CN108059698A - A kind of preparation method of the hydroxyl acrylic aqueous dispersion of polyether polyol-unsaturated polyester modified - Google Patents
A kind of preparation method of the hydroxyl acrylic aqueous dispersion of polyether polyol-unsaturated polyester modified Download PDFInfo
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- CN108059698A CN108059698A CN201810004659.2A CN201810004659A CN108059698A CN 108059698 A CN108059698 A CN 108059698A CN 201810004659 A CN201810004659 A CN 201810004659A CN 108059698 A CN108059698 A CN 108059698A
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- unsaturated polyester
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- polyether polyol
- aqueous dispersion
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The present invention relates to a kind of preparation methods of the unsaturated polyester modified hydroxyl acrylic aqueous dispersion of polyether polyol, include the following steps：(1) organic epoxide, the compound containing active hydrogen group, solvent, catalyst and unsaturated polyester (UP) are mixed, is warming up to 140 145 DEG C, is stirred to react 0.5 1h and obtains reaction mixture；(2) initiator and acrylic ester monomer are added in two steps into the reaction mixture that step (1) obtains, after 1 2h is kept the temperature after being added dropwise, it is cooled to 75 80 DEG C, add in neutralizer, deionized water is added to be dispersed with stirring after 1 2h to get the hydroxyl acrylic aqueous dispersion that the polyether polyol is unsaturated polyester modified.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of hydroxy acrylic acid of polyether polyol-unsaturated polyester modified
The preparation method of dispersion.
Background technology
Aqueous two-component polyurethane is mainly by hydroxy functional group in water-based hydroxyl acrylic acid dispersion and aqueous polyisocyanate cyanogen
Acid esters curing agent solidification is crosslinked.Aqueous two-component polyurethane has many advantages, such as high gloss, colour retention and good weatherability, with
Economic and society development, the diversification in market and environmental requirement it is increasingly strict, the dosage of solvent type resin is increasingly
Control is arrived, water-base resin increasingly receives consumers in general and market because it waits clear superiorities with VOC content is low
Favor.Traditional hydroxyl acrylic aqueous dispersion prepared by acrylic ester monomer, solvent content is relatively high, it is relatively low to contain admittedly,
Viscosity is larger, and water resistance is also relatively poor, in addition, traditional water-based hydroxyl acrylic acid dispersion is since it is admittedly containing relatively low,
Cause its gloss, richness there is also to a certain degree the defects of.Therefore, there is an urgent need to seek one kind to effectively improve double groups
Divide the water resistance of polyurethane system paint film, reduce the viscosity of resin, the material contained of consolidating of raising dispersion replaces traditional poly- ammonia
Ester material.The present invention provides a kind of hydroxy of novel polyether polyol-unsaturated polyester modified to overcome these limitations
The preparation method of sour dispersion, Gu containing for 54 ± 1.0%, viscosity is 2100 ± 50mpa.s, hydroxyl value 5.2 ± 0.1, VOC content
26±4.0μg/g。
The content of the invention
The present invention provides a kind of preparation method of the hydroxyl acrylic aqueous dispersion of polyether polyol-unsaturated polyester modified,
It is characterized by comprising following steps：
(1) organic epoxide, the compound containing active hydrogen group, solvent, catalyst and unsaturated polyester (UP) are mixed, risen
Temperature is stirred to react 0.5-1h and obtains reaction mixture to 140-145 DEG C；
(2) initiator and acrylic ester monomer are added in two steps into the reaction mixture that step (1) obtains, drip
After keeping the temperature 1-2h after finishing, 75-80 is cooled tooC adds in neutralizer, deionized water is added to be dispersed with stirring after 1-2h to get the polyethers
The hydroxyl acrylic aqueous dispersion of polyalcohol-unsaturated polyester modified.
