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CN111423615B - 一种乳液冰冻破乳制备聚合物通孔材料的方法及其应用 - Google Patents

一种乳液冰冻破乳制备聚合物通孔材料的方法及其应用 Download PDF

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CN111423615B
CN111423615B CN202010402402.XA CN202010402402A CN111423615B CN 111423615 B CN111423615 B CN 111423615B CN 202010402402 A CN202010402402 A CN 202010402402A CN 111423615 B CN111423615 B CN 111423615B
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CN111423615A (zh
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赵骞
陈狄
江永波
谢涛
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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Abstract

本发明公开了一种乳液冰冻破乳制备聚合物通孔材料的方法，包括：(1)制备含有未交联的聚合物与交联剂的乳液，未交联的聚合物存在于乳液有机相液滴中，交联剂存在于乳液有机相液滴中或溶于水相中；将乳液置于冷冻条件下，乳液破乳，之后交联剂与聚合物发生相互作用发生化学交联；(2)去除冰晶，得到具有通孔结构的聚合物材料。本发明提供的之别方法操作简单，能够良好地调节聚合物内多孔形貌，并适用于大面积连续化制造。同时，所发明工艺能够方便地调整聚合物单体种类来拓展材料的功能。特别是能够制备具有抗菌，大通量竖直孔结构，且能高温消毒的熔喷布，可应用于口罩等医用防护用品中。

Description

一种乳液冰冻破乳制备聚合物通孔材料的方法及其应用
技术领域
本发明涉及聚合物多孔材料的制造加工领域，具体涉及一种乳液冰冻破乳制备聚合物通孔材料的方法及其应用。
背景技术
具有通孔结构的聚合物材料，由于相互贯通的孔结构以及较大的比表面积和较低的表观密度，在各种领域均有良好应用，典型地能够作为过滤材料来代替防护口罩的熔喷层以及作为胶棉材料来制备胶棉拖把及洁具。其中，工业上对口罩熔喷布的生产往往采用线性聚丙烯纤维热压的方式。采用线性聚丙烯纤维热压的方式：一方面对孔形貌的调控能力较弱，另一方面由于利用热塑性聚丙烯为原料，使其只能采用环氧乙烷等化学消毒剂对所制备口罩进行消毒，导致口罩需要一周以上的过渡时间以使化学消毒剂挥发完全，无法做到及时供应。又如，传统胶棉是由聚乙烯醇利用淀粉溶解制孔，并用甲醛交联，其大量高VOC废水排放造成现有该类型企业纷纷由于环保问题而关门。
发泡法与模板法是另外两种用来制备聚合物通孔材料的常见方法。通过在聚合物基体材料中添加发泡基元，包括化学发泡剂或者惰性气体等，利用发泡基元的物理或化学变化实现多孔结构的生成，从而制备得到聚合物通孔材料。但该类方法通常要求聚合物本体具有较高粘度以固定生成的多孔结构，同时对孔结构形貌的调控能力较低，从而限制了材料的功能化应用。
此外，传统模板法以及相分离法等均能够制备聚合物通孔材料，但往往工艺流程较复杂，无法适配大面积制造要求，同时模板等的除去会造成极大的环境问题。
与上述致孔方法不同，以冰冻致孔法为代表的新型多孔材料制备方式，能够以溶剂的相变过程来实现多孔结构的塑造，并且可以方便地通过冷冻方式等的调节来调控所得多孔结构的孔径、孔隙率等的形貌特性。传统方式中往往采用水作为溶剂，所得聚合物通孔材料耐水耐候性较差，但若采用有机溶剂又会造成较大环境问题。同时该类方法仅限于实验室制备，无法满足大面积制备的需求。
为解决上述矛盾，有研究者开始关注通过乳液体系的冷冻干燥来制备聚合物通孔材料。典型地采用疏水性聚合物溶液分散于水中形成乳液，通过冷冻干燥引起聚合物聚并从而构造多孔结构，并且由于采用疏水性聚合物，其具有良好耐水性。但该方法需要聚合物具有较大的力学刚性以支撑多孔结构，这限制了乳液法应用的广度。另一方面，冰冻干燥过程耗时耗能，不适合大规模工业化生产。
