CN110330657A - Aqueous silicon epoxy modified acrylic resin and aqueous amido coatings containing the resin - Google Patents
Aqueous silicon epoxy modified acrylic resin and aqueous amido coatings containing the resin Download PDFInfo
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- CN110330657A CN110330657A CN201910334701.1A CN201910334701A CN110330657A CN 110330657 A CN110330657 A CN 110330657A CN 201910334701 A CN201910334701 A CN 201910334701A CN 110330657 A CN110330657 A CN 110330657A
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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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
- 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
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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
- 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
- C09D5/1687—Use of special additives
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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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The present invention relates to aqueous silicon epoxy modified acrylic resin and the aqueous amido coatings containing the resin, the aqueous silicon epoxy modified acrylic resin by the synthesis of siliceous epoxy modified acrylic resin, be neutralized into salt and deionized water added to disperse three steps and obtain, easy to operate, safety and environmental protection, products obtained therefrom performance are good.Aqueous amido coatings based on resin preparation possess good hardness, gloss and chemical resistance.
Description
Technical field
The invention belongs to water-based acrylic resin technical fields, and in particular to a kind of aqueous silicon epoxy-modified acrylic acid tree
Rouge and using it as the aqueous amido coatings of primary raw material.
Background technique
With the continuous development of society, people are more and more stronger to the protective awareness of environment, the development of water paint at
For mainstream.Aqueous amido coatings are very fast in the development of many fields, such as auto-parts, glass, household electrical appliance, hardware
Deng.Aqueous amido coatings are generally made of amino resins and water-based acrylic resin etc., and water-based acrylic resin synthesized at present
Generally existing viscosity is excessive in journey, needs the problems such as hot setting, is unfavorable for being attached to substrate, is also unfavorable for stablizing storage.Cause
This, needs to develop a kind of water-based acrylic resin easy to operate and better performances.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, the novel aqueous silicon epoxy of one kind is provided and is changed
Property acrylic resin, by the synthesis of siliceous epoxy modified acrylic resin, be neutralized into salt and add deionized water dispersion three
A step obtains, easy to operate, safety and environmental protection, and products obtained therefrom performance is good.
Aqueous silicon epoxy modified acrylic resin of the present invention, in parts by weight, by 10 parts~15 parts solvents, 21 parts
~30 parts of non-functional acrylic ester monomers, 0.5 part~0.8 part hydroxy acrylic acid esters monomer, 3.5 parts~8.7 parts propylene
Acrylic monomer, 2 parts~3 parts silane monomers containing tri-alkoxy, 0.4~0.8 part of initiator, 0.1 part~0.3 part chain regulator, 3
Part~6 parts of epoxy resin, after siliceous epoxy modified acrylic resin is prepared in 0.1 part~0.15 part catalyst reaction, then with
3.5 parts~5.5 parts neutralizers carry out being neutralized into salt, are eventually adding 32 parts~55 parts deionized waters and are dispersed to obtain solid content and are
40%~45% aqueous silicon epoxy modified acrylic resin；
Wherein, the solvent is butyl glycol ether, butyl, propylene glycol monomethyl ether, dipropylene glycol methyl ether, propylene glycol
One of butyl ether, dipropylene, propylene glycol methyl ether acetate are a variety of；
The non-functional acrylic ester monomer be methyl acrylate, methyl methacrylate, isobornyl acrylate,
The tertiary fourth of isobornyl methacrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, methacrylic acid
Ester, lauryl acrylate, lauryl methacrylate, ethyl acrylate, acrylic acid-2-ethyl caproite, Isooctyl acrylate monomer, third
At least two in olefin(e) acid cyclohexyl, styrene；
The hydroxy acrylic acid esters monomer is methacrylic acid -2- hydroxy methacrylate, 2-Hydroxy ethyl acrylate, methyl
One of 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate are a variety of；
The acrylic monomer is one or both of methacrylic acid, acrylic acid；
The silane monomer containing tri-alkoxy is vinyl silane triisopropoxide or n- octyltri-ethoxysilane；
The epoxide equivalent of the epoxy resin is 185~212.
Aqueous silicon epoxy modified acrylic resin of the present invention and amino resins interworking are at high temperature after film-forming
Glossiness is good, and hardness is high, and water-fast, salt spray resistance, ageing-resistant performance are excellent.
