CN109608575A - A kind of hydroxyl polyacrylate second level aqueous dispersion and preparation method thereof - Google Patents
A kind of hydroxyl polyacrylate second level aqueous dispersion and preparation method thereof Download PDFInfo
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- CN109608575A CN109608575A CN201811549053.3A CN201811549053A CN109608575A CN 109608575 A CN109608575 A CN 109608575A CN 201811549053 A CN201811549053 A CN 201811549053A CN 109608575 A CN109608575 A CN 109608575A
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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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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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
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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Abstract
The present invention relates to a kind of aqueous hydroxy acryl acid resin secondary breakup bodies and preparation method thereof, it is mainly prepared according to the following steps by the component of following mass parts: 1-3 parts of cosolvent, 0.5-2 parts of carboxyl group-containing monomer, 5-15 parts of hydroxyl monomer, 15-35 parts of acrylate monomer, 5-15 parts of vinyl monomer, 0.5-1 parts of initiator, 0.5-2 parts of neutralizer, 48-55 parts of deionized water, aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention, using two-stage polymerization process, the carboxyl in copolymer is set to be arranged in the molecule chain end of copolymer, in this way during phase inversion, polymer being capable of preferably hydrophilic dispersion, and it can be under the conditions of very low acid value, prepare aqueous hydroxy acryl acid resin secondary breakup body.
Description
Technical field
The present invention relates to belong to technical field of coatings, and in particular to a kind of aqueous hydroxy acryl acid resin secondary breakup body
And preparation method thereof.
Background technique
Traditional solvent borne polyurethane coating because its adhesive force is strong, elastic adjustable, high temperature resistant and low temperature, solvent resistant, it is wear-resisting,
The advantages that gloss is high, film is plentiful is widely used in various fields, but its containing toluene, dimethylbenzene etc. to environment and
The organic solvent of human hazard.Aqueous polyurethane coating has many advantages, such as nontoxic, non-ignitable, free from environmental pollution, the saving energy,
Gradually replace traditional solvent reducible coatings, meets the direction of paint development.
Water-based acrylic resin has the characteristics that excellent film forming, good weatherability, splendid guarantor's color gloss retention, extensively
The general covering with paint applied to fields such as exterior wall, woodenware, metal, plastic and glasses.By isocyanate curing agent and hydroxyl aqueous third
The double-component waterborne polyurethane of olefin(e) acid resin cross-linking and curing reaction, due to film crosslink density height, with excellent physical mechanical
Performance and chemical mediator-resitant property can replace same type solvent based product to be used as automobile coating, high-class woodenware paint, plastic paint and industry
Anticorrosive paint etc..
Water soluble acrylic acid ester dispersion is generally divided into level-one dispersion and secondary breakup body.Acrylate level-one dispersion is not
It is to polymerize acrylate monomer in water phase to obtain, polymer molecular weight is big, lotion containing solvent
Partial size it is larger, appearance is in milky white, and due to the presence of emulsifier, and often water resistance is bad for paint film.Use this dispersion
The amino-stoving varnish gloss of preparation is usually lower, and appearance is undesirable.Acrylate secondary breakup body is then to first pass through polymerisation in solution to obtain
Hydrophilic radical is partly or entirely neutralized into salt to the resin containing hydrophilic radical, then with neutralizer, finally by phase transfer process
It is dispersed in water.It compares, is prepared using the acrylate secondary breakup body of hydroxyl aqueous double with level-one dispersion
Component polyurethane coating, gloss of film is high, richness is good, and appearance can match in excellence or beauty solvent type dual-component polyurethane.
In order to pursue dispersibility and storage stability, most of acrylate secondary breakup body (anionic) exists at present
More carboxyl is introduced when synthesis, to improve the acid value of resin, water-fast, the alkali resistance of Hydroxylated acrylic resin is caused to go out
It now drops, and the raising of acid value keeps the viscosity of resulting dispersion larger, solid content can not improve.In the higher situation of acid value,
The polyurethane coating water resistance of preparation is poor, is suitable only for for preparing amino Baking Paint.Chinese patent CN101914185A and
For CN102850703A in order to reduce the viscosity of system, the solvent being added in reaction process is more, but the later period do not remove to
Cause the VOC content of product higher.Chinese patent CN104356291A provides a kind of water-based hydroxyl acrylic acid of simple process
The preparation method of resin, but its polymerization temperature is too low, the response type dilution dosage of introducing again considerably less (less than 4%), synthesizes
Resin viscosity is very big in the process, and in the case where cosolvent additive amount is few, a possibility that realization is non-in actual production operation
It is often small, and since resin viscosity is excessive, the inhomogeneity for neutralizing emulsification causes the storage stability of resin very poor.In addition,
Under lower reaction temperature, reactive lower, the remaining tertiary carbonic acid glycidyl ester pair of tertiary carbonic acid glycidyl ester and carboxyl
The performance of resin and coating generates adverse effect.Chinese patent CN201610446235.2, CN201710503885.0 and
CN201710562230.0 participates in reaction by introducing reactive diluent, reduces system viscosity, to improve solid content, but is turning
Dispersion can not be overcome to be converted into the viscosity occurred during oil-in-water O/W type by Water-In-Oil w/o type when phase to sharply increase
The problem of, since resinous acid value is low, there is no high speed dispersion to be difficult to emulsify when adding water dispersion, or even additional response type is also needed to emulsify
Agent increases production cost.
