CN114605812A - 一种导电型热塑性弹性体及其制备方法、应用 - Google Patents
一种导电型热塑性弹性体及其制备方法、应用 Download PDFInfo
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- CN114605812A CN114605812A CN202011404931.XA CN202011404931A CN114605812A CN 114605812 A CN114605812 A CN 114605812A CN 202011404931 A CN202011404931 A CN 202011404931A CN 114605812 A CN114605812 A CN 114605812A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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Abstract
本发明提供一种导电型热塑性弹性体及其制备方法，将热塑性弹性体、发泡剂、石墨或石墨烯、MOFs材料等混合于模腔中保温保压，形成具有一定压力的熔融态物质，高温混炼过程使得石墨化程度提高，同时对MOFs材料进行热处理，将所述均相溶体注入模腔，利用热塑性弹性体的急剧释压发泡，对石墨进行机械剥离，同时与MOFs衍生物原位复合，制得导电型石墨烯/MOFs/热塑性弹性体互穿网络结构。该制备方法简单，一步成型，效率高，成本低，利用石墨烯及MOFs优良的电学性能，使得制品可广泛应用于导电、储能、电磁屏蔽等柔性器件。
Description
技术领域
本发明属于聚氨酯制品技术领域，涉及一种导电型热塑性弹性体复合材料及其制备方法、应用。
背景技术
石墨烯独特的二维结构赋予了其极高的电导率，其作为导电组分可广泛用于聚合物基导电复合材料。热塑性聚氨酯是一种极性较强的热塑性弹性体，可以通过结构与组成设计，实现其性能的变化。而它与碳系材料具有良好的亲和力，能够制备具有三维网状结构和较优力学性能的复合材料，热塑性聚氨酯基导电复合材料的研究和应用愈加受到人们的关注。但石墨烯与热塑性聚氨酯等极性聚合物的相容性不良，因此在复合时易团聚，因此常利用石墨烯的前驱体——氧化石墨烯与聚氨酯弹性体复合，氧化石墨烯表面性质决定了它与聚氨酯弹性体的相容性较好，但其导电性不良，使得基于石墨烯的导电性热塑性弹性体的应用受到限制。
目前，公开报道石墨烯/热塑性弹性体复合材料的制备方法主要是基于冷冻干燥、化学腐蚀等处理工艺，但上述方法存在工艺流程复杂、制备效率低、成本高等问题，且存在潜在的健康和环境危害。
为了克服上述问题，本发明提供了一种基于石墨烯改性的导电型热塑性弹性体的方法，改善了石墨烯团聚引起的性能下降，具有优异的电化学性能，可广泛用于储能领域。
发明内容
本发明的目的在于提供一种导电性优良的导电型热塑性弹性体及其制备方法。所述的导电型热塑性弹性体制备方法简单，混炼一步成型，效率高，成本低，所得制品电学性能优良。
本发明的另一目的在于提供上述热塑性弹性体的应用，其可用于超级电容器电极材料，所述的导电型热塑性弹性体作为电极具有较高的比电容、良好的倍率性能以及循环稳定性。
为达到以上技术目的，本发明采用以下技术方案：
一种导电型热塑性弹性体，包括以下组分：
以上为基于各组分的总质量。
优选的，所述的热塑性弹性体为热塑性聚氨酯弹性体。