In one embodiment, the initiator is azodiisobutyronitrile or dibenzoyl peroxide.
In another embodiment, the initiator is added is reacted in two batches, first in react start when be added,
Additional amount is 0.28 part~0.56 part, and second batch is rear initiator, additional amount is 0.12 part~0.24 part.
In another embodiment, the chain regulator is lauryl mercaptan or mercaptoethanol.
In another embodiment, the catalyst is tetrabutylammonium bromide.
In another embodiment, the neutralizer is N, N- dimethylethanolamine, triethylamine, ammonia, diethanol amine or 2-
Amino-2-methyl -1- propyl alcohol.
In yet another embodiment, in parts by weight, the aqueous silicon epoxy modified acrylic resin is by 12 parts~15
Part solvent, 21.5 parts~29 parts non-functional acrylic ester monomers, 0.7 part of hydroxy acrylic acid esters monomer, 3.5 parts~6.5
Part acrylic monomer, 2 parts~3 parts silane monomers containing tri-alkoxy, 0.6~0.7 part of initiator, 0.1 part~0.2 part chain tune
Agent, 3.5 parts~5.5 parts epoxy resin are saved, 0.1 part~0.15 part catalyst reaction is prepared；
Wherein, the solvent is dipropylene glycol methyl ether or dipropylene；
The non-functional acrylic ester monomer is by 7 parts~9 parts methyl methacrylates, 5.5 parts~7.5 parts acrylic acid
N-butyl, 1.5 parts~3 parts styrene and 7.5 parts~9.5 parts acrylic acid-2-ethyl caproite compositions, or by 7 parts~9 parts methyl
Methyl acrylate, 5.5 parts~7.5 parts n-butyl acrylates, 1.5 parts~3 parts styrene and 7.5 parts~9.5 parts acrylic acid -2- second
The own ester composition of base；
The hydroxy acrylic acid esters monomer is 2-hydroxypropyl acrylate；
The acrylic monomer is methacrylic acid；
The silane monomer containing tri-alkoxy is vinyl silane triisopropoxide or n- octyltri-ethoxysilane；
The initiator is dibenzoyl peroxide；
The chain regulator is mercaptoethanol；
The epoxide equivalent of the epoxy resin is 185~212；
The catalyst is tetrabutylammonium bromide.
The aqueous silicon epoxy modified acrylic resin and amino resins interworking are at high temperature after film-forming, hardness
(pencil hardness) is all larger than that 92, water resistance (at least 30d) is unchanged, salt spray resistance test (at least 980 up to 2H, glossiness (60 °)
It is secondary) unchanged, weather-proof test (at least 810h) is unchanged.
Also in one embodiment, in parts by weight, the aqueous silicon epoxy modified acrylic resin is by 10 parts~13
Part solvent, 21 parts~25 parts non-functional acrylic ester monomers, 0.5 part~0.6 part hydroxy acrylic acid esters monomer, 4 parts~5
Part acrylic monomer, 2.5 parts~3 parts silane monomers containing tri-alkoxy, 0.4~0.6 part of initiator, 0.2 part~0.3 part chain
Regulator, 4 parts~5 parts epoxy resin, 0.1 part~0.12 part catalyst reaction are prepared；
Wherein, the solvent is butyl or propandiol butyl ether；
The non-functional acrylic ester monomer is by 6.5 parts~8 parts methyl acrylates, 4.5 parts~6 parts methacrylic acids
Lauryl, 1.5 parts~2.5 parts styrene and 8 parts~9 parts Isooctyl acrylate monomer compositions；
The hydroxy acrylic acid esters monomer is methacrylic acid -2- hydroxy methacrylate；
The acrylic monomer is acrylic acid；
The silane monomer containing tri-alkoxy is vinyl silane triisopropoxide；
The initiator is azodiisobutyronitrile；
The chain regulator is lauryl mercaptan；
The epoxide equivalent of the epoxy resin is 185~212；
The catalyst is tetrabutylammonium bromide.
The aqueous silicon epoxy modified acrylic resin and amino resins interworking are at high temperature after film-forming, hardness
(pencil hardness) is all larger than that 91, water resistance (at least 30d) is unchanged, salt spray resistance test (at least 950 up to 2H, glossiness (60 °)
It is secondary) unchanged, weather-proof test (at least 810h) is unchanged.
