CN115537013B - 耐核辐射聚氨酯弹性体材料及其制备方法 - Google Patents

耐核辐射聚氨酯弹性体材料及其制备方法 Download PDF

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CN115537013B
CN115537013B CN202211327818.5A CN202211327818A CN115537013B CN 115537013 B CN115537013 B CN 115537013B CN 202211327818 A CN202211327818 A CN 202211327818A CN 115537013 B CN115537013 B CN 115537013B
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杨雪
何琳
帅长庚
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Naval University of Engineering PLA
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Abstract

本发明涉及一种耐核辐射聚氨酯弹性体材料及其制备方法，解决了现有核领域减振器用弹性材料存在的力学性能和粘弹性不足，吸收核辐射能力有限的问题，其方法为将1,5‑萘二异氰酸酯、四氢呋喃‑氧化丙烯共聚醚二元醇、芳香族聚碳酸酯二元醇，苯酐聚酯二元醇在85摄氏度反应5小时，然后加入蒽醌和多元纳米线130摄氏度反应10小时制得。本发明弹性体材料由上述方法制备而成，其力学性能、耐核辐射性能和减振降噪性能优异。

Description

耐核辐射聚氨酯弹性体材料及其制备方法
技术领域
本发明涉及核领域，具体的说是一种耐核辐射聚氨酯弹性体材料及其制备方法。
背景技术
核领域减振器常用基体材料为硅橡胶、乙丙橡胶或丁腈橡胶，这些材料力学性能较差，动静模量比较大，不利于减振降噪，而且这些材料本身耐核辐射性能不佳，为了提高这些材料的耐核辐射性能常采用以下两方法：(1)主要加入抗氧剂，捕获自由基，这种方法在惰性气氛下有效，而在氧气存在时效果不佳；(2)加入能吸收辐射能的材料，如金属或添加剂。这种方法容易降低基体材料力学性能和粘弹性，而且吸收核辐射能力比较有限。
现有技术中聚氨酯材料作为弹性体多有报导，如公开号为109608607A公开了一种高性能聚氨酯弹性体材料及其制备方法，高性能聚氨酯弹性体材料，由A组分和B组分组成，A组分由甘油聚醚多元醇、增韧聚醚多元醇、扩链剂、催化剂和硅烷改性二硫化钨纳米材料组成，B组分为多异氰酸酯固化剂。本发明制备的硅烷改性二硫化钨纳米材料改性聚氨酯弹性体材料在冲击强度、耐磨性和防火阻燃性方面也有了显著的提高。又如110156947A公开了一种具有纳米孔道有机无机复合氧化锗纳米线掺杂聚氨酯弹性体合成方法，采用将硅烷偶联剂溶于丙酮溶剂中，加入氧化锗纳米线进行偶联反应，随后进行真空抽滤，粒子烘干备用，将聚己二酸丁二醇酯PBAG加入甲苯二异氰酸酯TDI反应生成预聚体，将两产物进行接枝，然后将制成掺杂聚氨酯弹性体的具有纳米孔道有机无机复合氧化锗纳米线。本发明可以在弹性体聚合过程充分吸收水分以及空气，使得材料更加致密，提高产品强度以及耐溶剂性。
现有聚氨酯弹性体制备多集中于如何提高弹性体的各项力学性能，但如果用于核领域的减振器制备时，由于处于核辐射下，同样存在耐核辐射性能不佳导致各项力学性能严重下降的问题。
发明内容
本发明的目的是为了解决上述技术问题，提供一种工艺简单、生产成本低、易于生产的耐核辐射聚氨酯弹性体材料的制备方法。
本发明的另一目的是提供使用上述方法制备的力学性能、耐核辐射性能和减振降噪性能优异的耐核辐射聚氨酯弹性体材料。
本发明耐核辐射聚氨酯弹性体材料的制备方法为：
将1,5-萘二异氰酸酯、四氢呋喃-氧化丙烯共聚醚二元醇、芳香族聚碳酸酯二元醇，苯酐聚酯二元醇在85摄氏度反应5小时，然后加入蒽醌和多元纳米线130摄氏度反应10小时制得。
所述四氢呋喃-氧化丙烯共聚醚二元醇的分子量为500-1500；芳香族聚碳酸酯二元醇的分子量为1500-2500，苯酐聚酯二元醇的分子量为500-1500。
所述蒽醌为1,2,4-三羟蒽醌，1,2,3-三羟蒽醌，1,4,5-三羟基蒽醌中的至少一种。
所述多元纳米线由银纤维、铅纤维与羟基化碳纳米管纤维编织而成。
所述银纤维、铅纤维和羟基化碳纳米管纤维的重量比为1:(1-2)：(0.1-1)。
所述多元纳米线的直径为50-150纳米。
所述各原料的重量份数比为：
1,5-萘二异氰酸酯30-60份、四氢呋喃-氧化丙烯共聚醚二元醇10-35份、芳香族聚碳酸酯二元醇40-60份、苯酐聚酯二元醇15-40、蒽醌15份、多元纳米线6.5-9.75份。
本发明耐核辐射聚氨酯弹性体材料由上述方法制得。
针对背景技术中存在的问题，发明人对现有耐核辐射高分子材料进行了深入研究，创造性地采用聚氨酯材料作为基体材料，基于应用的核辐射环境，以及作为制造减振器所需性能考虑，聚氨酯基体材料是由1,5-萘二异氰酸酯、四氢呋喃-氧化丙烯共聚醚二元醇、芳香族聚碳酸酯二元醇，苯酐聚酯二元醇和蒽醌组成，其中，1,5-萘二异氰酸酯中的萘环具有优异的耐核辐射性能和动态疲劳性能，芳香族聚碳酸酯二元醇和苯酐聚酯二元醇中的苯环具有优异的耐核辐射性能和力学性能；蒽醌具有优异的力学性能，其中的苯环具有优异的耐核辐射性能。在此基础上加入多元纳米线，当聚氨酯材料受到核辐射导致聚氨酯分子链断裂时，纳米线中的羟基可以和聚氨酯中的软段或硬段分子之间产生氢键相互作用力或交联反应，从而修复断裂的分子链段。所述多元纳米线由银纤维、铅纤维与羟基化碳纳米管纤维编织而成。其中，银纤维具有优异的耐核辐射性能和增强聚氨酯材料强度，铅纤维具有优异的耐核辐射性能，羟基化碳纳米管纤维具有优异的耐辐射性能，且能够和聚氨酯材料产生共价键或氢键作用，从而改善聚氨酯材料的自修复能力，三者共同作用可以实现优异的耐核辐照性能和自修复能力。优选的所述银纤维、铅纤维和羟基化碳纳米管纤维的重量比为1:(1.2-2)：(0.3-1)，所述羟基化碳纳米管纤维的添加量过高会导致聚氨酯材料力学强度降低和碎裂，而且也会使聚氨酯复合材料难以加工成型，过低会弱化聚氨酯材料的自修复能力，过多会导致聚氨酯材料力学强度降低，而且也会使聚氨酯复合材料难以加工成型，过少会减弱聚氨酯材料耐核辐射性能和自修复能力。
所述羟基化碳纳米管纤维是市场购买材料，此为现有技术，不作详述。
本发明耐辐射的原理：聚氨酯分子结构中含有大量的苯环，苯环结构中的大π结构能够吸收大量的γ辐射；材料中多元纳米线为银纤维、铅纤维与羟基化碳纳米管纤维编织成，该纳米线中银纤维和铅纤维原子序数较大，有很多电子，能够吸收大量γ辐射；碳纳米管中的大π键具有优异的电子离域能力，具有优异的导电性能，因此可以吸收大量的γ辐射，提高材料的耐核辐射性能。与此同时，加入纳米线后也提高了材料的弹性和力学性能，单一的纳米纤维耐核辐射性能有限，且对聚氨酯材料的弹性产生不利结果。
本发明方法简单、不需要苛刻的反应条件，生产制造成本低、周期短，制备的耐核辐射聚氨酯弹性体材料具有优异的力学性能、耐核辐射性能和减振降噪性能，特别适用于核领域减振器的制备。
具体实施方式
本发明实施例中各原料均可市购。
实施例
各原料配比参见表1：
表1实施例配比(重量比)
银纤维、铅纤维与羟基化碳纳米管纤维编织成直径为20-150nm的多元纳米线，实施例1-5中三者重量比值如表2所示：
表2
制备方法：
将1,5-萘二异氰酸酯、四氢呋喃-氧化丙烯共聚醚二元醇、芳香族聚碳酸酯二元醇，苯酐聚酯二元醇85摄氏度反应5小时，然后加入蒽醌和多元纳米线130摄氏度反应10小时制得，反应结束后即得弹性体。将弹性体放置1周后测试其耐核辐射性能(在250KGy辐照下拉伸强度保持率)、力学性能，结果见表3，对比结果表明，本发明的弹性体材料摩擦性能优异。
将表1所述实施例1-5的组分，按照上述方法进行制备，条件参数见表3，分别得到弹性体1-5。
表3力学性能

