CN111825839A - 一种低介电聚酰亚胺、其制备方法及低介电聚酰亚胺薄膜 - Google Patents
一种低介电聚酰亚胺、其制备方法及低介电聚酰亚胺薄膜 Download PDFInfo
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Abstract
本发明提供的一种低介电聚酰亚胺。本发明还提供了上述高性能低介电聚酰亚胺的制备方法。本发明还提供了一种低介电聚酰亚胺薄膜，包括所述低介电聚酰亚胺、含氟硅氧烷、多孔壳聚糖；其中，含氟硅氧烷的质量为低介电聚酰亚胺质量的1‑2％，多孔壳聚糖为低介电聚酰亚胺质量的0.5‑1％。本发明的聚酰亚胺薄膜，采用特殊的聚酰亚胺大大降低了介电常数，兼具优良的耐热稳定性、高玻璃化转变温度、高透明性以及优异的阻燃性能，同时通过添加含氟硅氧烷、多孔壳聚糖，获得一种具有低介电常数、高耐水性的聚酰亚胺薄膜，并且在改善上述性能的同时不会损伤聚酰亚胺薄膜自身的绝缘性能及各项力学性能。
Description
技术领域
本发明涉及材料领域，特别涉及一种低介电聚酰亚胺。
背景技术
聚酰亚胺是指主链上含有酰亚胺环(-CO-NH-CO-)的一类聚合物，其中以含有酞酰亚胺结构的聚合物最为重要。聚酰亚胺是综合性能最佳的有机高分子材料之一，具有耐高温、低介电常数、耐腐蚀等优点，其耐高温性能达到400℃以上，长期使用温度范围为-200～300℃，具有很高的绝缘性能。聚酰亚胺作为一种特种工程材料，已广泛应用在航空、航天、微电子、纳米、液晶、分离膜、激光等领域，并成为一种综合性能优异的不可替代的功能性材料。
聚酰亚胺(PI)具有优异的耐热性、良好的机械性能、稳定的化学性能、优良的介电性能、无毒、耐辐照等性能，而且制备工艺相对简单，综合性能优良，正受到越来越多的重视。
制备低介电常数聚酰亚胺薄膜的方法有多种，包括：
一、引入含氟基团或以氟取代氢合成低介电常数聚酰亚胺：即利用含氟二酐和二胺反应生成预聚物(聚酰胺酸或聚酰胺酯)，再通过化学亚胺化或热处理得到含氟聚酰亚胺。目前研究最多的是部分氟代聚酰亚胺，因为全氟代聚酰亚胺单体种类较少，毒性较大，且很难合成，成本很高。
二、含芴基团的低介电常数聚酰亚胺：由于芴基具有庞大的自由体积及稠环结构，使得含芴基的聚酰亚胺具有较好的溶解性能、热氧化稳定性能、机械性能、低介电常数与介电损耗等。广泛应用在微电子、分离膜及先进显示屏等高新技术产业。
三、聚酰亚胺/二氧化硅复合材料：将SiO2前驱体与水的混合溶液加入到聚酰胺酸溶液中搅拌，得到SiO2和聚酰胺酸的混合溶液，再通过适当的方法制膜。最后，经过亚胺化热处理制得聚酰亚胺和纳米SiO2复合材料。
四、纳孔化低介电常数聚酰亚胺：如上文所述，利用空气的低介电常数(接近1)，在聚酰亚胺薄膜材料中引入纳米级的孔洞，可以有效的降低材料的介电常数。
显然，在制备低介电常数聚酰亚胺薄膜的四种方法中，以第四种即纳孔化最为简单易行，适用范围最广。借鉴其他领域纳孔材料的制备方法，可通过二次沉积法、溶胶凝胶法、热分解法、超临界发泡法等手段在聚酰亚胺薄膜中构建纳孔结构。但所得纳孔孔径往往分布较宽(均匀性差)，使得材料的应用性能变差。如在微电子领域，含有大量孔径不均匀纳孔结构的聚酰亚胺薄膜往往耐电击穿性能很差，而此性能显然是电介质材料的重要性能之一。有鉴于此，需要提供新方法在聚酰亚胺薄膜中构建均匀的纳孔结构，并进而制备出具有超低介电常数的聚酰亚胺薄膜。
然而，目前聚酰亚胺的介电常数仍然不能满足要求。
发明内容
技术问题：为了解决现有技术的缺陷，本发明提供了一种低介电聚酰亚胺及其制备方法与应用。
本发明还提供了一种低介电聚酰亚胺薄膜。
