CN112574402A - 一种热致性抗熔滴芳香族液晶共聚酯及其制备方法 - Google Patents
一种热致性抗熔滴芳香族液晶共聚酯及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种热致性抗熔滴芳香族液晶共聚酯及其制备方法,该热致性抗熔滴芳香族液晶共聚酯包括主链由刚性的介晶基元和聚酯粒料共聚而成,端封基团为苯乙炔类或降冰片烯乙炔类基团;介晶基元由4,4’‑二羟基联苯;对苯二甲酸和2,7‑萘二甲酸;同时含端羧基A和端羟基B的6‑羟基‑2‑萘甲酸构成。本发明的热致性抗熔滴芳香族液晶共聚酯具有较低的熔融加工温度和阻燃抗溶滴性能,能有效降低因火灾造成的生命财产损失,因此在民用纺织品和高温防护材料领域具有广泛的应用前景,另外聚合过程中分子量可控,制备过程更简便、高效、环保,燃烧时不会产生有害气体。
Description
技术领域
本发明涉及高分子材料领域,具体涉及一种热致性抗熔滴芳香族液晶共聚酯及其制备方法。
背景技术
半芳香族聚酯作为一种应用广泛的高聚物材料,自面世以来,以其高强高模、低吸水性的特点,在民用及工业方面都有广泛的用途。聚酯纤维又称涤纶,占据了化纤产业大部分的份额。已市场化的聚酯种类包括PET、PBT、PTT等。由于该聚合物在高温下会发生氧化,降解等反应,一旦燃烧很容易形成火灾,会严重影响人们生命财产安全。因此提高聚酯材料阻燃性能具有重大意义。
较为成熟的聚酯阻燃改性技术是采用聚酯和磷系阻燃剂共混或共聚的方法赋予聚酯阻燃的特性,专利CN107938014A公开了一种阻燃热致聚芳酯液晶纤维的制备方法,通过在主链引入含磷的芳香族单元得到热致液晶聚芳酯切片,再将切片通过熔融挤出纺成丝,最后经过后处理制得阻燃热致聚芳酯液晶纤维。这种工艺流程简单,纤维阻燃效果良好,但是由于含有磷系阻燃剂,燃烧时会放出白烟和产生熔滴。因此,为了减少阻燃聚酯纤维熔滴和对人体产生的危害,亟需研究新的无磷阻燃聚酯材料。另一方面,如果液晶聚芳酯主链为刚性直链型结构,则需要在较高的温度(300℃以上)下熔融后才能成型,且液晶聚芳酯单体比较昂贵,会进一步增加生产成本。
发明内容
本发明的目的,就是为了解决上述问题而提供了一种热致性抗熔滴芳香族液晶共聚酯及其制备方法,具有熔点低、具有抗熔滴性以及燃烧时不产生有害气体的特性。
本发明的目的是这样实现的:
本发明的一种热致性抗熔滴芳香族液晶共聚酯包括主链由刚性的介晶基元和聚酯粒料共聚而成,端封基团为苯乙炔类或降冰片烯乙炔类基团;介晶基元由全芳族二酚单体、全芳族二酸单体和同时含端羧基A和端羟基B的AB型全芳族单体构成;
全芳族二酚单体为对苯二酚;
全芳族二酸单体为对苯二甲酸和2,7-萘二甲酸;
同时含端羧基A和端羟基B的AB型全芳族单体为6-羟基-2-萘甲酸。
上述的热致性抗熔滴芳香族液晶共聚酯中聚酯颗粒为聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯和聚对苯二甲酸丁二醇酯中的一种或多种。
上述的热致性抗熔滴芳香族液晶共聚酯中苯乙炔类或降冰片烯乙炔类基团为以下化合物中的一种或多种:
其中,Y为氨基或亚氨基;Z为羟基、羧基、酯基或羰基。
上述的热致性抗熔滴芳香族液晶共聚酯中聚酯颗粒为聚对苯二甲酸丙二醇酯;
上述的热致性抗熔滴芳香族液晶共聚酯中热致性抗熔滴芳香族液晶共聚酯的结构式如下:
其中,m=90~100,n=2~20。
上述的热致性抗熔滴芳香族液晶共聚酯中热致性抗熔滴芳香族液晶共聚酯的分子量介于1000~10000克/摩尔。
