CN111205631A - 一种通电加热自修复聚氨酯弹性体及其制备方法 - Google Patents
一种通电加热自修复聚氨酯弹性体及其制备方法 Download PDFInfo
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- CN111205631A CN111205631A CN202010126211.5A CN202010126211A CN111205631A CN 111205631 A CN111205631 A CN 111205631A CN 202010126211 A CN202010126211 A CN 202010126211A CN 111205631 A CN111205631 A CN 111205631A
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- polyurethane elastomer
- self
- repairing
- dihydrazide
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Abstract
本发明提供了一种通电加热自修复聚氨酯弹性体及其制备方法。所述通电加热自修复聚氨酯弹性体由含酰腙键的二元醇扩链剂和聚氨酯预聚体制备，通过加入一系列导电填料赋予导电性能，并加入聚苯胺赋予其仅加热即可自修复的能力。所述自修复聚氨酯弹性体在受到机械损伤后，在通电条件下断口处生热量加大，至120℃以上时，通过聚苯胺的催化作用，促使聚合物交联分子链上的酰腙键通过动态交换反应实现材料自修复。本发明所述通电自修复交联聚氨酯弹性体材料制备简单，仅在通电条件下即可实现自修复，修复简便，步骤容易，且不破坏材料，并扩大了自修复聚氨酯的应用范围。
Description
技术领域
本发明属于聚合物材料领域，具体涉及一种通电加热自修复聚氨酯弹性体及其制备方法。
背景技术
自修复材料是一种在物体受损时能够进行自我修复的新型材料。目前聚合物基自修复体系可分为两种：一种是外援型自修复，即将载有修复剂的微胶囊、液芯纤维或者毛细管网络埋植于基体材料中，外部损伤导致微胶囊、液芯纤维和毛细管网络的破裂，液态修复剂释放进入裂缝后固化，从而对裂缝完成修复；一种是本征型自修复，即将可逆化学键(包括可逆共价键和可逆非共价键)引入聚合物中，通过加热等方式向体系提供能量，使可逆化学键发生可逆反应而实现自修复。
外援型自修复聚合物材料，修复的次数有限，修复剂的释放在微胶囊或者中空纤维中又形成了新的空隙，成为材料的新缺陷。本征型自修复聚合物材料可实现多次自修复，而且可以修复断裂的材料，但为了修复完全需要不间断的提供能量，甚至还需要复杂的设备技术等进行支持。而添加导电填料后的导电自修复聚氨酯材料可以在一直通电条件下达到自修复的条件，并且能够自我检测断裂并持续提供能量进行修复，操作简便，节约人力，而且导电填料的加入使得聚氨酯材料的综合力学性能有不同程度的提高，因此可以用来制备修复性能更好且强度更高的自修复材料。
目前关于利用酰腙键制备不含溶剂且无需其他外加复杂条件仅在通电条件下即可实现自发检测并自修复的本体聚合物还未见相关文献的报道。
发明内容
本发明提供了一种通电加热自修复聚氨酯弹性体及其制备方法。所述自修复聚氨酯弹性体为本体聚合物，弹性体分子中含有酰腙键及导电填料，并通过加入的填料聚苯胺实现该弹性体在室温下无需施加任何外界刺激仅仅通电达到一定温度后即可实现自修复，不仅修复速度快，而且修复效果好，同时制备的弹性体具有较好的物理机械性能。
为实现上述发明目的，本发明采用以下技术方案予以实现：
一种通电加热自修复聚氨酯弹性体的制备方法，所述制备方法包括以下步骤：
(1)将10-25重量份含酰腙键的二元醇扩链剂溶于15-50重量份的二甲基亚砜中；
(2)加入25-50重量份的端异氰酸酯基聚氨酯预聚体，混合均匀，在 50℃-80℃下反应0.5-4h；
(3)依次加入8-40重量份导电填料、1-5重量份聚苯胺，混合均匀，搅拌，抽真空脱除气泡，在30℃-80℃下固化12-48h，得到通电加热自修复聚氨酯弹性体。
