CN104371827B - 一种大胶囊组装物及其制备方法 - Google Patents
一种大胶囊组装物及其制备方法 Download PDFInfo
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- CN104371827B CN104371827B CN201410630893.8A CN201410630893A CN104371827B CN 104371827 B CN104371827 B CN 104371827B CN 201410630893 A CN201410630893 A CN 201410630893A CN 104371827 B CN104371827 B CN 104371827B
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0007—Aliphatic compounds
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Abstract
本发明提供了一种新型高性能的大胶囊组装物及其制备方法，该组装物将香精或相变材料与聚合物熔体或海藻酸盐溶液混合均匀，进行切粒造粒或滴加造粒得到10微米～5毫米范围内的颗粒，功能囊芯分布在聚合物基材中，干燥后在其表面涂覆稀类不饱和单体，并采用光固化的方法使其在颗粒表面固化，制备以稀类不饱和单体共聚物为囊壁的具有单一核壳结构的大胶囊。这可大大提高大胶囊的生产效率，同时达到节能减排的目的。
Description
技术领域
本发明涉及一种新型大胶囊及其制备方法，具体涉及到一种具有单一核壳结构的大胶囊制备方法。
背景技术
大胶囊技术是一种用成膜材料将固体或液体包裹起来形成颗粒的技术，得到的颗粒尺寸一般大于10微米。通过选择胶囊囊壁材料的种类，或调控囊壁材料的微观结构，可以达到控制囊芯释放的目的。如将相变储能材料进行大胶囊化，可应用于储热调温马甲、智能节能建筑中。也可将香精等材料大胶囊化，调节囊壁微观结构，达到控制香精释放的目的。将囊芯材料和壁材混合，然后经过造粒，便可得到一种定形大胶囊，如Ahmet Sari等(Energy Conversion andManagement，2004，45(13-14)：2033～2042)都是以石蜡为相变材料、以高密度聚乙烯为支撑材料制备定形相变材料。虽然这种大胶囊生产效率高，但是对囊芯材料的密封性能很差，容易造成泄露。申请者在发明专利(授权公告号CN101838520B)中，制备了以定型相变材料为囊芯，以非异氰酸酯型聚氨酯为囊壁的核壳结构大胶囊。然而这种制备方法制备周期较长，不利于工业生产。
光固化技术在涂料、粘合剂等领域是很成熟的技术，它可以在几分钟甚至几秒钟就可以完成固化反应。然而，采用光固化技术制备具有单一核壳结构却几乎没有报道。采用光固化技术制备核壳结构的大胶囊，可大大提高生产效率，而且不涉及到热引发，对节能减排有重大意义。根据囊芯材料的性能，这种大胶囊可广泛用于节能减排领域，智能温度调节服装等
发明内容
本发明提供了一种新型高性能的大胶囊组装物及其制备方法，该组装物以香精、相变材料为功能囊芯，海藻酸钠或聚合物为基材，功能囊芯分布在基材中，同时以稀类不饱和单体为外壳原料，采用光固化的方法，制备以稀类不饱和单体共聚物为囊壁的具有单一核壳结构的大胶囊。这可大大提高大胶囊的生产效率，同时达到节能减排的目的。
本发明制备核壳结构大胶囊组装物的具体步骤如下：
(1)按质量计，将100份熔融态的有机相变材料或香精加入100～1000份聚合物熔体中或海藻酸钠水溶液中，混合均匀得到均一稳定溶液。将该溶液进行切粒造粒或滴加至凝固浴中造粒，得到粒径范围在10微米～5毫米的颗粒。
