CN110951059B - 一种热致性液晶高分子材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种热致性液晶聚合物(TLCP)及其制备方法，属于液晶高分子材料领域，同时属于有机化学合成技术领域。
Description
技术领域
本发明涉及一种热致性液晶聚合物(TLCP)及其制备方法，属于液晶高分子材料领域，同时属于有机化学合成技术领域。
背景技术
热致性液晶聚合物(TLCP)是一种高性能材料。在熔融状态下，TLCP呈现液晶性，并具有规整的直链结构，冷却后分子排列方式依然保持不变，采用这种材料加工出的产品，尺寸稳定性好，耐高温，强度不亚于金属和陶瓷，性能远超一般的工程塑料，基于上述优点，TLCP被誉为“超级工程塑料”，可广泛应用在消费电子、汽车、医疗、体育器械等领域。自从20世纪70年代Jackson报道了第一个热致性液晶聚酯后，人们对热致性液晶聚芳酯展开了大规模的研究。
热致性液晶聚合物与其它有机高分子材料相比，具有较为独特的分子结构和热行为，它的分子由刚性棒状大分子链组成，受热熔融或被溶剂溶解后形成一种兼有固体和液体部分性质的液晶态。液晶聚合物的这种特殊相态结构，导致其具有自增强效果、线膨胀系数小、耐热性优良、具有自阻燃性等优点。但作某些模塑制件时，其流动性和热稳定性有待进一步改善。
发明内容
本发明提供了一种热致性液晶聚合物，其特征在于，由对羟基苯甲酸、对苯二酚、对苯二甲酸和4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇经缩聚反应制得。
本发明的一些方案中，上述热致性液晶聚合物，其特征在于，包括以下摩尔百分比的组分：
对羟基苯甲酸30-60％；
对苯二酚10-20％；
对苯二甲酸10-30％；
4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇5-10％，
上述4种组分的摩尔数之和为100％。
本发明还提供了热致性液晶聚合物的制备方法，其特征在于，包括熔融聚合步骤和固相缩聚步骤。
本发明的一些方案中，上述熔融聚合步骤中，在氮气保护下，以醋酸镁或醋酸锌为催化剂，以醋酸酐为酰化剂，在130-150℃下乙酰化2-5小时，然后匀速升温至340-360℃，此升温过程持续2.5-3小时，升温完毕后，保持340-360℃继续反应0.5-2小时，抽真空后制得预聚物。
本发明的一些方案中，上述固相缩聚步骤为在40Pa，低于预聚物熔点30-55℃条件下反应5-15小时。
本发明的一些方案中，催化剂的量为单体重量的0.001-0.005％。
本发明的一些方案中，上述熔融聚合步骤和固相缩聚步骤中间包括预聚物真空干燥过程。
本发明的一些方案中，上述真空干燥温度为110-130℃。
本发明的一些方案中，上述真空干燥时间为1-3小时。
本发明所述的热致性液晶聚合物及其制备方法，取得的优异效果在于：
热致性液晶聚合物在其链结构中引入4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇重复单元后，除了具有通常热致性液晶聚合物的优良性能之外，还赋予了含该重复单元的液晶聚合物具有较好的流动性和良好的热稳定性；使得产品工艺应用价值增加，可广泛用于电子电器及其它精密设备等领域。
具体实施方式
下面结合具体实施，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。本发明实施例中所用原料或仪器，若非特别说明，均市售可得。
实施例1
将对羟基苯甲酸690.15g(5mol)、对苯二酚220.08g(2mol)、对苯二甲酸415.08g(2.5mol)和4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇145.06g(0.5mol)、醋酸酐1123g(10mol)和醋酸镁78mg加入到反应器中，搅拌均匀，通氮气置换空气3次，并在氮气保护条件下，将反应液升温至140℃，进行乙酰化反应2.5小时。此后，将反应液在2.5小时内，匀速升温至350℃，升温完毕后，保持350℃继续反应1小时。反应结束后，取出预聚物，用粉碎机粉碎，粉碎料在120℃下真空干燥2小时。在低于预聚物熔点40℃，真空度40Pa条件下，固相缩聚反应10小时，得终产品。
实施例2
将对羟基苯甲酸828.28g(6mol)、对苯二酚165.06g(1.5mol)、对苯二甲酸332.06g(2mol)和4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇145.06g(0.5mol)、醋酸酐1123g(10mol)和醋酸镁82mg加入到反应器中，搅拌均匀，通氮气置换空气3次，并在氮气保护条件下，将反应液升温至150℃，进行乙酰化反应2小时。此后，将反应液在3小时内，匀速升温至360℃，升温完毕后，保持360℃继续反应0.5小时。反应结束后，取出预聚物，用粉碎机粉碎，粉碎料在120℃下真空干燥2小时。在低于预聚物熔点35℃，真空度40Pa条件下，固相缩聚反应8小时，得终产品。
实施例3
