CN106752625A - Cleaning hydrophobic coating material cleaning agent - Google Patents
Cleaning hydrophobic coating material cleaning agent Download PDFInfo
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- CN106752625A CN106752625A CN201611109888.8A CN201611109888A CN106752625A CN 106752625 A CN106752625 A CN 106752625A CN 201611109888 A CN201611109888 A CN 201611109888A CN 106752625 A CN106752625 A CN 106752625A
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- Prior art keywords
- methyl
- weight portions
- coating material
- hydrophobic coating
- trifluoro
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Classifications
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
Abstract
The present invention provides a kind of cleaning hydrophobic coating material cleaning agent, and its preparing raw material is included：Alkene radical siloxane, styrene, fluorinated acrylate monomer, methyl trifluoro silicones, 3,4 ethene dioxythiophenes and ethanol, the cleaning agent have excellent adhesive force, abrasion resistance, resistance to ag(e)ing, stain resistance and alkali resistance.
Description
Technical field
The present invention relates to one kind cleaning hydrophobic coating material, more it is related to by the cleaning hydrophobic coating material cleaning agent,
It is more specific to be related to B05D.
Background technology
In the case where outdoor environment dust is more and more, building, vehicle, human body clothing can be subjected to infringement.
Some multi-functional intelligent dress ornaments, such as Water-proof and oil-proof dress ornament occur at this stage.But such clothes is often deposited
In two kinds of shortcomings：1st, repeatedly after washing, waterproof oil-proof result can be significantly reduced；2nd, the general gas permeability of such clothes can be very poor.
Meanwhile, present water proof anti-soil material mainly reaches the property of water proof anti-soil using the low-surface-energy of perfluorinated material
Can, but perfluorinated material is often expensive, while perfluorinated material tends not to high temperature resistant, therefore can not be wide in real life
It is general to use.
Regarding to the issue above, the present invention provides a kind of cleaning agent, and the composition not only can be long-term under high temperature, low temperature
Used, while having excellent water proof anti-soil and the fabric tack relatively strong, advantage of good permeability.
The content of the invention
The present invention provides a kind of cleaning hydrophobic coating material cleaning agent, and by weight, its preparing raw material is included：
The alkene radical siloxane of 0.1-5 weight portions
The styrene of 1-10 weight portions
The fluorinated acrylate monomer of 1-10 weight portions
The methyl trifluoro silicones of 0.1-1.5 weight portions
The 3,4- ethene dioxythiophenes of 0.1-5 weight portions
The ethanol of 1-20 weight portions.
Used as one embodiment of the present invention, by weight, its preparing raw material is included：
The alkene radical siloxane of 0.5-2 weight portions
The styrene of 1-5 weight portions
The acrylic acid trifluoro methyl esters of 1-5 weight portions
The methyl trifluoro silicones of 0.1-0.5 weight portions
The 3,4- ethene dioxythiophenes of 0.1-2.5 weight portions
The ethanol of 1-10 weight portions.
Used as one embodiment of the present invention, by weight, its preparing raw material also includes 0.01-0.3 weight portions
Vinyl amino acid.
Used as one embodiment of the present invention, the vinyl amino acid is the vinyl amino acid of C3-C30.
Used as one embodiment of the present invention, the vinyl amino acid is the vinyl amino acid of C5-C20.
As one embodiment of the present invention, the fluorinated acrylate monomer be selected from methacrylic acid trifluoro methyl esters,
Acrylic acid trifluoro methyl esters, trifluoroethyl methacrylate, acrylic acid trifluoro ethyl ester, Hexafluorobutyl mathacrylate, acrylic acid six
Fluorine butyl ester, methacrylic acid octafluoro propyl ester, acrylic acid octafluoro propyl ester, dodecafluoroheptyl methacrylate, acrylic acid ten difluoro heptan
Ester, the trifluoro monooctyl ester of methacrylic acid ten, perluorooctyl acrylate, the fluorine monooctyl ester of methacrylic acid 17, the fluorine of acrylic acid 17 are pungent
One or more in ester of combination.
As one embodiment of the present invention, the fluorinated acrylate monomer be selected from methacrylic acid trifluoro methyl esters,
Acrylic acid trifluoro methyl esters, Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, acrylic acid
One or more in ten difluoro heptyl esters of combination.