It is necessary to provide a kind of preparation methods of aqueous hydroxy acryl acid resin secondary breakup body as a result, existing to solve
The problem of with the presence of technology.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of aqueous two fractions of hydroxy acryl acid resin
Granular media and preparation method thereof, method of the invention use two-stage polymerization process, and the carboxyl of dispersion is made to be arranged in point of copolymer
Subchain tail end, while using the phase transfer process of oil droplet water, polymer is gradually diluted in the aqueous solution of neutralizer, in this way can
Preferably phase inversion, and stable aqueous hydroxy acryl acid resin secondary breakup can be prepared under the conditions of very low acid value
Body.
The invention is realized by the following technical scheme
Scheme one:
A kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body, is mainly pressed by the component of following mass parts
It is prepared according to following steps: 1~3 part of cosolvent, 0.5~2 part of carboxyl group-containing monomer, 5~15 parts of hydroxyl monomer, acrylate
15~35 parts of monomer, 5~15 parts of vinyl monomer, 0.5~1 part of initiator, 0.5~2 part of neutralizer, deionized water 48~55
Part,
Including following preparation step:
(1) carboxyl group-containing monomer, hydroxyl monomer, acrylate monomer, vinyl monomer are mixed into mix monomer,
Then it is continually fed into nitrogen into reaction kettle and excludes aqueous vapor, air, then adds cosolvent, stirring is warming up to assigned temperature,
Start that first part's mix monomer and first part's initiator is added dropwise, dripped off in 2~3 hours, keeps the temperature 0.5~1 hour, it is described
First part's mix monomer account for 50~80wt% of mix monomer total amount, first part's mix monomer and first part
The mass ratio of initiator is 100:1.4-2.4；
(2) it keeps temperature-resistant to continue that second part mix monomer and second are added dropwise into the material that step (1) obtains
Divide initiator, dripped off in 2~3 hours, keeps the temperature 1~2 hour, the second part mix monomer and second part initiator
Mass ratio be 100:1.4-2.4；
(3) cosolvent (130 DEG C, under the conditions of 0.01MPa, decompression vacuum pumping 1h) are evaporated under reduced pressure out, nitrogen is then passed to, obtains
To copolymer solids；
(4) deionized water and neutralizer are added in thinning tank, stirs and is warming up to 60-70 DEG C；
(5) copolymer solids in reaction kettle are heated to 100-140 DEG C, then instill step within 2~3 hour time
(4) in the thinning tank described in, while keeping the temperature of dispersion in thinning tank is 70-80 DEG C；
(6) it keeps temperature-resistant after dripping off, Part III initiator is added dropwise, filtering and discharging after keeping the temperature 0.5~1 hour, i.e.,
Obtain the aqueous hydroxyl polyacrylate aqueous dispersion.
Preferably, decomposition temperature of step (1) specific temperature for the half-life period of initiator used in polymerization reaction, step
(1) specified time is 2~3 hours in.The temperature of half-life period is 1~3 hour.
Preferably, the mix monomer of carboxyl group-containing monomer described in step (2) is carboxyl group-containing monomer, hydroxyl monomer, propylene
The mixture of acid ester monomer, vinyl monomer.
Preferably, the cosolvent is acetone, methyl ethyl ketone, butyl acetate, No. 100 solvent naphthas, No. 200 solvent naphthas, two
Toluene, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, dipropyl two
Alcohol methyl ether, dipropylene, dimethyl ether, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol first
One of ether acetate or propylene-glycol ethyl ether acetate any two or more are mixed according to arbitrary proportion.
Preferably, the carboxyl group-containing monomer is in acrylic acid, methacrylic acid, itaconic acid, fumaric acid or maleic acid
It is one or any two or more to be mixed according to arbitrary proportion.
Preferably, the hydroxyl monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl-prop
One of olefin(e) acid hydroxyl ethyl ester, hydroxy propyl methacrylate or methacrylate are any two or more according to any
Ratio mixes.
Preferably, the acrylate monomer is that methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid are different
Butyl ester, tert-butyl acrylate, acrylic acid-2-ethyl caproite, octadecyl acrylate, glycidyl acrylate, acrylic acid
Cyclohexyl, acrylic acid -4- t-butyl cyclohexyl methacrylate, Isooctyl acrylate monomer, isobornyl acrylate, methyl methacrylate, methyl
Ethyl acrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid benzene first
Ester, methacrylic acid -2- ethylhexyl, octadecyl methacrylate, glycidyl methacrylate, methacrylic acid
One of isobornyl thiocyanoacetate, cyclohexyl methacrylate or methacrylic acid -4- t-butyl cyclohexyl methacrylate are any two or more
It is mixed according to arbitrary proportion.
Preferably, the vinyl monomer is styrene, p-methylstyrene, vinyl acetate, tertiary ethylene carbonate
VeoVa9, acrylamide, N hydroxymethyl acrylamide, Diacetone Acrylamide, m- methyl styrene, acrylonitrile or methyl-prop
One of alkene nitrile any two or more is mixed according to arbitrary proportion.