进一步的，所述步骤(1)含酰腙键的二元醇扩链剂通过以下步骤反应获得： (1)将15-30重量份的羟基羰基化合物溶于有机溶剂中，将10-20重量份的二酰肼化合物溶于去离子水中，混合；(2)在20℃-60℃下反应2～4h，得到含酰腙键的二元醇扩链剂。
进一步的，所述的二酰肼化合物为丙二酸二酰肼、庚二酰肼、辛二酰肼、戊烷二酰肼、癸二酸二酰肼、十二烷二羧酸二酰肼、对苯二甲酸二酰肼、邻苯二甲酸二酰肼、丁二酸二酰肼、壬二酸二酰肼、己二酸二酰肼或二水杨酰肼中的任一种或多种的混合物；
所述的羟基羰基化合物为对羟基苯甲醛、水杨醛、香草醛、羟基乙醛、3- 羟基丙醛、3-羟基丁醛、2-羟基丙醛、5-羟基戊醛、4-羟基丁醛、4-羟基苯乙醛、 4-羟基苯丙醛、4-羟基肉桂醛或2-羟基肉桂醛中的任一种或多种的混合物。
进一步的，所述步骤(1)中有机溶剂为二甲基亚砜、N,N-二甲基甲酰胺、异丙醇、丙酮、无水乙醇或乙酸乙酯；所述去离子水和有机溶剂的重量份数之和为 120-140份。
进一步的，所述步骤(2)中端异氰酸酯基聚氨酯预聚体通过以下制备方法获得：将50-100重量份的聚醚-聚酯多元醇混合物与5-30重量份的二异氰酸酯混合，加入二月桂酸二丁基锡，在50℃-80℃下反应1-4h得到端异氰酸酯基聚氨酯预聚体。
进一步的，所述聚醚-聚酯多元醇混合物中聚醚和聚酯多元醇的摩尔比为1:1.5-1:6；所述二月桂酸二丁基锡的用量为0.2-0.9重量份。
进一步的，所述二异氰酸酯为甲苯-2,4-二异氰酸酯、二苯基甲烷-2,2’-二异氰酸酯、二苯基甲烷-2,4′-二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯、六亚甲基二异氰酸酯、亚苯二甲基二异氰酸酯或异佛尔酮二异氰酸酯中的任一种或多种的混合物。
进一步的，所述步骤(3)导电填料为碳系导电填料或金属材料中的任一种或多种的混合物。
进一步的，所述碳系导电填料为石墨烯、碳纳米管、导电石墨、导电炭黑、乙炔炭黑、超导炭黑或膨胀石墨；所述金属材料为二氧化锰、二氧化钛、氧化锌或含铝、锌、铁、镍、银或紫铜的金属颗粒、金属纤维。
进一步的，所述步骤(3)搅拌的时间为30～40min。
进一步的，所述聚醚和聚酯多元醇的数均分子量均为400-10000。
本发明还提供了所述的制备方法制得的通电加热自修复聚氨酯弹性体。
与现有技术相比，本发明的优点和有益效果为：
(1)本发明利用含酰腙键的二元醇作为扩链剂，与聚氨酯预聚体反应，通过添加特殊导电填料，合成出含酰腙键导电聚氨酯弹性体，合成的弹性体除去溶剂后得到本体聚合物。室温下，含酰腙键导电的本体聚合物在持续通电的时候，切开的弹性体沿切开的横断面接触5min内即可实现自修复。
(2)本发明利用酰腙键制备的聚氨酯弹性体为不含溶剂的本体聚合物，故具有更好的物理机械性能，可实现多次自修复；与目前自修复聚合物相比，本发明制备的含酰腙键聚氨酯弹性体可仅在通电条件下自行检测裂缝愈合，且物理机械性能更高。
(3)本发明所制备的通电加热自修复聚氨酯弹性体结构简单，原料易于获取。制备工艺简单，原料均为已商业化生产的产品，材料性能可控性强，具有广泛应用前景。
附图说明
图1为本发明实施例1.2中香草醛丁二酸二甲酰腙的红外光谱图；
图2为本发明实施例1.2中香草醛丁二酸二甲酰腙的核磁光谱图；
图3为本发明实施例3.1制备的通电加热自修复聚氨酯弹性体的通电加热性能；
图4为本发明实施例3.5制备的通电加热自修复聚氨酯弹性体的自修复性能：a)聚氨酯弹性体修复前裂纹，b)通电加热修复后的聚氨酯弹性体。
具体实施方式
下面结合附图和实施例对本发明的技术方案进行具体的描述。
本发明提供的通电加热自修复聚氨酯弹性体，通过以下方法制备获得：(1) 将按重量份数计，将10-25份含酰腙键的二元醇扩链剂溶于15-50份的二甲基亚砜中；(2)加入25-50份的端异氰酸酯基聚氨酯预聚体，混合均匀，在50℃-80℃下反应0.5-4h；(3)依次加入8-40份导电填料；加入1-5份聚苯胺，混合均匀，在室温下搅拌反应30～40min后，抽真空脱除气泡，在30℃-80℃下固化12-48h，得到通电加热自修复聚氨酯弹性体。
