CN114541043A - 一种实时硫化弹性体纤维膜的制备方法 - Google Patents
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Abstract
本发明属于弹性体纤维膜制备技术领域，涉及一种实时硫化弹性体纤维膜的制备方法，在静电纺丝过程中实时硫化弹性体纤维膜，将常温下塑性的高分子材料加工成具有一定拉伸强度的弹性体，通过溶液静电纺丝的方法将类似橡胶的热塑性弹性体，制备微纳弹性体纤维膜，首次提出在纺丝过程中实时硫化弹性体纤维膜，得到均匀的微纳级别的纤维膜，比表面积大，具有一定的孔隙率，亲油疏水，亲肤性好，应用领域广泛，包括药物缓释、柔性传感器、透气防水织物、烟气过滤、水油过滤、催化剂负载等；其将静电纺丝工艺与实时硫化工艺结合，提升纤维膜的性能，使弹性体纤维膜交联，增加断裂伸长率和拉伸强度，为橡胶和塑料的加工方法提出新思路。
Description
技术领域：
本发明属于弹性体纤维膜制备技术领域，涉及一种实时硫化弹性体纤维膜的制备方法，为橡胶和塑料的加工方法提出新思路，拓宽热塑性弹性体和橡胶的应用领域。
背景技术：
柔性电子皮肤是一种新型机器人皮肤，覆盖在机器人的机械臂上，可以让机器人获得“感觉”，能够灵活避开前进中遇到的各种障碍。柔性电子皮肤因为其良好的肤感以及实时对周边环境进行检测的功能，成为机器人领域的研究热点。柔性电子皮肤必须具有高灵敏度、良好的拉伸性、长时间的耐久性，基于此，既具有透气性又具有柔性的高分子弹性纤维膜成为柔性电子皮肤的最佳选择。现有技术，中国专利202011144017.6公开的一种制备具有卷曲结构的柔性弹性体纤维膜的方法为：将柔性弹性体纤维膜在低表面张力的醇类物质中浸泡处理10～60min；其中，所述柔性弹性体纤维膜采用下述方法制得：将柔性弹性体粒料溶解于相应的溶剂中，搅拌得到均匀的柔性弹性体溶液；然后由带有高速辊筒的静电纺丝机纺丝；其中，辊筒转速为1000～3000rpm；所述低表面张力的醇类物质选自：乙醇、甲醇、丙醇或二丁醇中的至少一种；其制备的柔性弹性纤维膜的导电性是通过金属沉积构建导电层实现的，存在金属颗粒易脱落，拉伸时导电不连续，耐久性差的问题。
油水分离膜主要分为疏水性膜和亲水性膜两种，中国专利202011236256.4公开的一种基于多尺度纤维素纳米纤维油水分离膜的制备方法，包括如下步骤：(1)滤膜制备，准备聚丙烯腈纤维并将其溶解制得纤维溶液，采用异形喷丝孔制得聚丙烯腈纤维滤膜；(2)亲水疏油剂制备，准备纳米纤维并与溶剂混合制得混合液，采用超声分散均匀，制得聚合物溶液后进行备用；(3)滤膜浸润，采用无菌工具夹持聚丙烯腈纤维滤膜，将聚丙烯腈纤维滤膜浸润在制备的纳米纤维和聚酰亚胺水溶液中，两小时后取出制得油水分离膜；(4)滤膜处理，将取出的油水分离膜置于风干装置处，利用热风机经低温风干，待滤膜溶剂挥发后制得油水分离膜；其制备的油水分离膜在浸润过程中纤维素纳米纤维分布不均匀，从而导致整张膜的亲疏水性不一致。
综上所述，现有技术中的柔性传感器和油水分离膜虽然取得了较大的进展，但是也存在一些问题。因此，需要继续深入研究，以寻找一种加工简单，品质优良且环境友好的功能性纤维膜。
发明内容：
本发明的目的在于克服现有技术存在的缺点，寻求设计一种实时硫化弹性体纤维膜的制备方法，将静电纺丝工艺和实时硫化工艺结合，提升纤维膜的性能。
本发明涉及的一种实时硫化弹性体纤维膜的制备方法的工艺过程为：
首先，在纺丝溶液中加入功能填料，配制成弹性体纺丝溶液；
然后，通过静电纺丝工艺，将弹性体纺丝溶液加工成弹性体纤维；
最后，在收集弹性体纤维的过程中进行恒温实时硫化，得到弹性体纤维膜。
本发明涉及的一种实时硫化弹性体纤维膜的制备方法的具体工艺过程为：
(1)配制弹性体纺丝液：将可纺弹性体溶解于有机溶剂中，加入功能填料，通过水浴加热和磁力搅拌的方式溶解，制得分散均匀的质量百分比浓度为1-8％的弹性体纺丝溶液，备用；