Preferably, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, two t-amyl peroxy compounds, two tertiary fourths
Base peroxide, tert-butyl hydroperoxide, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxidating tert-butyl acetate, mistake
Aoxidize t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -2 ethyl hexanoic acid
Tert-pentyl ester, the peroxidating trimethylacetic acid tert-butyl ester, potassium peroxydisulfate, ammonium persulfate, sodium chlorate, sodium sulfite, sodium hydrogensulfite or company two
One of sodium sulfite any two or more is mixed according to arbitrary proportion.
Preferably, the neutralizer is ammonium hydroxide, triethylamine, triethanolamine, dimethylethanolamine, 2- methyl-2-amino third
One of alcohol, dimethylisopro panolamine, methyl diethanolamine, ethyl diisopropylamine or diethyl ethylene diamine are two kinds any
It is mixed above according to arbitrary proportion.
Scheme two:
The aqueous hydroxy acryl acid resin second level that preparation method described in a kind of any of the above-described embodiment is prepared
Dispersion.
On the one hand acrylic resin secondary breakup body needs first to be added neutralizer and carries out to resin in traditional phase transfer process
Salt-forming reaction causes neutralization reaction not even if the reaction also results in resin viscosity in the presence of a solvent and steeply rises
It is uniform；On the other hand, when adding water dispersion to resin after neutralization reaction, due to can be undergone in dispersion process inversion process (with
The dispersion that increases of dampening additional amount is converted into O/W type by w/o type), the viscosity change of system is very big, starts to be diluted with water
When, viscosity decline is very fast, and resin viscosity increased dramatically again when continuing to be diluted with water, reach after maximum value viscosity again sharply under
Drop, the dispersion process need sufficiently strong shearing force, otherwise easily cause the inhomogenous of emulsification.The present invention solves existing aqueous
Needed in acrylic resin secondary breakup production procedure high-speed stirred disperse and exist neutralize, emulsify it is inhomogenous caused by resin
The bad problem of storage stability.
Compared to the prior art, the beneficial effects of the present invention are:
(1) the aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention is made altogether using two-stage polymerization process
Carboxyl in polymers is arranged in the molecule chain end of copolymer, and in this way during phase inversion, polymer can preferably hydrophilic point
It dissipates, and aqueous hydroxy acryl acid resin secondary breakup body can be prepared under the conditions of very low acid value；
(2) the aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention, using slowly copolymer is added dropwise
Dispersing technology into water, compared with traditional dispersing technology being diluted with water into resin, the neutralization emulsification degree of resin is more
Uniform, dispersions obtained stability is higher.
(3) phase is not present in the aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention during phase inversion
Reversion, system is always oil-in-water state, and compared with traditional phase transfer process, phase inversion is easier, and does not need high-speed stirred.
(4) the aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention, since acid value is low, phase inversion process is viscous
It spends low, therefore can be made that viscosity is low, hydroxy acryl acid resin secondary breakup body of solid content 50% or so；Simultaneously as
With lower acid value, water resistance is substantially better than general polyacrylate dispersion；
(5) the aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention, using the technique of " afterwards remove residual list ",
Residual monomer is removed again after the completion of copolymer phase inversion, it is in and preceding except compared with residual single technique with tradition, since system is viscous
Spend it is much lower, except it is residual it is single it is more efficient more thoroughly.
(6) the aqueous hydroxy acryl acid resin secondary breakup body obtained by the present invention, with water-compatible amino resin or aqueous
The film that diisocyanate curing agent prepares has the characteristics that gloss is high, hardness is high, chemical-resistant is excellent.
Specific embodiment
The present invention is further described With reference to embodiment: but it is not only limited only to following embodiment,
All any improvement or replacement according to the principle of the invention, should all be within protection scope of the present invention.
(1) embodiment
A kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body, it is characterised in that: mainly by following matter
The component of amount part is prepared according to the following steps: 1~3 part of cosolvent, 0.5~2 part of carboxyl group-containing monomer, hydroxyl monomer 5~
15 parts, 15~35 parts of acrylate monomer, 5~15 parts of vinyl monomer, 0.5~1 part of initiator, 0.5~2 part of neutralizer, go
48~55 parts of ionized water,
Including following preparation step:
(1) carboxyl group-containing monomer, hydroxyl monomer, acrylate monomer, vinyl monomer are mixed into mix monomer,
Then it is continually fed into nitrogen into reaction kettle and excludes aqueous vapor, air, then adds cosolvent, stirring is warming up to assigned temperature,
Start that first part's mix monomer and first part's initiator is added dropwise, dripped off in 2~3 hours, keeps the temperature 0.5~1 hour, it is described
First part's mix monomer account for 50~80wt% of mix monomer total amount, first part's mix monomer and first part
The mass ratio of initiator is 100:1.4-2.4；
(2) it keeps temperature-resistant to continue that second part mix monomer and second are added dropwise into the material that step (1) obtains
Divide initiator, dripped off in 2~3 hours, keeps the temperature 1~2 hour, the second part mix monomer and second part initiator
Mass ratio be 100:1.4-2.4；
(3) cosolvent (130 DEG C, under the conditions of 0.01MPa, decompression vacuum pumping 1h) are evaporated under reduced pressure out, nitrogen is then passed to, obtains
To copolymer solids；
(4) deionized water and neutralizer are added in thinning tank, stirs and is warming up to 60-70 DEG C；
(5) copolymer solids in reaction kettle are heated to 100-140 DEG C, then instill step within 2~3 hour time
(4) in the thinning tank described in, while keeping the temperature of dispersion in thinning tank is 70-80 DEG C；
(6) it keeps temperature-resistant after dripping off, Part III initiator is added dropwise, filtering and discharging after keeping the temperature 0.5~1 hour, i.e.,
Obtain the aqueous hydroxyl polyacrylate aqueous dispersion.
