CN114989401A - 一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法 - Google Patents
一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法,选择共轭单体在聚酯合成后期原位封端,得到两个端基为共轭结构的线性遥爪聚酯;利用功能端基的π‑π堆积作用,起到扩大聚合度的等效效果,同时对加工流变性能不造成负面影响,所述遥爪聚酯具有大幅度提高的断裂伸长率及拉伸韧性,适用于机械注塑件等高端装备制造领域。
Description
技术领域
本发明涉及聚酯分子设计、加工与合成领域,特别是涉及一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法。
背景技术
聚酯树脂目前用途主要集中在纤维领域,其在注塑件方向的应用和新技术开发发展较为滞后。但是国外高附加值新型聚酯材料主要是适用于注塑领域,例如PTT、PBT等,这类产品多属于工程聚酯领域,利润空间大且技术壁垒高。因此,开发新型工程聚酯材料,改善其性能并拓宽其应用领域,是聚酯树脂行业的必然发展方向和可持续性动力。高韧性聚酯新材料,可以适应大型发动机等尖端机械部件的使用要求,可以替代尼龙、聚碳酸酯等工程塑料的使用,市场前景广阔,意义重大。
按照高分子材料的通用性特征,大分子链长和分子量的提高,对于材料力学性能的提高具有推动作用,是一种有效的改性思路。但是聚合度上限往往还需要受到材料加工流变性能的限制,聚合度过大,材料熔融粘度升高,加工难度提升,例如当聚酯特性粘度大于1dL/g时,就无法进行双向拉伸成膜。因此在提高材料本体强度、韧性等力学性能的同时,需要兼顾其加工流变性能。
发明内容
π-π堆积作用,作为分子间作用力,是次级键的一种。本发明在大分子链末段引入π-π共轭端基。利用π-π堆积的物理作用,起到增长分子链长度的等效效果,但是在高温熔融状态下的π-π堆积作用可逆,降低共聚酯熔体的粘弹性,不影响其加工成型。利用功能遥爪聚合物结构,解决化学键扩链和超分子热塑性聚合物的粘弹性过高的严重弊端。
在本发明一个较佳实施例中,本发明采用的技术方案提供一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法,包括以下配比原料进行合成:
二酸单体:10000-18000质量份,
二醇单体:与二酸单体的摩尔份数比为1.1-1.8:1,
催化剂1:5-10份,
催化剂2:5-10份
稳定剂:2-10份,
第一次加入共轭封端单体:50-80份,
第二次加入共轭封端单体:15-20份。
在本发明一个较佳实施例中,所述的二酸单体包括但不限于对苯二甲酸、间苯二甲酸、萘二甲酸、己二酸、丁二酸中的一种或几种;
在本发明一个较佳实施例中,所述的二醇单体包括但不限于乙二醇、丁二醇、己二醇、新戊二醇、1,4-环己烷二甲醇、三羟甲基丙烷中的一种或几种;
在本发明一个较佳实施例中,所述的催化剂1为对甲苯磺酸、醋酸锌、钛酸四丁酯中的一种。
在本发明一个较佳实施例中,所述的催化剂2为锑系、钛系或锗系金属催化剂中的一种。
在本发明一个较佳实施例中,所述的稳定剂为磷酸脂类或亚磷酸脂类中的一种。
在本发明一个较佳实施例中,所述的共轭封端单体的加入按不同比例分两次进行。
在本发明一个较佳实施例中,所述的共轭封端单体为2-氰基-3-苯丙烯酰胺、萘甲酸、萘乙酸、呋喃甲酸、呋喃乙酸中的一种。
在本发明一个较佳实施例中,所述的基于共轭堆积的遥爪型高韧性聚酯,包括以下步骤进行合成:
(1)将二甲酸单体、二醇单体、催化剂1、和稳定剂按比例称量好混合均匀,加入到反应釜中,然后加热进行酯化反应,通过出水量判断酯化反应程度,当酯化达到95%以上后,酯化反应结束;
(2)酯化反应结束后,加入催化剂2,随后高真空进行缩聚反应;
(3)缩聚末期当电机搅拌功率达到一定值以后,第一次加入一定比例的共轭封端单体;
