CN112521604A - 一种低热膨胀系数热塑性聚酰亚胺树脂及其制备方法 - Google Patents
一种低热膨胀系数热塑性聚酰亚胺树脂及其制备方法 Download PDFInfo
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Abstract
本发明涉及热塑性聚酰亚胺树脂技术领域,公开了一种低热膨胀系数热塑性聚酰亚胺树脂及其制备方法,该树脂具有如式1、式2或式3所示的结构式;其制备方法是以刚性二酐、刚性二胺与柔性二酐和/或柔性二胺为聚合单体,在溶剂中反应制备得到采用刚性二酐、刚性二胺单体组成的刚性聚酰亚胺链段,通过共聚调控,达到非晶、低的热膨胀系数、良好的热塑加工性的目的,其中熔融指数为2‑15g/10min,可以满足热塑加工,热膨胀系数在10‑45ppm/K,远低于常规的热塑性聚酰亚胺树脂。
Description
技术领域
本发明涉及热塑性聚酰亚胺树脂技术领域,具体涉及一种低热膨胀系数热塑性聚酰亚胺树脂及其制备方法。
背景技术
热塑性聚酰亚胺树脂一般都需要引入柔性的氧醚键来提高其热塑加工性,因此其热膨胀系数(CTE)一般较高,在50-60ppm/K,如无定型的Ultem 1000的CTE在56ppm/K,结晶性的热塑性聚酰亚胺Aurum的CTE也很高,在60ppm/K。
目前知道的CTE最低的商品化热塑性聚酰亚胺树脂是Torlon,其CTE在31ppm/K,但是由于Torlon是结晶料,不透明。另一方面,具有低CTE的聚酰亚胺都是薄膜产品,均采用刚性的二酐和刚性的二胺制备得到,如均苯二酐(PMDA)和对苯二胺(p-PDA)制备的聚酰亚胺薄膜的CTE是2ppm/K左右;PMDA和4,4’-二氨基-2,2’-双三氟甲基联苯(TFDB)制备的聚酰亚胺薄膜其CTE甚至能达到负数,为-4.7ppm/K;联苯二酐(BPDA)和p-PDA制备的聚酰亚胺薄膜的CTE—般认为是11ppm/K左右;PMDA、BPDA、对-亚苯基-双苯偏三酸酯二酐(TAHQ)与反式1,4-环己烷二胺(trans-1,4-CHDA)反应所得的聚酰亚胺的热膨胀系数都小于13ppm/K,分别为9.6、10、12.7ppm/K。这些刚性结构制备的聚酰亚胺薄膜虽然CTE比较低,但是其玻璃化转变温度一般大于320℃,没有热塑加工性,一般用来制作聚酰亚胺薄膜产品。
申请人在早期研究中CN 111234225 A提供了一种低热膨胀系数的热塑性聚酰亚胺树脂及其制备方法,以4,4’-二氨基-2,2’-双三氟甲基联苯、间苯二甲酰氯和4,4-联苯二酐为聚合单体,在溶剂中反应制备得到。该聚酰亚胺树脂将含有酰胺键的结构引入到聚酰亚胺体系中,通过分子内氢键的相互作用力,降低聚酰亚胺树脂的热膨胀系数,此外通过间位的不对称结构来提高热塑性,使得该分子结构同时兼具热塑性和低热膨胀系数两大优点,其中熔融指数为0.1~2g/10min,可以满足热塑加工,热膨胀系数在20~40ppm/K。
同样在CN111057236A提供一种低热膨胀系数热塑性聚酰亚胺树脂,以偏苯三酸酐酰氯和二元伯胺为聚合单体,在反应溶剂中进行反应制备聚酰胺酸,并用封端剂封端,然后进行亚胺化反应制备得到。其中熔融指数为0.1-5g/10min,可以满足热塑加工,热膨胀系数在10-30ppm/K。
但这均采用了酰亚胺和酰胺两种结构单元相结合的方法,制备低热膨胀系数热塑性聚酰亚胺树脂,但是由于分子结构中酰胺键的存在,导致其加工时候的热稳定性差,容易交联,无法满足长期连续注塑的要求,耐热加工性有待提高,因此目前迫切需要开发一种不带酰胺结构单元的同时具有低热膨胀系数的无定形热塑性聚酰亚胺树脂材料。
发明内容
本发明针对上述技术难题,本发明提供一种不含酰胺结构单元的低热膨胀系数热塑性聚酰亚胺树脂,该低热膨胀系数热塑性聚酰亚胺树脂是无定形的非晶结构。该热塑性聚酰亚胺树脂的热膨胀系数可以达到45ppm/K以下,能够实现热塑加工。
为实现上述目的,本发明采用的技术方案是:
一种低热膨胀系数热塑性聚酰亚胺树脂,具有如式1、式2或式3所示的结构式:
其中,Ar1是刚性二酐单体残基,Ar2是刚性二胺单体残基,Ar3是柔性二酐单体残基,Ar4是柔性二胺单体残基,n、m是大于0的整数,其中n/m=1~10。
所述Ar1是下列基团中的一种或两种以上:
