CN110527065A - 一种高性能聚氨酯阻尼材料及其一步法制备方法 - Google Patents
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Abstract
本发明公开了一种高性能聚氨酯阻尼材料及其一步法制备方法,由如下重量百分比的原料制成:大分子多元醇10%~80%、异氰酸酯15%~70%、扩链剂5%~20%、催化剂0%~2%、其它助剂0~10%,各组分重量百分比之和为100%,其特征是所述扩链剂具有如下结构式:
Description
技术领域
本发明属于聚氨酯技术领域,具体涉及一种高强度、高损耗因子的聚氨酯材料及其制备方法。
背景技术
随着现代工业的迅猛发展,振动和噪声出现的频率和场所越来越多,高度自动化产生的振动及噪声充斥着生活的各个角落。振动、冲击和噪声等对社会生产和社会生活会造成严重的危害,一方面剧烈的振动直接影响仪器和仪表的正常工作,并且给电子器件、仪器仪表、工程结构及环境保护带来很多突出的问题,另一方面,振动、噪声等严重干扰了人们的工作和生活,危害人体健康。因此,减振降噪是当前许多领域迫切需要解决的重要问题。其中使用阻尼材料是最有效控制振动和噪声的方法之一。
聚氨酯材料具有一定的阻尼因子,为了进一步提高聚氨酯材料的阻尼性能,通常采用共混加入阻尼填料、接枝改性或引入阻尼结构单元等方法来提高阻尼因子,如专利文献CN 108034344A中采取加入羟基丙烯酸树脂、阻尼填料、吸声填料、加入含二氮芴结构的材料等来改善阻尼性能;专利文献CN105153394A中加入了填料碳纳米管和二氧化硅等来改善材料的耐热性和阻尼性;专利文献CN 107033324A采用使用端羟基超支化的聚酯、悬挂链预聚物等来改善阻尼性;专利文献CN 104448289A中在聚醚主链上引入侧基,增大内摩擦提高阻尼性。但引入阻尼填料、接枝改性或引入阻尼结构单元等易造成物料体系粘度增大、填料分散不均匀等,引起材料强度下降、硬度上升、阻尼性能不均匀等问题。
发明内容
本发明要解决的第一个技术问题是提供一种高性能聚氨酯阻尼材料,该材料不引入阻尼填料、接枝改性或引入阻尼结构单元,不会增大物料体系粘度。且具备优异的综合力学性能,提高材料的阻尼性能,以满足在某些特殊的减振工作环境下对材料制备工艺和强度的要求。
本发明要解决的第二个技术问题是提供一种该高性能聚氨酯阻尼材料的一步法制备工艺,操作简单便捷。
为解决第一个技术问题,本发明所采用的技术方案为:一种高性能聚氨酯阻尼材料,由如下重量百分比的原料制成:大分子多元醇10%~80%、异氰酸酯15%~70%、扩链剂5%~20%、催化剂0%~2%、其它助剂0~10%,各组分重量百分比之和为100%。
其中所述大分子多元醇分子量为400~8000,优选800~4000,平均官能度1.8~3.0。包括聚酯二元醇、聚醚二元醇、聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯三元醇。其中,聚酯二元醇包括小分子二元羧酸和小分子二元醇的反应产物,还包括各种内酯与二元醇反应得到的产物,如己内酯与乙二醇、二甘醇等反应制备的ε-聚己内酯二元醇(PCL)等。聚己内酯三元醇为己内酯与TMP反应制备的ε-聚己内酯三元醇。
所述二异氰酸酯包括芳香族二异氰酸酯、脂肪族二异氰酸酯或脂环族二异氰酸酯等,例如甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、对苯二异氰酸酯(PPDI)、1,5-萘二异氰酸酯(NDI)、3,3’-二甲基-4,4’-联苯二异氰酸酯(TODI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)或4,4’-二环己基甲烷二异氰酸酯(H12MDI)等。
所述扩链剂具有如下结构式:
其中R为烷基、支链烷基、环烷基、芳香基、含取代基的芳香基等。R1、R2、R3、R4为H、烷基、支链烷基、环烷基、芳香基或含取代基的芳香基等。
所述催化剂为叔胺类、有机铋类或有机锡类化合物等中的一种或多种混合物。叔胺类催化剂优选三乙烯二胺;有机铋类化合物选自异辛酸铋、羧酸铋或其组合,有机锡类化合物选自辛酸亚锡(T-9)、二辛酸二丁锡或二月桂酸二丁锡(T-12)等中的一种或多种。
