CN102702438B - Quick-drying weather-resistant high-solid-content acrylic resin and preparation method thereof - Google Patents
Quick-drying weather-resistant high-solid-content acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a quick-drying weather-resistant high-solid-content acrylic resin, which comprises the following steps: 1) sequentially adding solvent and glycidyl tertiary carboxylic ester into a reactor while introducing protective nitrogen, and gradually heating to reaction temperature; 2) uniformly and dropwisely adding comonomer, initiator and solvent into the reactor, wherein the comonomer comprises 70-95% of unsaturated monomer and 5-30% of macromolecular monomer; and 3) after finishing dropwise addition, supplementing the initiator and solvent, keeping the temperature for 2 hours, cooling to 100 DEG C, filtering and discharging.. Compared with the prior art, the high-solid-content acrylic resin has the characteristics of low viscosity and high solid content; and the prepared paint has the advantages high drying rate and good weather resistance.
Description
Technical field
The invention belongs to organic polymer coating production, relate to a kind of preparation method of quick-drying weather resistant High solids Acrylic Resin.
Background technology
Along with day by day strengthening and growing tension that the energy is used of environmental regulation, research and develop the volatile organic compounds (VOC) in eco-friendly coating and application techniques and reduction coating material production and construction, become the center of gravity of domestic and international most of coating and resin design research work.The coating of high solid is exactly the good kind of development prospect wherein, and this product has reduced the VOC discharge in coating material production and construction, has reduced the pollution to ecotope, has saved painting cost simultaneously.Since the nineties in 20th century, rapidly, range of application constantly expands, and is mainly used in the fields such as sedan car top coat and retouching paint, motorcycle paints, top-grade furniture coating paint and industrial finish in high solid coating development.And for the crucial starting material of high solid coating---therefore High solids Acrylic Resin is also developed rapidly.Compare with conventional acrylic resin, High solids Acrylic Resin has advantages of environmental protection, energy-conservation, and the varnish that the solidifying agent such as it and carbimide is made into has high clarity, fullness ratio is good, speed of response is fast feature.
As everyone knows, graftomer is one of important means realizing high-polymer material functional.The polymkeric substance of Grafting Structure has less hydrodynamic volume, and its soltion viscosity is lower.So the Hydroxylated acrylic resin of preparation Grafting Structure can obviously improve solid content, reduces organic solvent usage quantity.As disclosed a kind of preparation method of ultra-high solid content hydroxy acrylic resin in the notification number Chinese patent that is CN101173030B.It adopts methyl acrylic ester macromonomer and vinyl monomer copolymerization, obtains that viscosity is little, solid content is at more than 80% Grafting Structure Hydroxylated acrylic resin.But the acrylic resin that this patent system is standby application performance, as not very good in rate of drying, ageing-resistant performance etc.The present invention looks for another way and releases originally a short-cut method drawing the advantage of prior art and overcome under the weakness of prior art.It utilizes catalysis chain transferring free-radical polymerization (CCTP) technology and particular monomers graft modification technology, prepares the High solids Acrylic Resin that meets rate of drying and weathering resistance requirement, the present invention that Here it is development and successfully background.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of quick-drying weather resistant High solids Acrylic Resin.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of quick-drying weather resistant High solids Acrylic Resin, comprises the steps:
Step 1): add solvent and tertiary carbonic acid glycidyl ester successively in reactor, pass into nitrogen protection simultaneously, be progressively warming up to temperature of reaction;
Step 2): in reactor, evenly drip comonomer, initiator and solvent, wherein, this comonomer comprises 5～30% the macromonomer that accounts for 70～95% unsaturated monomer of monomer total amount (amount of substance) and account for monomer total amount (amount of substance);
Step 3): after dropwising, add initiator and solvent, be incubated 2 hours, cool to 100 ℃, filter discharging.
Wherein, the consumption of this tertiary carbonic acid glycidyl ester accounts for 1～20% of monomer total amount (amount of substance) in step 1).
This unsaturated monomer comprises that mass percent is (methyl) alkyl acrylate of 30～79%, 0～20% unsaturated vinyl monomer, 20～40% (methyl) acrylic acid hydroxy alkyl ester and 1～10% unsaturated carboxylic acid.
