CN116640304A - 一种可交联的热塑性聚酰亚胺树脂及其制备方法 - Google Patents
一种可交联的热塑性聚酰亚胺树脂及其制备方法 Download PDFInfo
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Abstract
本发明涉及聚合物合成技术领域，公开一种可交联的热塑性聚酰亚胺树脂及其制备方法，所述热塑性聚酰亚胺树脂具有如下结构式，所述封端剂的摩尔量为二胺类化合物和二酐类化合物总摩尔量的0.5‑10％；所述封端剂包括可交联封端剂和不可交联封端剂，其中可交联封端剂与不可交联封端剂的摩尔比为3:1～1:2；所述封端剂为单酐或单胺的化合物；所述热塑性聚酰亚胺树脂熔融指数为1～50g/10min，热膨胀系数为3.0*10‑5～5.0*10‑5。本发明利用可交联封端剂和不可交联封端剂的组合物对树脂进行封端，得到同时兼具加工性能优异、耐溶剂性能优异和低热膨胀系数等优点的树脂。
Description
技术领域
本发明涉及聚合物合成技术领域，具体涉及一种可交联的热塑性聚酰亚胺树脂及其制备方法。
背景技术
聚酰亚胺是一种具有耐高温、耐化学腐蚀、低膨胀系数和优异的机械性能等特征的高性能高分子材料，广泛用于汽车、航空航天、电子电器等领域。聚酰亚胺按加工特性可分为热塑性聚酰亚胺和热固性聚酰亚胺，热固性聚酰亚胺有良好的耐溶剂性和超低的热膨胀系数等优点；而热塑性聚酰亚胺具有加工成型简单，具有一次成型结构复杂的制品，无需二次加工的优点。但从目前来看两者的优点不能兼具，热塑性聚酰亚胺不耐溶剂且一般热膨胀系数较高，热固性聚酰亚胺加工成型手段单一，不能用于复杂构件成型。
CN102634021A公开了一种热塑性聚酰亚胺树脂及其制备方法。该热塑性聚酰亚胺树脂是由1,2,3,4-连苯四酸二酐与其他常用四酸二酐组成的混合二酐、二胺以及邻苯二甲酸酐或者苯胺反应，使混合二酐与二胺发生聚合，邻苯二甲酸酐或者苯胺作为封端剂控制分子量而得到的具有良好的热稳定性和优异的热塑加工性的聚酰亚胺树脂。但是该树脂耐溶剂性能差，热膨胀系数偏高。
因此，开发一种兼具热塑性加工性和耐溶剂、低热膨胀系数的聚酰亚胺就显得十分必要了。CN 114149584 A公开了一种聚酰亚胺树脂及其制备方法通过在制备过程中加入可交联组分，使聚酰亚胺树脂带有可交联官能团，使该聚酰亚胺树脂同时具有热塑性聚酰亚胺树脂和热固性聚酰亚胺树脂的优异性能，既具有良好的韧性和可加工性能，又具有良好的力学性能和耐高低温性能，改善其使用性能，拓宽聚酰亚胺树脂的应用领域。但其是在反应主体中引入含乙炔基的双苯酐类化合物，得到的聚酰亚胺树脂仅能进行模压成型，加工性能仍然较差，且热膨胀系数如何也无法得知，其原因在于在二酐中引入交联部分，会导致分子链的交联位点在分子链中间，从而限制了分子链的运动影响了树脂加工性。
因此，同时兼具可注塑级别的加工性，又具有较低的热膨胀系数等综合性能优异的聚酰亚胺树脂仍存在较高难度。
发明内容
本发明针对热塑性聚酰亚胺存在的耐溶剂性差，热膨胀系数高，而热固性聚酰亚胺又存在加工性能差的问题，提供一种可交联的热塑性聚酰亚胺树脂，通过引入部分可交联封端剂，实现聚酰亚胺树脂内部的微交联，获得同时兼具加工性能优异、耐溶剂性能优异和低热膨胀系数等优点的树脂。
为实现上述目的，本发明采用的技术方案是：
一种可交联的热塑性聚酰亚胺树脂，所述热塑性聚酰亚胺树脂具有如下结构式：
其中，Ar1是二胺类化合物的残基，Ar2是二酐类化合物的残基，EG为封端剂，n是大于1的整数；所述封端剂的摩尔量为二胺类化合物和二酐类化合物总摩尔量的0.5-10％；
