CN109337364A - 一种高强度的芳杂环聚合物薄膜及其制备方法和应用 - Google Patents

一种高强度的芳杂环聚合物薄膜及其制备方法和应用 Download PDF

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CN109337364A
CN109337364A CN201811145196.8A CN201811145196A CN109337364A CN 109337364 A CN109337364 A CN 109337364A CN 201811145196 A CN201811145196 A CN 201811145196A CN 109337364 A CN109337364 A CN 109337364A
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aromatic heterocyclic
heterocyclic polymer
polymer film
high intensity
sulfate
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潘鑫
刘文熙
王庭辉
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Abstract

本发明涉及薄膜技术领域，具体涉及一种高强度的芳杂环聚合物薄膜及其制备方法和应用，所述芳杂环聚合物薄膜由芳杂环聚合物树脂经酸浴湿法拉伸成膜工艺制得,所述芳杂环聚合物树脂的制备方法为：以对苯二甲酸和邻苯二甲酸中的至少一种和硫酸肼为反应原料，在发烟硫酸中进行缩聚反应，得到所述芳杂环聚合物树脂。本发明的芳杂环聚合物薄膜具有较高的强度，还具有良好的尺寸稳定性、耐热性、耐氧化、电绝缘、耐溶剂性、特殊的导电性以及电致发光等性能，综合性能优异。

