CN114149608A - 一种乳液聚合制备的粒径在1-100微米的热膨胀微球 - Google Patents
一种乳液聚合制备的粒径在1-100微米的热膨胀微球 Download PDFInfo
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- CN114149608A CN114149608A CN202010938010.5A CN202010938010A CN114149608A CN 114149608 A CN114149608 A CN 114149608A CN 202010938010 A CN202010938010 A CN 202010938010A CN 114149608 A CN114149608 A CN 114149608A
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
-
- 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
-
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- 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
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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Abstract
为克服现有技术的缺点和不足，本发明的目的旨在采用新型的合成技术和配方，乳液聚合来合成热膨胀发泡微球。新型制备方法制备的高效热膨胀微球，以质量分数记，其组分为：丙烯酸类单体20～30份、丙烯腈50～80份、交联剂1～2份、发泡剂40～80份、氧化剂0.2～0.6份、乳化剂1～2份、助乳化剂0.5～2份、还原剂0.2～0.6份、稳定剂3～6份、水100～250份。本发明具有如下优点：发泡剂利用率更高；热膨胀微球强度更高；热膨胀微球的粒径分布更加均匀且更小，表面光滑且核壳结构完善。
Description
技术领域本发明涉及一种新型的制备方法，乳液聚合来制备热膨胀发泡微球，属于高分子材料技术领域。
技术背景
热膨胀微球是微胶囊的一种，是指由聚合物外壳包裹发泡剂内核形成的具有核壳结构的颗粒。微球受热至聚合物软化点时，内部发泡剂产生的蒸汽压使微球膨胀，冷却后，微球会保持发泡状态。由于其质轻及均一发泡的特性，膨胀后的微球在隔热、隔声、减重、减震等方面具有广泛应用，因而热膨胀微球也受到广泛的研究。目前热膨胀微球的制备方法主要有两种，一是先通过悬浮等聚合方法制得聚合物微球，然后再浸渍发泡剂；二是通过发泡剂存在下的悬浮或细乳液等聚合方法直接制得包覆发泡剂的聚合物微球。丙烯酸酯、丙烯腈等是制备热膨胀聚合物微球的常用单体。
Whinnery等人把市售的Expancel热膨胀微球为原料，在特定的模具中，通过简单加热的方式制得了一些列不同密度和机械性能的大块刚性泡沫材料，这为大块泡沫材料的制备提供了一种新方法。吴明华等人将热膨胀微球掺混入印花浆料中，在保持图案原有效果的基础上，使得图案更加的生动具体，提升了织物的品质感。
Yasuhiro等人在AN/MAN聚合体系新增加了第三种单体，并且研究了第三种单体和热膨胀微球的发泡关系。谢贵明等人则研究了其它助剂对热膨胀微球体系的影响。他们用偏氯乙烯、AN、甲基丙烯酸甲酯(MMA)为共聚单体，特别研究了氯化钠、柠檬酸和重铬酸钾等水相添加剂对聚合物微球结构和膨胀性能的影响。刘峰课题组以AN和MMA为主单体，通过添加甲基丙烯酸(MAA)、NN-二甲基丙烯酰胺(DMAA)等极性共聚单体，合成了具有优异发泡性能的高温热膨胀微球。
尽管已有较多国内学者参与了热膨胀微球的研究工作，但是从工业化生产的角度来看，由于生产热膨胀微球的工艺复杂、生产周期长、对生产设备要求高，再加之影响微球结构和性能的因素众多，难以合成粒径分布均匀、形态规整、发泡倍率高、稳泡性能优越的热膨胀微球。
发明内容
