CN106117423A - 温敏性纳米胶囊及其制备方法 - Google Patents
温敏性纳米胶囊及其制备方法 Download PDFInfo
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- CN106117423A CN106117423A CN201610504888.1A CN201610504888A CN106117423A CN 106117423 A CN106117423 A CN 106117423A CN 201610504888 A CN201610504888 A CN 201610504888A CN 106117423 A CN106117423 A CN 106117423A
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Abstract
本发明涉及一种温敏性纳米胶囊及其制备方法,制备的温敏性纳米胶囊包括芯材和壁材。制备方法包括:首先分别制备水相和油相,混合后高速剪切形成微乳液,经超声或高压均质作用形成纳米乳液;再向乳液中通入氮气,然后在40‑80℃的条件下反应3h~4h,整个过程保持在氮气环境中进行,即制得包埋率为90%~94%、纳米胶囊粒径PDI为0.09~0.17且粒径<150nm的温敏性纳米胶囊。本发明形成纳米胶囊壁材的单体是常用的生物材料,具有良好的生物相容性;形成的纳米胶囊壁材具有温敏性,可通过温度的变化使内部的芯材得到控制缓释,在日化品、纺织品及医药领域有广泛的应用前景。
Description
技术领域
本发明属纳米胶囊及其制备技术领域,涉及温敏性纳米胶囊及其制备方法。
背景技术
一般微胶囊粒径在1~1000μm之间,随着微胶囊技术的不断进步和纳米技术的不断发展,制备的微胶囊粒径能够<1μm,在1~1000nm之间,这种粒径在纳米范围的微胶囊称为纳米胶囊。与传统的微胶囊相比,纳米胶囊的优越性在于:(1)便于材料进一步表面修饰、提高包埋率、改变分布状态和靶向性;(2)纳米微胶囊成品稳定性好,便于加工应用和储藏运输;(3)纳米胶囊生物相容性好,毒副作用小;(4)可制成缓释颗粒,延长药物疗效;(5)能够防止食品的其他组分的破坏。纳米胶囊技术已被国际上列为21世纪重点研究开发的高新技术,纳米胶囊已经被应用于食品调味品、农业及生物技术、生物医药、以及化妆品和纺织品等领域。
有关纳米胶囊的制备的报道很多,如Polymerization mechanism of poly(ethylene glycol dimethacrylate)fragrance nanocapsules中采用细乳液聚合法包覆香精但其不具备温敏性;Preparation and characteristics of nanocapsulescontaining essential oil for textile application中采用乳液聚合法制备香精纳米胶囊但其包埋率仅为85.4%;Synthesis of fragrance/silica nanocapsules through asol-gel process in miniemulsions and their application as aromatic finishingagents中采用溶胶凝胶法制备纳米胶囊但其反应体系具有一定的毒性;Novelbiocompatible nanocapsules for slow release of fragrances on the human skin中采用纳米沉淀发制备香精胶囊但其释放不具有温敏性。因此关于制备出具有良好的生物相容性壁材,高包埋率且具有控制释放纳米胶囊还未见报道。本发明采用绿色环保体系,制备方法简单温和,得到的纳米胶囊无毒,包埋率较高且具有温敏性,可对芯材进行控制缓释,在医药、日化、纺织品等领域有广泛的应用前景。
发明内容
本发明所要解决的技术问题是提供温敏性纳米胶囊及其制备方法,所使用的反应单体是
两种不同的N-烷基丙烯酰胺单体,该两种单体具有良好的生物相容性,交联剂为二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯和二甲基丙烯酸1,6-己二醇酯中的一种及以上,该交联剂无毒绿色环保,并含有两个双键,能在聚合形成高分子长链的同时与前两种单体发生交联,形成高密度三维网状高聚物从而包埋芯材。该发明中合成的纳米胶囊壁材使用的高聚物无毒环保。
为实现上述目的,本发明采用的技术方案包括:
温敏性纳米胶囊的制备方法,采用两种不同的N-烷基丙烯酰胺单体进行自由基聚合形成壁材,制得温敏性纳米胶囊;
制备步骤为:
(1)配制乳化剂水溶液:将乳化剂和去离子水混合,得到水相;
(2)将芯材、两种不同的N-烷基丙烯酰胺单体、交联剂、引发剂和共稳定剂混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,剪切形成微乳液,再或高压均质形成纳米乳液;
(4)向所述纳米乳液通入氮气,40-80℃反应,得到温敏性纳米胶囊;
其中N-烷基丙烯酰胺单体的结构通式为:
R1为
R2为或—H;
m1=2,3,4…;m2=1,2,3,4…;
其中交联剂的结构通式为:
R1为
R2为或—H;
R3为或—H;
R4为或—H;
n1=2,3,4…;n2=1,2,3,4…;n3=2,3,4…;n4=1,2,3,4…;
n5=2,3,4…;n6=1,2,3,4…;n7=2,3,4…;n8=1,2,3,4…。