Organic epoxide described in step (1) be selected from ethylene oxide, propylene oxide, epoxychloropropane, epoxy butane,
One or more of furans, tetrahydrofuran；The compound containing active hydrogen group is selected from propylene glycol, glycerine, trihydroxy methyl
Propane, ethylenediamine pentaerythrite, xylitol, triethylene diamine, sorbierite, sucrose, bisphenol-A, bisphenol S, three (2- ethoxys) are different
Cyanate, toluenediamine, ethylene glycol, m-xylene diamine, ethylenediamine, isocyanates, butanediol, triethanolamine, n-butanol, isopropyl
Any one of alcohol；Solvent is Conventional solvents prepared by resin, preferably propylene glycol methyl ether acetate, propylene glycol diacetate, third
One kind in glycol ether；Catalyst is prepares the conventional catalyst of polyether polyol, and preferred alkali metal hydroxide is (such as
NaOH、KOH、CsOH)。
Initiator described in step (2) is selected from peroxidized t-butyl perbenzoate, tert-butyl peroxide, diphenyl peroxide first
In acyl, ammonium persulfate, azodiisobutyronitrile, peroxidized t-butyl perbenzoate, cumyl hydroperoxide or cumyl peroxide
One kind；Neutralizer is：Triethylamine, N, N- dimethylethanolamines, ammonium hydroxide or tripropyl amine (TPA), acrylic ester monomer are selected from acrylic acid
Methyl esters, ethyl acrylate, butyl acrylate, the mixing of one or more of methyl methacrylate, hydroxyethyl methacrylate.
The parts by weight of each component raw material are as follows in above-mentioned steps (1), (2)：
2-3 parts of organic epoxide, 2-5 parts of the compound containing active hydrogen group, 2-3 parts of solvent, catalyst 0.01-0.03
Part and 2-3 part of unsaturated polyester (UP), 1-2 parts of initiator, 30-40 parts of acrylic ester monomer, 4-6 parts of neutralizer, remaining be go from
Sub- water amounts to 100 parts.
Polyether polyol-unsaturated polyester modified hydroxy acrylic acid that the above-mentioned preparation method of the present invention is prepared disperses
Body, Gu containing for 54 ± 1.0%, viscosity is 2100 ± 50mpa.s, hydroxyl value 5.2 ± 0.1,26 ± 4.0 μ g/g of VOC content.
Another embodiment of the present invention provides above-mentioned polyether polyol-unsaturated polyester modified hydroxy acrylic acid and disperses
Application of the body in painting, coating.
Of the present invention to add in initiator and acrylic ester monomer in two steps, the preferably first step adds in half quality
Initiator and acrylic monomer；Second step adds in the initiator and acrylic monomer of remaining half quality.
Unsaturated polyester (UP) of the present invention, containing unsaturated double-bond, acid value is 10-25 milligram KOH/g solids, Gu contain and be
70-78%, the unsaturated polyester (UP) further preferably include acrylic copolymer.Purpose containing unsaturated double-bond primarily to
It is copolymerized effectively to be grafted with acrylic ester monomer by the unsaturated double-bond in polyester.It is interior containing acrylic acid
Purpose effectively realizes Water-borne modification, achievees the effect that self-emulsifying primarily to the later stage can be neutralized into salt with amine neutralizer.
Compared with prior art, the advantage of the invention is that：(1) present invention is using organic epoxide, active hydrogen chemical combination
Object, catalyst, a small amount of Conventional solvents not only for synthesizing polyether glycol, but also with unsaturated polyester (UP) (as bottoming solvent) one
The reaction medium as synthesis of hydroxy acrylic acid dispersion is played, the dosage of cosolvent can be efficiently reduced, so as to from source
Reduce VOC total amounts discharge (unsaturated polyester (UP) is not only as reaction medium, but also improves consolidating for system and contained, and reduces the usage amount of solvent,
Reduce VOC content)；(2) unsaturated polyester (UP) has many advantages, such as richness height, and flexibility is good, passes through the insatiable hunger in unsaturated polyester (UP)
It is copolymerized with double bond and acrylic ester monomer by free radical, so as to be grafted together, hydroxyl third can be effectively improved
The gloss and richness of olefin(e) acid dispersion；(3) organic epoxide and active hydrogen compounds generate under the effect of the catalyst
Polyether polyol, polyether polyol have stronger hydrophobicity, and polyether polyol is introduced into hydroxyl acrylic aqueous dispersion can
To effectively improve the water resistance of two-component polyurethane systems paint film, the viscosity of resin is reduced, consolidating for dispersion is improved and contains, separately
Outside, the introducing of polyether polyol also improves the gloss and richness of paint film to a certain extent；(4) hydroxyl prepared by the present invention
Acrylic acid dispersion has following features：It is 1. lower solvent content, environmental-friendly；2. high hydroxyl content relatively high is consolidated
Contain, relatively low viscosity；It is 3. richness, gloss, water-fast excellent；4. particle size distribution range is narrow, blue light is strong；5. relatively low cost,
Preparation process is simple, easily controllable, economic value is high.
Description of the drawings
The IR figures of Fig. 1 products A
The grain size distribution of Fig. 2 products A
Specific embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But
It is that these embodiments only are not used for limiting the scope of the present invention or implementation principle, reality of the invention for being better understood from inventing
The mode of applying is not limited to herein below.