本发明所述的含酰腙键的二元醇扩链剂的制备方法，它包括以下步骤：将 15-30重量份的羟基羰基化合物溶于有机溶剂中，将10-20重量份的二酰肼化合物溶于去离子水中，混合，在20℃-60℃下反应2～4h，得到含酰腙键的二元醇扩链剂；其中，所述有机溶剂为二甲基亚飒、N,N-二甲基甲酰胺、异丙醇、丙酮、无水乙醇或乙酸乙酯，所述去离子水和有机溶剂的重量份数之和为120-140份。
所述的二酰肼化合物为丙二酸二酰肼、庚二酰肼、辛二酰肼、戊烷二酰肼、癸二酸二酰肼、十二烷二羧酸二酰肼、对苯二甲酸二酰肼、邻苯二甲酸二酰肼、丁二酸二酰肼、壬二酸二酰肼、己二酸二酰肼或二水杨酰肼中的任一种或多种的混合物。
所述的羟基羰基化合物为对羟基苯甲醛、水杨醛、香草醛、羟基乙醛、3- 羟基丙醛、3-羟基丁醛、2-羟基丙醛、5-羟基戊醛、4-羟基丁醛、4-羟基苯乙醛、 4-羟基苯丙醛、4-羟基肉桂醛或2-羟基肉桂醛中的任一种或多种的混合物。
所述的端异氰酸酯基聚氨酯预聚体通过以下方法制备:按重量份数计,在 50℃-80℃的温度条件下,向50-100份的聚醚-聚酯多元醇混合物与5-30重量份的二异氰酸酯中,加入适量催化剂二月桂酸二丁基锡,反应1-4h,得到端异氰酸酯基聚氨酯预聚体。所述二月桂酸二丁基锡的用量为0.35-0.8重量份，所述聚醚-聚酯多元醇混合物中聚醚多元醇和聚酯多元醇的摩尔为1:2-1:6，所述聚醚或聚酯多元醇的数均分子量均为400-10000。
所述的二异氰酸酯为甲苯-2,4-二异氰酸酯(TDI)、二苯基甲烷-2,2’-二异氰酸酯(MDI)、二苯基甲烷-2,4’-二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯、六亚甲基二异氰酸酯(HDI)、亚苯二甲基二异氰酸酯和异佛尔酮二异氰酸酯(IPDI)中的任一种或多种的混合物。
所述的导电填料为碳系导电填料包括石墨烯、碳纳米管、导电石墨、导电炭黑、乙炔炭黑、超导炭黑、膨胀石墨等；金属材料包括二氧化锰、二氧化钛、氧化锌以及含铝、锌、铁、镍、银、紫铜等的金属颗粒、金属纤维等中的一种或多种的混合物。
实施例1.1：制备丁二酸二酰腙二元醇扩链剂
取对羟基苯甲醛8.9g(0.08mol-CHO)溶解在48.8g无水乙醇中，取丁二酸二酰肼7.52g(酰肼基团0.08mol)溶解在87.0g去离子水中；两者混合液混合均匀后在45℃，250rpm搅拌下反应3h。减压过滤，所得产物在室温下，依次用 150g乙醇(分3次，每次50g)洗，干燥后得到含酰腙键的二元醇，即为对羟基苯甲醛丁二酸二甲酰腙。产物为白色固体粉末。产率86％，得到的产物的分子结构式如下所示：
实施例1.2：制备丁二酸二酰腙二元醇扩链剂
取香草醛12.16g(0.08mol-CHO)溶解在48.8g无水乙醇中，取丁二酸二酰肼7.52g(酰肼基团0.08mol)溶解在87.0g去离子水中；两者混合液混合均匀后在35℃，250rpm搅拌下反应2h。减压过滤，所得产物在室温下，依次用150g 乙醇(分3次，每次50g)洗，干燥后得到含酰腙键的二元醇，即为香草醛丁二酸二甲酰腙。香草醛丁二酸二甲酰腙的红外光谱图见图1，核磁光谱图见图2；产物为白色固体粉末。产率96％，得到的产物的分子结构式如下所示：
实施例2.1：制备端异氰酸酯基的聚氨酯预聚体
取33.90g弹性体聚乙二醇PEG-1000二元醇与聚醚TEP-240、5.05g六亚甲基二异氰酸酯(HDI)、0.19gDBTDL(二月桂酸二丁基锡)于三口烧瓶中；其中,聚醚TEP-240与弹性体聚乙二醇PEG1000的摩尔比为1：4。上述反应在70℃，250rpm搅拌下抽真空反应4h，得到异氰酸酯基封端预聚物。
实施例2.2：制备端异氰酸酯基的聚氨酯预聚体
取49.88gPPG2000(聚丙二醇2000)与聚醚TEP-240、6.67g异弗尔酮二异氰酸酯IPDI、0.16gDBTDL(二月桂酸二丁基锡)于三口烧瓶中；其中,弹性体聚醚TEP-240与聚丙二醇PPG2000的摩尔比为1:3。上述反应在70℃，250rpm 搅拌下抽真空反应4h，得到异氰酸酯基封端预聚物。
