CN105924572A - 一种固化交联苯乙烯-丙烯酸酯树脂的制备方法 - Google Patents

一种固化交联苯乙烯-丙烯酸酯树脂的制备方法 Download PDF

Info

Publication number
CN105924572A
CN105924572A CN201610451311.9A CN201610451311A CN105924572A CN 105924572 A CN105924572 A CN 105924572A CN 201610451311 A CN201610451311 A CN 201610451311A CN 105924572 A CN105924572 A CN 105924572A
Authority
CN
China
Prior art keywords
cross
acrylate
preparation
styrene
mix monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610451311.9A
Other languages
English (en)
Inventor
孙云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taicang Dongming Chemical Co Ltd
Original Assignee
Taicang Dongming Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taicang Dongming Chemical Co Ltd filed Critical Taicang Dongming Chemical Co Ltd
Priority to CN201610451311.9A priority Critical patent/CN105924572A/zh
Publication of CN105924572A publication Critical patent/CN105924572A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明公开了一种固化交联苯乙烯‑丙烯酸酯树脂的制备方法，包括如下步骤：（1）单体预处理；（2）制备乳液；（3）固化交联。本发明一种固化交联苯乙烯‑丙烯酸酯树脂的制备方法，操作简便，容易实现，其通过先乳化后交联及水性交联剂的制备，一方面提高了树脂的交联密度，改善产品性能，另一方面，提高了交联固化的效率并降低环境污染，综合性能优异。

Description

一种固化交联苯乙烯 - 丙烯酸酯树脂的制备方法
技术领域
本发明涉及树脂制备技术领域，特别是涉及一种固化交联苯乙烯-丙烯酸酯树脂的制备方法。
背景技术
苯乙烯-丙烯酸酯乳液共聚物（styrene acrylicemulision，SAE）强度高，耐候性和保光性良好，被广泛应用于涂料、造纸、纺织、皮革等领域。但因其线性分子缺少交联点，涂膜硬度较低，易被刮伤；热稳定性较差，高温易返粘，低温时又缺乏弹性，限制了SAE的应用。提高苯乙烯-丙烯酸树脂乳液共聚物性能的直接方法就是提高其交联度。但现有对其进行交联的方法存在如下问题：1、交联效果差，时间长；2、交联剂为有机溶剂，环境污染严重。
发明内容
本发明主要解决的技术问题是提供一种固化交联苯乙烯-丙烯酸酯树脂的制备方法，能够解决现有交联方法存在的上述问题。
为解决上述技术问题，本发明采用的一个技术方案是：提供一种固化交联苯乙烯-丙烯酸酯树脂的制备方法，包括如下步骤：
（1）单体预处理：将苯乙烯单体用碱液冲洗5～8次；
（2）制备乳液：向带加热搅拌装置的反应釜中加入一定量的乳化剂、引发剂、链转移剂和亚硫酸氢钠，然后以恒定速率滴加混合单体，滴毕，恒温反应一段时间，冷却至室温；
（3）固化交联：在连续搅拌状态下，向步骤（2）中所得乳液中依次加入聚乙烯醇单甲醚，异佛尔酮二异氰酸酯，然后再以恒定速率滴加六亚甲基二异氰酸酯，滴毕，持续搅拌1～2h，得到所述固化交联苯乙烯-丙烯酸酯树脂。
在本发明一个较佳实施例中，所述步骤（1）中，所述碱液为质量浓度为3～5%的氢氧化钠或氢氧化钾溶液。
在本发明一个较佳实施例中，所述步骤（2）中，所述乳化剂、引发剂、链转移剂和亚硫酸氢钠的加入量分别为所述混合单体总质量的20～30%、3～5%、8～10%和1～2%；所述混合单体的加入速率为2～5ml/min，所述反应温度为70～80℃，时间为7～8h。
在本发明一个较佳实施例中，所述乳化剂为质量浓度为15%的聚乙烯醇溶液和乳化剂OP-10以1：1的体积比混合的混合物；所述引发剂为亚硫酸钾；所述链转移剂为巯基乙酸；所述混合单体为步骤（1）中处理后的苯乙烯和丙烯酸正丁酯以1：2～3的质量比混合的混合物。
在本发明一个较佳实施例中，所述步骤（3）中，所述聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯的质量比为3～5：2～3：1；所述聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯的总质量为所述混合单体总质量的0.1～0.2%。
在本发明一个较佳实施例中，所述步骤（3）中，所述六亚甲基二异氰酸酯的滴加速率为5～8ml/min。
本发明的有益效果是：本发明一种固化交联苯乙烯-丙烯酸酯树脂的制备方法，操作简便，容易实现，其通过先乳化后交联及水性交联剂的制备，一方面提高了树脂的交联密度，改善产品性能，另一方面，提高了交联固化的效率并降低环境污染，综合性能优异。
具体实施方式
下面对本发明的较佳实施例进行详细阐述，以使本发明的优点和特征能更易于被本领域技术人员理解，从而对本发明的保护范围做出更为清楚明确的界定。
本发明实施例包括：
实施例1
一种固化交联苯乙烯-丙烯酸酯树脂的制备方法，具体步骤如下：
（1）单体预处理：将苯乙烯单体用质量浓度为3～5%的氢氧化钠或氢氧化钾溶液冲洗5～8次，以去除单体中的阻聚剂- 对叔丁基邻苯二酚；
（2）制备乳液：向带加热搅拌装置的反应釜中加入占混合单体总质量20%的乳化剂、占混合单体总质量3%的引发剂、占混合单体总质量8%的链转移剂和占混合单体总质量1%的亚硫酸氢钠，然后以2ml/min的恒定速率滴加混合单体，滴毕，70℃恒温反应8h，冷却至室温；
所述乳化剂为质量浓度为15%的聚乙烯醇溶液和乳化剂OP-10以1：1的体积比混合的混合物；所述引发剂为亚硫酸钾；所述链转移剂为巯基乙酸；所述混合单体为步骤（1）中处理后的苯乙烯和丙烯酸正丁酯以1：2的质量比混合的混合物；
（3）固化交联：在连续搅拌状态下，向步骤（2）中所得乳液中按3：2：1的质量比依次加入聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯，并确保聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯的加入总质量为所述混合单体总质量的0.1%；其中，六亚甲基二异氰酸酯在前两种物质加完之后，以5ml/min的恒定速率滴加，滴毕，持续搅拌1h，得到所述固化交联苯乙烯-丙烯酸酯树脂。
实施例2
一种固化交联苯乙烯-丙烯酸酯树脂的制备方法，具体步骤如下：
（1）单体预处理：将苯乙烯单体用质量浓度为3～5%的氢氧化钠或氢氧化钾溶液冲洗5～8次，以去除单体中的阻聚剂- 对叔丁基邻苯二酚；
（2）制备乳液：向带加热搅拌装置的反应釜中加入占混合单体总质量30%的乳化剂、占混合单体总质量5%的引发剂、占混合单体总质量10%的链转移剂和占混合单体总质量2%的亚硫酸氢钠，然后以5ml/min的恒定速率滴加混合单体，滴毕， 80℃恒温反应7h，冷却至室温；
所述乳化剂为质量浓度为15%的聚乙烯醇溶液和乳化剂OP-10以1：1的体积比混合的混合物；所述引发剂为亚硫酸钾；所述链转移剂为巯基乙酸；所述混合单体为步骤（1）中处理后的苯乙烯和丙烯酸正丁酯以1：3的质量比混合的混合物；
（3）固化交联：在连续搅拌状态下，向步骤（2）中所得乳液中按5：3：1的质量比依次加入聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯，并确保聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯的加入总质量为所述混合单体总质量的0.2%；其中，六亚甲基二异氰酸酯在前两种物质加完之后，以8ml/min的恒定速率滴加，滴毕，持续搅拌2h，得到所述固化交联苯乙烯-丙烯酸酯树脂。
上述实施例所制备的固化交联苯乙烯-丙烯酸酯树脂，经测试，其拉伸强度为14.6～15.8MPa，断裂伸长率大于120%，乳液粒径增大，粒径分布均一，粒径分布系数为0.089，耐水性能优异。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (6)