Used as one embodiment of the present invention, the weight average molecular weight of the methyl trifluoro silicones is 1 × 103-5×
104。
Used as one embodiment of the present invention, the weight average molecular weight of the methyl trifluoro silicones is 1.5 × 103-2.5
×104。
Above-mentioned cleaning hydrophobic coating material cleaning agent, it is applied to building, fabric, coating, ocean, lithic drainage commander
Domain.
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 cleaning hydrophobic coating material cleaning agent, and by weight, its preparing raw material is included：
The alkene radical siloxane of 0.1-5 weight portions
The styrene of 1-10 weight portions
The fluorinated acrylate monomer of 1-10 weight portions
The methyl trifluoro silicones of 0.1-1.5 weight portions
The 3,4- ethene dioxythiophenes of 0.1-5 weight portions
The ethanol of 1-20 weight portions.
Alkene radical siloxane
Heretofore described alkene radical siloxane is the silicon-containing compound with double bond and two or more alkoxy, such as second
Alkenyl siloxane, acryl silicone, butylene radical siloxane, amylene radical siloxane, vinyl siloxanes, heptene radical siloxane,
Octene radical siloxane, nonene radical siloxane, decene radical siloxane.
Used as one embodiment of the present invention, the alkene radical siloxane is selected from VTES, ethene
Base trimethoxy silane, methylvinyldimethoxysilane, vinyl three (2- methoxy ethoxies) silane, the second of pi-allyl three
TMOS, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trichlorosilane, vinyl triacyloxysilanes, three uncles
Vinyl butyl ether base silane, vinyl silane tri-butyl peroxy, allyltrimethoxysilanis, allyltriethoxysilane
Or the one kind in allyltrichlorosilane.
Used as a kind of preferred embodiment of the invention, the alkene radical siloxane is selected from VTES, ethene
Base trimethoxy silane, vinyl three (2- methoxy ethoxies) silane, allyltriethoxysilane or the (β-first of vinyl three
Epoxide ethyoxyl) one kind in silane.
Styrene
Styrene (C8H8) be the organic compound formed with a hydrogen atom of benzene substituted ethylene, the electronics of vinyl with
Phenyl ring is conjugated, water insoluble, is dissolved in ethanol, ether.
Polystyrene is usually the height obtained by Raolical polymerizable in the presence of initiator by styrene monomer
Molecularly Imprinted Polymer.Polystyrene backbone is saturated carbon chains, and side base is conjugation phenyl ring, with big steric effect.Polystyrene
Row mainly include ordinary polystyrene, expandable polystyrene, impact resilience polystyrene), versatility polystyrene.It is common poly-
Styrene is amorphous polymer, 1.04~1.06g/cm of density3, with the glass transition temperature higher than 100 DEG C.Polyphenyl second
Alkene property can vivaciously carry out the reaction such as chlorination, nitrification, sulfonation.In addition, polystyrene is oxidizable and turn yellow, become fragile in air.
The polymerization of styrene can use any method well known by persons skilled in the art at this stage.For example：Suspend
Polymerization, emulsion polymerization, dispersin polymerization and surfactant- free emulsion polymerization etc..
Emulsion polymerization is the polymerization carried out in the emulsion being configured in the presence of emulsifying agent by monomer and water.Emulsion is gathered
The system composition of conjunction is typically made up of hydrophobic monomer, water, four kinds of bases of emulsifying agent and water soluble starter.Emulsion is gathered
Close, polymerisation in bulk and suspension polymerisation emulsion belong to radical reaction, compared in Raolical polymerizable other method, emulsion is gathered
Conjunction has the advantages that its is unique：Easy heat radiation, can not only obtain reaction rate higher but also can radiate rapidly, in order to avoid radiating is bad make
Degenerate or scrap into the product quality that hot-spot causes.
The conventional emulsifying agent of emulsion polymerization has：Lauryl sodium sulfate (SDS), neopelex (SBS).
Initiator is one of most important component in emulsion polymerization systems, and the species and consumption of initiator can directly affect product
The yield and quality of product, and influence polymerization rate.Mechanism according to generation free radical can be by drawing for emulsion polymerization
Hair agent is divided into two major classes, and a class is thermal decomposition initiating, and another kind of is the initiator of redox system.