本发明中的热塑性弹性体是由异氰酸酯与羟基封端的中间体，在扩链剂作用下反应制备而成，异氰酸酯与羟基封端的中间体的摩尔比为0.90-1.20，优选为0.92-1.10，更优选为0.95-1.05；扩链剂的加入量为基于多异氰酸酯与羟基封端的中间体总质量的2％-30％，优选为3％-25％，更优选为5％-20％。
本发明中的异氰酸酯选自NCO官能度≥2的脂肪族、芳香族二异氰酸酯及其衍生物中的一种或多种，优选芳香族二异氰酸酯及其衍生物中的一种或多种，更优选甲苯二异氰酸酯及二苯基甲烷二异氰酸酯中的一种或多种。具体实例包括但不限于万华化学集团股份有限公司的TDI-100、TDI-80、TDI-65、MDI-100、MDI-50等。
本发明中的端羟基封端的中间体优选为线型聚酯多元醇(羟基封端聚酯)和线型聚醚多元醇(羟基封端聚醚)中的一种或两种或多种；
本发明中的线型端羟基聚酯多元醇是二元醇与二元羧酸(酐)或二元羧酸酯的缩聚产物。所述的二元羧酸(酐)或二元羧酸酯为脂肪族、脂环族和芳族二元羧酸或酸酐或羧酸酯中的一种或多种，优选具有4至15个碳原子的二元羧酸、酸酐或羧酸酯中的一种或多种，更优选为苯二甲酸、苯二甲酸酐、邻苯二甲酸二甲酯、对苯二甲酸二甲酯、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、间苯二甲酸、对苯二甲酸、环己二甲酸、邻苯二甲酸酐和四氢邻苯二甲酸酐中的一种或多种，进一步优选为己二酸、邻苯二甲酸酐和四氢邻苯二甲酸酐中的一种或多种；所述的二元醇优选为脂肪族和芳香族二元醇中的一种或多种，更优选为具有2至12个碳原子的二元醇中的一种或多种，包括但不限于乙二醇、丙二醇、丁二醇、戊二醇、己二醇、1,4-环己二甲醇、癸二醇和十二烷二醇中的一种或多种，进一步优选1,4-丁二醇。
本发明中线型端羟基聚酯多元醇的数均分子量为300-10000，优选为500-8000，更优选为600-6000。
本发明中的线型端羟基聚醚制备过程中使用的起始剂为含羟基或氨基的低分子化合物，优选为水、丙二醇、甘油、三羟甲基丙烷、乙二胺、季戊四醇、木糖醇、三乙烯二胺、山梨醇、乙二醇、双酚A和甲苯二胺中的一种或多种，更优选为水、丙二醇和甘油；
本发明中的线型端羟基聚醚的数均分子量为300-10000，优选400-8000，更优选500-6000。
本发明中制备热塑性聚氨酯所使用的扩链剂为具有2-10个碳原子的二醇，作为优选的扩链剂包括但不限于乙二醇、二乙二醇、丙二醇、二丙二醇、1,4-丁二醇、1,6-己二醇、1,3-丁二醇、1,5-戊二醇、1,4-环己二醇、新戊二醇、氢醌二(羟乙基)醚等，更优选1,4-丁二醇和/或氢醌二(羟乙基)醚。
本发明中的热塑性聚氨酯弹性体包括但不限于为万华化学集团股份有限公司生产的WHT-1565、WHT-1180、WHT-1164、WHT-8175、WHT-8185、WHT-8254、WHT-2190、WHT-7185、WHT-7190。
本发明中的发泡剂为有机类化学发泡剂，主要包括偶氮二异丁腈、偶氮二甲酰胺、偶氮二碳酸二异丙酯、二亚硝基五次甲基四胺、对甲苯磺酰肼、二磺酰肼二苯醚、三肼基均三嗪、N-硝基胍等，优选偶氮二异丁腈、偶氮二甲酰胺、偶氮二碳酸二异丙酯、二亚硝基五次甲基四胺中的一种或多种，更有选偶氮二异丁腈、偶氮二甲酰胺中的一种或多种；例如常州一耕化工有限公司的偶氮二异丁腈，浙江舜泰科技的偶氮二甲酰胺。
本发明中的石墨为纯度大于等于99.5％鳞片石墨。
优选的，本发明中的石墨烯厚度＜20层，比表面积200-2630m2/g，杨氏模量500-1100GPa，导热系数2000-5000W(m K)。
