CN115368534A - 一种高电致应变聚氨酯弹性体及其成型方法 - Google Patents
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Abstract
本发明公开一种高电致应变聚氨酯弹性体及其成型方法，所述弹性体材料是将15‑35摩尔份双官能度二元醇、50摩尔份二异氰酸酯、15‑35摩尔份二硫扩链剂，通过预聚和扩链两步法获得的超分子弹性体。本发明通过模压成型工艺调控聚氨酯微相分离结构，使得聚氨酯弹性体的电致伸缩效应大幅度提高，最终产生较优异的电致驱动性能，同时弹性体还具有较低的模量，解决了聚氨酯弹性体模量高、驱动应变低的难题。该方法操作简单，工艺容易控制，在介电弹性体驱动器领域具有广阔的应用前景。
Description
技术领域
本发明属于介电弹性体材料领域，具体涉及一种高电致应变聚氨酯弹性体及其成型方法，可应用于电致驱动器领域。
背景技术
介电弹性体由于具有响应迅速、机械能量密度高、感应位移大、机电转化效率高等特点，在驱动器、传感器、人工肌肉和能量收集等方面具有广阔的应用前景。聚氨酯和硅树脂、丙烯酸树脂并称为三大介电弹性体，其中聚氨酯弹性体具有结构简单可控、易加工、介电常数和击穿强度高等优势。但是，其内部丰富的氢键导致材料本身模量偏高，如何在低电压下实现大的驱动应变成为聚氨酯弹性体的研究瓶颈。
从驱动机理出发，由于聚氨酯弹性体兼具麦克斯韦应力和电致伸缩效应，因此其有较大的潜力可以获得高电致应变。前期研究表明，在热塑性聚氨酯弹性体的驱动过程中，电致伸缩效应的贡献在整个机电耦合作用中占60％以上，且依赖于聚氨酯的微相分离结构。此外，在低电场下，其驱动应变由电致伸缩效应主导。由此，探究提高聚氨酯弹性体电致伸缩效应的有效手段可以达到提高驱动应变的目的。
针对聚氨酯弹性体的微相分离结构，当前的发明手段主要通过改变硬软段的结构和比例进行调控，从而优化各类性能。本发明从控制弹性体分子结构和成型方法出发，获得具有优化微相分离结构的聚氨酯弹性体材料，目前有关方向的专利并不多见，而利用分子结构和成型方法提高聚氨酯电致驱动性能的专利更是未见报道。
发明内容
鉴于现有技术的不足，本发明的目的在于探寻一种具有高电致应变的聚氨酯弹性体及其成型方法。通过在聚氨酯弹性体主链中引入二硫化物形成动态二硫键，降低了聚氨酯弹性体的模量，并同时结合模压成型工艺获得优化的微相分离结构。由于电致伸缩效应在整个机电耦合作用中所占比例上升，弹性体薄膜用于电致驱动器时具有更出色的电致应变。
本发明采用的技术方案如下：
本发明提供一种高电致应变聚氨酯弹性体及其成型方法，主要原料及具体制备步骤为：
(1)首先将15-35摩尔份双官能度二元醇和50摩尔份二异氰酸酯在良溶剂中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、40-80℃条件下反应2-8h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入15-35摩尔份二硫扩链剂，同时升温至40-60℃，继续反应4-12h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体。
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力5-20MPa；温度80-150℃；预热时间5-20min；模压时间3-15min；冷却速率30-100℃/min；排气5-10次。
优选地，所述双官能度二元醇至少选自聚四亚甲基醚二醇、聚己内酯二醇、聚乙二醇、端羟基聚丁二烯。
优选地，所述二异氰酸酯至少选自异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4,4'-亚甲基双(异氰酸苯酯)、二环己甲烷4,4'-二异氰酸酯。
优选地，所述二硫扩链剂至少选自胱胺、双(4-羟苯基)二硫醚、双(2-羟乙基)二硫化物、4,4'-二氨基二苯二硫醚。
优选地，所述步骤(1)中良溶剂至少选自四氢呋喃、二甲基甲酰胺/二甲基乙酰胺、二氯甲烷。
优选地，所述的聚氨酯弹性体薄膜，在1kHz下介电常数为8-12，杨氏模量为1.2-3.5MPa。
优选地，所述的聚氨酯弹性体薄膜，经两侧涂覆柔性碳润滑脂后作为电致驱动器，其能够在50MV/m电场下产生14％-25％的面积应变，且其中电致伸缩效应贡献比例为64％-89％。
相比于现有技术，本发明产生的有益效果主要体现在以下几个方面：
(1)本发明通过二硫扩链剂将二硫键引入到聚氨酯主链中，利用二硫动态特性降低聚氨酯弹性体模量，与普通聚氨酯相比，含二硫键的超分子聚氨酯弹性体表现出柔软、超拉伸的力学特点，适合应用于介电弹性体领域；
