CN110591010B - Water-resistant styrene-free artificial stone resin and preparation method thereof - Google Patents
Water-resistant styrene-free artificial stone resin and preparation method thereof Download PDFInfo
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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Abstract
The invention discloses a waterproof styrene-free artificial stone resin which comprises the following components in parts by weight: 20-40 parts of dihydric alcohol, 30-45 parts of organic acid, organic acid anhydride or a mixture thereof, 0.01-0.1 part of catalyst, 0.01-0.05 part of polymerization inhibitor, 0.05-0.5 part of paraffin, 15-27 parts of tertiary carbon glycidyl ester and 3-8 parts of crosslinking functional monomer, wherein the organic acid, the organic acid anhydride or the mixture thereof contains unsaturated organic acid and/or organic acid anhydride. The invention also discloses a preparation method of the waterproof styrene-free artificial stone resin, which comprises the steps of preparing an unsaturated polyester prepolymer for later use; mixing and reacting tertiary carbon glycidyl ester, a crosslinking functional monomer and p-toluenesulfonic acid, mixing and reacting with the polyester prepolymer in the first reaction kettle, and discharging. The waterproof styrene-free artificial stone resin has low VOC content and better water resistance; the preparation method of the waterproof styrene-free artificial stone resin has the advantages of simple process and low pollution.
Description
Technical Field
The invention relates to the field of artificial stones, in particular to a waterproof styrene-free artificial stone resin and a preparation method thereof.
Background
Engineered stone is typically referred to as engineered stone solid facestock, engineered quartz stone, engineered stone granite, and the like. The artificial stone resin usually consists of matrix resin and a diluting solvent, and the unsaturated polyester resin matrix resin can be conventional unsaturated polyester taking dihydric alcohol and dibasic acid as main raw materials; a conventional diluent is styrene monomer. The Chinese patent application with publication number CN108047433A and name of unsaturated resin for artificial stone, the raw materials for preparing modified unsaturated resin comprise maleic anhydride and tetrahydrophthalic anhydride as acid raw materials; propylene glycol, diethylene glycol and neopentyl glycol as alcohol raw materials; the catalyst also comprises styrene and a polymerization inhibitor, wherein the dosage of the styrene is 30-33% of the total mass of the acid raw material and the alcohol raw material. The raw material contains a large amount of styrene. Generally, the unsaturated resin adopts styrene as a diluent, the styrene has low flash point, is volatile, has strong irritation and anesthetic effects and potential carcinogenicity and teratogenicity, and the styrene which does not participate in curing is also an important source of VOC. The problem of the prior art is that the artificial stone resin contains a large amount of styrene and is not environment-friendly.
In order to reduce VOC in unsaturated polyesters, non-styrene unsaturated polyesters are the subject of intense research. The Chinese patent application with the publication number of CN109734890A and the name of a preparation method of styrene-free unsaturated resin discloses the following steps: (1) melt polymerizing monohydric alcohol, polyhydric alcohol, monobasic acid/anhydride, saturated polybasic acid/anhydride and/or unsaturated polybasic acid/anhydride to obtain saturated or unsaturated polyester; (2) uniformly mixing glycidyl methacrylate or glycidyl acrylate with the saturated or unsaturated polyester, and carrying out ring-opening addition reaction under the action of a catalyst to obtain unsaturated resin; (3) and mixing the unsaturated resin, the reactive diluent and the polymerization inhibitor to obtain the styrene-free unsaturated resin. The principle is that saturated or unsaturated polyester is modified by glycidyl methacrylate or glycidyl acrylate, and the modified polyester reacts with reactive diluent to carry out crosslinking. The method adopts an active diluent with a higher boiling point, such as hydroxyethyl methacrylate, to reduce VOC in a reaction system, and the used catalyst is one or more of amines and triphenylphosphine.
In the technical scheme, the modifier is glycidyl acrylate, and after the glycidyl acrylate reacts with the terminal carboxyl group of the resin prepolymer, the chain end of the resin molecule is an acrylate group with a hydrophilic side hydroxyl branched chain, so that the water resistance is poor.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the waterproof styrene-free artificial stone resin is prepared from styrene-free raw materials, and solves the problems that the artificial stone resin in the prior art is not environment-friendly and has poor water resistance.