Based on aforementioned aqueous silicon epoxy modified acrylic resin, the present invention also provides a kind of aqueous silicon is epoxy-modified
The preparation method of acrylic resin, includes the following steps
(1) synthesis of siliceous epoxy modified acrylic resin: stirring solvent is warming up to 100 DEG C~105 DEG C, and thereto
Be added dropwise by non-functional acrylic ester monomer, hydroxy acrylic acid esters monomer, acrylic monomer, containing the silane of tri-alkoxy
The mixed solution of monomer, initiator and chain regulator composition after 1.5 hours~2 hours drip, keeps the temperature 2 hours, adds initiation
Agent causes after carrying out, and continues heat preservation until conversion ratio reaches 98% or more；Temperature is adjusted to 110 DEG C~115 DEG C, and thereto
The mixed solution of epoxy resin and catalyst is added dropwise, after 15 minutes drip, keeps the temperature 1 hour~1.5 hours, measures acid value；
(2) it is neutralized into salt: being cooled to 50 DEG C~70 DEG C, neutralizer is added, stir 10 minutes~15 minutes；
(3) plus deionized water dispersion: deionized water is added and is dispersed, make the solid content of final products control 40%~
45%, it keeps the temperature 20 minutes~obtains aqueous silicon epoxy modified acrylic resin after forty minutes.
Based on aforementioned aqueous silicon epoxy modified acrylic resin, invention further provides a kind of aqueous amino to apply
Material is prepared by the aqueous silicon epoxy modified acrylic resin and amino resins participation.
In one embodiment, the aqueous amido coatings are by the aqueous silicon epoxy modified acrylic resin, and
Amino resins, pigment, dispersing agent, defoaming agent, levelling agent, wetting agent, thickener, solvent and water are prepared.
In another embodiment, the aqueous amido coatings are by 50 parts of aqueous silicon epoxy-modified acrylic acid trees
Rouge, 20 parts of pigment, 10 parts of amino resins, 1.6 parts of dispersing agents, 0.1 part of defoaming agent, 0.3 part of levelling agent, 0.3 part of wetting agent, 0.3
Part thickener, 8 parts of solvents and 6.4 parts of water are prepared.
In yet another embodiment, the amino resins is special 303 amino resins of cyanogen or special 325 amino resins of cyanogen.
Also in one embodiment, in parts by weight, the aqueous silicon epoxy modified acrylic resin and the cyanogen are special
The additional amount ratio of 325 amino resins is 5:1.
Beneficial effects of the present invention:
On the one hand aqueous silicon epoxy modified acrylic resin of the present invention introduces element silicon and is modified, Ke Yiti
Water resistance, chemical corrosion resistance, weatherability and the mildew resistance of high amino-stoving varnish, and can improve paint film steel, glass and
Adhesive force on aluminium, and the pollution resistance of paint film can be promoted.On the other hand epoxy resin is introduced in synthesis, paint can be increased
Film adhesive force on base material, improves the performances such as the water-fast of paint film, salt spray resistance and chemical resistance.
Aqueous silicon epoxy modified acrylic resin of the present invention is milky liquid, and the viscosity at 25 DEG C is
1500~2000mPas, stability is high, stores 1 year or more at 35 DEG C.
Possess using aqueous silicon epoxy modified acrylic resin of the present invention as the aqueous amido coatings of primary raw material good
The advantages that hardness well, gloss and chemical resistance, and it can be with rapid curing at 110 DEG C~140 DEG C, drying rate
Fastly, the time is saved.
Specific embodiment
Performance of the invention described further below, but they are not constituted a limitation of the invention, it is only for example.
