CN114057952B - 一种发动机隔音垫及其制备方法 - Google Patents

一种发动机隔音垫及其制备方法 Download PDF

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CN114057952B
CN114057952B CN202111534390.7A CN202111534390A CN114057952B CN 114057952 B CN114057952 B CN 114057952B CN 202111534390 A CN202111534390 A CN 202111534390A CN 114057952 B CN114057952 B CN 114057952B
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杜歆耘
皮佳鑫
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Ningbo Shangwei Automotive Trim Co ltd
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Abstract

本发明公开了一种发动机隔音垫的制备方法,其包括以下步骤:S1:在惰性气体保护下,卤代均三嗪与不饱和烯烃醇在催化剂作用下回流反应,得到三嗪衍生物;S2:三嗪衍生物与6‑异氰酸己烷‑1‑胺继续加热回流反应,得到三嗪中间体;S3:低聚物二元醇和二异氰酸酯反应,得到羟基封端的聚氨酯预聚体;S4:三嗪中间体加入聚氨酯预聚体中进行扩链反应,得到主链含三嗪的聚氨酯弹性体;S5:乙烯基二茂铁加入到聚氨酯弹性体,再加入引发剂和发泡剂进行发泡反应,得到发动机隔音垫。本发明发动机隔音垫,不仅具有良好的隔音效果,而且具有优异的阻燃和耐热性,满足发动机严苛条件下对隔音垫长期使用的性能要求。

Description

一种发动机隔音垫及其制备方法
技术领域
本发明涉及隔音垫的技术领域,尤其涉及一种发动机隔音垫及其制备方法。
背景技术
发动机作为汽车重要部件工作时,不仅产生巨大的噪音污染,降低驾乘人员的舒适感,严重时带来驾驶危险;而且产生的高温会对发动机舱盖表面的车漆产生破坏作用,造成车漆加速老化,降低车漆的使用寿命。
发动机隔音垫起到很好的保护作用,越来越多的被应用在发动机上。现有发动机隔音垫材料主要有树脂/玻纤、树脂/棉纤或聚氨酯制作而成;其中,树脂/玻纤、树脂/棉纤制作而成的隔音垫重量重,成本高,对环境污染大;现有聚氨酯材料制作而成的隔音垫则隔音隔热效果一般。
发明内容
鉴于以上现有技术的不足之处,本发明提供了一种发动机隔音垫,以解决现有发动机隔音垫隔音效果一般,其阻燃和耐热性能较低,无法满足发动机严苛条件下对隔音垫长期使用的问题。
为达到以上目的,本发明采用的技术方案为:
一种发动机隔音垫的制备方法,所述制备方法包括以下步骤:
步骤S1:在惰性气体保护下,将卤代均三嗪与不饱和烯烃醇按摩尔比1:1搅拌溶解在溶剂中,再加入催化剂在温度为5~30℃的条件下回流反应6~48h,减压蒸馏后,得到结构式I所示的三嗪衍生物;所述卤代均三嗪与催化剂的质量比为100:0.5~5;
式中,X为氯或溴;R1选自1个碳或2个碳的烷烃基;R2、R3、R4独自选自H、甲基或乙基中的一种;
步骤S2:在惰性气体保护下,将步骤S1得到的三嗪衍生物与6-异氰酸己烷-1-胺按摩尔比1:2~5搅拌溶解在溶剂中,在温度为50~110℃的条件下回流反应5~24h,减压蒸馏后,得到结构式II所示的三嗪中间体;
步骤S3:将摩尔比为1.1~1.2:1的低聚物二元醇和二异氰酸酯混合,在温度为90~150℃,惰性气体保护条件下,搅拌反应2~5h,得到羟基封端的聚氨酯预聚体;