(4)缩聚末期出料之前,第二次加入剩余的共轭封端单体进行封端,随后出料、冷却、切粒;
(5)将所得聚酯溶于三氟乙酸,随后滴入甲醇中析出沉淀,得到产物遥爪型高韧性聚酯。
本发明的有益效果是:本发明给出基于共轭堆积的遥爪型高韧性聚酯,断裂伸长率和拉伸韧性大幅度提高,有效拓展材料使用范围;同时能满足纺丝、双向拉伸和注塑的加工条件要求,流变性能优良。本材料具备良好的机械性能,特别适用于建筑基材、工程结构件的应用领域。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1:
一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法,包括以下质量配比的原料进行合成:对苯二甲酸10000g,乙二醇4500g,醋酸锌5g,乙二醇锑5g,磷酸三甲酯3g,第一次加入萘甲酸50g,第二次加入萘甲酸20g。
该遥爪型高韧性聚酯的生产方法,包括以下步骤:
(1)将对苯二甲酸、乙二醇、醋酸锌、和磷酸三甲酯按比例称量好混合均匀,加入到反应釜中,然后在265℃,350kPa的压力下进行酯化反应,通过出水量判断酯化反应程度,当酯化达到95%以上后,酯化反应结束;
(2)酯化反应结束后,加入乙二醇锑,随后高真空进行缩聚反应,期间釜内温度维持在270-275℃;
(3)缩聚末期当电机搅拌功率达到一定值以后,第一次加入萘甲酸进行封端,此时搅拌功率会下降,待聚合度逐渐提高后,搅拌功率会再次升高;
(4)缩聚末期出料之前,第二次加入剩余的萘甲酸进行封端,随后出料、冷却、切粒;
(5)将所得聚酯溶于三氟乙酸,随后滴入甲醇中析出沉淀,得到产物遥爪型高韧性聚酯。
实施例2:
一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法,包括以下质量配比的原料进行合成:对苯二甲酸10000g,丁二醇7620g,对甲苯磺酸6g,氧化锗8g,磷酸三甲酯3g,第一次加入萘乙酸80g,第二次加入萘乙酸15g。
该遥爪型高韧性聚酯的生产方法,包括以下步骤:
(1)将对苯二甲酸、丁二醇、对甲苯磺酸、和磷酸三甲酯按比例称量好混合均匀,加入到反应釜中,然后在265℃,350kPa的压力下进行酯化反应,通过出水量判断酯化反应程度,当酯化达到95%以上后,酯化反应结束;
(2)酯化反应结束后,加入氧化锗,随后高真空进行缩聚反应,期间釜内温度维持在270-275℃;
(3)缩聚末期当电机搅拌功率达到一定值以后,第一次加入萘乙酸进行封端,此时搅拌功率会下降,待聚合度逐渐提高后,搅拌功率会再次升高;
(4)缩聚末期出料之前,第二次加入剩余的萘乙酸进行封端,随后出料、冷却、切粒;
(5)将所得聚酯溶于三氟乙酸,随后滴入甲醇中析出沉淀,得到产物遥爪型高韧性聚酯。
实施例3:
一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法,包括以下质量配比的原料进行合成:对己二酸10000g,丁二醇5342g,钛酸四丁酯8g,乙二醇锑5g,磷酸三乙酯5g,第一次加入2-氰基-3-苯丙烯酰胺80g,第二次加入2-氰基-3-苯丙烯酰胺20g。
该遥爪型高韧性聚酯的生产方法,包括以下步骤:
(1)将己二酸、丁二醇、钛酸四丁酯、和磷酸三乙酯按比例称量好混合均匀,加入到反应釜中,然后在265℃,350kPa的压力下进行酯化反应,通过出水量判断酯化反应程度,当酯化达到95%以上后,酯化反应结束;
(2)酯化反应结束后,加入乙二醇锑,随后高真空进行缩聚反应,期间釜内温度维持在270-275℃;
(3)缩聚末期当电机搅拌功率达到一定值以后,第一次加入2-氰基-3-苯丙烯酰胺进行封端,此时搅拌功率会下降,待聚合度逐渐提高后,搅拌功率会再次升高;
(4)缩聚末期出料之前,第二次加入剩余的2-氰基-3-苯丙烯酰胺进行封端,随后出料、冷却、切粒;