本发明中的MOFs材料为金属有机骨架材料，是一种由无机金属中心与桥连的有机配体通过自组装相互连接，形成的一类具有周期性网络结构的晶态多孔材料。通过简单热处理得到的衍生物具有多孔以及高比表面积的特点，还具有更加丰富的活性位点、更高的导电性、更优异的稳定性。多孔的特点可使其与聚氨酯弹性体进行原位复合，形成互穿网络结构，赋予最终材料优异的电化学性能。所述的MOFs材料按金属分类包括但不限于含铁MOF材料、含铜MOF材料、含铝MOF材料、含锆MOF材料、含锌MOF材料、含钛MOF材料、含铬MOF材料、含镍MOF材料、含钴MOF材料，优选含铁MOF材料、含铜MOF材料、含钴MOF材料，更优选含铁MOF材料、含铜MOF材料；如北京北科新材科技有限公司的MOF&MIL-88B(Fe)、CHEMSOON公司的DUT-8(Co)及Cu-HHTP。
本发明中所制备的导电型热塑性弹性体密度为80-1000kg/m3，优选为100～800kg/cm3；邵氏硬度为40A-40D，优选的硬度范围为40A-30D；电导率10-500S/m；采用本发明的方法得到的多孔碳化电极材料，其内部为多孔结构，孔径范围为0.5nm-0.5cm，其比表面积为100-2500m2g-1。
本发明还提供上述导电型热塑性弹性体的制备方法：将热塑性弹性体、石墨或石墨烯、发泡剂、MOFs材料在模具中熔融混炼，所得到的热塑性弹性体为柔性泡沫制品，石墨在弹性体释压发泡过程中被机械剥离为石墨烯，同时MOFs材料经热处理得到MOFs衍生物，石墨烯、MOFs衍生物与热塑性弹性体形成互穿网络结构，制备得到石墨烯/MOFs/热塑性弹性体导电复合材料。
本发明中的模腔温度为100-350℃，优选为120-320℃；更优选150-300℃；
本发明中的模腔压力为25-80MPa，优选为30-70MPa，更优选35-60MPa。
本发明还涉及所述导电型热塑性弹性体的应用，其可用于超级电容器电极材料，所述的导电型热塑性弹性体作为电极具有较高的比电容、良好的倍率性能以及循环稳定性。所述的导电型热塑性弹性体作为超级电容器电极材料使用，比容量100-500F/g，10000次循环后，容量保持率为≥95％。
本发明的积极效果在于：
(1)本发明所述制备方法工艺简单，混炼一步成型，效率高，且可作为基础方法，用于启示其他复合材料的制备；
(2)本发明热塑性弹性体在发泡剂的作用下，急剧释压发泡，使得石墨被机械剥离为石墨烯，借助石墨烯良好的导电性及电化学特性，赋予复合材料良好的性能；
(3)本发明借助混炼过程中的高温，不仅对碳材料进行一定程度的碳化处理，提高碳材料石墨化程度，赋予复合材料优良的导电性及储能性能，另外还可对MOFs材料同步热处理，得到MOFs衍生物，其微观多孔以及高比表面积的特点，赋予复合材料更加丰富的活性位点、更高的导电性、更优异的储能稳定性；
(4)本发明中石墨、MOFs材料以及聚氨酯弹性体之间具有紧密的协同作用。多孔的MOFs及聚氨酯弹性体对石墨烯有阻聚作用，解决了石墨烯与其他材料复合时易团聚影响比表面积的难题；石墨及MOFs材料与聚氨酯弹性体一步复合成型，在弹性体的结构中原位镶嵌石墨烯及MOFs材料，使得热塑性弹性体基复合材料具有优异的导电性能及电化学性能；经过热处理的MOFs材料衍生物为多孔结构，与多孔的热塑性弹性体形成网络互穿结构，使弹性体泡孔更细腻，MOFs材料分布更均匀，赋予了复合材料优异的综合性能。
(5)本发明从微观尺度对热塑性弹性体进行修饰，所制备的复合材料拥有良好的导电性和高的比表面积，可直接用作柔性超级电容器电极，并且具有高的比电容、良好的倍率性能以及循环稳定性。
