CN115057984A - 一种具有自修复功能的高强度聚丁二烯聚氨酯脲 - Google Patents
一种具有自修复功能的高强度聚丁二烯聚氨酯脲 Download PDFInfo
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Abstract
一种具有自修复功能的高强度聚丁二烯聚氨酯脲,按重量份,由100份异氰酸酯封端的液体聚丁二烯树脂和30‑55份胺苯基封端的液体聚硫橡胶混合均匀,在20‑80℃下固化反应2‑7天制备,其中异氰酸酯封端的聚丁二烯树脂由端羟基聚丁二烯与异佛尔酮二异氰酸酯按摩尔比1∶2.0‑2.5反应而成,胺苯基封端的液体聚硫橡胶由液体聚硫橡胶与2,2′‑二氨基二苯二硫醚按重量比1∶0.3‑0.8反应制备。本发明利用一定分子量的液体聚丁二烯和聚硫橡胶极性差异,基于异氰酸酯与胺苯基扩链反应形成微相分离的聚集态结构,制成的聚丁二烯聚氨酯脲,在保持高力学强度前提下,实现了高的自修复效率。切断的样品在75℃下相互接触48小时,修复后强度可达10MPa以上,修复率为85‑95%。
Description
技术领域
本发明是一种具有自修复功能的高强度聚丁二烯聚氨酯脲,属于聚氨酯技术领域。
背景技术
聚丁二烯聚氨酯脲具有优异的弹性、韧性、耐水性以及耐低温性能,广泛用于粘合剂、密封胶等。发明专利申请CN110167987A提供了一种涉及压敏胶粘性的可熔融的羟基官能化聚丁二烯聚氨酯热熔性预聚物,由羟基聚丁二烯和二异氰酸酯及扩链剂等制备,其包括如下的化学反应产物:至少一种聚丁二烯二醇、至少一种具有2的羟基官能度和小于或等于300g/mol的摩尔质量的扩链剂、以及任选地至少一种具有在大于2.0和小于或等于3.0之间的数均平均官能度的聚丁二烯多元醇与至少一种脂族或脂环族二异氰酸酯。
另外,由于自修复材料能够自主地修复因环境疲劳和机械疲劳所造成的材料物理损伤,从而延长材料使用寿命,具有自修复功能的聚氨酯材料成为了一种重要新材料。发明专利申请CN113372527A公开了一种基于聚丁二烯的自修复聚氨酯材料的制备,由端羟基聚丁二烯、二异氰酸酯、2,2′-二氨基二苯二硫醚及多巴胺等制备,包括步骤:将羟基聚丁二烯与异佛尔酮二异氰酸酯在70℃下持续搅拌反应3h,得到异氰酸酯封端的液体聚丁二烯,然后加入2,2′-二氨基二苯二硫醚继续反应2h,再加入盐酸多巴胺固化,产物的修复效率可达到96%,拉伸强度为0.13-0.2MPa。
作为粘合密封胶应用,上述的聚丁二烯聚氨酯脲自修复材料的强度偏低。综合分析现有技术,有些聚丁二烯聚氨酯脲材料具有高强度,但没有自修复功能;有高自修复性能的,其机械强度较低,如何研制同时具有高自修复性能和高强度的聚丁二烯聚氨酯材料,成为一个技术问题。
发明内容
本发明是一种具有自修复功能的高强度聚丁二烯聚氨酯脲,按重量份,由100份异氰酸酯封端的液体聚丁二烯树脂和30-55份胺苯基封端的液体聚硫橡胶组成,上述组分混合均匀后,在20-80℃下固化2-7天得到聚丁二烯聚氨酯脲,该材料同时具有高强度和高自修复性能的特点。反应物分子结构如下所示。
发明原理:自修复功能聚氨酯材料研制存在着一个技术难题:要实现高自修复效率,要求材料中分子链段相互作用小、交联度低,以提高链段运动能力和增加化学键的交换作用,但这会导致材料的机械强度降低;具有高机械强度的材料,其分子链段相互作用大,则会使自修复的链段运动变弱,导致较低的自修复性。本发明是将羟基液体聚丁二烯树脂用二异氰酸酯封端后,再与胺苯基封端的液体聚硫橡胶反应制备得到。基于异氰酸酯和胺苯基官能团之间的高反应活性,以及特定分子量的聚丁二烯橡胶与聚硫橡胶的极性差异,使聚丁二烯和聚硫橡胶的这两种链段强迫相容,形成微米尺度相分离的聚集态结构,结构中以聚丁二烯链段为主体、聚硫链段为分散相,这样聚丁二烯聚氨酯赋予材料高的力学强度,而聚硫链段中丰富的二硫键可实现自修复功能;进一步由于聚丁二烯和聚硫链段形成微米相态结构,使聚硫分子链段富集,大幅度增加了二硫键交换几率,提高自修复效率,实现了高强度聚氨酯材料的自修复功能设计,从而完成了本发明。
所述的异氰酸酯封端的聚丁二烯树脂,由端羟基液体聚丁二烯树脂与异佛尔酮二异氰酸酯按摩尔比1∶2.0-2.5在50-70℃下反应3小时后制成,其中端羟基液体聚丁二烯分子量为1200-1600,羟值为1.4-1.6mmol/g,使用前在100℃真空脱水2-3小时。