The unsaturated polyester (UP) used in the embodiment of the present invention is bought from Changzhou Ke Xiang high molecular materials Co., Ltd, the insatiable hunger
Contain unsaturated double-bond with polyester, acid value is 10-25 milligrams of KOH/g solids, Gu containing being 70-78%, includes acrylic copolymer.
Embodiment 1
(1) it is propylene oxide 2g, butanediol 3.0g, propylene glycol methyl ether acetate 2g, potassium hydroxide 0.02g, unsaturation is poly-
Ester 2.0g is mixed, and is warming up to 140-145 DEG C, is stirred to react 0.5-1h and obtains reaction mixture；
(2) into the reaction mixture that step (1) obtains be added dropwise di-tert-butyl peroxide 0.5g and methyl acrylate 5g,
Methyl methacrylate 6g, butyl acrylate 4g after keeping the temperature 1h after being added dropwise, continue that remaining di-tert-butyl peroxide is added dropwise
Object 0.5g and methyl acrylate 5g, methyl methacrylate 6g, butyl acrylate 4g, after keeping the temperature 1-2h after being added dropwise, cooling
To 75-80oC, add in N, N dimethyl ethanolamine 4g is neutralized, after suitable deionized water is added to be dispersed with stirring 1-2h, discharge to get
The hydroxyl acrylic aqueous dispersion (hereinafter referred to as product A) of the polyether polyol-unsaturated polyester modified.
Embodiment 2
(1) by epoxychloropropane 3g, propylene glycol 5.0g, propylene glycol methyl ether acetate 3g, potassium hydroxide 0.03g, unsaturation
Polyester 3.0g is mixed, and is warming up to 140-145 DEG C, is stirred to react 0.5-1h and obtains reaction mixture；
(2) dibenzoyl peroxide 1.0g and methyl acrylate 8g, first are added in into the reaction mixture that step (1) obtains
Base methyl acrylate 2g, hydroxyethyl methacrylate 5g, ethyl acrylate 5g after keeping the temperature 1h after adding, are continuously added remaining
Dibenzoyl peroxide 1.0g and methyl acrylate 8g, methyl methacrylate 2g, hydroxyethyl methacrylate 5g, acrylic acid second
Ester 5g after keeping the temperature 1-2h after adding, is cooled to 75-80oC, adds in triethylamine 6g and neutralizes, suitable deionized water is added to be dispersed with stirring
After 1-2h, discharge to get hydroxyl acrylic aqueous dispersion (the hereinafter referred to as product of the polyether polyol-unsaturated polyester modified
B)。
Embodiment 3
(1) by propylene oxide 2.37g, butanediol 3.66g, propylene glycol methyl ether acetate 3g, potassium hydroxide 0.02g, insatiable hunger
It is mixed with polyester 2.21g, is warming up to 140-145 DEG C, is stirred to react 0.5-1h and obtains reaction mixture；
(2) di-tert-butyl peroxide 0.56g and esters of acrylic acid list are added dropwise into the reaction mixture that step (1) obtains
(methyl acrylate, methyl methacrylate, the mass ratio of butyl acrylate are 1 to body:1:1) 18.0g keeps the temperature 1h after being added dropwise
Afterwards, continue that remaining di-tert-butyl peroxide 0.56g and acrylic ester monomer (methyl acrylate, methacrylic acid is added dropwise
Methyl esters, the mass ratio of butyl acrylate are 1:1:1) 18.0g after keeping the temperature 1-2h after being added dropwise, is cooled to 75-80oC is added in
N, N dimethyl ethanolamine 5.4g are neutralized, and after suitable deionized water is added to be dispersed with stirring 1-2h, are discharged to get the polyether polyols
The hydroxyl acrylic aqueous dispersion (hereinafter referred to as products C) of alcohol-unsaturated polyester modified.
Embodiment 4
(1) by tetrahydrofuran 3.0g, butanediol 3.0g, propylene glycol methyl ether acetate 2.5g, potassium hydroxide 0.01g, insatiable hunger
It is mixed with polyester 2.0g, is warming up to 140-145 DEG C, is stirred to react 0.5-1h and obtains reaction mixture；
(2) into the reaction mixture that step (1) obtains be added dropwise di-tert-butyl peroxide 0.5g and methyl acrylate 5g,
Methyl methacrylate 6g, butyl acrylate 4g after keeping the temperature 1h after being added dropwise, continue that remaining di-tert-butyl peroxide is added dropwise
Object 0.5g and methyl acrylate 5g, methyl methacrylate 6g, butyl acrylate 4g, after keeping the temperature 1-2h after being added dropwise, cooling
To 75-80oC, add in N, N dimethyl ethanolamine 4g is neutralized, after suitable deionized water is added to be dispersed with stirring 1-2h, discharge to get
The hydroxyl acrylic aqueous dispersion (hereinafter referred to as product D) of the polyether polyol-unsaturated polyester modified.