实施例2.3：制备端异氰酸酯基的聚氨酯预聚体
取57.9g弹性体聚丙二醇PPG2000与聚碳酸酯二元醇(PC230)的混合物、 5.22g甲苯-2,4-二异氰酸酯TDI、0.35gDBTDL(二月桂酸二丁基锡)于三口烧瓶中；其中,弹性体聚丙二醇PPG2000与聚碳酸酯二元醇(PC230)的摩尔比为1:4。上述反应在70℃，250rpm搅拌下抽真空反应4h，得到异氰酸酯基封端预聚物。
实施例2.4：制备端异氰酸酯基的聚氨酯预聚体
取30g PTMEG1000与聚己内酯二元醇(PCL210)的混合物、15.02g二苯基甲烷-2,4′-二异氰酸酯MDI、0.36g DBTDL(二月桂酸二丁基锡)于三口烧瓶中，在70℃，250rpm搅拌下抽真空反应2.5h得到端异氰酸酯基的聚氨酯预聚体，其中PTMEG1000与聚己内酯二元醇(PCL210)的摩尔比为1:5。
实施例3.1：制备通电加热自修复聚氨酯弹性体
取5.31g实施例1.1制备的丁二酸二酰腙二元醇扩链剂(对羟基苯甲醛丁二酸二甲酰腙)溶解于15g二甲基亚砜中,加入39.14g实施例2.1制备的聚氨酯预聚体,75℃下搅拌(搅拌桨转速270rpm)反应4h后，取3.56g碳纳米管，0.45g 聚苯胺，常温下加入20g二甲基亚砜，混合均匀后，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌30min后抽真空30min脱除气泡浇注于敞口模具中, 在75℃下固化成型24h既得到本发明所述的通电加热自修复聚氨酯弹性体。通电加热自修复聚氨酯弹性体的通电加热性能见图3。
实施例3.2：制备通电加热自修复聚氨酯弹性体
取5.31g实施例1.1制备的丁二酸二酰腙二元醇扩链剂(对羟基苯甲醛丁二酸二甲酰腙)溶解于15g二甲基亚砜中，加入56.71g实施例2.2制备的聚氨酯预聚体,75℃下搅拌(搅拌桨转速270rpm)反应4h后，取4.96g导电炭黑，0.45g 聚苯胺，常温下加入20g二甲基亚砜中，将分散后的导电炭黑，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min 后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h，即得到本发明所述的通电加热自修复聚氨酯弹性体。
实施例3.3：制备通电加热自修复聚氨酯弹性体
取5.31g实施例1.1制备的丁二酸二酰腙二元醇扩链剂(对羟基苯甲醛丁二酸二甲酰腙)溶解于15g二甲基亚砜中,加入63.47g实施例2.3制备的聚氨酯预聚体,75℃下搅拌(搅拌桨转速270rpm)反应4h后，取10.32g导电石墨，0.45 g聚苯胺，常温下加入25g二甲基亚砜中，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h，即得到本发明所述的通电加热自修复聚氨酯弹性体。
实施例3.4：制备通电加热自修复聚氨酯弹性体
取10.62g实施例1.1制备的丁二酸二酰腙二元醇扩链剂(对羟基苯甲醛丁二酸二甲酰腙)溶解于15g二甲基亚砜中,加入45.38g实施例2.4制备的聚氨酯预聚体,75℃下搅拌(搅拌桨转速270rpm)反应4h后，取4.48g导电炭黑，0.45g 聚苯胺，常温下加入15g二甲基亚砜中，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h，即得到本发明所述的通电加热自修复聚氨酯弹性体。
实施例3.5：制备通电加热自修复聚氨酯弹性体
取6.21g实施例1.2制备的丁二酸二酰腙二元醇扩链剂(香草醛丁二酸二甲酰腙)溶解于17.54g二甲基亚砜中,加入39.14实施例2.1制备的聚氨酯预聚体, 75℃下搅拌(搅拌桨转速270rpm)反应4h后，取3.63g二氧化锰，0.45g聚苯胺，常温下加入15g二甲基亚砜中，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h，即得到本发明所述的通电加热自修复聚氨酯弹性体。