This macromonomer is the methacrylic ester macromonomer of end band polymerizable double bond, and its synthetic method generally comprises the preparation of prepolymer and the introducing of functional end-group.Wherein, the preparation of prepolymer can adopt free radical chain transfer polymerization method or living polymerization method, as methods such as atom transfer radical polymerization (ATRP), group transfer polymerizations (GTP).Catalytic chain transfer polymerization technology adopts efficient chain transfer catalyst: II valency or III valency cobalt complex only need a step can prepare the methyl acrylic ester macromonomer of the two keys of end band under mild reaction conditions.In the present invention, the preparation method of this macromonomer adopts catalytic chain transfer polymerization technology, comprise the steps: to take methyl methacrylate (MMA), hydroxyethyl methylacrylate (HEMA), butyl methacrylate (BMA), butylacetate, Diisopropyl azodicarboxylate (AIBN) and two hydrations two (boron difluoride benzene two ketoximes) and close cobalt acid (II) salt (COPhBF), after evenly being mixed, it adds in reaction flask, heated and stirred under nitrogen atmosphere, reacts after some hours and obtains product.
Particularly, (methyl) alkyl acrylate in this unsaturated monomer contains that to account for its carbonatoms that contains of 60～80% be (methyl) alkyl acrylate of 1～4, and contains and account for its (methyl) vinylformic acid cycloalkyl ester of 20～40%.
Further, this contains carbonatoms is that (methyl) alkyl acrylate of 1～4 comprises: one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, wherein, preferred (methyl) isobutyl acrylate and (methyl) tert-butyl acrylate.
Further, should comprise by (methyl) vinylformic acid cycloalkyl ester: (methyl) cyclohexyl acrylate and/or (methyl) isobornyl acrylate, wherein, preferred (methyl) isobornyl acrylate.
Further, (methyl) acrylic acid hydroxy alkyl ester in this unsaturated monomer comprises: one or more in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate and (methyl) vinylformic acid hydroxy butyl ester.
Further, the unsaturated vinyl monomer in this unsaturated monomer comprises: vinylbenzene and/or alpha-methyl styrene.
And the unsaturated carboxylic acid in this unsaturated monomer comprises: (methyl) vinylformic acid and/or methylene-succinic acid.
The solvent that the present invention adopts comprises: one or more in toluene, dimethylbenzene, trimethylbenzene, durene, ethyl acetate, butylacetate, ethylene glycol ether acetate and diethylene glycol ether acetic ester.Wherein, preferred trimethylbenzene and butylacetate.
Step 2 of the present invention) be Raolical polymerizable, wherein, this initiator is radical initiator, comprises azo-initiator and/or peroxide initiator.Azo-initiator comprises Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile).Peroxide initiator comprises one or more in benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, di-t-butyl peroxide, peroxidation two tert-pentyls, tertbutyl peroxide, t-amyl peroxy hydrogen, preferably peroxidized t-butyl perbenzoate and peroxidation two tert-pentyls.The consumption of this initiator is 1～5% of monomer total amount, and preferable range is 2～4%.
The temperature of Raolical polymerizable this step 2) should be controlled at 130～170 ℃, is preferably 140～160 ℃.
Further, in step 2) in, by tertiary carbonic acid glycidyl ester, acrylic resin is carried out to modification, by tertiary carbonic acid glycidyl ester and carboxylic acid reaction, obtain.Because the carboxyl on the polymkeric substance on this comonomer is low compared with the activity of acrylic or methacrylic acid, so the speed of response of polymkeric substance and tertiary carbonic acid glycidyl ester is slow compared with the speed of response of monomer, therefore, can in reaction, add catalyzer, this catalyzer is stannous octoate and/or triphenyl ethyl phosphonium iodide (ETPPI), to accelerate step 2) speed of response.Under the reaction conditions of 150 ℃, if do not add catalyzer, this step 2) speed of response be 4 ~ 6 hours, if add 0.1 ~ 0.3% catalyzer ETPPI, this reaction can complete in 1 hour, but that the color of resin does not add the color of catalyzer is relatively dark.
In addition, the present invention also provides the quick-drying weather resistant High solids Acrylic Resin of utilizing aforesaid method to prepare.
With respect to prior art, the preparation method of quick-drying weather resistant High solids Acrylic Resin provided by the present invention uses tertiary carbonic acid glycidyl ester to carry out modification to acrylic resin, when reducing resin viscosity, provides the ageing-resistant performance of resin excellence.Secondly, adopt the methacrylic ester macromonomer of end band polymerizable double bond, can effectively reduce resin viscosity, reach the low viscous object of high solid.Further, methacrylic acid cycloalkyl ester class Acrylic Acid Monomer in unsaturated monomer participates in copolymerization, and the ageing resistance of resin excellence can be provided on the one hand, makes on the other hand resin have higher hardness and rate of drying faster.
With respect to prior art, quick-drying weather resistant High solids Acrylic Resin provided by the invention has the advantages that viscosity is low, solid part is high, and the coating of preparing with it has that rate of drying is fast, the excellent properties of good weatherability.