可纺弹性体包括反式-1，4-聚异戊二烯、异戊橡胶、杜仲胶和聚氨酯；
有机溶剂为极性溶剂，包括氯仿、四氢呋喃、环己烷、二氯甲烷、甲苯、正己烷、二甲苯和N,N-二甲基甲酰胺中的一种或几种的组合；
功能填料为硫化体系，包括促进剂、防老剂和硫，其中，促进剂包括DPG、CZ、TMTD和DM中的一种或几种的组合；防老剂包括防老剂4020、防老剂4010、防老剂4010NA和防老剂RD中的一种或几种的组合；硫包括不溶性硫磺；
(2)制备弹性体纤维：将弹性体纺丝液保持在恒温条件下，经电场作用，通过静电纺丝制成微纳米级的弹性体纤维；
弹性体纺丝液的进给速率为0.15-0.25mm/min，纺丝温度为10-60℃，喷嘴针头为10-25G，电场的电压为1-50kV，弹性体纤维的直径为0.1-5μm，厚度取决于纺丝时间的长短，一般为10-100μm；
(3)制备弹性体纤维膜：收集弹性体纤维，等离子实时处理弹性体纤维，通风后将弹性体纤维取下，用去离子水冲洗干净，室温干燥，得到弹性体纤维膜；
喷嘴针头到收集设备之间的距离为5-30cm，收集设备的转速为50-300转，等离子处理设备的气源输入压力为4-10bar，等离子处理设备到收集设备之间的距离为1-30cm。
本发明制备的弹性体纤维膜能够用于水油过滤和烟气过滤，以及柔性电子皮肤领域。
用于水油过滤和烟气过滤领域时，基于弹性好，拉伸强度高，作为抽烟滤嘴过滤油污，克服常规水油过滤膜强度低的缺陷，能够承受水流的冲击和烟气的喷射，满足动态水油分离需求，进行海水除油；
用于柔性电子皮肤领域时，既能够提供光滑柔软有弹性且透气的肤感，又能够为电子传感器提供弹性和顺应性，减少拉伸对纤维的损伤，进行循环回弹，纤维被拉伸，纤维粗细长短发生变化，电阻随之变化，将拉伸力撤掉，纤维又迅速变回原来的形态，具有高灵敏度、良好的周期稳定性和耐用性，透气性使柔性电子皮肤更加人性化，减少闷气不适感，特别适合应用于人工智能机器人和医疗保健检测。
本发明与现有技术相比，在静电纺丝过程中实时硫化弹性体纤维膜，将常温下塑性的高分子材料加工成具有一定拉伸强度的弹性体，通过溶液静电纺丝的方法将类似橡胶的热塑性弹性体，制备微纳弹性体纤维膜，首次提出在纺丝过程中实时硫化弹性体纤维膜，得到均匀的微纳级别的纤维膜，比表面积大，具有一定的孔隙率，亲油疏水，亲肤性好，应用领域广泛，包括药物缓释、柔性传感器、透气防水织物、烟气过滤、水油过滤、催化剂负载等；其将静电纺丝工艺与实时硫化工艺结合，提升纤维膜的性能，使弹性体纤维膜交联，增加断裂伸长率和拉伸强度，静电纺丝设备简单，技术成熟，生产成本低，产量高，为橡胶和塑料的加工方法提出新思路，拓宽了热塑性弹性体和橡胶的应用领域。
附图说明：
图1为本发明的工艺流程图。
图2为实施例4制备的TPI弹性体纤维膜的形貌轮廓仪表征图。
图3为实施例4制备的TPI弹性体纤维膜的烟气过滤图。
图4为实施例4制备的TPI弹性体纤维膜的水接触角表征图。
图5为实施例4制备的TPI弹性体纤维膜的水浸润照片。
图6为实施例4制备的TPI弹性体纤维膜的油浸润照片。
图7为实施例5制备的TPI弹性体纤维膜的形貌轮廓仪表征图。
具体实施方式：
下面通过实施例并结合附图对本发明作进一步说明。
实施例1：
本实施例涉及的实时硫化弹性体纤维膜的制备方法的具体工艺过程为：
(1)配制弹性体纺丝液：将反式-1，4-聚异戊二烯(TPI)溶解于四氢呋喃中，加入功能填料，在温度为60℃的条件下水浴加热，磁力搅拌4h，制得分散均匀的质量百分比浓度为2％的弹性体纺丝溶液，备用；
(2)制备弹性体纤维：将弹性体纺丝液保持在恒温条件下，经电场作用，通过静电纺丝技术，参照电纺成型设备，采用烧瓶、高压电源、高速接收辊筒、蠕动泵、手套箱、红外加热灯和纺丝喷嘴等进行纺丝，射流经过蒸发得到固体状的弹性体纤维，其中，弹性体纺丝液的进给速率为0.2mm/min，纺丝温度为40℃，喷嘴针头为20G，高压电源的电场电压为13.5kV，得到的弹性体纤维的直径为2μm，厚度为50μm；