实施例3.6：制备通电加热自修复聚氨酯弹性体
取6.21g实施例1.2制备的丁二酸二酰腙二元醇扩链剂(香草醛丁二酸二甲酰腙)溶解于17.54g二甲基亚砜中,加入56.71g实施例2.2制备的聚氨酯预聚体, 75℃下搅拌(搅拌桨转速270rpm)反应4h后，取6.29g石墨烯，0.45g聚苯胺，常温下加入15g二甲基亚砜中，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h，即得到本发明所述的通电加热自修复聚氨酯弹性体。
实施例3.7：制备通电加热自修复聚氨酯弹性体
取6.21g实施例1.2制备的含酞踪键的芳香族端羟基扩链剂(香草醛丁二酸二甲酰腙)溶解于17.54g二甲基亚砜中,加入63.47g实施例2.3制备的聚氨酯预聚体,75℃下搅拌(搅拌桨转速270rpm)反应4h后，取10.45g聚吡咯，0.45g 聚苯胺，常温下加入25g二甲基亚砜中，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h，即得到本发明所述的通电加热自修复聚氨酯弹性体。
实施例3.8：制备通电加热自修复聚氨酯弹性体
取12.24g实施例1.2制备的含酞踪键的芳香族端羟基扩链剂(香草醛丁二酸二甲酰腙)溶解于17.54g二甲基亚砜中,加入45.38g实施例2.2制备的聚氨酯预聚体,75℃下搅拌(搅拌桨转速270rpm)反应4h后，取5.76g石墨烯，0.45g聚苯胺，常温下加入15g二甲基亚砜中，混合均匀，加入到上述含有扩链剂的聚氨酯预聚体中，室温下搅拌(搅拌桨转速1300rpm)30min后抽真空30min脱除气泡浇注于敞口模具中,在80℃下固化成型24h既得到本发明所述的通电加热自修复聚氨酯。
实施例4：采用拉伸实验表征材料力学性能及自修复效率
采用拉伸测试方法评价材料的修复效率：将实施例3.1-实施例3.6制备的聚氨酯弹性体按照GB/T528-2009制备拉伸样条。在样条中部沿垂直于拉伸轴线的方向将样条切割出裂痕。室温下，含酰腙键的聚氨酯样条裂痕处紧密接触在一起，在样条两端进行通电使其温度达到120℃，接触1min左右即可实现自修复。拉伸速率100mm/min。自修复效率可用以下两式表示：
经测试，实施例3.1-3.6制备的通电加热自修复聚氨酯弹性体的自修复性能良好，如图4所示，实施例3.5所示自修复聚氨酯弹性体其R(σ)＝20％，R(ε)＝7.6％。
以上实施例仅用以说明本发明的技术方案，而非对其进行限制；尽管参照前述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。
Claims (10)
1.一种通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述制备方法包括以下步骤：
（1）将10-25重量份含酰腙键的二元醇扩链剂溶于15-50重量份的二甲基亚砜中；
（2）加入25-50重量份的端异氰酸酯基聚氨酯预聚体，混合均匀，在50℃-80℃下反应0.5-4h；
（3）依次加入8-40重量份导电填料、1-5重量份聚苯胺，混合均匀，搅拌，抽真空脱除气泡，在30℃-80℃下固化12-48h，得到通电加热自修复聚氨酯弹性体。
2.根据权利要求1所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述步骤（1）含酰腙键的二元醇扩链剂通过以下步骤反应获得：(1)将15-30重量份的羟基羰基化合物溶于有机溶剂中，将10-20重量份的二酰肼化合物溶于去离子水中，混合；(2)在20℃-60℃下反应2~4h，得到含酰腙键的二元醇扩链剂。
3.根据权利要求2所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述的二酰肼化合物为丙二酸二酰肼、庚二酰肼、辛二酰肼、戊烷二酰肼、癸二酸二酰肼、十二烷二羧酸二酰肼、对苯二甲酸二酰肼、邻苯二甲酸二酰肼、丁二酸二酰肼、壬二酸二酰肼、己二酸二酰肼或二水杨酰肼中的任一种或多种的混合物；