本发明的热致性抗熔滴芳香族液晶共聚酯的制备方法包括以下步骤:
(1)将摩尔比为10~40:10~40:80~20:100~500:2~8的4,4’-二羟基联苯、对苯二甲酸和2,7-萘二甲酸、6-羟基-2-萘甲酸、聚酯颗粒、含苯乙炔类或降冰片烯乙炔类基团化合物以及醋酸酐和催化剂加入反应器中;在惰性气体保护、120~150℃条件下乙酰化反应30~60min;
(2)以0.5~1.5℃/min的升温速率升温至300~340℃,酯交换反应1~3h;
(3)在300~320℃、真空度为1~3mbar条件下反应10~30min;
(4)在惰性气体气氛中冷却至室温,将步骤(3)所得产物研磨成粉末,在温度为200~260℃、真空度为1~3mbar的条件下进行后缩聚反应18~36h,即可。
上述的热致性抗熔滴芳香族液晶共聚酯的制备方法中催化剂为醋酸钠、醋酸钾、醋酸锌、三氧化二锑、钛酸四丁酯和二氧化锗中的一种或多种,和/或,催化剂质量为全部原料总质量的0.1~0.5%;
上述的热致性抗熔滴芳香族液晶共聚酯的制备方法中醋酸酐摩尔量大于全芳族二酚单体、全芳族二酸单体、同时含端羧基A和端羟基B的AB型全芳族单体、聚酯颗粒、含苯乙炔类或降冰片烯乙炔类基团化合物中羟基总摩尔量。
上述的热致性抗熔滴芳香族液晶共聚酯的制备方法包括以下步骤:
(1)按摩尔比10:8:2:80:100:8:8加入对苯二酚、对苯二甲酸、2,7-萘二甲酸、6-羟基-2-萘甲酸、PBT颗粒、3-乙炔基-N-甲基苯胺、2-(3-乙炔基苯基)-1,3-二氧异吲哚-5-羧酸以及180毫升乙酸酐,以0.2wt%的二氧化锗为催化剂,烧瓶配以密封玻璃桨式搅拌器,一个氮气入口管和一个保温蒸馏头,通入适中的氮气流,在流沙浴中使反应混合物在140℃下乙酰化40min;
(2)以0.5℃/min的升温速率升至300℃进行2h的酯交换反应;
(3)将反应体系缓慢地抽成真空,使真空度为2mbar且温度设为310℃并保持20min;
(4)将步骤(3)获得的不透明的熔体冷却至室温,将产物由烧瓶中移出,并研磨为精细粉末,在230℃,真空度2mbar条件下固态缩聚反应24h,即可。
本发明的热致性抗熔滴芳香族液晶共聚酯材料共聚物分子链中引入有萘类单体破坏主链线性程度,分子链呈半芳族结构,与直链型全芳族液晶材料相比,具有较低的熔融加工温度,另一方面,分子链两端由苯乙炔类或降冰片烯乙炔类等可热固化的活性基团封端,在燃烧时的高温环境(350-500℃)下会发生环加成发应形成固化的交联网络结构,该交联网络结构的形成过程中具有一定的包覆能力,可有效减少燃烧时的熔滴现象,本发明材料不含磷系阻燃剂,因此燃烧时不产生有害气体。
与现有技术相比,本发明具有以下技术效果:
(1)本发明的热致性抗熔滴芳香族液晶共聚酯材料的高分子链呈半芳族结构具有较低的熔融加工温度,引入活性端基热固化反应后所形成的交联网络结构具有优异的阻燃抗溶滴性能,能有效降低因火灾造成的生命财产损失,因此在民用纺织品和高温防护材料领域具有广泛的应用前景。
(2)本发明的热致性抗熔滴芳香族液晶共聚酯在聚合过程中分子量可控,可根据需要获得而不同分子量的材料。
(3)本发明制得的热致性抗熔滴芳香族液晶共聚酯本身不含任何溶剂,其固化过程中也无任何小分子生成,可以通过热压或熔融纺丝制备热致性液晶聚芳酯板材和纤维,过程中无需脱溶剂,使得制备过程更简便、高效、环保;
(4)本发明制得的热致性抗熔滴芳香族液晶共聚酯本身不含磷系阻燃剂,因此燃烧时不会产生有害气体。
附图说明