Embodiment
embodiment 1
First, carry out the preparation of macromonomer (Macro monomer): take methyl methacrylate (MMA) 90g, hydroxyethyl methylacrylate (HEMA) 120g, butyl methacrylate (BMA) 140g, butylacetate 150g, Diisopropyl azodicarboxylate (AIBN) 2.05g, cobalt acid (II) salt (COPhBF) 100mg is closed in two hydrations two (boron difluoride benzene two ketoximes), after it is evenly mixed, add in reaction flask, 75 ℃ of heated and stirred under nitrogen atmosphere, react 5 hours.The solid content that obtains product is 68.4%, GPC result Mn=1581, Mw/Mn=1.56.
Next, in the four-hole boiling flask of band stirring and condenser, add trimethylbenzene 150g and tertiary carbonic acid glycidyl ester 50g, stirring at low speed also passes into nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions being formed by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: butyl methacrylate (BMA) 100g, isobornyl methacrylate (IBOMA) 75g, vinylbenzene (ST) 82g, hydroxyethyl methylacrylate (HEMA) 152g, vinylformic acid (AA) 16g and macromonomer 75g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxidation two tert-pentyl 9g.
After dropwising, at the temperature of 150 ℃, be incubated 30 minutes, then in 10 minutes, add as the initiator solution of peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition, and then be incubated 2 hours at the temperature of 150 ℃, cool to subsequently 100 ℃, filter discharging.
Products therefrom viscosity is 3200Pa.s, and solid content is that 69.3%, GPC result is: Mn=5381, Mw/Mn=1.92.
embodiment 2
The preparation of the macromonomer of embodiment 2 (Macro monomer) is identical with embodiment's 1, and its difference is only following step:
In the four-hole boiling flask of band stirring and condenser, add trimethylbenzene 150g and tertiary carbonic acid glycidyl ester (Cardura E10P) 50g, stirring at low speed also passes into nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions being formed by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: butyl methacrylate (BMA) 125g, isobornyl methacrylate (IBOMA) 75g, vinylbenzene (ST) 82g, hydroxyethyl methylacrylate (HEMA) 152g, vinylformic acid (AA) 16g and macromonomer 50g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxidation two tert-pentyl 9g.
After dropwising, at the temperature of 150 ℃, be incubated 30 minutes, then in 10 minutes, add as the initiator solution of peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition, and then be incubated 2 hours at the temperature of 150 ℃, cool to subsequently 100 ℃, filter discharging.
Products therefrom viscosity is 4280Pa.s, and solid content is that 70.1%, GPC result is: Mn=5250, Mw/Mn=1.98.
embodiment 3
The preparation of the macromonomer of embodiment 3 (Macro monomer) is identical with embodiment's 1, and its difference is only following step:
In the four-hole boiling flask of band stirring and condenser, add trimethylbenzene 165g and tertiary carbonic acid glycidyl ester (Cardura E10P) 75g, stirring at low speed also passes into nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions being formed by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: methyl methacrylate (MMA) 60g, butyl methacrylate (BMA) 83g, isobornyl methacrylate (IBOMA) 50g, vinylbenzene (ST) 82g, hydroxyethyl methylacrylate (HEMA) 152g, vinylformic acid (AA) 23.2g and macromonomer 50g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxidation two tert-pentyl 9g.
After dropwising, at the temperature of 150 ℃, be incubated 30 minutes, then in 10 minutes, add as the initiator solution of peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition, and then be incubated 2 hours at the temperature of 150 ℃, cool to subsequently 100 ℃, filter discharging.
Products therefrom viscosity is 3850Pa.s, and solid content is that 69.8%, GPC result is: Mn=5510, Mw/Mn=2.08.
embodiment 4
The preparation of the macromonomer of embodiment 4 (Macro monomer) is identical with embodiment's 1, and its difference is only following step:
In the four-hole boiling flask of band stirring and condenser, add trimethylbenzene 125g and tertiary carbonic acid glycidyl ester (Cardura E10P) 25g, stirring at low speed also passes into nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions being formed by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: methyl methacrylate (MMA) 52g, isobornyl methacrylate (IBOMA) 95g, vinylbenzene (ST) 82g, Hydroxyethyl acrylate (HEA) 132g, vinylformic acid (AA) 14g and macromonomer 125g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxidation two tert-pentyl 9g.
After dropwising, at the temperature of 150 ℃, be incubated 30 minutes, then in 10 minutes, add as the initiator solution of peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition, and then be incubated 2 hours at the temperature of 150 ℃, cool to subsequently 100 ℃, filter discharging.
