CN107163192A - Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof - Google Patents
Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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Abstract
The present invention relates to cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof.The composition and weight/mass percentage composition of the dispersion be：The cation-type water-thinned % of Hydroxylated acrylic resin 40~45, the % of organic solvent 2~9, the % of deionized water 46~58.The dispersion of the present invention has the performances such as higher adhesive force, alkali resistant closure, shielding and stain resistant permeability.Average grain diameter is small, and average grain diameter is 90~160 nm, and particle diameter distribution is narrow, and polydispersity coefficient PDI is 0.05~0.15, with good homogeneity, is conducive to improving the combination property of film.Viscosity is smaller, is conducive to the mixer subsequent construction with curing agent during coating.Dispersion, which has, stands storage more than 60 days without changes such as any layering, sedimentation, precipitations under preferable mobility, stability height, room temperature condition, particle size and distribution, viscosity are without significant change.
Description
Technical field
The present invention relates to a kind of cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof.
Background technology
With the continuous reinforcement of people's environmental consciousness and awareness of safety, and related environmental regulation increasingly perfect, green
The water paint of environmental protection has started to gradually replace solvent based coating, it has also become the main flow of paint development.
Water based acrylic resin dispersion, with low VOC, molecule designability, dispersion stabilization, using flexible
The advantages of property, widespread popularity, it is used for the chemistry painting industry fields such as woodenware, exterior wall.United States Patent (USP) US6399691,
US2007282049A1 and Chinese patent CN101914185A, CN102850703A describe the fraction of water-based acrylic resin two
The preparation method of granular media.Described dispersion passes through two step free radical solution polymerization methods, the core part of first synthesizing hydrophobic（Be free of
Carboxylic acid）, then it is grafted hydrophilic shell parts（Rich in carboxylic acid）, nertralizer is added, is added water after neutralization scattered, few solvent, height is made
Gu low glutinous, stable storing secondary breakup body.These are all the dispersions using anion as hydrophilic radical, are had during as coating good
Good film forming, guarantor's light colour retention, chemical resistance and weatherability, but in specific occasions such as the antifouling antirusts in metal surface, because dividing
Granular media anionic group feature, its adhesive force, alkali resistant closure, shielding and stain resistant permeability can not meet its and specific use
It is required that.
At present, Chinese patent CN103314025A, CN104086745A is scattered there is provided a kind of waterborne cation polyurethane
Body and preparation method thereof；Chinese patent CN1709945A, CN101314626A are there is provided a kind of cationic-type polyacrylamide point
Granular media and preparation method thereof；CN105778027A provides a kind of cation-type water-thinned polythiourethane dispersion and its preparation side
Method.Cation type dispersible body is because of the feature of its cation group, and its film has excellent adhesive force in some specific occasions, resisted
The correlated performances such as alkali closure, shielding and stain resistant permeability.
The content of the invention
An object of the present invention is the provision of a kind of cation-type water-thinned Hydroxylated acrylic resin secondary breakup body.
The second object of the present invention is the preparation method for providing the dispersion.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of cation-type water-thinned Hydroxylated acrylic resin secondary breakup body, it is characterised in that the composition and quality of the dispersion
Percentage composition is：The cation-type water-thinned % of Hydroxylated acrylic resin 40~45, the % of organic solvent 2~9, deionized water 46~58
%。
A kind of method for preparing above-mentioned cation-type water-thinned Hydroxylated acrylic resin secondary breakup body, it is characterised in that should
Method is comprised the following steps that：
A. oleophylic section PoSynthesis：Add 5~20 parts of solvents and 0.1~0.8 part of initiator heats up in advance, be then at the uniform velocity added dropwise 0.5
~6 parts of initiators, 0~2 part of chain-transferring agent and 50~80 parts are free of the mix monomer M of cationic hydrophilic groups1Mixture,
Polymerization forms hydrophobic oleophylic section Po；
B. hydrophilic section PwSynthesis：In step a resulting solutions, continue that 0.5~2 part of initiator and 20~50 parts of cations are added dropwise
The mix monomer M of type hydrophilic radical2Mixture, oleophylic section on block or grafting synthesis hydrophilic section Pw；
C. 70~95 DEG C are cooled to, organic acid neutralizing agent is added, 10~30 min are stirred；The degree of neutralization for making solution is 80~130
%；
D. in step c resulting polymers solution, by the amount of calculation of required solid content it is uniform, deionized water, 1~3 are added dropwise at a slow speed
Completion of dropping in h, is down to room temperature, that is, obtains the secondary breakup of the cation-type water-thinned Hydroxylated acrylic resin with core shell structure
Body.