(3)制备弹性体纤维膜：通过高速收集辊筒收集弹性体纤维，等离子实时处理弹性体纤维，通风12h后将弹性体纤维取下，用去离子水冲洗3遍，室温干燥，得到弹性体纤维膜，其中，针头到高速收集辊筒之间的距离为20cm，高速收集辊筒的转速为120转，等离子处理设备的气源输入压力为6bar，等离子处理设备的喷头到高速收集辊筒的距离为10cm。
本实施例制备的弹性体纤维膜裁成小哑铃试样后进行力学性能测试，拉伸强度为10-20MPa，断裂伸长率为150-500％，较纯TPI弹性体纤维膜的拉伸强度(1-2MPa)和断裂伸长率(60-110％)均有大幅度提升；水接触角为116°，接近超疏水材料，亲疏水性均匀稳定；其直接将导电填料加入纺丝液中，减少了填料的脱落，并使填料分布均匀，在被拉伸时导电连续且稳定。
实施例2：
本实施例涉及的实时硫化弹性体纤维膜的制备方法的工艺过程为：将白色颗粒状的TPI与硫化体系充分溶解在四氢呋喃和N,N-二甲基甲酰胺组成的混合有机溶剂中，在手套箱内打开红外加热灯，控制环境温度，利用电场纺丝得到TPI弹性体纤维，等离子喷头置于高速收集辊筒非收集一侧10cm处，在高速收集辊筒收集TPI弹性体纤维的同时，等离子设备实时处理弹性体纤维，得到均匀的等离子实时硫化TPI弹性体纤维膜。
实施例3：
本实施例涉及的实时硫化弹性体纤维膜的制备方法的具体工艺过程为：
将青岛竣翔科技有限公司生产的密度≥0.940的TPI-40充分溶解在分析纯的四氢呋喃和二甲基甲酰胺中，加入由不溶性硫磺、TMTD、CZ、RD和4010组成的功能填料，配制成弹性体纺丝溶液；
将弹性体纺丝液保持在40℃的恒温条件下，经电场作用，进行纺丝，射流经过蒸发得到固体状的弹性体纤维；
收集弹性体纤维，同时用等离子设备处理硫化弹性体纤维，等离子实时硫化气源的气压为6bar，通风后将弹性体纤维取下，用去离子水冲洗，室温干燥，得到弹性体纤维膜。
本实施例制备的弹性纤维膜用形貌轮廓仪表征，直径为0.1-5μm，分布均匀。
实施例4：
本实施例涉及的实时硫化弹性体纤维膜的制备方法的具体工艺过程为：
步骤1：将1gTPI放入干净的磨口烧瓶中，加入44ml的四氢呋喃溶剂和5ml的N,N-二甲基甲酰胺溶剂，在温度为60℃的条件下水浴加热的同时磁力搅拌4h，充分溶解，得到质量百分比浓度为2％的TPI弹性体纺丝溶液；
步骤2：用针管抽取TPI弹性体纺丝溶液，在推进速率为0.2mm/min的蠕动泵的推动下从20G规格的针头挤出，纺丝喷头前方20cm处放置高速收集辊筒，高压电场的电压为15kV，电场力使TPI弹性体纺丝溶液被拉伸成TPI弹性体纤维；
步骤3：通过高速收集辊筒收集TPI弹性体纤维，散气12h后取下，用去离子水冲洗3次，室温干燥12h，得到厚度均匀的TPI弹性体纤维膜。
本实施例涉及的实时硫化弹性体纤维膜的制备方法的整个纺丝过程都在手套箱中进行，并且将红外灯设置在纺丝喷头与高速收集辊筒之间，进行持续加温，保持手套箱与纺丝距离间温度40℃恒定，纺丝8h结束后将所有装置关闭，打开手套箱散去有机溶剂挥发的气体。
本实施例制备的TPI弹性体纤维膜裁成小哑铃试样后的纤维形貌如图2所示，经烟气过滤图如图3所示，水接触角如图4所示，油浸润照片如图5所示，水浸润照片如图6所示。
实施例5：
本实施例涉及的实时硫化弹性体纤维膜的制备方法的具体工艺过程为：
步骤1：将1gTPI放入磨口烧瓶后，加入由0.015g的TMTD、0.02g的4010、0.01g的RD、0.015g的DM和0.01g的不溶性硫磺组成的硫化体系，与44ml的四氢呋喃溶剂和5ml的N,N-二甲基甲酰胺溶剂配置成质量百分比浓度为2％的TPI弹性体纺丝溶液；
步骤2：用针管抽取TPI弹性体纺丝溶液，在推进速率为0.2mm/min的蠕动泵的推动下从20G规格的针头挤出，纺丝喷头前方20cm处放置高速收集辊筒，高压电场的电压为15kV，电场力使TPI弹性体纺丝溶液被拉伸成TPI弹性体纤维；