作为优选的技术方案:
如上所述的温敏性纳米胶囊的制备方法,所述乳化剂为十二烷基磺酸钠、阿拉伯树胶或聚乙烯醇(水解度为80~90%)。
如上所述的温敏性纳米胶囊的制备方法,所述芯材为紫外吸收剂、香精香料、相变材料和医药中的至少一种;所述紫外吸收剂为奥克立林或二苯酮-3或水杨酸辛酯或巴松1789或甲氧基肉桂酸异辛酯;所述香精香料为薄荷素油或玫瑰香精或柠檬香精或薰衣草香精或绿茶香精或水清莲花香精或花香香精;所述相变材料为石蜡或正十四烷或正十五烷或正十六烷或正十七烷或正十八烷或正十九烷或正二十烷或正二十一烷或正二十二烷或正二十三烷或正二十四烷;所述医药为维生素油或抗肿瘤药物。
如上所述的温敏性纳米胶囊的制备方法,所述单体为N,N-二乙基丙烯酰胺或N,N-二甲基丙烯酰胺或N-异丙基丙烯酰胺或N-乙基丙烯酰胺或N-叔丁基丙烯酰胺或N-正丙基丙烯酰胺或N-甲基,N-乙基丙烯酰胺。
如上所述的温敏性纳米胶囊的制备方法,所述交联剂为二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯和二甲基丙烯酸1,6-己二醇酯中的至少一种。
如上所述的温敏性纳米胶囊的制备方法,所述引发剂为偶氮二异丁腈或过氧化苯甲酰;所述共稳定剂为十六烷或十六醇或十八烷基硫醇。
如上所述的温敏性纳米胶囊的制备方法,所述水相和油相中,按重量份数计,各组分为:
如上所述的温敏性纳米胶囊的制备方法,所述剪切的剪切速率为6000~10000rpm,剪切时间为3~6min;所述超声的振幅为50%,超声时间为10~30min。
如上所述的温敏性纳米胶囊的制备方法,所述通入氮气是指在形成纳米乳液之后持续通入氮气保护至反应结束;所述反应的时间为3h~4h。
采用如上所述的制备方法制得的温敏性纳米胶囊,所述温敏性纳米胶囊为将芯材包埋在高聚物壁层中,所述高聚物壁层为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层;所述具有温敏性纳米胶囊的包埋率为90%~94%,形成的纳米胶囊粒径PDI为0.09~0.17且粒径<150nm。
本发明以两种不同的N-烷基丙烯酰胺单体自由基聚合形成新型纳米胶囊的壁材,以紫外吸收剂、香精香料、相变材料和医药中的一种以上材料作为芯材,利用细乳液聚合法制备纳米胶囊。其中,水相是水溶性乳化剂的水溶液,油相是芯材、两种不同的N-烷基丙烯酰胺单体、交联剂、引发剂和共稳定剂的混合物。水相和油相混合后经高速剪切形成微乳液又经过超声作用形成纳米乳液。随后,在一定温度及N2环境下,引发剂引发油相中的单体发生自由基聚合形成高聚物壁层,将芯材包埋其中。
所应用的细乳液聚合原理如下:
细乳液聚合定义如下:以亚微米液滴(50-500nm)构成稳定的乳液分散体系称为细乳液,相应的液滴成核的聚合方式称为细乳液聚合。在细乳液体系中,由于乳化剂和共稳定剂的共同作用,单体形成稳定的、分散均匀的亚微米液滴,与传统乳液的大单体液滴相比,其表面积大大增加,使得大部分乳化剂都吸附到这些液滴表面,致使水相中没有足够的游离乳化剂形成胶束或稳定均相成核,此时液滴成为成核的主要场所。其既保留了传统乳液聚合的大部分优点又具有独特的特点,拓展了乳液聚合的应用范围。
本发明使用的单体如N,N-二乙基丙烯酰胺和N,N-二甲基丙烯酰胺,由于其本身的结构特点,在作为反应单体的同时,能发生交联作用,其结构分别如下所示:
有益效果
(1)本发明以两种不同的N-烷基丙烯酰胺为单体,该单体具有良好的生物相容性,本身无毒,故不存在反应后留下未反应完的有毒单体残基;
(2)本发明合成的壁材属于无毒且具有良好的温敏性,使得这类微胶囊能很好的应用于和人体相关的产品中;
(3)本发明使用的乳化剂无毒环保,不会给反应体系引入任何有毒的物质,使得该发明体系绿色环保;
(4)本发明所使用的引发剂在低温下便能分解产生初级自由基而激活成壁单体自由基聚合反应。不仅能有效完全地引发反应的进行,而且也大大降低了能源的消耗;
(5)本发明所采用的方法是细乳液聚合法,以亚微米液滴成核,在一定温度及N2环境下,引发剂引发油相中的单体在水油界面发生自由基聚合形成高聚物壁层,将芯材包埋其中;形成的壁材是完全覆盖在芯材的表面上,对芯材的包埋率高,形成的纳米胶囊粒径均一且小于150nm;本发明制备的纳米胶囊及制备过程都是绿色环保,制备的纳米胶囊对人体无害,在香精香料、生物医药、日用化妆品及纺织纳米胶囊等行业有广泛的应用前景。
附图说明
图1为本发明中以亚微米液滴成核,在一定温度及N2环境下,引发剂引发油相中的单体发生自由基聚合形成高聚物壁层的机理示意图;
图2为纳米胶囊的透射电镜图;
图3为纳米胶囊的粒径分布图;
图4为纳米胶囊温敏性图。
具体实施方式
下面结合具体实施方式,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1~5
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将1.5份十二烷基磺酸钠和10份去离子水混合,得到水相;
(2)将10份芯材、6份N,N-二乙基丙烯酰胺、6份N,N-二甲基丙烯酰胺、1份二甲基丙烯酸乙二醇酯、0.1份偶氮二异丁腈和1份十六烷混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以6000rpm的剪切速率剪切3min形成微乳液,再以50%的振幅超声10min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,40℃反应3h,得到温敏性纳米胶囊。