The solution of the invention for solving the technical problem is as follows:
the waterproof styrene-free artificial stone resin comprises the following raw materials in parts by weight: 20-40 parts of dihydric alcohol, 30-45 parts of organic acid, organic acid anhydride or a mixture thereof, 0.01-0.1 part of catalyst, 0.01-0.05 part of polymerization inhibitor, 0.05-0.5 part of paraffin, 15-27 parts of tertiary carbon glycidyl ester and 3-8 parts of crosslinking functional monomer, wherein the organic acid, the organic acid anhydride or the mixture thereof contains unsaturated organic acid and/or organic acid anhydride, and the crosslinking functional monomer is one or a mixture of acrylic acid, methacrylic acid, acrylic ester and methacrylic ester.
In the application, alcohol, organic acid and organic acid anhydride are condensed to form unsaturated polyester prepolymer; the epoxy group on the tertiary carbon glycidyl ester and the carboxyl group on the crosslinking functional monomer carry out ring-opening reaction to generate unsaturated ester containing terminal hydroxyl, the unsaturated carbon-carbon bond on the unsaturated ester still has crosslinking effect on the unsaturated polyester prepolymer, the unsaturated ester can partially or completely replace the conventional diluent styrene monomer in the unsaturated polyester, the molecular weight and the boiling point of the unsaturated ester are higher than those of the crosslinking functional monomer, the unsaturated ester has lower viscosity and lower volatility, and the boiling point of the tertiary carbon glycidyl ester is higher, so that the VOC in the waterproof styrene-free artificial stone resin is lower. The tertiary carbon glycidyl ester can also react with hydroxyl and carboxyl on the unsaturated polyester prepolymer, and the polymerization inhibitor and paraffin are often used in an unsaturated resin reaction system at the same time; the tertiary carbonic acid glycidyl ester is used as a modifier, the tertiary carbon group greatly increases the steric hindrance between molecules, reduces the winding between resin molecules, reduces the viscosity of the resin and ensures that ester groups which are easy to hydrolyze originally have good water resistance. The water-resistant styrene-free artificial stone resin is suitable for the field of home decoration building materials and suitable for serving as artificial stone resin.
Optionally, the glycol is a mixture of 7-11 parts by weight ethylene glycol, 4-10 parts by weight propylene glycol, 4-10 parts by weight diethylene glycol, 4-10 parts by weight methyl propylene glycol.
Further, the diol is a mixture of 9.8 parts by weight of ethylene glycol, 6.5 parts by weight of propylene glycol, 6.5 parts by weight of diethylene glycol, 6.5 parts by weight of methyl propylene glycol.
Optionally, the organic acid, organic anhydride or mixture thereof is a mixture of 12 to 18 parts by weight of phthalic anhydride, 10 to 18 parts by weight of maleic anhydride, 10 to 15 parts by weight of fumaric acid.
Further, the organic acid anhydride or the mixture thereof is a mixture of 16.3 parts by weight of phthalic anhydride, 11.8 parts by weight of maleic anhydride, and 13.2 parts by weight of fumaric acid.
The phthalic anhydride, maleic anhydride and fumaric acid are all binary acids, wherein unsaturated bonds on the maleic anhydride and the fumaric acid can react with a crosslinking functional monomer to improve the crosslinking degree, so that the curing is carried out. The dihydric alcohol, the dibasic acid and the dibasic acid anhydride react to generate straight-chain unsaturated polyester, and the cured unsaturated polyester has higher bending strength, bending modulus and hardness and is suitable to be used as a raw material of artificial stones in household building materials.
Optionally, 29.3 parts of dihydric alcohol, 41.3 parts of dibasic acid, dibasic acid anhydride or a mixture thereof, 0.04 part of catalyst, 22.9 parts of tertiary carbon glycidyl ester, 0.01 part of polymerization inhibitor, 6.35 parts of crosslinking functional monomer and 0.1 part of paraffin are included.
Optionally, the polymerization inhibitor is p-hydroxyanisole and the catalyst is p-toluenesulfonic acid.
Alternatively, the glycidyl ester of a tertiary carbon is glycidyl neodecanoate. After the neodecanoic acid glycidyl ester reacts with hydroxyl and carboxyl on the unsaturated polyester prepolymer, the end of a molecular chain has a tertiary carbon group with larger volume and hydrophobicity, so that the intermolecular steric hindrance is greatly increased, the winding among resin molecules is reduced, the viscosity of the resin is reduced, and the ester group which is easy to hydrolyze originally has good water resistance.