Embodiment 5
(1) by propylene oxide 2g, butanediol 3.0g, propylene glycol methyl ether acetate 2g, potassium hydroxide 0.02g, styrene
2.0g is mixed, and is warming up to 140-145 DEG C, is stirred to react 0.5-1h and obtains reaction mixture；
(2) into the reaction mixture that step (1) obtains be added dropwise di-tert-butyl peroxide 0.5g and methyl acrylate 5g,
Methyl methacrylate 6g, butyl acrylate 4g after keeping the temperature 1h after being added dropwise, continue that remaining di-tert-butyl peroxide is added dropwise
Object 0.5g and methyl acrylate 5g, methyl methacrylate 6g, butyl acrylate 4g, after keeping the temperature 1-2h after being added dropwise, cooling
To 75-80oC adds in N, and N dimethyl ethanolamine 4g is neutralized, and after suitable deionized water is added to be dispersed with stirring 1-2h, discharging must produce
Product E.
Embodiment 6
(1) propylene glycol methyl ether acetate 2g, unsaturated polyester (UP) 2.0g are mixed, is warming up to 140-145 DEG C, is stirred to react
0.5-1h obtains reaction mixture；
(2) into the reaction mixture that step (1) obtains be added dropwise di-tert-butyl peroxide 0.5g and methyl acrylate 5g,
Methyl methacrylate 6g, butyl acrylate 4g after keeping the temperature 1h after being added dropwise, continue that remaining di-tert-butyl peroxide is added dropwise
Object 0.5g and methyl acrylate 5g, methyl methacrylate 6g, butyl acrylate 4g, after keeping the temperature 1-2h after being added dropwise, cooling
To 75-80oC adds in N, and N dimethyl ethanolamine 4g is neutralized, and after suitable deionized water is added to be dispersed with stirring 1-2h, discharging must produce
Product F.
Embodiment 7
The viscosity of each embodiment dispersion is measured using rotational viscometer, using 160 DEG C of baking 1h, measurement is scattered
Consolidating for body contains.Specific data are shown in Table 1.
Table 1
"-" represents undetermined.
Embodiment 8
By product A, 1121 product of commercially available model and Chinese invention patent (application number：201611200208.3)
The hydroxyl acrylic aqueous dispersion of embodiment 1 (abbreviation patented product) is crosslinked painting with polyisocyanate curing agent, makees
Contrast experiment, specific data are shown in Table 2.
Table 2
The polyether polyol that it can be seen from the test result of embodiment 7-8 prepared by the present invention-unsaturated polyester modified
Hydroxyl acrylic aqueous dispersion, admittedly contain, hydroxyl value it is higher, VOC content is low, and its painting water resistance is superior, can 2 days it is not blistering,
It does not fall off, is non-discolouring.
Claims (5)
1. a kind of polyether polyol-preparation method of unsaturated polyester modified hydroxyl acrylic aqueous dispersion, it is characterised in that bag
Include following steps：
(1) organic epoxide, the compound containing active hydrogen group, solvent, catalyst and unsaturated polyester (UP) are mixed, are warming up to
It 140-145 DEG C, is stirred to react 0.5-1h and obtains reaction mixture；
(2) initiator and acrylic ester monomer are added in two steps into the reaction mixture that step (1) obtains, after being added dropwise
After keeping the temperature 1-2h, 75-80 DEG C is cooled to, neutralizer is added in, deionized water is added to be dispersed with stirring after 1-2h to get the polyether polyols
The hydroxyl acrylic aqueous dispersion of alcohol-unsaturated polyester modified.