Preferably, decomposition temperature of step (1) specific temperature for the half-life period of initiator used in polymerization reaction, step
(1) specified time is 2~3 hours in.The temperature of half-life period is 1~3 hour.
Preferably, the mix monomer of carboxyl group-containing monomer described in step (2) is carboxyl group-containing monomer, hydroxyl monomer, propylene
The mixture of acid ester monomer, vinyl monomer.
Preferably, the cosolvent is acetone, methyl ethyl ketone, butyl acetate, No. 100 solvent naphthas, No. 200 solvent naphthas, two
Toluene, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, dipropyl two
Alcohol methyl ether, dipropylene, dimethyl ether, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol first
One of ether acetate or propylene-glycol ethyl ether acetate any two or more are mixed according to arbitrary proportion.
Preferably, the carboxyl group-containing monomer is in acrylic acid, methacrylic acid, itaconic acid, fumaric acid or maleic acid
It is one or any two or more to be mixed according to arbitrary proportion.
Preferably, the hydroxyl monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl-prop
One of olefin(e) acid hydroxyl ethyl ester, hydroxy propyl methacrylate or methacrylate are any two or more according to any
Ratio mixes.
Preferably, the acrylate monomer is that methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid are different
Butyl ester, tert-butyl acrylate, acrylic acid-2-ethyl caproite, octadecyl acrylate, glycidyl acrylate, acrylic acid
Cyclohexyl, acrylic acid -4- t-butyl cyclohexyl methacrylate, Isooctyl acrylate monomer, isobornyl acrylate, methyl methacrylate, methyl
Ethyl acrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid benzene first
Ester, methacrylic acid -2- ethylhexyl, octadecyl methacrylate, glycidyl methacrylate, methacrylic acid
One of isobornyl thiocyanoacetate, cyclohexyl methacrylate or methacrylic acid -4- t-butyl cyclohexyl methacrylate are any two or more
It is mixed according to arbitrary proportion.
Preferably, the vinyl monomer is styrene, p-methylstyrene, vinyl acetate, tertiary ethylene carbonate
VeoVa9, acrylamide, N hydroxymethyl acrylamide, Diacetone Acrylamide, m- methyl styrene, acrylonitrile or methyl-prop
One of alkene nitrile any two or more is mixed according to arbitrary proportion.
Preferably, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, two t-amyl peroxy compounds, two tertiary fourths
Base peroxide, tert-butyl hydroperoxide, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxidating tert-butyl acetate, mistake
Aoxidize t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -2 ethyl hexanoic acid
Tert-pentyl ester, the peroxidating trimethylacetic acid tert-butyl ester, potassium peroxydisulfate, ammonium persulfate, sodium chlorate, sodium sulfite, sodium hydrogensulfite or company two
One of sodium sulfite any two or more is mixed according to arbitrary proportion.
Preferably, the neutralizer is ammonium hydroxide, triethylamine, triethanolamine, dimethylethanolamine, 2- methyl-2-amino third
One of alcohol, dimethylisopro panolamine, methyl diethanolamine, ethyl diisopropylamine or diethyl ethylene diamine are two kinds any
It is mixed above according to arbitrary proportion.
(2) specific embodiment
Embodiment 1
It is passed through nitrogen into four mouthfuls of reaction flask A, the 100# solvent naphtha of 200g is added in reaction flask, stirring is warming up to 140-
150 DEG C, start that 144g hydroxy-ethyl acrylate, 151.2g methyl methacrylate, 54g butyl acrylate, 78g metering system is added dropwise
Speed is added dropwise in tert-butyl hydroperoxide -3,5 of sour N-butyl, the mixture of 154.8g styrene and 9g, 5- tri-methyl hexanoic acid ester, control
Degree uniformly, drips off in 3h, after 45min is kept the temperature after dripping off starts that 31g acrylic acid, 96g hydroxy-ethyl acrylate, 100.8g first is added dropwise
The tertiary fourth of base methyl acrylate, 36g butyl acrylate, 52g n-BMA, the mixture of 103.2g styrene and 6g
Base peroxidating -3,5,5- tri-methyl hexanoic acid ester, at the uniform velocity drips off in 2h, keeps the temperature 1.5h, is evaporated under reduced pressure out 100# solvent naphtha, makes to remain
Lower 30g, is filled with nitrogen；Another four mouthfuls of reaction flask B is taken, 1000g deionized water and 33g dimethylethanolamine, stirring is added
It is warming up at 60-70 DEG C, 100-130 DEG C and the resin in reaction flask A is added drop-wise in reaction flask B, dripped off in 2~3h, keep anti-
It answers the temperature in bottle at 70-80 DEG C, drips off and keep temperature-resistant, be added at one time 3g tert-butyl hydroperoxide, after stirring 5min,
The hydrosulfurous acid sodium water solution that 20g concentration is 0.8wt% is at the uniform velocity added dropwise in 30min, keeps the temperature rear filtering and discharging after 30min,
Obtain the aqueous hydroxyl polyacrylate aqueous dispersion.
