CN115109180B - Antibacterial styrene-acrylic resin and preparation method thereof - Google Patents
Antibacterial styrene-acrylic resin and preparation method thereof Download PDFInfo
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- CN115109180B CN115109180B CN202210608759.2A CN202210608759A CN115109180B CN 115109180 B CN115109180 B CN 115109180B CN 202210608759 A CN202210608759 A CN 202210608759A CN 115109180 B CN115109180 B CN 115109180B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention belongs to the field of preparation and application of novel functional polymer materials, and relates to an antibacterial styrene-acrylic resin and a preparation method thereof. The introduction of the diethyl itaconate and the isobornyl methacrylate ensures that the styrene-acrylic resin has excellent mechanical property, low water absorption, high hardness and good antibacterial property, and has wide application prospect in the fields of building and aviation paint, adhesive, papermaking and the like.
Description
Technical Field
The invention relates to a preparation method of styrene-acrylic resin, in particular to an antibacterial styrene-acrylic resin and a preparation method thereof, belonging to the technical field of preparation and application of novel functional polymer materials.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The styrene-acrylic resin is prepared by emulsion polymerization and copolymerization of styrene and acrylic monomers, has excellent performances such as good film forming property, transparency, cohesiveness, glossiness, aging resistance, environmental protection and the like, and is widely applied to the fields of aviation and building coating, papermaking, adhesive, printing ink, textile printing and dyeing and the like. However, with the application in various fields, the defects of the conventional styrene-acrylic material are continuously found, for example, the water resistance and mechanical properties thereof are poor, and the mechanical properties are affected by temperature. In addition, when used as a coating material, bacteria are easily grown by attack of microorganisms, which affect the beauty of the coating substrate (discoloration of the coating), malodor is generated, and the substrate is corroded by microorganisms, which affect the actual industrial performance. Therefore, the modification of styrene-acrylic latex by various methods has received extensive attention from researchers.
The modification of the styrene-acrylic resin comprises organosilicon modification, organic fluorine modification, epoxy resin modification, functional monomer modification and the like. Wherein, the modification of the functional monomer can improve the comprehensive performance of the styrene-acrylic resin, and the functional groups according to different monomers can improve the mechanical property, adhesive force, hardness, water resistance, solvent resistance and pollution resistance of the styrene-acrylic resin and can endow the resin with antibacterial property, thereby obtaining the styrene-acrylic resin with specific functions. Generally, antibacterial materials are obtained by incorporating monomers or fillers having antibacterial properties into polymers to impart antibacterial properties. Based on the differences in antimicrobial agents, the antimicrobial mechanism can be divided into two categories, one by killing bacteria on the surface of the material, primarily by interaction with phospholipid components to disrupt the integrity of the cell membrane. Another is to remove bacteria by reducing their adhesion to the surface of the material. Compared with the former, the antibacterial mode of the latter is more efficient and environment-friendly.
Patent CN 108822241A discloses a preparation method of an environment-friendly wet strength agent, which comprises the following steps: an environment-friendly wet strength agent emulsion for papermaking is prepared from styrene, butyl acrylate and glycidyl methacrylate. Patent CN 113214432A discloses a preparation method of styrene-acrylic building emulsion, which comprises the following steps: a styrene-acrylic building emulsion was prepared from styrene, butyl acrylate and acrylamide. The emulsion has excellent flexibility, adhesive property, adhesive force, alkali resistance, water resistance, scrubbing resistance, elongation at break, tensile strength and the like. The styrene-acrylic emulsion prepared by the two patents has excellent performance but has no antibacterial performance.
Patent CN 113136003A discloses a preparation method of an antibacterial styrene-acrylic emulsion containing thiazole structure, which comprises the following steps: styrene, butyl acrylate, (methyl) acrylic acid and (methyl) acrylic ester monomer containing thiazole structure are polymerized by emulsion to prepare the antibacterial styrene-acrylic emulsion containing thiazole structure, and the styrene-acrylic emulsion has excellent antibacterial performance but higher water absorption rate.
Disclosure of Invention
In order to overcome the problems, the invention provides an antibacterial styrene-acrylic resin and a preparation method thereof. The styrene-acrylic resin is prepared by semi-continuous seed emulsion polymerization, and the obtained resin has excellent mechanical property, low water absorption, high hardness and good antibacterial property. The preparation method is simple and efficient, has strong practicability and is easy to popularize.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing an antibacterial styrene-acrylic resin, comprising:
uniformly mixing styrene, butyl acrylate, functional monomers, water and a composite emulsifier to obtain a pre-emulsion;
taking part of the pre-emulsion as seed emulsion, adding a reducing agent under the protection of inert gas, heating to 40-60 ℃, adding an oxidizing agent, and carrying out seed emulsion polymerization;
after the polymerization reaction is completed, continuously adding an oxidant and the rest of the pre-emulsion, and reacting to obtain latex;
drying the latex to obtain the final product.