Claims (7)

1.一种耐核辐射聚氨酯弹性体材料的制备方法，其特征在于，
将1,5-萘二异氰酸酯、四氢呋喃-氧化丙烯共聚醚二元醇、芳香族聚碳酸酯二元醇、苯酐聚酯二元醇在85摄氏度反应5小时，然后加入蒽醌和多元纳米线130摄氏度反应10小时制得；
所述多元纳米线由银纤维、铅纤维与羟基化碳纳米管纤维编织而成。
2.如权利要求1所述的耐核辐射聚氨酯弹性体材料的制备方法，其特征在于，所述四氢呋喃-氧化丙烯共聚醚二元醇的分子量为500-1500；芳香族聚碳酸酯二元醇的分子量为1500-2500，苯酐聚酯二元醇的分子量为500-1500。
3.如权利要求1所述的耐核辐射聚氨酯弹性体材料的制备方法，其特征在于，所述蒽醌为1,2,4-三羟蒽醌，1,2,3-三羟蒽醌，1,4,5-三羟基蒽醌中的至少一种。
4.如权利要求3所述的耐核辐射聚氨酯弹性体材料的制备方法，其特征在于，银纤维、铅纤维和羟基化碳纳米管纤维的重量比为1:(1-2)：(0.1-1)。
5.如权利要求3所述的耐核辐射聚氨酯弹性体材料的制备方法，其特征在于，所述多元纳米线的直径为50-150纳米。
6.如权利要求1-5任一项所述的耐核辐射聚氨酯弹性体材料的制备方法，其特征在于，所述各原料的重量份数比为：
1,5-萘二异氰酸酯30-60份、四氢呋喃-氧化丙烯共聚醚二元醇10-35份、芳香族聚碳酸酯二元醇40-60份、苯酐聚酯二元醇15-40、蒽醌15份、多元纳米线6.5-9.75份。
7.一种耐核辐射聚氨酯弹性体材料，其特征在于，由权利要求1-6任一项方法制得。
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