The solid content 50% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 260mPas, acid value
22mgKOH/g, hydroxyl value 114mgKOH/g.
Embodiment 2
It is passed through nitrogen into four mouthfuls of reaction flask A, the butyl acetate of 200g/dimethylbenzene mixed liquor is added in reaction flask, is stirred
Mix and be warming up to 140-150 DEG C, start be added dropwise 182g hydroxypropyl acrylate, 196g methyl methacrylate, 42g butyl acrylate,
Two uncles penta of 70g n-BMA, 126g styrene, the mixture of 56g tertiary ethylene carbonate VeoVa 9 and 12.6g
Base peroxide, control rate of addition it is uniform, dripped off in 2.5h, after dripping off keep the temperature 30min after start be added dropwise 34g acrylic acid,
78g hydroxypropyl acrylate, 84g methyl methacrylate, 18g butyl acrylate, 30g n-BMA, 54g benzene second
Two t-amyl peroxy compounds of alkene, the mixture of 24g tertiary ethylene carbonate VeoVa 9 and 5.4g, at the uniform velocity drip off in 2h, heat preservation
2h is evaporated under reduced pressure out solvent, makes remaining 30g, is filled with nitrogen；Another four mouthfuls of reaction flask B is taken, 1000g deionized water is added
With 36g dimethylethanolamine, mixing speed 300r/min is warming up to the resin in reaction flask A at 60-70 DEG C, 100-130 DEG C
It is added drop-wise in reaction flask B, is dripped off in 2~3h, keep the temperature in reaction flask at 70-80 DEG C, drip off and keep temperature-resistant, once
Property be added 3g tert-butyl hydroperoxide, stir 5min after, be at the uniform velocity added dropwise in 30min 29g concentration be 0.8wt% sodium sulfite
Aqueous solution keeps the temperature rear filtering and discharging after 30min, obtains the aqueous hydroxyl polyacrylate aqueous dispersion.
The solid content 50% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 300mPas, acid value
26mgKOH/g, hydroxyl value 110mgKOH/g.
Embodiment 3
It is passed through nitrogen into four mouthfuls of reaction flask A, the propandiol butyl ether of 200g is added in reaction flask, stirring is warming up to 140-
150 DEG C, it is different pungent to start dropwise addition 252.24g methacrylate, 67.56g methymethacrylate, 58.08g acrylic acid
Ester, 58.4g glycidyl acrylate, 102.4g Tert-butyl Methacrylate, 84g m-methyl styrene mixture and
The peroxide -2-ethyl hexanoic acid tert-butyl of 14.72g, control rate of addition is uniform, drips off in 3h, after keeping the temperature 60min after dripping off
It is different to start dropwise addition 42g itaconic acid, 63.06g methacrylate, 16.89g methyl methacrylate, 14.52g acrylic acid
Monooctyl ester, 14.6g glycidyl acrylate, 25.6g Tert-butyl Methacrylate, 21g m-methyl styrene mixture and
The peroxide -2-ethyl hexanoic acid tert-butyl of 3.68g, at the uniform velocity drips off in 2h, keeps the temperature 1.5h, is evaporated under reduced pressure out solvent, makes to be left
63g is filled with nitrogen；Another four mouthfuls of reaction flask B is taken, 1156g deionized water and 41.58g diethyl ethylene diamine, stirring is added
Speed 300r/min is warming up at 60-70 DEG C, 100-130 DEG C and the resin in reaction flask A is added drop-wise in reaction flask B, 2~3h
It inside drips off, keeps the temperature in reaction flask at 70-80 DEG C, drip off and keep temperature-resistant, be added at one time 2.6g ammonium persulfate, protect
Filtering and discharging after after warm 30min obtains the aqueous hydroxyl polyacrylate aqueous dispersion.
The solid content 48% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 620mPas, acid value
31mgKOH/g, hydroxyl value 129mgKOH/g.
Embodiment 4
It is passed through nitrogen into four mouthfuls of reaction flask A, the propylene glycol methyl ether acetate of 200g is added in reaction flask, stirring heating
To 140-150 DEG C, start that 141.18g hy-droxybutyl, 48.4g methymethacrylate, 66.04g methacrylic acid is added dropwise
Isobornyl thiocyanoacetate, 73.45g glycidyl methacrylate, 103.68g benzyl methacrylate, 138.58g vinyl acetate,
The mixture of 66.43g tertiary ethylene carbonate VeoVa9 and the di-tert-butyl peroxide of 12.29g, control rate of addition is uniform,
It is dripped off in 3h, after 60min is kept the temperature after dripping off starts that 10.5g fumaric acid, 76.02g hy-droxybutyl, 26.06g methyl is added dropwise
Methacrylate, 35.56g isobornyl methacrylate, 39.55g glycidyl methacrylate, 55.83g metering system
Sour benzene methyl, 74.62g vinyl acetate, the mixture of 35.77g tertiary ethylene carbonate VeoVa9 and 6.62g di-t-butyl peroxide
Compound at the uniform velocity drips off in 2h, keeps the temperature 1.5h, is evaporated under reduced pressure out solvent, makes remaining 21g, is filled with nitrogen；Take another four mouthfuls
Reaction flask B, is added 1051g deionized water and 17.4g triethylamine, mixing speed 300r/min are warming up to 60-70 DEG C, 100-130
The resin in reaction flask A is added drop-wise in reaction flask B at DEG C, is dripped off in 2~3h, keeps the temperature in reaction flask at 70-80 DEG C,
It drips off and keeps temperature-resistant, be added at one time 2.1g potassium peroxydisulfate, filtering and discharging after keeping the temperature after 30min obtains described aqueous
Hydroxyl polyacrylate aqueous dispersion.