步骤S4:在惰性气体保护下,将步骤S2得到的三嗪中间体加入到步骤S3得到的聚氨酯预聚体中混合均匀;按摩尔比,二异氰酸酯和三嗪中间体的总和与低聚物二元醇之比为0.9~1.1:1,二异氰酸酯和三嗪中间体的摩尔比为0.5~2.5:1;在温度为50~100℃的条件下持续搅拌至反应完全,得到主链含三嗪的聚氨酯弹性体;
步骤S5:将乙烯基二茂铁加入到步骤S4得到的聚氨酯弹性体中,加入引发剂和发泡剂进行发泡反应,反应2~5h后,依次用乙醇和去离子水冲洗,以最后得到的聚氨酯弹性体作为中间层,无纺布设置在中间层的上下两个表面,模压裁切后,得到所述发动机隔音垫。
本发明以卤代均三嗪与不饱和烯烃醇为原料在催化剂作用下进行亲核取代反应,使卤代均三嗪其中一个活性位点被不饱和烯烃醇所取代,得到带有烯烃双键的三嗪衍生物;该三嗪衍生物继续与6-异氰酸己烷-1-胺进行亲核取代反应,使三嗪衍生物另外两个卤族元素活性位点被6-异氰酸己烷-1-胺所取代,得到带有二异氰酸结构的三嗪中间体;该三嗪中间体与羟基封端的聚氨酯预聚体继续进行扩链反应,得到主链含三嗪的聚氨酯弹性体。通过主链引入三嗪结构,提高了聚氨酯弹性体的耐高温和阻燃性,延长了发动机隔音垫的使用寿命。步骤5中,通过乙烯基二茂铁与主链含三嗪的聚氨酯弹性体上所带的烯烃双键进行加成反应,使得聚氨酯弹性体引入二茂铁结构,进一步提高了聚氨酯弹性体的耐高温和阻燃性,延长了发动机隔音垫的使用寿命;另外通过二茂铁结构的引入,使得聚氨酯弹性体具有一定的杀菌和减烟效果,防止细菌滋生,并降低隔音垫由于发动机舱着火造成的大量烟雾产生。
优选地,所述卤代均三嗪为2,4,6-三溴-1,3,5-三嗪或2,4,6-三氯-1,3,5-三嗪。
优选地,所述催化剂由适量羟丙基-β-环糊精添加的碳酸氢钠水溶液组成。所述碳酸氢钠的摩尔浓度为0.1~1.5mol/L,优选的是0.5~1mol/L;所述羟丙基-β-环糊精的添加量占碳酸氢钠水溶液总质量的0.05~2wt%,优选的是0.1~1wt%。
优选地,所述不饱和烯烃醇为丙烯醇、2-甲基-3-丁烯-2-醇、2-甲基烯丙醇、3-甲基-3-丁烯-2-醇、2-甲基-3-丁烯-1-醇、2-甲基-1-丁烯-4-醇中的至少一种。
优选地,所述低聚物二元醇为聚醚二元醇和聚酯二元醇中的至少一种。所述聚酯二元醇为聚己二酸乙二醇酯二醇和/或聚己二酸丁二醇酯二醇;所述聚醚二元醇为聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇中的至少一种。
优选地,所述二异氰酸酯为脂环类二异氰酸酯和芳香类二异氰酸酯中的至少一种。所述脂环类二异氰酸酯为异佛尔酮二异氰酸酯和/或4,4'-二环己基甲烷二异氰酸酯;所述芳香类二异氰酸酯为对苯二异氰酸酯、2,4-二苯甲烷二异氰酸酯、4,4’-二苯甲烷二异氰酸酯、苯二亚甲基二异氰酸酯中的至少一种。
优选地,在所述步骤S5前,先将步骤S4得到的聚氨酯弹性体在超临界CO2中进行一次发泡。通过超临界CO2中的一次发泡结合步骤S5发泡剂的二次发泡,使得本发明制备得到的聚氨酯弹性体具有高发泡倍率的特性,而且两次不同发泡条件造成孔隙的孔径分布范围广;聚氨酯弹性体内部丰富的孔隙使得传入的声音有效起到吸音和隔音效果。另外,通过二次发泡的聚氨酯弹性体作为发动机隔音垫减轻了隔音垫的重量,使其轻量化,更加环保安全。
优选地,所述乙烯基二茂铁加入量按乙烯基二茂铁与三嗪中间体摩尔比为1:1添加。
优选地,所述引发剂为过氧化二叔丁基、过氧化二异丙苯、过硫酸钾、过硫酸钠中的至少一种。
优选地,所述发泡剂为二氧化碳、二氧化碳/氮气、二氧化碳/乙醇、二氧化碳/水、二氧化碳/丙酮、二氧化碳/四氢呋喃中的至少一种。
本发明的另一方面是提供一种发动机隔音垫,其采用如上述发动机隔音垫的制备方法制备得到。
本发明的有益效果:
相对于现有发动机隔音垫,本发明发动机隔音垫,不仅具有良好的隔音效果,而且具有优异的阻燃和耐热性,并且还具有一定的抗菌和减烟作用,满足发动机严苛条件下对隔音垫长期使用的性能要求。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。