In traditional emulsion polymerization, conventional emulsifier used is attached to emulsion particle surface in the way of physical absorption, from
And the stability to emulsion system is realized, this conventional emulsion agent molecule is easily influenceed to desorb by external environment, is caused
Emulsion particle collision cohesion.And after emulsion film forming, emulsifier molecules are remained in polymer solids, easily occur in polymer
Migration causes the water resistance of polymer film to decline.
The main method using emulsifier-free emulsion polymerization is prepared in the present invention.
Emulsifier-free emulsion polymerization refers to be not added with emulsifying agent completely during the course of the reaction or only add micro emulsifying agent (its concentration is small
In its critical micelle concentration CMC) emulsion polymerization process.Compared with traditional emulsion polymerization, surfactant- free emulsion polymerization is not due to
With addition emulsifying agent, it is to avoid isolation in the presence of emulsifying agent, absorb water, ooze out, prepared polymer microballoon size uniformity, table
Face is clean.The purity that improve product eliminates pollution of the emulsifying agent to environment in conventional emulsion polymerizations again simultaneously.
The characteristics of surfactant- free emulsion polymerization has following some obvious：1st, emulsifying agent is not used, production cost is reduced, while
Also the last handling process except emulsifying agent is eliminated, is polluted small；2nd, the latex particle surface for obtaining is clean, it is to avoid some were applied
Due to the harmful effect of the presence to polymeric articles performance of emulsifying agent in journey；3rd, gained latex particle monodispersity is good, particle diameter
Also it is bigger than conventional emulsion polymerizations, approach micron order.
Why polymer microballoon prepared by emulsifier-free emulsion polymerization is uniformly dispersed, and main cause is：1st, during particulate nucleation
Between it is short.When conversion ratio reaches 15-20%, nucleation process terminates traditional emulsion polymerization, and emulsifier-free emulsion polymerization is then in conversion
Rate is in 10% or so just no longer nucleation.Within the so short time, particle size will not differ too big naturally；2nd, different size
Emulsion particle between exist absorption freely and mutually coalescence competition.In emulsifier-free emulsion polymerization, less particle surface electricity
Lotus density is relatively low, is more easy to adsorb the free radical in liquid phase than bulky grain, also easily coalesces each other, so that distribution of particles
Tend to uniform.In Micellar nucleation system, the smallest particles being able to observe that is up to 5-10nm.It is general in homogeneous nucleation system
Less than 10nm, these cores or start just than more uniform, or by coalescing each other, competitive reaction and reach uniformly.
The specific method that the soap-free emulsion prepares polystyrene is as follows：By sodium chloride, monomer styrene and distilled water elder generation
It is added in there-necked flask, nitrogen flooding oxygen 15-30min is led under agitation, is then warmed up to 60-80 DEG C, after reaching equalized temperature,
Add initiator potassium persulfate KPS (K2S2O8) aqueous solution, start polymerization.Polymerisation is carried out under nitrogen protection, polymerization time
It is 12-24 hours.After reaction terminates, room temperature is cooled to, obtains polymer emulsion.Polymer emulsion centrifugation, remove supernatant
Solution, again plus deionized water be put into ultrasonic wave disperse.Then by the sample after dispersion, through low speed centrifuge, (rotating speed is 300r/
Min) settle, use deionized water cyclic washing, to ensure to remove KPS, sodium chloride and unreacted monomer styrene.Work as supernatant
Electrical conductivity when no longer changing, the polystyrene that will be obtained saves backup after ultrasonic wave dispersion in fluid form again, or
Polystyrene drying is saved backup in solid form.
Fluorinated acrylate monomer
Acrylate refers to the general name of the esters of acrylic acid and its homologue.For example：Methyl acrylate, ethyl acrylate,
2- methyl methacrylates and ethyl 2-methacrylate etc..
The fluorinated acrylate monomer refers to that fluorine element is introduced in acrylate.
Used as one embodiment of the present invention, the acrylate containing fluorine monomer is selected from (methyl) acrylic acid fluoroform
Ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) hexafluorobutyl acrylate, (methyl) acrylic acid octafluoro propyl ester, (methyl) propylene
One or more in sour ten difluoro heptyl esters, (methyl) perluorooctyl acrylate, the fluorine monooctyl ester of (methyl) acrylic acid 17 of group
Close.
