CN106065046A - 一种醇溶性丙烯酸树脂 - Google Patents
一种醇溶性丙烯酸树脂 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- 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
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
本发明提供一种醇溶性丙烯酸树脂,所述的醇溶性丙烯酸树脂是由玻璃化转变温度高于25℃的硬单体与玻璃化转变温度低于25℃的软硬单体按质量比为50∶50~90∶10通过自由基共聚反应而成;所述的软单体选自甲基丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸乙氧基乙酯中的至少一种;所述的硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、苯乙烯中的至少一种。本发明醇溶性丙烯酸树脂的玻璃化转变温度为25~45℃,重均分子量为30,000至100,000。本发明具有适中的附着力和较好的韧性,可以溶解于乙醇等醇类溶剂,能满足环保油墨及环保涂料的使用性能要求。
Description
技术领域:
本发明涉及高分子材料领域,尤其涉及一种醇溶性丙烯酸树脂。
技术背景
丙烯酸树脂是指以丙烯酸和/或甲基丙烯酸系列不饱和化合物为单体,通过自由基聚合反应制得的一类高分子聚合物树脂,具有优良的机械性能和耐候性,广泛用于涂料、油墨、建筑、航空等领域。选择不同的单体配比,可以制得各种不同性能的丙烯酸树脂。一般的丙烯酸树脂在使用时需要用有机溶剂如甲苯、二甲苯、丁酮、环己酮等溶解,这类溶剂不但有易挥发的特性,而且存在一定的毒性,开发一种可以用低毒或无毒的溶剂的丙烯酸树脂,一方面可以改善环境,另外还可以减少对操作人员的毒害。
发明内容
本发明的目的是为了解决现有技术的不足,提供一种醇溶性丙烯酸树脂,可完全溶解于乙醇等醇类溶剂,并可改善操作人员的工作环境,降低对操作人员的健康危害。
本发明的目的是通过以下技术方案实现的:
一种醇溶性丙烯酸树脂,所述的醇溶性丙烯酸树脂是由玻璃化转变温度高于25℃的硬单体与玻璃化转变温度低于25℃的软硬单体按质量比为50∶50~90∶10通过自由基共聚反应而成;所述醇溶性丙烯酸树脂的玻璃化转变温度为25~45℃,重均分子量为30,000至100,000。
反应时加入引发剂和分子量调节剂,同时加入二氯甲烷和硬脂酸,可以改善树脂的流动性和脱模性,所述引发剂的用量按质量百分比计为单体总量的0.01~10%,所述分子量调节剂的用量按质量百分比计为单体总量的0.01~10%,所述二氯甲烷和硬脂酸的用量按质量百分比计为单体总量的0.01-0.5%。
所述的软单体选自甲基丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸乙氧基乙酯中的至少一种;所述的硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、苯乙烯中的至少一种。
作为进一步的优选方案,所述的软单体选自丙烯酸乙酯、丙烯酸正丁酯中的至少一种;所述的硬单体选自甲基丙烯酸甲酯、甲基丙烯酸异丁酯、甲基丙烯酸羟乙酯、苯乙烯中的至少一种。
上述的醇溶性丙烯酸树脂,其中,所述的自由基共聚反应采用悬浮聚合反应、本体聚合反应或溶液聚合反应。
上述的醇溶性丙烯酸树脂,其中,所述的自由基共聚反应所用的引发剂选用过氧类化合物和/或偶氮类化合物中的至少一种。
所述的过氧类化合物选自过氧化苯甲酰、过氧化苯甲酸叔丁酯、过氧化二异丙苯、过氧化十二酰、过氧化二碳酸二异丙酯、1,4-过氧环己二甲酸二叔丁酯、过氧化二碳酸二环己酯、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷、过氧化二叔丁基、叔丁基过氧化氢、过氧化2-乙基己酸叔丁酯中的至少一种。
所述的偶氮类化合物选自偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮异丁氰基甲酰胺、偶氮二环己基甲腈、偶氮二异丁酸二甲酯中的至少一种。
进一步的优选方案,共聚反应所用的引发剂选用过氧化苯甲酰、过氧化十二酰、1,4-过氧环己二甲酸二叔丁酯、过氧化二碳酸二异丙酯、过氧化2-乙基己酸叔丁酯、偶氮二异丁腈、偶氮二异庚腈中的至少一种。