Description

一种高强度的芳杂环聚合物薄膜及其制备方法和应用
技术领域
本发明涉及薄膜技术领域，具体涉及一种高强度的芳杂环聚合物薄膜及其制备方法和应用。
背景技术
杂环化合物环状有机化合物中，构成环的原子除碳原子外还有其他原子时，这类环状有机化合物叫作杂环化合物，非碳原子称为杂原子。最常见的杂原子是氧和硫，杂环上可以有一个杂原子，也可以有两个或更多个杂原子，杂原子可以是一种原子，也可以是两种不同的原子。和环烷烃一样，杂环也可以分为脂杂环和芳杂环两大类。一般来说，芳杂环的环系都有一定程度的稳定性和芳香性，在一般化学反应中，环不易破裂。部分芳杂环可以聚合成高分子树脂，由于其独特的优良性能而具有广泛的潜在应用价值。
发明内容
为了克服现有技术中存在的缺点和不足，本发明的目的在于提供一种高强度的芳杂环聚合物薄膜，该芳杂环聚合物薄膜具有较高的强度，还具有良好的尺寸稳定性、耐热性、耐氧化、电绝缘、耐溶剂性、特殊的导电性以及电致发光等性能，综合性能优异。
本发明的另一个目的在于提供一种高强度的芳杂环聚合物薄膜的制备方法，该制备方法步骤简单，操作控制方便，质量稳定，生产效率高，生产成本低，可大规模化工业生产。
本发明的还一个目的在于提供一种高强度的芳杂环聚合物薄膜的应用。
本发明的目的通过下述技术方案实现：一种高强度的芳杂环聚合物薄膜，所述芳杂环聚合物薄膜包括芳杂环聚合物树脂，所述芳杂环聚合物树脂的结构式如下：
其中，m、n、x和y均为正整数。
优选的，所述芳杂环聚合物树脂的制备方法为：以对苯二甲酸和邻苯二甲酸中的至少一种和硫酸肼为反应原料，在发烟硫酸中进行缩聚反应，得到所述芳杂环聚合物树脂。
具体的，当以对苯二甲酸作为单体时，对苯二甲酸、硫酸肼和发烟硫酸的摩尔比为1：(1.01-5.0)：(5-15)，其中发烟硫酸摩尔数以发烟硫酸中SO3摩尔数计。
当以邻苯二甲酸作为单体时，邻苯二甲酸、硫酸肼和发烟硫酸的摩尔比为1：(1.01-5.0)：(5-15)，其中发烟硫酸摩尔数以发烟硫酸中SO3摩尔数计。
当以对苯二甲酸和邻苯二甲酸作为单体时，对苯二甲酸、邻苯二甲酸、硫酸肼和发烟硫酸的摩尔比为(0.01-0.99)：(0.99-0.01)：(1.01-5.0)：(5-15)，其中发烟硫酸摩尔数以发烟硫酸中SO3摩尔数计。当以对苯二甲酸和邻苯二甲酸作为单体时，其聚合方式有无规共聚、交替共聚或嵌段共聚。申请人研究发现，当以对苯二甲酸为单体聚合时，得到的芳杂环聚合物树脂虽然强度较高，但收缩率稍微偏大，而加入邻苯二甲酸作为单体一起聚合时，得到的芳杂环聚合物树在保持较高强度的基础上，收缩率可以得到改善。
优选的，所述芳杂环聚合物树脂采用无机填料进行改性。
优选的，所述无机填料为云母、炭黑、白炭黑、滑石粉、硅灰石、氮化物、碳化物、氧化物、硫酸盐、碳酸盐、硅酸盐、氟硅酸盐和磷酸盐中的至少一种。
优选的，所述氮化物为氮化硅和/或氮化硼；所述碳化物为碳化硅和/或碳化硼；所述氧化物为氧化钙、氧化锌、氧化镁、氧化铁、二氧化硅和二氧化钛中的至少一种。
优选的，所述二氧化硅为纳米二氧化硅，所述二氧化钛为纳米二氧化钛。
优选的，所述硫酸盐为硫酸钙、硫酸镁、硫酸锌、硫酸钡、硫酸铁、硫酸亚铁中的至少一种；所述硅酸盐为硅酸钠、硅酸铝和硅酸镁中的至少一种；所述碳酸盐为碳酸钙、碳酸镁和碳酸锌中的至少一种；所述氟硅酸盐为氟硅酸钠、氟硅酸钾和氟硅酸镁中的至少一种；所述磷酸盐为磷酸钙、磷酸氢钙、磷酸镁和磷酸氢镁中的至少一种。
优选的，所述芳杂环聚合物树脂采用改性剂进行改性，所述改性剂为玻璃微珠、晶须、碳纤维、玻璃纤维、芳纶浆粕、芳纶短纤、硅酮和聚四氟乙烯中的至少一种。
本发明的另一个目的通过下述技术方案实现：一种高强度的芳杂环聚合物薄膜的制备方法，所述芳杂环聚合物薄膜由芳杂环聚合物树脂经酸浴湿法拉伸成膜工艺制得。
本发明的还一个目的通过下述技术方案实现：一种高强度的芳杂环聚合物薄膜的应用，所述芳杂环聚合物薄膜应用于高温胶带、FPC基材、COF基材、FCCL基材、碳化膜基材、石墨化散热膜基材、高温保护膜、LED灯条、OLED柔性显示基材、导电膜基材、高温绝缘膜或手机盖板。
本发明的有益效果在于：本发明的芳杂环聚合物薄膜具有较高的强度，还具有良好的尺寸稳定性、耐热性、耐氧化、电绝缘、耐溶剂性、特殊的导电性以及电致发光等性能，综合性能优异。
本发明的制备方法步骤简单，操作控制方便，质量稳定，生产效率高，生产成本低，可大规模化工业生产。
本发明的高强度的芳杂环聚合物薄膜在高温胶带、FPC基材、COF基材、FCCL基材、碳化膜基材、石墨化散热膜基材、高温保护膜、LED灯条、OLED柔性显示基材、导电膜基材、高温绝缘膜或手机盖板的应用。
具体实施方式
为了便于本领域技术人员的理解，下面结合实施例对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。
实施例1
一种高强度的芳杂环聚合物薄膜，所述芳杂环聚合物薄膜包括芳杂环聚合物树脂，所述芳杂环聚合物树脂的结构式如下：
其中，m为正整数。
所述芳杂环聚合物树脂的制备方法为：以对苯二甲酸和硫酸肼为反应原料，在发烟硫酸中进行缩聚反应，得到所述芳杂环聚合物树脂。对苯二甲酸、硫酸肼和发烟硫酸的摩尔比为1：(1.01、2.0、3.0、4.0或5.0)：(5、8、10、12或15)，其中发烟硫酸摩尔数以发烟硫酸中SO3摩尔数计。
所述芳杂环聚合物树脂采用无机填料进行改性。
所述无机填料为云母、炭黑、白炭黑、滑石粉、硅灰石、氮化物、碳化物和氧化物中的至少一种。
所述氮化物为氮化硅和/或氮化硼；所述碳化物为碳化硅和/或碳化硼；所述氧化物为氧化钙、氧化锌、氧化镁、氧化铁、二氧化硅和二氧化钛中的至少一种。
所述二氧化硅为纳米二氧化硅，所述二氧化钛为纳米二氧化钛。
实施例2
一种高强度的芳杂环聚合物薄膜，所述芳杂环聚合物薄膜包括芳杂环聚合物树脂，所述芳杂环聚合物树脂的结构式如下：
其中，n为正整数。
所述芳杂环聚合物树脂的制备方法为：以邻苯二甲酸和硫酸肼为反应原料，在发烟硫酸中进行缩聚反应，得到所述芳杂环聚合物树脂。邻苯二甲酸、硫酸肼和发烟硫酸的摩尔比为1：(1.01、2.0、3.0、4.0或5.0)：(5、8、10、12或15)，其中发烟硫酸摩尔数以发烟硫酸中SO3摩尔数计。
所述芳杂环聚合物树脂采用无机填料进行改性。
所述无机填料为硫酸盐、碳酸盐、硅酸盐、氟硅酸盐和磷酸盐中的至少一种。
所述硫酸盐为硫酸钙、硫酸镁、硫酸锌、硫酸钡、硫酸铁、硫酸亚铁中的至少一种；所述硅酸盐为硅酸钠、硅酸铝和硅酸镁中的至少一种；所述碳酸盐为碳酸钙、碳酸镁和碳酸锌中的至少一种；所述氟硅酸盐为氟硅酸钠、氟硅酸钾和氟硅酸镁中的至少一种；所述磷酸盐为磷酸钙、磷酸氢钙、磷酸镁和磷酸氢镁中的至少一种。
实施例3
一种高强度的芳杂环聚合物薄膜，所述芳杂环聚合物薄膜包括芳杂环聚合物树脂，所述芳杂环聚合物树脂的结构式如下：
其中，x和y均为正整数。
所述芳杂环聚合物树脂的制备方法为：以对苯二甲酸、邻苯二甲酸和硫酸肼为反应原料，在发烟硫酸中进行缩聚反应，得到所述芳杂环聚合物树脂。对苯二甲酸、邻苯二甲酸、硫酸肼和发烟硫酸的摩尔比为(0.01、0.30、0.50、0.80或0.99)：(0.99、0.80、0.50、0.30或0.01)：(1.01、2.0、3.0、4.0或5.0)：(5、8、10、12或15)，其中发烟硫酸摩尔数以发烟硫酸中SO3摩尔数计。
所述芳杂环聚合物树脂采用改性剂进行改性，所述改性剂为玻璃微珠、晶须、碳纤维、玻璃纤维、芳纶浆粕、芳纶短纤、硅酮和聚四氟乙烯中的至少一种。
实施例4
一种高强度的芳杂环聚合物薄膜的制备方法，所述芳杂环聚合物薄膜由芳杂环聚合物树脂经酸浴湿法拉伸成膜工艺制得。
实施例5
一种高强度的芳杂环聚合物薄膜的应用，所述芳杂环聚合物薄膜应用于高温胶带、FPC基材、COF基材、FCCL基材、碳化膜基材、石墨化散热膜基材、高温保护膜、LED灯条、OLED柔性显示基材、导电膜基材、高温绝缘膜或手机盖板。
经测试，本发明制得的芳杂环聚合物薄膜横向拉伸强度可以达到92-96MPa，纵向拉伸强度可以达到150-158MPa,具有较高的强度。
上述实施例为本发明较佳的实现方案，除此之外，本发明还可以其它方式实现，在不脱离本发明构思的前提下任何显而易见的替换均在本发明的保护范围之内。

