CN106243272B - A kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and application - Google Patents
A kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and application Download PDFInfo
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- CN106243272B CN106243272B CN201610605397.6A CN201610605397A CN106243272B CN 106243272 B CN106243272 B CN 106243272B CN 201610605397 A CN201610605397 A CN 201610605397A CN 106243272 B CN106243272 B CN 106243272B
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and applications, the acrylic resin is by the reaction monomers of following mass percent with silane coupler modified, and polymerisation occurs in alcohol ethers solvent medium under initiator effect, then be neutralized into salt with organic amine and be made：Methacrylate 0-30%, acrylate 0-30%, (methyl) acrylic acid hydroxy alkyl ester 5-18%, unsaturated carboxylic acid 1-10%, vinyl aromatic compounds 0-20%.Acrylic resin paint prepared by the present invention has aluminium excellent adhesive force, and gloss of film is high, and richness is good, and intensity is big, can provide excellent protective value and splendid decorative effect for high-grade aluminium.
Description
Technical field
The present invention relates to paint field, more specifically to a kind of high adhesion force aqueous thermosetting acrylic resin and
Preparation method and application.
Background technology
Aluminium and its alloy have many advantages, such as good corrosion resistance, electrical and thermal conductivity and easily processed into type, so aluminium closes
Gold is widely used in national defence, aerospace, traffic, instrument, both mechanically and electrically device, the fields such as home decoration.Due to gold
Belong to the chemical property of aluminium and its active, is directly exposed in air and is easily blacked by oxidation dimmed, influence appearance and use the longevity
Life, therefore take measures to protect Al alloy parts and decorate very necessary.
Generally use oil paint and powdery paints are coated in the effect that aluminium shape surface plays protection and decoration in industry,
But oil paint often discharges the poisonous and hazardous organic matter such as benzene class, aldehydes (VOC) in production, allotment and work progress,
Seriously affect people's health and ecological environment.Therefore, corresponding environmental regulation has been formulated in countries in the world, to limit the row of VOC
It puts.China was formulated in 2001 is directed to 10 kinds of enforceable safety standards of interior architecture finishing material, and 2008 are even more to establish
Chinese coating low stainization develops safe national development system standard, reinforces supervision and oversight of the country to organic emission.
Compared with traditional oil paint, influence of the water paint to human body and environment is substantially reduced.With the increasing of people's environmental consciousness
By force, water paint is identified as the one kind of " green coating ", quickly grows.
Waterborne Acrylate Coatings in " green coating " protect color because shallow with color, protect light, weathering, corrosion-resistant and resistant
Dye etc. have advantage and in acrylic coating much favored by the market but common often containing more hydroaropic substance and water resistance and
Intensity is poor, seriously affects the paint film property and service life of workpiece to be protected.
Patent CN1887926A describes a kind of organic-silicon-modified acrylic resin, and the modifying agent used in the patent is profit
Silicone intermediate is prepared with the organic silicon monomer containing halogen, the process is more complicated, and has a large amount of waste water, and
Halogen contamination is easy tod produce during synthesizing the intermediate, is polluted to environment.
Patent CN94194922.2 and CN01105010.1 are synthesized using emulsion polymerization.Although emulsion polymerization is adopted
Solvent is replaced by medium with water, the advantages of environment-protecting clean, this is emulsion polymerization.But it is bound in emulsion polymerization using breast
Agent, this makes final products gloss and water resistance be deteriorated, these disadvantages limit the application of lotion.
Invention content
The technical problem to be solved in the present invention is, for the drawbacks described above of the prior art, provides a kind of high adhesion force water
Property thermosetting acrylic resin and preparation method and application.Silane is used in the high attachment water-based acrylic resin preparation process of invention
It is coupling agent modified.The high adhesion force acrylic resin can provide a kind of such as high adhesion force, high glaze, excellent water resistance and hard
The performances such as degree and richness, it is sufficient to meet the coating of the functionality and cosmetic requirement of high-grade aluminium.The acrylic resin can be made
Standby high adhesion force water paint reaches the adhesive force for improving coating to aluminum substrate, reduces the purpose of coating VOC.
The technical solution adopted by the present invention to solve the technical problems is：A kind of high adhesion force aqueous thermosetting propylene is provided
Acid resin, it by the reaction monomers of following mass percent with silane coupler modified, and initiator effect under in alcohol ethers
Polymerisation occurs in solvent medium, then is neutralized into salt with organic amine and is made：
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein the methacrylate is methyl
Methyl acrylate, ethyl methacrylate, butyl methacrylate, one kind in Isobutyl methacrylate.