实施例1
本实施例的发动机隔音垫的制备方法,其包括以下步骤:
步骤S1:在惰性气体氮气的保护下,所述将2,4,6-三溴-1,3,5-三嗪与丙烯醇按摩尔比1:1搅拌溶解在THF(四氢呋喃)溶剂中,再加入催化剂在温度为10℃的条件下回流反应24h,减压蒸馏后,得到结构式I所示的三嗪衍生物;所述2,4,6-三溴-1,3,5-三嗪与催化剂的质量比为100:0.5;所述催化剂由适量羟丙基-β-环糊精添加的碳酸氢钠水溶液组成。所述碳酸氢钠的摩尔浓度为0.5mol/L;所述羟丙基-β-环糊精的添加量占碳酸氢钠水溶液总质量的0.5wt%;
步骤S2:在惰性气体氮气的保护下,将步骤S1得到的三嗪衍生物与6-异氰酸己烷-1-胺按摩尔比1:2.5搅拌溶解在THF溶剂中,在温度为50℃的条件下回流反应24h,减压蒸馏后,得到结构式II所示的三嗪中间体;
步骤S3:将摩尔比为1.1:1的聚四氢呋喃醚二醇(分子量为2000)和2,4-二苯甲烷二异氰酸酯混合,在温度为120℃,惰性气体氮气的保护条件下,搅拌反应5h,得到羟基封端的聚氨酯预聚体;
步骤S4:在惰性气体氮气的保护下,将步骤S2得到的三嗪中间体加入到步骤S3得到的聚氨酯预聚体中混合均匀;按摩尔比,2,4-二苯甲烷二异氰酸酯和三嗪中间体的总和与聚四氢呋喃醚二醇之比为1.1:1,2,4-二苯甲烷二异氰酸酯和三嗪中间体的摩尔比为2:1;在温度为90℃的条件下持续搅拌至反应完全,得到主链含三嗪的聚氨酯弹性体;
步骤S5:先将步骤S4得到的聚氨酯弹性体在超临界CO2中进行一次发泡,然后将乙烯基二茂铁加入到聚氨酯弹性体中,加入引发剂过氧化二叔丁基和由质量比为5:1的二氧化碳和乙醇复配的物理发泡剂进行二次发泡反应,反应3h后,依次用乙醇和去离子水冲洗,以最后得到的聚氨酯弹性体作为中间层,其体积密度18kg/m3,而面密度为100g/cm2的无纺布设置在中间层的上下两个表面,模压裁切后,得到所述发动机隔音垫。所述乙烯基二茂铁加入量按乙烯基二茂铁与三嗪中间体摩尔比为1:1添加,所述引发剂加入量占乙烯基二茂铁质量的0.15wt%,所述发泡剂加入量占聚氨酯弹性体质量的0.7wt%。所述一次发泡条件包括:温度为低于聚氨酯弹性体熔点的50℃,压力为10MPa,发泡时间为10min。所述二次发泡条件包括:温度为80℃,压力为7MPa,发泡时间为60min。聚氨酯弹性体的发泡倍率为2倍,孔径尺寸为50~200nm。
实施例2
本实施例的发动机隔音垫的制备方法,其包括以下步骤:
步骤S1:在惰性气体氮气的保护下,所述将2,4,6-三溴-1,3,5-三嗪与2-甲基烯丙醇按摩尔比1:1搅拌溶解在THF(四氢呋喃)溶剂中,再加入催化剂在温度为10℃的条件下回流反应48h,减压蒸馏后,得到结构式I所示的三嗪衍生物;所述2,4,6-三溴-1,3,5-三嗪与催化剂的质量比为100:1.5;所述催化剂由适量羟丙基-β-环糊精添加的碳酸氢钠水溶液组成。所述碳酸氢钠的摩尔浓度为0.8mol/L;所述羟丙基-β-环糊精的添加量占碳酸氢钠水溶液总质量的1wt%;
步骤S2:在惰性气体氮气的保护下,将步骤S1得到的三嗪衍生物与6-异氰酸己烷-1-胺按摩尔比1:3搅拌溶解在THF溶剂中,在温度为90℃的条件下回流反应24h,减压蒸馏后,得到结构式II所示的三嗪中间体;
步骤S3:将摩尔比为1.15:1的聚四氢呋喃醚二醇(分子量为2000)和2,4-二苯甲烷二异氰酸酯混合,在温度为120℃,惰性气体氮气的保护条件下,搅拌反应5h,得到羟基封端的聚氨酯预聚体;
步骤S4:在惰性气体氮气的保护下,将步骤S2得到的三嗪中间体加入到步骤S3得到的聚氨酯预聚体中混合均匀;按摩尔比,2,4-二苯甲烷二异氰酸酯和三嗪中间体的总和与聚四氢呋喃醚二醇之比为1.1:1,2,4-二苯甲烷二异氰酸酯和三嗪中间体的摩尔比为1.5:1;在温度为90℃的条件下持续搅拌至反应完全,得到主链含三嗪的聚氨酯弹性体;