The solid content 49% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 580mPas, acid value
15mgKOH/g, hydroxyl value 89mgKOH/g.
Embodiment 5
It is passed through nitrogen into four mouthfuls of reaction flask A, 2-Butoxyethyl acetate/methyl ethyl ketone of 200g is added in reaction flask,
Stirring is warming up to 140-150 DEG C, starts that 68.38g hydroxypropyl acrylate, 140.79g methacrylate, 68.64g acrylic acid is added dropwise
Cyclohexyl, 101.73g glycidyl acrylate, 167.05g octadecyl acrylate, 34.45g methacrylonitrile,
The mixture of 33.93g p-methylstyrene and peroxide acid tert-amyl acetate/azobisisoheptonitrile of 12.29g, control are added dropwise
Speed is uniform, drips off in 3h, after dripping off keep the temperature 45min after start be added dropwise 42g maleic anhydride, 36.82g hydroxypropyl acrylate,
75.81g methacrylate, 36.96g cyclohexyl acrylate, 54.78g glycidyl acrylate, 89.95g octadecyl
Base ester, 18.55g methacrylonitrile, the mixture of 18.27g p-methylstyrene and 6.62g peroxide acid tert-amyl acetate/
Azobisisoheptonitrile at the uniform velocity drips off in 2h, keeps the temperature 1.5h, is evaporated under reduced pressure out solvent, makes remaining 63g, is filled with nitrogen；It takes in addition
One four mouthfuls of reaction flask B, is added 1012.6g deionized water and 17.4g triethylamine, mixing speed 300r/min are warming up to 60-70
DEG C, the resin in reaction flask A is added drop-wise in reaction flask B at 100-130 DEG C, is dripped off in 2~3h, the temperature in reaction flask is kept
It at 70-80 DEG C, drips off and keeps temperature-resistant, 2.1g sodium chlorate/sodium sulfite is added portionwise, keep the temperature rear filtering and discharging after 30min,
Obtain the aqueous hydroxyl polyacrylate aqueous dispersion.
The solid content 49% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 450mPas, acid value
64mgKOH/g, hydroxyl value 42mgKOH/g.
Comparative example 1
It is passed through nitrogen into four mouthfuls of reaction flask A, the 100# solvent naphtha of 200g is added in reaction flask, stirring is warming up to 140-
150 DEG C, start that 144g hydroxy-ethyl acrylate, 151.2g methyl methacrylate, 54g butyl acrylate, 78g metering system is added dropwise
Speed is added dropwise in tert-butyl hydroperoxide -3,5 of sour N-butyl, the mixture of 154.8g styrene and 9g, 5- tri-methyl hexanoic acid ester, control
Degree uniformly, drips off in 3h, after 45min is kept the temperature after dripping off starts that 31g acrylic acid, 96g hydroxy-ethyl acrylate, 100.8g first is added dropwise
The tertiary fourth of base methyl acrylate, 36g butyl acrylate, 52g n-BMA, the mixture of 103.2g styrene and 6g
Base peroxidating -3,5,5- tri-methyl hexanoic acid ester, at the uniform velocity drips off in 2h, after keeping the temperature 1.5h, adds 3.16g tert-butyl hydroperoxide -
3,5,5- tri-methyl hexanoic acid esters continue to keep the temperature 1h, are evaporated under reduced pressure out 100# solvent naphtha, make remaining 30g, are filled with nitrogen；It is cooled to
70 DEG C, 33g dimethylethanolamine is added, stirring neutralizes 30min, keeps temperature-resistant, is vigorously stirred down (mixing speed 2000r/
Min), in instillation 1000g deionized water in 2~3h；Continue to stir 30min after dripping off, filtering and discharging obtains described aqueous contain
Hydroxy polyacrylate aqueous dispersion.
The solid content 50% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 1850mPas, acid value
22mgKOH/g, hydroxyl value 114mgKOH/g.
Comparative example 2
It is passed through nitrogen into four mouthfuls of reaction flask A, the butyl acetate of 200g/dimethylbenzene mixed liquor is added in reaction flask, is stirred
Mix and be warming up to 140-150 DEG C, start be added dropwise 182g hydroxypropyl acrylate, 196g methyl methacrylate, 42g butyl acrylate,
Two uncles penta of 70g n-BMA, 126g styrene, the mixture of 56g tertiary ethylene carbonate VeoVa 9 and 12.6g
Base peroxide, control rate of addition it is uniform, dripped off in 2.5h, after dripping off keep the temperature 30min after start be added dropwise 34g acrylic acid,
78g hydroxypropyl acrylate, 84g methyl methacrylate, 18g butyl acrylate, 30g n-BMA, 54g benzene second
Two t-amyl peroxy compounds of alkene, the mixture of 24g tertiary ethylene carbonate VeoVa 9 and 5.4g, at the uniform velocity drip off in 2h, heat preservation
2h, adds 3.23g tert-butyl hydroperoxide -3,5, and 5- tri-methyl hexanoic acid ester continues to keep the temperature 1h, is evaporated under reduced pressure out solvent, makes to be left
30g is filled with nitrogen；70 DEG C are cooled to, 36g dimethylethanolamine is added, stirring neutralizes 30min, keeps temperature-resistant, acutely stirs
(mixing speed 2000r/min) is mixed down, in instillation 1000g deionized water in 2~3h；Continue to stir 30min after dripping off, filter out
Material obtains the aqueous hydroxyl polyacrylate aqueous dispersion.