当芯材为奥克立林、二苯酮-3、水杨酸辛酯、巴松1789或甲氧基肉桂酸异辛酯时,制得的温敏性纳米胶囊为将芯材包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,温敏性纳米胶囊的基本性能如下表所示。
实施例6~10
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将2份十二烷基磺酸钠和15份去离子水混合,得到水相;
(2)将20份芯材、8份N,N-二乙基丙烯酰胺、6份N,N-二甲基丙烯酰胺、5份二甲基丙烯酸1,4-丁二醇酯、0.2份偶氮二异丁腈和1.1份十六烷混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以6500rpm的剪切速率剪切4min形成微乳液,再以50%的振幅超声12min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,42℃反应4h,得到温敏性纳米胶囊。
当芯材为薄荷素油、玫瑰香精、柠檬香精、薰衣草香精或绿茶香精时,制得的温敏性纳米胶囊为将芯材包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,温敏性纳米胶囊的基本性能如下表所示。
实施例11~15
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将3份十二烷基磺酸钠和20份去离子水混合,得到水相;
(2)将50份水清莲花香精、N,N-二乙基丙烯酰胺、N,N-二甲基丙烯酰胺、2份二甲基丙烯酸1,6-己二醇酯、0.3份偶氮二异丁腈和1.2份十六烷混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以7000rpm的剪切速率剪切5min形成微乳液,再以50%的振幅超声15min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,45℃反应3h,得到温敏性纳米胶囊。
当N,N-二乙基丙烯酰胺的重量份数分别为14份、12份、10份、8份和6份,N,N-二甲基丙烯酰胺的重量份数分别为6份、8份、10份、12份和14份时,制得的温敏性纳米胶囊为将水清莲花香精包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,温敏性纳米胶囊的温敏性图如图4所示,相关数据及其它性能结果如下表所示。
实施例16
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将4.5份阿拉伯树胶和26份去离子水混合,得到水相;
(2)将66份花香香精、7份N-异丙基丙烯酰胺、8份N-乙基丙烯酰胺、3份二甲基丙烯酸乙二醇酯与二甲基丙烯酸1,4-丁二醇酯的混合物(质量比为1:1)、0.4份偶氮二异丁腈和1.5份十六烷混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以7500rpm的剪切速率剪切6min形成微乳液,再以50%的振幅超声18min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,46℃反应3h,得到温敏性纳米胶囊,反应过程中,以亚微米液滴成核,偶氮二异丁腈引发油相中的N-异丙基丙烯酰胺和N-乙基丙烯酰胺发生自由基聚合形成高聚物壁层,反应机理示意图如图1所示。
测试表明,制得的温敏性纳米胶囊为将花香香精包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,透射电镜下显示该微胶囊为球形,有明显的核壳结构,分散性好,无聚集状大颗粒,如图2所示,具有温敏性纳米胶囊的包埋率为93%,形成的纳米胶囊粒径PDI为0.1,粒径为140~149nm,如图3所示。
实施例17
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将4份阿拉伯树胶和30份去离子水混合,得到水相;
(2)将70份石蜡、9份N-异丙基丙烯酰胺、10份N-乙基丙烯酰胺、4份二甲基丙烯酸1,4-丁二醇酯与二甲基丙烯酸1,6-己二醇酯的混合物(质量比为1:2)、0.5份偶氮二异丁腈和1.6份十六烷混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以8000rpm的剪切速率剪切3min形成微乳液,再以50%的振幅超声20min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,50℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将石蜡包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为94%,形成的纳米胶囊粒径PDI为0.15,粒径为110~130nm。
实施例18
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将3份阿拉伯树胶和35份去离子水混合,得到水相;