In a second aspect of the present invention, there is provided an antibacterial styrene-acrylic resin prepared by the above method.
The invention has the beneficial effects that:
(1) The styrene-acrylic resin prepared by semi-continuous seed emulsion polymerization has excellent mechanical property, low water absorption, high hardness and good antibacterial property, and has good application prospect.
(2) The isobornyl methacrylate disclosed by the invention is a bio-based antibacterial monomer, wherein isobornyl is a natural antibacterial agent with antibacterial and anti-inflammatory effects, and is mainly derived from natural Chinese herbal medicines such as lavender, chamomile and the like. In addition, the isobornyl methacrylate monomer has higher rigidity and hydrophobicity, can reduce the water absorption rate of styrene-acrylic resin, improve the hardness and endow the resin with antibacterial property after participating in polymerization in a chemical bonding mode, and can be used for preparing novel environment-friendly polymer materials with broad-spectrum and durable antibacterial property.
(3) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application.
FIG. 1 is an FT-IR chart of styrene-acrylic resins prepared in examples 1-2 and comparative example 1.
FIG. 2 is a stress-strain curve of the styrene-acrylic resins prepared in examples 1 to 6 and comparative example 1.
FIG. 3 is a graph showing the water absorption of the styrene-acrylic resins prepared in examples 1 to 6 and comparative example 1.
Fig. 4 is a graph of the shore hardness of the styrene-acrylic resins prepared in examples 1-6 and comparative example 1.
FIG. 5 is a graph showing the antibacterial properties of the styrene-acrylic resin prepared in example 1-2 against E.coli.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As described in the background art, the problems that the existing styrene-acrylic resin material has poor mechanical property and water resistance and can be used as a coating layer to influence the appearance and sanitary performance due to bacterial growth are solved. The invention provides a preparation method of a styrene-acrylic resin with high performance, low water absorption, high hardness and antibacterial property, which comprises the following steps:
mixing styrene, butyl acrylate, functional monomer, deionized water and a composite emulsifier to prepare a pre-emulsion, taking out a part of the pre-emulsion as seed emulsion, adding the seed emulsion into a four-neck flask with a stirring paddle and a reflux condenser, adding a reducing agent in a nitrogen atmosphere, heating to 40-60 ℃, and adding an oxidizing agent.
After the seed emulsion is polymerized, the rest oxidant and the pre-emulsion are slowly dripped for 1-2 h. After the dripping is finished, the reaction is continued for 4 to 8 hours, and the white bluish latex is obtained. The latex was dried in a vacuum oven to prepare a styrene-acrylic resin having high performance and antibacterial properties.
In some examples, the functional monomer is one or more of acrylamide, glycidyl methacrylate, diethyl itaconate, and isobornyl methacrylate.
In some examples, the complex emulsifier is an anionic surfactant and a nonionic surfactant.
In some examples, the anionic surfactant is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl alcohol polyoxyethylene ether sulfate and sodium fatty alcohol hydroxyethyl sulfonate, and the nonionic surfactant is one of polyoxyethylene octyl phenol ether-10, polyoxyethylene alkylamine and polyoxyethylene alkyl alcohol amide.
In some examples, the oxidizing agent in the redox initiator is one of ammonium persulfate and potassium persulfate and the reducing agent is one of sodium sulfite and sodium bisulfite.
In some examples, the mixing is performed in a homogenizer, dispersion or ultrasound.
In some examples, the temperature of the vacuum oven is 40-80 ℃.
In some examples, the styrene is used in an amount of 8 to 12 parts, the butyl acrylate is used in an amount of 12 to 18 parts, the total amount of glycidyl methacrylate and diethyl itaconate is 1 to 2 parts, the acrylamide is used in an amount of 1 to 2 parts, the isobornyl methacrylate is used in an amount of 1 to 8 parts, the deionized water is used in an amount of 50 to 80 parts, the composite emulsifier is used in an amount of 0.5 to 1.5 parts, and the redox initiator is used in an amount of 0.1 to 0.5 part.