As a kind of preferred embodiment of the invention, the fluorinated acrylate monomer be selected from methacrylic acid trifluoro methyl esters,
Acrylic acid trifluoro methyl esters, Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, acrylic acid
One or more in ten difluoro heptyl esters of combination.
As the present invention more preferred embodiment, the methacrylic acid trifluoro methyl esters, trifluoroethyl methacrylate, third
One or more in olefin(e) acid hexafluoro butyl ester, the difluoro propyl ester of acrylic acid ten of combination.
Non- fluorinated acrylate monomer
Used as one embodiment of the present invention, the preparing raw material of the cleaning hydrophobic coating material cleaning agent is also comprising non-
Fluorinated acrylate monomer.
In the present invention, the non-fluorinated acrylate monomer can be selected from alkyl acrylate, alkyl methacrylate,
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid can specifically be enumerated different
Propyl ester, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, the tertiary fourth of (methyl) acrylic acid
Ester, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (first
Base) 2-ethyl hexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, (first
Base) the different nonyl ester of acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester,
(methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) third
Olefin(e) acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (methyl) acrylic acid 18
The alkyl of the carbon numbers 1~20 (C1-20) such as Arrcostab, (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester
(methyl) acrylate etc..
As a kind of preferred embodiment of the invention, a length of C2-C7 of carbochain of the alkyl acrylate, the metering system
The a length of C1-C3 of carbochain of acid alkyl ester.
Used as a kind of preferred embodiment of the invention, the alkyl acrylate is preferably the relatively low acrylic acid of glass transition temperature
Arrcostab, such as tert-butyl acrylate.
Acrylate may be used singly or in combination of two or more.Alkyl acrylate of the present invention and methyl-prop
The weight ratio of olefin(e) acid Arrcostab is (0.1~2):(0.1~0.3), preferably (1~2):(0.2~0.3).
As one embodiment of the present invention, the weight of the fluorinated acrylate monomer and non-fluorinated acrylate monomer
Amount is than being (1-3)：(0.1-2), it is more further to be preferably 2：0.5.
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 compared to non-fluorinated acrylate monomer
For example, 0.01~2 weight portion %, preferably 0.04~1 mass %.
When the shell structure of water-repelling agent has various of monomer copolymerization to form, can be by adjusting the species and in the copolymer of monomer
Shared percentage synthesizes the shell structure of the water-repelling agent with particular glass temperature.Wherein, the glass transition temperature is high
Polymers is changed into the temperature of glassy state by elastomeric state, has reacted the condition changed between high polymer elasticity and fragility.Water-repelling agent
Shell structure belongs to typical copolymer, and 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 shell of water-repelling agent
The physical and mechanical properties of structure, therefore methacrylate polymers are harder than acrylate polymer, resistance to ag(e)ing is more preferable.
For the viscosity of acrylic polymer solution, such as it is 0.5~80Pas, preferably 1~45Pa at 30 DEG C
s。
If the viscosity of monomer mixture is unsatisfactory for above range, formability or processability become insufficient sometimes.
The preparation method of the shell structure of water-repelling agent 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.
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 nitriles), the azo-compound such as 2,2 '-azo-bis-iso-dimethyl.
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.
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.
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.
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.This
A little 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.
Methyl trifluoro silicones
Organic siliconresin is that a class constitutes skeleton by alternate silicon and oxygen atom, and different organic groups link with silicon atom again
Polymer general designation.
The advantage and disadvantage of organic siliconresin are as follows：
(1) advantage：Silicone backbone is made up of Si-O chain links, and side chain is then other various organic groups, therefore, organosilicon
Existing organic structure, there is inorganic structure again in resin.The relative electronegativies of two kinds of atoms differ greatly in Si-O keys, therefore Si-O
Key polarity is big.Due to above reason, organic siliconresin has the double grading of organic matter and inorganic matter concurrently, therefore, organic siliconresin
With excellent weatherability, heat resistance, Acid Rain, resist staining, gloss retention, moisture resistance, water proofing property, stable chemical nature and
Electric insulating quality etc..