为克服现有技术的缺点和不足，本发明的目的旨在采用新型的合成技术，乳液聚合来合成热膨胀发泡微球。新型制备方法制备的高效热膨胀微球，以质量分数记，其组分为：丙烯酸类单体20～30份、丙烯腈50～80份、交联剂1～2份、发泡剂40～80份、氧化剂0.2～ 0.6份、乳化剂1～2份、助乳化剂0.5～2份、还原剂0.2～0.6份、稳定剂3～6份、水100～250份。所述的新型的制备方法，乳液聚合法如下：
(1)在常温常压情况下，将单体丙烯腈和丙烯酸单体：3∶1～5∶1加入到反应器中，再加入20～60份的发泡剂，再加入一定量的氧化剂，然后常温搅拌，混合30min，得到均一的油相；
(2)在常温常压的情况下将乳化剂、分散剂、稳定剂，去离子水等按一定比例加入到反应容器中，常温搅拌得到均一混合的水相。
(3)将水相和油相通过均质机混合，再加入到烧瓶中加温30～70℃，搅拌12～24小时。
(4)水浴升温30～70℃度，保温10h以上，干燥造粒。
所述的丙烯酸类单体为丙烯酸甲酯、甲基丙烯酸甲酯中的至少一种。
所述的交联剂为1，4-丁二醇二丙烯酸酯，1，6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三丙二醇类二丙烯酸酯、三羟基丙烷三丙烯酸酯、二缩三羟甲基丙烷四丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯中的至少一种。
所述的发泡剂为正丁烷、异丁烷、正戊烷、异戊烷、新戊烷、环戊烷中的至少一种。
所述的氧化剂为过氧化苯甲酰、过氧化二月桂酸乙酯、偶氮二异丁腈、叔丁基过氧化氢、异丙苯过氧化氢、过氧化二酰基；所述的还原剂为巯基乙酸、巯基丙酸、三乙胺、N，N-二甲基对甲苯胺、DMP30中的至少一种。
所述的自乳化剂为2-丙烯酰胺-2，2-二甲基乙磺酸钠、烯丙基聚乙二醇、烯丙基磺基烷氧基琥珀酸双酯钠盐、烯丙基-2-丙基乙磺酸钠、乙烯基-2-丙基乙磺酸钠、聚氧化乙烯壬酚醚丙烯酸酯、十八烷基二甲基乙烯苯基氯化铵、十二烷基硫酸钠、十二烷基二甲基乙烯苯基氯化铵中的至少一种。
所述的助乳化剂为正丁醇、乙二醇、乙醇、丙二醇、甘油中的至少一种；所述的稳定剂为硫酸钙、氢氧化钙、硝酸镁、氯化钙、氢氧化钠、氢氧化钾、硫酸镁、硝酸镁中的至少一种。
所述的新型方法，乳液聚合法制备的高效热膨胀微球，制备方法如下：
将丙烯酸单体溶液、丙烯腈主单体、交联剂、发泡剂、氧化剂充分混合均匀，制得油性液；将自乳化单体、助乳化剂、还原剂、稳定剂、水加入到反应器中，高速乳化均匀，然后加入油性液，充分搅拌均匀后，加热至30～70℃℃反应12～24h，降温后出料，分离微球并用乙醇洗涤，然后40～50℃干燥，即得所述的高效热膨胀微球。
相对于现有技术，本发明具有以下优点或益处：(1)采用氧化还原引发体系制备热膨胀微球，引发温度更低，发泡剂利用率更高；(2)首次采用乳液聚合，加工工艺更加简单，所述的热膨胀微球强度更高；(3)采用乳液聚合法合成，能得到粒径分布更加均匀的热膨胀微球，热膨胀微球表面光滑且核-壳结构完善。
附图说明图1为热膨胀微球的粒径图。
具体实施方式
下面结合实施例对本发明的一种新型方法制备的热膨胀微球做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种乳液聚合制备的热膨胀微球，以质量计组成如下：丙烯腈30份、丙烯酸甲酯10份、异辛烷40份、烯丙基-2-丙基乙磺酸钠2份、过氧化苯甲酰0.1份、纳米二氧化硅30份、水140份。
本实施例中的丙烯酸改性聚酰亚胺低聚物溶液的制备方法如下：
(1)在常温常压情况下，将单体丙烯腈和丙烯酸单体：3∶1加入到反应器中，再加入40 份异辛烷，再加入过氧化苯甲酰0.1份，然后常温搅拌，混合30min，得到均一的油相；
(2)在常温常压的情况下将烯丙基-2-丙基乙磺酸钠2份、米二氧化硅30份、去离子水 140份加入到反应容器中，常温搅拌得到均一混合的水相。
(3)将水相和油相通过均质机混合，再加入到烧瓶中加温50℃，搅拌12小时。
(4)水浴升温50℃度，保温10h以上，干燥造粒。
实施例2
一种乳液聚合制备的热膨胀微球，以质量计组成如下：丙烯腈50份、丙烯酸甲酯10份、异辛烷60份、烯丙基-2-丙基乙磺酸钠2份、过氧化苯甲酰0.2份、纳米二氧化硅50份、水200份。
本实施例中的丙烯酸改性聚酰亚胺低聚物溶液的制备方法如下：
(1)在常温常压情况下，将单体丙烯腈和丙烯酸单体：5∶1加入到反应器中，再加入60 份异辛烷，再加入过氧化苯甲酰0.2份，然后常温搅拌，混合30min，得到均一的油相；