(2)在二硫动态键的基础上，结合模压成型工艺对聚氨酯微相分离结构进行优化。相较于目前大多数溶液成型的聚氨酯弹性体，该弹性体不仅模量低，而且电致伸缩效应在整个机电耦合作用中所占比例明显上升，弹性体的电致应变得到大幅度提升。由于出色的电致驱动性能，使得其在驱动器和柔性电子等领域具有巨大的应用潜力。
具体实施方式
下面给出具体实施例以对本发明的技术方案作进一步说明。但是值得说明的是以下实施例不能理解为对本发明保护范围的限制，该领域的技术熟练人员根据上述本发明的内容，对本发明作一些非本质性的改进和调整仍属于本发明的保护范围。
实施例1
本实施例提供的一种高电致应变聚氨酯弹性体及其成型方法，包括以下步骤：
(1)首先将15摩尔份聚四亚甲基醚二醇和50摩尔份异佛尔酮二异氰酸酯在二甲基乙酰胺中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、60℃条件下反应3h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入35摩尔份胱胺，同时升温至40℃，继续反应6h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体。
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力15MPa；温度150℃；预热时间15min；模压时间10min；冷却速率100℃/min；排气8次。
如表1所示，制得的弹性体薄膜材料在1kHz下介电常数为11，杨氏模量为2.8MPa。在弹性体薄膜两侧涂覆柔性碳润滑脂用于电致驱动器，其在50MV/m电场下能够产生15％的面积应变，其中电致伸缩效应贡献比例达到72％。
实施例2
本实施例提供的一种高电致应变聚氨酯弹性体及其成型方法，包括以下步骤：
(1)首先将25摩尔份聚四亚甲基醚二醇和50摩尔份异佛尔酮二异氰酸酯在二甲基甲酰胺中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、70℃条件下反应2h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入25摩尔份胱胺，同时升温至40℃，继续反应4h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体。
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力10MPa；温度120℃；预热时间10min；模压时间8min；冷却速率60℃/min；排气5次。
如表1所示，制得的弹性体薄膜材料在1kHz下介电常数为10，杨氏模量为1.9MPa。在弹性体薄膜两侧涂覆柔性碳润滑脂用于电致驱动器，其在50MV/m电场下能够产生22％的面积应变，其中电致伸缩效应贡献比例达到86％。
实施例3
本实施例提供的一种高电致应变聚氨酯弹性体及其成型方法，包括以下步骤：
(1)首先将35摩尔份聚己内酯二醇和50摩尔份六亚甲基二异氰酸酯在四氢呋喃中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、40℃条件下反应6h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入15摩尔份双(2-羟乙基)二硫化物，同时升温至60℃，继续反应8h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体。
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力5MPa；温度100℃；预热时间5min；模压时间12min；冷却速率50℃/min；排气10次。
如表1所示，制得的弹性体薄膜材料在1kHz下介电常数为10，杨氏模量为1.2MPa。在弹性体薄膜两侧涂覆柔性碳润滑脂用于电致驱动器，其在50MV/m电场下能够产生25％的面积应变，其中电致伸缩效应贡献比例达到89％。
实施例4
本实施例提供的一种高电致应变聚氨酯弹性体及其成型方法，包括以下步骤：
(1)首先将25摩尔份聚乙二醇和50摩尔份二环己甲烷4,4'-二异氰酸酯在二甲基甲酰胺中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、80℃条件下反应2h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入25摩尔份双(4-羟苯基)二硫醚，同时升温至40℃，继续反应4h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体。
