CN113024994B - 一种纳米凹凸棒土/酚醛气凝胶的制备方法及其在制备耐磨汽车轮胎中的应用 - Google Patents

一种纳米凹凸棒土/酚醛气凝胶的制备方法及其在制备耐磨汽车轮胎中的应用 Download PDF

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CN113024994B
CN113024994B CN202110186380.2A CN202110186380A CN113024994B CN 113024994 B CN113024994 B CN 113024994B CN 202110186380 A CN202110186380 A CN 202110186380A CN 113024994 B CN113024994 B CN 113024994B
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戴李宗
刘晓惠
曹和胜
陈国荣
罗伟昂
袁丛辉
曾碧榕
许一婷
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Xiamen University
Cheng Shin Petrel Tire Xiamen Co Ltd
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Abstract

本发明公开了一种纳米凹凸棒土/酚醛气凝胶的制备方法及其在制备汽车轮胎中的应用，原料选用橡胶80‑100份、白炭黑3‑8份、抗老化剂3‑6份、热稳定剂3‑4份、相容剂3‑5份，并添加纳米凹凸棒土/酚醛气凝胶颗粒阻燃剂3‑12份，制备汽车轮胎橡胶复合材料。该方法在汽车轮胎的橡胶中引入了纳米凹凸棒土/酚醛气凝胶颗粒，并进行了改性处理，以提高橡胶轮胎的耐磨性能。本发明方法制备的汽车轮胎的耐磨性强，韧性高，阻燃性能好。

Description

一种纳米凹凸棒土/酚醛气凝胶的制备方法及其在制备耐磨 汽车轮胎中的应用
技术领域
本发明属于汽车轮胎橡胶技术领域，具体涉及一种纳米凹凸棒土/酚醛气凝胶的制备方法及其在制备耐磨汽车轮胎中的应用。
背景技术
汽车轮胎对于现代的运输至关重要。橡胶复合材料是汽车轮胎的主要组成部分，其耐磨性能、阻燃性能、散热性能、抗湿滑性能和节能环保等都是非常重要的指标。
发展节能耐磨轮胎对轮胎行业至关重要。自2012年以来，汽车轮胎的燃油效率已被欧盟轮胎相关法规作为重要指标之一，我国自1988年开始高速公路的修建以来，规模发展迅速，截止至2019年年底，高速公路总里程达到14.96万公里，位居全球第一，近几年增长率趋缓也反映出国内高速公路建设布局日趋完善，因此必须发展具有高效阻燃的节能耐磨轮胎。轮胎的耐磨耗性和耐切割性是关乎轮胎使用寿命与汽车行驶安全性的重要因素，而现有的轮胎橡胶的生产路线，已不能满足国家对高性能且安全放心的汽车轮胎制造的要求，需要在轮胎耐磨性能上进行改性，以获得耐磨性好、阻燃能力强且适合远距离长时间运输的轮胎。另外，相比于在正常公路行驶的轻型轮胎，广泛应用于矿山、工地、重载荷装载机轮胎对胎体材料的耐磨性和耐切割性有更高的要求。
纳米凹凸棒土气凝胶是一种性能优异的纳米材料，其较高的孔隙率、膨胀体积和较大的比表面积，使其较原始凹凸棒土具有很好的分散特性，以及其优异的力学和热学性能使得纳米凹凸棒土气凝胶可作为补强材料应用于橡胶复合材料中。但纳米凹凸棒土本身具有很强的亲水性，较高的表面能并且极易发生聚集难以实现在橡胶中的均匀分散，阻碍了改善橡胶性能的可能性。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种纳米凹凸棒土/酚醛气凝胶的制备方法。