Degree of neutralization is the concept for arranging to be commonly called as during water paint dispersion is synthesized, and referring to the acidic-group in organic acid will can close
Into resin neutral and alkali group acid-base neutralization degree, belong in theoretical calculation, experimentation without by instrument, method carry out
Detection.
Above-mentioned step a's concretely comprises the following steps：Under inert atmosphere protection, 5~20 parts of solvents and 0.1~0.8 part are drawn
Send out agent and add reaction vessel, stirring is warming up to 120~170 DEG C, is incubated 0~30 min, and 0.5~6 part of initiator, 0 is at the uniform velocity added dropwise
~2 parts of chain-transferring agents and 50~80 parts of mix monomer M without cationic hydrophilic groups1Mixture, drip off in 1~3 h,
Continue to be incubated 0~30 min；The described mix monomer M without cationic hydrophilic groups1Composition and weight/mass percentage composition
For：
Acrylic acid alkyl or alicyclic esters monomer：50~70%；
Hydroxy acryl acid esters monomer：10~35%；
Vinyl monomer：0~20%.
Above-mentioned step b's concretely comprises the following steps：0.5~2 part of initiator and 20~50 is added dropwise in mixed liquor obtained by step a
The mix monomer M of part cation type hydrophilic radical2Mixture, drip off in 0.5~2 h, continue to be incubated 1~2 h；Described
The mix monomer M of cation type hydrophilic radical2The composition and weight/mass percentage composition of sum be：
Acrylic acid alkyl or alicyclic esters monomer：50~70%；
Hydroxy acryl acid esters monomer：10~35%；
Acrylic monomer containing tertiary amine groups：3~15%；
Vinyl monomer：0~20%.
Above-mentioned alkyl acrylate base class monomer is：C1~C18 of acrylic or methacrylic acid Arrcostab.
The alicyclic esters monomer of above-mentioned acrylic acid is：Cyclohexyl acrylate, acrylic acid -4- t-butyl cyclohexyl methacrylates, propylene
Sour isobornyl thiocyanoacetate cyclohexyl methacrylate, methacrylic acid -4- t-butyl cyclohexyl methacrylates or isobornyl methacrylate.
Above-mentioned hydroxy acryl acid esters monomer is：Hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl,
Hydroxyethyl methacrylate, hydroxy propyl methacrylate or methacrylate.
Above-mentioned acrylic monomer containing tertiary amine groups is：Acrylate, acrylic acid diethylamino second
Ester, acrylate propyl ester, acrylic acid dibutylamino propyl ester, dimethylaminoethyl methacrylate, methyl-prop
In olefin(e) acid diethylamino ethyl ester, dimethylamine propyl ester and methacrylic acid dibutylamino propyl ester at least
It is a kind of.
Above-mentioned vinyl monomer is：Styrene, vinyltoluene, vinyl naphthalene, acrylonitrile or methacrylonitrile.
Above-mentioned organic acid is：In acetic acid, propionic acid, butyric acid, octanoic acid, lactic acid, phosphoric acid, phosphate and p-methyl benzenesulfonic acid extremely
Few one kind.