所述的羟基羰基化合物为对羟基苯甲醛、水杨醛、香草醛、羟基乙醛、3-羟基丙醛、3-羟基丁醛、2-羟基丙醛、5-羟基戊醛、4-羟基丁醛、4-羟基苯乙醛、4-羟基苯丙醛、4-羟基肉桂醛或2-羟基肉桂醛中的任一种或多种的混合物。
4.根据权利要求2所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述步骤(1)中有机溶剂为二甲基亚砜、N,N-二甲基甲酰胺、异丙醇、丙酮、无水乙醇或乙酸乙酯；所述去离子水和有机溶剂的重量份数之和为120-140份。
5.根据权利要求1所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述步骤（2）中端异氰酸酯基聚氨酯预聚体通过以下制备方法获得：将50-100重量份的聚醚-聚酯多元醇混合物与5-30重量份的二异氰酸酯混合，加入二月桂酸二丁基锡，在50℃-80℃下反应1-4h得到端异氰酸酯基聚氨酯预聚体。
6.根据权利要求5所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述聚醚-聚酯多元醇混合物中聚醚和聚酯多元醇的摩尔比为1:1.5-1:6；所述二月桂酸二丁基锡的用量为0.2-0.9重量份。
7.根据权利要求5所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述二异氰酸酯为甲苯-2,4-二异氰酸酯、二苯基甲烷-2,2’-二异氰酸酯、二苯基甲烷-2,4′-二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯、六亚甲基二异氰酸酯、亚苯二甲基二异氰酸酯或异佛尔酮二异氰酸酯中的任一种或多种的混合物。
8.根据权利要求1所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述步骤（3）导电填料为碳系导电填料或金属材料中的任一种或多种的混合物。
9.根据权利要求8所述的通电加热自修复聚氨酯弹性体的制备方法，其特征在于：所述碳系导电填料为石墨烯、碳纳米管、导电石墨、导电炭黑、乙炔炭黑、超导炭黑或膨胀石墨；所述金属材料为二氧化锰、二氧化钛、氧化锌或含铝、锌、铁、镍、银或紫铜的金属颗粒、金属纤维。
10.权利要求1~9所述的制备方法制得的通电加热自修复聚氨酯弹性体。
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| CN113755001B (zh) * | 2020-06-03 | 2022-07-19 | 南京理工大学 | 聚（脲-氨基甲酸酯）/聚苯胺/氧化石墨烯复合自愈合防腐材料 |
| CN113321924A (zh) * | 2021-05-26 | 2021-08-31 | 同济大学 | 一种具备光热自愈合功能的复合材料及其制备方法 |
| WO2023151174A1 (zh) * | 2022-02-14 | 2023-08-17 | 浙江理工大学绍兴柯桥研究院有限公司 | 一种环保型柔性导电聚氨酯及其制备方法 |
| US11987662B2 (en) | 2022-02-14 | 2024-05-21 | Shaoxing-Keqiao Instisute Of Zhejiang Sci-Tech University Co., Ltd. | Environmentally-friendly flexible conductive polyurethane (PU) and preparation method thereof |
| CN116925528A (zh) * | 2023-06-07 | 2023-10-24 | 安徽精一门科技发展有限公司 | 一种自修复电致变色器件材料及电致变色器件 |
| CN116925528B (zh) * | 2023-06-07 | 2024-02-02 | 安徽精一门科技发展有限公司 | 一种自修复电致变色器件材料及电致变色器件 |
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