2. preparation method described in claim 1, it is characterised in that the organic epoxide described in step (1) is selected from epoxy second
One or more of alkane, propylene oxide, epoxychloropropane, epoxy butane, furans, tetrahydrofuran；It is described to contain active hydrogen group
Compound be selected from propylene glycol, glycerine, trimethylolpropane, ethylenediamine pentaerythrite, xylitol, triethylene diamine, sorbierite,
Sucrose, bisphenol-A, bisphenol S, three (2- ethoxys) isocyanates, toluenediamine, ethylene glycol, m-xylene diamine, ethylenediamine, isocyanide
Any one of acid esters, butanediol, triethanolamine, n-butanol, isopropanol；The Conventional solvents that solvent is prepared for resin, preferably third
One kind in glycol methyl ether acetate, propylene glycol diacetate, propylene-glycol ethyl ether；Catalyst is the routine for preparing polyether polyol
Catalyst, preferred alkali metal hydroxide (such as NaOH, KOH, CsOH).
3. claim 1-2 any one of them preparation methods, it is characterised in that the initiator described in step (2) is selected from peroxidating
T-butyl perbenzoate, tert-butyl peroxide, dibenzoyl peroxide, ammonium persulfate, azodiisobutyronitrile, perbenzoic acid
One kind in the tert-butyl ester, cumyl hydroperoxide or cumyl peroxide；Neutralizer is：Triethylamine, N, N- dimethyl ethanols
Amine, ammonium hydroxide or tripropyl amine (TPA), acrylic ester monomer are selected from methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid
The mixing of one or more of methyl esters, hydroxyethyl methacrylate.
4. claim 1-3 any one of them preparation methods, it is characterised in that the weight of each component raw material in step (1), (2)
Number is as follows：
2-3 parts of organic epoxide, 2-5 parts of the compound containing active hydrogen group, 2-3 parts of solvent, 0.01-0.03 parts of catalyst and
2-3 parts of unsaturated polyester (UP), 1-2 parts of initiator, 30-40 parts of acrylic ester monomer, 4-6 parts of neutralizer, remaining is deionized water,
100 parts altogether.
5. claim 1-4 any one of them preparation methods, it is characterised in that the polyether polyol-unsaturated polyester modified
Hydroxyl acrylic aqueous dispersion, Gu containing for 54 ± 1.0%, viscosity is 2100 ± 50mpa.s, hydroxyl value 5.2 ± 0.1, VOC content
26±4.0μg/g。
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| CN201810004659.2A CN108059698B (en) | 2018-01-02 | 2018-01-02 | Preparation method of polyether polyol-unsaturated polyester modified hydroxyl acrylic acid dispersoid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467638A (en) * | 2018-10-25 | 2019-03-15 | 无锡洪汇新材料科技股份有限公司 | Diamond Search, hydroxyl acrylic aqueous dispersion of polyester modification and preparation method thereof |
| CN112759715A (en) * | 2020-12-29 | 2021-05-07 | 沧州优美特新材料科技有限公司 | High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof |
| CN113817308A (en) * | 2021-08-30 | 2021-12-21 | 无锡洪汇新材料科技股份有限公司 | Polyhydroxy aqueous dispersion and preparation method thereof |
| CN115232263A (en) * | 2022-08-05 | 2022-10-25 | 黄山联固新材料科技有限公司 | Preparation method of acrylic polyol dispersion |
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| WO2017191653A1 (en) * | 2016-05-02 | 2017-11-09 | Asian Paints Ltd. | Water borne castor oil modified acrylic copolymer dispersions for surface coatings |
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| CN105622857A (en) * | 2016-04-01 | 2016-06-01 | 武汉大学 | Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material |
| WO2017191653A1 (en) * | 2016-05-02 | 2017-11-09 | Asian Paints Ltd. | Water borne castor oil modified acrylic copolymer dispersions for surface coatings |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467638A (en) * | 2018-10-25 | 2019-03-15 | 无锡洪汇新材料科技股份有限公司 | Diamond Search, hydroxyl acrylic aqueous dispersion of polyester modification and preparation method thereof |
| CN109467638B (en) * | 2018-10-25 | 2020-10-16 | 无锡洪汇新材料科技股份有限公司 | zero-VOC, polyester-modified hydroxyacrylic acid dispersions and process for their preparation |
| CN112759715A (en) * | 2020-12-29 | 2021-05-07 | 沧州优美特新材料科技有限公司 | High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof |
| CN112759715B (en) * | 2020-12-29 | 2023-09-08 | 沧州优美特新材料科技有限公司 | High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof |
| CN113817308A (en) * | 2021-08-30 | 2021-12-21 | 无锡洪汇新材料科技股份有限公司 | Polyhydroxy aqueous dispersion and preparation method thereof |
| CN115232263A (en) * | 2022-08-05 | 2022-10-25 | 黄山联固新材料科技有限公司 | Preparation method of acrylic polyol dispersion |
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| CN108059698B (en) | 2020-07-21 |
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