所述的Ar2是下列基团中的一种或两种以上:
所述的Ar3是下列基团中的一种或两种以上:
所述的Ar4是下列基团中的一种或两种以上:
优选地,所述Ar1是下列基团中的一种或两种以上:
所述的Ar2是下列基团中的一种或两种以上:
所述的Ar3是下列基团中的一种或两种以上:
所述的Ar4是下列基团中的一种或两种以上:
所述低热膨胀系数热塑性聚酰亚胺树脂为无定形的非晶结构,玻璃化转变温度为250-320℃,熔融指数为2-15g/10min,热膨胀系数在10-45ppm/K。
本发明还提供所述的低热膨胀系数热塑性聚酰亚胺树脂的制备方法,方法操作简便、易于控制,以刚性二酐、刚性二胺与柔性二酐和/或柔性二胺为聚合单体,在溶剂中进行反应生成聚酰胺酸,并加入封端剂封端,再经亚胺化反应后,将产物沉淀、洗涤、干燥得到所述的热塑性聚酰亚胺树脂。
所述刚性二酐包括如下结构的单体,对应获得Ar1部分:
所述刚性二胺包括如下结构的单体,对应获得Ar2部分:
所述柔性二酐包括如下结构的单体,对应获得Ar3部分:
所述柔性二胺包括如下结构的单体,对应获得Ar4部分:
所述溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中任一种或多种。
所述刚性二酐和柔性二酐两者的总摩尔量与刚性二胺和柔性二胺两者的总摩尔量的比为92~99.9:100。
所述的封端剂包括苯酐、萘酐或乙酸酐。
所述亚胺化反应采用化学亚胺化,化学亚胺化的试剂为酸酐类和有机胺类的混合物。酸酐类可选用乙酸酐等,有机胺类可选用三乙胺、吡啶等。
所述的亚胺化反应采用热亚胺化进行制备,热亚胺的试剂为苯类溶剂,例如甲苯、乙苯等。
作为优选,亚胺化反应采用化学亚胺化的方法,化学亚胺化的试剂为乙酸酐和吡啶的混合物。
采用化学亚胺化方法可以有效的控制制备的聚酰亚胺的分子量,使反应更稳定。其中以乙酸酐和吡啶的混合物左右化学亚胺化制备,可以有效的控制反应过程中的溶解性。
与现有技术相比,本发明具有以下有益效果:
(1)采用刚性二酐、刚性二胺单体组成的刚性聚酰亚胺链段,由柔性二酐与刚性二胺单体,或者刚性二酐与柔性二胺单体,或者柔性二酐与柔性二胺单体组成的柔性聚酰亚胺链段,通过共聚调控,达到非晶、低的热膨胀系数、良好的热塑加工性的目的,其中熔融指数为2-15g/10min,可以满足热塑加工,热膨胀系数在10-45ppm/K,远低于常规的热塑性聚酰亚胺树脂。
(2)聚酰亚胺结构设计中避免了酰胺等不耐热的基团,提高了树脂的整体耐热性,提高加工性能。
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。
本发明中采用的原料均购于市场。
实施例1:
本实施例中,聚酰亚胺树脂材料具有如下结构式(n/m=2/1):
制备方法如下:
氮气保护下,向2L三口瓶中投入4,4’-二氨基-2,2’-双三氟甲基联苯(160.12g)和N,N-二甲基乙酰胺(1335.41g),室温下机械搅拌至完全溶解,投入4,4-联苯四甲酸二酐(92.19g);2,2'-双[4-(3,4-二羧苯氧基)苯基]丙烷四酸二酐(81.54g),室温搅拌18h,加入封端剂苯酐(17.77g),继续室温搅拌1h,加入乙酸酐(118ml)与吡啶(60ml),80℃反应2h。在乙醇中析出粉末并煮洗两次;普通烘箱下干燥。
树脂性能测定如下:玻璃化转变温度为259℃,熔融指数为6.0g/10min,注塑成型的样条的热膨胀系数41ppm/K。
实施例2
本实施例中,聚酰亚胺树脂材料具有如下结构式(n/m=2.5/1):
制备方法如下:
氮气保护下,向2L三口瓶中投入4,4’-二氨基-2,2’-双三氟甲基联苯(96.07g)和N,N-二甲基乙酰胺(789.95g),室温下机械搅拌至完全溶解,投入4,4-联苯四甲酸二酐(59.39g);2,2'-双[4-(3,4-二羧苯氧基)苯基]丙烷四酸二酐(42.02g),室温搅拌18h后加入封端剂苯酐(10.30g),继续室温搅拌1h,然后加入乙酸酐(71ml)与吡啶(35ml),80℃反应2h。在乙醇中析出粉末并煮洗两次;普通烘箱下干燥。
树脂性能测定如下:玻璃化转变温度为266℃,熔融指数为5.1g/10min,注塑成型的样条的热膨胀系数为40ppm/K。
实施例3
本实施例中,聚酰亚胺树脂材料具有如下结构式(n/m=4/1):
