CN116278518B - 一种防扎防爆的聚氨酯轮胎及其制备方法 - Google Patents
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Abstract
本发明涉及聚氨酯轮胎技术领域，公开了一种防扎防爆的聚氨酯轮胎，包括轮胎本体和防扎防爆弹性体，所述防扎防爆弹性体包括依次设置在轮胎本体外胎内侧的基底层和弹性层；所述基底层包括如下质量份数的原料：聚酯多元醇50‑60份、甲苯二异氰酸酯10‑20份、扩链剂1‑3份；所述弹性层包括如下质量份数的原料：甲苯二异氰酸酯10份、氨丙基双封端聚二甲基硅氧烷1‑5份、氨基化多壁碳纳米管1‑5份、聚醚胺1‑5份、4,4'‑二氨基二环己基甲烷1‑5份。本发明的有益效果是：本发明中通过聚酯多元醇与二异氰酸酯发生反应，添加扩链剂反应后，得到基底液，基底液涂抹在轮胎本体外胎内侧，得到基底层，弹性液涂抹在基底层上，经过固化干燥得到防扎防爆的聚氨酯轮胎。
Description
技术领域
本发明涉及聚氨酯轮胎技术领域，尤其涉及一种防扎防爆的聚氨酯轮胎及其制备方法。
背景技术
轮胎是在各种车辆或机械上装配的接地滚动的圆环形弹性橡胶制品。在复杂和苛刻的条件下使用，它在行驶时承受着各种变形、负荷、力以及高低温作用，因此必须具有较高的承载性能、牵引性能、缓冲性能。同时，还要求具备高耐磨性和耐屈挠性，以及低的滚动阻力与生热性。
随着汽车工业的的发展以及汽车数量的持续增长，机动车轮胎的安全性能显得尤为重要。汽车在高速行驶过程中遭受异物，刺破轮胎，发生轮胎漏气是一件非常危险的事情，严重时会造成车毁人亡的交通事故，因此有必要开发出遭受异物，能保持胎压稳定，异物拔出后能够自愈密封的轮胎。
发明内容
为了解决上述背景技术中提到的问题，本发明提供一种防扎防爆的聚氨酯轮胎及其制备方法。
本发明第一方面提供了一种防扎防爆的聚氨酯轮胎，包括轮胎本体和防扎防爆弹性体，所述防扎防爆弹性体包括依次设置在轮胎本体外胎内侧的基底层和弹性层；
所述基底层包括如下质量份数的原料：
聚酯多元醇50-60份、甲苯二异氰酸酯10-20份、扩链剂1-3份；
所述弹性层包括如下质量份数的原料：
甲苯二异氰酸酯10份、氨丙基双封端聚二甲基硅氧烷1-5份、氨基化多壁碳纳米管1-5份、聚醚胺1-5份、4,4'-二氨基二环己基甲烷1-5份。
优选的，所述基底层、弹性层的总厚度≥2mm。
优选的，所述聚酯多元醇通过如下方法制备：
按照质量比将5-氟间苯二甲酸100份、乙二醇50份、1，3-丁二醇40份投入反应釜内搅拌混合，在氮气保护下加热，保持物料温度为150℃，保温0.5h，升温至物料温度180℃，加入催化剂反应，当酸值达到20mg KOH/g后，抽真空，加速反应，酸值和羟值达到设计值时，得到聚酯多元醇；
优选的，所述催化剂为4,5-双(二环己基膦)-9,9-二甲基氧杂蒽。
优选的，所述催化剂的添加量为5-氟间苯二甲酸、乙二醇、1，3-丁二醇总质量的200ppm。
优选的，所述扩链剂由组分A、4,7-二羟基-1,10-菲啰啉按照质量比2:1复配而成；
所述组分A通过如下方法制备：
在氮气氛围下，向容器内加入碳酸乙烯酯1.05mol、乙醇钠0.01mol，滴加2,6-二氨基-3,5-二氟吡啶1mol，滴加完毕后在80℃反应20h，降温出料，得到组分A。
本发明第二方面提供了一种防扎防爆聚的氨酯轮胎制备方法，包括如下步骤：
S1、将聚酯多元醇进行脱水，加入甲苯二异氰酸酯混合均匀，在60-80℃反应，制得预聚体；
S2、将扩链剂加入后搅拌反应，待反应完成，得到基底液；
S3、将甲苯二异氰酸酯、聚醚胺和甲苯在60-80℃混合搅拌反应，得到异氰酸预聚物，然后将氨丙基双封端聚二甲基硅氧烷、氨基化多壁碳纳米管、4,4'-二氨基二环己基甲烷和甲苯混合均匀后添加至上述异氰酸预聚物溶液中，待反应完成后，得到弹性液；
S4、将基底液、弹性液依次均匀的涂抹在轮胎本体外胎内侧，60-80℃干燥，得到防扎防爆的聚氨酯轮胎。
优选的，步骤S1中的脱水方法为：在温度为110℃，真空度为0.09MPa下，脱水至含水率小于0.03％。
与现有技术相比，本发明的有益效果是：