Optionally, the crosslinking functional monomer is one of acrylic acid, methacrylic acid or a mixture thereof.
The preparation method of the low-volatility waterproof styrene-free artificial stone resin is used for preparing the waterproof styrene-free artificial stone resin and comprises the following steps: s1, adding 20-40 parts by weight of dihydric alcohol, 30-50 parts by weight of organic acid or anhydride and a mixture thereof into a first reaction kettle, heating to 195-210 ℃, reducing the temperature to 185-193 ℃, and adding 0.01-0.05 part by weight of polymerization inhibitor and 0.05-0.5 part by weight of paraffin wax to obtain an unsaturated polyester prepolymer for later use, wherein the acid value of the reaction system reaches 35-40mgKOH/g, and the viscosity at 130 ℃ reaches 300-500 cp; s2, adding 15-27 parts by weight of tertiary carbon glycidyl ester, 3-8 parts by weight of crosslinking functional monomer and 0.01-0.1 part by weight of p-toluenesulfonic acid into a second reaction kettle, heating to 110-.
Reacting dihydric alcohol, organic acid or anhydride and a mixture thereof in a first reaction kettle, and adding a polymerization inhibitor and paraffin to obtain an unsaturated polyester prepolymer; set up the second reation kettle, tertiary carbon glycidyl ester and cross-linking function monomer react with unsaturated polyester prepolymer after reacting each other, can be through adding the tertiary carbon glycidyl ester of formula equivalent, carry out quantitative reaction with cross-linking monomer's carboxyl or resin prepolymer's carboxyl, make cross-linking function monomer's reaction complete, thereby avoid excessive cross-linking function monomer to cause the VOC increase in the reaction system, make the tertiary carbon structure that has great steric hindrance of resin molecule chain end, the rostone that comes out with this resin production also has good water resistance.
The invention has the beneficial effects that: the waterproof styrene-free artificial stone resin has low VOC content and better water resistance; the preparation method of the waterproof styrene-free artificial stone resin has the advantages of simple process and low pollution.
Detailed Description
The conception, the specific structure, and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below, so that the objects, the features, and the effects of the present invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example one
S1, adding 8 parts by weight of ethylene glycol, 4 parts by weight of propylene glycol, 4 parts by weight of diethylene glycol, 4 parts by weight of methyl propylene glycol, 12 parts by weight of phthalic anhydride, 8 parts by weight of maleic anhydride and 10 parts by weight of fumaric acid into a first reaction kettle, heating to 195 ℃, carrying out heat preservation reaction, cooling to 185 ℃ after the acid value of a reaction system reaches 35mgKOH/g and the viscosity of 130 ℃ reaches 300cp, and adding 0.01 part by weight of p-hydroxyanisole and 0.05 part by weight of paraffin to obtain an unsaturated polyester prepolymer for later use; s2, adding 15 parts by weight of glycidyl neodecanoate, 3 parts by weight of acrylic acid and 0.01 part by weight of p-toluenesulfonic acid into a second reaction kettle, heating to 110 ℃, mixing with the polyester prepolymer in the first reaction kettle after the acid value reaches 1mgKOH/g, stirring, carrying out heat preservation reaction at 110 ℃, reducing the temperature to room temperature after the acid value reaches 10mgKOH/g (the acid value can be reached after the reaction lasts for about 3 hours) and the viscosity reaches 3500 and 4500cp, and discharging.
Example two
S1, adding 11 parts by weight of ethylene glycol, 9 parts by weight of propylene glycol, 9 parts by weight of diethylene glycol, 9 parts by weight of methyl propylene glycol, 18 parts by weight of phthalic anhydride, 12 parts by weight of maleic anhydride and 15 parts by weight of fumaric acid into a first reaction kettle, heating to 205 ℃, reducing the temperature to 192 ℃ after the acid value of a reaction system reaches 40mgKOH/g and the viscosity at 130 ℃ reaches 500cp, and adding 0.05 part by weight of p-hydroxyanisole and 0.5 part by weight of paraffin wax to obtain an unsaturated polyester prepolymer for later use; s2, adding 27 parts by weight of glycidyl neodecanoate, 8 parts by weight of acrylic acid and 0.1 part by weight of p-toluenesulfonic acid into a second reaction kettle, heating to 130 ℃, preserving heat until the acid value reaches 3mgKOH/g, mixing with the polyester prepolymer in the first reaction kettle, stirring, preserving heat for reaction at 130 ℃, reducing the acid value to room temperature after the acid value reaches 15mgKOH/g (the acid value can be reached after about 5 hours of reaction), and discharging.