(2)将75份正十四烷、11份N-异丙基丙烯酰胺、12份N-乙基丙烯酰胺、5份二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯与二甲基丙烯酸1,6-己二醇酯的混合物(质量比为1:1:1)、0.6份偶氮二异丁腈和1.7份十六烷混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以8500rpm的剪切速率剪切3min形成微乳液,再以50%的振幅超声22min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,52℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正十四烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为94%,形成的纳米胶囊粒径PDI为0.15,粒径为130~149nm。
实施例19
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将1.5份水解度为80%的聚乙烯醇和40份去离子水混合,得到水相;
(2)将80份正十五烷、13份N-叔丁基丙烯酰胺、14份N-正丙基丙烯酰胺、1份二甲基丙烯酸乙二醇酯、0.7份偶氮二异丁腈和1.8份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以9000rpm的剪切速率剪切3min形成微乳液,再以50%的振幅超声23min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,55℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正十五烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为91%,形成的纳米胶囊粒径PDI为0.11,粒径为110~130nm。
实施例20
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将2份水解度为80%的聚乙烯醇和45份去离子水混合,得到水相;
(2)将85份正十六烷、12份N-叔丁基丙烯酰胺、14份N-正丙基丙烯酰胺、2份二甲基丙烯酸乙二醇酯、0.8份过氧化苯甲酰和1.9份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以9500rpm的剪切速率剪切3min形成微乳液,再以50%的振幅超声24min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,60℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正十六烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为92%,形成的纳米胶囊粒径PDI为0.11,粒径为110~130nm。
实施例21
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将3份水解度为80%的聚乙烯醇和50份去离子水混合,得到水相;
(2)将90份正十七烷、8份N-叔丁基丙烯酰胺、13份N-正丙基丙烯酰胺、3份二甲基丙烯酸乙二醇酯、0.1份过氧化苯甲酰和2份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以10000rpm的剪切速率剪切4min形成微乳液,再以50%的振幅超声25min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,62℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正十七烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为93%,形成的纳米胶囊粒径PDI为0.12,粒径为110~130nm。
实施例22
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将1.5份水解度为85%的聚乙烯醇和55份去离子水混合,得到水相;
(2)将95份正十八烷、7份N-甲基,N-乙基丙烯酰胺、6份N,N-二乙基丙烯酰胺、4份二甲基丙烯酸乙二醇酯、0.2份过氧化苯甲酰和2.1份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以6000rpm的剪切速率剪切4min形成微乳液,再以50%的振幅超声26min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,65℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正十八烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为94%,形成的纳米胶囊粒径PDI为0.12,粒径为110~130nm。
实施例23
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将3份水解度为85%的聚乙烯醇和60份去离子水混合,得到水相;