1、本发明中通过聚酯多元醇与二异氰酸酯发生反应，添加扩链剂反应后，得到基底液，基底液涂抹在轮胎本体外胎内侧，得到基底层，弹性液涂抹在基底层上，经过固化干燥得到防扎防爆的聚氨酯轮胎。
2、本发明聚氨酯轮胎，防扎性能十分优异，当铁钉扎入轮胎时，防扎防爆弹性体没有破裂、也没有出现明显漏气；当铁钉拔出轮胎后，防扎防爆弹性体会在胎压的作用下，自动填充到破损处，具有良好的自愈密封效果，尤其是实施例8的配方，防扎效果最优，插入铁钉10天后，胎压没有变化，保持2.40，拔出铁钉10天后，胎压仍然没有变化，继续保持2.40。
3、本发明聚氨酯的原料之一，聚酯多元醇采用一锅法制备，减少了操作步骤，简化了反应，发明人开发了新的催化剂，4,5-双(二环己基膦)-9,9-二甲基氧杂蒽，该催化剂市场上购买即可，不含金属，具有极高的催化活性，绿色环保。
4、本发明的扩链剂由组分A、4,7-二羟基-1,10-菲啰啉按照质量比2:1复配而成；采用组分A和4,7-二羟基-1,10-菲啰啉替代常规扩链剂，通过双羟基菲啰啉和含双羟基的氟吡啶的协同作用，制备得到的聚氨酯轮胎具有优异的力学性能。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，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他实施例，都属于本发明保护的范围。
如无特别说明，本发明使用的原料均来源于市场购买的常规产品。
其中，氨丙基双封端聚二甲基硅氧烷：采购于阿拉丁，分子量为1000；
氨基化多壁碳纳米管：采购于阿拉丁，外径：8-15nm，长度：～50μm；
聚醚胺：采购于阿拉丁，average Mn～2000。
制备例1
按照质量比将5-氟间苯二甲酸100份、乙二醇50份、1，3-丁二醇40份投入反应釜内搅拌混合，在氮气保护下，温度为150℃，保温0.5h，加入催化剂4,5-双(二环己基膦)-9,9-二甲基氧杂蒽(添加量为二元羧酸、二元醇总质量的200ppm)，反应2h，当酸值达到30mgKOH/g后，开始抽真空，加速反应，酸值和羟值达到设计值时，得到聚酯多元醇，羟基值为38.54mgKOH/g，酸值为0.4mg KOH/g。
制备例2
扩链剂由组分A、4,7-二羟基-1,10-菲啰啉按照质量比2:1复配而成；
所述组分A通过如下方法制备：
在氮气氛围下，向容器内加入碳酸乙烯酯1.05mol、乙醇钠0.01mol，滴加2,6-二氨基-3,5-二氟吡啶1mol，滴加完毕后在80℃反应20h，降温出料，得到组分A。
实施例1
一种防扎防爆的聚氨酯轮胎的制备方法，包括如下步骤：
S1、将聚酯多元醇50份进行脱水，加入甲苯二异氰酸酯10份混合均匀，在70℃反应1h，制得预聚体；
S2、将扩链剂1份加入后搅拌反应，待反应完成，得到基底液；
S3、将甲苯二异氰酸酯10份、聚醚胺2份和适量甲苯在80℃混合搅拌反应1h，得到异氰酸预聚物，然后将氨丙基双封端聚二甲基硅氧烷1份、氨基化多壁碳纳米管1份、4,4'-二氨基二环己基甲烷6份和适量甲苯混合均匀后添加至上述异氰酸预聚物溶液中，反应2h，待反应完成后，得到弹性液；
S4、将基底液、弹性液依次均匀的涂抹在轮胎本体外胎内侧，涂抹厚度2mm，60-80℃干燥1h，得到防扎防爆的聚氨酯轮胎。
步骤S1中的脱水方法为：在温度为110℃，真空度为0.09MPa下，脱水至含水率小于0.03％
实施例2
本实施例与实施例1的不同之处在于“甲苯二异氰酸酯20份”，其余和实施例1完全一样。
实施例3
本实施例与实施例1的不同之处在于“聚酯多元醇60份”，其余和实施例1完全一样。
实施例4
本实施例与实施例1的不同之处在于“聚酯多元醇60份，甲苯二异氰酸酯20份”，其余和实施例1完全一样。
实施例5
本实施例与实施例1的不同之处在于“扩链剂2份”，其余和实施例1完全一样。
实施例6
本实施例与实施例1的不同之处在于“扩链剂3份”，其余和实施例1完全一样。
实施例7
本实施例与实施例1的不同之处在于“氨丙基双封端聚二甲基硅氧烷3份、4,4'-二氨基二环己基甲烷4份”，其余和实施例1完全一样。
