CN112694595A - 一种高度交联聚脲弹性体及其制备方法 - Google Patents
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Abstract
本发明涉及一种高度交联聚脲弹性体及其制备方法，包括A组分和B组分，按重量百分比计：A组份：异氰酸酯封端含不饱和键的聚合物100份；B组份：氨基化合物80～110份、引发剂10～20份、促进剂10～20份、填料1～100份。本发明解决聚脲弹性体交联度有限的问题，所制备的高度交联聚脲弹性体交联度高、防水性能和防腐能力高，提高材料耐热性能，提高材料结构稳定性。
Description
技术领域
本发明涉及聚脲材料技术领域，特别涉及一种高度交联聚脲弹性体及其制备方法。
背景技术
聚脲弹性体是由端异氰酸酯预聚物与氨基化合物反应生成的具有脲键的高分子聚合物材料。聚脲弹性体具有较高的机械性能，耐磨、耐酸碱、耐腐蚀、防湿滑等优异的理化性能。在建筑防水、海洋防腐、汽车涂装、道路防护、军用设备防护等领域应用广泛，随着其性能的提升与工艺的优化，其应用前景更为广阔。常规聚脲弹性体由于异氰酸酯与氨基反应活性较高，反应凝胶时间很短，聚脲弹性体交联度提升空间有限。为了获得更优的机械性能、防水性能、防腐性能只能增加聚脲弹性体厚度来实现。材料固化交联度的提升有利于提高材料机械性能，有利于提高材料防水性能和防腐能力，有利于提高材料耐热性能，有利于提高材料结构稳定性。因此，本发明提供一种高度交联聚脲弹性体及其制备方法，进一步提升聚脲弹性体综合性能。
发明内容
本发明一方面提供一种高度交联聚脲弹性体，解决聚脲弹性体交联度有限的问题，本发明制备的高度交联聚脲弹性体交联度高、防水性能和防腐能力高，提高材料耐热性能，提高材料结构稳定性。
本发明提供一种高度交联聚脲弹性体，包括A组分和B组分，按重量百分比计，A组分和B组分分别包括如下物质：
A组份：异氰酸酯封端含不饱和键的聚合物100份；
B组份：氨基化合物80～110份、引发剂10～20份、促进剂10～20份、填料1～100份。
进一步地，所述异氰酸酯封端含不饱和键的聚合物采用线性异氰酸酯封端含不饱和键的聚合物和支化异氰酸酯封端含不饱和键的聚合物。
进一步地，所述氨基化合物采用端氨基聚醚、端氨基聚乙二醇、聚天门冬氨酸酯中的一种或两种。
进一步地，所述引发剂采用有机过氧化物引发剂、有机偶氮类引发剂、UV引发剂或氧化还原引发剂。
进一步地，所述促进剂采用过渡金属的羧酸盐、叔胺类化合物或硫醇类化合物。
进一步地，所述填料为金属氧化物及其混合物、石墨烯、四氟乙烯粉末中的一种或多种。
本发明的另一个目的是提供一种高度交联聚脲弹性体的制备方法，包括如下步骤：
1）A组分的制备：将端羟基或端氨基含不饱和键聚合物与多异氰酸酯化合物在一定条件下反应聚合，得到具有一定分子量异氰酸酯封端含不饱和键的聚合物；
2）B组分的制备：将氨基化合物与引发剂、促进剂以及填料等组分混合均匀；
3）高度交联聚脲弹性体成型：A组分和B组分可以采用溶剂喷涂或无溶剂喷涂方法成型，成型后依据引发剂所需温度，再进一步引发不饱和键自由基交联反应，最终获得高度交联聚脲弹性体材料。
本发明制备的高度交联聚脲弹性体交联度高、防水性能和防腐能力高，提高材料耐热性能，提高材料结构稳定性。
附图说明
图1. A组份的制备机理；
图2. B组份的制备机理；
图3. 高度交联聚脲弹性体成型机理。
具体实施方式
下面结合具体实施例对本发明做进一步说明。但本发明的保护范围并不局限于此，应包括权利要求的全部范围。任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。
实施例1：
将1000g端羟基聚丁二烯（分子量500～600）与750gMDI在纯氮气保护条件下，使用有机锡催化剂，加热60～70℃，搅拌反应3～4h，得到异氰酸酯封端含有双键的预聚物，异氰酸酯含量约为2.7%，作为A组分。
将800g端氨基聚醚D2000、240g端氨基聚醚D5000、8g二甲硫基甲苯二胺、17g过氧化苯甲酰、15g N,N-二甲基苯胺，搅拌均匀。再加入150g脱水后的氧化锌，10g四氟乙烯粉，搅拌混合均匀，作为B组分。
A组分和B组分采用聚脲专用喷枪，喷涂压力0.7～0.8MPa，喷涂成型后，继续室温固化24～36h或加热70～80℃固化2～3h,获得高度交联的聚脲弹性体。
实施例2：
将1000g端羟基聚丁二烯（分子量40000左右，羟值0.48mmol/g）与60gIPDI在纯氮气保护条件下，使用有机锡催化剂，加热70～80℃，搅拌反应5～6h，得到异氰酸酯封端含有双键的预聚物，异氰酸酯含量约为6.2%，作为A组分。