本发明的另一目的在于提供一种应用上述纳米凹凸棒土/酚醛气凝胶的耐磨橡胶材料。
本发明的再一目的在于提供上述耐磨橡胶材料制成的重型载荷汽车轮胎。
本发明的技术方案如下：
一种纳米凹凸棒土/酚醛气凝胶的制备方法，包括如下步骤：
(1)将双酚A、四乙烯五胺和多聚甲醛分散于1，4-二氧六环中，冰浴下搅拌0.8-1.2h后，恢复至室温继续搅拌4-12h，得到BA-TEPA单体，其结构式为：
Figure GDA0003305728190000021
n＝10-100；
(2)将原凹凸棒土分散于超纯水中，搅拌0.8-1.2h，接着加入乙二酸，于120-160℃进行水热反应2-8h后，再与80-140℃热处理10-40h，洗至中性后得到纳米凹凸棒土；
(3)将步骤(2)制得的纳米凹凸棒土超声分散在体积浓度为50％的乙醇水溶液中，再加入壳聚糖和醋酸，搅拌20-25h，接着加入步骤(1)制得的BA-TEPA单体，搅拌均匀后加入甲醛，搅拌2-4min后静置以形成凝胶，最后老化，形成湿凝胶；
(4)将步骤(3)制得的湿凝胶用乙醇和水的体积比为1-3∶100的溶剂置换3-4d后，进行冷冻干燥，即得所述纳米凹凸棒土/酚醛气凝胶。
在本发明的一个优选实施方案中，所述双酚A、四乙烯五胺、多聚甲醛和1，4-二氧六环的比例为1-4mol∶1-4mol∶4-16mol∶100-500mL。
在本发明的一个优选实施方案中，所述原凹凸棒土与超纯水的质量比为1∶5-30，加入所述乙二酸至终浓度为0.5-5M。
在本发明的一个优选实施方案中，所述步骤(3)为：将步骤(2)制得的纳米凹凸棒土超声分散在体积浓度为50％的乙醇水溶液中，再加入0.05-5wt％的壳聚糖和体积百分比为0.05-5％的醋酸，搅拌20-25h，接着加入步骤(1)制得的BA-TEPA单体，搅拌均匀后加入甲醛，搅拌2-4min后静置以形成凝胶，最后在20-70℃老化6-30h，形成湿凝胶。
进一步优选的，所述纳米凹凸棒土和BA-TEPA单体的质量比为0.05-0.5∶0.05-0.5。
更进一步优选的，所述纳米凹凸棒土、乙醇水溶液和所述醛的比例为0.05-0.5g∶9-11mL∶50-500μL。
在本发明的一个优选实施方案中，所述老化的温度为20-70℃，时间为6-30h。
本发明的另一技术方案如下：
一种耐磨橡胶材料，其原料包括上述制备方法制备的纳米凹凸棒土/酚醛气凝胶。
在本发明的一个优选实施方案中，其原料包括橡胶80-100份、白炭黑3-8份、抗老化剂3-6份、热稳定剂3-4份、相容剂3-5份和所述纳米凹凸棒土/酚醛气凝胶3-12份。
本发明的再一技术方案如下：
一种重型载荷汽车轮胎，由上述耐磨橡胶材料在内的原料制成。
本发明的有益效果是：
1、本发明以纳米凹凸棒土和壳聚糖为模板，甲醛为交联剂，制备纳米凹凸棒土/酚醛气凝胶，其中的BA-TEPA单体原位开环聚合得到的酚醛为交联剂，构筑阻燃的复合气凝胶材料，制备步骤简单，合成方法易操作，原料廉价易得，反应条件易控制；
2、本发明制备的纳米凹凸棒土/酚醛气凝胶具有超低的密度，能够有效减重橡胶复合材料，在提高汽车轮胎耐磨性的同时，又能提升汽车轮胎的阻燃性能，极大的满足对汽车轮胎制造高性能且安全放心的要求，尤其适合于对耐磨耗性能具有更高要求的装载机重载轮胎。
3、本发明制备的纳米凹凸棒土/酚醛气凝胶既能解决现有技术中纳米凹凸棒土团聚的问题，又能提高其在橡胶组分中相容性与分散性。