图1是实施例1和比较例1-2的DSC曲线图。
具体实施方式
下面将结合附图,对本发明作进一步说明。
以下实施例1和比较例1-2中所用原料均采购自上海百灵威化学技术有限公司,100g/瓶,纯度>98%。
实施例1
本实施例的热致性抗熔滴芳香族液晶共聚酯具有以下化学结构式:
其中,n=2~20,m=90~100;
在一个250毫升三口圆底烧瓶中按摩尔比10:8:2:80:100:8:8加入对苯二酚、对苯二甲酸、2,7-萘二甲酸、6-羟基-2-萘甲酸、PBT颗粒、3-乙炔基-N-甲基苯胺、2-(3-乙炔基苯基)-1,3-二氧异吲哚-5-羧酸以及180毫升乙酸酐,以0.2wt%的二氧化锗为催化剂。烧瓶配以密封玻璃桨式搅拌器,一个氮气入口管和一个保温蒸馏头。通入适中的氮气流,在流沙浴中使反应混合物在140℃下乙酰化40min,然后以0.5℃/min的升温速率升至300℃进行2h的酯交换反应。此时,将反应体系缓慢地抽成真空,使真空度为2mbar且温度设为310℃并保持20min。不透明的熔体冷却至室温,将产物由烧瓶中移出,并研磨为精细粉末。在230℃,真空度2mbar条件下固态缩聚反应24h,即得本实施例的样品。
比较例1
在一个250毫升三口圆底烧瓶中按摩尔比10:8:2:80:8:8加入4,4’-二羟基联苯、对苯二甲酸、2,6-萘二甲酸、对羟基苯甲酸、N-(3-羧苯基)-4-苯乙炔基邻苯二甲酰亚胺、N-(3-羟基苯基)-4-苯基乙炔基邻苯二甲酰亚胺、以及150毫升乙酸酐和0.1wt%的乙酸钾。烧瓶配以密封玻璃桨式搅拌器,一个氮气入口管和一个保温蒸馏头。通入适中的氮气流,在流沙浴中使反应混合物在140℃下乙酰化40min,然后以0.5℃/min的升温速率升至300℃进行2h的酯交换反应。此时,将反应体系缓慢地抽成真空,使真空度为2mbar且温度设为310℃并保持20min。不透明的熔体冷却至室温,将产物由烧瓶中移出,并研磨为精细粉末。在230℃,真空度2mbar条件下固态缩聚反应24h,即得到目标产物化学式如下:
比较例2
在一个250毫升三口圆底烧瓶中按摩尔比10:8:2:80加入4,4’-二羟基联苯、双(对羧苯基)苯基氧化磷、2,6-萘二甲酸、对羟基苯甲酸、以及150毫升乙酸酐和0.1wt%的乙酸钾。烧瓶配以密封玻璃桨式搅拌器,一个氮气入口管和一个保温蒸馏头。通入适中的氮气流,在流沙浴中使反应混合物在140℃下乙酰化40min,然后以0.5℃/min的升温速率升至300℃进行2h的酯交换反应。此时,将反应体系缓慢地抽成真空,使真空度为2mbar且温度设为310℃并保持20min。不透明的熔体冷却至室温,将产物由烧瓶中移出,并研磨为精细粉末。在230℃,真空度2mbar条件下固态缩聚反应24h,即得到目标产物化学式如下:
性能测试
采用差式扫描量热法(DSC)及热失重分析(TGA)测试产物的热学性能,以及通过测试产物的垂直燃烧确定其阻燃性能同时测试产物的特性粘度,热学性能和阻燃性能以及特性粘度测试结果分别见表1和表2所示:
表1采用差式扫描量热法测试结果
表2热失重分析测试结果
比较例1~2和实施例1的DSC曲线如图1所示。
结合图1和表1可以看出,比较例1和比较例2的纯热致性液晶高聚物熔点分别为267℃和270℃,而实施例1的共聚物的熔点相对于比较例1~2和PET(Tm=250~260℃)都要低,一定程度上能够减少共聚酯材料成型生产成本;与此同时,本发明的液晶共聚酯的热分解温度Td5%在370℃以上,具有较高的热稳定性。