步骤S5:先将步骤S4得到的聚氨酯弹性体在超临界CO2中进行一次发泡,然后将乙烯基二茂铁加入到聚氨酯弹性体中,加入引发剂过氧化二异丙苯和由质量比为4:1的二氧化碳和氮气复配的物理发泡剂进行二次发泡反应,反应5h后,依次用乙醇和去离子水冲洗,以最后得到的聚氨酯弹性体作为中间层,其体积密度13kg/m3,而面密度为100g/cm2的无纺布设置在中间层的上下两个表面,模压裁切后,得到所述发动机隔音垫。所述乙烯基二茂铁加入量按乙烯基二茂铁与三嗪中间体摩尔比为1:1添加,所述引发剂加入量占乙烯基二茂铁质量的0.25wt%,所述发泡剂加入量占聚氨酯弹性体质量的0.5wt%。所述一次发泡条件包括:温度为低于聚氨酯弹性体熔点的50℃,压力为15MPa,发泡时间为15min。所述二次发泡条件包括:温度为100℃,压力为8MPa,发泡时间为120min。聚氨酯弹性体的发泡倍率为3倍,孔径尺寸为50~200nm。
实施例3
本实施例的发动机隔音垫的制备方法,其包括以下步骤:
步骤S1:在惰性气体氮气的保护下,所述将2,4,6-三氯-1,3,5-三嗪与2-甲基-3-丁烯-1-醇按摩尔比1:1搅拌溶解在THF(四氢呋喃)溶剂中,再加入催化剂在温度为25℃的条件下回流反应48h,减压蒸馏后,得到结构式I所示的三嗪衍生物;所述2,4,6-三氯-1,3,5-三嗪与催化剂的质量比为100:5;所述催化剂由适量羟丙基-β-环糊精添加的碳酸氢钠水溶液组成。所述碳酸氢钠的摩尔浓度为1.2mol/L;所述羟丙基-β-环糊精的添加量占碳酸氢钠水溶液总质量的1.5wt%;
步骤S2:在惰性气体氮气的保护下,将步骤S1得到的三嗪衍生物与6-异氰酸己烷-1-胺按摩尔比1:5搅拌溶解在THF溶剂中,在温度为100℃的条件下回流反应12h,减压蒸馏后,得到结构式II所示的三嗪中间体;
步骤S3:将摩尔比为1.2:1的聚四氢呋喃醚二醇(分子量为2000)和2,4-二苯甲烷二异氰酸酯混合,在温度为120℃,惰性气体氮气的保护条件下,搅拌反应5h,得到羟基封端的聚氨酯预聚体;
步骤S4:在惰性气体氮气的保护下,将步骤S2得到的三嗪中间体加入到步骤S3得到的聚氨酯预聚体中混合均匀;按摩尔比,2,4-二苯甲烷二异氰酸酯和三嗪中间体的总和与聚四氢呋喃醚二醇之比为1.1:1,2,4-二苯甲烷二异氰酸酯和三嗪中间体的摩尔比为1:1;在温度为90℃的条件下持续搅拌至反应完全,得到主链含三嗪的聚氨酯弹性体;
步骤S5:先将步骤S4得到的聚氨酯弹性体在超临界CO2中进行一次发泡,然后将乙烯基二茂铁加入到聚氨酯弹性体中,加入引发剂过氧化二叔丁基和由质量比为5:1的二氧化碳和乙醇复配的物理发泡剂进行二次发泡反应,反应5h后,依次用乙醇和去离子水冲洗,以最后得到的聚氨酯弹性体作为中间层,其体积密度15kg/m3,而面密度为100g/cm2的无纺布设置在中间层的上下两个表面,模压裁切后,得到所述发动机隔音垫。所述乙烯基二茂铁加入量按乙烯基二茂铁与三嗪中间体摩尔比为1:1添加,所述引发剂加入量占乙烯基二茂铁质量的0.05wt%,所述发泡剂加入量占聚氨酯弹性体质量的0.2wt%。所述一次发泡条件包括:温度为低于聚氨酯弹性体熔点的20℃,压力为12MPa,发泡时间为5min。所述二次发泡条件包括:温度为80℃,压力为6MPa,发泡时间为30min。聚氨酯弹性体的发泡倍率为1.5倍,孔径尺寸为50~200nm。
将实施例1~3制备得到的发动机隔音垫进行性能测试,其性能结果如表1和表2所示:
其中,拉伸强度和伸长率采用CTM6000万能试验机(上海协强仪器)测试;氧指数按GB/T2406.2-2009进行测试,燃烧增长速率指数按GB20284-2006进行测试,烟密度按GB/T8627-2007进行测试。
耐湿热性测试:以实施例1~3制备得到的发动机隔音垫为样品(仅为中间层聚氨酯弹性体,两侧未设置无纺布),将样品置于温度为80℃,相对湿度为95%(RH)的条件下进行测试,连续试验48h检查一次,两次检查后,每间隔24h检查,以样品出现裂纹、颜色变化等外观缺陷的时间作为评价指标。