(2)将100份正十九烷、9份N-甲基,N-乙基丙烯酰胺、8份N,N-二乙基丙烯酰胺、5份二甲基丙烯酸1,4-丁二醇酯、0.3份过氧化苯甲酰和2.2份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以6200rpm的剪切速率剪切4min形成微乳液,再以50%的振幅超声28min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,66℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正十九烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为90%,形成的纳米胶囊粒径PDI为0.13,粒径为110~130nm。
实施例24
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将4.5份水解度为85%的聚乙烯醇和65份去离子水混合,得到水相;
(2)将105份正二十烷、11份N-甲基,N-乙基丙烯酰胺、10份N,N-二乙基丙烯酰胺、1份二甲基丙烯酸1,4-丁二醇酯、0.4份过氧化苯甲酰和2.3份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以6600rpm的剪切速率剪切5min形成微乳液,再以50%的振幅超声29min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,68℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正二十烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为90%,形成的纳米胶囊粒径PDI为0.13,粒径为110~130nm。
实施例25
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将1.8份水解度为86%的聚乙烯醇和70份去离子水混合,得到水相;
(2)将110份正二十一烷、11份N,N-二甲基丙烯酰胺、8份N-甲基,N-乙基丙烯酰胺、2份二甲基丙烯酸1,4-丁二醇酯、0.5份过氧化苯甲酰和2.4份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以6800rpm的剪切速率剪切5min形成微乳液,再以50%的振幅超声30min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,70℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正二十一烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为91%,形成的纳米胶囊粒径PDI为0.14,粒径为110~130nm。
实施例26
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将2.2份水解度为86%的聚乙烯醇和75份去离子水混合,得到水相;
(2)将115份正二十二烷、13份N,N-二甲基丙烯酰胺、10份N-甲基,N-乙基丙烯酰胺、3份二甲基丙烯酸1,4-丁二醇酯、0.6份过氧化苯甲酰和2.5份十六醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以7000rpm的剪切速率剪切5min形成微乳液,再以50%的振幅超声10min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,72℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正二十二烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为91%,形成的纳米胶囊粒径PDI为0.14,粒径为90~110nm。
实施例27
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将2.8份水解度为86%的聚乙烯醇和80份去离子水混合,得到水相;
(2)将120份正二十三烷、14份N,N-二甲基丙烯酰胺、12份N-甲基,N-乙基丙烯酰胺、4份二甲基丙烯酸1,4-丁二醇酯、0.1份偶氮二异丁腈和1份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以7500rpm的剪切速率剪切6min形成微乳液,再以50%的振幅超声11min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,75℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正二十三烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为92%,形成的纳米胶囊粒径PDI为0.15,粒径为90~110nm。
实施例28
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将1.5份水解度为88%的聚乙烯醇和85份去离子水混合,得到水相;
