CN111716834B - 一种轮胎自修复胶条及其制备方法 - Google Patents

一种轮胎自修复胶条及其制备方法 Download PDF

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CN111716834B
CN111716834B CN202010617423.3A CN202010617423A CN111716834B CN 111716834 B CN111716834 B CN 111716834B CN 202010617423 A CN202010617423 A CN 202010617423A CN 111716834 B CN111716834 B CN 111716834B
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蒋凯
朱渊
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Wuxi I Reach Technology Co ltd
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Abstract

本发明提供了一种轮胎自修复胶条，从外到内共四层，分别为A层防穿透层、B层弹力层、C层抗压层、D层防护层。所述A层组成成分为热塑性弹性体、软化剂、抗氧剂、抗紫外线剂770；所述B层组成成分为聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂、橡胶；所述C层组成成分为橡胶、热塑性弹性体、树脂、软化剂、填料、抗氧剂；D层为离型纸或者PE膜。本发明制备的轮胎自修复胶条制备过程绿色环保具有良好的扯断伸长率、回弹性，低透气性，使轮胎在严苛的路面上具有良好的防护自愈功能。

Description

一种轮胎自修复胶条及其制备方法
技术领域
本发明涉及一种轮胎胶条，尤其属于轮胎自修复胶条。
背景技术
轮胎作为汽车和地面接触的唯一部件，直接影响着汽车的安全性能。在快速行驶的过程中，轮胎损伤引起的爆裂时刻影响着车内人员的生命安全。据统计，我国由于轮胎造成的交通事故高达70％。轮胎安全性能是未来发展基本要求。超耐磨、抗刺穿、舒适性好的轮胎被受关注。提高轮胎的使用寿命变得非常迫切。为提高胎面的抗刺扎性能及胎冠部位整体抗冲击性能，多采用调整胎面胶配或增加胎冠花纹沟基部胶厚度的方法进行，但对轮胎以上各性能的提高收效并不大，且不环保还增加了制造成本。
发明内容
由于现有技术中存在上述不足，本发明提供了一种轮胎自修复胶条。本发明提供的自修复胶条，可以用于轮胎，使轮胎在严苛的路面上具有良好的防护自愈功能。
具体地，本发明是通过下述技术方案实现的：
一种轮胎自修复胶条，从外到内共四层，分别为A层防穿透层、B层弹力层、C层抗压层、D层防护层，其中，所述A层组成成分按重量计为热塑性弹性体22-36份、软化剂50-75份、抗氧剂2-4份、抗紫外线剂770 1-2份；所述B层组成成分按重量计为聚酰胺树脂20-32份、聚醚酯纤维18-25份、填料5-10份、偶联剂2-4份、抗氧剂1-2份、橡胶10-15份；所述C层组成成分按重量计为橡胶11-16份、热塑性弹性体14-20份、树脂15-21份、软化剂40-55份、填料6-9份、抗氧剂1-3份；D层为离型纸或者PE膜。
优选地，橡胶为溴化丁基橡胶与天然橡胶的混合物，其中溴化丁基橡胶与天然橡胶的重量比为(0.2-1):1。
优选地，填料为纳米碳酸钙，高岭土、炭黑的组合物，其中，纳米碳酸钙，高岭土、炭黑的重量比为5:3:(1-2)。
优选地，热塑性弹性体为SBS、SIS、SEBS、SEPS、EVA、APAO中的一种或多种混合。
优选地，树脂为C5树脂、C5加氢树脂，C9树脂，C9加氢树脂，松香树脂、萜烯树脂、萜烯酚醛树脂中的一种或多种混合。
优选地，软化剂为环烷油、白油、聚异丁烯、增塑剂DOA、DOS中的一种或多种混合。
优选地，抗氧剂为抗氧剂2246、1010、16、264、770中的一种或多种混合。
轮胎自修复胶条的制备方法，其特征在于，包括下述步骤：
(1)A层制备：反应釜中加入软化剂、抗氧剂、抗紫外线剂770，220-250℃高温反应2-4h，然后加入热塑性弹性体，搅拌2-4h后出料，然后用涂布机做成厚度为1mm～3mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到220-250℃，投入软化剂，橡胶和热塑性弹性体，搅拌3-5h后加入抗氧剂、树脂和填料，再搅拌反应2-4h后，放料经过模头进行涂布，两面用D层粘贴，复合成厚度为0.5～1mm，宽度为1.2m的双面胶待用。
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂混合并在220～250℃下搅拌2-4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面D层的C层和A层复合成3～6mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