(5)将所得聚酯溶于三氟乙酸,随后滴入甲醇中析出沉淀,得到产物遥爪型高韧性聚酯。
实施例4:
一种基于共轭堆积的遥爪型高韧性聚酯及其制备方法,包括以下质量配比的原料进行合成:对苯二甲酸10000g,间苯二甲酸2000g,乙二醇4500g,1,4-环己烷二甲醇2090g,醋酸锌8g,三氧化二锑10g,磷酸三甲酯8g,第一次加入呋喃甲酸60g,第二次加入呋喃甲酸20g。
该遥爪型高韧性聚酯的生产方法,包括以下步骤:
(1)将对苯二甲酸、间苯二甲酸、乙二醇、1,4-环己烷二甲醇、醋酸锌、和磷酸三甲酯按比例称量好混合均匀,加入到反应釜中,然后在265℃,350kPa的压力下进行酯化反应,通过出水量判断酯化反应程度,当酯化达到95%以上后,酯化反应结束;
(2)酯化反应结束后,加入三氧化二锑,随后高真空进行缩聚反应,期间釜内温度维持在270-275℃;
(3)缩聚末期当电机搅拌功率达到一定值以后,第一次加入呋喃甲酸进行封端,此时搅拌功率会下降,待聚合度逐渐提高后,搅拌功率会再次升高;
(4)缩聚末期出料之前,第二次加入剩余的呋喃甲酸进行封端,随后出料、冷却、切粒;
(5)将所得聚酯溶于三氟乙酸,随后滴入甲醇中析出沉淀,得到产物遥爪型高韧性聚酯。
实施例1-实施例4所得基于共轭堆积的遥爪型高韧性聚酯的性能测试如表1所示。
表1
本发明与普通聚酯相比,产品具有高断裂伸长率及高韧性,熔融状态具有与大有光聚酯切片相同的流变性能,满足纺丝、注塑及双向拉伸的加工需求。在建筑材料,复合材料制备,机械构件等方面具有重要的应用价值。以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
1.一种基于共轭堆积的遥爪型高韧性聚酯,其特征在于,包括以下质量配比的原料进行合成:
二酸单体:10000-18000质量份;
二醇单体:与二酸单体的摩尔份数比为1.1-1.8:1;
催化剂1:5-10份;
催化剂2:5-10份;
稳定剂:2-10份;
第一次加入共轭封端单体:50-80份;
第二次加入共轭封端单体:15-20份。
2.按照权利要求1所述基于共轭堆积的遥爪型高韧性聚酯,其特征在于:所述二酸单体包括但不限于对苯二甲酸、间苯二甲酸、萘二甲酸、己二酸、丁二酸中的一种或几种。
3.按照权利要求1所述基于共轭堆积的遥爪型高韧性聚酯,其特征在于:所述二醇单体包括但不限于乙二醇、丁二醇、己二醇、新戊二醇、1,4-环己烷二甲醇、三羟甲基丙烷中的一种或几种。
4.按照权利要求1所述基于共轭堆积的遥爪型高韧性聚酯,其特征在于:所述催化剂1为对甲苯磺酸、醋酸锌、钛酸四丁酯中的一种。
5.按照权利要求1所述基于共轭堆积的遥爪型高韧性聚酯,其特征在于:所述催化剂2为锑系、钛系或锗系金属催化剂中的一种。
6.按照权利要求1所述基于共轭堆积的遥爪型高韧性聚酯,其特征在于:所述稳定剂为磷酸脂类或亚磷酸脂类中的一种。
7.按照权利要求1所述的遥爪型高韧性聚酯,其特征在于:共轭封端单体的加入按不同比例分两次进行。
8.按照权利要求1所述的遥爪型高韧性聚酯,其特征在于:所述共轭封端单体为2-氰基-3-苯丙烯酰胺、萘甲酸、萘乙酸、呋喃甲酸、呋喃乙酸中的其一种。
9.一种基于共轭堆积的遥爪型高韧性聚酯制备方法,其特征在于,包括以下步骤:
(1)将二甲酸单体、二醇单体、催化剂1、和稳定剂按比例称量好混合均匀,加入到反应釜中,然后加热进行酯化反应,通过出水量判断酯化反应程度,当酯化达到95%以上后,酯化反应结束;
(2)酯化反应结束后,加入催化剂2,随后高真空进行缩聚反应;
(3)缩聚末期当电机搅拌功率达到一定值以后,第一次加入一定比例的共轭封端单体;
(4)缩聚末期出料之前,第二次加入剩余的共轭封端单体进行封端,随后出料、冷却、切粒;
(5)将所得聚酯溶于三氟乙酸,随后滴入甲醇中析出沉淀,得到产物遥爪型高韧性聚酯。
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