(2) shortcoming：Organic siliconresin Si-O keys polarity is big, under the attack of electrophilic reagent or nucleopilic reagent, it is easy to
There is the fracture of Si-O keys, therefore the film forming of organic siliconresin is poor, solidification temperature is higher, and (solidification temperature is 150 DEG C~250
DEG C), the adhesive force to ground is poor, while its high-temperature anticorrosion ability is also very poor.
Organic fluorine has many excellent performances, is occupied an important position in coatings industry.Contain in organic fluorine
There is fluorine atom, electronegativity maximum (4.0) of fluorine atom, atomic radius very little (0.13nm), the C-F key bond distances of formation are short by (1.35
× 10-10m), bond energy is big (486KJ/mol), therefore assigns organic fluorine many excellent performances, it is widely used in sea
In the anticorrosive paint of gunship and large bridge.
The advantage and disadvantage of organic fluorine are as follows：
Advantage：Organic fluorine side base is short and small, structure saturation, thus with excellent chemical proofing and chemically stable
Property；Organic fluorine totally nontoxic, can apply to medicine and food service industry；The larger imparting organic fluorine of cohesive force of segment
Very strong surface self-cleaning.
Shortcoming：Organic fluorine has many excellent performances, but it also has some problems of its own simultaneously.Organic fluoride
Resin is poor to the wetability of color stuffing, in organic solvent dissolubility it is bad.
Fluorine silicon resin is also known as the fluorine-silicon copolymer resin by organic siliconresin and organic fluorine structure.
Used as a kind of preferred embodiment of the invention, the fluorine silicon resin is preferably methyl trifluoro silicones.
In the present invention, the structural formula of the methyl trifluoro silicones is as follows：
Wherein n=8-180.
Used as one embodiment of the present invention, the fluorine silicon resin is the methyl trifluoro silicon tree containing polar group end-blocking
The blend of fat.
In the present invention, as long as group of the polar group with the atom beyond carbon atom and hydrogen atom, example
Such as can be carboxylic acid group, carboxylic acid derivatives, anhydride group, isocyanate group, sulfonic group, phosphate, hydroxyl, amino, thiol base, ester
Base, cyano group, silicyl etc..
Wherein, as a kind of preferred embodiment of the invention, the polar group is preferably carboxyl, hydroxyl and amino, more
Preferably amino.
Now, the preparation method of the methyl trifluoro silicones containing polar group end-blocking is as follows：
With 10 parts of (trifluoromethyl) dimethoxysilanes (No. CAS：173162-22-6) to prepare monomer, 11~16 are added
Distilled water, 0.001~0.003 part of chloroplatinic acid and Pt/C, react 4~7 hours under 50~60 DEG C of temperature conditionss, are subsequently adding
0.1 part of end-capping reagent, the end-capping reagent is hydroxy amino silane, reacts 30min, you can.
Used as one embodiment of the present invention, the fluorine silicon resin is that weight average molecular weight is 1 × 103-5×104, more
It is further to be preferably 1.5 × 103-2.5×104。
Weight average molecular weight is to be based on gel permeation chromatography (hreinafter referred to as " GPC ".) determine and carry out polystyrene and change
Value after calculation.The condition determination of GPC uses 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.
Vinyl amino acid
Heretofore described vinyl amino acid is selected from following structures
Middle one kind.
Used as a kind of preferred embodiment of the invention, the vinyl amino acid is
Used as a kind of preferred embodiment of the invention, the weight portion of the vinyl amino acid is 0.01-0.3.
Used as a kind of preferred embodiment of the invention, the weight portion of the vinyl amino acid is 0.08.
3,4- ethene dioxythiophenes：Heretofore described 3,4-rthylene dioxythiophene CAS is 126213-50-1, its
The weight portion of addition is 0.1-5 weight portions.
The third aspect of the present invention provide described cleaning hydrophobic coating material cleaning agent its be applied to building, fabric, painting
The fields such as material, ocean, ground water regime.
It is described cleaning hydrophobic coating material cleaning agent preparation method be：
Deionized water, emulsifying agent SDBS, alkene radical siloxane, styrene, fluorine-containing propene are once added in reaction vessel
Acid ester monomer, 3,4-rthylene dioxythiophene, vinyl amino acid, initiator KPS, prepolymerization 4 hours under being stirred at 70 DEG C, then
Progressively dropping temperature controls the methyl trifluoro silicones at 70 DEG C, while slowly rising high reaction temperature, constant temperature is anti-when reaching 85 DEG C
Answer 1.5h.Take above-mentioned emulsion to be put into culture dish, be placed in 50 DEG C, in the constant temperature and pressure baking oven of humidity 55%, stand 24 hours, plus
Enter ethanol blended under agitation, obtain final product the cleaning hydrophobic coating material cleaning agent.