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein the acrylate is acrylic acid second
Ester, butyl acrylate, Isooctyl acrylate monomer, tert-butyl acrylate, dodecyl acrylate, Process Conditions of Cetane Acrylate, acrylic acid 18
One kind in ester.
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein (methyl) acrylic acid hydroxy alkyl
Ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, methacrylic acid contracting
The mixture of any one or its arbitrary proportion in water glyceride.
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein the unsaturated carboxylic acid be acrylic acid,
One kind in methacrylic acid, itaconic acid, maleic anhydride；The vinyl aromatic compounds are styrene, to methylbenzene second
One kind in alkene, tert-butyl ester styrene.
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein the dosage of the silane coupling agent is
The 1-10% of reaction monomers total weight；Silane coupling agent includes amino silicane coupling agent, epoxy silane coupling, allyl silicon
The mixture of one or more of alkane coupling agent, aryloxy silane coupling agent, acyl silanes coupling agent.
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein the dosage of the initiator is reaction
The 1-4% of total monomer weight；The initiator is one or more of azo-initiator, peroxide initiator；It should
Azo-initiator is the mixture of one or both of azodiisobutyronitrile, azobisisoheptonitrile；The peroxide initiator
For one kind in dibenzoyl peroxide, di-t-butyl peroxide, di t-amyl peroxide.
High adhesion force aqueous thermosetting acrylic resin of the present invention, wherein the dosage of the alcohol ethers solvent is
The 50-70% of reaction monomers total weight；It with volume ratio is 1 that the alcohol ethers solvent, which is alcohols solvent and ether solvent,:(1-4's)
Mixed solvent, the alcohols solvent are the mixture of one or more of isopropanol, n-butanol, isobutanol；The ethers is molten
Agent is the mixture of one or more of butyl glycol ether, propandiol butyl ether.
The present invention also provides a kind of preparation methods of high adhesion force aqueous thermosetting acrylic resin as described above, including
Following steps：
(1) alcohol ethers solvent is added in the four-hole boiling flask equipped with agitating paddle, thermometer and condenser pipe, is warming up to 80-200
℃；
(2) all reaction monomers and initiator are mixed, stirring makes to be uniformly mixed；
(3) mixed liquor in step (2) is divided into A and B two parts, wherein A:B volume ratios are (1-9)：1；
(4) part A is packed into Dropping feeder, is added dropwise with constant speed in 2-5 hours, after part A completion of dropwise addition, is connect
Dropwise addition part B, and silane coupling agent is added in part B solution, is added dropwise in 0.5-2 hours；It, will after being added dropwise
Temperature increases 5-10 DEG C and keeps the temperature 2 hours；
(5) temperature be reduced to 70 DEG C and hereinafter, plus organic amine neutralize, stirring 10-30 minutes after discharge.
The present invention also provides a kind of applications of high adhesion force aqueous thermosetting acrylic resin as described above, that is, are used as aluminium
The water paint of Surface of profile coating.
The high adhesion force aqueous thermosetting acrylic resin for implementing the present invention, has the advantages that：
(1) acrylic resin paint prepared by the present invention has aluminium excellent adhesive force, and gloss of film is high, richness
Good, intensity is big, can provide excellent protective value and splendid decorative effect for high-grade aluminium.
(2) the features such as its synthesis technology of the acrylic resin of the present invention is simple, low raw-material cost, reaction process is easily-controllable,
Prepared resin has high adhesion force, high glaze, high rigidity and excellent water resistance, can fully meet all kinds of aluminiums to coating
The demand of energy.
(3) present invention novelty and bright spot：First, using the method for polymerisation in solution, environmentally friendly cosolvent is scientifically selected, than
Such as propandiol butyl ether carrys out reaction medium the most, does not contain benzene and substituted benzene toxic solvent, reduces to ecological environment and behaviour
Make the harm of worker.
Second, solution polymerization process uses environmentally friendly solvent for medium, is conducive to the mass-and heat-transfer control in reaction process,
The polymer molecular weight prepared moderate, narrow distribution few greatly, modest viscosity improve construction when being conducive to paint and contain admittedly, improve
Product comprehensive performance.
Third, polymerisation in solution difference and emulsion polymerization, final products emulsifier-free, this fundamentally improves the light of product
Pool and water resistance, improve the patience of product.
4th, organic silicon monomer is selected from MOLECULE DESIGN angle science, makes the silica containing polyfunctionality in molecule segment
Alkane is hydrolyzing in membrane process with painting, the adhesive force of enhancing base materials, to improve the comprehensive performance of product.