技术方案：本发明提供的本发明提供的一种低介电聚酰亚胺，其结构式如式V所示：
本发明还提供了上述高性能低介电聚酰亚胺的制备方法，包括以下步骤：
(1)式VI所示的化合物与式VII所示的化合物反应，得式VIII所示的中间体；
(2)VIII所示的中间体反应，得式V所示的化合物；
反应式如下：
优选地，低介电聚酰亚胺的制备方法，包括以下步骤：
(1)在氮气保护和一定温度条件下，式VI所示的化合物与式VII所示的化合物在有机溶剂中搅拌反应，得式VIII所示的中间体；
(2)加入脱水剂和催化剂，VIII所示的中间体于一定温度下继续搅拌反应，清洗，过滤，烘干，得式V所示的化合物。
步骤(1)中，所述有机溶剂为N-甲基吡咯烷酮、N，N-二甲基乙酰胺或N，N-二甲基甲酰胺的一种；反应温度为5-25℃。
步骤(2)中，所述脱水剂为三氟乙酸酐、乙酸酐、氯化亚砜或有机硅化合物的一种或几种的混合物；脱水剂与化合物VII的摩尔比为3:1～5:1。
步骤(2)中，所述催化剂为三乙胺或吡啶中的一种或两种混合，催化剂与化合物VII的摩尔比为2:1～4:1。
步骤(2)中，反应温度为40～60℃。
本发明还提供了上述低介电聚酰亚胺在柔性AMOLED中的应用。
本发明还提供了一种低介电聚酰亚胺薄膜，包括所述低介电聚酰亚胺、含氟硅氧烷、多孔壳聚糖；其中，含氟硅氧烷的质量为低介电聚酰亚胺质量的1-2％，多孔壳聚糖为低介电聚酰亚胺质量的0.5-1％。
优选地，所述含氟硅氧烷为七氟戊基三乙氧基硅烷、七氟戊基三甲氧基硅烷、七氟戊基三氯硅烷、全氟辛基乙基三氯硅烷、全氟辛基乙基三甲氧基硅烷、全氟辛基乙基三乙氧基硅烷、十三氟辛基三乙氧基硅烷、十三氟辛基三甲氧基硅烷、十三氟辛基三氯硅烷中的一种或几种。
本发明还提供了上述低介电聚酰亚胺薄膜的制备方法，包括以下步骤：
(1)将含氟硅氧烷和壳聚糖分别加入有机溶剂中，得到含氟硅氧烷溶液和壳聚糖溶液；
(2)将所述低介电聚酰亚胺加热至50-60℃，恒温搅拌；再滴加含氟硅氧烷溶液，边滴加边搅拌；搅拌并自然降温至30-40℃，降温同时滴加壳聚糖溶液；
(3)将步骤(2)的产物制成薄膜，即为低介电聚酰亚胺薄膜。
本发明还提供了上述低介电聚酰亚胺在高频通讯中的应用。
有益效果：本发明的聚酰亚胺薄膜，采用特殊的聚酰亚胺大大降低了介电常数，兼具优良的耐热稳定性、高玻璃化转变温度、高透明性以及优异的阻燃性能，同时通过添加含氟硅氧烷、多孔壳聚糖，获得一种具有低介电常数、高耐水性的聚酰亚胺薄膜，并且在改善上述性能的同时不会损伤聚酰亚胺薄膜自身的绝缘性能及各项力学性能。
具体实施方式
下面对本发明作出进一步说明。
以下实施例中，反应式如下：
实施例1
低介电聚酰亚胺的制备方法，包括以下步骤：
(1)在氮气保护和一定温度条件下，式VI所示的化合物与式VII所示的化合物在有机溶剂中搅拌反应，得式VIII所示的中间体；所述有机溶剂为N-甲基吡咯烷酮；反应温度为15℃；
(2)加入脱水剂和催化剂，VIII所示的中间体于一定温度下继续搅拌反应，清洗，过滤，烘干，得式V所示的化合物；所述脱水剂为三氟乙酸酐；脱水剂与化合物VII的摩尔比为4:1；所述催化剂为三乙胺，催化剂与化合物VII的摩尔比为3:1；反应温度为50℃。
聚合物分子结构评价方法：傅里叶红外光谱(FT-IR)：将制备的PI薄膜在红外光谱仪(德国Bruker Tensor-27)进行；
实施例1制备得到的聚合度为1的聚酰亚胺红外光谱图显示：波数1781cm-1和1702cm-1处分别出现了聚酰亚胺环上羰基C＝O不对称和对称伸展峰，1355cm-1归属于酰亚胺环上C-N伸展峰，738cm-1归属于酰亚胺环上C＝O弯曲振动吸收峰，1607cm-1对应于苯环的特征峰。