Mechanism is explained：Applicants have discovered that by adding alkene radical siloxane, vinyl amino acid and 3,4- ethylene dioxies
Thiophene, resulting cleaning hydrophobic coating material cleaning agent is in the case of beneficial hydrophobic performance is kept, and it is lasting to have to fabric
Docile property.Possible the reason for be alkene radical siloxane, vinyl amino acid to fabric have very strong penetrability, such that it is able to depth
Enter fabric nexine；The presence of 3,4- ethene dioxythiophenes simultaneously can improve the gas permeability of clothing.
Implementation method 1：Present embodiment provides a kind of cleaning hydrophobic coating material cleaning agent, by weight, its preparation
Raw material is included：
The alkene radical siloxane of 0.1-5 weight portions
The styrene of 1-10 weight portions
The fluorinated acrylate monomer of 1-10 weight portions
The methyl trifluoro silicones of 0.1-1.5 weight portions
The 3,4- ethene dioxythiophenes of 0.1-5 weight portions
The ethanol of 1-20 weight portions.
Implementation method 2：Cleaning hydrophobic coating material cleaning agent described in implementation method 1, by weight, its preparing raw material
Comprising：
The alkene radical siloxane of 0.5-2 weight portions
The styrene of 1-5 weight portions
The acrylic acid trifluoro methyl esters of 1-5 weight portions
The methyl trifluoro silicones of 0.1-0.5 weight portions
The 3,4- ethene dioxythiophenes of 0.1-2.5 weight portions
The ethanol of 1-10 weight portions.
Implementation method 3：Cleaning hydrophobic coating material cleaning agent described in implementation method 1, by weight, its preparing raw material
Also include the vinyl amino acid of 0.01-0.3 weight portions.
Implementation method 4：Cleaning hydrophobic coating material cleaning agent described in implementation method 3, the vinyl amino acid is C3-
The vinyl amino acid of C30.
Implementation method 5：Cleaning hydrophobic coating material cleaning agent described in implementation method 3, the vinyl amino acid is C5-
The vinyl amino acid of C20.
Implementation method 6：Cleaning hydrophobic coating material cleaning agent described in implementation method 1, the fluorinated acrylate monomer
Selected from methacrylic acid trifluoro methyl esters, acrylic acid trifluoro methyl esters, trifluoroethyl methacrylate, acrylic acid trifluoro ethyl ester, methyl
Hexafluorobutyl acrylate, hexafluorobutyl acrylate, methacrylic acid octafluoro propyl ester, acrylic acid octafluoro propyl ester, methacrylic acid ten
Difluoro heptyl ester, dodecafluorhe-ptylacrylate, the trifluoro monooctyl ester of methacrylic acid ten, perluorooctyl acrylate, methacrylic acid ten
One or more in seven fluorine monooctyl esters, the fluorine monooctyl ester of acrylic acid 17 of combination.
Implementation method 7：Cleaning hydrophobic coating material cleaning agent described in implementation method 1, the fluorinated acrylate monomer
Selected from methacrylic acid trifluoro methyl esters, acrylic acid trifluoro methyl esters, Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, methyl
One or more in dodecafluorhe-ptylacrylate, dodecafluorhe-ptylacrylate of combination.
Implementation method 8：Cleaning hydrophobic coating material cleaning agent described in implementation method 1, the methyl trifluoro silicones
Weight average molecular weight is 1 × 103-5×104。
Implementation method 9：Cleaning hydrophobic coating material cleaning agent described in implementation method 1, the methyl trifluoro silicones
Weight average molecular weight is 1.5 × 103-2.5×104。
Implementation method 10：Cleaning hydrophobic coating material cleaning agent described in implementation method any one of 1-8, it is applied to build
Build, fabric, coating, ocean, ground water regime field.
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, and number used by following material is weight
Part.