Specific implementation mode
In the following, in conjunction with specific implementation mode, the present invention is described further：
A kind of high adhesion force aqueous thermosetting acrylic resin, it is by the reaction monomers of following mass percent with silane idol
Join agent to be modified, and occur polymerisation in alcohol ethers solvent medium under initiator effect, then be neutralized into salt with organic amine and
It is made：
The methacrylate is methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl-prop
One kind in olefin(e) acid isobutyl ester.
The acrylate is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, tert-butyl acrylate, acrylic acid
Ten diester, Process Conditions of Cetane Acrylate, one kind in octadecyl acrylate.
(methyl) acrylic acid hydroxy alkyl ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate
The mixture of any one or its arbitrary proportion in propyl ester, hydroxypropyl acrylate, glycidyl methacrylate.
The unsaturated carboxylic acid is one kind in acrylic acid, methacrylic acid, itaconic acid, maleic anhydride；The vinyl
Aromatic compound is one kind in styrene, p-methylstyrene, tert-butyl ester styrene.
The dosage of the silane coupling agent is the 1-10% of reaction monomers total weight；It is preferred that 3-6%；Reaction monomers are in two steps
It is added dropwise, silane coupling agent is added in second part.Silane coupling agent include amino silicane coupling agent, epoxy silane coupling,
The mixture of one or more of allyl silicane coupling agent, aryloxy silane coupling agent, acyl silanes coupling agent.Tool
Body can be methoxy silane, Ethoxysilane, amino silane, epoxy radicals silicone hydride, aryloxy silane, formyloxy silane, second
Acyloxy silane, vinyltrimethoxysilane, vinyltrimethoxysilane etc..
The dosage of the initiator is the 1-4% of reaction monomers total weight；The initiator is azo-initiator, peroxide
One or more of class initiator；The azo-initiator is one kind in azodiisobutyronitrile, azobisisoheptonitrile
Or two kinds of mixture；The peroxide initiator is in dibenzoyl peroxide, di-t-butyl peroxide, di t-amyl peroxide
One kind.
The dosage of the alcohol ethers solvent is the 50-70% of reaction monomers total weight；The alcohol ethers solvent is that alcohols is molten
Agent and ether solvent are with volume ratio for 1:The mixed solvent of (1-4), the alcohols solvent are in isopropanol, n-butanol, isobutanol
One or more kinds of mixtures；The ether solvent is one or more of butyl glycol ether, propandiol butyl ether
Mixture.
The present invention also provides a kind of preparation methods of high adhesion force aqueous thermosetting acrylic resin as described above, pass through
The copolymer of solwution method synthesis, (1) is using (methyl) acrylate and vinyl aromatic compounds as comonomer；(2) (methyl)
Acrylic acid hydroxy alkyl ester is function monomer；(3) there is carboxylic functional acrylic monomers；(4) silane coupling agent is to be modified
Agent.When the combination present invention is in application, the hydroxyl on (methyl) acrylic acid hydroxy alkyl ester will be with such as amino resins and epoxy
Resinoid cross-linking reaction；The dosage for adjusting silane coupling agent can be changed the molecular weight of synthetic resin and improve the adhesive force of resin,
The acrylic resin molecular weight of this law synthesis is as follows：Number-average molecular weight is 10000-80000, weight average molecular weight 30000-
100000.Adjust (methyl) ratio between acrylic acid hydroxy alkyl ester and other monomers can effectively synthesize a kind of hydroxyl value between
Resin between 20-150mgKOH/g；Solid content >=60wt.% of the acrylic resin, range of viscosities 6000-
60000mPa.s。
During preparing acrylic resin, reaction monomers are added dropwise in two steps, and silane coupling agent is added in building-up process,
80-200 DEG C of range of reaction temperature, the acrylic resin obtained in the reactor by free radical polymerization, obtained acrylic acid
Resin has the feature of high adhesion force.
The preparation method includes the following steps：
(1) alcohol ethers solvent is added in the four-hole boiling flask equipped with agitating paddle, thermometer and condenser pipe, is warming up to 80-200
℃；Reaction temperature is 80-200 DEG C, and preferably 80-150 DEG C, actual temp is because depending on the initiator type that uses.
(2) all reaction monomers and initiator are mixed, stirring makes to be uniformly mixed；
(3) mixed liquor in step (2) is divided into A and B two parts, wherein A:B volume ratios are (1-9)：1；
(4) part A is packed into Dropping feeder, is added dropwise with constant speed in 2-5 hours, after part A completion of dropwise addition, is connect
Dropwise addition part B, and silane coupling agent is added in part B solution, is added dropwise in 0.5-2 hours；It, will after being added dropwise
Temperature increases 5-10 DEG C and keeps the temperature 2 hours；
(5) temperature be reduced to 70 DEG C and hereinafter, plus organic amine neutralize, stirring 10-30 minutes after discharge.The dosage of organic amine
For the 4-11% of reaction monomers total amount.