Above-mentioned solvent is:200# solvent naphthas, 100# solvent naphthas, acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, first
Alcohol, ethanol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, ethylene glycol, propane diols, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, two
Butyl glycol ether, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propyleneglycol monobutyl
Ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene, propylene glycol methyl ether acetate and propylene-glycol ethyl ether acetate
At least one of.
Above-mentioned initiator is：Azodiisobutyronitrile, ABVN, benzoyl peroxide, dilauroyl peroxide,
Di t-amyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, tert-butyl peroxy acetate, peroxidating diisopropyl
The special pentyl ester of benzene, isopropyl benzene hydroperoxide, cumyl t-butyl peroxide, peroxidating -2 ethyl hexanoic acid, the tertiary fourth of peroxidating pivalic acid
Ester, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -3,5,5 Trimethylhexanoic acid tert-butyl ester or peroxidating acetic acid tert-pentyl ester.
Above-mentioned chain-transferring agent is a-Methylstyrene Low-Polymer or mercaptoethanol thio-alcohol.
In the present invention, the consumption of each component is as follows by weight in the preparation process of described aqueous dispersion：
（Note：For convenience of measuring, monomer weight is 100 parts, other components parts by weight in terms of this）
In the present invention, M1With M2Used monomer weight ratio is 80：20~50：50, preferably 75：25~60：40.
In the present invention, because alcohol ethers solvent toxicity is relatively low, boiling point is higher, and it is advantageous to propane diols ethers and oil miscible solvent
Bonding solvent.Ensure the dissolving of monomer and polymer in solution polymerization process and disperse, and control the volatile of dispersion to have
Machine compounds content（VOC）, solvent load is 5~20 parts by weight, preferably 12~18 parts by weight.
In the present invention, described acrylic acid alkyl or alicyclic esters monomer, combination property according to needed for its resin come
Combination of monomers is selected, its consumption is 50~70 parts by weight.
In the present invention, the consumption of the acrylic monomer containing tertiary amine groups is 3~15 parts by weight, preferably amine in solid point
It is worth for 17~23 mgKOH/g parts by weight.
In the present invention, described vinyl monomer is one or several kinds of combinations of following compounds：Styrene, vinyl
Toluene, vinyl naphthalene, acrylonitrile and methacrylonitrile etc..Optimization styrene, its consumption is 0~20 parts by weight, preferably 10~20
Parts by weight.
In the present invention, the molecular weight that the consumption of described initiator is depended on needed for the polymer of synthesis, is 1~8 weight
Part, preferably 3~6 parts by weight.
In the present invention, described chain-transferring agent cooperatively controls the molecular weight of polymer with initiator, and its consumption is 0~
2 parts by weight, preferably 0~0.8 parts by weight.
In the present invention, described nertralizer is one or several kinds of combinations of following acid compounds：Acetic acid, propionic acid, breast
The organic acids such as acid, phosphoric acid, phosphate, p-methyl benzenesulfonic acid.Lactic acid is that have certain oil-soluble organic compound, not only hydrophilic but also parent
Oil, is capable of the dispersion stabilization of resin, the preferred lactic acid of nertralizer.Its consumption is 3~8.5 parts by weight, and the degree of neutralization for making resin is
80~130 %, preferably 90~110 %.
In the present invention, the consumption of described deionized water is 110~150 parts by weight, and the solid content for making dispersion is
40~45 %.
The advantage of the present invention is as follows：
（1）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body of the present invention introduces cation group, improves
The performances such as adhesive force, alkali resistant closure, shielding and the stain resistant permeability of Hydroxylated acrylic resin dispersion film.
（2）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body of the present invention is baked available for amino is prepared
Paint, aqueous double-component polyurethane coating etc., for paint fields such as metal, anti-corrosion, antirusts.
（3）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body average grain diameter of the present invention is small, average grain
Footpath is 90~160 nm, and particle diameter distribution is narrow, and polydispersity coefficient PDI is 0.05~0.15, with good homogeneity, is conducive to carrying
The combination property of high film.