具体实施方式
为了更好的理解本发明的技术方案，下面结合实施例进一步阐述本发明的内容，但本发明的内容并不仅仅局限于以下实施例。
以下实施例中的检测所用仪器说明如下：
电导率：仪器为四探针电阻测试仪，型号Keithley 2400(Lab Tracer 2.0software)，仪器厂家为泰克有限责任公司。
总比表面积及平均孔径：仪器为全自动比表面和孔径分布分析仪，型号：Autosorb-iQ2，仪器厂家为美国Quantachrome公司。
电容量：仪器为电化学工作站，型号为CHI 660C，仪器厂家为上海辰华仪器公司。
以下实施例中所用原料说明如下：
热塑性聚氨酯弹性体为万华化学集团股份有限公司生产，其中：
万华化学WHT-1565，聚酯型TPU，硬度65A；
万华化学WHT-8254，聚醚型TPU，硬度54D。
发泡剂：常州一耕化工有限公司的偶氮二异丁腈，上海依赫生物科技有限公司的三肼基均三嗪；
MOFs：北京北科新材科技有限公司的MOF&MIL-88B(Fe)、CHEMSOON公司的DUT-8(Co)、CHEMSOON公司的Cu-HHTP；
石墨：Aldrich；
石墨烯：厦门烯成石墨烯科技有限公司；
乙炔黑：电池级，深圳比克电池有限公司；
泡沫镍：纯度99.99％，天宇科技开发有限责任公司；
聚四氟乙烯：纯度99.99％，Aldrich；
Fe-MOFs负载石墨烯的制备：向反应瓶中加入100gN,N-二甲基甲酰胺溶剂、28g氧化石墨烯、20g配体对苯二甲酸和24g Fe(NO3)3，将反应瓶置于80℃下进行超声分散60min，搅拌均匀后加入28g醋酸钠溶液，后转移至高压水热反应釜，置于烘箱中加热至160℃，匀速搅拌反应24h，冷却至室温，过滤除去溶剂，使用蒸馏水和乙醇洗涤固体产物，并充分干燥，制备得到铁基金属有机骨架Fe-MOFs负载石墨烯。
实施例1
将热塑性弹性体WHT-1565 45质量份、石墨30质量份、偶氮二异丁腈15质量份、MOF&MIL-88B(Fe)10质量份混合于模腔中，模腔温度200℃，模腔压力50MPa，在热和机械剪切作用下，形成均相熔融态物质。释压发泡注入模具，待模具冷却，打开模具，取出最终的热塑性弹性体复合材料。
制备工作电极的方法：将8mg的该复合材料在研钵中研磨成粉，随后加入1.5mg的乙炔黑作导电剂，等研磨均匀后再加入0.5mg的聚四氟乙烯作粘结剂，将三者研磨成片状以后涂在10mm×10mm的泡沫镍上，然后将其置于压片机下用10MPa的压力压实。即得工作电极。再以金属Pt为对电极，以Hg/HgO电极作为参比电极，电解液为6M KOH，进行电化学性能测试。
实施例2-4的原材料与实施例1保持一致。所不同在于模腔温度及模腔压力，具体见表2。
实施例5-9及对比例1-3的工艺条件与实施例1保持一致。所不同在于原材料种类及相对比例，具体见表1。
表1实施例对比例配方(加入量为质量份数)
表2工艺参数
表3各实施例对比例制得的材料的性能：
以上测试充放电截止电压为-1～0V。循环稳定性是指在1A/g时，充放电10000次后，比电容的保持率。
本领域技术人员可以理解，在本说明书的教导之下，可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (9)
1.一种导电型热塑性弹性体，其特征在于，包括以下组分：
以上为基于各组分的总质量；
优选的，所述的热塑性弹性体为热塑性聚氨酯弹性体。
2.根据权利要求1所述的导电型热塑性弹性体，其特征在于，
