CN1048191C - 微胶囊发泡剂的制备方法 - Google Patents
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Abstract
一种碱法制备微胶囊发泡剂的工艺，把单体偏氯乙烯、丙烯腈及发泡剂等组成的油相与复合悬浮剂、碱性调节剂、水组成的水相按比例混合分数，并在45-80℃下反应12小时以上聚合成囊。产物经分离、水洗，并以脂肪醇聚氧乙烯醚溶液浸渍处理，干燥后得白色分散性及稳定性良好的微胶囊发泡剂，平均粒径11微米，加热至125℃体积膨胀达27倍以上，用以配制发泡树脂组合物，分散性和使用性能良好，常温贮存半年，质量保持稳定。
Description
本发明涉及微胶囊合成方法，特别是一种碱法制微胶囊发泡剂的工艺。
在本发明作出之前，现有技术中关于微胶囊发泡剂的制备方法有过一些报道，如美国专利U.S.P 3615972中曾介绍必须使用酸性介质与等克分子比例的己二酸和二乙醇胺组成的共聚物水溶液悬浮体系，这在生产控制上存在相当的困难，常使不同批次的产品质量不一致。美国专利U.S.P 4016110介绍采用悬浮于水中的胶体二氧化硅悬浮剂，并加入柠檬酸来代替等克分子量的已二酸和二乙醇胺的共聚物，可使产品质量稳定，使不同批次的发泡剂产品质量基本一致。上述两种方法都采用酸性反应条件，酸性物质的加入会降低悬浮剂二氧化硅的稳定性并影响微胶囊发泡剂的均匀性和可分散性。而且，在酸性条件下进行聚合反应，往往引起某些单体如偏氯乙烯的分解，使形成的微胶囊发泡剂产品呈较强酸性(PH＜4)，这种强酸性微胶囊发泡剂配制的发泡树脂组合物贮存稳定性低，并影响使用性能。
本发明的目的是提供一种简单且易于控制的微胶囊发泡剂制备方法，采用碱性聚合条件和复合悬浮剂以克服现有技术的酸性反应条件所产生的不稳定因素，从而使由本法制成的微胶囊发泡剂所配制的发泡树脂组合物稳定性与使用性能得到提高。
本发明是这样实现：反应物油相由低沸点液体如饱和烃类、氟氯甲烷、氟氯乙烷等发泡剂与单体偏氯乙烯、丙烯腈和第三单体如甲基丙烯酸低碳数烷基酯、丙烯酸低碳数烷基酯醋酸乙烯酯等组成，还可加入微量交联单体如二乙烯基苯，并使用油溶性引发剂。水相则以胶体二氧化硅和水溶性树脂如明胶、纤维素醚、聚乙烯醇、聚丙烯酸钠盐等组成复合悬浮剂，以钠、钾、铵的碳酸盐、磷酸盐、硼酸盐以及它们的氢氧化物等作为碱性调节剂，水相中各组分配比(重量百分比)如下：胶体二氧化硅5-10％、碱性调节剂15-25％、水溶性树脂0.3-0.8％、水60-8O％。上述油相和水相按1∶3-6比例(最佳为1∶3.5-4.5)于经氮气清洗过的带搅拌反应器中混合，此时体系PH＞7，最佳为PH＝7-10，然后均匀分散成约10微米的稳定液滴，在45-80℃(最佳为45-60℃)下反应12小时以上，降温并离心分离，用水洗涤至PH＝7，再加入1-3％脂肪醇聚氧乙烯醚溶液浸渍8-12小时，干燥、过筛得白色粉末为微胶囊发泡剂。这一合成过程的反应机理是：在形成的悬浮体系中，每一个悬浮的液滴以溶液沉淀聚合物的方式实现微胶囊的包裹。这一微胶囊化的过程可描述为四个阶段：(1)稳定的悬浮体系的形成，水相和油相互相混合，在强烈的剪切力作用下，油相被分散成为平均直径约10微米的稳定小液滴。(2)聚合反应初期——溶液沉淀聚合开始，当温度升至引发剂的分解温度时，分解产生游离基引发单体聚合，当高分子链增长于一定程度，由于聚合物不溶于发泡剂而沉淀析出，这是溶液沉淀聚合的过程。(3)聚合反应中期——微胶囊皮膜成长阶段。随着聚合反应的进行，高分子链不断从溶液中沉淀析出，沉淀出来的高分子链相互缠绕成线团，在搅拌作用下，每一颗被分散的液滴产生强烈的转动，离心力的作用使线团向液滴表面沉淀，相互粘接，逐步形成一层胶囊的皮膜。发泡剂则由于表面张力的作用，逐步收缩聚集于胶囊的中心面形成一个单核心胶囊。(4)聚合反应后期——胶囊形成。随着链转移和链终止，粘稠的皮膜逐步增厚，强度增加变成坚韧的固态，生成微胶囊。
采用本发明的方法可以制备高分散性的单核颗粒的微胶囊，而在反应器的器壁和搅拌器上几乎无粘附物产生，制成的微胶囊发泡剂平均粒径10微米，PH接近中性。当加热至125℃时，其体积膨胀达27倍，储存一年后，其PH仍大于5，发泡性能不变。用本发明制备的微胶囊发泡剂配制的发泡树脂组合物，外观均匀、分散性好，常温贮存半年，其流动性良好，质量稳定。
实施例：
先按下面配方配制油相和水相。
油相(重量百分比) ％
偏氯乙烯 47.5
丙烯腈 20
丙烯酸甲酯 11
二乙烯基苯 1
正戊烷 20
过氧化碳酸二异丙酯 0.5
总 计 100
水相(重百分比) ％
硼砂 22.2
胶体二氧化硅 8.9
聚乙烯醇 0.7
水 68.2
在经氮气清洗的带搅拌的不锈钢反应器中，加入100份油相，450份水相，通氮气至0.5MPa，搅拌分散成平均直径10微米的稳定液滴，此时PH＞7，再在55℃下反应16小时，然后降温，卸压，离心分离，用清水洗涤至PH＝7。最后加入1％脂肪醇聚氧乙烯醚溶液浸渍作表面处理8小时，干燥过筛得白色分散性良好的微胶囊发泡剂80份。
附图说明：先将单体、引发剂和发泡剂混合配制成油相，悬浮剂、碱性调节剂和水混合为水相，再将油相和水相按比例加入聚合反应釜中混合分散，再聚合成囊。然后离心分离，生成物经水洗至PH为7，再加入脂肪醇聚氧乙烯醚溶液表面处理(浸渍)8-12小时，干燥过筛得到微胶囊发泡剂成品。