所述封端剂包括可交联封端剂和不可交联封端剂，其中可交联封端剂与不可交联封端剂的摩尔比为3:1～1:2；所述封端剂为单酐或单胺的化合物；
所述热塑性聚酰亚胺树脂熔融指数为1～50g/10min，测试条件为340℃；12.5kg；热膨胀系数为3.0*10-5～5.0*10-5，测试条件为25～150℃。
优选地，所述热塑性聚酰亚胺树脂熔融指数为2～20g/10min，进一步优选3～20g/10min。
本发明中以封端剂为改性点，设计了在端基部分引入半交联部分，使树脂获得热固树脂的优点(热膨胀系数降低等)，且保留热塑树脂的优异加工特点(可以注塑)。
所述可交联封端剂选自如下结构中一种或多种：
所述不可交联封端剂选自如下结构中一种或多种：
本发明中以单酐类或单胺类的可交联和不可交联的封端剂进行封端，实现对聚酰亚胺结构的微交联，对分子结构本身的活动影响较小，因此得到的聚酰亚胺加工性能好；在端基部分引入半交联部分，使树脂获得热固树脂的优点(热膨胀系数降低等)，且保留热塑树脂的优异加工特点(可以注塑)。
所述封端剂的摩尔量为二胺类化合物和二酐类化合物总摩尔量的1-6％；封端剂量太多会影响树脂的分子量，从而有可能使树脂成不了高聚物，1～6％的比例下产品的性最佳。
所述封端剂包括可交联封端剂和不可交联封端剂，其中可交联封端剂与不可交联封端剂的摩尔比为1:1～3:2。不可交联封端剂的量要不小于可交联封端剂的量才能保护树脂的热塑性(可注塑)。
优选地，所述可交联封端剂选自如下结构中一种或多种，以下结构比较稳定交联时降解物产生较少，且商品化的产品，易于购买：
所述不可交联封端剂选自如下结构中一种或多种，以下结构高温下更为稳定：
所述Ar1选自下列基团中的一种或几种：
所述Ar2选自下列基团中的一种或几种：
优选地，所述Ar1选自下列基团中的一种或几种：
所述Ar2选自下列基团中的一种或几种：
所述EG的摩尔量为Ar1和Ar2摩尔之差的两倍。使分子链的端基完全被EG保护，不出现二胺或二酐其中一个氨基或者酐基裸露的情况。
本发明还提供所述的可交联的热塑性聚酰亚胺树脂的制备方法，包括步骤：在氮气保护下，将二胺、二酐、封端剂、溶剂和成环剂混合，升温进行聚合反应得到聚酰亚胺聚合溶液；将聚酰亚胺聚合溶液在沉淀剂中析出，过滤干燥得到所述热塑性聚酰亚胺树脂。
优选地，聚合过程温度为160-200℃，聚合时间为10-20h。
优选地，产物析出过滤后，进行250-380℃下进行干燥。该温度下能够进一步热亚胺化，促使未完全反应的预聚物反应完全。干燥时间2-6h。
优选地，制备方法包括步骤：
步骤1，在氮气保护下，将二胺、二酐、溶剂和成环剂混合，升温进行聚合得到聚酰亚胺前驱体溶液；
步骤2，向步骤1的聚酰亚胺前驱体溶液中加入封端剂继续反应，得到聚酰亚胺聚合溶液，将聚合溶液在沉析剂中析出，过滤干燥得到所述热塑性聚酰亚胺树脂。
二酐二胺反应先得到高分子链，避免了二酐、二胺以及封端剂一起加入时可能会产生的二胺完全被封端剂封端的小分子酰亚胺结构，影响树脂的热塑性。
优选地，加入封端剂继续反应3-6h。
进一步优选地，制备方法包括步骤：
步骤1，在氮气保护下，将二胺、二酐、溶剂和成环剂混合，升温进行聚合得到聚酰亚胺前驱体溶液；
步骤2，先向聚酰亚胺前驱体溶液中加入不可交联封端剂与可交联封端剂的混合物反应3～6h，得到聚酰亚胺聚合溶液，将聚合溶液在沉析剂中析出，过滤干燥得到所述热塑性聚酰亚胺树脂。混合加入封端剂，比分步加入封端剂的优点是，分步加入会产生完全不可交联端基封端的以及完全可交联端基封端的分子链，会影响树脂的耐溶剂性。