制备方法如下:
氮气保护下,向2L三口瓶中投入4,4’-二氨基-2,2’-双三氟甲基联苯(102.47g);4,4-二氨基二苯砜(19.86g)和N,N-二甲基乙酰胺(1010.79g),室温下机械搅拌至完全溶解,投入4,4-联苯四甲酸二酐(90.38g);2,2'-双[4-(3,4-二羧苯氧基)苯基]丙烷四酸二酐(39.97g),室温搅拌18h,加入封端剂苯酐(9.48g),继续室温搅拌1h,加入乙酸酐(95ml)与吡啶(47ml),80℃反应2h。在乙醇中析出粉末并煮洗两次,普通烘箱下干燥。
树脂性能测定如下:玻璃化转变温度为250℃,熔融指数为11.2g/10min,注塑成型的样条的热膨胀系数在42ppm/K。
实施例4
本实施例中,聚酰亚胺树脂材料具有如下结构式(n/m=4/1):
制备方法如下:
氮气保护下,向2L三口瓶中投入4,4’-二氨基-2,2’-双三氟甲基联苯(64.04g);4,4-二氨基二苯砜(12.41g)和N,N-二甲基乙酰胺(607.38g),室温下机械搅拌至完全溶解,投入4,4-联苯四甲酸二酐(54.72g);4,4'-(六氟异丙烯)二酞酸酐(20.65g),室温搅拌18h,加入封端剂苯酐(8.88g),继续室温搅拌1h,加入乙酸酐(59ml)与吡啶(30ml),80℃反应2h。在乙醇中析出粉末并煮洗两次,普通烘箱下干燥。
树脂性能测定如下:玻璃化转变温度为276℃,熔融指数为5.5g/10min,注塑成型的样条的热膨胀系数在33ppm/K。
实施例5
本实施例中,聚酰亚胺树脂材料具有如下结构式(n/m=1.5/1):
制备方法如下:
氮气保护下,向2L三口瓶中投入间苯二胺(40.56g)、3,3-二氨基二苯砜(62.07g)和N-甲基吡咯烷酮(1438.39g),室温下机械搅拌至完全溶解,投入均苯四甲酸二酐(89.95g);2,2'-双[4-(3,4-二羧苯氧基)苯基]丙烷四酸二酐(127.52g),室温搅拌18h,加入封端剂苯酐(11.84g),继续室温搅拌1h,加入乙酸酐(118ml)与吡啶(60ml),80℃反应2h。在乙醇中析出粉末并在煮洗两次;普通烘箱下干燥。
树脂性能测定如下:玻璃化转变温度为279℃,熔融指数为3.0g/10min,注塑成型的样条的热膨胀系数35ppm/K。
从实施例中可见,制备得到的聚酰亚胺树脂的热膨胀系数均在42ppm/K以下,且结构中不含酰胺结构,不存在不耐热的问题,同时树脂的熔融指数均在3.0-11.2g/10min内,满足热塑性树脂的加工性能参数。
Claims (10)
4.根据权利要求1所述的低热膨胀系数热塑性聚酰亚胺树脂,其特征在于,所述低热膨胀系数热塑性聚酰亚胺树脂为无定形的非晶结构,玻璃化转变温度为250-320℃,熔融指数为2-15g/10min,热膨胀系数在10-45ppm/K。
5.根据权利要求1-4任一项所述的低热膨胀系数热塑性聚酰亚胺树脂的制备方法,其特征在于,以刚性二酐、刚性二胺与柔性二酐和/或柔性二胺为聚合单体,在溶剂中进行反应生成聚酰胺酸,并加入封端剂封端,再经亚胺化反应后,将产物沉淀、洗涤、干燥得到所述的热塑性聚酰亚胺树脂。
6.根据权利要求5所述的低热膨胀系数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N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中任一种或多种。
7.根据权利要求5所述的低热膨胀系数热塑性聚酰亚胺树脂的制备方法,其特征在于,所述刚性二酐和柔性二酐两者的总摩尔量与刚性二胺和柔性二胺两者的总摩尔量的比为92~99.9:100。
8.根据权利要求5所述的低热膨胀系数热塑性聚酰亚胺树脂的制备方法,其特征在于,所述的封端剂包括苯酐、萘酐或乙酸酐。
9.根据权利要求5所述的低热膨胀系数热塑性聚酰亚胺树脂的制备方法,其特征在于,所述的亚胺化反应采用化学亚胺化,化学亚胺化的试剂为酸酐类和有机胺类的混合物。
10.根据权利要求5所述的低热膨胀系数热塑性聚酰亚胺树脂的制备方法,其特征在于,所述的亚胺化反应采用热亚胺化进行制备,热亚胺化的试剂为苯类溶剂。
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