发明内容
本发明的目的在于提供一种乳液冰冻破乳制备聚合物通孔材料的方法及其应用，本发明提供的制备方法操作简单，能够良好地调节聚合物内多孔形貌，并适用于大面积连续化制造；同时，制备方法能够方便地调整聚合物单体种类来拓展材料的功能和应用。
本发明提供如下技术方案：
(1)制备含有未交联的聚合物与交联剂的乳液，未交联的聚合物存在于乳液有机相液滴中，交联剂存在于乳液有机相液滴中或溶于水相；将乳液置于冷冻条件下，乳液破乳，之后交联剂与聚合物发生相互作用发生化学交联；
(2)去除冰晶，得到具有通孔结构的聚合物材料。
在乳液状态时，由于聚合物被包裹在乳胶粒之中，而交联剂则分散在水相中，聚合物不会发生交联，所以体系稳定存在；当通过冰冻的方法制孔时，分散相由水变成冰晶，大量的冰晶使聚合物乳胶粒破乳，并使得水相中溶解的交联剂等挤出，在聚合物表面富集，满足交联条件，产生交联结构，可以稳定多孔形貌。
本发明中，步骤(1)所述乳液的形成采用单种或多种乳化剂配合。作为优选，乳化剂可以选用牌号为A-980、A-6828、102、T-40、A-246、DSB等。
为实现乳液消泡过程，步骤(1)所述乳液中可以添加单种或多种消泡剂。作为优选，消泡剂能够采用但不限于聚二甲基硅氧烷，脂肪酸甘油脂以及聚醚消泡剂。
在步骤(1)中，所述聚合物选自聚丙烯酸酯类、聚氨酯类、环氧树脂类、聚碳酸酯类或聚苯乙烯类中的一种或至少两种的组合；所述聚合物中含有能够被交联的结构。同时，乳液油相内聚合物可以通过直接添加，或者油相内反应性单体在引发剂作用下原位聚合产生。
进一步的，所述反应性单体可采用多种型号，作为优选，可以选用但不限于丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯等。进一步的，聚合方式，可以采用热引发聚合，或氧化还原引发聚合，或光照引发聚合。其中，热引发聚合时可以采用但不限于过氧化二苯甲酰、偶氮二异丁腈；氧化还原引发时，可以采用但不限于过硫酸铵、过硫酸钾组成氧化体系，亚硫酸氢钠、四甲基乙二胺组成还原体系；光照引发时可以采用但不限于2,4,6-(三甲基苯甲酰基)二苯基氧化膦、4-二甲氨基-苯甲酸乙酯，可采用光源波长为200-500nm。进一步，反应能够在不同温度下发生，作为优选，温度设定在室温至70℃，反应时间为2-12h。
进一步的，当聚合物由反应性单体在引发剂作用下原位聚合生成时，乳液中能够添加其余种类单体(功能单体)来调节最终聚合物通孔材料性能，作为优选，利用但不限于甲基丙烯酸甲酯、苯乙烯等来调节所得聚合物通孔材料的玻璃化转变温度，利用但不限于聚离子或相应离子型反应性单体来调节材料抗菌、抗病毒性能，进一步优选，离子型反应性单体可以选用3-(甲基丙烯酰氨基)丙基三甲基氯化铵、N,N-二甲胺基丙烯酸乙酯、甲基丙烯酸磺酸甜菜碱、羧酸甜菜碱甲基丙烯酸酯。
进一步的，为使步骤(2)中交联过程顺利发生，乳液油相聚合物中需含能够被交联的结构，作为优选，被交联的结构包括但不限于双丙酮丙烯酰胺结构，甲基丙烯酸缩水甘油酯结构，单端环氧丙烯酸酯结构。
进一步的，为实现油相内所含聚合物的交联，乳液中的水相需要加入单种或多种交联剂。作为优选，交联剂可以采用但不限于己二酰肼，己二胺、三乙基四胺，二硫苏糖醇，亚甲基双丙烯酰胺。
本发明中，乳液能够在不同温度下进行冷冻，冷冻温度为-5℃以下。作为优选，将冷冻温度设定在-180～-50℃。在冷冻时长上，作为优选，冷冻时间为0.5-10min。通过在不同温度下冷冻来调节冰晶大小，进而调节聚合物通孔材料的孔径。进一步作为优选，冷冻方式能够采用以冷台冷冻为代表的定向冷冻或以恒温箱为代表的无规冷冻。
在本发明中，冷冻时乳液能够处于不同状态以实现对成型材料三维形态的调节，适用于大面积制造。作为优选，乳液能够利用涂附或流延制备薄层状聚合物通孔材料，或利用三维模具制备块状聚合物通孔材料。
在本发明中，步骤(2)所述交联结构的产生方式，作为优选，可以是冰冻下自发形成，或冰冻下经过光照形成。
在本发明中，步骤(3)所述冰晶能够采用多种方式进行去除，作为优选，采用但不限于冷冻干燥或者常温融化蒸发。作为优选，去除冰晶的方式为自然干燥、真空干燥或加热干燥。