1.一种固化交联苯乙烯-丙烯酸酯树脂的制备方法，其特征在于，包括如下步骤：
（1）单体预处理：将苯乙烯单体用碱液冲洗5～8次；
（2）制备乳液：向带加热搅拌装置的反应釜中加入一定量的乳化剂、引发剂、链转移剂和亚硫酸氢钠，然后以恒定速率滴加混合单体，滴毕，恒温反应一段时间，冷却至室温；
（3）固化交联：在连续搅拌状态下，向步骤（2）中所得乳液中依次加入聚乙烯醇单甲醚，异佛尔酮二异氰酸酯，然后再以恒定速率滴加六亚甲基二异氰酸酯，滴毕，持续搅拌1～2h，得到所述固化交联苯乙烯-丙烯酸酯树脂。
2.根据权利要求1所述的固化交联苯乙烯-丙烯酸酯树脂的制备方法，其特征在于，所述步骤（1）中，所述碱液为质量浓度为3～5%的氢氧化钠或氢氧化钾溶液。
3.根据权利要求1所述的固化交联苯乙烯-丙烯酸酯树脂的制备方法，其特征在于，所述步骤（2）中，所述乳化剂、引发剂、链转移剂和亚硫酸氢钠的加入量分别为所述混合单体总质量的20～30%、3～5%、8～10%和1～2%；所述混合单体的加入速率为2～5ml/min，所述反应温度为70～80℃，时间为7～8h。
4.根据权利要求1所述的固化交联苯乙烯-丙烯酸酯树脂的制备方法，其特征在于，所述乳化剂为质量浓度为15%的聚乙烯醇溶液和乳化剂OP-10以1：1的体积比混合的混合物；所述引发剂为亚硫酸钾；所述链转移剂为巯基乙酸；所述混合单体为步骤（1）中处理后的苯乙烯和丙烯酸正丁酯以1：2～3的质量比混合的混合物。
5.根据权利要求1所述的固化交联苯乙烯-丙烯酸酯树脂的制备方法，其特征在于，所述步骤（3）中，所述聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯的质量比为3～5：2～3：1；所述聚乙烯醇单甲醚，异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯的总质量为所述混合单体总质量的0.1～0.2%。
6.根据权利要求1所述的固化交联苯乙烯-丙烯酸酯树脂的制备方法，其特征在于，所述步骤（3）中，所述六亚甲基二异氰酸酯的滴加速率为5～8ml/min。
CN201610451311.9A 2016-06-21 2016-06-21 一种固化交联苯乙烯-丙烯酸酯树脂的制备方法 Pending CN105924572A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610451311.9A CN105924572A (zh) 2016-06-21 2016-06-21 一种固化交联苯乙烯-丙烯酸酯树脂的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610451311.9A CN105924572A (zh) 2016-06-21 2016-06-21 一种固化交联苯乙烯-丙烯酸酯树脂的制备方法