上述的醇溶性丙烯酸树脂,优选的,引发剂的用量按质量百分比计为单体总量的0.05~5.0%。
上述的醇溶性丙烯酸树脂,其中,共聚反应所用的分子量调节剂选用十二烷基硫醇、异丁基硫醇、α-甲基苯乙烯及其二聚物中的至少一种。
上述的醇溶性丙烯酸树脂,优选的,所述的分子量调节剂的用量按质量百分比计为单体总量的0.05~5.0%。
综上所述,由于采用了上述技术方案,本发明与现有技术相比,具有如下有益效果:
本发明提供的醇溶性丙烯酸树脂的玻璃化转变温度为25~45℃,重均分子量为30,000至100,000,具有适中附着力和较好韧性;可以溶于乙醇等醇类溶剂,可采用悬浮聚合或本体聚合制备成固体树脂,也可采用溶液聚合制备成液体树脂,具有较强的实用性和工业化推广价值。
具体实施方式
下面通过具体实施例对本发明作进一步详细介绍。
实施例1
采用本体聚合工艺进行共聚反应。
软单体:丙烯酸乙酯20质量份。
硬单体:甲基丙烯酸甲酯5质量份;甲基丙烯酸异丁酯70质量份;甲基丙烯酸羟乙酯5质量份。
引发剂:采用过氧化十二酰、1,4-过氧环己二甲酸二叔丁酯、过氧化2-乙基己酸叔丁酯、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷复合引发剂,用量为0.25质量份。
分子量调节剂:采用十二烷基硫醇,用量为0.59质量份。
二氯甲烷和硬脂酸:0.1质量份。
经测试,所得聚合物:丙烯酸树脂的玻璃化转变温度为33℃,重均分子量为55,000。
实施例2
采用悬浮聚合工艺进行共聚反应。
软单体:丙烯酸正丁酯10质量份;丙烯酸甲酯15份。
硬单体:甲基丙烯酸乙酯25质量份;甲基丙烯酸异丁酯45质量份;甲基丙烯酸羟乙酯5质量份。
引发剂采用过氧化十二酰、1,4-过氧环己二甲酸二叔丁酯复合引发剂,总用量为0.3质量份。
分子量调节剂采用十二烷基硫醇与α-甲基苯乙烯及其二聚体按质量比为5∶1形成的的复配物,总用量为0.5质量份。
二氯甲烷和硬脂酸:0.2质量份。
经测试,所得聚合物:丙烯酸树脂的玻璃化转变温度为31℃,重均分子量为62,000。
实施例3
采用溶液聚合工艺进行共聚反应。
软单体:丙烯酸乙酯25质量份。
硬单体:甲基丙烯酸甲酯10质量份;苯乙烯5质量份;甲基丙烯酸羟乙酯5质量份;甲基丙烯酸乙酯55质量份。
引发剂采用偶氮二异丁腈,用量为0.5质量份。
分子量调节剂采用异丁基硫醇与α-甲基苯乙烯及其二聚体的复合物,用量为0.6质量份;
二氯甲烷和硬脂酸:0.25质量份。
使用乙醇作为溶剂,使反应体系的固含量为45%。
经测试,所得聚合物:丙烯酸树脂的玻璃化转变温度为41℃,重均分子量为48,000。
以上所述的实施例仅用于说明本发明的技术思想及特点,其目的在于使本领域内的技术人员能够了解本发明的内容并据以实施,不能仅以本实施例来限定本发明的专利范围,即凡依本发明所揭示的精神所作的同等变化或修饰,仍落在本发明的专利范围内。
Claims (8)
1.一种醇溶性丙烯酸树脂,其特征在于,所述的醇溶性丙烯酸树脂是由玻璃化转变温度高于25℃的硬单体与玻璃化转变温度低于25℃的软硬单体按质量比为50∶50~90∶10通过自由基共聚反应而成;所述醇溶性丙烯酸树脂的玻璃化转变温度为25~45℃,重均分子量为30,000至100,000;
反应时加入引发剂和分子量调节剂,同时加入二氯甲烷和硬脂酸,所述引发剂的用量按质量百分比计为单体总量的0.01~10%,所述分子量调节剂的用量按质量百分比计为单体总量的0.01~10%,所述二氯甲烷和硬脂酸的用量按质量百分比计为单体总量的0.01-0.5%;
所述的软单体选自甲基丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸乙氧基乙酯中的至少一种;所述的硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、苯乙烯中的至少一种。
2.如权利要求1所述的醇溶性丙烯酸树脂,其特征在于,所述的软单体选自丙烯酸乙酯、丙烯酸正丁酯中的至少一种;所述的硬单体选自甲基丙烯酸甲酯、甲基丙烯酸异丁酯、甲基丙烯酸羟乙酯、苯乙烯中的至少一种。
3.如权利要求1所述的醇溶性丙烯酸树脂,其特征在于,所述的自由基共聚反应采用悬浮聚合反应、本体聚合反应或溶液聚合反应。
4.如权利要求3所述的醇溶性丙烯酸树脂,其特征在于,所述的自由基共聚反应所用的引发剂选用过氧类化合物和/或偶氮类化合物中的至少一种;
