CN102702438A - 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 fast dried weather resistant High solids Acrylic Resin.
Background technology
Along with strengthening day by day and growing tension that the energy uses of environmental regulation; Research and develop the volatile organic compounds (VOC) in eco-friendly coating and application techniques and reduction coating material production and the 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 development prospect kind preferably wherein, and this product has reduced the VOC discharging in coating material production and the construction, has reduced the pollution to ecotope, has practiced thrift painting cost simultaneously.Since the nineties in 20th century, the high solid coating development is rapid, and range of application constantly enlarges, and is mainly used in fields such as car finish paint and retouching paint, motorcycle lacquer, top-grade furniture coating paint and industrial finish.And be used for that the crucial starting material of high solid coating---therefore High solids Acrylic Resin has also obtained fast development.Compare with conventional acrylic resin, High solids Acrylic Resin has environmental protection, energy-saving advantages, and the varnish that solidifying agent such as it and carbimide is made into has high clarity, fullness ratio is good, speed of response is fast characteristics.
As everyone knows, graftomer is one of important means that realizes 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 the organic solvent usage quantity.Like notification number the preparation method who discloses a kind of ultra-high solid content hydroxy acrylic resin in the Chinese patent of CN101173030B.It adopts methyl acrylic ester macromonomer and vinyl monomer copolymerization, obtains that viscosity is little, solid content is at the Grafting Structure Hydroxylated acrylic resin more than 80%.But the vinyl resin of this patent preparation application performance, not very good like rate of drying, ageing-resistant performance etc.The present invention is in the advantage of drawing prior art and overcomes to look for another way under the weakness of prior art and release a short-cut method originally.It utilizes catalysis chain transfer radical polymerization (CCTP) technology and particular monomers graft modification technology, prepares the High solids Acrylic Resin that satisfies rate of drying and weathering resistance requirement, the present invention that Here it is development and successful background.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of fast dried weather resistant High solids Acrylic Resin.
The objective of the invention is to realize through following technical scheme: a kind of preparation method of fast dried weather resistant High solids Acrylic Resin comprises the steps:
Step 1): in reactor drum, add solvent and tertiary carbonic acid glycidyl ester successively, feed nitrogen protection simultaneously, progressively be warming up to temperature of reaction;
Step 2): in reactor drum, evenly drip comonomer, initiator and solvent; Wherein, this comonomer comprises 70～95% the unsaturated monomer that accounts for monomer total amount (amount of substance) and 5～30% the macromonomer that accounts 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 the 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 terminal 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 be adopted free radical chain transfer polymerization method or living polymerization method, like ATRP (ATRP), group transfer polymerization methods such as (GTP).The catalytic chain transfer polymerization technology then adopts efficient chain transfer catalyst: II valency or III valency cobalt complex need a step can prepare the methyl acrylic ester macromonomer of the two keys of terminal band following of mild reaction conditions.In the present invention; The preparation method of this macromonomer adopts the catalytic chain transfer polymerization technology; Comprise the steps: to take by weighing TEB 3K (MMA), Rocryl 400 (HEMA), NSC 20956 (BMA), butylacetate, Diisopropyl azodicarboxylate (AIBN) and two hydrations two (boron difluoride benzene two ketoximes) and close cobalt acid (II) salt (COPhBF); With adding behind its uniform mixing in the reaction flask; Heated and stirred under nitrogen atmosphere obtains product behind the reaction some hrs.
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) Bing Xisuandingzhi, (methyl) NSC 20949, (methyl) tert-butyl acrylate; Wherein, preferred (methyl) NSC 20949 and (methyl) tert-butyl acrylate.
Further, should comprise by (methyl) vinylformic acid cycloalkyl ester: (methyl) cyclohexyl acrylate and/or (methyl) IBOA, wherein, preferred (methyl) IBOA.
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, YLENE, trimethylbenzene, durene, ETHYLE ACETATE, butylacetate, ethylene glycol ether acetate and the diethylene glycol ether acetic ester.Wherein, preferred trimethylbenzene and butylacetate.