本发明所述高性能聚氨酯阻尼材料,还可以加入常规助剂,例如阻燃剂、脱模剂、颜料、水解稳定剂、抗氧剂、增塑剂、抗静电剂、增强剂等。
为解决第二个技术问题,本发明提供一种该高性能聚氨酯阻尼材料的一步法制备方法:将除水后的大分子多元醇、扩链剂、催化剂和其它助剂保持在液体状态,按比例混合后,再加入异氰酸酯,混合均匀并脱泡,注入模具,待可脱模时脱模,在80~120℃下熟化16~24h,常温放置7d后,测试性能。
所得材料的性能如表1所示。
表1本发明所述高性能聚氨酯阻尼材料性能
项目 | 性能 |
硬度/邵A | 50~90 |
拉伸强度/MPa | 18~48 |
断裂伸长率/% | 400~650 |
最大损耗因子(tanδ) | ≥0.6 |
本发明高性能聚氨酯阻尼材料,在保持材料高力学强度的同时,避免使用阻尼填料或接枝改性或引入阻尼结构单元等造成物料体系粘度增大、填料分散不均匀造成材料强度下降、硬度上升、阻尼性能不均匀等问题。不仅具备普通聚氨酯弹性体的优点,即硬度可调范围较大、高强度和高伸长率、较好的耐磨性,还具有一般聚氨酯弹性体不具备的高阻尼性。可应用于对材料力学强度和阻尼性能要求均较高的阻尼减振场合。本发明制备高性能聚氨酯阻尼材料方法,采用一步法工艺,制备工艺简单、便捷。
具体实施方式
以下结合实施例对本发明作进一步说明。
扩链剂分子式:
实施例中扩链剂种类说明:
实施例 | 扩链剂种类 | R | R1 | R2 | R3 | R4 |
实施例1 | 扩链剂1 | -(CH<sub>2</sub>)<sub>2</sub>- | H | -CH<sub>3</sub> | H | H |
实施例2 | 扩链剂2 | -C(CH<sub>3</sub>)<sub>2</sub>- | H | H | H | H |
实施例3 | 扩链剂1 | -(CH<sub>2</sub>)<sub>2</sub>- | H | -CH<sub>3</sub> | H | H |
实施例4 | 扩链剂1 | -(CH<sub>2</sub>)<sub>2</sub>- | H | -CH<sub>3</sub> | H | H |
实施例1
(1)多元醇脱水:将400g数均分子量为2000的聚己内酯二元醇、在95~100℃,真空度-0.1MPa下脱水2h,水分合格后,出料备用。
(2)弹性体的制备:将脱水后数均分子量为2000的聚己内酯二元醇、扩链剂1和催化剂(使用丙二醇配制的三乙基二胺含量为33%的溶液),按比例100g/26.6g/0.05g混合均匀后,保持温度70℃,加入40g MDI混合均匀并脱泡后,浇入120℃的模具中,60min脱模,100℃后硫化20h,室温放置7天后测性能。所得材料性能见表2。
实施例2
(1)多元醇脱水:将400g数均分子量为1000的聚己内酯二元醇在95~100℃,真空度-0.1MPa下脱水2h,出料备用;将400g数均分子量为550的聚己内酯三元醇在95~100℃,真空度-0.1MPa下脱水2h,出料备用;
(2)弹性体的制备:将脱水后的聚己内酯二元醇、聚己内酯三元醇、扩链剂2,催化剂(使用丙二醇配制的三乙基二胺含量为33%的溶液)按比例100/31.2/19.7/0.08混合均匀后,保持温度在70℃,加入55g MDI混合均匀并脱泡后,浇入120℃的模具中,120min脱模,100℃后硫化20h,室温放置7天后测性能。所得材料性能见表2。
实施例3
(1)多元醇脱水:将400g数均分子量为2000的聚四氢呋喃二元醇在95~100℃,真空度-0.1MPa下脱水2h,出料备用。
(2)弹性体的制备:将脱水后数均分子量为2000的聚四氢呋喃二元醇、扩链剂1,催化剂T-12按比例100g//13.8g/0.0g8混合均匀,保持温度在80℃,加入18.5g TDI,混合均匀并脱泡后,浇入120℃的模具中,120min脱模,100℃后硫化24h,室温放置7天后测性能。所得材料性能见表2。
实施例4
(1)多元醇脱水:将400g数均分子量为1000的聚己二酸丁二醇酯二元醇在95~100℃,真空度-0.1MPa下脱水2h,水分合格后,出料备用。