所述的过氧类化合物选自过氧化苯甲酰、过氧化苯甲酸叔丁酯、过氧化二异丙苯、过氧化十二酰、过氧化二碳酸二异丙酯、1,4-过氧环己二甲酸二叔丁酯、过氧化二碳酸二环己酯、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷、过氧化二叔丁基、叔丁基过氧化氢、过氧化2-乙基己酸叔丁酯中的至少一种;
所述的偶氮类化合物选自偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮异丁氰基甲酰胺、偶氮二环己基甲腈、偶氮二异丁酸二甲酯中的至少一种。
5.如权利要求4所述的醇溶性丙烯酸树脂,其特征在于,共聚反应所用的引发剂选用过氧化苯甲酰、过氧化十二酰、1,4-过氧环己二甲酸二叔丁酯、过氧化二碳酸二异丙酯、过氧化2-乙基己酸叔丁酯、偶氮二异丁腈、偶氮二异庚腈中的至少一种。
6.如权利要求1、4、5任意所述的醇溶性丙烯酸树脂,其特征在于,引发剂的用量按质量百分比计为单体总量的0.05~5.0%。
7.如权利要求3所述的醇溶性丙烯酸树脂,其特征在于,共聚反应所用的分子量调节剂选用十二烷基硫醇、异丁基硫醇、α-甲基苯乙烯及其二聚物中的至少一种。
8.如权利要求7所述的醇溶性丙烯酸树脂,其特征在于,所述的分子量调节剂的用量按质量百分比计为单体总量的0.05~5.0%。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343208A (zh) * | 2019-06-11 | 2019-10-18 | 中山华明泰科技股份有限公司 | 一种粉状丙烯酸树脂制备方法及应用 |
| CN112354305A (zh) * | 2020-10-30 | 2021-02-12 | 南京捷立德环保科技有限公司 | 用于除尘的喷雾装置 |
| CN115216251A (zh) * | 2021-12-26 | 2022-10-21 | 上海路嘉胶粘剂有限公司 | 一种水性封口胶及其制备方法和应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084860A (zh) * | 1992-09-30 | 1994-04-06 | 施振冰 | 用α-甲基苯乙烯二聚体调节的不同分子量的丙烯酸酯聚合物及其制备和应用 |
| CN102219875A (zh) * | 2010-01-22 | 2011-10-19 | 北京高盟新材料股份有限公司 | 醇溶性树脂组合物、醇溶性上光油及其制备方法 |
| CN104311727A (zh) * | 2014-11-06 | 2015-01-28 | 任婧 | 一种转印油墨用丙烯酸树脂 |
-
2016
- 2016-06-12 CN CN201610405651.8A patent/CN106065046A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084860A (zh) * | 1992-09-30 | 1994-04-06 | 施振冰 | 用α-甲基苯乙烯二聚体调节的不同分子量的丙烯酸酯聚合物及其制备和应用 |
| CN102219875A (zh) * | 2010-01-22 | 2011-10-19 | 北京高盟新材料股份有限公司 | 醇溶性树脂组合物、醇溶性上光油及其制备方法 |
| CN104311727A (zh) * | 2014-11-06 | 2015-01-28 | 任婧 | 一种转印油墨用丙烯酸树脂 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343208A (zh) * | 2019-06-11 | 2019-10-18 | 中山华明泰科技股份有限公司 | 一种粉状丙烯酸树脂制备方法及应用 |
| CN112354305A (zh) * | 2020-10-30 | 2021-02-12 | 南京捷立德环保科技有限公司 | 用于除尘的喷雾装置 |
| CN115216251A (zh) * | 2021-12-26 | 2022-10-21 | 上海路嘉胶粘剂有限公司 | 一种水性封口胶及其制备方法和应用 |
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