Embodiment 1：One kind cleaning hydrophobic coating material cleaning agent, by weight, its preparing raw material is included：
The alkene radical siloxane of 0.8 weight portion
The styrene of 3 weight portions
The fluorinated acrylate monomer of 3 weight portions
The methyl trifluoro silicones of 1 weight portion
The 3,4- ethene dioxythiophenes of 1.3 weight portions
The vinyl amino acid of 0.08 weight portion
The ethanol of 15 weight portions,
Wherein described alkylene siloxanes is VTES, the fluorinated acrylate monomer is acrylic acid
Trifluoro methyl esters and Hexafluorobutyl mathacrylate are according to weight part ratio 2：1 mixture；The cleaning hydrophobic coating material cleaning
The preparing raw material of agent also has propyl acrylate, and the ratio of the fluorinated acrylate monomer and propyl acrylate is 2：0.5.
The vinyl amino acid is
The methyl trifluoro silicones is amino-terminated methyl trifluoro silicones.
Wherein, the preparation method of the amino-terminated methyl trifluoro silicones is：With 10 parts of (trifluoromethyl) dimethoxies
Base silane (No. CAS：173162-22-6) to prepare monomer, add 11~16 distilled water, 0.001~0.003 part of chloroplatinic acid and
Pt/C, reacts 4~7 hours under 50~60 DEG C of temperature conditionss, is subsequently adding 0.1 part of end-capping reagent, and the end-capping reagent is amino
Silicol, reacts 30min, you can.
The weight average molecular weight of the amino-terminated methyl trifluoro silicones is 8 × 103。
It is described cleaning hydrophobic coating material cleaning agent preparation method be：Once added in reaction vessel deionized water,
Emulsifying agent SDBS, alkene radical siloxane, styrene, fluorinated acrylate monomer, 3,4- ethene dioxythiophenes, ethyleneamino
Acid, initiator KPS, prepolymerization 4 hours under being stirred at 70 DEG C, then progressively dropping temperature controls the methyl trifluoro silicon tree at 70 DEG C
Fat, while high reaction temperature is slowly risen, isothermal reaction 1.5h when reaching 85 DEG C.Take above-mentioned emulsion to be put into culture dish, be placed in 50
DEG C, in the constant temperature and pressure baking oven of humidity 55%, 24 hours are stood, ethanol blended under agitation is added, obtain final product the cleaning hydrophobic coating
Material cleaning agent.The weight ratio of all reaction raw materials is according to described above, the emulsifying agent SDBS：Deionized water：Reaction raw materials：
The weight ratio of initiator KPS (potassium peroxydisulfate) is 125：0.005：1：0.015.
Embodiment 2：Difference with embodiment 1 is that the preparing raw material of the cleaning agent is without alkene radical siloxane.
Embodiment 3：Difference with embodiment 1 is that institute's alkene radical siloxane is replaced by trimethoxy silane.
Embodiment 4：Difference with embodiment 1 is that the preparing raw material of the cleaning agent is without 3,4-rthylene dioxythiophene.
Embodiment 5：Difference with embodiment 1 is that the preparing raw material of the cleaning agent is without vinyl amino acid.
Embodiment 6：Difference with embodiment 1 is that the vinyl amino acid is replaced by glycine.
Embodiment 7：Difference with embodiment 1 is that the weight portion of the alkene radical siloxane is 16 weight portions.
Embodiment 8：Difference with embodiment 1 is that the weight portion of the vinyl amino acid is 0.5 weight portion.
Embodiment 9：Difference with embodiment 1 is that the weight portion of the 3,4-rthylene dioxythiophene is 3 weight portions.
Embodiment 10：Difference with embodiment 1 is that the weight portion of the alkene radical siloxane is 0.08 weight portion.
Embodiment 11：Difference with embodiment 1 is that the weight portion of the vinyl amino acid is 0.008 weight portion.
Embodiment 12：Difference with embodiment 1 is that the weight portion of the 3,4-rthylene dioxythiophene is 0.08 weight
Part.
Embodiment 13：Difference with embodiment 1 is that the preparing raw material of the cleaning agent is included：
The alkene radical siloxane of 6 weight portions
The styrene of 0.11 weight portion
The fluorinated acrylate monomer of 0.5 weight portion
The methyl trifluoro silicones of 2 weight portions
The 3,4- ethene dioxythiophenes of 0.5 weight portion
The vinyl amino acid of 8 weight portions
The ethanol of 20 weight portions.