Embodiment 1
Equipped with agitating paddle, thermometer, reflux condensing tube reaction unit in be added ethyl alcohol 20g, propandiol butyl ether 40g,
It is heated to 90 DEG C.By methyl methacrylate 20g, butyl acrylate 28g, Isooctyl acrylate monomer 20g, acrylic acid 5g, first
Base hydroxy-ethyl acrylate 7g, E styrene 20g, initiator azodiisobutyronitrile 3g divide A, two components of B, two components after mixing
Mass ratio is A:B=2：1, after component A is added dropwise for 3 hours, silane coupling agent 5g vinyl trimethoxies are added in B component
Silane is added dropwise in 1 hour, and temperature is increased to 100 DEG C and keeps the temperature 2 hours after reaction, and N, N- diformazans are added after being cooled to 70 DEG C
Ethylethanolamine 4.5g is neutralized, and stirring discharges after twenty minutes, obtains finished product.
Embodiment 2
Equipped with agitating paddle, thermometer, reflux condensing tube reaction unit in be added butanol 20g, propandiol butyl ether 40g,
It is heated to 130 DEG C.By methyl methacrylate 28g, butyl acrylate 28g, acrylic acid 9g, hydroxyethyl methacrylate
15g, styrene 20g, initiator di-t-butyl peroxide 3g, it is A to divide A, two components of B, two constituent mass ratios after mixing:B
=3：1, after component A is added dropwise for 3 hours, silane coupling agent 3g, 3- (2,3- the third oxygen of epoxy) propyl front three is added in B component
Oxysilane is added dropwise in 1 hour, and temperature is increased to 135 DEG C and keeps the temperature 2 hours after reaction, is cooled to after 70 DEG C added with machine
Amine 9g is neutralized, and stirring discharges after twenty minutes, obtains finished product.
Embodiment 3
Equipped with agitating paddle, thermometer, reflux condensing tube reaction unit in be added butanol 20g, propandiol butyl ether 40g,
It is heated to 130 DEG C.By A methyl methacrylates 29g, B Isooctyl acrylate monomer 27g, D acrylic acid 8g, C hydroxyethyl methacrylate
Ethyl ester 18g, E styrene 18g, initiator di-t-butyl peroxide 4g divide A, two components of B, two constituent mass ratios after mixing
For A:B=5：1, after component A is added dropwise for 4 hours, silane coupling agent 2g trimethoxy silanes and 3g ethylene are added in B component
Ethyl triethoxy silicane alkane is added dropwise in 1 hour, and temperature is increased to 135 DEG C and keeps the temperature 2 hours after reaction, after being cooled to 70 DEG C
Organic amine 8g is added to neutralize, stirring discharges after twenty minutes, obtains finished product.
Comparative example 1
Comparative example 1 is prepared according to method described in CN1887926A patents.
Comparative example 2
Comparative example 2 is prepared according to method described in CN94194922.2 patents.
In the following, being detected to embodiment 1-3 and the performance of acrylic resin made from comparative example 1-2, detection refers to
Mark includes weight average molecular weight, solid content, viscosity, pH value, wherein and weight average molecular weight is detected using gel permeation chromatography, admittedly contain
Amount is according to viscosity is measured using GB1723-79 detections under GB1725-79 (88) item, pH value is detected using pH test paper, as a result such as table
1：
Table 1 is the performance parameter of acrylic resin made from embodiment 1-3 and comparative example 1-2
In the following, embodiment 1-3 and acrylic resin made from comparative example 1-2 are made according to the formula of such as the following table 2
Then water paint is tested for the property the coating, as a result such as table 3：
The formula of 2 water paint of table
3 coating property of table tests table
By embodiment using test result it is found that coating prepared by the acrylic resin of the present invention uses paint on aluminium
Film properties can reach requirement, and especially adhesion performance is excellent.
It will be apparent to those skilled in the art that technical solution that can be as described above and design, make various other
Corresponding change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention
Within.