The method comprises the following specific steps:
step one: 8 to 12 parts of styrene, 12 to 18 parts of butyl acrylate, 1 to 2 parts of glycidyl methacrylate and diethyl itaconate, 50 to 80 parts of deionized water and 0.5 to 1.5 parts of compound emulsifier are stirred in a homogenizer for 10 to 20 minutes to obtain a pre-emulsion.
Step two: taking a part of the pre-emulsion as seed emulsion, adding the seed emulsion into a four-neck flask with a mechanical stirring paddle and a reflux condenser, and introducing nitrogen for 5-15 min. Dripping 0.05-0.3 part of sodium bisulphite into the pre-emulsion, and adding 0.03-0.1 part of potassium persulfate after the temperature is raised to 40-60 ℃.
Step three: after seed emulsion polymerization, dropwise adding an acrylamide aqueous solution, 0.08-0.2 part of potassium persulfate and the residual pre-emulsion into the mixture for 1-2 h. After the dripping is finished, continuing to react for 4-8 hours to obtain white bluish latex. The latex was dried in a vacuum oven at 40-80 ℃ to prepare an itaconate modified styrene-acrylic resin.
Step four: and (3) after the prepared itaconate modified styrene-acrylic resin is characterized, selecting a group with the best performance, adding 1-8 parts of isobornyl methacrylate on the basis, and repeating the steps one to three to obtain the isobornyl methacrylate monomer modified styrene-acrylic resin.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Example 1
10.8g of styrene, 16.2g of butyl acrylate, 1.38g of glycidyl methacrylate, 0.12g of diethyl itaconate, 0.9g of a complex emulsifier and 30g of deionized water were mixed in a beaker and stirred with a high-speed dispersion homogenizer to obtain a pre-emulsion. One quarter of the pre-emulsion was added to a 250mL four port round bottom glass flask with a mechanical stirrer under nitrogen atmosphere. 0.1g of an aqueous sodium hydrogensulfite solution was added dropwise to the mixture. After the temperature was raised to 50 ℃, 0.08g of potassium persulfate aqueous solution was added dropwise, and after polymerization was initiated, 0.12g of potassium persulfate aqueous solution, 1.5g of acrylamide aqueous solution and pre-emulsion were simultaneously added dropwise to the mixture, and the reaction was continued for 7 hours to obtain a white bluish latex. Pouring the product into a mould and drying in vacuum at 60 ℃ to finally obtain the itaconate modified styrene-acrylic resin.
Example 2
The procedure of example 1 was repeated except for 9.18g of styrene, 15.12g of butyl acrylate, 1.25g of glycidyl methacrylate, 0.1g of diethyl itaconate, 3g of isobornyl methacrylate and 1.35g of acrylamide.
Example 3
The procedure of example 1 was repeated except for 1.47g of glycidyl methacrylate and 0.03g of diethyl itaconate.
Example 4
The procedure described in example 1 was repeated except for 1.44g of glycidyl methacrylate and 0.06g of diethyl itaconate.
Example 5
The procedure of example 1 was repeated except for 1.41g of glycidyl methacrylate and 0.09g of diethyl itaconate.
Example 6
The procedure described in example 1 was repeated except for 1.35g of glycidyl methacrylate and 0.15g of diethyl itaconate.
Comparative example 1
The procedure described in example 1 was repeated except that diethyl itaconate, 1.5g of glycidyl methacrylate, was not added.
The test results show that: as shown in FIG. 1, 700cm -1 、761cm -1 And 1248cm -1 The absorption peak at the position is respectively due to the asymmetric and symmetric stretching vibration of the epoxy group, and the absorption peak of the ester carbonyl is 1725cm -1 At 3383cm -1 The peak at this point is the N-H stretching vibration peak in acrylamide. The c=c double bond peak did not appear, indicating successful participation of diethyl itaconate and isobornyl methacrylate in the polymerization. As shown in FIG. 2, the tensile properties of the styrene-acrylic resins prepared by the different masses of diethyl itaconate and isobornyl methacrylate were different, wherein the tensile strength could reach 20.4MPa at a mass of diethyl itaconate of 0.12 g. As shown in fig. 3, the water absorption of the styrene-acrylic resin can be as low as 2.2% after the introduction of isobornyl methacrylate. As shown in FIG. 4, the styrene-acrylic resin has a hardness of 89.6A due to the presence of the rigid isobornyl. As shown in FIG. 5, the styrene-acrylic resin exhibited 86% antibacterial efficiency against E.coli due to the stereochemistry of the polymer surface of isobornyl group.
While the foregoing describes the embodiments of the present invention, it should be understood that the present invention is not limited to the embodiments, and that various modifications and changes can be made by those skilled in the art without any inventive effort.