(2)将100份正二十四烷、6份N-异丙基丙烯酰胺、7份N-叔丁基丙烯酰胺、3份二甲基丙烯酸1,6-己二醇酯、0.2份偶氮二异丁腈和1.5份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以8000rpm的剪切速率剪切6min形成微乳液,再以50%的振幅超声12min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,76℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将正二十四烷包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为92%,形成的纳米胶囊粒径PDI为0.15,粒径为90~110nm。
实施例29
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将2份水解度为88%的聚乙烯醇和90份去离子水混合,得到水相;
(2)将130份维生素油、9份N-异丙基丙烯酰胺、10份N-叔丁基丙烯酰胺、4份二甲基丙烯酸1,6-己二醇酯、0.3份过氧化苯甲酰和1.6份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以8200rpm的剪切速率剪切6min形成微乳液,再以50%的振幅超声15min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,78℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将维生素油包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为93%,形成的纳米胶囊粒径PDI为0.15,粒径为90~110nm。
实施例30
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将3份水解度为88%的聚乙烯醇和10份去离子水混合,得到水相;
(2)将110份抗肿瘤药物、12份N-异丙基丙烯酰胺、14份N-叔丁基丙烯酰胺、5份二甲基丙烯酸1,6-己二醇酯、0.4份过氧化苯甲酰和1.8份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以9000rpm的剪切速率剪切3min形成微乳液,再以50%的振幅超声16min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,60℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将抗肿瘤药物包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为93%,形成的纳米胶囊粒径PDI为0.16,粒径为90~110nm。
实施例31
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将1.5份水解度为90%的聚乙烯醇和35份去离子水混合,得到水相;
(2)将116份芯材奥克立林与玫瑰香精的混合物(质量比为1:1)、6份N-乙基丙烯酰胺、10份正丙基丙烯酰胺、2份二甲基丙烯酸乙二醇酯与二甲基丙烯酸1,4-丁二醇酯的混合物(质量比为1:1)、0.5份偶氮二异丁腈和2份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以9200rpm的剪切速率剪切4min形成微乳液,再以50%的振幅超声18min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,66℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将芯材包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为94%,形成的纳米胶囊粒径PDI为0.16,粒径为90~110nm。
实施例32
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将2份水解度为90%的聚乙烯醇和52份去离子水混合,得到水相;
(2)将118份芯材二苯酮-3、玫瑰香精、石蜡和抗肿瘤药物的混合物(质量比为1:1:1:1)、12份N-乙基丙烯酰胺、12份正丙基丙烯酰胺、3份二甲基丙烯酸1,4-丁二醇酯与二甲基丙烯酸1,6-己二醇酯的混合物(质量比为1:2)、0.6份偶氮二异丁腈和2.2份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以9500rpm的剪切速率剪切5min形成微乳液,再以50%的振幅超声20min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,75℃反应4h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将芯材包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为94%,形成的纳米胶囊粒径PDI为0.17,粒径为90~110nm。
实施例33
一种温敏性纳米胶囊的制备方法,制备步骤为:
(1)配制乳化剂水溶液:将3份水解度为90%的聚乙烯醇和63份去离子水混合,得到水相;