Embodiment 1
12 parts of dipropylene glycol methyl ethers are added in the reactor with condensing unit and stirring rod, are warming up to 105 DEG C.It is permanent
Wen Hou starts that mixed solution (7.8 parts of methyl methacrylate, 5.9 parts of n-butyl acrylate, 1.7 parts of styrene, propylene is added dropwise
8.6 parts of acid -2- ethylhexyl, 0.7 part of 2-hydroxypropyl acrylate, 5.7 parts of methacrylic acid, three isopropoxy silicon of vinyl
2.4 parts of alkane, 0.42 part of dibenzoyl peroxide, 0.1 part of mercaptoethanol), rate of addition is controlled, is added dropwise within 1.5~2 hours
It finishes, continues heat preservation 2 hours, cause after adding 0.18 part of dibenzoyl peroxide progress, continue heat preservation 1 hour, it is small every half
When measure conversion ratio, until conversion ratio reaches 98% or more, temperature is adjusted to 110 DEG C, 4.5 parts of epoxy resin and four fourths are added dropwise
The mixed solution that 0.12 part of base ammonium bromide drips in 15 minutes, keeps the temperature 1~1.5 hour and reacts, and measurement acid value is 50mg
KOH/g。
The temperature of system is down to 50 DEG C, revolving speed is controlled between 200rpm~400rpm, 4 parts of N, N- dimethyl second is added
Hydramine neutralizes, and after stirring 15min, controls revolving speed between 600rpm~800rpm, 34 parts of deionized waters are added and are dispersed, protect
Aqueous silicon epoxy modified acrylic resin is obtained after warm half an hour.
Through detecting: this experiment products obtained therefrom is the liquid of milky, Gu containing being 45%.
Embodiment 2
15 parts of dipropylenes are added in the reactor with condensing unit and stirring rod, are warming up to 105 DEG C.It is permanent
Wen Hou starts that mixed solution (8.8 parts of methyl methacrylate, 7.3 parts of n-butyl acrylate, 2.8 parts of styrene, propylene is added dropwise
9.1 parts of acid -2- ethylhexyl, 0.7 part of 2-hydroxypropyl acrylate, 6.3 parts of methacrylic acid, three isopropoxy silicon of vinyl
2.8 parts of alkane, 0.48 part of dibenzoyl peroxide, 0.2 part of mercaptoethanol), rate of addition is controlled, is added dropwise within 1.5~2 hours
It finishes, continues heat preservation 2 hours, cause after adding 0.18 part of dibenzoyl peroxide progress, continue heat preservation 1 hour, it is small every half
When measure conversion ratio, until conversion ratio reaches 98% or more, temperature is adjusted to 110 DEG C, 5.5 parts of epoxy resin and four fourths are added dropwise
The mixed solution that 0.15 part of base ammonium bromide drips in 15 minutes, keeps the temperature 1~1.5 hour and reacts, and measurement acid value is 45mg
KOH/g。
The temperature of system is down to 60 DEG C, revolving speed is controlled between 200rpm~400rpm, 4.2 parts of N, N- dimethyl is added
Ethanol amine neutralizes, and after stirring 10min, controls revolving speed between 600rpm~800rpm, 51 parts of deionized waters are added and are dispersed,
Aqueous silicon epoxy modified acrylic resin is obtained after heat preservation half an hour.
Through detecting: this experiment products obtained therefrom is the liquid of milky, Gu containing being 41.7%.
Embodiment 3
14 parts of dipropylenes are added in the reactor with condensing unit and stirring rod, are warming up to 105 DEG C.It is permanent
Wen Hou starts that mixed solution (8.5 parts of methyl methacrylate, 7 parts of n-butyl acrylate, 2.6 parts of styrene, acrylic acid-is added dropwise
7.9 parts of 2- ethylhexyl, 0.7 part of 2-hydroxypropyl acrylate, 3.5 parts of methacrylic acid, n- octyltri-ethoxysilane 2.8
Part, 0.49 part of dibenzoyl peroxide, 0.2 part of mercaptoethanol), rate of addition is controlled, is added dropwise within 1.5~2 hours,
Continue heat preservation 2 hours, causes after adding 0.21 part of dibenzoyl peroxide progress, continue heat preservation 1 hour, measured every half an hour
Temperature is adjusted to 110 DEG C, 3.8 parts of epoxy resin and tetrabutyl phosphonium bromide is added dropwise by conversion ratio until conversion ratio reaches 98% or more
The mixed solution that 0.1 part of ammonium drips in 15 minutes, keeps the temperature 1~1.5 hour and reacts, and measurement acid value is 42mgKOH/g.
The temperature of system is down to 70 DEG C, revolving speed is controlled between 200rpm~400rpm, 3.5 parts of N, N- dimethyl is added
Ethanol amine neutralizes, and after stirring 15min, controls revolving speed between 600rpm~800rpm, 42 parts of deionized waters are added and are dispersed,
Aqueous silicon epoxy modified acrylic resin is obtained after heat preservation half an hour.
Through detecting: this experiment products obtained therefrom is the liquid of milky, Gu containing being 40%.