(2)将步骤(1)制备的颗粒干燥处理后，表面蘸取乙烯基单体溶液，其中乙烯基单体溶液中光引发剂质量分数为0～30wt％。
(3)将步骤(2)得到表面附有乙烯基单体的颗粒，加入到水中并搅拌，搅拌速度控制在1～1000rpm。采用功率为10瓦～10千瓦的紫外光照射0～3hr，即可得到具有核壳结构的大胶囊组装物。
其中所述海藻酸钠水溶液浓度范围为0.1～10wt％。
所述凝固浴可以为质量浓度在0～80wt％的硫酸镁水溶液，氯化钙水溶液，硫酸铜水溶液，氯化锌水溶液。
所述相变材料可以是脂肪烃中碳链长度在10～80的长链烷烃。脂肪醇优选十二醇、十四醇、十六醇、十八醇、环己醇、叔丁醇、2，2-二甲基1，3丙二醇或2-氨基-2甲基-1，3丙三醇；脂肪酸优选为癸酸、月桂酸、十四烷酸、十五烷酸、十六烷酸、十八烷酸或它们的至少两种的混合物。直链烷基酯中硬脂酸正丁酯、二硬脂酸乙二醇酯、十二烷酸甲酯、十四酸甲酯、十六酸甲酯、十八酸甲酯、硬脂酸甲酯、二十酸甲酯、十二酸乙酯、十四酸乙酯、十六酸乙酯、十八烷乙酯、硬脂酸乙酯、二十酸乙酯、十四酸异丙酯十六酸异丙酯、十二酸丁酯、十四酸丁酯、十六酸丁酯、十八酸丁酯中至少一种。
所述香精包括人造香精和天然香精，如合成麝香、结晶玫、香兰素、香豆素、乙酰丁香酚、苯甲酸苄酯或苯乙酸芳芳樟酯中一种或混合物；柏树精油、玫瑰香精、茉莉油、柠檬油、椰子香精、薰衣草香精、安息香脂、鸢尾香脂、檀香油、岩兰草油中的至少一种。
作为基材的聚合物可以是，聚烯烃中的聚丙烯，聚乙烯中一种或混合物，聚酯中的聚对苯二甲酸乙二醇酯、聚甲基丙烯酸酯中一种或其混合物，聚酰胺，聚苯乙烯。
大胶囊囊壁的原料单体包括以下一种或几种单体混合物，苯乙烯，二乙烯基苯，甲基丙烯酸甲酯，甲基丙烯酸丁酯，甲基丙烯酸乙酯，丙烯酸，丙烯酸酯，丙烯酸酯同系物，甲基丙烯酸烯丙酯，1，4-丁二醇二丙烯酸酯，N’N’-亚甲基双丙烯酰胺，聚氨酯丙烯酸酯齐聚物的官能度为1～8的聚氨酯丙烯酸酯齐聚物或官能度为1～8的聚氨酯丙烯酸酯齐聚物的混合物。
所述光引发剂为二苯甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基-环己基-苯基丙酮、2，4，6-三甲基苯甲酰基-二苯基氧化膦、2，4，6-三甲基苯甲酰基膦酸乙酯、2-甲基-1-(4-甲硫基苯基)-2-吗琳基-1-丙酮、2-异丙基硫杂蒽酮、4-二甲胺基-苯甲酸乙酯、安息香双甲醚、邻苯甲酰苯甲酸甲酯和4-氯二苯甲酮中的任意一种或任意几种以任意比的混合物。
所述光引发波段为紫外光，波长分布在200～650nm。
本发明利用光固化方法制备核壳结构的大胶囊，避免了原位聚合法、悬浮聚合法、界面聚合法以及喷雾干燥法等传统胶囊化工艺中热能的消耗，降低了排放，减少对环境的危害。同时光引发胶囊化具有效率高，设备简单，操作方便等优点，利于大规模的工业生产。更重要的是这种新型核壳结构的胶囊密封性能良好且可以调控，具有很大的潜在应用价值。
附图说明
图1是实施例1所制备大胶囊组装物照片。
图2是实施例1所制得的大胶囊组装物断面形貌图(扫描电子显微图片)
具体实施方式
以下通过具体实施例用于进一步说明本发明描述的方法，但是并不意味着本发明局限于这些实施例。
实施例1：
一种核壳结构大胶囊的制备方法，包括如下步骤：
(1)称取100g正十八烷，加热熔融后，在50g浓度为2wt％海藻酸钠溶液中充分搅拌混合均匀，得到均一稳定溶液。然后滴加到浓度为5wt％氯化钙水溶液中，得到3毫米粒径的圆球状颗粒。
(2)将制备的圆球状颗粒干燥处理，在丙烯酸烯丙酯溶液中蘸取后，其中丙烯酸烯丙酯中含有10wt％的2-羟基-2-甲基-1-苯基-1-丙酮作为光引发剂。