Claims (10)

1.一种高强度的芳杂环聚合物薄膜，所述芳杂环聚合物薄膜包括芳杂环聚合物树脂，其特征在于：所述芳杂环聚合物树脂的结构式如下：
或者
或者
其中，m、n、x和y均为正整数。
2.根据权利要求1所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述芳杂环聚合物树脂的制备方法为：以对苯二甲酸和邻苯二甲酸中的至少一种和硫酸肼为反应原料，在发烟硫酸中进行缩聚反应，得到所述芳杂环聚合物树脂。
3.根据权利要求1所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述芳杂环聚合物树脂采用无机填料进行改性。
4.根据权利要求3所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述无机填料为云母、炭黑、白炭黑、滑石粉、硅灰石、氮化物、碳化物、氧化物、硫酸盐、碳酸盐、硅酸盐、氟硅酸盐和磷酸盐中的至少一种。
5.根据权利要求4所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述氮化物为氮化硅和/或氮化硼；所述碳化物为碳化硅和/或碳化硼；所述氧化物为氧化钙、氧化锌、氧化镁、氧化铁、二氧化硅和二氧化钛中的至少一种。
6.根据权利要求5所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述二氧化硅为纳米二氧化硅，所述二氧化钛为纳米二氧化钛。
7.根据权利要求4所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述硫酸盐为硫酸钙、硫酸镁、硫酸锌、硫酸钡、硫酸铁、硫酸亚铁中的至少一种；所述硅酸盐为硅酸钠、硅酸铝和硅酸镁中的至少一种；所述碳酸盐为碳酸钙、碳酸镁和碳酸锌中的至少一种；所述氟硅酸盐为氟硅酸钠、氟硅酸钾和氟硅酸镁中的至少一种；所述磷酸盐为磷酸钙、磷酸氢钙、磷酸镁和磷酸氢镁中的至少一种。
8.根据权利要求1所述的一种高强度的芳杂环聚合物薄膜，其特征在于：所述芳杂环聚合物树脂采用改性剂进行改性，所述改性剂为玻璃微珠、晶须、碳纤维、玻璃纤维、芳纶浆粕、芳纶短纤、硅酮和聚四氟乙烯中的至少一种。
9.如权利要求1-8任一项所述的一种高强度的芳杂环聚合物薄膜的制备方法，其特征在于：所述芳杂环聚合物薄膜由芳杂环聚合物树脂经酸浴湿法拉伸成膜工艺制得。
10.如权利要求1-8任一项所述的一种高强度的芳杂环聚合物薄膜的应用，其特征在于：所述芳杂环聚合物薄膜应用于高温胶带、FPC基材、COF基材、FCCL基材、碳化膜基材、石墨化散热膜基材、高温保护膜、LED灯条、OLED柔性显示基材、导电膜基材、高温绝缘膜或手机盖板。
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Citations (1)

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WO1994004253A2 (en) * 1992-08-13 1994-03-03 The Dow Chemical Company Polyazole polymer-based membranes for fluid separation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004253A2 (en) * 1992-08-13 1994-03-03 The Dow Chemical Company Polyazole polymer-based membranes for fluid separation

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