4、相比于酚醛及无机纳米凹凸棒土，本发明制备的纳米凹凸棒土/酚醛气凝胶与橡胶具有更高的内聚力，故其结合强度比酚醛颗粒粘结强度大很多。
5、本发明制备的纳米凹凸棒土/酚醛气凝胶通过成型加工后可作为与有机高分子、无机材料或金属基体复合作为增强力学性能的结构复合材料，并协同BA-TEPA与橡胶上的烯烃的交联作用，提高气凝胶与在橡胶中的分散性；其中的酚醛具有较好的阻燃性能和疏水性，同时还能提高橡胶的阻燃和耐湿滑性能。
附图说明
图1为本发明实施例1中的BA-TEPA单体的核磁氢谱图。
图2为本发明实施例1中的BA-TEPA单体的红外谱图。
图3为本发明实施例1中的纳米凹凸棒土的SEM图。
图4为本发明中对比例1(a)和实施例1(b)中所制备纳米凹凸棒土/酚醛气凝胶的压缩应力-应变曲线。
图5为本发明中对比例1(a)和实施例1(b)所制备纳米凹凸棒土/酚醛气凝胶的热重曲线图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)制备酚醛单体BA-TEPA：将双酚A、四乙烯五胺和多聚甲醛溶于100mL1，4-二氧六环中，冰浴下机械搅拌1h后，恢复至室温继续机械搅拌8h，得到均匀的黄色粘稠状流体，即为如图1和2所示的BA-TEPA单体，结构式为：
Figure GDA0003305728190000041
n＝10-100
其中，所述双酚A、四乙烯五胺(TEPA)、多聚甲醛和1，4-二氧六环的摩尔及用量比为1mol∶1mol∶4mol∶100mL。该BA-TEPA单体改性橡胶的反应原理如下：
Figure GDA0003305728190000042
(2)制备纳米凹凸棒土：将原凹凸棒土以质量比1∶20分散在超纯水中，搅拌1h，加入1M的乙二酸，经过140℃水热处理6h后，再120℃热处理24h后得到如图3所示的纳米凹凸棒土。
(3)制备气凝胶：将0.25g纳米凹凸棒土超声分散于10mL浓度为50％的乙醇水溶液中，取1％(wm)壳聚糖，1％(Vm)醋酸，搅拌24h，再加入0.05g BA-TEPA单体，搅拌均匀后，加入甲醛100μL，搅拌3min后静置以形成凝胶，最后在60℃老化8h后形成纳米凹凸棒土/酚醛的湿凝胶；
(4)将上述湿凝胶用乙醇和水的体积比为1∶100的溶剂置换3天后，-30℃冷冻干燥保持原有的凝胶空间结构，最终得到所述纳米凹凸棒土/酚醛气凝胶。
将本实施例制得的纳米凹凸棒土/酚醛气凝胶3-12份、橡胶80-100份、白炭黑3-8份、抗老化剂3-6份、热稳定剂3-4份和相容剂3-5份在密炼机混炼后的橡胶中，继续混炼后卸料到开料机经压延、压出和成型这三个过程出片，得到具有一定形状的可用于制备汽车耐磨轮胎的耐磨橡胶材料。
对比例1
本对比例制备了一种壳聚糖/酚醛气凝胶，与实施例1的区别在于：省略步骤(2)，取1％(wm)壳聚糖，1％(Vm)醋酸，搅拌24h，再加入0.05g BA-TEPA单体，搅拌均匀后，加入甲醛100μL，搅拌3min后静置以形成凝胶，最后在60℃老化8h后形成壳聚糖/酚醛的湿凝胶。
本对比例中的橡胶材料的制备同实施例1。
对比例2
本对比例制备了一种纳米凹凸棒土/壳聚糖气凝胶，与实施例1的区别在于：步骤(3)中，将0.25g纳米凹凸棒土超声分散在水/乙醇(VH2O/VEtOH＝1∶1)，取1％(wm)壳聚糖，1％(Vm)醋酸，搅拌24h，再加入甲醛100μL，搅拌3min后静置以形成凝胶。最后在60℃老化8h后形成湿凝胶。
本对比例中的橡胶材料的制备同实施例1。