抗菌性测试:以革兰氏阴性菌大肠杆菌与革兰氏阳性菌金黄色葡萄球菌为评价对象,采用摇瓶法测试样品颗粒的抗菌性能,将细菌液与样品混合在摇床中培养24h,在600nm紫外波长下检测培养前后细菌浓度的变化,从而评价样品颗粒的抗菌性。
表1
表2
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。

Claims (9)

1.一种发动机隔音垫的制备方法,其特征在于,所述制备方法包括以下步骤:
步骤S1:在惰性气体保护下,将卤代均三嗪与不饱和烯烃醇按摩尔比1:1搅拌溶解在溶剂中,再加入催化剂在温度为5~30℃的条件下回流反应6~48h,减压蒸馏后,得到结构式I所示的三嗪衍生物;
式中,X为氯或溴;R1选自1个碳的烷烃基;R2、R3、R4独自选自H、甲基或乙基中的一种;
步骤S2:在惰性气体保护下,将步骤S1得到的三嗪衍生物与6-异氰酸己烷-1-胺按摩尔比1:2~5搅拌溶解在溶剂中,在温度为50~110℃的条件下回流反应5~24h,减压蒸馏后,得到结构式II所示的三嗪中间体;
步骤S3:将摩尔比为1.1~1.2:1的低聚物二元醇和二异氰酸酯混合,在温度为90~150℃,惰性气体保护条件下,搅拌反应2~5h,得到羟基封端的聚氨酯预聚体;
步骤S4:在惰性气体保护下,将步骤S2得到的三嗪中间体加入到步骤S3得到的聚氨酯预聚体中混合均匀;按摩尔比,二异氰酸酯和三嗪中间体的总和与低聚物二元醇之比为0.9~1.1:1,二异氰酸酯和三嗪中间体的摩尔比为0.5~2.5:1;在温度为50~100℃的条件下持续搅拌至反应完全,得到主链含三嗪的聚氨酯弹性体;
步骤S5:将乙烯基二茂铁加入到步骤S4得到的聚氨酯弹性体中,加入引发剂和发泡剂进行发泡反应,反应2~5h后,依次用乙醇和去离子水冲洗,以最后得到的聚氨酯弹性体作为中间层,无纺布设置在中间层的上下两个表面,模压裁切后,得到所述发动机隔音垫;所述发泡剂为二氧化碳、二氧化碳复配氮气、二氧化碳复配乙醇、二氧化碳复配水、二氧化碳复配丙酮、二氧化碳复配四氢呋喃中的至少一种;
在所述步骤S5前,先将步骤S4得到的聚氨酯弹性体在超临界CO2中进行一次发泡,然后进行步骤S5发泡剂的二次发泡。
2.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述卤代均三嗪为2,4,6-三溴-1,3,5-三嗪或2,4,6-三氯-1,3,5-三嗪。
3.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述催化剂由适量羟丙基-β-环糊精添加的碳酸氢钠水溶液组成。
4.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述不饱和烯烃醇为丙烯醇、2-甲基-3-丁烯-2-醇、2-甲基烯丙醇、3-甲基-3-丁烯-2-醇中的至少一种。
5.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述低聚物二元醇为聚醚二元醇和聚酯二元醇中的至少一种。
6.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述二异氰酸酯为脂环类二异氰酸酯和芳香类二异氰酸酯中的至少一种。
7.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述乙烯基二茂铁加入量按乙烯基二茂铁与三嗪中间体摩尔比为1:1添加。
8.如权利要求1所述的发动机隔音垫的制备方法,其特征在于,所述引发剂为过氧化二叔丁基、过氧化二异丙苯、过硫酸钾、过硫酸钠中的至少一种。
9.一种发动机隔音垫,其特征在于,所述发动机隔音垫采用如权利要求1~8任一项所述发动机隔音垫的制备方法制备得到。
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