Products therefrom viscosity is 3120Pa.s, and solid content is that 69.2%, GPC result is: Mn=5020, Mw/Mn=2.20.
embodiment 5
The preparation of the macromonomer of embodiment 5 (Macro monomer) is identical with embodiment's 1, and its difference is only following step:
In the four-hole boiling flask of band stirring and condenser, add trimethylbenzene 180g and tertiary carbonic acid glycidyl ester (Cardura E10P) 100g, stirring at low speed also passes into nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions being formed by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: methyl methacrylate (MMA) 40g, butyl methacrylate (BMA) 80g, isobornyl methacrylate (IBOMA) 75g, vinylbenzene (ST) 91g, hydroxyethyl methylacrylate (HEMA) 152g, vinylformic acid (AA) 32g and macromonomer 25g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxidation two tert-pentyl 9g.
After dropwising, at the temperature of 150 ℃, be incubated 30 minutes, then in 10 minutes, add as the initiator solution of peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition, and then be incubated 2 hours at the temperature of 150 ℃, cool to subsequently 100 ℃, filter discharging.
Products therefrom viscosity is 4400Pa.s, and solid content is that 70.8%, GPC result is: Mn=5340, Mw/Mn=2.01.
comparative example 6
In this comparative example, do not add tertiary carbonic acid glycidyl ester, macromonomer and (methyl) vinylformic acid cycloalkyl ester, to compare with above-described embodiment 1 ~ 5, the step of stating specific as follows:
In the four-hole boiling flask of band stirring and condenser, add trimethylbenzene 155g, stirring at low speed also passes into nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions being formed by mix monomer 500g and initiator solution 68g.Wherein, this mix monomer comprises: methyl methacrylate (MMA) 60g, butyl methacrylate (BMA) 200g, vinylbenzene (ST) 82g, hydroxyethyl methylacrylate (HEMA) 152g and vinylformic acid (AA) 6g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxidation two tert-pentyl 9g.
After dropwising, at the temperature of 150 ℃, be incubated 30 minutes, then in 10 minutes, add as the initiator solution of peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition, and then be incubated 2 hours at the temperature of 150 ℃, cool to subsequently 100 ℃, filter discharging.
Products therefrom viscosity is 5810Pa.s, and solid content is that 69.7%, GPC result is: Mn=5610, Mw/Mn=2.10.
As can be seen here, the viscosity of comparative example's 6 products therefroms is far above the viscosity of products therefrom in embodiment 1 ~ 5.
Further, by the resin sample of preparation, by following lacquer formulation, join paint.
| Composition | Consumption |
| Resin | 75.50 |
| Flow agent-1 | 1.00 |
| Siccative-1 | 3.00 |
| Flow agent-2 | 3.00 |
| X | 5.50 |
| B | 4.25 |
| AC | 2.00 |
| Ultraviolet absorbers 1 | 3.75 |
| Ultraviolet absorbers 2 | 2.00 |
| Add up to | 100.00 |
By NCO/OH=1:1 add Beyer Co., Ltd 3390 solidifying agent, wet touch wet spray on aluminum primer, at the temperature of 70 ℃, toast 30 minutes, room temperature was placed after 30 minutes, test initial hardness; Room temperature was placed after 7 days, and test final hardness carries out ageing-resistant (QUV) test simultaneously, and result is as follows:
Wherein, initial hardness value is in order to evaluate the quick-drying performance of coating, and initial hardness more Gao Ze represents dry faster of coating; And the ageing-resistant test loss of gloss rate of 1000 hours requires to be less than 10%, value of chromatism requires to be less than 3.By test result, can be obtained, the initial hardness value of embodiment 1 ~ 5 is much larger than comparative example 6 initial hardness value, and the loss of gloss rate of embodiment 1 ~ 5 and aberration rate be all within claimed range, but that 6 loss of gloss rate and aberration rate are implemented in contrast is not up to standard.
Although the present invention is described with reference to concrete embodiment, those skilled in the art, by reading after foregoing description, can make apparent modification and modification to the present invention, and without prejudice to the intent of the present invention and essence.The present invention comprises these modifications and modification within the scope of the claims intentionally.