Embodiment 4
10 parts of propandiol butyl ethers are added in the reactor with condensing unit and stirring rod, are warming up to 100 DEG C.Constant temperature
Afterwards, start that mixed solution (6.5 parts of methyl acrylate, 4.5 parts of lauryl methacrylate, 1.5 parts of styrene, acrylic acid is added dropwise
8 parts of different monooctyl ester, 0.5 part of methacrylic acid -2- hydroxy methacrylate, 4 parts of acrylic acid, 2.4 parts of vinyl silane triisopropoxide, azo
0.28 part of bis-isobutyronitrile, 0.2 part of lauryl mercaptan), rate of addition is controlled, is added dropwise within 1.5~2 hours, is continued
Heat preservation 2 hours caused after adding 0.12 part of azodiisobutyronitrile progress, continues heat preservation 1 hour, measures and converts every half an hour
Temperature is adjusted to 110 DEG C, 4 parts of epoxy resin and tetrabutylammonium bromide 0.1 is added dropwise by rate until conversion ratio reaches 98% or more
The mixed solution of part, drips in 15 minutes, keeps the temperature 1~1.5 hour and reacts, and measurement acid value is 44mg KOH/g.
The temperature of system is down to 60 DEG C, revolving speed is controlled between 200rpm~400rpm, is added in 3.8 parts of triethylamines
With after stirring 10min, control revolving speed between 600rpm~800rpm, 40 parts of deionized waters be added and are dispersed, heat preservation is half small
When after obtain aqueous silicon epoxy modified acrylic resin.
Through detecting: this experiment products obtained therefrom is the liquid of milky, Gu containing being 42.1%.
Embodiment 5
13 parts of propandiol butyl ethers are added in the reactor with condensing unit and stirring rod, are warming up to 100 DEG C.Constant temperature
Afterwards, start that mixed solution (7.9 parts of methyl acrylate, 5.6 parts of lauryl methacrylate, 2.5 parts of styrene, acrylic acid is added dropwise
9 parts of different monooctyl ester, 0.6 part of methacrylic acid -2- hydroxy methacrylate, 5 parts of acrylic acid, 2.8 parts of vinyl silane triisopropoxide, azo
0.49 part of bis-isobutyronitrile, 0.3 part of lauryl mercaptan), rate of addition is controlled, is added dropwise within 1.5~2 hours, is continued
Heat preservation 2 hours causes after adding 0.21 part of azodiisobutyronitrile progress, continues heat preservation 1 hour, measures and converts every half an hour
Temperature is adjusted to 110 DEG C, 5 parts of epoxy resin and tetrabutylammonium bromide 0.12 is added dropwise by rate until conversion ratio reaches 98% or more
The mixed solution of part, drips in 15 minutes, keeps the temperature 1~1.5 hour and reacts, and measurement acid value is 47mg KOH/g.
The temperature of system is down to 70 DEG C, revolving speed is controlled between 200rpm~400rpm, is added in 4.3 parts of triethylamines
With after stirring 12min, control revolving speed between 600rpm~800rpm, 46 parts of deionized waters be added and are dispersed, heat preservation is half small
When after obtain aqueous silicon epoxy modified acrylic resin.
Through detecting: this experiment products obtained therefrom is the liquid of milky, Gu containing being 44.5%.
Embodiment 6
Examples 1 to 5 is synthesized into resulting resin and carries out painting according to the following formulation:
After raw material 1~11 is stirred, it is coated on carbon sheet surface, is toasted 15 minutes at 120 DEG C, paint film
It is tested for the property after solidification, concrete outcome is as shown in table 1:
Table 1: resin obtained by Examples 1 to 5 is applied to the performance after amino-stoving varnish
Aqueous silicon epoxy modified acrylic resin of the present invention and amino resins interworking be at high temperature after film-forming,
Hardness (pencil hardness) up to 2H, glossiness (60 °) be all larger than 90,50cm shock-testing can pass through, appearance of film it is smooth
Smooth, water resistance (at least 30d) is unchanged, salt spray resistance test (at least 950 times) is unchanged, weather-proof test (at least 800h) is without change
Change, it is seen that made amino-stoving varnish glossiness is good, and hardness is high, and water-fast, salt spray resistance, ageing-resistant performance are excellent.
The content that this specification is not described in detail belongs to the prior art well known to professional and technical personnel in the field.