所述的胺苯基封端的液体聚硫橡胶,由端巯基液体聚硫橡胶与2,2′-二氨基二苯二硫醚按重量比1∶0.3-0.8反应得到,其中端巯基液体聚硫橡胶的分子量为800-1200,巯基含量为5.9-7.2%。
所述的胺苯基封端的液体聚硫橡胶制备步骤如下:将100重量份端巯基液体聚硫橡胶,30-80重量份2,2′-二氨基二苯二硫醚,加入1-2重量份的叔胺,在惰性气体保护下100-120℃反应12-24小时,通过二硫键交换反应,得到一端为胺苯基、一端为巯基的液体聚硫橡胶预聚体;冷却至50℃,加入20重量份的二氧化锰粉末,在50℃继续反应3-5小时,使巯基氧化偶联成二硫键,过滤固体粉末后,制备得到全部由胺苯基封端的液体聚硫橡胶。
发明效果:胺苯基封端的液体聚硫橡胶,其端基为胺苯基,与异氰酸酯反应的活性高;与异氰酸酯封端的液体聚丁二烯反应,形成微相分离结构,使制备聚氨酯脲材料兼具聚丁二烯聚氨酯的高强度和聚硫橡胶的高自修复效率优点;根据应用需要,通过调控两种组分的比例,可以改变材料的拉伸强度和拉断伸长率。发明材料样品被切断后,在75℃下相互接触修复48小时,拉伸强度可达10MPa以上,修复率为85-95%。
拉伸强度的修复率定义为材料修复后的拉伸强度与材料修复前的拉伸强度之比;拉断伸长率的修复率定义为材料修复后的拉断伸长率与材料修复前的拉断伸长率之比。
具体实施例
实施例1
一种具有自修复功能的高强度聚丁二烯聚氨酯脲,按重量份,由100份异氰酸酯封端的液体聚丁二烯树脂和48份胺苯基封端的液体聚硫橡胶混合均匀,在50℃下固化反应4天制备。
所述的异氰酸酯封端的聚丁二烯树脂,由端羟基液体聚丁二烯树脂与异佛尔酮二异氰酸酯按摩尔比1∶2.4在60℃下反应3小时后制成,其中端羟基液体聚丁二烯的羟值为1.45mmol/g。
所述的胺苯基封端的液体聚硫橡胶制备步骤如下:将100重量份端巯基液体聚硫橡胶、60重量份2,2′-二氨基二苯二硫醚、2重量份叔胺混合,惰性气体保护下100℃反应24小时,然后冷却至50℃,加入20重量份的二氧化锰粉末,在50℃继续反应4小时,过滤固体粉末后,制成胺苯基封端的液体聚硫橡胶。
制备的聚丁二烯聚氨酯脲的主要性能:拉伸强度11.5MPa,拉断伸长率489%;切断的样品在75℃下相互接触48小时,拉伸强度恢复为10.6MPa,拉断伸长率465%,其修复率分别为92%和95%。
实施例2
一种具有自修复功能的高强度聚丁二烯聚氨酯脲,按重量份,由100份异氰酸酯封端的聚丁二烯树脂和40份胺苯基封端的液体聚硫橡胶混合均匀,在75℃下固化反应2天制备。
所述的异氰酸酯封端的聚丁二烯树脂,由端羟基液体聚丁二烯树脂与异佛尔酮二异氰酸酯按摩尔比1∶2.4在60℃下反应3小时后制成,其中端羟基液体聚丁二烯的羟值为1.45mmol/g。
所述的胺苯基封端的液体聚硫橡胶制备步骤如下:将100重量份端巯基液体聚硫橡胶、80重量份2,2′-二氨基二苯二硫醚、2重量份叔胺混合,惰性气体保护下100℃反应24小时,然后冷却至50℃,加入20重量份的二氧化锰粉末,在50℃继续反应4小时,过滤固体粉末后,制成胺苯基封端的液体聚硫橡胶。
制备的聚丁二烯聚氨酯脲的主要性能:拉伸强度13.2MPa,拉断伸长率390%;切断的样品在75℃下相互接触48小时,拉伸强度恢复为11.4MPa,拉断伸长率351%,其修复率分别为86%和90%。
Claims (1)
1.一种具有自修复功能的高强度聚丁二烯聚氨酯脲,按重量份,由100份异氰酸酯封端的液体聚丁二烯树脂,其特征在于加30-55份胺苯基封端的液体聚硫橡胶混合均匀,在20-80℃下固化反应2-7天得到聚丁二烯聚氨酯脲;其中所述的异氰酸酯封端的液体聚丁二烯树脂是由端羟基聚丁二烯橡胶与异佛尔酮二异氰酸酯按摩尔比1∶2.0-2.5反应制备而得,所述的端羟基液体聚丁二烯分子量为1200-1600,羟值为1.4-1.6mmol/g;所述的胺苯基封端的液体聚硫橡胶由分子量为800-1200的端巯基液体聚硫橡胶与2,2′-二氨基二苯二硫醚按重量比1∶0.3-0.8反应制备而得;所述的聚丁二烯聚氨酯脲的拉伸强度大于10MPa。
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