在一些实施方式中，聚合反应结束后再进行化学亚胺化，得到聚酰亚胺溶液，经析出后、过滤干燥得到所述热塑性聚酰亚胺树脂。
所述溶剂包括邻二氯苯、间甲酚、邻苯二甲醚、二甲乙酰胺、N-甲基吡咯烷酮、二甲亚砜中一种或多种；
所述成环剂包括邻二氯苯、异喹啉、苯基次磷酸钠、甲苯、二甲苯、六乙基氯化胍中一种或多种；
所述沉析剂包括乙醇、水、甲醇、乙二醇、丙酮中一种或多种。
与现有技术相比，本发明具有以下有益效果：
利用可交联封端剂和不可交联封端剂的组合物对树脂进行封端，使得该树脂同时兼具热塑性树脂的优良的加工性和热固性树脂的良好的耐溶剂性和超低的热膨胀系数，解决两者不能兼顾的问题。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。本领域技术人员在理解本发明的技术方案基础上进行修改或等同替换，而未脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围内。
以下具体实施方式中所采用的原料均购于市场，以下将通过实施例对本发明进行详细描述。以下实施例及对比例中树脂的各项性能测试方法如下：
粘度：将各实施例和对比例制得的聚酰亚胺在30℃下，以N-甲基吡咯烷酮(NMP)为溶剂进行测定。
拉伸强度：采用GB/T 1040.2-2006测得。
弯曲强度：采用GB/T 9341-2008测得。
弯曲模量：采用GB/T 9341-2008测得。
熔融指数：采用GB/T 3682-2000测得，测试条件为340℃；12.5kg。
热膨胀系数测试：采用GB/T 1036-2008测得，测试温度范围是25～150℃。
耐溶剂测试：采用ISO 22088-3-2006方法进行测试。
实施例1
在氮气保护下，将4,4'-双(3-氨基苯氧基)二苯基砜(432.4900g，1000mmol)、4,4'-(4,4-异丙基二苯氧基)双(邻苯二甲酸酐)(510.0802g,980mmol)、邻苯二甲酸酐(3.5546g,24mmol)、3-苯炔基苯酐(3.9718g,16mmol)以及3800g邻二氯苯混合，升温至180℃，回流条件下反应14h，得到聚酰亚胺溶液；将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空250℃处理2h，得到聚酰亚胺树脂S1，结构如下：
实施例2
在氮气保护下，将4,4'-双(3-氨基苯氧基)二苯基砜(432.4900g，1000mmol)、均苯四甲酸二酐(171.0061g,784mmol)、1,2,3,4-连苯四酸二酐(42.7515g,196mmol)、50mL异喹啉、3700g间甲酚混合，升温至180℃，回流条件下反应8h后，加入2,3-萘二羧酸酐(4.9545g,25mmol)以及3-苯炔基苯酐(3.7236g,15mmol,)继续反应6h，得到聚酰亚胺溶液。将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空250℃处理2h，得到聚酰亚胺树脂S2，结构如下：
实施例3
在氮气保护下，将4,4'-二氨基二苯砜(248.3g,1000mmol)、2,2',3,3'-三苯二醚四甲酸二酐(191.0973g,475mmol)、3,3',4,4'-三苯二醚四甲酸二酐(191.0973g,475mmol)、2g苯基次磷酸钠、1500g邻苯二甲醚混合，升温至200℃，回流条件下反应6h后，加入3,4-联苯二羧酸酐(6.7263g,30mmol)继续反应6h后，继续加入4-苯炔基苯酐(17.3768g,70mmol)再反应6h，得到聚酰亚胺溶液。将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空380℃处理2h，得到聚酰亚胺树脂S3，结构如下：
