CN104497572A - 一种无色高透明型的聚酰亚胺薄膜及其制备方法 - Google Patents
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Abstract
本发明提供了一种聚酰亚胺，用于制备该聚酰亚胺的聚酰胺酸、聚酰胺酸溶液及其制备方法，含有该聚酰亚胺的薄膜及其制备方法。其中聚酰胺酸由摩尔比为0.9-1∶1的芳香族四酸二酐和芳香族二胺反应制备而成，其中，所述芳香族四酸二酐为式A、式B或式C所示化合物：
Description
技术领域
本发明属于高分子材料领域，具体涉及一种聚酰胺酸及其制备方法，还涉及一种上述聚酰胺酸亚胺化而成的聚酰亚胺，还涉及一种聚酰亚胺薄膜及其制备方法。
背景技术
我国对聚酰亚胺的研究开发始于1962年，1963年漆包线问世，1966年后薄膜、模塑料、粘合剂相继问世。到目前为止，研究开发形成合理的格局，长春应用化学研究所以聚联苯四甲酰亚胺的研究开发为主，中科院化学所专门从事PMR聚酰亚胺的研究开发，四川联合大学(成都科技大学)研究双马来酰亚胺树脂及制品，西北工业大学以聚氨基酰亚胺的研究开发为主，上海市合成树脂研究所以研究开发聚均苯四甲酰亚胺、聚醚酰亚胺为主，桂林电器科学研究所以研究开发聚酰亚胺薄膜的流延装置为主。据不完全统计，聚酰亚胺的研究开发和应用单位约50多家，主要研究生产厂家约20家。生产发展已初具规模，目前全国生产能力已达700t/a，随着我国航空、航天、电器、电子工业和汽车工业的发展,聚酰亚胺行业也会有大的发展。
无色高透明性聚酰亚胺(PI)是功能性聚酰亚胺材料研究领域内的热点研究话题之一。无色透明性PI材料在许多高技术领域中均具有广泛的应用，例如在光纤通讯领域内用于制作光波导管，在航空航天领域用作太阳能电池阵列的基板材料以及天线反射/收集器材料等。但是传统的聚酰亚胺膜材很难做到高透明性，如以均苯四酐和4,4'-二苯醚二胺合成的聚酰亚胺(PMDA/4,4’-ODA)为代表的那样，通常的聚酰亚胺的可见光吸收端延长至500nm左右，着色成黄褐色或茶褐色。故需要在保持聚酰亚胺原有的特性上进行改性开发新品，以提高聚酰亚胺材料的透明性。
另外，聚酰亚胺由四酸二酐与二胺聚合而成，合成方法有一步合成法、二步合成法、三步合成法和气相沉积法，其中气相沉积法是二胺和二酐的蒸气在高温下分别单独送入混炼室，混合生成薄膜，是由单体直接合成PI涂层的方法。此法需要高温，控制比较困难。也需要对聚酰亚胺的制备方法进行改进。
发明内容
本发明的第一个目的是克服现有聚酰亚胺材料着色成黄褐色或茶褐色，透光性低的缺陷，提供一种无色高透明型的聚酰亚胺薄膜，还提供了一种用于制备上述聚酰亚胺薄膜的聚酰亚胺和聚酰胺酸。本发明的第二个目的是克服现有聚酰亚胺制备工艺难控制的缺陷，提供了一种采用聚酰胺酸溶液热胺化制备成聚酰亚胺薄膜的制备方法，易控制。
本发明的第一个方面是提供了一种聚酰胺酸，由摩尔比为0.9-1∶1的芳香族四酸二酐和芳香族二胺反应制备而成，其中，所述芳香族四酸二酐为式A、式B或式C所示化合物：
所述芳香族二胺为1,4-双(3'-氨基-5'-三氟甲基苯氧基)联苯。
本发明的第二个方面是提供一种聚酰亚胺，由本发明第一个方面所述的聚酰胺酸亚胺化制备而成。
本发明的第三个方面是提供一种聚酰胺酸溶液含有本发明第一个方面所述的聚酰胺酸和有机溶剂。
优选地，所述聚酰亚酸溶液的固含量为22-28％。
优选地，所述聚酰亚酸溶液的固含量为25％。
优选地，所述聚酰亚酸溶液的表观粘度为15500-20000CPS。
优选地，所述有机溶剂为非质子极性溶剂，所述非质子极性溶剂为化工领域常用的非质子极性溶剂。例如可以为二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜等中的一种或多种。
本发明的第四个方面是提供一种本发明第三个方面所述的聚酰胺酸溶液的制备方法，将芳香族二胺溶解在有机溶剂，惰性气体保护下加入芳香族四酸二酐，搅拌反应15-22h，既得。
优选地，对所得产品进行脱泡处理。
优选地，对所得产品进行过滤处理，以除掉可能存在的不溶物。
本发明的第五个方面是提供一种聚酰亚胺薄膜，所述聚酰亚胺薄膜含有本发明第二个方面所述的聚酰亚胺。