Comparative example
Adding 11 parts by weight of ethylene glycol, 9 parts by weight of propylene glycol, 9 parts by weight of diethylene glycol, 9 parts by weight of methyl propylene glycol, 18 parts by weight of phthalic anhydride, 12 parts by weight of maleic anhydride and 15 parts by weight of fumaric acid into a first reaction kettle, heating to 205 ℃, reducing the temperature to 192 ℃ after the acid value of a reaction system reaches 35mgKOH/g and the viscosity at 130 ℃ reaches 680cp, adding 0.05 part by weight of p-hydroxyanisole and 0.5 part by weight of paraffin wax to obtain an unsaturated polyester prepolymer, cooling to 110 ℃, adding 35 parts by weight of styrene, cooling to room temperature, and discharging.
Table 1 shows the results of the performance test of the water-resistant styrene-free artificial stone resins of examples one and two.
TABLE 1
As can be seen from Table 1, the water-resistant styrene-free artificial stone resin of the present application has a hardness and a bending strength which are not significantly reduced, while the impact toughness is improved and the water absorption is greatly reduced, compared with the artificial stone resin using styrene as a diluent in the prior art.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions, all of which are within the scope of the claims appended hereto.
Claims (6)
1. The preparation method of the waterproof styrene-free artificial stone resin is characterized by comprising the following steps of:
s1, adding 20-40 parts by weight of dihydric alcohol, 30-50 parts by weight of organic acid or anhydride and a mixture thereof into a first reaction kettle, heating to 195-210 ℃, reducing the temperature to 185-193 ℃, and adding 0.01-0.05 part by weight of polymerization inhibitor and 0.05-0.5 part by weight of paraffin wax to obtain an unsaturated polyester prepolymer for later use, wherein the acid value of the reaction system reaches 35-40mgKOH/g, and the viscosity at 130 ℃ reaches 300-500 cp;
s2, adding 15-27 parts by weight of tertiary carbon glycidyl ester, 3-8 parts by weight of crosslinking functional monomer and 0.01-0.1 part by weight of p-toluenesulfonic acid into a second reaction kettle, heating to 110-130 ℃, preserving heat until the acid value reaches 1-3mgKOH/g, mixing with the polyester prepolymer in the first reaction kettle, stirring, carrying out heat preservation reaction at 110-130 ℃, cooling to room temperature after the acid value reaches 10-15mgKOH/g, and discharging;
wherein, the crosslinking functional monomer is one or a mixture of acrylic acid, methacrylic acid, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
2. A water-resistant styrene-free artificial stone resin prepared by the method of claim 1, which comprises the following raw materials in parts by weight: 20-40 parts of dihydric alcohol, 30-45 parts of organic acid, organic acid anhydride or a mixture thereof, 0.01-0.1 part of catalyst, 0.01-0.05 part of polymerization inhibitor, 0.05-0.5 part of paraffin, 15-27 parts of tertiary carbon glycidyl ester and 3-8 parts of crosslinking functional monomer; the dihydric alcohol is a mixture of 7-11 parts by weight of ethylene glycol, 4-10 parts by weight of propylene glycol, 4-10 parts by weight of diethylene glycol and 4-10 parts by weight of methyl propylene glycol, the organic acid anhydride or the mixture thereof contains unsaturated organic acid and/or organic acid anhydride, the unsaturated organic acid and/or organic acid anhydride is a mixture of 12-18 parts by weight of phthalic anhydride, 10-18 parts by weight of maleic anhydride and 10-15 parts by weight of fumaric acid, the polymerization inhibitor is p-hydroxyanisole, and the catalyst is p-toluenesulfonic acid.
3. A water-resistant styrene-free artificial stone resin according to claim 2, wherein: the diol is a mixture of 9.8 parts by weight ethylene glycol, 6.5 parts by weight propylene glycol, 6.5 parts by weight diethylene glycol, 6.5 parts by weight methyl propylene glycol.
4. A water-resistant styrene-free artificial stone resin according to claim 2, wherein: the organic acid, the organic acid anhydride or the mixture thereof is a mixture of 16.3 parts by weight of phthalic anhydride, 11.8 parts by weight of maleic anhydride and 13.2 parts by weight of fumaric acid.