The cleaning hydrophobic coating material cleaning agent that above-described embodiment is prepared, (material nylon is put down to be sprayed on clothes
Line) on, tested.
Adhesive force：Determined by GB/T1720-1979 (1989).
Abrasion resistance：Determined by GB/T9266-1998.
Resistance to ag(e)ing：Determined by GB/T1865-88.
Stain resistance：Determined by GB/T9780-2013.
Alkali resistance：Determined by GB/T 9265-2009, alkali resistance >=48h is without exception, and it is qualified to be considered as.
Permeability test：Tested by GB/T5453-1997.
As can be seen from the table, alkene radical siloxane, 3,4-rthylene dioxythiophene and vinyl ammonia are contained in the present invention
The cleaning agent of base acid, it has excellent adhesive force, gas permeability, abrasion resistance, resistance to ag(e)ing, stain resistance and alkali resistance.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.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 (10)
1. it is a kind of to clean hydrophobic coating material cleaning agent, it is characterised in that by weight, its preparing raw material is included：
The alkene radical siloxane of 0.1-5 weight portions；
The styrene of 1-10 weight portions；
The fluorinated acrylate monomer of 1-10 weight portions；
The methyl trifluoro silicones of 0.1-1.5 weight portions；
The 3,4- ethene dioxythiophenes of 0.1-5 weight portions；
The ethanol of 1-20 weight portions.
2. the cleaning hydrophobic coating material cleaning agent described in claim 1, it is characterised in that by weight, its preparing raw material
Comprising：
The alkene radical siloxane of 0.5-2 weight portions；
The styrene of 1-5 weight portions；
The acrylic acid trifluoro methyl esters of 1-5 weight portions；
The methyl trifluoro silicones of 0.1-0.5 weight portions；
The 3,4- ethene dioxythiophenes of 0.1-2.5 weight portions；
The ethanol of 1-10 weight portions.
3. the cleaning hydrophobic coating material cleaning agent described in claim 1, it is characterised in that by weight, its preparing raw material
Also include the vinyl amino acid of 0.01-0.3 weight portions.
4. the cleaning hydrophobic coating material cleaning agent described in claim 3, it is characterised in that the vinyl amino acid is C3-
The vinyl amino acid of C30.
5. the cleaning hydrophobic coating material cleaning agent described in claim 3, it is characterised in that the vinyl amino acid is C5-
The vinyl amino acid of C20.
6. the cleaning hydrophobic coating material cleaning agent described in claim 1, it is characterised in that the fluorinated acrylate monomer choosing
From methacrylic acid trifluoro methyl esters, acrylic acid trifluoro methyl esters, trifluoroethyl methacrylate, acrylic acid trifluoro ethyl ester, methyl-prop
Olefin(e) acid hexafluoro butyl ester, hexafluorobutyl acrylate, methacrylic acid octafluoro propyl ester, acrylic acid octafluoro propyl ester, methacrylic acid 12
Fluorine heptyl ester, dodecafluorhe-ptylacrylate, the trifluoro monooctyl ester of methacrylic acid ten, perluorooctyl acrylate, methacrylic acid 17
One or more in fluorine monooctyl ester, the fluorine monooctyl ester of acrylic acid 17 of combination.
7. the cleaning hydrophobic coating material cleaning agent described in claim 1, it is characterised in that the fluorinated acrylate monomer choosing
From methacrylic acid trifluoro methyl esters, acrylic acid trifluoro methyl esters, Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, methyl-prop
One or more in the difluoro heptyl ester of olefin(e) acid ten, dodecafluorhe-ptylacrylate of combination.
8. the cleaning hydrophobic coating material cleaning agent described in claim 1, it is characterised in that the weight of the methyl trifluoro silicones
Average molecular weight is 1 × 103-5×104。
9. the cleaning hydrophobic coating material cleaning agent described in claim 1, it is characterised in that the weight of the methyl trifluoro silicones
Average molecular weight is 1.5 × 103-2.5×104。
10. the cleaning hydrophobic coating material cleaning agent described in any one of claim 1-8, its be applied to building, fabric, coating,
Ocean, ground water regime field.
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