CN115305063A - 基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 - Google Patents
基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法 Download PDFInfo
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Abstract
本发明提供了一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法。本方法以水为凝固浴,通过同轴湿法纺丝技术实现胶囊化。采用上述工艺制备的毫米级相变胶囊,具有典型的储热/蓄冷功能,潜热高,适用温度范围无泄漏、循环稳定性好,相变温度稳定,具备良好的力学性能,无需其它外供能源。本方法加工过程简单、快速、经济,安全,无需使用特殊设备,能够降低成本,提高生产效率。
Description
技术领域
本发明涉及一种具有储热/蓄冷功能毫米级核壳相变胶囊的制备方法。尤其涉及一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法。
本发明提供了一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法。本方法以水为凝固浴,通过同轴湿法纺丝技术实现胶囊化。采用上述工艺制备的毫米级相变胶囊,具有典型的储热/蓄冷功能,潜热高,适用温度范围无泄漏、循环稳定性好,相变温度稳定,具备良好的力学性能,无需其它外供能源。本方法加工过程简单、快速、经济,安全,无需使用特殊设备,能够降低成本,提高生产效率。
背景技术
相变材料能够在其相变点附近吸收和释放能量,具有储热/蓄冷功能。大多数相变材料在发生相变时会出现固液转变,导致泄漏,因此将相变材料胶囊化成为一种防止相变材料泄漏和维持其形状稳定的重要方法。相变胶囊通常以聚合物或无机材料为壳,以相变材料为核,胶囊壳层的存在确保了相变发生时液体的泄漏,维持了整体的形状稳定。
近年来,相变微胶囊由于性能稳定、使用方便、应用前景广阔,因此成为研究热点,相关研究较多。目前研究中相变微胶囊的尺寸一般从不到1μm到300μm以上。原位悬浮聚合、界面聚合或乳液聚合是最常用的微胶囊化方法,其他方法包括凝聚法、喷雾干燥法、溶胶-凝胶法等。J.S.Cho通过界面缩聚以甲苯二异氰酸酯(TDI)和二乙烯三胺(DETA)为单体,以十八烷为相变材料,以壬基酚聚氧乙烯醚NP-10非离子表面活性剂为乳化剂,在乳液体系中制备了直径为1μm左右的聚脲微胶囊,微胶囊的相变温度在29-30℃。A.Sari等以聚甲基丙烯酸甲酯(PMMA)为壳材通过乳液聚合将正二十八烷胶囊化,相变胶囊的熔融和结晶温度分别为50.6和53.2℃,熔融和结晶潜热分别为86.4和-88.5J/g。X.Lan等以正二十烷为核,以DETA和TDI为单体,通过乳液界面聚合制备了聚脲微胶囊。N.Sar1er和E.Onder制备了几种聚脲醛微胶囊,所用的胶囊核材包括正十六烷、正十八烷、正二十烷、PEG600、PEG1000和十水碳酸钠,并探讨了它们在织物领域的应用前景。美国Triangle公司合成了直径15-40μm的微胶囊。这种微胶囊具有吸热作用,将其整理在织物表面,就使织物具有了调节温度的功能。Triangle公司申请了一项关于具有可逆蓄热特点纤维的专利,这种纤维是在直径为1-10μm的微胶囊中封入石蜡类碳氢化合物,然后经过和聚合物溶液一起纺丝而制得的。在某些应用场景下,纳米胶囊比微米胶囊具有更好的结构稳定性,相对而言不容易在通过流体进行输运过程中发生破坏,也有利于降低流体粘度,因此相关研究也很活跃。G.Fang等以正十四烷为核,以十二烷基硫酸钠为乳化剂,以间苯二酚为体系调节剂,制备了直径在100nm左右的纳米聚脲醛胶囊,其潜热可达134.16kJ/kg。Y.Fang等以聚苯乙烯为壳,以十八烷为核,通过超声辅助微乳液原位聚合制备了直径范围在100nm到123nm的相变纳米胶囊。H.Li等以十六醇为核,交联聚苯乙烯为壳,通过一步乳液沉淀聚合制备了相变纳米胶囊,胶囊平均直径约为120nm,熔融潜热达到124.85J/g,具备良好的机械性能和热稳定性。