本发明的第六个方面是提供一种本发明第五个方面所述的聚酰亚胺薄膜制备方法，将本发明第三个方面所述的聚酰胺酸溶液、或由本发明第四个方面所述的制备方法制得的聚酰胺酸溶液涂覆在支持体上，热胺化，既得。
优选地，采用阶梯升温法使聚酰胺酸溶液胺化成聚酰亚胺薄膜。
进一步优选地，阶梯升温程序如下：
1-3h内升温至200℃，恒温0.5-2h；然后0.2-1h内升温至300℃，恒温0.2-1h；再0.5-2h内升温至350℃，恒温0.5-2h；最后2-4h内降温至室温。
本发明的聚酰亚胺具有优良的综合性能，在保持良好的耐热性能和力学性能的同时，提高了介电性能与可见光范围内的透光性，在光通讯领域具有广泛的发展和应用前景。
具体实施方式
下面结合具体的实施例对本发明作进一步的描述，以更好地理解本发明。
实施例1
取1000ml三口瓶中加入350ml二甲基乙酰胺(DMAC)，加入1mol1,4-双(3'-氨基-5'-三氟甲基苯氧基)联苯，搅拌20min，溶解完全，得到浅黄色溶液，冲入氮气进行保护，再加入0.99mol的式A所示芳香族四酸二酐：
搅拌，溶液逐渐变粘稠，用DMAC进行固含量的调节，使之达到25％。将该反应液在氮气的保护下搅拌反应18h得到近似无色的聚酰胺酸(PPA)粘稠液。把PAA粘稠液进行真空脱泡，再用5um Teflon过滤器除去不溶物以得到均匀的表观粘度为15500-20000CPS的PAA粘稠液。
将该粘稠液均匀涂覆在干净的30cm×50cm玻璃板上，然后用高温无氧烤箱进行环化，环化的程式如下：
| 室温-200℃ | 200℃ | 200-300℃ | 300℃ | 300-350℃ | 350℃ | 350℃-室温 |
| 2h | 1h | 1h | 0.5h | 1h | 1h | 3h |
通过程式环化后得到接近透明色的聚酰亚胺薄膜(PI-A)。
实施例2
本实施例与实施例1的不同之处在于，采用式B所示芳香族四酸二酐代替式A所示芳香族四酸二酐，制得表观粘度为15500-20000CPS的聚酰胺酸粘稠液，最终得到聚酰亚胺薄膜(PI-B)。
实施例3
本实施例与实施例1的不同之处在于，采用式C所示芳香族四酸二酐代替式A所示芳香族四酸二酐，制得表观粘度为15500-20000CPS的聚酰胺酸粘稠液，最终得到聚酰亚胺薄膜(PI-C)。
性能测试
对实施例1-3提供的样品进行性能测试，结果如表2、表3和表4所示。其中要达到的技术指标如表1所示。
表1 要达到的技术指标
表2 热性能
| Tg(℃) | Td(℃) | T10％(℃) | Rw(％) |
| PI-A | 281.5 | 615.8 | 636.3 | 68 |
| PI-B | 290.2 | 600.1 | 618.4 | 72 |
| PI-C | 292.4 | 618.8 | 640.3 | 67 |
*Tg：玻璃化转变温度；Td：起始热解温度；T10％：10％失重温度；Rw：在700℃时残余质量分数。
由表2可知，实施例1-3在氮气中表现出了相近的耐热性能，且PI-A的起始热分解温度与10％失重温度略低于PI-B，比PI-C低11℃，其它热性能参数基本接近。这种优良的耐热稳定性是由于在酐与胺分子结构中存在刚性基团的缘故，PI-B的不对称的结构对聚酰亚胺的耐热性的负面性比较小。
表3力学性能与介电性能
| Ts(MPa) | Eb(％) | Tm(GPa) | Ds(V/um) | Dk(1MHz) | Df | |
| PI-A | 114.2 | 12 | 2.28 | 105.6 | 2.85 | 0.0012 |
| PI-B | 105.9 | 11 | 2.09 | 100.4 | 2.67 | 0.0005 |
| PI-C | 120.5 | 13 | 2.5 | 110.2 | 3.05 | 0.0037 |
*Ts：抗拉强度；Eb：断裂伸长率；Tm：拉伸模量；Ds：击穿强度；Dk：介电常数；Df：介电损耗；
由表3可知，三种PI薄膜都具有较好的力学性能，由于引入了环氧基对拉伸强度与断裂伸长率有轻微的影响，但也比较的好；PI-B的介电常数与介电损耗最低，是由于分子结构中含有低摩尔极化率的三氟甲基和不对称分子结构利于增大分子链的自由体积，故表现出优异的低介电常数与介电损耗。
表4光学性能与吸水率