Claims (10)
1. aqueous silicon epoxy modified acrylic resin, it is characterised in that: in parts by weight, by 10 parts~15 parts solvents, 21 parts
~30 parts of non-functional acrylic ester monomers, 0.5 part~0.8 part hydroxy acrylic acid esters monomer, 3.5 parts~8.7 parts propylene
Acrylic monomer, 2 parts~3 parts silane monomers containing tri-alkoxy, 0.4~0.8 part of initiator, 0.1 part~0.3 part chain regulator, 3
Part~6 parts of epoxy resin, after siliceous epoxy modified acrylic resin is prepared in 0.1 part~0.15 part catalyst reaction, then with
3.5 parts~5.5 parts neutralizers carry out being neutralized into salt, are eventually adding 32 parts~55 parts deionized waters and are dispersed to obtain solid content and are
40%~45% aqueous silicon epoxy modified acrylic resin；
Wherein, the solvent is butyl glycol ether, butyl, propylene glycol monomethyl ether, dipropylene glycol methyl ether, propylene glycol fourth
One of ether, dipropylene, propylene glycol methyl ether acetate are a variety of；
The non-functional acrylic ester monomer is methyl acrylate, methyl methacrylate, isobornyl acrylate, methyl
Isobornyl acrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, Tert-butyl Methacrylate, third
Olefin(e) acid lauryl, lauryl methacrylate, ethyl acrylate, acrylic acid-2-ethyl caproite, Isooctyl acrylate monomer, acrylic acid
At least two in cyclohexyl, styrene；
The hydroxy acrylic acid esters monomer is methacrylic acid -2- hydroxy methacrylate, 2-Hydroxy ethyl acrylate, metering system
One of acid -2- hydroxy propyl ester, 2-hydroxypropyl acrylate are a variety of；
The acrylic monomer is one or both of methacrylic acid, acrylic acid；
The silane monomer containing tri-alkoxy is vinyl silane triisopropoxide or n- octyltri-ethoxysilane；
The epoxide equivalent of the epoxy resin is 185~212.
2. aqueous silicon epoxy modified acrylic resin according to claim 1, it is characterised in that: the initiator is even
Nitrogen bis-isobutyronitrile or dibenzoyl peroxide.
3. aqueous silicon epoxy modified acrylic resin according to claim 2, it is characterised in that: the initiator is divided to two
It criticizes to be added and be reacted, first is added when reacting and starting, additional amount is 0.28 part~0.56 part, and second batch causes after being
Agent, additional amount are 0.12 part~0.24 part.
4. aqueous silicon epoxy modified acrylic resin according to claim 2 or 3, it is characterised in that: the chain is adjusted
Agent is lauryl mercaptan or mercaptoethanol.
5. aqueous silicon epoxy modified acrylic resin according to claim 4, it is characterised in that: the catalyst is four
Butylammonium bromide.
6. aqueous silicon epoxy modified acrylic resin according to claim 5, it is characterised in that: the neutralizer is N,
N- dimethylethanolamine, triethylamine, ammonia, diethanol amine or 2-amino-2-methyl-1-propanol.
7. aqueous silicon epoxy modified acrylic resin according to claim 6, it is characterised in that: in parts by weight, institute
Aqueous silicon epoxy modified acrylic resin is stated by 12 parts~15 parts solvents, 21.5 parts~29 parts non-functional esters of acrylic acid lists
Body, 0.7 part of hydroxy acrylic acid esters monomer, 3.5 parts~6.5 parts acrylic monomers, 2 parts~3 parts silane containing tri-alkoxy
Monomer, 0.6~0.7 part of initiator, 0.1 part~0.2 part chain regulator, 3.5 parts~5.5 parts epoxy resin, 0.1 part~0.15 part
Catalyst reaction is prepared；
Wherein, the solvent is dipropylene glycol methyl ether or dipropylene；
The non-functional acrylic ester monomer is by 7 parts~9 parts methyl methacrylates, 5.5 parts~7.5 parts positive fourths of acrylic acid
Ester, 1.5 parts~3 parts styrene and 7.5 parts~9.5 parts acrylic acid-2-ethyl caproite compositions, or by 7 parts~9 parts metering systems
Sour methyl esters, 5.5 parts~7.5 parts n-butyl acrylates, 1.5 parts~3 parts styrene and 7.5 parts~9.5 parts acrylic acid-2-ethyls oneself
Ester composition；
The hydroxy acrylic acid esters monomer is 2-hydroxypropyl acrylate；
The acrylic monomer is methacrylic acid；
The silane monomer containing tri-alkoxy is vinyl silane triisopropoxide or n- octyltri-ethoxysilane；
The initiator is dibenzoyl peroxide；
The chain regulator is mercaptoethanol；
The epoxide equivalent of the epoxy resin is 185~212；
The catalyst is tetrabutylammonium bromide.