实施例2
低介电聚酰亚胺的制备方法，包括以下步骤：
(1)在氮气保护和一定温度条件下，式VI所示的化合物与式VII所示的化合物在有机溶剂中搅拌反应，得式VIII所示的中间体；所述有机溶剂为N，N-二甲基乙酰胺；反应温度为5℃；
(2)加入脱水剂和催化剂，VIII所示的中间体于一定温度下继续搅拌反应，清洗，过滤，烘干，得式V所示的化合物；所述脱水剂为乙酸酐；脱水剂与化合物VII的摩尔比为5:1；所述催化剂为吡啶，催化剂与化合物VII的摩尔比为4:1；反应温度为40℃。
实施例3
低介电聚酰亚胺的制备方法，包括以下步骤：
(1)在氮气保护和一定温度条件下，式VI所示的化合物与式VII所示的化合物在有机溶剂中搅拌反应，得式VIII所示的中间体；所述有机溶剂为N，N-二甲基甲酰；反应温度为25℃；
(2)加入脱水剂和催化剂，VIII所示的中间体于一定温度下继续搅拌反应，清洗，过滤，烘干，得式V所示的化合物；所述脱水剂为氯化亚砜；脱水剂与化合物VII的摩尔比为3:1；所述催化剂为三乙胺，催化剂与化合物VII的摩尔比为2:1；反应温度为60℃。
实施例4
低介电聚酰亚胺薄膜的制备方法，包括以下步骤：
(1)将含氟硅氧烷和壳聚糖分别加入有机溶剂中，得到含氟硅氧烷溶液和壳聚糖溶液；
(2)将实施例1的低介电聚酰亚胺加热至55℃，恒温搅拌；再滴加含氟硅氧烷溶液，边滴加边搅拌；搅拌并自然降温至305℃，降温同时滴加壳聚糖溶液；
(3)将步骤(2)的产物制成薄膜，即为低介电聚酰亚胺薄膜。
制得的低介电聚酰亚胺薄膜，包括实施例1的低介电聚酰亚胺、含氟硅氧烷、多孔壳聚糖；其中，含氟硅氧烷的质量为低介电聚酰亚胺质量的1.5％，多孔壳聚糖为低介电聚酰亚胺质量的0.75％。
所述含氟硅氧烷为质量比1:2的七氟戊基三乙氧基硅烷和七氟戊基三甲氧基硅烷。
实施例5
低介电聚酰亚胺薄膜的制备方法，包括以下步骤：
(1)将含氟硅氧烷和壳聚糖分别加入有机溶剂中，得到含氟硅氧烷溶液和壳聚糖溶液；
(2)将实施例2的低介电聚酰亚胺加热至50℃，恒温搅拌；再滴加含氟硅氧烷溶液，边滴加边搅拌；搅拌并自然降温至30℃，降温同时滴加壳聚糖溶液；
(3)将步骤(2)的产物制成薄膜，即为低介电聚酰亚胺薄膜。
制得的低介电聚酰亚胺薄膜，包括实施例2的低介电聚酰亚胺、含氟硅氧烷、多孔壳聚糖；其中，含氟硅氧烷的质量为低介电聚酰亚胺质量的1％，多孔壳聚糖为低介电聚酰亚胺质量的1％。
所述含氟硅氧烷为质量比1:1的七氟戊基三氯硅烷和全氟辛基乙基三氯硅烷。
实施例6
低介电聚酰亚胺薄膜的制备方法，包括以下步骤：
(1)将含氟硅氧烷和壳聚糖分别加入有机溶剂中，得到含氟硅氧烷溶液和壳聚糖溶液；
(2)将实施例3的低介电聚酰亚胺加热至60℃，恒温搅拌；再滴加含氟硅氧烷溶液，边滴加边搅拌；搅拌并自然降温至40℃，降温同时滴加壳聚糖溶液；
(3)将步骤(2)的产物制成薄膜，即为低介电聚酰亚胺薄膜。
制得的低介电聚酰亚胺薄膜，包括实施例3的低介电聚酰亚胺、含氟硅氧烷、多孔壳聚糖；其中，含氟硅氧烷的质量为低介电聚酰亚胺质量的2％，多孔壳聚糖为低介电聚酰亚胺质量的0.5％。
所述含氟硅氧烷为质量比1:2:1的全氟辛基乙基三甲氧基硅烷、全氟辛基乙基三乙氧基硅烷、十三氟辛基三乙氧基硅烷。
实施例7测试实施例4至6的产品性能
方法：
(1)介电常数(Dk)及损耗因子(Df)测试：将待测样品于去离子水中浸泡10分钟，接着置于烘箱中以温度约110℃烘烤约30分钟进行干燥，以精密阻抗分析仪(型号Agilent4294A)测定该测试样品的Dk/Df值。
