-13 | 贵州大学 | A kind of use for electronic products Nano waterproof paint |
| CN107884426A (en) * | 2017-12-26 | 2018-04-06 | 上海够得实业有限公司 | A kind of Novel button detection device |
| CN108219668A (en) * | 2018-01-12 | 2018-06-29 | 邯郸市富奥新材料有限公司 | A kind of polysiloxanes coatings on railway bracket and preparation method thereof |
| CN108410180A (en) * | 2018-04-24 | 2018-08-17 | 山东东都新材料科技有限公司 | A kind of environment-friendly type silica gel sebific duct and preparation method thereof |
| CN112513196A (en) * | 2018-07-30 | 2021-03-16 | 3M创新有限公司 | Transparent elastomeric nanocomposite blends |
| CN112513196B (en) * | 2018-07-30 | 2023-01-10 | 3M创新有限公司 | Transparent elastomeric nanocomposite blends |
| CN112452687A (en) * | 2020-11-18 | 2021-03-09 | 李英南 | Bendable light and thin toughened glass and preparation method thereof |
| CN114644885A (en) * | 2020-12-17 | 2022-06-21 | 中国石油化工股份有限公司 | Coating liquid composition for film-coated rubber plug, method for preparing coating liquid through esterification reaction, coating liquid, film-coated rubber plug and preparation method of film-coated rubber plug |
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