(2)将150份芯材巴松1789、花香香精和正十七烷的混合物(质量比为1:1:1)、14份N-乙基丙烯酰胺、14份正丙基丙烯酰胺、4份二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯与二甲基丙烯酸1,6-己二醇酯的混合物(质量比为1:1:1)、0.8份过氧化苯甲酰和2.5份十八烷基硫醇混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,以10000rpm的剪切速率剪切6min形成微乳液,再以50%的振幅超声30min形成纳米乳液;
(4)在形成纳米乳液之后持续通入氮气保护至反应结束,80℃反应3h,得到温敏性纳米胶囊。
测试表明,制得的温敏性纳米胶囊为将芯材包埋在为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层中,具有温敏性纳米胶囊的包埋率为94%,形成的纳米胶囊粒径PDI为0.17,粒径为90~110nm。
Claims (10)
1.温敏性纳米胶囊的制备方法,其特征是:采用两种不同的N-烷基丙烯酰胺单体进行自由基聚合形成壁材,制得温敏性纳米胶囊;
制备步骤为:
(1)配制乳化剂水溶液:将乳化剂和去离子水混合,得到水相;
(2)将芯材、两种不同的N-烷基丙烯酰胺单体、交联剂、引发剂和共稳定剂混合,搅拌均匀,得到油相;
(3)将水相加入到油相中,剪切形成微乳液,再超声形成纳米乳液;
(4)向所述纳米乳液通入氮气,40-80℃反应,得到温敏性纳米胶囊;
其中N-烷基丙烯酰胺单体的结构通式为:
R1为
R2为或—H;
m1=2,3,4…;m2=1,2,3,4…;
其中交联剂的结构通式为:
R1为
R2为或—H;
R3为或—H;
R4为或—H;
n1=2,3,4…;n2=1,2,3,4…;n3=2,3,4…;n4=1,2,3,4…;
n5=2,3,4…;n6=1,2,3,4…;n7=2,3,4…;n8=1,2,3,4…。
2.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述乳化剂为十二烷基磺酸钠、阿拉伯树胶或水解度为80~90%的聚乙烯醇。
3.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述芯材为紫外吸收剂、香精香料、相变材料和医药中的至少一种;所述紫外吸收剂为奥克立林或二苯酮-3或水杨酸辛酯或巴松1789或甲氧基肉桂酸异辛酯;所述香精香料为薄荷素油或玫瑰香精或柠檬香精或薰衣草香精或绿茶香精或水清莲花香精或花香香精;所述相变材料为石蜡或正十四烷或正十五烷或正十六烷或正十七烷或正十八烷或正十九烷或正二十烷或正二十一烷或正二十二烷或正二十三烷或正二十四烷;所述医药为维生素油或抗肿瘤药物。
4.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述单体为N,N-二乙基丙烯酰胺或N,N-二甲基丙烯酰胺或N-异丙基丙烯酰胺或N-乙基丙烯酰胺或N-叔丁基丙烯酰胺或N-正丙基丙烯酰胺或N-甲基,N-乙基丙烯酰胺。
5.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述交联剂为二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯和二甲基丙烯酸1,6-己二醇酯中的至少一种。
6.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述引发剂为偶氮二异丁腈或过氧化苯甲酰;所述共稳定剂为十六烷或十六醇或十八烷基硫醇。
7.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述水相和油相中,按重量份数计,各组分为:
8.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述剪切的剪切速率为6000~10000rpm,剪切时间为3~6min;所述超声的振幅为50%,超声时间为10~30min。
9.根据权利要求1所述的温敏性纳米胶囊的制备方法,其特征在于,所述通入氮气是指在形成纳米乳液之后持续通入氮气保护至反应结束;所述反应的时间为3h~4h。
10.如权利要求1~9中任一方法所制得的温敏性纳米胶囊,其特征是:所述温敏性纳米胶囊为将芯材包埋在高聚物壁层中,所述高聚物壁层为由油相中的单体在水油界面发生自由基聚合而形成高聚物壁层;所述具有温敏性纳米胶囊的包埋率为90%~94%,形成的纳米胶囊粒径PDI为0.09~0.17且粒径<150nm。
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US10543471B2 (en) | 2020-01-28 |
CN106117423B (zh) | 2018-04-03 |
ES2871857T3 (es) | 2021-11-02 |
EP3479820A4 (en) | 2020-03-18 |
US20190329211A1 (en) | 2019-10-31 |
EP3479820B1 (en) | 2021-04-07 |
EP3479820A1 (en) | 2019-05-08 |
WO2018000423A1 (zh) | 2018-01-04 |
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