Step 2 of the present invention) be Raolical polymerizable, wherein, this initiator is a radical initiator, comprises azo-initiator and/or peroxide initiator.Azo-initiator comprises Diisopropyl azodicarboxylate and/or AMBN.The peroxide initiator comprises one or more in Lucidol, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, di-t-butyl peroxide, peroxo-two tert-pentyls, tertbutyl peroxide, the t-amyl peroxy hydrogen, preferred peroxidized t-butyl perbenzoate and peroxo-two tert-pentyls.The consumption of this initiator is 1～5% of a 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, through tertiary carbonic acid glycidyl ester vinyl resin is carried out modification, get through tertiary carbonic acid glycidyl ester and carboxylic acid reaction.Because the carboxyl on the polymkeric substance on this comonomer is than sour active low of acrylic or methacrylic; So the more monomeric speed of response of the speed of response of polymkeric substance and tertiary carbonic acid glycidyl ester is slow; 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 150 ℃ reaction conditions, if do not add catalyzer, this step 2) speed of response be 4 ~ 6 hours, if add 0.1 ~ 0.3% catalyzer ETPPI, then this reaction can be accomplished in 1 hour, but that the color of resin does not add the color of catalyzer relatively is dark.
In addition, the present invention also provides the fast dried weather resistant High solids Acrylic Resin of utilizing method for preparing.
With respect to prior art, the preparation method of fast dried weather resistant High solids Acrylic Resin provided by the present invention uses tertiary carbonic acid glycidyl ester that vinyl resin is carried out modification, when reducing resin viscosity, provides resin excellent ageing-resistant performance.Secondly, adopt the methacrylic ester macromonomer of terminal band polymerizable double bond, can effectively reduce resin viscosity, reach the low viscous purpose of high solid.Further, methylacrylic acid cycloalkyl ester class Acrylic Acid Monomer in the unsaturated monomer is participated in copolymerization, can provide resin excellent ageing resistance on the one hand, makes resin have higher hardness and rate of drying faster on the other hand.
With respect to prior art, fast dried weather resistant High solids Acrylic Resin provided by the invention has the advantages that viscosity is low, solid is high, has with the coating of its preparation that rate of drying is fast, the excellent properties of good weatherability.
Embodiment
Embodiment 1
At first, carry out the preparation of macromonomer (Macro monomer): take by weighing TEB 3K (MMA) 90g, Rocryl 400 (HEMA) 120g; NSC 20956 (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); With adding in the reaction flask behind its uniform mixing, 75 ℃ of heated and stirred under nitrogen atmosphere were reacted 5 hours.The solid content that obtains product is 68.4%, and GPC is Mn=1581 as a result, Mw/Mn=1.56.
Next, in the four-hole boiling flask of band stirring and condensing surface, add trimethylbenzene 150g and tertiary carbonic acid glycidyl ester 50g, stirring at low speed also feeds nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions of forming by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: NSC 20956 (BMA) 100g, isobornyl methacrylate (IBOMA) 75g, vinylbenzene (ST) 82g, Rocryl 400 (HEMA) 152g, vinylformic acid (AA) 16g and macromonomer 75g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxo-two tert-pentyl 9g.
After dropwising; Insulation is 30 minutes under 150 ℃ temperature, in 10 minutes, adds the initiator solution like peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition then, and then under 150 ℃ temperature, is incubated 2 hours; Cool to 100 ℃ subsequently, filter discharging.
Products therefrom viscosity is 3200Pa.s, and solid content is 69.3%, and 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 only is following step:
In the four-hole boiling flask of band stirring and condensing surface, add trimethylbenzene 150g and tertiary carbonic acid glycidyl ester (Cardura E10P) 50g, stirring at low speed also feeds nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions of forming by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: NSC 20956 (BMA) 125g, isobornyl methacrylate (IBOMA) 75g, vinylbenzene (ST) 82g, Rocryl 400 (HEMA) 152g, vinylformic acid (AA) 16g and macromonomer 50g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxo-two tert-pentyl 9g.
After dropwising; Insulation is 30 minutes under 150 ℃ temperature, in 10 minutes, adds the initiator solution like peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition then, and then under 150 ℃ temperature, is incubated 2 hours; Cool to 100 ℃ subsequently, filter discharging.
Products therefrom viscosity is 4280Pa.s, and solid content is 70.1%, and 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 only is following step:
In the four-hole boiling flask of band stirring and condensing surface, add trimethylbenzene 165g and tertiary carbonic acid glycidyl ester (Cardura E10P) 75g, stirring at low speed also feeds nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions of forming by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: TEB 3K (MMA) 60g, NSC 20956 (BMA) 83g, isobornyl methacrylate (IBOMA) 50g, vinylbenzene (ST) 82g, Rocryl 400 (HEMA) 152g, vinylformic acid (AA) 23.2g and macromonomer 50g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxo-two tert-pentyl 9g.