（4）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body viscosity of the present invention is smaller, 25 DEG C, 45
During % solid contents, viscosity is less than 8000 mPas, is conducive to the mixer subsequent construction with curing agent during coating.
（5）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body solid content of the present invention is higher, solid content
For 40~45 %, dispersion has preferable mobility.
（6）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body stability of the present invention is high, room temperature condition
Lower to stand storage more than 60 days without changes such as any layering, sedimentation, precipitations, particle size and distribution, viscosity substantially do not become
Change.
（7）Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body solvent of the present invention is relatively low, always waves
Hair property organic compound content（VOC）Less than 80 g/Kg.
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited only to this.
Embodiment 1
This example is intended to show cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof, specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 32, the g of n-butyl acrylate 46, methacrylic acid
The g of hydroxyl ethyl ester 29.2, the g of styrene 12.8, the g of α-methylstyrene dimer 0.96 and the g of di-t-butyl peroxide 4.8 mixing
Thing is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；By the g of methyl methacrylate 18, third
The g of olefin(e) acid N-butyl 26, the g of hydroxyethyl methacrylate 16.8, the g of styrene 7.2, dimethylaminoethyl methacrylate 12
G and the g of di-t-butyl peroxide 3.2 mixture are at the uniform velocity added in reaction vessel, and control is dripped off in 1 h, continue to be incubated 1 h；
90 DEG C are cooled to, the g of lactic acid 6.88 is added, 15 min are stirred；The g of deionized water 228 is slowly at the uniform velocity added into reaction vessel, soon
Fast dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain the translucent cationic water of milky
Property Hydroxylated acrylic resin secondary breakup body.After tested, the relevant parameter index of the dispersion obtained by the embodiment 1 is shown in Table 1.
Embodiment 2
Compared with Example 1, this example is intended to show the cation-type water-thinned hydroxyl of the acrylic monomer containing tertiary amine groups of different content
Base acrylic resin secondary breakup body and preparation method thereof.
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, is led to
Nitrogen, stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 31.8, the g of n-butyl acrylate 45.6, first
The g of base hydroxy-ethyl acrylate 29, the g of styrene 12.6, the g of α-methylstyrene dimer 0.96 and the g of di-t-butyl peroxide 4.8
Mixture at the uniform velocity instill in reaction vessel, control dripped off in 1.5 h, continue be incubated 10 min；By methyl methacrylate
18.6 g, the g of n-butyl acrylate 26.6, the g of hydroxyethyl methacrylate 17, the g of styrene 7.4, dimethylaminoethyl acrylate methyl base ammonia
The g of base ethyl ester 10.4 and the g of di-t-butyl peroxide 3.2 mixture are at the uniform velocity added in reaction vessel, and control is dripped off in 1 h,
Continue to be incubated 1 h；90 DEG C are cooled to, the g of lactic acid 5.96 is added, 15 min are stirred；The g of deionized water 286.5 is slowly at the uniform velocity added
Enter reaction vessel, quick dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain milky semi-transparent
Bright cation-type water-thinned Hydroxylated acrylic resin secondary breakup body.After tested, the dispersion obtained by the embodiment 2 is corresponding
Parameter index is shown in Table 2.
Embodiment 3
Compared with Example 1, this example is intended to show different M1/M2The fraction of cation-type water-thinned Hydroxylated acrylic resin two of ratio
Granular media and preparation method thereof.