Claims (7)
1. a preparation method for quick-drying weather resistant High solids Acrylic Resin, comprises the steps:
Step 1): in reactor, add solvent and tertiary carbonic acid glycidyl ester successively, pass into nitrogen protection simultaneously, be progressively warming up to temperature of reaction;
Step 2): in reactor, evenly drip comonomer, initiator and solvent, wherein, this comonomer comprises the methacrylic ester macromonomer that accounts for 70～95% unsaturated monomer of its total amount and account for 5～30% end band polymerizable double bond of its total amount;
Step 3): after dropwising, add initiator and solvent, be incubated 2 hours, cool to 100 ℃, filter discharging;
Wherein, described unsaturated monomer comprises that mass percent is (methyl) alkyl acrylate of 30～79%, 0～20% vinylbenzene and/or alpha-methyl styrene, 20～40% (methyl) acrylic acid hydroxy alkyl ester and 1～10% unsaturated carboxylic acid;
It is (methyl) alkyl acrylate of 1,2 and/or 4 and (methyl) vinylformic acid cycloalkyl ester of 20～40% that described (methyl) alkyl acrylate comprises carbonatoms on 60～80% alkyl, and described (methyl) vinylformic acid cycloalkyl ester is (methyl) isobornyl acrylate.
2. preparation method according to claim 1, is characterized in that: the consumption of tertiary carbonic acid glycidyl ester accounts for 1～20% of described comonomer total amount.
3. preparation method according to claim 1, it is characterized in that: the preparation method of this methacrylic ester macromonomer comprises step: take methyl methacrylate, hydroxyethyl methylacrylate, butyl methacrylate, butylacetate, Diisopropyl azodicarboxylate, two hydrations two (boron difluoride benzene two ketoximes) and close cobalt acid (II) salt, after evenly being mixed, it adds in reaction flask, heated and stirred under nitrogen atmosphere, reacts after some hours and obtains product.
4. preparation method according to claim 1, is characterized in that: the unsaturated carboxylic acid in this unsaturated monomer comprises (methyl) vinylformic acid and/or methylene-succinic acid.
5. preparation method according to claim 1, it is characterized in that: this initiator is radical initiator, comprise azo-initiator and/or peroxide initiator, wherein, azo-initiator comprises Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile), and peroxide initiator comprises one or more in benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, di-t-butyl peroxide, peroxidation two tert-pentyls, tertbutyl peroxide, t-amyl peroxy hydrogen.
6. preparation method according to claim 1, is characterized in that: this solvent comprises one or more in toluene, dimethylbenzene, trimethylbenzene, durene, ethyl acetate, butylacetate, ethylene glycol ether acetate and diethylene glycol ether acetic ester.
7. a quick-drying weather resistant High solids Acrylic Resin, is characterized in that: according to the preparation method described in any one in claim 1～6, make.
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| CN103923251B (en) * | 2014-04-28 | 2016-07-06 | 无锡德贝尔光电材料有限公司 | A kind of quick-dry type acrylate polymer and preparation method thereof |
| CN107286286A (en) * | 2016-04-05 | 2017-10-24 | 昆山石梅精细化工有限公司 | A kind of acrylic resin and its preparation technology for mending paint coating |
| CN108948254B (en) * | 2018-07-06 | 2019-06-04 | 莱阳红安化工有限公司 | A kind of feature of environmental protection acrylic resin and preparation method thereof |
| CN110713572B (en) * | 2018-07-11 | 2022-07-22 | 广东华润涂料有限公司 | High-solid-content low-viscosity resin composition containing acrylic copolymer |
| CN110003366B (en) * | 2019-04-10 | 2021-06-22 | 泰兴盛嘉树脂有限公司 | Preparation method of E-10P modified acrylic resin capable of reducing resin color |
| CN116515073B (en) * | 2023-04-07 | 2024-05-14 | 广东豪美新材股份有限公司 | Preparation method of energy-absorbing material |
| CN117801647A (en) * | 2023-11-17 | 2024-04-02 | 雅图高新材料股份有限公司 | Water-based paint composition suitable for wet-on-wet construction and preparation method and application thereof |
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| CN101121770A (en) * | 2006-08-11 | 2008-02-13 | 上海市涂料研究所 | Water acrylic resin and preparing method thereof |
| CN101173030A (en) * | 2007-10-20 | 2008-05-07 | 中山大桥化工有限公司 | Method for producing ultra-high solid content hydroxy acrylic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101121770A (en) * | 2006-08-11 | 2008-02-13 | 上海市涂料研究所 | Water acrylic resin and preparing method thereof |
| CN101173030A (en) * | 2007-10-20 | 2008-05-07 | 中山大桥化工有限公司 | Method for producing ultra-high solid content hydroxy acrylic resin |
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Application publication date: 20121003 Assignee: Hefei Zhi Heng Chemical Co., Ltd. Assignor: Zhongshan Daoqum Chemical Group Co., Ltd. Contract record no.: 2014440000503 Denomination of invention: Quick-drying weather-resistant high-solid-content acrylic resin and preparation method thereof Granted publication date: 20140910 License type: Exclusive License Record date: 20141218 |
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