实施例4
在氮气保护下，分别将3,3'-二氨基二苯砜(198.64g,800mmol)与4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)(249.8352g,480mmol)、1800g二甲乙酰胺混合；对苯二胺(21.628g,200mmol)与3,3'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)(249.8352g,480mmol)、1000g二甲基乙酰胺混合，两者同时室温反应6h后，将两种聚酰胺酸溶液混合继续室温反应12h后加入马来酸酐(3.9224g,40mmol)、3,4-二羧基苯基苯砜酐(11.5308g,40mmol)继续反应4h后加入乙酸酐(255.2250g，2500mmol)以及吡啶(79.1000g,1000mmol)，80℃反应2h，得到聚酰亚胺溶液。将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空280℃处理2h，得到聚酰亚胺S4，结构如下：
实施例5
在氮气保护下，将2,2-双[4-(4-氨基苯氧基)苯基]丙烷(358.3752g,873mmol)、间苯二胺(10.4896g,97mmol)、4,4'-氧双邻苯二甲酸酐(310.2200g,1000mmol)、2700g N-甲基吡咯烷酮混合，室温反应12h后加入5-降冰片烯-2-甲胺(3.6960g,30mmol)、4-氨基苯基醚(5.5569g,30mmol)继续反应8h后加入700g二甲苯升温至180℃回流带水8h，得到聚酰亚胺溶液。将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空380℃处理2h，得到聚酰亚胺S5，其结构如下：
实施例6
在氮气保护下，将4,4'-双(3-氨基苯氧基)二苯基砜(432.4900g，1000mmol)、4,4'-(4,4-异丙基二苯氧基)双(邻苯二甲酸酐)(468.4410g,900mmol)、邻苯二甲酸酐(17.7730g,120mmol)、3-苯炔基苯酐(19.8590g,80mmol)以及3750g邻二氯苯混合，升温至180℃，回流条件下反应14h，得到聚酰亚胺溶液；将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空250℃处理2h，得到聚酰亚胺树脂S6，结构如下：
对比例1
在氮气保护下，将4,4'-双(3-氨基苯氧基)二苯基砜(432.4900g，1000mmol)、4,4'-(4,4-异丙基二苯氧基)双(邻苯二甲酸酐)(510.0802g,980mmol)、邻苯二甲酸酐(5.9244g,40mmol)以及3800g邻二氯苯混合，升温至180℃，回流条件下反应14h，得到聚酰亚胺溶液。将所得聚酰亚胺溶液冷却至室温，倒入乙醇中析出固体粉末，过滤得固体粉末，用乙醇洗涤两次，真空320℃处理2h，得到聚酰亚胺D1，其结构如下：
对各实施例和对比例制备的聚酰亚胺进行粘度、注塑样条进行力学性能测试结果如表1所示，熔融指数测试结果如表2所示。注塑样条浸泡在甲基乙基酮中168h，并进行应力-应变测试，检查其开裂情况结果汇总于表3。