(2)热膨胀系数：使用梅特勒公司静态热机械测试仪TMA/SDTA 2+，在测定温度范围为50-200℃，升温速度为10℃/分钟的条件下测定；
(3)力学性能：将聚酰亚胺薄膜分别制作成长宽尺寸为25.4mm×3.2mm的膜材，使用万能试验机(由岛津科学仪器股份有限公司(SHIMADZU)制造，设备名为AG-1S)来测量膜材的抗拉强度(MPa)、伸长率(％)。
(4)吸水率：将烘干至恒重的膜裁成一片约0.2-0.3g大小，80℃下浸泡在去离子水中24小时，随后将膜取出，用纸擦干其表面，迅速的在天平上称重。吸水率S可由公式算出S＝(Ws–Wd)/Wd*100(％)。
结果如下：
Claims (10)
1.一种低介电聚酰亚胺，其结构式如式V所示：
2.权利要求1所述的低介电聚酰亚胺的制备方法，其特征在于：包括以下步骤：
(1)式VI所示的化合物与式VII所示的化合物反应，得式VIII所示的中间体；
(2)VIII所示的中间体反应，得式V所示的化合物；
反应式如下：
3.根据权利要求2所述的一种低介电聚酰亚胺的制备方法，其特征在于：包括以下步骤：
(1)在氮气保护和一定温度条件下，式VI所示的化合物与式VII所示的化合物在有机溶剂中搅拌反应，得式VIII所示的中间体；
(2)加入脱水剂和催化剂，VIII所示的中间体于一定温度下继续搅拌反应，清洗，过滤，烘干，得式V所示的化合物。
4.根据权利要求3所述的一种低介电聚酰亚胺的制备方法，其特征在于：步骤(1)中，所述有机溶剂为N-甲基吡咯烷酮、N，N-二甲基乙酰胺或N，N-二甲基甲酰胺的一种；反应温度为5-25℃。
5.根据权利要求3所述的一种低介电聚酰亚胺的制备方法，其特征在于：步骤(2)中，所述脱水剂为三氟乙酸酐、乙酸酐、氯化亚砜或有机硅化合物的一种或几种的混合物；脱水剂与化合物VII的摩尔比为3:1～5:1；所述催化剂为三乙胺或吡啶中的一种或两种混合，催化剂与化合物VII的摩尔比为2:1～4:1；反应温度为40～60℃。
6.权利要求1所述的低介电聚酰亚胺在高频通讯中的应用。
7.一种低介电聚酰亚胺薄膜，其特征在于：包括权利要求1的低介电聚酰亚胺、含氟硅氧烷、多孔壳聚糖；其中，含氟硅氧烷的质量为低介电聚酰亚胺质量的1-2％，多孔壳聚糖为低介电聚酰亚胺质量的0.5-1％。
8.根据权利要求7所述的一种低介电聚酰亚胺薄膜，其特征在于：所述含氟硅氧烷为七氟戊基三乙氧基硅烷、七氟戊基三甲氧基硅烷、七氟戊基三氯硅烷、全氟辛基乙基三氯硅烷、全氟辛基乙基三甲氧基硅烷、全氟辛基乙基三乙氧基硅烷、十三氟辛基三乙氧基硅烷、十三氟辛基三甲氧基硅烷、十三氟辛基三氯硅烷中的一种或几种。
9.权利要求8所示的低介电聚酰亚胺薄膜的制备方法，其特征在于：包括以下步骤：
(1)将含氟硅氧烷和壳聚糖分别加入有机溶剂中，得到含氟硅氧烷溶液和壳聚糖溶液；
(2)将权利要求1所述的低介电聚酰亚胺加热至50-60℃，恒温搅拌；再滴加含氟硅氧烷溶液，边滴加边搅拌；搅拌并自然降温至30-40℃，降温同时滴加壳聚糖溶液；
(3)将步骤(2)的产物制成薄膜，即为低介电聚酰亚胺薄膜。
10.权利要求7所述的低介电聚酰亚胺在高频通讯中的应用。
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| CN111081470A (zh) * | 2019-12-19 | 2020-04-28 | 南京中鸿润宁新材料科技有限公司 | 一种聚酰亚胺电容器 |
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Application publication date: 20201027 |