After dropwising; Insulation is 30 minutes under 150 ℃ temperature, in 10 minutes, adds the initiator solution like peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition then, and then under 150 ℃ temperature, is incubated 2 hours; Cool to 100 ℃ subsequently, filter discharging.
Products therefrom viscosity is 3850Pa.s, and solid content is 69.8%, and 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 only is following step:
In the four-hole boiling flask of band stirring and condensing surface, add trimethylbenzene 125g and tertiary carbonic acid glycidyl ester (Cardura E10P) 25g, stirring at low speed also feeds nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions of forming by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: TEB 3K (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 peroxo-two tert-pentyl 9g.
After dropwising; Insulation is 30 minutes under 150 ℃ temperature, in 10 minutes, adds the initiator solution like peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition then, and then under 150 ℃ temperature, is incubated 2 hours; Cool to 100 ℃ subsequently, filter discharging.
Products therefrom viscosity is 3120Pa.s, and solid content is 69.2%, and 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 only is following step:
In the four-hole boiling flask of band stirring and condensing surface, add trimethylbenzene 180g and tertiary carbonic acid glycidyl ester (Cardura E10P) 100g, stirring at low speed also feeds nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions of forming by comonomer 500g and initiator solution 68g.Wherein, this comonomer comprises: TEB 3K (MMA) 40g, NSC 20956 (BMA) 80g, isobornyl methacrylate (IBOMA) 75g, vinylbenzene (ST) 91g, Rocryl 400 (HEMA) 152g, vinylformic acid (AA) 32g and macromonomer 25g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxo-two tert-pentyl 9g.
After dropwising; Insulation is 30 minutes under 150 ℃ temperature, in 10 minutes, adds the initiator solution like peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition then, and then under 150 ℃ temperature, is incubated 2 hours; Cool to 100 ℃ subsequently, filter discharging.
Products therefrom viscosity is 4400Pa.s, and solid content is 70.8%, and GPC result is: Mn=5340, Mw/Mn=2.01.
The comparative example 6
In this comparative example, do not add tertiary carbonic acid glycidyl ester, macromonomer and (methyl) vinylformic acid cycloalkyl ester, to compare the step of stating specific as follows with the foregoing description 1 ~ 5:
In the four-hole boiling flask of band stirring and condensing surface, add trimethylbenzene 155g, stirring at low speed also feeds nitrogen, is warming up to 150 ℃.In 4 hours, evenly drip the mixing solutions of forming by mix monomer 500g and initiator solution 68g.Wherein, this mix monomer comprises: TEB 3K (MMA) 60g, NSC 20956 (BMA) 200g, vinylbenzene (ST) 82g, Rocryl 400 (HEMA) 152g and vinylformic acid (AA) 6g; This initiator solution comprises: butylacetate 50g, peroxidized t-butyl perbenzoate 9g and peroxo-two tert-pentyl 9g.
After dropwising; Insulation is 30 minutes under 150 ℃ temperature, in 10 minutes, adds the initiator solution like peroxidized t-butyl perbenzoate 2g and butylacetate 21g composition then, and then under 150 ℃ temperature, is incubated 2 hours; Cool to 100 ℃ subsequently, filter discharging.
Products therefrom viscosity is 5810Pa.s, and solid content is 69.7%, and GPC result is: Mn=5610, Mw/Mn=2.10.
This shows that the viscosity of comparative example's 6 products therefroms is far above the viscosity of products therefrom among the embodiment 1 ~ 5.
Further, with the resin sample of preparation, join lacquer by following lacquer formulation.
| 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 bump wet spray on aluminum primer, baking is 30 minutes under 70 ℃ temperature, room temperature was placed after 30 minutes, the test initial hardness; Room temperature was placed after 7 days, and the test final hardness carries out ageing-resistant (QUV) test simultaneously, and the result is following:
Wherein, the initial hardness value in order to the quick-drying of estimating coating can, initial hardness Gao Ze more represent dried fast more of coating; And 1000 hours loss of gloss rate of ageing-resistant test requires to be less than 10%, and value of chromatism requires less than 3.Can be obtained by test result, 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.
Though the present invention describes with reference to concrete embodiment, those skilled in the art can make conspicuous modification and modification to the present invention through after reading foregoing description, and without prejudice to the intent of the present invention and essence.The present invention is included in these modifications and modification in the scope of claim intentionally.