表1实施例和对比例制备的聚酰亚胺树脂的粘度和力学性能
表2实施例1和对比例1的聚酰亚胺树脂熔融指数和热膨胀系数
表3样条开裂情况
从表中数据可见，由S1与S6比较可发现封端剂量添加量的多少影响树脂的加工性能，加入太多封端剂不能得到有力学性能的注塑件；S1与D1的比对体现出虽然引入半封端结构略微影响了树脂的熔体流动性，但降低了树脂的热膨胀系数。表3可发现引入半交联结构提高了树脂的耐溶剂性，但是分步加入封端剂会产生完全不可交联端基封端的以及完全可交联端基封端的分子链，会影响树脂的耐溶剂性。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。
Claims (10)
1.一种可交联的热塑性聚酰亚胺树脂，其特征在于，所述热塑性聚酰亚胺树脂具有如下结构式：
其中，Ar1是二胺类化合物的残基，Ar2是二酐类化合物的残基，EG为封端剂，n是大于1的整数；所述封端剂的摩尔量为二胺类化合物和二酐类化合物总摩尔量的0.5-10％；
所述封端剂包括可交联封端剂和不可交联封端剂，其中可交联封端剂与不可交联封端剂的摩尔比为3:1～1:2；所述封端剂为单酐或单胺的化合物；
所述热塑性聚酰亚胺树脂熔融指数为1～50 g/10 min，热膨胀系数为3.0*10-5～5.0*10-5。
2.根据权利要求1所述的可交联的热塑性聚酰亚胺树脂，其特征在于，所述可交联封端剂选自如下结构中一种或多种：
3.根据权利要求1所述的可交联的热塑性聚酰亚胺树脂，其特征在于，所述不可交联封端剂选自如下结构中一种或多种：
4.根据权利要求1所述的可交联的热塑性聚酰亚胺树脂，其特征在于，所述封端剂的摩尔量为二胺类化合物和二酐类化合物总摩尔量的1-6％；
所述封端剂包括可交联封端剂和不可交联封端剂，其中可交联封端剂与不可交联封端剂的摩尔比为1:1～3:2。
5.根据权利要求1所述的可交联的热塑性聚酰亚胺树脂，其特征在于，所述可交联封端剂选自如下结构中一种或多种：
所述不可交联封端剂选自如下结构中一种或多种：
6.根据权利要求1所述的可交联的热塑性聚酰亚胺树脂，其特征在于，所述Ar1选自下列基团中的一种或几种：
所述Ar2选自下列基团中的一种或几种：
7.根据权利要求1所述的可交联的热塑性聚酰亚胺树脂，其特征在于，所述EG的摩尔量为Ar1和Ar2摩尔之差的两倍。
8.根据权利要求1-7任一项所述的可交联的热塑性聚酰亚胺树脂的制备方法，其特征在于，包括步骤：在氮气保护下，将二胺、二酐、封端剂、溶剂和成环剂混合，升温进行聚合反应得到聚酰亚胺聚合溶液；将聚酰亚胺聚合溶液在沉淀剂中析出，过滤干燥得到所述热塑性聚酰亚胺树脂。
9.根据权利要求8所述的可交联的热塑性聚酰亚胺树脂的制备方法，其特征在于，包括步骤：
步骤1，在氮气保护下，将二胺、二酐、溶剂和成环剂混合，升温进行聚合得到聚酰亚胺前驱体溶液；
步骤2，向步骤1的聚酰亚胺前驱体溶液中加入封端剂继续反应，得到聚酰亚胺聚合溶液，将聚合溶液在沉析剂中析出，过滤干燥得到所述热塑性聚酰亚胺树脂。
10.根据权利要求8所述的可交联的热塑性聚酰亚胺树脂的制备方法，其特征在于，所述溶剂包括邻二氯苯、间甲酚、邻苯二甲醚、二甲乙酰胺、N-甲基吡咯烷酮、二甲亚砜中一种或多种；
和/或，所述成环剂包括邻二氯苯、异喹啉、苯基次磷酸钠、甲苯、二甲苯、六乙基氯化胍中一种或多种；
和/或，所述沉析剂包括乙醇、水、甲醇、乙二醇、丙酮中一种或多种。
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