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, is led to
Nitrogen, stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 40.2, the g of n-butyl acrylate 52.2, first
The g of base hydroxy-ethyl acrylate 31. 6, the g of styrene 14.9, the g of α-methylstyrene dimer 1.12 and di-t-butyl peroxide
5.6 g mixture is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；By methacrylic acid
The g of methyl esters 14, the g of n-butyl acrylate 18.3, the g of hydroxyethyl methacrylate 10.6, the g of styrene 5.1, dimethylaminoethyl acrylate methyl
The g of base amino ethyl ester 12 and the g of di-t-butyl peroxide 2.4 mixture are at the uniform velocity added in reaction vessel, and control is dripped in 1 h
It is complete, continue to be incubated 1 h；90 DEG C are cooled to, the g of lactic acid 6.88 is added, 15 min are stirred；The g of deionized water 228 is slow at the uniform velocity
Reaction vessel is added, quick dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain milky half
Transparent cation-type water-thinned Hydroxylated acrylic resin secondary breakup body.After tested, the phase of the dispersion obtained by the embodiment 3
Parameter index is answered to be shown in Table 3.
Embodiment 4
Compared with Example 1, this example is intended to show the cation-type water-thinned hydroxy of different acrylic ester monomer combinations
Acid resin secondary breakup body and preparation method thereof, it is specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 26, the g of isobornyl methacrylate 6, acrylic acid
The g of N-butyl 46, the g of hydroxyethyl methacrylate 29.2, the g of styrene 12.8, the g of α-methylstyrene dimer 0.96 and peroxide
The mixture for changing the g of di-t-butyl 4.8 is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；Will
The g of methyl methacrylate 14, the g of isobornyl methacrylate 4, the g of n-butyl acrylate 26, hydroxyethyl methacrylate
16.8 g, the g of styrene 7.2, the g of dimethylaminoethyl methacrylate 12 and the g of di-t-butyl peroxide 3.2 mixture
At the uniform velocity add in reaction vessel, control is dripped off in 1 h, continue to be incubated 1 h；90 DEG C are cooled to, the g of lactic acid 6.88 is added, stirs
Mix 15 min；The g of deionized water 228 is slowly at the uniform velocity added into reaction vessel, quick dispersed with stirring, control is dripped off in 1.5 h；
It is cooled to less than 50 DEG C, you can obtain the translucent cation-type water-thinned Hydroxylated acrylic resin secondary breakup body of milky.Through
Test, the relevant parameter index of the dispersion obtained by the embodiment 4 is shown in Table 4.
Embodiment 5
Compared with Example 1, this example is intended to show the cation-type water-thinned hydroxy of different acrylic ester monomer combinations
Acid resin secondary breakup body and preparation method thereof, it is specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 37.6, the g of acrylic acid-2-ethyl caproite 38.4, first
The g of base hydroxy-ethyl acrylate 29.2, the g of styrene 12.8, the g of α-methylstyrene dimer 0.96 and di-t-butyl peroxide 4.8
G mixture is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；By methyl methacrylate
22.4 g, the g of acrylic acid-2-ethyl caproite 21.6, the g of hydroxyethyl methacrylate 16.8, the g of styrene 7.2, methacrylic acid
The g of dimethylamino ethyl ester 12 and the g of di-t-butyl peroxide 3.2 mixture are at the uniform velocity added in reaction vessel, are controlled in 1 h
Drip off, continue to be incubated 1 h；90 DEG C are cooled to, the g of lactic acid 6.88 is added, 15 min are stirred；The g of deionized water 228 is slowly even
Speed adds reaction vessel, and quick dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain milky
Translucent cation-type water-thinned Hydroxylated acrylic resin secondary breakup body.After tested, dispersion obtained by the embodiment 5
Relevant parameter index is shown in Table 5.