(2)在常温常压的情况下将烯丙基-2-丙基乙磺酸钠2份、米二氧化硅50份、去离子水 200份加入到反应容器中，常温搅拌得到均一混合的水相。
(3)将水相和油相通过均质机混合，再加入到烧瓶中加温50℃，搅拌12小时。
(4)水浴升温60℃度，保温10h以上，干燥造粒。
实施例3
一种乳液聚合制备的热膨胀微球，以质量计组成如下：丙烯腈50份、丙烯酸甲酯20份、异辛烷50份、烯丙基-2-丙基乙磺酸钠2份、过氧化苯甲酰0.2份、纳米二氧化硅50份、水200份。
本实施例中的丙烯酸改性聚酰亚胺低聚物溶液的制备方法如下：
(1)在常温常压情况下，将单体丙烯腈和丙烯酸单体：5∶2加入到反应器中，再加入50 份异辛烷，再加入过氧化苯甲酰0.2份，然后常温搅拌，混合30min，得到均一的油相；
(2)在常温常压的情况下将烯丙基-2-丙基乙磺酸钠2份、米二氧化硅50份、去离子水 200份加入到反应容器中，常温搅拌得到均一混合的水相。
(3)将水相和油相通过均质机混合，再加入到烧瓶中加温50℃，搅拌12小时。
(4)水浴升温60℃度，保温10h以上，干燥造粒。
粒径测试：取1-2g左右洗净干燥后的样品，加入20-30mL去离子水，搅拌均匀后超声2 min，通过激光粒度分析仪测定微球平均粒径。
Claims (9)
1.一种乳液聚合制备的粒径在1-100微米的热膨胀微球，其特征在于，所诉产物包括以下
重量份数的组份：
一种热膨胀微球的新型制备方法，其特征在于采用乳液聚合，将水相和油相充分混合均匀，加热至35～50℃反应12～24h，降温后出料，分离微球并用乙醇洗涤，然后40～50℃干燥，即得到粒径在1-100μm的热膨胀微球。
2.根据权利要求1所述的新型制备方法，其制备步骤为：把一定比例的去离子水、乳化剂、分散剂和乳化助剂等其他的助剂混合，然后匀速搅拌，得到乳液聚合所需的水相。将一定比例的单体、引发剂、和交联剂等匀速搅拌，得到乳液聚合所需的油相。水相油相混合之后，在转速10000rpm/min以上的均质机设备，搅拌30min，所制备的乳液水浴升温55度，保温10h以上，干燥造粒。
3.根据权利要求2所述的新型制备方法，其特征在于，所述的分散剂为纳米氢氧化镁或者纳米二氧化硅中的一种或多种。
4.根据权利要求1所述的新型制备方法，其特征在于：所述的单体为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯腈中的至少一种。
5.根据权利要求1所述的新型制备方法，其特征在于：所述的交联剂为1，4-丁二醇二丙烯酸酯，1，6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三丙二醇类二丙烯酸酯、三羟基丙烷三丙烯酸酯、二缩三羟甲基丙烷四丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯中的至少一种。
6.根据权利要求1所述的新型制备方法，其特征在于：所述的发泡剂为正丁烷、异丁烷、正戊烷、异戊烷、新戊烷、环戊烷中的至少一种。
7.根据权利要求1所述的新型制备方法，其特征在于：所述的氧化剂为过氧化苯甲酰、过氧化二月桂酸乙酯、偶氮二异丁腈、叔丁基过氧化氢、异丙苯过氧化氢、过氧化二酰基；所述的还原剂为巯基乙酸、巯基丙酸、三乙胺、N，N-二甲基对甲苯胺、DMP30中的至少一种。
8.根据权利要求1所述的新型制备方法，其特征在于：所述的乳化剂为2-丙烯酰胺-2，2-二甲基乙磺酸钠、烯丙基聚乙二醇、烯丙基磺基烷氧基琥珀酸双酯钠盐、烯丙基-2-丙基乙磺酸钠、乙烯基-2-丙基乙磺酸钠、聚氧化乙烯壬酚醚丙烯酸酯、十八烷基二甲基乙烯苯基氯化铵、十二烷基硫酸钠、十二烷基二甲基乙烯苯基氯化铵中的至少一种。
9.根据权利要求1至9任一项所述制备方法制得的热膨胀微球，其特征在于：所述的热膨胀微球为采用乳液聚合，以质量份数计，其组分为：丙烯酸类单体20～30份、丙烯腈50～80份、交联剂1～2份、发泡剂4～8份、氧化剂0.2～0.6份、乳化剂1～2份、助乳化剂0.5～2份、还原剂0.2～0.6份、稳定剂3～6份、水100～250份。
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