5. A water-resistant styrene-free artificial stone resin according to claim 2, comprising the following raw materials in parts by weight: 29.3 parts of dihydric alcohol, 41.3 parts of dibasic acid, dibasic acid anhydride or a mixture thereof, 0.04 part of catalyst, 22.9 parts of tertiary carbon glycidyl ester, 0.01 part of polymerization inhibitor, 6.35 parts of crosslinking functional monomer and 0.1 part of paraffin.
6. A water-resistant styrene-free artificial stone resin according to claim 2, wherein: the tertiary glycidyl ester is glycidyl neodecanoate.
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| CN111234179B (en) * | 2020-03-12 | 2022-11-04 | 浙江晨诺高分子材料有限公司 | Vinyl ester resin containing polyester structure and preparation method thereof |
| CN113292829A (en) * | 2021-06-30 | 2021-08-24 | 长春人造树脂厂股份有限公司 | Polyester composition, preparation method thereof and polyester composition film layer containing same |
| CN114316234B (en) * | 2021-12-29 | 2023-04-07 | 常州华科聚合物股份有限公司 | Preparation method of flame-retardant styrene-free hyperbranched unsaturated resin |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1511796A (en) * | 1975-09-25 | 1978-05-24 | Sumitomo Chemical Co | Low profile unsaturated polyester resin composition |
| CN102863592A (en) * | 2012-10-18 | 2013-01-09 | 常州华日新材有限公司 | Preparation method for transparent thixotropic unsaturated polyester resin |
| CN103788354A (en) * | 2012-10-26 | 2014-05-14 | 常州市华润复合材料有限公司 | Application of unsaturated polyester in packing material enhancement |
| WO2015058685A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified saturated polyester resin |
| CN107099227A (en) * | 2017-05-17 | 2017-08-29 | 恒昌涂料（惠阳）有限公司 | The unsaturated polyester resin of solid content 100% and the net taste PE varnish of low VOC |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
| CN109734890A (en) * | 2018-11-29 | 2019-05-10 | 常州华科聚合物股份有限公司 | A kind of preparation method of no styrene unsaturated-resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8546486B2 (en) * | 2007-09-18 | 2013-10-01 | Ccp Composites Us Llc | Low VOC thermosetting polyester acrylic resin for gel coat |
-
2019
- 2019-08-28 CN CN201910799672.6A patent/CN110591010B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1511796A (en) * | 1975-09-25 | 1978-05-24 | Sumitomo Chemical Co | Low profile unsaturated polyester resin composition |
| CN102863592A (en) * | 2012-10-18 | 2013-01-09 | 常州华日新材有限公司 | Preparation method for transparent thixotropic unsaturated polyester resin |
| CN103788354A (en) * | 2012-10-26 | 2014-05-14 | 常州市华润复合材料有限公司 | Application of unsaturated polyester in packing material enhancement |
| WO2015058685A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified saturated polyester resin |
| CN104761685A (en) * | 2013-10-21 | 2015-07-08 | 北京金汇利应用化工制品有限公司 | Preparation method of waterborne acrylic modified saturated polyester resin |
| CN107099227A (en) * | 2017-05-17 | 2017-08-29 | 恒昌涂料（惠阳）有限公司 | The unsaturated polyester resin of solid content 100% and the net taste PE varnish of low VOC |
| CN109734890A (en) * | 2018-11-29 | 2019-05-10 | 常州华科聚合物股份有限公司 | A kind of preparation method of no styrene unsaturated-resin |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 不饱和聚酯树脂的研究进展;徐刚，等;《江西师范大学学报(自然科学版)》;19980831;第22卷(第3期);第264-270页 * |
| 酯交换法改性低溶剂羟基丙烯酸分散体的制备及其应用;周国强，等;《染整技术》;20180620;第40卷(第06期);第33-38页 * |
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Effective date of registration: 20220812 Address after: Office Building, Yunfu Chenbao New Materials Co., Ltd., Industrial Park, Dawan Town, Yunan County, Yunfu City, Guangdong Province, 527100 Patentee after: Yunfu Chenbao New Material Co.,Ltd. Address before: No.5 Xingtang Road, Datang Industrial Park, Datang Town, Sanshui District, Foshan City, Guangdong Province 528100 Patentee before: Guangdong Chenbao composite material Co.,Ltd. |
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