8. aqueous silicon epoxy modified acrylic resin according to claim 6, it is characterised in that: in parts by weight, institute
Aqueous silicon epoxy modified acrylic resin is stated by 10 parts~13 parts solvents, 21 parts~25 parts non-functional esters of acrylic acid lists
Body, 0.5 part~0.6 part hydroxy acrylic acid esters monomer, 4 parts~5 parts acrylic monomers, 2.5 parts~3 parts containing tri-alkoxy
Silane monomer, 0.4~0.6 part of initiator, 0.2 part~0.3 part chain regulator, 4 parts~5 parts epoxy resin, 0.1 part~0.12 part
Catalyst reaction is prepared；
Wherein, the solvent is butyl or propandiol butyl ether；
The non-functional acrylic ester monomer is by 6.5 parts~8 parts methyl acrylates, 4.5 parts~6 parts lauryls
Ester, 1.5 parts~2.5 parts styrene and 8 parts~9 parts Isooctyl acrylate monomer compositions；
The hydroxy acrylic acid esters monomer is methacrylic acid -2- hydroxy methacrylate；
The acrylic monomer is acrylic acid；
The silane monomer containing tri-alkoxy is vinyl silane triisopropoxide；
The initiator is azodiisobutyronitrile；
The chain regulator is lauryl mercaptan；
The epoxide equivalent of the epoxy resin is 185~212；
The catalyst is tetrabutylammonium bromide.
9. the preparation method of aqueous silicon epoxy modified acrylic resin described in any one of claim 1-8, it is characterised in that:
Include the following steps
(1) synthesis of siliceous epoxy modified acrylic resin: stirring solvent is warming up to 100 DEG C~105 DEG C, and is added dropwise thereto
By non-functional acrylic ester monomer, hydroxy acrylic acid esters monomer, acrylic monomer, the silane list containing tri-alkoxy
The mixed solution of body, initiator and chain regulator composition after 1.5 hours~2 hours drip, keeps the temperature 2 hours, adds initiator
Cause after progress, continues heat preservation until conversion ratio reaches 98% or more；Temperature is adjusted to 110 DEG C~115 DEG C, and is dripped thereto
Add the mixed solution of epoxy resin and catalyst, after 15 minutes drip, keeps the temperature 1 hour~1.5 hours, measure acid value；
(2) it is neutralized into salt: being cooled to 50 DEG C~70 DEG C, neutralizer is added, stir 10 minutes~15 minutes；
(3) plus deionized water dispersion: deionized water is added and is dispersed, make the solid content of final products control 40%~
45%, it keeps the temperature 20 minutes~obtains aqueous silicon epoxy modified acrylic resin after forty minutes.
10. aqueous amido coatings, it is characterised in that: by aqueous silicon of any of claims 1-8 epoxy-modified third
Olefin(e) acid resin and amino resins participation are prepared.
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| CN110982371A (en) * | 2019-12-18 | 2020-04-10 | 万华化学集团股份有限公司 | Environment-friendly water-based high-gloss high-fullness high-temperature baking varnish |
| CN111019069A (en) * | 2019-12-17 | 2020-04-17 | 上海树脂厂有限公司 | Water-based epoxy organic silicon acrylate composite resin and preparation method thereof |
| CN113372511A (en) * | 2021-06-30 | 2021-09-10 | 湖南松井新材料股份有限公司 | Acrylic resin, water-based amino baking paint, and preparation method and application thereof |
| CN115010937A (en) * | 2022-06-24 | 2022-09-06 | 安徽尚德轨道设备制造有限公司 | Ternary composite resin and preparation method of waterproof coating thereof |
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| CN115010937A (en) * | 2022-06-24 | 2022-09-06 | 安徽尚德轨道设备制造有限公司 | Ternary composite resin and preparation method of waterproof coating thereof |
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