以上实施例仅供说明本发明之用,而非对本发明的限制,有关技术领域的技术人员,在不脱离本发明的精神和范围的情况下,还可以作出各种变换或变型,因此所有等同的技术方案也应该属于本发明的范畴,应由各权利要求所限定。
Claims (10)
1.一种热致性抗熔滴芳香族液晶共聚酯,其特征在于,其包括主链由刚性的介晶基元和聚酯粒料共聚而成,端封基团为苯乙炔类或降冰片烯乙炔类基团;所述介晶基元由全芳族二酚单体、全芳族二酸单体和同时含端羧基A和端羟基B的AB型全芳族单体构成;
所述全芳族二酚单体为对苯二酚;
所述全芳族二酸单体为对苯二甲酸和2,7-萘二甲酸;
所述同时含端羧基A和端羟基B的AB型全芳族单体为6-羟基-2-萘甲酸。
2.如权利要求1所述的热致性抗熔滴芳香族液晶共聚酯,其特征在于,所述聚酯颗粒为聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯和聚对苯二甲酸丁二醇酯中的一种或多种。
6.如权利要求1~5所述的任一种热致性抗熔滴芳香族液晶共聚酯,其特征在于,所述热致性抗熔滴芳香族液晶共聚酯的分子量介于1000~10000克/摩尔。
7.如权利要求1所述的热致性抗熔滴芳香族液晶共聚酯的制备方法,其特征在于,包括以下步骤:
(1)将摩尔比为10~40:10~40:80~20:100~500:2~8的4,4’-二羟基联苯、对苯二甲酸和2,7-萘二甲酸、6-羟基-2-萘甲酸、聚酯颗粒、含苯乙炔类或降冰片烯乙炔类基团化合物以及醋酸酐和催化剂加入反应器中;在惰性气体保护、120~150℃条件下乙酰化反应30~60min;
(2)以0.5~1.5℃/min的升温速率升温至300~340℃,酯交换反应1~3h;
(3)在300~320℃、真空度为1~3mbar条件下反应10~30min;
(4)在惰性气体气氛中冷却至室温,将步骤(3)所得产物研磨成粉末,在温度为200~260℃、真空度为1~3mbar的条件下进行后缩聚反应18~36h,即可。
8.如权利要求7所述的热致性抗熔滴芳香族液晶共聚酯的制备方法,其特征在于,所述催化剂为醋酸钠、醋酸钾、醋酸锌、三氧化二锑、钛酸四丁酯和二氧化锗中的一种或多种,和/或,所述催化剂质量为全部原料总质量的0.1~0.5%;
9.如权利要求7所述的热致性抗熔滴芳香族液晶共聚酯的制备方法,其特征在于,所述醋酸酐摩尔量大于所述全芳族二酚单体、全芳族二酸单体、同时含端羧基A和端羟基B的AB型全芳族单体、聚酯颗粒、含苯乙炔类或降冰片烯乙炔类基团化合物中羟基总摩尔量。
10.如权利要求7所述的热致性抗熔滴芳香族液晶共聚酯的制备方法,其特征在于,包括以下步骤:
(1)按摩尔比10:8:2:80:100:8:8加入对苯二酚、对苯二甲酸、2,7-萘二甲酸、6-羟基-2-萘甲酸、PBT颗粒、3-乙炔基-N-甲基苯胺、2-(3-乙炔基苯基)-1,3-二氧异吲哚-5-羧酸以及180毫升乙酸酐,以0.2wt%的二氧化锗为催化剂,烧瓶配以密封玻璃桨式搅拌器,一个氮气入口管和一个保温蒸馏头,通入适中的氮气流,在流沙浴中使反应混合物在140℃下乙酰化40min;
(2)以0.5℃/min的升温速率升至300℃进行2h的酯交换反应;
(3)将反应体系缓慢地抽成真空,使真空度为2mbar且温度设为310℃并保持20min;
(4)将步骤(3)获得的不透明的熔体冷却至室温,将产物由烧瓶中移出,并研磨为精细粉末,在230℃,真空度2mbar条件下固态缩聚反应24h,即可。
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