(2)弹性体的制备:将脱水后数均分子量为1000的聚己二酸丁二醇酯二元醇、扩链剂1和(使用丙二醇配制的三乙基二胺含量为33%的溶液),按比例100g/36.8g/0.03g混合均匀,保持温度在85℃,加入40g PPDI混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化24h,室温放置7天后测性能。所得材料性能见表2。
对比例1
(1)多元醇脱水:将400g数均分子量为2000的聚己内酯二元醇、在95~100℃,真空度-0.1MPa下脱水2h,水分合格后,出料备用。
(2)弹性体的制备:将脱水后数均分子量为2000的聚己内酯二元醇、BDO和催化剂(使用丙二醇配制的三乙基二胺含量为33%的溶液),按比例100g/9.2g/0.05g混合均匀,保持温度在70℃,加入40g MDI,混合均匀并脱泡后,浇入120℃的模具中,60min脱模,100℃后硫化20h,室温放置7天后测性能。所得材料性能见表2。
表2 实施例所得材料性能
编号 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 |
硬度/邵A | 61 | 55 | 50 | 87 | 88 |
拉伸强度/MPa | 34 | 20 | 18 | 47 | 38 |
断裂伸长率/% | 550 | 440 | 620 | 590 | 560 |
最大损耗因子(tanδ) | 0.8 | 1.0 | 0.6 | 0.65 | 0.45 |
Claims (10)
1.一种高性能聚氨酯阻尼材料,由如下重量百分比的原料制成:大分子多元醇10%~80%、异氰酸酯15%~70%、扩链剂5%~20%、催化剂0%~2%、其它助剂0~10%,各组分重量百分比之和为100%,其特征是所述扩链剂具有如下结构式:
其中R为烷基、支链烷基、环烷基、芳香基、含取代基的芳香基;R1、R2、R3、R4为H、烷基、支链烷基、环烷基、芳香基或含取代基的芳香基。
2.根据权利要求1所述高性能聚氨酯阻尼材料,所述大分子多元醇是指聚酯二元醇、聚醚二元醇、聚四氢呋喃二元醇、聚碳酸酯二元醇或聚己内酯三元醇,分子量为400~8000,平均官能度1.8~3.0。
3.根据权利要求2所述高性能聚氨酯阻尼材料,所述聚酯二元醇是指小分子二元羧酸和小分子二元醇的反应产物,及各种内酯与二元醇反应得到的产物。
4.根据权利要求3所述高性能聚氨酯阻尼材料,聚酯二元醇是指己内酯与乙二醇、二甘醇反应制备的ε-聚己内酯二元醇(PCL)。
5.根据权利要求2所述高性能聚氨酯阻尼材料,所述聚己内酯三元醇是指己内酯与TMP反应制备的ε-聚己内酯三元醇。
6.根据权利要求1所述高性能聚氨酯阻尼材料,所述二异氰酸酯是指芳香族二异氰酸酯、脂肪族二异氰酸酯或脂环族二异氰酸酯。
7.根据权利要求6所述高性能聚氨酯阻尼材料,所述二异氰酸酯是指甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、对苯二异氰酸酯(PPDI)、1,5-萘二异氰酸酯(NDI)、3,3’-二甲基-4,4’-联苯二异氰酸酯(TODI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)或4,4’-二环己基甲烷二异氰酸酯(H12MDI)。
8.根据权利要求1所述高性能聚氨酯阻尼材料,所述催化剂为叔胺类、有机铋类或有机锡类化合物中的一种或多种混合物。叔胺类催化剂优选三乙烯二胺;有机铋类化合物选自异辛酸铋、羧酸铋或其组合,有机锡类化合物选自辛酸亚锡(T-9)、二辛酸二丁锡或二月桂酸二丁锡(T-12)中的一种或多种。
9.根据权利要求1所述高性能聚氨酯阻尼材料,其特征是还包括阻燃剂、脱模剂、颜料、水解稳定剂、抗氧剂、增塑剂、抗静电剂、增强剂。
10.一种制备权利要求1~9之一所述高性能聚氨酯阻尼材料的方法,将除水后的大分子多元醇、扩链剂、催化剂和其它助剂保持在液体状态,按比例混合后,再加入异氰酸酯,混合均匀并脱泡,注入模具,待可脱模时脱模,在80~120℃下熟化16~24h。
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