本发明中所得到聚合物通孔材料的多孔结构能够通过乳液中加入添加剂来调控孔形貌，或调整冷冻基底浸润性来调控孔径，作为优选，添加剂采用但不限于聚乙烯醇、聚乙二醇以及聚丙烯酸钠；基底浸润性调控采用但不限于涂附聚二甲基硅氧烷、聚甲基丙烯磺酸钠、聚丙烯酸钠以及聚乙烯醇。
作为优选，在步骤(2)中得到的聚合物通孔材料具有竖直通孔结构。
本发明还提供了上述聚合物通孔材料的应用，可作为过滤材料、机械阻尼材料、隔音材料、减震材料、形状记忆材料(利用自身的玻璃化转变温度)、抗菌材料、抗病毒材料或吸收吸附材料。进一步的，所述聚合物通孔材料替代熔喷布，制备组织夹或作为胶棉材料。
本发明所建立的冰冻-破乳制备聚合物通孔材料的方法能够应用于多种乳液配方体系，作为优选，可以采用但并不限于的配方组成如下，以重量份的原料组成表示：
Figure BDA0002489997270000051
进一步，本发明所建立的乳液冰冻破乳制备聚合物通孔材料的方法能够拓展出聚合物通孔材料连续化制备工艺并可应用于熔喷布生产。
本发明提供的聚合物通孔材料的制备方法可以在其他辅助交联条件下(如紫外光等)进一步提高交联密度，达到定型空隙及功能设计目的；本发明通过调整冰晶结晶方向来控制开孔方向，调整冰晶晶体大小来控制孔径，通过调整不同区域冰晶大小的分布来设计功能单元。
本发明开发的基于乳液冰冻破乳制备聚合物通孔材料的方法，通过在乳液体系的水相中加入交联剂，利用冰晶生长将交联剂挤压到聚合物胶乳表面，从而在一定条件下引起聚合物交联，使得多孔形貌被良好地固定下来。相较于传统方式，该方法简单、实用性强，对所采用聚合物力学性能的要求大大降低。另一方面，本发明所建立的聚合物通孔材料制备工艺简单环保，其材料性能能够通过分子结构设计、冰冻工艺调整来调控，并且能够构造具有较大流体通量的竖直孔结构，同时可方便地通过功能单体组分的共聚，赋予材料抗菌、吸附等的特性。另外，所开发方法制备的是热固性通孔材料，从而可以采用高温高压来进行材料的杀菌消毒。这些优势能够解决上文所提及的通孔材料在制造中存在的技术限制，特别是应用于口罩、隔离服等医用品的生产当中。
附图说明
图1为实施例1中制备的聚合物通孔材料的宏观照片；
图2为实施例1中制备的聚合物通孔材料的扫描电镜图；
图3为实施例2中制备的聚合物通孔材料的扫描电镜图；
图4为实施例3中制备的聚合物通孔材料的扫描电镜图；
图5为实施例6中制备的小孔径聚合物通孔材料的扫描电镜；
图6为实施例7中的聚合物通孔材料连续化制备工艺示意图；
图7为聚合物通孔材料的制备方法示意图。
具体实施方式
以下结合实施例对本发明做进一步说明，但本发明要求保护的范围并不局限于实施例表达的范围。
本发明提供的乳液冰冻破乳制备聚合物通孔材料的方法的示意图如图7所示。
实施例1(双丙酮丙烯酰胺与己二酸二酰肼形成交联)
采用原料以及比例：
打底液配方：
Figure BDA0002489997270000071
预乳化液配方：
Figure BDA0002489997270000072
引发剂配方：
Figure BDA0002489997270000073
后处理液配方：
Figure BDA0002489997270000074
制备步骤：
(1)按照打底液配方在釜中将原料配好，在60℃下搅拌并保温20分钟，直至蓝光出现；然后再按照预乳化配方，乳化剂等助剂加入水中，待完全溶解后加入其它单体，并在高剪切乳化机中乳化形成稳定预乳液，并在打底蓝光出现后滴加到釜中，滴加时间为4小时；
(2)在预乳化液滴加开始30分钟后，滴加引发剂，滴加时间为4小时。
(3)预乳液和引发剂滴加结束后继续反应2小时，降温至45℃，加入后处理液保温15分钟，过滤出料。
(4)将上述丙烯酸酯乳液倒入容器中，放在-100℃环境中，冰冻10min；将冻好的乳液放置于常温下，通过冰晶的融化蒸发得到聚丙烯酸酯通孔材料。
实施例2(丙烯酸缩水甘油酯与三乙基四胺形成交联)
采用原料及比例组成如下：
打底液配方：
Figure BDA0002489997270000081
预乳化液配方：
Figure BDA0002489997270000082
后处理液配方：
Figure BDA0002489997270000083
制备步骤，同实例1中步骤类似：