步骤3：保持温度为40℃的恒定条件，在高速收集辊筒收集TPI弹性体纤维的同时，用等离子设备处理硫化弹性体纤维，散气12h后取下，用去离子水冲洗3次，室温干燥12h，得到厚度均匀的等离子实时硫化TPI弹性体纤维膜。
本实施例制备的等离子实时硫化TPI弹性体纤维膜裁成小哑铃试样后的纤维形貌如图7所示。
实施例6：
本实施例涉及实施例4和5制备的TPI弹性体纤维膜的力学性能对比分析，二者的力学性能如下表所示：
可知，实施例4制备的TPI弹性体纤维膜的应力为1.745MPa，应变为74.4％，实施例5制备的等离子实时硫化TPI弹性体纤维膜的应力和应变相较于实施例4的都有所提升，这是因为等离子使TPI纤维交联，提升其力学性能，说明等离子硫化实时处理能够提高TPI弹性体纤维膜的力学性能。
Claims (8)
1.一种实时硫化弹性体纤维膜的制备方法，其特征在于，工艺过程为：
首先，在纺丝溶液中加入功能填料，配制成弹性体纺丝溶液；
然后，通过静电纺丝工艺，将弹性体纺丝溶液加工成弹性体纤维；
最后，在收集弹性体纤维的过程中进行恒温实时硫化，得到弹性体纤维膜。
2.根据权利要求1所述的实时硫化弹性体纤维膜的制备方法，其特征在于，具体工艺过程为：
(1)配制弹性体纺丝液：将可纺弹性体溶解于有机溶剂中，加入功能填料，通过水浴加热和磁力搅拌的方式溶解，制得分散均匀的质量百分比浓度为1-8％的弹性体纺丝溶液，备用；
(2)制备弹性体纤维：将弹性体纺丝液保持在恒温条件下，经电场作用，通过静电纺丝制成微纳米级的弹性体纤维；
(3)制备弹性体纤维膜：收集弹性体纤维，等离子实时处理弹性体纤维，通风后将弹性体纤维取下，用去离子水冲洗干净，室温干燥，得到弹性体纤维膜。
3.根据权利要求1或2所述的实时硫化弹性体纤维膜的制备方法，其特征在于，制备的弹性体纤维膜能够用于水油过滤和烟气过滤，以及柔性电子皮肤领域。
用于水油过滤和烟气过滤领域时，基于弹性好，拉伸强度高，作为抽烟滤嘴过滤油污，克服常规水油过滤膜强度低的缺陷，能够承受水流的冲击和烟气的喷射，满足动态水油分离需求，进行海水除油；
用于柔性电子皮肤领域时，既能够提供光滑柔软有弹性且透气的肤感，又能够为电子传感器提供弹性和顺应性，减少拉伸对纤维的损伤，进行循环回弹，纤维被拉伸，纤维粗细长短发生变化，电阻随之变化，将拉伸力撤掉，纤维又迅速变回原来的形态。
4.根据权利要求2所述的实时硫化弹性体纤维膜的制备方法，其特征在于，可纺弹性体包括反式-1，4-聚异戊二烯、异戊橡胶、杜仲胶和聚氨酯。
5.根据权利要求2所述的实时硫化弹性体纤维膜的制备方法，其特征在于，有机溶剂为极性溶剂，包括氯仿、四氢呋喃、环己烷、二氯甲烷、甲苯、正己烷、二甲苯和N,N-二甲基甲酰胺中的一种或几种的组合。
6.根据权利要求2所述的实时硫化弹性体纤维膜的制备方法，其特征在于，功能填料为硫化体系，包括促进剂、防老剂和硫，其中，促进剂包括DPG、CZ、TMTD和DM中的一种或几种的组合；防老剂包括防老剂4020、防老剂4010、防老剂4010NA和防老剂RD中的一种或几种的组合；硫包括不溶性硫磺。
7.根据权利要求2所述的实时硫化弹性体纤维膜的制备方法，其特征在于，弹性体纺丝液的进给速率为0.15-0.25mm/min，纺丝温度为10-60℃，喷嘴针头为10-25G，电场的电压为1-50kV，弹性体纤维的直径为0.1-5μm，厚度取决于纺丝时间的长短，为10-100μm。
8.根据权利要求2所述的实时硫化弹性体纤维膜的制备方法，其特征在于，喷嘴针头与收集设备之间的距离为5-30cm，收集设备的转速为50-300转，等离子处理设备的气源输入压力为4-10bar，等离子处理设备与收集设备之间的距离为1-30cm。
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002027096A1 (fr) * | 2000-09-27 | 2002-04-04 | Toyo Fibre Co., Ltd. | Fibre vulcanisee et son procede de production |