(3)得到表面附有丙烯酸烯丙酯单体的颗粒，加入到水中并搅拌，搅拌速度为50rpm。并采用功率为500瓦的紫外光照射0.5hr，使其在颗粒表面光引发聚合，即可得到具有核壳结构的大胶囊组装物，过滤、洗涤并烘干可得到具有核壳结构的大胶囊组装物。
制备所得到具有核壳结构的大胶囊组装物，如图1所示，可以看出球形的大胶囊直径约为3毫米。图2是大胶囊断面的扫描电子显微镜图，由图可以看出，大胶囊具有核壳结构，囊壁较致密。
实施例2：
一种大胶囊组装物的制备方法，包括如下步骤：
(1)称取1kg柏树精油，在1000kg浓度为10wt％海藻酸钠溶液中充分搅拌混合均匀，得到均一稳定溶液。然后滴加到浓度为30wt％氯化钙水溶液中，可得到10毫米粒径的非规则颗粒。
(2)把颗粒干燥处理，在六官能团的聚氨酯丙烯酸树脂中蘸取后，其中聚氨酯丙烯酸光固化剂二苯甲酮含量为20wt％。
(3)得到表面附有聚氨酯丙烯酸树脂单体的颗粒，加入到水中并搅拌，搅拌速度为1000rpm。并采用功率为500瓦的紫外光(波长在600nm左右)照射3hr，使其在颗粒表面光引发聚合，即可得到具有核壳结构的大胶囊组装物，过滤、洗涤并烘干可得到具有核壳结构的大胶囊组装物。
实施例3：
一种核壳结构大胶囊组装物的制备方法，包括如下步骤：
(1)称取10kg硬脂酸正丁酯与50kg的聚乙烯在螺杆挤出机上熔融混合，挤出造粒，得到1～5毫米范围的柱形颗粒。
(2)干燥处理柱形颗粒后，在质量分数为1∶1的苯乙烯和二官能团聚氨酯丙烯酸树脂均匀溶液中蘸取三次，其中均匀溶液中光引发剂1-羟基-环己基-苯基丙酮含量为30wt％。
(3)得到表面附有乙烯基单体的颗粒后，加入到水中并缓慢搅拌，搅拌速度为10rpm。并采用功率为10k瓦的紫外光照射3hr，紫外光波长范围在360-380nm，使其在颗粒表面光引发聚合，即可得到具有核壳结构的大胶囊组装物，过滤、洗涤并烘干可得到具有核壳结构的大胶囊组装物。
实施例4：
一种核壳结构大胶囊组装物的制备方法，包括如下步骤：
(1)称取5kg正十二醇与0.5kg的聚苯乙烯在螺杆挤出机上熔融混合，挤出造粒，得到1～5毫米范围的柱形颗粒。
(2)干燥处理柱形颗粒后，在质量分数比为1∶3的二乙烯苯和六官能团聚氨酯丙烯酸树脂均匀溶液中蘸取三次，其中均匀溶液中光引发剂1-羟基-环己基-苯基丙酮含量为8wt％。
(3)得到表面附有乙烯基单体的颗粒后，加入到水中并缓慢搅拌，搅拌速度为60rpm。并采用功率为500瓦的紫外光照射0.5hr，紫外光波长范围在360-380nm，使其在颗粒表面光引发聚合，即可得到具有核壳结构的大胶囊组装物，过滤、洗涤并烘干可得到具有核壳结构的大胶囊组装物。
Claims (4)
1.一种具有核壳结构的大胶囊组装物的制备方法，其包括如下步骤：
(1)按质量计，将100份熔融态的有机相变材料或香精加入100～1000份聚合物熔体中或海藻酸钠水溶液中，混合均匀得到均一稳定溶液，将该溶液进行切粒造粒或滴加至凝固浴中造粒，得到粒径范围在10微米～5毫米的颗粒；
(2)将步骤(1)制备的颗粒干燥处理后，表面蘸取乙烯基单体溶液，其中乙烯基单体溶液中光引发剂质量分数为0～30wt％；
(3)将步骤(2)得到表面附有乙烯基单体的颗粒，加入到水中并搅拌，搅拌速度控制在1～1000rpm，采用功率为10瓦～10千瓦的紫外光照射0～3小时，即可得到具有核壳结构的大胶囊组装物。
2.如权利要求1所述的制备方法，所述海藻酸钠水溶液浓度为0.1～10wt％。
3.如权利要求1所述的制备方法，所述凝固浴为硫酸镁水溶液，氯化钙水溶液，硫酸铜水溶液，氯化锌水溶液，凝固浴浓度范围在0～80wt％。
4.如权利要求1所述的制备方法，其特征在于：所述紫外光波长为200～650nm。
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