Publications (1)

Publication Number Publication Date
CN105924572A true CN105924572A (zh) 2016-09-07

Family

ID=56830676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610451311.9A Pending CN105924572A (zh) 2016-06-21 2016-06-21 一种固化交联苯乙烯-丙烯酸酯树脂的制备方法

Country Status (1)

Country Link
CN (1) CN105924572A (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768895A (zh) * 2009-01-07 2010-07-07 湖北大学 一种苯丙乳液型高效表面施胶剂及其制备方法
CN104017452A (zh) * 2014-06-19 2014-09-03 舟山市恒泰漆业有限责任公司 一种异氰酸酯固化剂改性的水性丙烯酸复合金属防腐涂料的制备方法
CN104277188A (zh) * 2014-09-23 2015-01-14 合肥乐凯科技产业有限公司 一种自交联丙烯酸酯乳液、制备方法及其应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768895A (zh) * 2009-01-07 2010-07-07 湖北大学 一种苯丙乳液型高效表面施胶剂及其制备方法
CN104017452A (zh) * 2014-06-19 2014-09-03 舟山市恒泰漆业有限责任公司 一种异氰酸酯固化剂改性的水性丙烯酸复合金属防腐涂料的制备方法
CN104277188A (zh) * 2014-09-23 2015-01-14 合肥乐凯科技产业有限公司 一种自交联丙烯酸酯乳液、制备方法及其应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
安静等: "不同引发剂引发苯乙烯/丙烯酸丁酯微乳液共聚合竞聚率的研究", 《河北科技大学学报》 *
韦军等: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 *

Similar Documents

Publication Publication Date Title
CN105237675B (zh) 一种具有核壳双交联结构的聚丙烯酸木器乳液及其制备方法
CN102432773B (zh) 一种水性环氧丙烯酸酯接枝复合乳液及其制备方法
CN100462381C (zh) 丙烯酸本体杂化乳液组合物
CN106866869A (zh) 一种核壳结构羟基丙烯酸乳液的制备方法
CN105622862A (zh) 一种混凝土聚羧酸减水剂及其制备方法
CN101280035A (zh) 耐湿擦性苯丙乳液及其制备方法
CN101560278B (zh) 一种含氟丙烯酸酯-甲基丙烯酸甲酯-苯乙烯共聚物及其制备方法
CN102875723A (zh) 一种阻燃性核壳型丙烯酸类树脂的制备方法
CN109796554B (zh) 一种用于零钛体系的弹性乳液及其制备方法
CN104559508A (zh) 含相变微胶囊的隔热保温涂料及其制备方法
CN102911540A (zh) 一种疏水性mma树脂地坪涂料及其制备方法
CN106543374A (zh) 含氟丙烯酸酯共聚物乳液及其制备方法和制备乳胶膜方法
CN105315413A (zh) 一种新型改性丙烯酸酯乳液胶粘剂及其制备方法
CN102675529A (zh) 含有叔碳酸乙烯酯的水性苯丙乳液及其制备方法
CN104262578A (zh) 一种多批次加料方式合成聚氨酯固化剂的方法及其产品
CN106752606B (zh) 一种水性氟硅丙烯酸涂料及其制备方法
CN105693944B (zh) 一种耐高温改性苯丙乳液的制备方法
CN109679017A (zh) 一种单组份水性丙烯酸分散体及其制备方法
CN102702909A (zh) 水性防石击汽车底涂材料及其制备方法
CN103553426A (zh) 一种聚合物水泥复合防水涂料的制备方法
CN103232566B (zh) 密封胶用高固含量低粘度丙烯酸酯乳液的制备方法
CN105566582A (zh) 一种水性防腐环氧树脂丙烯酸酯乳液的制备方法
CN102911580B (zh) 交联型防水涂料丙烯酸乳液的制备方法
CN102060964B (zh) 氨基丙烯酸树脂的制备方法及应用
CN105924572A (zh) 一种固化交联苯乙烯-丙烯酸酯树脂的制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160907