Claims (5)
1、一种微胶囊发泡剂的制备方法，反应物油相由低沸点发泡剂与单体偏氯乙烯和丙烯晴及第三单体与微量交联单体组成，并加入油溶性引发剂，发泡剂是饱和烃类、氟氯甲烷或氟氯乙烷，第三单体是甲基丙烯酸低碳数烷基酯、丙烯酸低碳数烷基酯或醋酸乙烯，交联单体是二乙烯基苯，其特征是以胶体二氧化硅和水溶性树脂形成复合悬浮剂，使反应在碱性条件下进行，反应物水相组成(重量百分比)为胶体二氧化硅5-10％，0.1N碱性调节剂15-25％，水溶性树脂0.3-0.8％、水60-80％，油相和水相按1∶3-6(重量比)混合于经氮气清洗过的反应器中，均匀分散成约10微米液滴，在45-80℃下反应12小时以上，聚合成囊，再经离心分离、水洗过滤、表面处理获得微胶囊发泡剂。
2、根据权利要求1所述的方法，其特征是水溶性树脂是明胶、纤维素醚、聚乙烯醇或聚丙烯酸钠盐。
3、根据权利要求1所述的方法，其特征是碱性调节剂为钠、钾或氨的碳酸盐、磷酸盐、硼酸盐以及它们的氢氧化物。
4、根据权利要求1所述的方法，其特征是反应在10≤PH＞7条件下进行。
5、根据权利要求1所述的方法，其特征是反应产物微胶囊发泡剂经洗涤后，用1-3％脂肪醇聚氧化乙烯醚溶液浸渍8-12小时。
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| CN1309765C (zh) * | 2005-10-20 | 2007-04-11 | 北京科技大学 | 采用微胶囊发泡剂进行波聚合制备多孔水凝胶的方法 |
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|---|---|---|---|---|
| KR101307108B1 (ko) | 2011-05-17 | 2013-09-11 | 율촌화학 주식회사 | 전분 용기용 조성물, 이를 이용한 전분 용기 및 이를 이용한 전분 용기의 제조방법 |
| CN102775550B (zh) * | 2012-07-12 | 2014-09-10 | 西能化工科技(上海)有限公司 | 一种中高温热膨胀性微球及减少其中残余单体的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615972A (en) * | 1967-04-28 | 1971-10-26 | Dow Chemical Co | Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same |
| US3740359A (en) * | 1972-07-10 | 1973-06-19 | Dow Chemical Co | Vinylidene chloride expandable microspheres |
| US4016110A (en) * | 1972-07-26 | 1977-04-05 | The Dow Chemical Company | Process for the preparation of expandable microspheres |
| JPS62286534A (ja) * | 1986-06-04 | 1987-12-12 | Matsumoto Yushi Seiyaku Kk | 熱膨張性マイクロカプセルの製造法 |
-
1993
- 1993-06-18 CN CN93107289A patent/CN1048191C/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615972A (en) * | 1967-04-28 | 1971-10-26 | Dow Chemical Co | Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same |
| US3740359A (en) * | 1972-07-10 | 1973-06-19 | Dow Chemical Co | Vinylidene chloride expandable microspheres |
| US4016110A (en) * | 1972-07-26 | 1977-04-05 | The Dow Chemical Company | Process for the preparation of expandable microspheres |
| JPS62286534A (ja) * | 1986-06-04 | 1987-12-12 | Matsumoto Yushi Seiyaku Kk | 熱膨張性マイクロカプセルの製造法 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309765C (zh) * | 2005-10-20 | 2007-04-11 | 北京科技大学 | 采用微胶囊发泡剂进行波聚合制备多孔水凝胶的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1088849A (zh) | 1994-07-06 |
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