Embodiment 6
Compared with Example 1, this example is intended to show the cation-type water-thinned hydroxyl of different types of hydroxy acryl acid esters monomer
Base acrylic resin secondary breakup body and preparation method thereof, it is specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 43, the g of n-butyl acrylate 34.8, acrylic acid hydroxyl
The g of propyl ester 29.4, the g of styrene 12.8, the g of α-methylstyrene dimer 0.96 and the g of di-t-butyl peroxide 4.8 mixture
At the uniform velocity instill in reaction vessel, control is dripped off in 1.5 h, continue to be incubated 10 min；By the g of methyl methacrylate 24.4, third
The g of olefin(e) acid N-butyl 19.8, the g of hydroxypropyl acrylate 16.6, the g of styrene 7.2, the g of dimethylaminoethyl methacrylate 12
At the uniform velocity added with the g of di-t-butyl peroxide 3.2 mixture in reaction vessel, control is dripped off in 1 h, continue to be incubated 1 h；
90 DEG C are cooled to, the g of lactic acid 6.88 is added, 15 min are stirred；The g of deionized water 228 is slowly at the uniform velocity added into reaction vessel, soon
Fast dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain the translucent cationic water of milky
Property Hydroxylated acrylic resin secondary breakup body.After tested, the relevant parameter index of the dispersion obtained by the embodiment 6 is shown in Table 6.
Embodiment 7
Compared with Example 1, this example is intended to show the cation-type water-thinned hydroxy acrylic acid of different types of vinyl monomer
Resin secondary breakup body and preparation method thereof, it is specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 32.6, the g of n-butyl acrylate 45.4, methyl-prop
The g of olefin(e) acid hydroxyl ethyl ester 29.2, the g of acrylonitrile 12.8, the g of α-methylstyrene dimer 0.96 and the g of di-t-butyl peroxide 4.8
Mixture is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；By methyl methacrylate
18.4 g, the g of n-butyl acrylate 25.6, the g of hydroxyethyl methacrylate 16.8, the g of acrylonitrile 7.2, dimethylaminoethyl acrylate methyl base
The g of amino ethyl ester 12 and the g of di-t-butyl peroxide 3.2 mixture are at the uniform velocity added in reaction vessel, and control is dripped off in 1 h,
Continue to be incubated 1 h；90 DEG C are cooled to, the g of lactic acid 6.88 is added, 15 min are stirred；The g of deionized water 228 is slowly at the uniform velocity added
Reaction vessel, quick dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain milky translucent
Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body.After tested, the corresponding ginseng of the dispersion obtained by the embodiment 7
Number index is shown in Table 7.
Embodiment 8
Compared with Example 1, this example is intended to show the cation-type water-thinned Hydroxylated acrylic resin two of different types of initiator
Level dispersion and preparation method thereof, it is specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di t-amyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 32, the g of n-butyl acrylate 46, methacrylic acid
The g of hydroxyl ethyl ester 29.2, the g of styrene 12.8, the g of α-methylstyrene dimer 0.96 and the g of di t-amyl peroxide 4.8 mixing
Thing is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；By the g of methyl methacrylate 18, third
The g of olefin(e) acid N-butyl 26, the g of hydroxyethyl methacrylate 16.8, the g of styrene 7.2, dimethylaminoethyl methacrylate 12
G and the g of di t-amyl peroxide 3.2 mixture are at the uniform velocity added in reaction vessel, and control is dripped off in 1 h, continue to be incubated 1 h；
90 DEG C are cooled to, the g of lactic acid 6.88 is added, 15 min are stirred；The g of deionized water 228 is slowly at the uniform velocity added into reaction vessel, soon
Fast dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain the translucent cationic water of milky
Property Hydroxylated acrylic resin secondary breakup body.After tested, the relevant parameter index of the dispersion obtained by the embodiment 8 is shown in Table 8.