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力20MPa；温度120℃；预热时间10min；模压时间15min；冷却速率60℃/min；排气5次。
如表1所示，制得的弹性体薄膜材料在1kHz下介电常数为8，杨氏模量为2.5MPa。在弹性体薄膜两侧涂覆柔性碳润滑脂用于电致驱动器，其在50MV/m电场下能够产生18％的面积应变，其中电致伸缩效应贡献比例达到73％。
实施例5
本实施例提供的一种高电致应变聚氨酯弹性体及其成型方法，包括以下步骤：
(1)首先将25摩尔份端羟基聚丁二烯和50摩尔份4,4'-亚甲基双(异氰酸苯酯)在二氯甲烷中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、40℃条件下反应8h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入25摩尔份4,4'-二氨基二苯二硫醚，同时升温至60℃，继续反应12h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体。
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力5MPa；温度80℃；预热时间20min；模压时间3min；冷却速率30℃/min；排气8次。
如表1所示，制得的弹性体薄膜材料在1kHz下介电常数为12，杨氏模量为3.5MPa。在弹性体薄膜两侧涂覆柔性碳润滑脂用于电致驱动器，其在50MV/m电场下能够产生14％的面积应变，其中电致伸缩效应贡献比例达到64％。
本发明通过分子结构的设计和成型方法的优化，调控聚氨酯微相分离结构，使得聚氨酯弹性体的电致伸缩效应大幅度提高，最终产生较优异的电致驱动性能。材料整个制备过程简单，工艺易于掌握，生产成本低，容易实现大批量生产。使用本发明所述方法制备的弹性体材料不仅具有优异的力学性能，而且具有较高的电致驱动应变，从而能够满足驱动器件对介电弹性体的多种严苛要求。
表1
Claims (7)
1.一种高电致应变聚氨酯弹性体及其成型方法，其特征在于，主要原料及具体制备步骤为：
(1)首先将15-35摩尔份双官能度二元醇和50摩尔份二异氰酸酯在良溶剂中混合并搅拌，加入少量二月桂酸二丁基锡，然后在氮气气氛、40-80℃条件下反应2-8h得到预聚物溶液，待预聚物冷却至室温后，逐滴加入15-35摩尔份二硫扩链剂，同时升温至40-60℃，继续反应4-12h，最后在真空干燥箱中挥干溶剂后得到聚氨酯弹性体；
(2)聚氨酯弹性体在压片机中模压成型得到高电致应变的聚氨酯弹性体薄膜样品，模压成型的工艺条件为：压力5-20MPa；温度80-150℃；预热时间5-20min；模压时间3-15min；冷却速率30-100℃/min；排气5-10次。
2.根据权利要求1所述的高电致应变聚氨酯弹性体及其成型方法，其特征在于，所述双官能度二元醇至少选自聚四亚甲基醚二醇、聚己内酯二醇、聚乙二醇、端羟基聚丁二烯。
3.根据权利要求1所述的高电致应变聚氨酯弹性体及其成型方法，其特征在于，所述二异氰酸酯至少选自异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4,4'-亚甲基双(异氰酸苯酯)、二环己甲烷4,4'-二异氰酸酯。
4.根据权利要求1所述的高电致应变聚氨酯弹性体及其成型方法，其特征在于，所述二硫扩链剂至少选自胱胺、双(4-羟苯基)二硫醚、双(2-羟乙基)二硫化物、4,4'-二氨基二苯二硫醚。
5.根据权利要求1所述的高电致应变聚氨酯弹性体及其成型方法，其特征在于，所述步骤(1)中，良溶剂至少选自四氢呋喃、二甲基甲酰胺/二甲基乙酰胺、二氯甲烷。
6.根据权利要求1-5中任一项所述的高电致应变聚氨酯弹性体及其成型方法，其特征在于：制得的弹性体薄膜材料在1kHz下介电常数为8-12，杨氏模量为1.2-3.5MPa。
7.根据权利要求1-5中任一项所述的高电致应变聚氨酯弹性体及其成型方法，其特征在于：在弹性体薄膜两侧涂覆柔性碳润滑脂用于电致驱动器，其在50MV/m电场下能够产生14％-25％的面积应变，且其中电致伸缩效应贡献比例为64％-89％。
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Application publication date: 20221122 |