| T400nm(％) | λcutoff(nm) | Wu(％) | |
| PI-A | 80 | 335 | 0.55 |
| PI-B | 90 | 286 | 0.62 |
| PI-C | 75 | 342 | 0.48 |
*T400nm：在400nm处透光率；λcutoff：紫外线截止波长；Wu：吸水率；
由表4可知，PI-B薄膜的透光性比PI-A与PI-C都好，且宽范围的波长范围也具有良好的透明性，由于不对称分子的结构减弱了CTC的形成，分子中含有高电负性的三氟甲基印制CTC的形成，故PI-B的透明性最好；由于三氟甲基属疏水性的故具有低的吸水率，PI-B与PI-A中含有环氧基团导致吸水率比PI-C高些，PI-B分子链具有较大的自由体积使得吸水率稍高些。
总结：上述性能表明合成的透明聚酰亚胺薄膜具有优良的综合性能。采用不对称结构(PI-B)使聚酰亚胺保持原有的耐热性能、力学性能的同时，提高其介电性能与可见光范围内的透明性。PI-B薄膜优良的性能使得在光通讯领域得到广泛的发展和应用。
为了更好地比较采用不同芳香族四酸二酐对聚酰亚胺材料的影响，实施例1-3的采用相同的制备条件，应当理解的是，采用其他反应(15-22h)也能得到性质相似的聚酰亚胺材料。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。
Claims (10)
1.一种聚酰胺酸，其特征在于，由摩尔比为0.9-1∶1的芳香族四酸二酐和芳香族二胺反应制备而成，其中，所述芳香族四酸二酐为式A、式B或式C所示化合物：
所述芳香族二胺为1,4-双(3'-氨基-5'-三氟甲基苯氧基)联苯。
2.一种聚酰亚胺，其特征在于，由权利要求1所述聚酰胺酸亚胺化制备而成。
3.一种聚酰胺酸溶液，其特征在于，含有权利要求1所述的聚酰胺酸和有机溶剂。
4.根据权利要求3所述的聚酰胺酸溶液，其特征在于，所述聚酰亚酸溶液的固含量为22-28％。
5.根据权利要求4所述的聚酰胺酸溶液，其特征在于，所述聚酰亚酸溶液的固含量为25％。
6.根据权利要求3所述的聚酰胺酸溶液，其特征在于，所述聚酰亚酸溶液的表观粘度为15500-20000CPS。
7.一种权利要求4-6中任意一项所述的聚酰胺酸溶液的制备方法，其特征在于，将芳香族二胺溶解在有机溶剂，惰性气体保护下加入芳香族四酸二酐，搅拌15-22h，既得。
8.一种聚酰亚胺薄膜，其特征在于，所述聚酰亚胺薄膜含有权利要求2所述的聚酰亚胺。
9.一种权利要求8所述的聚酰亚胺薄膜的制备方法，其特征在于，将权利要求3-6中任意一项所述的聚酰胺酸溶液、或由权利要求7所述的制备方法制得的聚酰胺酸溶液涂覆在支持体上，热胺化，既得。
10.根据权利要求9所述的制备方法，其特征在于，采用阶梯升温法使聚酰胺酸溶液胺化成聚酰亚胺薄膜，阶梯升温程序如下：
1-3h内升温至200℃，恒温0.5-2h；然后0.2-1h内升温至300℃，恒温0.2-1h；再0.5-2h内升温至350℃，恒温0.5-2h；最后2-4h内降温至室温。
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| KR20170076114A (ko) * | 2015-12-24 | 2017-07-04 | 주식회사 두산 | 신규 구조의 산이무수물 모노머를 적용한 폴리아믹산 용액 및 이를 포함하는 폴리이미드 필름 |
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| KR102465044B1 (ko) * | 2015-12-24 | 2022-11-09 | 주식회사 두산 | 신규 구조의 산이무수물 모노머를 적용한 폴리아믹산 용액 및 이를 포함하는 폴리이미드 필름 |
| CN105461923A (zh) * | 2015-12-25 | 2016-04-06 | 南京理工大学 | 一种聚酰亚胺薄膜及其制备方法 |
| CN105461923B (zh) * | 2015-12-25 | 2018-01-05 | 南京理工大学 | 一种聚酰亚胺薄膜及其制备方法 |
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