(1)按照打底液配方在釜中将原料配好，在常温下搅拌20分钟，直至蓝光出现；然后再按照预乳化配方，乳化剂等助剂加入水中，待完全溶解后加入其它单体，并在高剪切乳化机中乳化形成稳定预乳液，并在打底蓝光出现后滴加到釜中，滴加时间为6小时；
(2)待滴加完全，将反应液温度上升到70℃，引发单体聚合，反应持续24h，随后降至常温。
(3)加入后处理液，搅拌15分钟，过滤出料。
(4)将上述丙烯酸酯乳液倒入容器中，放在-50℃环境中，冰冻5min；将冻好的乳液置于冷冻干燥机中，通过冻干得到聚合物通孔材料。
实施例3(甲基丙烯酸缩水甘油酯与二硫苏糖醇形成交联)
采用原料及比例组成如下：
打底液配方：
Figure BDA0002489997270000091
预乳化液配方：
Figure BDA0002489997270000092
后处理液配方：
Figure BDA0002489997270000093
Figure BDA0002489997270000101
制备步骤：
(1)按照打底液配方在釜中将原料配好，在40℃下搅拌直至蓝光出现；然后再按照预乳化配方配置稳定的预乳化液，并在打底蓝光出现后滴加到釜中，滴加时间为6小时；
(2)在预乳化液滴加开始10分钟后，升高温度至60℃，总滴加时间为6小时。
(3)预乳液滴加结束后继续反应6小时，降至室温，加入后处理液搅拌5分钟，过滤出料。
(4)将上述丙烯酸酯乳液倒入容器中，放在-180℃环境中，冰冻0.5min；将冻好的乳液加热熔化，除去水即得到聚合物通孔材料。
实施例4(玻璃化转变温度调节)
通过在原始单体组成中加入不同种类单体，实现聚合物玻璃化转变温度的调节，典型采用原料及比例组成如下：
打底液配方：
Figure BDA0002489997270000102
预乳化液配方：
Figure BDA0002489997270000103
Figure BDA0002489997270000111
引发剂配方：
Figure BDA0002489997270000112
后处理液配方：
Figure BDA0002489997270000113
制备步骤：
(1)按照打底液配方在釜中将原料配好，在60℃下搅拌并保温20分钟，直至蓝光出现；然后再按照预乳化配方，乳化剂等助剂加入水中，待完全溶解后加入其它单体，并在高剪切乳化机中乳化形成稳定预乳液，并在打底蓝光出现后滴加到釜中，滴加时间为4小时；
(2)在预乳化液滴加开始30分钟后，滴加引发剂，滴加时间为4小时。
(3)预乳液和引发剂滴加结束后继续反应2小时，降温至45℃，加入后处理液保温15分钟，过滤出料。
(4)将上述丙烯酸酯乳液倒入容器中，放在-100℃环境中，冰冻10min；将冻好的乳液内冰晶通过常温融化蒸发除去，即得到具有与实施例1中所制得的聚合物通孔材料不同玻璃化转变温度的材料。其中，实施例1所得聚合物玻璃化转变温度为20℃，该实施例中所制备材料玻璃化转变温度为61℃。
实施例5(添加剂调节材料孔形貌)
通过在原始单体组成中加入亲水性添加剂实现所得泡沫材料孔结构的调控，典型采用原料及比例组成如下：
打底液配方：
Figure BDA0002489997270000121
预乳化液配方：
Figure BDA0002489997270000122
引发剂配方：
Figure BDA0002489997270000123
后处理液配方：
Figure BDA0002489997270000124
制备步骤：
(1)按照打底液配方在釜中将原料配好，在60℃下搅拌并保温20分钟，直至蓝光出现；然后再按照预乳化配方，乳化剂等助剂加入水中，待完全溶解后加入其它单体，并在高剪切乳化机中乳化形成稳定预乳液，并在打底蓝光出现后滴加到釜中，滴加时间为4小时；
(2)在预乳化液滴加开始30分钟后，滴加引发剂，滴加时间为4小时。
(3)预乳液和引发剂滴加结束后继续反应2小时，降温至45℃，加入后处理液保温15分钟，过滤出料。
(4)将上述丙烯酸酯乳液倒入容器中，放在-18℃环境中，冰冻1小时；将冻好的乳液内冰晶通过常温融化蒸发除去，即得到具有与实施例1中所制得的聚合物通孔材料孔隙率不同的材料。其中，实施例1所制备材料的孔隙率为45％，该实施例中制备材料孔隙率为90％。
实施例6(冷冻基底浸润性调节孔形貌)