将对羟基苯甲酸966.21g(7mol)、对苯二酚110.04g(1mol)、对苯二甲酸249.04g(1.5mol)和4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇145.06g(0.5mol)、醋酸酐1123g(11mol)和醋酸镁87mg加入到反应器中，搅拌均匀，通氮气置换空气3次，并在氮气保护条件下，将反应液升温至135℃，进行乙酰化反应3小时。此后，将反应液在3小时内，匀速升温至355℃，升温完毕后，保持355℃继续反应1小时。反应结束后，取出预聚物，用粉碎机粉碎，粉碎料在120℃下真空干燥2小时。在低于预聚物熔点35℃，真空度40Pa条件下，固相缩聚反应12小时，得终产品。
对比例1
将对羟基苯甲酸828.28g(6mol)、对苯二酚220.08g(2mol)、对苯二甲酸415.08g(2mol)、醋酸酐1123g(11mol)和醋酸镁80mg加入到反应器中，搅拌均匀，通氮气置换空气3次，并在氮气保护条件下，将反应液升温至135℃，进行乙酰化反应3小时。此后，将反应液在3小时内，匀速升温至350℃，升温完毕后，保持350℃继续反应1小时。反应结束后，取出预物，用粉碎机粉碎，粉碎料在120℃下真空干燥2小时。在低于预聚物熔点35℃，真空度40Pa条件下，固相缩聚反应12小时，得终产品。
性能结果如表1所示。
表1
| 熔点(℃) | 粘度(dL/g) | 热失重温度(℃) | 流动性(mm) | |
| 实施例1 | 378 | 4.8 | 550 | 920 |
| 实施例2 | 367 | 4.3 | 543 | 880 |
| 实施例3 | 373 | 4.5 | 547 | 910 |
| 对比例1 | 365 | 4.5 | 532 | 730 |
结果测试表明，在热致性液晶聚合物中引入4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇后，产品的流动性增强，提高了产品的可加工性；同时热失重温度提升，改善了热稳定性，使得产品工艺应用价值大大提升。
以上实施例并没有对本发明做任何限制，凡是根据本发明技术实质对上述实施例所做的任何细微修改、等同变化或修饰，均属于本发明技术方案的范围之内。
Claims (5)
1.一种热致性液晶聚合物，其特征在于，由对羟基苯甲酸、对苯二酚、对苯二甲酸和4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇经缩聚反应制得。
2.根据权利要求1所述的热致性液晶聚合物，其特征在于，包括以下摩尔百分比的组分：
对羟基苯甲酸30-60％；
对苯二酚10-20％；
对苯二甲酸10-30％；
4,4”-二甲基-[1,1':4',1”-三联苯]-2',5'-二醇5-10％，
上述4种组分的摩尔数之和为100％。
3.根据权利要求1或2所述热致性液晶聚合物的制备方法，其特征在于，包括熔融聚合步骤和固相缩聚步骤。
4.根据权利要求3所述热致性液晶聚合物的制备方法，其特征在于，熔融聚合步骤中，在氮气保护下，以醋酸镁或醋酸锌为催化剂，以醋酸酐为酰化剂，在130-150℃下乙酰化2-5小时，然后匀速升温至340-360℃，此升温过程持续2.5-3小时，升温完毕后，保持340-360℃继续反应0.5-2小时，抽真空后制得预聚物。
5.根据权利要求3所述热致性液晶聚合物的制备方法，其特征在于，固相缩聚步骤为在40Pa，低于预聚物熔点30-55℃条件下反应5-15小时。
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| US5153300A (en) * | 1991-07-17 | 1992-10-06 | General Electric Company | Dihydroxy-meta-terphenyl polyesters and method of making |
| JP2004182702A (ja) * | 2002-12-06 | 2004-07-02 | Nitto Denko Corp | 重合性テルフェニル液晶化合物、液晶性組成物、コレステリック液晶組成物、光学フィルム、及び画像表示装置 |
| CN104017194A (zh) * | 2014-05-13 | 2014-09-03 | 华东理工大学 | 双釜串联工艺规模化制备热致性液晶聚合物的方法 |
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| US5153300A (en) * | 1991-07-17 | 1992-10-06 | General Electric Company | Dihydroxy-meta-terphenyl polyesters and method of making |
| JP2004182702A (ja) * | 2002-12-06 | 2004-07-02 | Nitto Denko Corp | 重合性テルフェニル液晶化合物、液晶性組成物、コレステリック液晶組成物、光学フィルム、及び画像表示装置 |
| CN104017194A (zh) * | 2014-05-13 | 2014-09-03 | 华东理工大学 | 双釜串联工艺规模化制备热致性液晶聚合物的方法 |
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