Claims (11)
1. the preparation method of a fast dried weather resistant High solids Acrylic Resin comprises the steps:
Step 1): in reactor drum, add solvent and tertiary carbonic acid glycidyl ester successively, feed nitrogen protection simultaneously, progressively be warming up to temperature of reaction;
Step 2): in reactor drum, evenly drip comonomer, initiator and solvent, wherein, this comonomer comprises 70～95% the unsaturated monomer that accounts for the monomer total amount and 5～30% the macromonomer that accounts for the monomer total amount;
Step 3): after dropwising, add initiator and solvent, be incubated 2 hours, cool to 100 ℃, filter discharging.
2. preparation method according to claim 1 is characterized in that: the consumption of tertiary carbonic acid glycidyl ester accounts for 1 ~ 20% of monomer total amount in the step 1).
3. preparation method according to claim 1; It is characterized in that: the preparation method of this macromonomer comprises step: take by weighing TEB 3K, Rocryl 400, NSC 20956, butylacetate, Diisopropyl azodicarboxylate, two hydrations two (boron difluoride benzene two ketoximes) and close cobalt acid (II) salt; With adding behind its uniform mixing in the reaction flask; Heated and stirred under nitrogen atmosphere obtains product behind the reaction some hrs.
4. preparation method according to claim 1 is characterized in that: 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.
5. preparation method according to claim 4 is characterized in that: the unsaturated vinyl monomer in this unsaturated monomer comprises: vinylbenzene and/or alpha-methyl styrene.
6. preparation method according to claim 4 is characterized in that: the unsaturated carboxylic acid in this unsaturated monomer comprises (methyl) vinylformic acid and/or methylene-succinic acid.
7. preparation method according to claim 4; It is characterized in that: contain in (methyl) alkyl acrylate in this unsaturated monomer that to account for its carbonatoms that contains of 60 ~ 80% be (methyl) alkyl acrylate of 1 ~ 4, and contain and account for its (methyl) vinylformic acid cycloalkyl ester of 20 ~ 40%.
8. preparation method according to claim 7 is characterized in that: should comprise by (methyl) vinylformic acid cycloalkyl ester: (methyl) cyclohexyl acrylate and/or (methyl) IBOA.
9. preparation method according to claim 4; It is characterized in that: this initiator is a radical initiator; Comprise azo-initiator and/or peroxide initiator; Wherein, Azo-initiator comprises Diisopropyl azodicarboxylate and/or AMBN, and the peroxide initiator comprises one or more in Lucidol, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, di-t-butyl peroxide, peroxo-two tert-pentyls, tertbutyl peroxide, the t-amyl peroxy hydrogen.
10. preparation method according to claim 4 is characterized in that: this solvent comprises one or more in toluene, YLENE, trimethylbenzene, durene, ETHYLE ACETATE, butylacetate, ethylene glycol ether acetate and the diethylene glycol ether acetic ester.
11. a fast dried weather resistant High solids Acrylic Resin is characterized in that: make according to each described preparation method in the claim 1 ~ 10.
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| CN103923251A (en) * | 2014-04-28 | 2014-07-16 | 无锡德贝尔光电材料有限公司 | Quick drying 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 |
| CN108948254A (en) * | 2018-07-06 | 2018-12-07 | 莱阳红安化工有限公司 | A kind of feature of environmental protection acrylic resin and preparation method thereof |
| CN110003366A (en) * | 2019-04-10 | 2019-07-12 | 泰兴盛嘉树脂有限公司 | A kind of preparation method that the E-10P that can reduce resin color is acrylic resin modified |
| CN110713572A (en) * | 2018-07-11 | 2020-01-21 | 广东华润涂料有限公司 | High-solid-content low-viscosity resin composition containing acrylic copolymer |
| CN116515073A (en) * | 2023-04-07 | 2023-08-01 | 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103923251A (en) * | 2014-04-28 | 2014-07-16 | 无锡德贝尔光电材料有限公司 | Quick drying acrylate polymer and preparation method thereof |
| 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 |
| CN108948254A (en) * | 2018-07-06 | 2018-12-07 | 莱阳红安化工有限公司 | A kind of feature of environmental protection acrylic resin and preparation method thereof |
| 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 |
| CN110713572A (en) * | 2018-07-11 | 2020-01-21 | 广东华润涂料有限公司 | High-solid-content low-viscosity resin composition containing acrylic copolymer |
| 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 |
| CN110003366A (en) * | 2019-04-10 | 2019-07-12 | 泰兴盛嘉树脂有限公司 | A kind of preparation method that the E-10P that can reduce resin color is acrylic resin modified |
| 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 |
| CN116515073A (en) * | 2023-04-07 | 2023-08-01 | 广东豪美新材股份有限公司 | Preparation method of energy-absorbing material |
| 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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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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