| US20050281973A1 (en) * | 2004-06-21 | 2005-12-22 | Park Edward H | Pre-molding heat treatment of dynamic vulcanizates of fluorocarbon elastomers |
| US20060004126A1 (en) * | 2004-06-30 | 2006-01-05 | Park Edward H | Thermoplastic vulcanizate with functional fillers |
| CN102070865A (zh) * | 2009-11-19 | 2011-05-25 | 青岛科技大学 | 一种改性tpi/pp动态硫化热塑性弹性体 |
| CN104292528A (zh) * | 2013-07-18 | 2015-01-21 | 宁波大学 | 一种高强度橡胶及其制备方法 |
| CN105195028A (zh) * | 2015-07-03 | 2015-12-30 | 东华大学 | 一种纳米纤维复合超滤膜的制备方法 |
| US20170119594A1 (en) * | 2015-11-04 | 2017-05-04 | The Procter & Gamble Company | Absorbent structure |
| CN108641316A (zh) * | 2018-03-24 | 2018-10-12 | 青岛科技大学 | 一种高分子复合材料、制备及应用 |
| US20200136113A1 (en) * | 2017-07-07 | 2020-04-30 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Electrospinning of pvdf-hfp: novel composite polymer electrolytes (cpes) with enhanced ionic conductivities for lithium-sulfur batteries |
| US20200274201A1 (en) * | 2017-09-15 | 2020-08-27 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Weavable, conformable, wearable and flexible components for advanced battery technology |
| CN112156662A (zh) * | 2020-09-30 | 2021-01-01 | 东华大学 | 一种自清洁静电纺纳米纤维滤膜、制备方法及应用 |
| CN113201211A (zh) * | 2021-06-15 | 2021-08-03 | 安徽展业塑胶制品有限公司 | 一种复合动态交联聚乳酸/天然橡胶/淀粉弹性体及其制备方法 |
| WO2021197462A1 (zh) * | 2020-04-03 | 2021-10-07 | 香港理工大学 | 一种弹性导体复合膜及其制备方法 |
| WO2022023745A1 (en) * | 2020-07-29 | 2022-02-03 | The Electrospinning Company Ltd | Fibrous composite material |
-
2022
- 2022-02-25 CN CN202210180501.7A patent/CN114541043A/zh active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002027096A1 (fr) * | 2000-09-27 | 2002-04-04 | Toyo Fibre Co., Ltd. | Fibre vulcanisee et son procede de production |