Claims (8)
1. a kind of preparation method of high adhesion force aqueous thermosetting acrylic resin, which is characterized in that the aqueous thermosetting of high adhesion force
Property acrylic resin by the reaction monomers of following mass percent with silane coupler modified, and initiator effect under in alcohol ether
Polymerisation occurs in class solvent medium, then is neutralized into salt with organic amine and is made：
Methacrylate 0-30%
Acrylate 0-30%
（Methyl）Acrylic acid hydroxy alkyl ester 5-18%
Unsaturated carboxylic acid 1-10%
Vinyl aromatic compounds 0-20%；
The dosage of the alcohol ethers solvent is the 50-70% of reaction monomers total weight；The alcohol ethers solvent is alcohols solvent and ether
Class solvent is with volume ratio for 1:（1-4）Mixed solvent, the alcohols solvent be isopropanol, n-butanol, one kind in isobutanol or
Two or more mixtures；The ether solvent is the mixture of one or both of butyl glycol ether, propandiol butyl ether；
The high adhesion force aqueous thermosetting acrylic resin is by including the following steps：
（1）Alcohol ethers solvent is added in the four-hole boiling flask equipped with agitating paddle, thermometer and condenser pipe, is warming up to 80-200 DEG C；
（2）All reaction monomers and initiator are mixed, stirring makes to be uniformly mixed；
（3）By step（2）In mixed liquor be divided into A and B two parts, wherein A:B volume ratios are（2-9）：1；
（4）Part A is packed into Dropping feeder, is added dropwise with constant speed in 2-5 hours, after part A completion of dropwise addition, is then dripped
Add part B, and silane coupling agent is added in part B solution, is added dropwise in 0.5-2 hours；After being added dropwise, by temperature
It increases 5-10 DEG C and keeps the temperature 2 hours；
（5）Temperature be reduced to 70 DEG C and hereinafter, plus organic amine neutralize, stirring 10-30 minutes after discharge.
2. the preparation method of high adhesion force aqueous thermosetting acrylic resin according to claim 1, which is characterized in that institute
It is methyl methacrylate, ethyl methacrylate, butyl methacrylate, Tert-butyl Methacrylate to state methacrylate
In one kind.
3. the preparation method of high adhesion force aqueous thermosetting acrylic resin according to claim 1, which is characterized in that institute
It is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, tert-butyl acrylate, dodecyl acrylate, propylene to state acrylate
One kind in sour hexadecyl ester, octadecyl acrylate.
4. the preparation method of high adhesion force aqueous thermosetting acrylic resin according to claim 1, which is characterized in that institute
It states（Methyl）Acrylic acid hydroxy alkyl ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid
The mixture of any one or two or more arbitrary proportions in hydroxypropyl acrylate.
5. the preparation method of high adhesion force aqueous thermosetting acrylic resin according to claim 1, which is characterized in that institute
It is one kind in acrylic acid, methacrylic acid, itaconic acid to state unsaturated carboxylic acid；The vinyl aromatic compounds are benzene second
One kind in alkene, p-methylstyrene.
6. the preparation method of high adhesion force aqueous thermosetting acrylic resin according to claim 1, which is characterized in that institute
The dosage for stating silane coupling agent is the 1-10% of reaction monomers total weight；Silane coupling agent is amino silicane coupling agent, epoxy group silicon
One or more of alkane coupling agent, allyl silicane coupling agent, aryloxy silane coupling agent, acyl silanes coupling agent
Mixture.
7. the preparation method of high adhesion force aqueous thermosetting acrylic resin according to claim 1, which is characterized in that institute
The dosage for stating initiator is the 1-4% of reaction monomers total weight；The initiator is in azo-initiator, peroxide initiator
One or two kinds of mixtures；The azo-initiator is one or both of azodiisobutyronitrile, azobisisoheptonitrile
Mixture；The peroxide initiator is one in dibenzoyl peroxide, di-t-butyl peroxide, di t-amyl peroxide
Kind.
8. a kind of high adhesion force aqueous thermosetting acrylic resin made from the preparation method as described in claim any one of 1-7
Application, which is characterized in that for aluminium shape surface coating water paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610605397.6A CN106243272B (en) | 2016-07-27 | 2016-07-27 | A kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610605397.6A CN106243272B (en) | 2016-07-27 | 2016-07-27 | A kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and application |
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| Publication Number | Publication Date |
|---|---|
| CN106243272A CN106243272A (en) | 2016-12-21 |
| CN106243272B true CN106243272B (en) | 2018-10-26 |
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| JP7118095B2 (en) | 2017-05-12 | 2022-08-15 | アンガス ケミカル カンパニー | Etheramine compositions and coatings |
| CN111253524B (en) * | 2020-03-12 | 2021-09-28 | 河南卓立膜材料股份有限公司 | Back coating material for thermal transfer bar code carbon ribbon and preparation method and application thereof |
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Inventor after: Cao Zhanxin Inventor after: Yang Jingbo Inventor after: Zheng Wei Inventor before: Cao Zhanxin Inventor before: Yang Jingbo |