Claims (9)
1. The preparation method of the antibacterial styrene-acrylic resin is characterized by comprising the following steps:
uniformly mixing styrene, butyl acrylate, functional monomers, water and a composite emulsifier to obtain a pre-emulsion;
taking part of the pre-emulsion as seed emulsion, adding a reducing agent under the protection of inert gas, heating to 40-60 ℃, adding an oxidizing agent, and carrying out seed emulsion polymerization;
after the polymerization reaction is completed, continuously adding an oxidant and the rest of the pre-emulsion, and reacting to obtain latex;
drying the latex to obtain the modified latex;
the functional monomers are acrylamide, glycidyl methacrylate, diethyl itaconate and isobornyl methacrylate;
the styrene is 8-12 parts, the butyl acrylate is 12-18 parts, the total amount of glycidyl methacrylate and diethyl itaconate is 1-2 parts, the acrylamide is 1-2 parts, the isobornyl methacrylate is 1-8 parts, the water is 50-80 parts, the composite emulsifier is 0.5-1.5 parts, and the redox initiator is 0.1-0.5 part.
2. The method for preparing an antibacterial styrene-acrylic resin according to claim 1, wherein the compound emulsifier is an anionic surfactant or a nonionic surfactant.
3. The method for preparing an antibacterial styrene-acrylic resin according to claim 2, wherein the anionic surfactant is at least one of sodium dodecylbenzene sulfonate, sodium dodecylsulfate, sodium laureth sulfate, and sodium fatty alcohol isethionate.
4. The method for preparing an antibacterial styrene-acrylic resin according to claim 2, wherein the nonionic surfactant is at least one of polyoxyethylene octyl phenol ether-10, polyoxyethylene alkylamine and polyoxyethylene alkyl alcohol amide.
5. The method for preparing an antibacterial styrene-acrylic resin according to claim 1, wherein the oxidizing agent in the redox initiator is ammonium persulfate or potassium persulfate.
6. The method for preparing an antibacterial styrene-acrylic resin according to claim 1, wherein the reducing agent is sodium sulfite or sodium bisulfite.
7. The method for preparing an antibacterial styrene-acrylic resin according to claim 1, wherein after the seed emulsion is polymerized, the remaining oxidant and the pre-emulsion are slowly added dropwise, the adding time is 1-2 h, and after the adding is completed, the reaction is continued for 4-8 h.
8. An antibacterial styrene-acrylic resin prepared by the method of any one of claims 1 to 7.
9. The antimicrobial styrene-acrylic resin of claim 8, wherein the antimicrobial styrene-acrylic resin is used in the fields of aviation, architectural coatings, papermaking, adhesives, inks, and textile printing.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037610A (en) * | 2015-09-18 | 2015-11-11 | 四川绿创环阅环保科技有限公司 | Preparation method for water-based acrylate antibacterial emulsion |
| WO2018007325A1 (en) * | 2016-07-04 | 2018-01-11 | Dsm Ip Assets B.V. | Aqueous polymer emulsion |
| CN111533840A (en) * | 2020-06-24 | 2020-08-14 | 浙江恒达新材料股份有限公司 | Environment-friendly water-resistant reinforced latex for paper and preparation method and application thereof |
| CN113136003A (en) * | 2021-03-18 | 2021-07-20 | 广州立邦涂料有限公司 | Antibacterial styrene-acrylic emulsion containing thiazole structure and preparation method and application thereof |
| CN113233995A (en) * | 2021-04-13 | 2021-08-10 | 华南理工大学 | Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037610A (en) * | 2015-09-18 | 2015-11-11 | 四川绿创环阅环保科技有限公司 | Preparation method for water-based acrylate antibacterial emulsion |
| WO2018007325A1 (en) * | 2016-07-04 | 2018-01-11 | Dsm Ip Assets B.V. | Aqueous polymer emulsion |
| CN109563369A (en) * | 2016-07-04 | 2019-04-02 | 帝斯曼知识产权资产管理有限公司 | Aqueous polymer emulsion |
| CN111533840A (en) * | 2020-06-24 | 2020-08-14 | 浙江恒达新材料股份有限公司 | Environment-friendly water-resistant reinforced latex for paper and preparation method and application thereof |
| CN113136003A (en) * | 2021-03-18 | 2021-07-20 | 广州立邦涂料有限公司 | Antibacterial styrene-acrylic emulsion containing thiazole structure and preparation method and application thereof |
| CN113233995A (en) * | 2021-04-13 | 2021-08-10 | 华南理工大学 | Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof |
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