将600g聚天门冬氨酸酯（胺值190～210mgKOH/g）、120g端氨基聚醚D5000、8g过氧化苯甲酰、6g N,N-二甲基苯胺、6g过氧化环己酮、5g环烷酸钴，搅拌均匀。再加入150g脱水后的氧化锌、10g四氟乙烯粉，搅拌混合均匀，作为B组分。
A组分和B组分采用聚脲专用喷枪，喷涂压力0.7～0.8MPa，喷涂成片材后，继续室温固化24～36h或加热70～80℃固化2～3h,获得高度交联的聚脲弹性体。
亦可将A组分和B组分分别溶解在溶剂中，使用普通喷枪，喷涂成型。室温固化24～36h或加热70～80℃固化2～3h,获得高度交联的聚脲弹性体。
实施例3：
将1000g端羟基聚丁二烯丙烯腈（分子量800～1000）与300gTDI在纯氮气保护条件下，使用有机锡催化剂，加热70～80℃，搅拌反应3～4h，得到异氰酸酯封端含有双键的预聚物，异氰酸酯含量约为3.9%，作为A组分。
将800g端氨基聚醚D2000、240g端氨基聚醚D5000、8g二甲硫基甲苯二胺、6g过氧化苯甲酰、5g N,N-二甲基苯胺、5g过氧化环己酮、4g环烷酸钴，搅拌均匀。再加入150g脱水后的氧化锌、10g四氟乙烯粉，搅拌混合均匀，作为B组分。
A组分和B组分采用聚脲专用喷枪，喷涂压力0.7～0.8MPa，喷涂成型后，继续室温固化24～36h或加热70～80℃固化2～3h,获得高度交联的聚脲弹性体。
对比例1：
将1000g端羟基聚丁二烯丙烯腈（分子量800～1000）与300gTDI在纯氮气保护条件下，使用有机锡催化剂，加热70～80℃，搅拌反应3～4h，得到异氰酸酯封端含有双键的预聚物，异氰酸酯含量约为4.5%，作为A组分。
将800g端氨基聚醚D2000、240g端氨基聚醚D5000、8g二甲硫基甲苯二胺、6g过氧化苯甲酰、5g N,N-二甲基苯胺、5g过氧化环己酮、4g环烷酸钴，搅拌均匀。再加入150g脱水后的氧化锌、10g四氟乙烯粉，搅拌混合均匀，作为B组分。
A组分和B组分采用聚脲专用喷枪，喷涂压力0.7～0.8MPa，获得普通聚脲弹性体。
以上实施例与对比例制备的聚脲弹性体，进行性能测试，相关测试数据见表1。
表1. 实施例相关性能数据
由上述测试数据可知，按照本发明制备的聚脲弹性体材料实施例1～3，抗拉强度比普通聚脲弹性体材料显著提升，最高提升123%；断裂伸长率有升高有降低，总体水平相当；实施例1～3获得的高度交联聚脲弹性体在溶剂中浸泡后体积变化率较对比例1材料显著下降，最高下降近50%，说明本发明提供高度交联聚脲弹性体可以有效提升材料耐溶胀性能；实施例1～3获得的高度交联聚脲弹性体经过旋转磨耗仪测试，磨耗量较对比例显著降低，磨耗量最高降低近70%，说明本发明制备的材料耐磨性显著提升。由此，说明本发明提供的高度交联聚脲弹性体材料具有更优的机械性能、耐溶剂性能、耐磨性，可以应用于防水、防腐、防爆、耐磨防护等领域。
Claims (7)
1.一种高度交联聚脲弹性体，包括A组分和B组分，其特征在于，按重量百分比计，A组分和B组分分别包括如下物质：
A组份：异氰酸酯封端含不饱和键的聚合物100份；
B组份：氨基化合物80～110份、引发剂10～20份、促进剂10～20份、填料1～100份。
2.根据权利要求1所述高度交联聚脲弹性体，其特征在于：所述异氰酸酯封端含不饱和键的聚合物采用线性异氰酸酯封端含不饱和键的聚合物和支化异氰酸酯封端含不饱和键的聚合物。
3.根据权利要求1所述高度交联聚脲弹性体，其特征在于：所述氨基化合物采用端氨基聚醚、端氨基聚乙二醇、聚天门冬氨酸酯中的一种或两种。
4.根据权利要求1所述高度交联聚脲弹性体，其特征在于：所述引发剂采用有机过氧化物引发剂、有机偶氮类引发剂、UV引发剂或氧化还原引发剂。
5.根据权利要求1所述高度交联聚脲弹性体，其特征在于：所述促进剂采用过渡金属的羧酸盐、叔胺类化合物或硫醇类化合物。
6.根据权利要求1所述高度交联聚脲弹性体，其特征在于：所述填料为金属氧化物及其混合物、石墨烯、四氟乙烯粉末中的一种或多种。
7.一种高度交联聚脲弹性体的制备方法，其特征在于，包括如下步骤：
1）A组分的制备：将端羟基或端氨基含不饱和键聚合物与多异氰酸酯化合物在一定条件下反应聚合，得到具有一定分子量异氰酸酯封端含不饱和键的聚合物；
2）B组分的制备：将氨基化合物与引发剂、促进剂以及填料等组分混合均匀；
3）高度交联聚脲弹性体成型：A组分和B组分可以采用溶剂喷涂或无溶剂喷涂方法成型，成型后依据引发剂所需温度，再进一步引发不饱和键自由基交联反应，最终获得高度交联聚脲弹性体材料。
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