利用实施例1中的原料组成与步骤，在其第(4)步前，先将冷冻基底涂附聚乙烯醇，再将乳液倒入冷冻基体上。通过在-100℃环境下冷冻10min，随后采用常温融化蒸发除去冰晶，实现聚合物通孔材料制备。在实施例1中材料孔径为100μm，而采用该方式制备材料孔径为1μm。
实施例7(聚合物通孔材料连续化制备)
利用实施例2中所述原料组成与实验步骤，在其第(4)步中采用乳液流延替代模具灌注过程。通过在牵引下的-180℃冷媒上运动，使乳液边冰冻边发生破乳交联，随后牵引至常温下，通过冰晶的融化蒸发，实现聚合物通孔材料的连续化制备。
实施例8(抗菌聚合物通孔材料)
按照实施例1中的原料组成与实验步骤，在其预乳化原料中增加20g丙烯酸酯化甜菜碱。通过冰晶常温融化蒸发去除后，所制备得到的聚合物通孔材料将具有抗菌特性。
实施例9(形状记忆聚合物通孔材料)
实施例1中所制备聚合物通孔材料，其玻璃化转变温度为20℃。通过在20℃以上将聚合物通孔材料进行形状的改变，并将温度下降到20℃以下来固定该形状。当温度再次升高到20℃以上时，材料将发生形状回复，从而实现形状记忆循环。
实施例10(吸水胶棉材料)
采用实施例1中的原始原料组成，同时在乳液中加入50g丙烯酸钠。通过在50℃下，引发乳液中各类单体聚合。反应12h后，待乳液冷却到室温，将其倒入长方体模具中进行冷冻。完全冰冻后，将材料转移到常温下，通过冰晶的融化蒸发即得到具有良好吸水性的聚合物通孔材料。经过测试，所制备材料能够吸收自身重量10倍的水，从而能够作为吸水胶棉应用于日常清洁用品中。

Claims (9)

1.一种乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，包括：
(1)制备含有未交联的聚合物与交联剂的乳液，未交联的聚合物存在于乳液有机相液滴中，交联剂在水相中；将乳液倾倒到冷冻基底后置于冷冻条件下，乳液破乳，之后交联剂与聚合物发生化学交联；
(2)去除冰晶，得到具有通孔结构的聚合物材料；
在乳液中加入添加剂或调整冷冻基底浸润性来调控孔结构，添加剂选自聚乙烯醇、聚乙二醇以及聚丙烯酸钠；基底浸润性调控采用但不限于涂附聚二甲基硅氧烷、聚甲基丙烯磺酸钠、聚丙烯酸钠或聚乙烯醇。
2.根据权利要求1所述的乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，在步骤(1)中，所述聚合物选自聚丙烯酸酯类、聚氨酯类、环氧树脂类、聚碳酸酯类或聚苯乙烯类中的一种或至少两种的组合；所述聚合物中含有能够被交联的结构；所述聚合物为直接添加，或由反应性单体在引发剂作用下原位聚合生成。
3.根据权利要求2所述的乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，所述被交联的结构选自双丙酮丙烯酰胺结构、甲基丙烯酸缩水甘油酯结构或单端环氧丙烯酸酯结构。
4.根据权利要求2所述的乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，当聚合物由反应性单体在引发剂作用下原位聚合生成时，同时加入功能性单体。
5.根据权利要求1所述的乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，在步骤(1)中，所述交联剂选自己二酰肼、己二胺、三乙基四胺、二硫苏糖醇或亚甲基双丙烯酰胺中的一种或至少两种的组合。
6.根据权利要求1所述的乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，在步骤(1)中，冷冻温度为-5℃以下，冷冻方式采用定向冷冻或无规冷冻。
7.根据权利要求1所述的乳液冰冻破乳制备聚合物通孔材料的方法，其特征在于，在步骤(2)中，去除冰晶的方式为自然干燥、真空干燥或加热干燥。
8.一种权利要求1-7任一所述的乳液冰冻破乳制备聚合物通孔材料的方法制备得到的聚合物通孔材料的应用，其特征在于，所述聚合物通孔材料作为过滤材料、机械阻尼材料、隔音材料、减震材料、形状记忆材料、抗菌材料、抗病毒材料或吸收吸附材料。
9.根据权利要求 8所述的聚合物通孔材料的应用，其特征在于，所述聚合物通孔材料替代熔喷布，制备组织夹或作为胶棉材料。
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