实施例8
本实施例与实施例1的不同之处在于“氨丙基双封端聚二甲基硅氧烷5份、4,4'-二氨基二环己基甲烷2份”，其余和实施例1完全一样。
实施例9
本实施例与实施例1的不同之处在于“氨基化多壁碳纳米管3份、4,4'-二氨基二环己基甲烷4份”，其余和实施例1完全一样。
实施例10
本实施例与实施例1的不同之处在于“氨基化多壁碳纳米管5份、4,4'-二氨基二环己基甲烷2份”，其余和实施例1完全一样。
本发明上述实施例1-10使用的轮胎本体为市面上常见的家用小汽车轮胎。
将实施例1-10制得的聚氨酯轮胎进行铁钉刺破轮胎内侧胎压试验，初始胎压为2.40kgf/cm2，铁钉直径为2mm，测试温度为50℃，插入铁钉10天后测胎压，然后将铁钉拔出，10天后再次测量胎压，另设置一空白对照，结果如下表1所示：
从表1中可知，本发明聚氨酯轮胎，防扎性能十分优异，当铁钉扎入轮胎时，防扎防爆弹性体没有破裂、也没有出现明显漏气；当铁钉拔出轮胎后，防扎防爆弹性体会在胎压的作用下，自动填充到破损处，具有良好的自愈密封效果，尤其是实施例8的配方，防扎效果最优，插入铁钉10天后，胎压没有变化，保持2.40，拔出铁钉10天后，胎压仍然没有变化，继续保持2.40。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种防扎防爆的聚氨酯轮胎，其特征在于，包括轮胎本体和防扎防爆弹性体，所述防扎防爆弹性体包括依次设置在轮胎本体外胎内侧的基底层和弹性层；
所述基底层包括如下质量份数的原料：
聚酯多元醇50-60份、甲苯二异氰酸酯10-20份、扩链剂1-3份；
所述弹性层包括如下质量份数的原料：
甲苯二异氰酸酯10份、氨丙基双封端聚二甲基硅氧烷1-5份、氨基化多壁碳纳米管1-5份、聚醚胺1-5份、4,4'-二氨基二环己基甲烷1-5份。
2.根据权利要求1所述的一种防扎防爆的聚氨酯轮胎，其特征在于，所述基底层、弹性层的总厚度≥2mm。
3.根据权利要求1所述的一种防扎防爆的聚氨酯轮胎，其特征在于，所述聚酯多元醇通过如下方法制备：
按照质量比将5-氟间苯二甲酸100份、乙二醇50份、1，3-丁二醇40份投入反应釜内搅拌混合，在氮气保护下加热，保持物料温度为150℃，保温0.5h，升温至物料温度180℃，加入催化剂反应，当酸值达到20mg KOH/g后，抽真空，加速反应，酸值和羟值达到设计值时，得到聚酯多元醇。
4.根据权利要求3所述的一种防扎防爆的聚氨酯轮胎，其特征在于，所述催化剂为4,5-双(二环己基膦)-9,9-二甲基氧杂蒽。
5.根据权利要求4所述的一种防扎防爆的聚氨酯轮胎，其特征在于，所述催化剂的添加量为5-氟间苯二甲酸、乙二醇、1，3-丁二醇总质量的200ppm。
6.根据权利要求1所述的一种防扎防爆的聚氨酯轮胎，其特征在于，所述扩链剂由组分A、4,7-二羟基-1,10-菲啰啉按照质量比2:1复配而成；
所述组分A通过如下方法制备：
在氮气氛围下，向容器内加入碳酸乙烯酯1.05mol、乙醇钠0.01mol，滴加2,6-二氨基-3,5-二氟吡啶1mol，滴加完毕后在80℃反应20h，降温出料，得到组分A。
7.一种如权利要求1-6任一项所述的防扎防爆的聚氨酯轮胎制备方法，其特征在于，包括如下步骤：
S1、将聚酯多元醇进行脱水，加入甲苯二异氰酸酯混合均匀，在60-80℃反应，制得预聚体；
S2、将扩链剂加入后搅拌反应，待反应完成，得到基底液；
S3、将甲苯二异氰酸酯、聚醚胺和甲苯在60-80℃混合搅拌反应，得到异氰酸预聚物，然后将氨丙基双封端聚二甲基硅氧烷、氨基化多壁碳纳米管、4,4'-二氨基二环己基甲烷和甲苯混合均匀后添加至上述异氰酸预聚物溶液中，待反应完成后，得到弹性液；
S4、将基底液、弹性液依次均匀的涂抹在轮胎本体外胎内侧，60-80℃干燥，得到防扎防爆的聚氨酯轮胎。
8.根据权利要求7所述的一种防扎防爆的聚氨酯轮胎制备方法，其特征在于，步骤S1中的脱水方法为：在温度为110℃，真空度为0.09MPa下，脱水至含水率小于0.03％。
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