所述的热塑性弹性体是由异氰酸酯与羟基封端的中间体，在扩链剂作用下反应制备而成，异氰酸酯与羟基封端的中间体的摩尔比为0.90-1.20，优选为0.92-1.10，更优选为0.95-1.05；扩链剂的加入量为基于多异氰酸酯与羟基封端的中间体总质量的2％-30％，优选为3％-25％，更优选为5％-20％；
优选的，所述的异氰酸酯选自NCO官能度≥2的脂肪族、芳香族二异氰酸酯及其衍生物中的一种或多种，优选芳香族二异氰酸酯及其衍生物中的一种或多种，更优选甲苯二异氰酸酯及二苯基甲烷二异氰酸酯中的一种或多种；
优选的，所述的端羟基封端的中间体为线型聚酯多元醇或线型聚醚多元醇中的一种或两种以上；
优选的，所述线型聚酯多元醇的数均分子量为300-10000，优选为500-8000，更优选为600-6000；
优选的，所述的线型聚醚多元醇的起始剂为含羟基或氨基的低分子化合物，优选为水、丙二醇、甘油、三羟甲基丙烷、乙二胺、季戊四醇、木糖醇、三乙烯二胺、山梨醇、乙二醇、双酚A和甲苯二胺中的一种或多种，更优选为水、丙二醇和甘油；
优选的，所述的线型聚醚多元醇的数均分子量为300-10000，优选400-8000，更优选500-6000；
优选的，所述的扩链剂为具有2-10个碳原子的二醇，优选为乙二醇、二乙二醇、丙二醇、二丙二醇、1,4-丁二醇、1,6-己二醇、1,3-丁二醇、1,5-戊二醇、1,4-环己二醇、新戊二醇、氢醌二(羟乙基)醚中的一种或多种，更优选1,4-丁二醇和/或氢醌二(羟乙基)醚。
3.根据权利要求1所述的导电型热塑性弹性体，其特征在于，所述的热塑性聚氨酯弹性体包括但不限于为万华化学集团股份有限公司生产的WHT-1565、WHT-1180、WHT-1164、WHT-8175、WHT-8185、WHT-8254、WHT-2190、WHT-7185、WHT-7190。
4.根据权利要求1所述的导电型热塑性弹性体，其特征在于，所述发泡剂包括偶氮二异丁腈、偶氮二甲酰胺、偶氮二碳酸二异丙酯、二亚硝基五次甲基四胺、对甲苯磺酰肼、二磺酰肼二苯醚、三肼基均三嗪、N-硝基胍，优选偶氮二异丁腈、偶氮二甲酰胺、偶氮二碳酸二异丙酯、二亚硝基五次甲基四胺中的一种或多种，优选偶氮二异丁腈、偶氮二甲酰胺中的一种或多种。
5.根据权利要求1所述的导电型热塑性弹性体，其特征在于，所述的MOFs材料包括但不限于含铁MOF材料、含铜MOF材料、含铝MOF材料、含锆MOF材料、含锌MOF材料、含钛MOF材料、含铬MOF材料、含镍MOF材料、含钴MOF材料，优选含铁MOF材料、含铜MOF材料、含钴MOF材料，更优选含铁MOF材料、含铜MOF材料。
6.根据权利要求1-5任一项所述的导电型热塑性弹性体，其特征在于，所述的导电型热塑性弹性体密度为80-1000kg/m3，优选为100～800kg/cm3；邵氏硬度为40A-40D，优选40A-30D；电导率为10-500S/m。
7.根据权利要求1-6任一项所述的导电型热塑性弹性体的制备方法，其特征在于，将热塑性弹性体、石墨或石墨烯、发泡剂、MOFs材料在模具中熔融混炼而成。
8.根据权利要求7所述的制备方法，其特征在于，模具的模腔温度为100-350℃，优选为120-320℃；更优选150-300℃；
优选的，模腔压力为25-80MPa，优选为30-70MPa，更优选35-60MPa。
9.一种权利要求1-6任一项所述导电型热塑性弹性体的应用，其用于超级电容器电极材料。
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