| US20050281973A1 (en) * | 2004-06-21 | 2005-12-22 | Park Edward H | Pre-molding heat treatment of dynamic vulcanizates of fluorocarbon elastomers |
| US20060004126A1 (en) * | 2004-06-30 | 2006-01-05 | Park Edward H | Thermoplastic vulcanizate with functional fillers |
| CN102070865A (zh) * | 2009-11-19 | 2011-05-25 | 青岛科技大学 | 一种改性tpi/pp动态硫化热塑性弹性体 |
| CN104292528A (zh) * | 2013-07-18 | 2015-01-21 | 宁波大学 | 一种高强度橡胶及其制备方法 |
| CN105195028A (zh) * | 2015-07-03 | 2015-12-30 | 东华大学 | 一种纳米纤维复合超滤膜的制备方法 |
| US20170119594A1 (en) * | 2015-11-04 | 2017-05-04 | The Procter & Gamble Company | Absorbent structure |
| US20200136113A1 (en) * | 2017-07-07 | 2020-04-30 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Electrospinning of pvdf-hfp: novel composite polymer electrolytes (cpes) with enhanced ionic conductivities for lithium-sulfur batteries |
| US20200274201A1 (en) * | 2017-09-15 | 2020-08-27 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Weavable, conformable, wearable and flexible components for advanced battery technology |
| CN108641316A (zh) * | 2018-03-24 | 2018-10-12 | 青岛科技大学 | 一种高分子复合材料、制备及应用 |
| WO2021197462A1 (zh) * | 2020-04-03 | 2021-10-07 | 香港理工大学 | 一种弹性导体复合膜及其制备方法 |
| WO2022023745A1 (en) * | 2020-07-29 | 2022-02-03 | The Electrospinning Company Ltd | Fibrous composite material |
| CN112156662A (zh) * | 2020-09-30 | 2021-01-01 | 东华大学 | 一种自清洁静电纺纳米纤维滤膜、制备方法及应用 |
| CN113201211A (zh) * | 2021-06-15 | 2021-08-03 | 安徽展业塑胶制品有限公司 | 一种复合动态交联聚乳酸/天然橡胶/淀粉弹性体及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 王超: "静电纺丝法制备反式-1,4-聚异戊二烯纳米纤维", 《青岛科技大学研究生学位论文》 * |
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