Embodiment 9
Compared with Example 1, this example is intended to show the cation-type water-thinned hydroxy acrylic acid of different types of organic acid neutralizing agent
Resin secondary breakup body and preparation method thereof, it is specific as follows：
By the g of ethylene glycol monobutyl ether 18,100#The solvent naphtha 18g and g of di-t-butyl peroxide 1 is added in reaction vessel, leads to nitrogen,
Stirring is warming up to 145 DEG C, is incubated 15 min；By the g of methyl methacrylate 32, the g of n-butyl acrylate 46, methacrylic acid
The g of hydroxyl ethyl ester 29.2, the g of styrene 12.8, the g of α-methylstyrene dimer 0.96 and the g of di-t-butyl peroxide 4.8 mixing
Thing is at the uniform velocity instilled in reaction vessel, and control is dripped off in 1.5 h, continues to be incubated 10 min；By the g of methyl methacrylate 18, third
The g of olefin(e) acid N-butyl 26, the g of hydroxyethyl methacrylate 16.8, the g of styrene 7.2, dimethylaminoethyl methacrylate 12
G and the g of di-t-butyl peroxide 3.2 mixture are at the uniform velocity added in reaction vessel, and control is dripped off in 1 h, continue to be incubated 1 h；
90 DEG C are cooled to, the g of propionic acid 5.66 is added, 15 min are stirred；The g of deionized water 228 is slowly at the uniform velocity added into reaction vessel, soon
Fast dispersed with stirring, control is dripped off in 1.5 h；It is cooled to less than 50 DEG C, you can obtain the translucent cationic water of milky
Property Hydroxylated acrylic resin secondary breakup body.After tested, the relevant parameter index of the dispersion obtained by the embodiment 9 is shown in Table 9.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, it is clear that those skilled in the art
Member can carry out various changes and modification to the present invention, but must not depart from the spirit and scope of the present invention.
Claims (13)
1. a kind of cation-type water-thinned Hydroxylated acrylic resin secondary breakup body, it is characterised in that the composition and matter of the dispersion
Measuring percentage composition is：The cation-type water-thinned % of Hydroxylated acrylic resin 40~45, the % of organic solvent 2~9, deionized water 46~58
%。
2. a kind of method for preparing cation-type water-thinned Hydroxylated acrylic resin secondary breakup body according to claim 1,
It is characterized in that this method is comprised the following steps that：
Oleophylic section PoSynthesis：Add 5~20 parts of solvents and 0.1~0.8 part of initiator heats up in advance, be then at the uniform velocity added dropwise 0.5~6
Part initiator, 0~2 part of chain-transferring agent and 50~80 parts are free of the mix monomer M of cationic hydrophilic groups1Mixture, gather
Close and form hydrophobic oleophylic section Po；
Hydrophilic section PwSynthesis：In step a resulting solutions, continue that 0.5~2 part of initiator and 20~50 parts of cation types are added dropwise
The mix monomer M of hydrophilic radical2Mixture, oleophylic section on block or grafting synthesis hydrophilic section Pw；
70~95 DEG C are cooled to, organic acid neutralizing agent is added, 10~30 min are stirred；The degree of neutralization for making solution is 80~130
%；
In step c resulting polymers solution, by the amount of calculation of required solid content it is uniform, deionized water, 1~3 h are added dropwise at a slow speed
Interior completion of dropping, is down to room temperature, that is, obtains the secondary breakup of the cation-type water-thinned Hydroxylated acrylic resin with core shell structure
Body.
3. method according to claim 2, it is characterised in that described step a's concretely comprises the following steps：Protected in inert atmosphere
Under shield, 5~20 parts of solvents and 0.1~0.8 part of initiator are added into reaction vessel, stirring is warming up to 120~170 DEG C, insulation 0
~30 min, at the uniform velocity 0.5~6 part of initiator of dropwise addition, 0~2 part of chain-transferring agent and 50~80 parts are free of cationic hydrophilic groups
Mix monomer M1Mixture, drip off in 1~3 h, continue to be incubated 0~30 min；Described is free of cationic hydrophilic base
The mix monomer M of group1Composition and weight/mass percentage composition be：
Acrylic acid alkyl or alicyclic esters monomer：50~70%；
Hydroxy acryl acid esters monomer：10~35%；
Vinyl monomer：0~20%.