对于相变胶囊而言,尺寸越小,壳材在胶囊中质量占比越高,为了提高胶囊的储能密度,将胶囊尺寸提升至毫米级是一个显而易见的策略。更关键的是,毫米尺寸相变胶囊在一些特定领域具有重要应用价值。可用于热管理服装,如医用防护服、极端环境服装等;以及建筑热管理领域,如用于地板下或墙体内。W.Li等首先以PMMA为壳,以十八烷为核,通过乳液聚合制备相变微胶囊,再将其分散在海藻酸钠溶液中形成悬浮液,将其滴加进氯化钙水溶液凝固浴中,通过锐孔-凝固浴法获得了以海藻酸钙为毫米胶囊壳材,以相变微胶囊为核的毫米胶囊结构。P.Han等采用类似方法制备了以十四烷为相变材料的毫米相变胶囊,首先通过乳液聚合将十四烷封装在微胶囊中,微胶囊壳材分别选用了聚脲醛和PMMA,再通过锐孔-凝固浴法制备毫米胶囊,其壳材为海藻酸钙,相变焓最高达到194.1J/g。H.Qi等利用乳液锐孔-凝固浴法制备了石蜡/壳聚糖毫米相变胶囊,胶囊尺寸可通过乳化剂用量进行调节,胶囊中石蜡含量最高达到85%,熔融潜热达112.6J/g,具备良好的循环稳定性。
除了上述锐孔-凝固浴法,还有一些方法也用来制备毫米级胶囊。T.Takei等利用液体弹珠制备了直径约2mm的胶囊,通过含有挥发性成分的单体液滴在超两亲粉末上滚动,再进行光固化,从而实现胶囊化。K.Nagai等通过固化乳液的方法制备了高球形度毫米级聚酰胺酸胶囊,其核为聚二甲基硅氧烷,但该方法非常耗时,N,N-二甲基乙酰胺挥发时长达到3天。P.Wang等通过同轴电驱方法,以鱼油为内芯液,以海藻酸钠溶液为外层液体,氯化钙水溶液为凝固浴,在20kV电压下驱动液滴进入凝固浴得到毫米胶囊。该方法将静电纺丝技术与锐孔-凝固浴法相结合,制备出了毫米级胶囊。这几种毫米级胶囊制备方法经过原料和工艺调整后也可用于制备毫米相变胶囊。
目前,上述毫米级核壳胶囊的制备方法中,锐孔-凝固浴法的壳材可选择范围较窄且胶囊的机械强度不高,液体弹珠法的壳材可选择范围有限且制备效率不高,乳液固化法的制备效率极低。因此,亟需一种制备简单、壳材可选择范围广、制备效率高、胶囊的机械性能好的毫米相变胶囊制备方法。
发明内容
本发明的目的在于提供一种简单、高效、原料可选择范围广的毫米级相变胶囊的制备方法。
为了实现上述目的,本发明所采用的技术方案为:基于同轴溶液湿法纺丝技术,通过调节和控制内外层纺丝液的组成和推进速度,在凝固浴中形成胶囊结构。
进一步地,本发明所述的毫米级相变核壳胶囊以石蜡烷烃为核,以可溶性聚合物为壳。
进一步地,本发明所述的胶囊化内外层纺丝液的配方如下:内层为一定量的石蜡烷烃(C14-C20);外层为可溶性聚合物溶液,其中溶质包括PMMA、聚苯乙烯(PS)、聚偏氟乙烯(PVDF)、聚乙烯醇缩丁醛(PVB)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、聚碳酸酯(PC)、热塑性聚氨酯弹性体(TPU)或聚丙烯腈(PAN)等,所用溶剂为甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿、N,N-二甲基甲酰胺(DMF)或其混合溶剂等。
进一步地,本发明所述的毫米相变胶囊制备,其步骤如下:
以甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿、DMF或其混合溶剂等为溶剂,制备质量分数为10%~40%的聚合物溶液(室温机械搅拌0.5~3h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.3~0.7mL/min、芯层0.5~1.2mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。设置推进速度较慢,使针头处无法形成连续溶液,溶液呈水滴状滴落进凝固浴,与去离子水接触时,壳层溶液中溶剂迅速与水交换,形成致密保护壳,将石蜡烷烃包覆在其中,形成相变胶囊。
发明的作用与效果
与现有技术相比,本发明的有益效果是:
1)具有典型的储热/蓄冷功能,无需其它外供能源;2)核/壳质量比高,潜热高;3)适用温度范围无泄漏、循环稳定性好4)相变温度可调,适用温度范围较宽;5)循环稳定性好;6)具备良好的机械性能;7)壳材可选择范围广;8)加工过程无需外加电场;9)本方法加工过程简单、快速、经济,安全,无需使用特殊设备,能够降低成本,提高生产效率。
附图说明
图1实施例1在凝固浴中形成的毫米胶囊照片;
图2实施例2和实施例3所制备的不同壳层材料球形毫米胶囊照片;
图3实施例4和实施例5所制备的不同壳层材料准球形毫米胶囊照片。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明确,以下结合实施例,对本发明进行进一步地详细说明。应当理解,此处所描述的实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:
以DMF为溶剂,制备质量分数为25%的PVDF溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为十八烷,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例2:
以二氯甲烷为溶剂,制备质量分数为30%的SBS溶液(室温机械搅拌3h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例3:
以二氯甲烷与甲苯的1:1混合液为溶剂,制备质量分数为20%的PMMA溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例4:
以二甲苯为溶剂,制备质量分数为30%的PS溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例5:
以DMF为溶剂,制备质量分数为20%的PAN溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例6:
以乙醇为溶剂,制备质量分数为20%的PVB溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例7:
以DMF为溶剂,制备质量分数为20%的ABS溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.6mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例8:
以二氯甲烷为溶剂,制备质量分数为20%的PC溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.8mL/min、芯层1.2mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
实施例9:
以DMF溶剂,制备质量分数为20%的TPU溶液(室温机械搅拌6h),得到壳层溶液,芯层溶液为液体石蜡烷烃,两者分别连通同轴针头两端,设置注射泵推进速度为:壳层0.5mL/min、芯层1mL/min。接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水。纺丝液和凝固浴温度均为室温。将所制备的胶囊在60℃干燥8h,使溶剂彻底挥发。
以上所述仅为本发明较佳实例,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,通过同轴溶液湿法纺丝制备具有储热/蓄冷功能的毫米级石蜡烷烃/可溶性聚合物核壳相变胶囊。
2.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,基于同轴溶液湿法纺丝技术,通过调节和控制内外层纺丝液的组成和推进速度,在凝固浴中形成胶囊结构。
3.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,以可溶性聚合物为壳层材料,采用石蜡烷烃作为相变材料。
4.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,所用可溶性聚合物至少包括聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、聚乙烯醇缩丁醛、丙烯腈-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、聚碳酸酯、热塑性聚氨酯弹性体或聚丙烯腈;所用溶剂为甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿或N,N-二甲基甲酰胺的任意一种或其混合溶剂。
5.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,其特征在于,以甲醇、乙醇、甲苯、二甲苯、丙酮、二氯甲烷、氯仿、N,N-二甲基甲酰胺的任意一种或其混合溶剂为溶剂,制备质量分数为10%~40%的聚合物溶液,室温水浴搅拌0.5~3h,得到壳层溶液,芯层溶液为液体石蜡烷烃。
6.根据权利要求1所述的基于溶液湿法纺丝的毫米级核壳相变胶囊的制备方法,分别将芯液储罐和壳层溶液储罐与同轴针头两端连通,设置注射泵推进速度为:壳层0.3~0.7mL/min、芯层0.5~1.2mL/min,接收端针头竖直设置,下端为凝固浴,凝固浴为去离子水,纺丝液和凝固浴温度均为室温。
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