上述实施例1和对比例2制得的耐磨橡胶材料的磨耗检测条件为：砂纸粗细度120A，打滑速度10m/min，打滑比为5％，荷重75N，时间15min。检测数据见下表：
Figure GDA0003305728190000051
图4中曲线a和曲线b分别为实施例1和对比例1所制备的气凝胶的压缩应力-应变曲线，表明实施例1所制备的气凝胶具有较好的机械性能。
图5中的a和b曲线分别为实施例1和对比例2所制备的气凝胶热重谱图，残炭率分别为63.4％和43.5％，表明实施例1所制备的气凝胶具有最好的阻燃效果。
由上述结果可知，本发明实施例制得的耐磨橡胶材料可用于制作重型载荷汽车轮胎。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (10)

1.一种纳米凹凸棒土/酚醛气凝胶的制备方法，其特征在于：包括如下步骤：
(1)将双酚A、四乙烯五胺和多聚甲醛分散于1，4-二氧六环中，冰浴下搅拌0.8-1.2h后，恢复至室温继续搅拌4-12h，得到BA-TEPA单体，其结构式为：
Figure FDA0003305728180000011
(2)将原凹凸棒土分散于超纯水中，搅拌0.8-1.2h，接着加入乙二酸，于120-160℃进行水热反应2-8h后，再于 80-140℃热处理10-40h，洗至中性后得到纳米凹凸棒土；
(3)将步骤(2)制得的纳米凹凸棒土超声分散在体积浓度为50％的乙醇水溶液中，再加入壳聚糖和醋酸，搅拌20-25h，接着加入步骤(1)制得的BA-TEPA单体，搅拌均匀后加入甲醛，搅拌2-4min后静置以形成凝胶，最后老化，形成湿凝胶；
(4)将步骤(3)制得的湿凝胶用乙醇和水的体积比为1-3∶100的溶剂置换3-4d后，进行冷冻干燥，即得所述纳米凹凸棒土/酚醛气凝胶。
2.如权利要求1所述的制备方法，其特征在于：所述双酚A、四乙烯五胺、多聚甲醛和1，4-二氧六环的比例为1-4mol∶1-4mol∶4-16mol∶100-500mL。
3.如权利要求1所述的制备方法，其特征在于：所述原凹凸棒土与超纯水的质量比为1：5-30，加入所述乙二酸至终浓度为0.5-5M。
4.如权利要求1所述的制备方法，其特征在于：所述步骤(3)为：将步骤(2)制得的纳米凹凸棒土超声分散在体积浓度为50％的乙醇水溶液中，再加入0.05-5wt％的壳聚糖和体积百分比为0.05-5％的醋酸，搅拌20-25h，接着加入步骤(1)制得的BA-TEPA单体，搅拌均匀后加入甲醛，搅拌2-4min后静置以形成凝胶，最后在20-70℃老化6-30h，形成湿凝胶。
5.如权利要求4所述的制备方法，其特征在于：所述纳米凹凸棒土和BA-TEPA单体的质量比为0.05-0.5∶0.05-0.5。
6.如权利要求5所述的制备方法，其特征在于：所述纳米凹凸棒土、乙醇水溶液和所述醛的比例为0.05-0.5g∶9-11mL∶50-500μL。
7.如权利要求1所述的制备方法，其特征在于：所述老化的温度为20-70℃，时间为6-30h。
8.一种耐磨橡胶材料，其特征在于：其原料包括权利要求1至7中任一权利要求所述的制备方法制备的纳米凹凸棒土/酚醛气凝胶。
9.如权利要求8所述的一种耐磨橡胶材料，其特征在于：其原料包括橡胶80-100份、白炭黑3-8份、抗老化剂3-6份、热稳定剂3-4份、相容剂3-5份和所述纳米凹凸棒土/酚醛气凝胶3-12份。
10.一种重型载荷汽车轮胎，其特征在于：由包括权利要求8或9所述的耐磨橡胶材料在内的原料制成。
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