4. method according to claim 2, it is characterised in that described step b's concretely comprises the following steps：Mixed obtained by step a
Close the mix monomer M that 0.5~2 part of initiator and 20~50 parts of cation type hydrophilic radicals are added dropwise in liquid2Mixture, 0.5
Dripped off in~2 h, continue to be incubated 1~2 h；The mix monomer M of described cation type hydrophilic radical2The composition and quality of sum
Percentage composition is：
Acrylic acid alkyl or alicyclic esters monomer：50~70%；
Hydroxy acryl acid esters monomer：10~35%；
Acrylic monomer containing tertiary amine groups：3~15%；
Vinyl monomer：0~20%.
5. the method according to claim 3 or 4, it is characterised in that described alkyl acrylate base class monomer is：Acrylic acid or
C1~C18 of methacrylic acid Arrcostab.
6. the method according to claim 3 or 4, it is characterised in that the alicyclic esters monomer of described acrylic acid is：Propylene
Sour cyclohexyl, acrylic acid -4- t-butyl cyclohexyl methacrylates, isobornyl acrylate cyclohexyl methacrylate, methacrylic acid -4- uncles
Butylcyclohexyl ester or isobornyl methacrylate.
7. the method according to claim 3 or 4, it is characterised in that described hydroxy acryl acid esters monomer is：Propylene
Sour hydroxyl ethyl ester, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate or methyl-prop
Olefin(e) acid hydroxy butyl ester.
8. method according to claim 4, it is characterised in that described acrylic monomer containing tertiary amine groups is：Acrylic acid two
Methylamino ethyl ester, acrylic acid diethylamino ethyl ester, acrylate propyl ester, acrylic acid dibutylamino propyl ester,
Dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, dimethylamine propyl ester and
At least one of methacrylic acid dibutylamino propyl ester.
9. according to the method described in claim 3 or 4, it is characterised in that described vinyl monomer is：Styrene, vinyl first
Benzene, vinyl naphthalene, acrylonitrile or methacrylonitrile.
10. method according to claim 2, it is characterised in that described organic acid is：Acetic acid, propionic acid, butyric acid, octanoic acid, lactic acid,
At least one of phosphoric acid, phosphate and p-methyl benzenesulfonic acid.
11. method according to claim 2, it is characterised in that described solvent is:200# solvent naphthas, 100# solvent naphthas, acetone,
MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, ethylene glycol, the third two
Alcohol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, butyl, ethylene glycol ether acetate, 2-Butoxyethyl acetate, third
Glycol methyl ether, propylene-glycol ethyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene, the third two
At least one of alcohol methyl ether acetate and propylene-glycol ethyl ether acetate.
12. method according to claim 2, it is characterised in that described initiator is：Azodiisobutyronitrile, azo two different heptan
The tertiary fourth of nitrile, benzoyl peroxide, dilauroyl peroxide, di t-amyl peroxide, di-t-butyl peroxide, perbenzoic acid
Ester, tert-butyl peroxy acetate, cumyl peroxide, isopropyl benzene hydroperoxide, cumyl t-butyl peroxide, peroxidating -2-
Thylhexoic acid spy pentyl ester, the peroxidating pivalic acid tert-butyl ester, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -3,5,5- trimethyls
Hecanoic acid t-butyl ester or peroxidating acetic acid tert-pentyl ester.
13. method according to claim 2, it is characterised in that described chain-transferring agent is a-Methylstyrene Low-Polymer or sulfydryl
Ethanol thio-alcohol.
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| CN110054976B (en) * | 2019-04-19 | 2020-11-20 | 华南理工大学 | Aqueous hydroxy acrylic acid dispersoid modified by multi-heterocyclic acrylate monomer and preparation method thereof |
| CN110283510A (en) * | 2019-04-24 | 2019-09-27 | 武汉仕全兴新材料科技股份有限公司 | A kind of woodcare paint high-permeability acrylic acid secondary breakup body and preparation method thereof |
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