The solid content 50% of the aqueous hydroxy acryl acid resin secondary breakup body of gained, viscosity 2200mPas, acid value
26mgKOH/g, hydroxyl value 110mgKOH/g.
Performance test
Residual single test: respectively by two fraction of aqueous hydroxy acryl acid resin obtained in embodiment 1-5 and comparative example 1-2
Granular media is dissolved into homogeneous phase solution with dimethylformamide (DMF), with the total amount of gas chromatographic detection residual monomer.As a result such as table 1
It is shown.
It is placed at room temperature for stability: respectively by aqueous hydroxy acryl acid resin obtained in embodiment 1-5 and comparative example 1-2
Secondary breakup body is sealed in transparent plastic bottle, is placed at room temperature, and stability is observed.The results are shown in Table 1.
High speed centrifugation stability: respectively by aqueous hydroxy acryl acid resin obtained in embodiment 1-5 and comparative example 1-2
Secondary breakup body is centrifuged 30 minutes under the centrifugal rotational speed of 3000rpm, observes delamination.The results are shown in Table 1.
The stability of 1 sample to be tested of table
From the results shown in Table 1, two fraction of aqueous hydroxy acryl acid resin that preparation method of the invention obtains
Granular media has preferable stability and lower single residual content.
The resulting aqueous hydroxy acryl acid resin secondary breakup body of example 1-5 and comparative example 1 is prepared by the formula of table 2
Aqueous woodware paint, and be compared, the results are shown in Table 3.
2 woodenware lacquer formula of table
3 aqueous woodware paint test result of table
(note: series is fewer, and performance is more superior)
As can be known from the results of Table 3, aqueous hydroxy acryl acid resin secondary breakup body of the invention is formulated aqueous
Woodcare paint hardness with higher, preferable water resistance, solvent resistance and anti-pollution.
In conclusion the aqueous hydroxy acryl acid resin secondary breakup body that the present invention obtains has preferable stability,
It can place steadily in the long term at room temperature, for preparing aqueous woodware paint, obtained aqueous woodware paint hardness with higher, preferably
Water resistance, solvent resistance and anti-pollution.
Therefore, aqueous hydroxy acryl acid resin secondary breakup body of the invention can be on water paint or water paint extensively
Using.
Embodiment disclosed above, which only embodies, illustrates technical solution of the present invention, rather than protection model for the purpose of limiting the invention
It encloses, although explaining in detail referring to preferred embodiment to the present invention, any those skilled in the art, which should be appreciated that, not to be taken off
From modifying within the scope of technical solution of the present invention or various change, equivalent replacement, protection model of the invention all should belong to
It encloses.
Claims (10)
1. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body, it is characterised in that: mainly by following quality
Part component be prepared according to the following steps: 1-3 parts of cosolvent, 0.5-2 parts of carboxyl group-containing monomer, 5-15 parts of hydroxyl monomer,
15-35 parts of acrylate monomer, 5-15 parts of vinyl monomer, 0.5-1 parts of initiator, 0.5-2 parts of neutralizer, deionized water 48-
55 parts,
Including following preparation step:
(1) carboxyl group-containing monomer, hydroxyl monomer, acrylate monomer, vinyl monomer are mixed into mix monomer, then
It is continually fed into nitrogen into reaction kettle and excludes aqueous vapor, air, then adds cosolvent, stirring is warming up to assigned temperature, starts
First part's mix monomer and first part's initiator is added dropwise, is dripped off in 2~3 hours, keeps the temperature 0.5~1 hour, described the
A part of mix monomer accounts for 50~80wt% of mix monomer total amount, and first part's mix monomer and first part cause
The mass ratio of agent is 100:1.4-2.4；
(2) keep it is temperature-resistant continue second part mix monomer and second part are added dropwise into the material that step (1) obtains draw
Agent is sent out, is dripped off in 2~3 hours, keeps the temperature 1~2 hour, the matter of the second part mix monomer and second part initiator
Amount is than being 100:1.4-2.4；
(3) it is evaporated under reduced pressure out cosolvent, then passes to nitrogen, obtains copolymer solids；
(4) deionized water and neutralizer are added in thinning tank, stirs and is warming up to 60-70 DEG C；
(5) copolymer solids in reaction kettle are heated to 100-140 DEG C, then instilled step (4) within 2~3 hour time
In the thinning tank, while keeping the temperature of dispersion in thinning tank is 70-80 DEG C；
(6) it keeps temperature-resistant after dripping off, remaining initiator is added dropwise, filtering and discharging is after heat preservation 0.5~1 hour to get described
Aqueous hydroxyl polyacrylate aqueous dispersion.
2. the preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, it is characterised in that:
Step (1) specific temperature is the decomposition temperature of the half-life period of initiator used in polymerization reaction.
3. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the cosolvent is acetone, methyl ethyl ketone, butyl acetate, No. 100 solvent naphthas, No. 200 solvent naphthas, dimethylbenzene, ethylene glycol
Ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, dipropylene glycol methyl ether, dipropyl
Glycol butyl ether, dimethyl ether, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol methyl ether acetate or
One of propylene-glycol ethyl ether acetate any two or more is mixed according to arbitrary proportion.
4. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the carboxyl group-containing monomer is selected from one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid or maleic acid or appoints
It anticipates and two or more is mixed according to arbitrary proportion.
5. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the hydroxyl monomer be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate,
One of hydroxy propyl methacrylate or methacrylate or it is any it is two or more according to arbitrary proportion mixing and
At.
6. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the acrylate monomer is methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid
The tert-butyl ester, acrylic acid-2-ethyl caproite, octadecyl acrylate, glycidyl acrylate, cyclohexyl acrylate, propylene
Acid -4- t-butyl cyclohexyl methacrylate, Isooctyl acrylate monomer, isobornyl acrylate, methyl methacrylate, ethyl methacrylate,
N-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, benzyl methacrylate, metering system
Acid -2- ethylhexyl, octadecyl methacrylate, glycidyl methacrylate, isobornyl methacrylate, first
One of base cyclohexyl acrylate or methacrylic acid -4- t-butyl cyclohexyl methacrylate are any two or more according to arbitrary proportion
It mixes.
7. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the vinyl monomer is styrene, p-methylstyrene, vinyl acetate, tertiary ethylene carbonate VeoVa9, acryloyl
One of amine, N hydroxymethyl acrylamide, Diacetone Acrylamide, m- methyl styrene, acrylonitrile or methacrylonitrile or
Person is arbitrarily two or more to be mixed according to arbitrary proportion.
8. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the initiator be azodiisobutyronitrile, azobisisoheptonitrile, two t-amyl peroxy compounds, di-tert-butyl peroxide,
Tert-butyl hydroperoxide, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, peroxidating tert-butyl acetate, perbenzoic acid
The tert-butyl ester, peroxide acid tert-amyl acetate, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -2 ethyl hexanoic acid tert-pentyl ester, mistake
It aoxidizes in the trimethylacetic acid tert-butyl ester, potassium peroxydisulfate, ammonium persulfate, sodium chlorate, sodium sulfite, sodium hydrogensulfite or sodium dithionite
One or any two or more mixed according to arbitrary proportion.
9. a kind of preparation method of aqueous hydroxy acryl acid resin secondary breakup body according to claim 1, feature
Be: the neutralizer is that ammonium hydroxide, triethylamine, triethanolamine, dimethylethanolamine, 2- methyl-2-amino propyl alcohol, dimethyl are different
One of Propanolamine, methyl diethanolamine, ethyl diisopropylamine or diethyl ethylene diamine are any two or more according to appointing
Meaning ratio mixes.
10. a kind of aqueous hydroxy acryl acid resin secondary breakup body, it is characterised in that: by any one of claim 1-9
The method is prepared.
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| CN111978474A (en) * | 2020-08-25 | 2020-11-24 | 浙江恒川新材料有限公司 | Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper |
| CN112266438A (en) * | 2020-11-04 | 2021-01-26 | 三棵树(上海)新材料研究有限公司 | Methyl methacrylate polymer and preparation method and application thereof |
| CN112500522A (en) * | 2020-11-24 | 2021-03-16 | 商丘市博大化工有限公司 | Aqueous hydroxyl acrylic resin dispersion and preparation method thereof |
| CN112694794A (en) * | 2020-11-09 | 2021-04-23 | 上海澍瑞化工科技有限公司 | Low-temperature cured water-based acrylic baking varnish resin |
| CN112708005A (en) * | 2020-12-28 | 2021-04-27 | 安徽匠星联创新材料科技有限公司 | Hydroxy acrylic polymer capable of using oily curing agent and preparation method and application thereof |
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| CN111978474A (en) * | 2020-08-25 | 2020-11-24 | 浙江恒川新材料有限公司 | Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper |
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| CN112694794A (en) * | 2020-11-09 | 2021-04-23 | 上海澍瑞化工科技有限公司 | Low-temperature cured water-based acrylic baking varnish resin |
| CN112500522A (en) * | 2020-11-24 | 2021-03-16 | 商丘市博大化工有限公司 | Aqueous hydroxyl acrylic resin dispersion and preparation method thereof |
| CN112708005A (en) * | 2020-12-28 | 2021-04-27 | 安徽匠星联创新材料科技有限公司 | Hydroxy acrylic polymer capable of using oily curing agent and preparation method and application thereof |
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| CN112940203A (en) * | 2021-04-01 | 2021-06-11 | 惠州市安品新材料有限公司 | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof |
| CN113105592A (en) * | 2021-04-01 | 2021-07-13 | 深圳市安品有机硅材料有限公司 | Modified acrylic resin emulsion and preparation method thereof |
| CN113861350A (en) * | 2021-10-14 | 2021-12-31 | 王俊生 | Preparation method of polymerizable resin, ink and coating |
| CN114736593A (en) * | 2022-03-14 | 2022-07-12 | 雅图高新材料股份有限公司 | High-gloss water-based bi-component finish paint and preparation method and application thereof |
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