一种自修复安全轮胎，包括胎面、胎肩、胎侧、束带层、内衬层、气密层、趾口，其特征在于，还包括如权利要求1所述的轮胎自修复胶条，该自修复胶条使用在轮胎生产的成型工序阶段，去除D层保护膜之后，由C层粘贴于轮胎最内侧的气密层内侧，经过轮胎成型机成型之后与轮胎胚体一起硫化成轮胎成品。轮胎在硫化时，由于硫化胶囊的膨胀，轮胎的周长必定增加，这就要求胶条也能在高温下随之增长，同时待轮胎冷却之后，胶条不收缩回弹，不产生永久应力。本发明制备的轮胎自修复胶条完全可以达到这一目的，本发明制备的轮胎自修复胶条可以在高温下随胎体拉伸，由于B、C层的高粘性使得胶条在高温下可以同时拉伸到特定长度且不脱胶，拉伸后在常温下由于A、B、C层的相互影响不产生应力，不回弹，与轮胎完美贴合，无缝隙。
本发明的有益之处在于：本发明制备的轮胎自修复胶条分为4层，其中A层自身没有粘性，常温下扯断伸长率大于1000％，玻璃化温度点低于零下40度，而且耐刺穿；B层具有较强的形变恢复能力，能够有效的包裹钉子，当钉子拔出后，中间层B具有高形变恢复能力和高粘性，瞬间恢复并自愈合；C层扯断伸长率300％以上，有良好的硬度和内聚力，与轮胎胚体一起硫化的过程中，吸收轮胎胚体或者气密层中的硫化剂和硫化促进剂，增加硫化剂和硫化促进剂有效利用率，绿色环保的同时使C层硫化从而增加与轮胎胚体的粘接强度，保证不脱胶；D层为PE膜或者离型纸。本发明将这四层结合，综合其优点制备了一种具有良好的扯断伸长率、回弹性，低透气性的自修复胶条，使轮胎在严苛的路面上具有良好的防护自愈功能。本发明选用的橡胶为天然橡胶和溴化丁基橡胶组合物，众所周知，溴化丁基橡胶价格昂贵，天然橡胶价格低廉，本发明将两者结合保持了溴化丁基橡胶的低透气性，同时降低了成本；本发明采用纳米碳酸钙，高岭土、炭黑作为填料，一方面由于纳米碳酸钙具有良好的热稳定性，高岭土具有良好的阻隔性能，另一方面纳米碳酸钙和高岭土可以作为改性剂，有效提高炭黑在橡胶以及树脂中的分散性，提高胶条的力学性能，同时还可以减少炭黑的用量，炭黑具有较高的挥发性有机物，降低其使用也达到了环保的目的。
具体实施方式
下面结合具体方式来对本发明进行进一步详细阐述，下述实施例仅用来解释本发明，并不能视为对本发明的进一步限定。
实施例1
本发明的一种轮胎自修复胶条，配方见下表1。
表1一种轮胎自修复胶条的配方
Figure GDA0002816215300000051
轮胎自修复胶条的制备方法，包括下述步骤：
(1)A层制备：反应釜中加入环烷油、抗氧剂2246、抗紫外线剂770，240℃高温反应2h，然后加入EVA，搅拌4h后出料，然后用涂布机做成厚度为2mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到240℃，投入环烷油，橡胶和EVA，搅拌4h后加入抗氧剂1010、松香树脂和填料，再搅拌反应4h后，放料经过模头进行涂布，两面用PE膜，复合成厚度为1mm，宽度为1.2m的双面胶待用。
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂1010混合并在240℃下搅拌4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面PE膜的C层和A层复合成5mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
实施例2
本发明的一种轮胎自修复胶条，配方见下表2。
表2一种轮胎自修复胶条的配方
Figure GDA0002816215300000061
Figure GDA0002816215300000071
轮胎自修复胶条的制备方法，包括下述步骤：
(1)A层制备：反应釜中加入聚异丁烯、抗氧剂264、抗紫外线剂770，240℃高温反应2h，然后加入EVA，搅拌4h后出料，然后用涂布机做成厚度为2mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到240℃，投入聚异丁烯，橡胶和EVA，搅拌4h后加入抗氧剂1010、松香树脂和填料，再搅拌反应4h后，放料经过模头进行涂布，两面用PE膜，复合成厚度为1mm，宽度为1.2米的双面胶待用。
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂1010混合并在240℃下搅拌4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面PE膜的C层和A层复合成5mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
实施例3
本发明的一种轮胎自修复胶条，配方见下表3。
表3一种轮胎自修复胶条的配方
Figure GDA0002816215300000081
(1)A层制备：反应釜中加入环烷油、抗氧剂2246、抗紫外线剂770，240℃高温反应2h，然后加入EVA，搅拌4h后出料，然后用涂布机做成厚度为2mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到240℃，投入环烷油，橡胶和EVA，搅拌4h后加入抗氧剂1010、松香树脂和填料，再搅拌反应4h后，放料经过模头进行涂布，两面用PE膜，复合成厚度为1mm，宽度为1.2m的双面胶待用。
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂1010混合并在240℃下搅拌4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面PE膜的C层和A层复合成5mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
实施例4
本发明的一种轮胎自修复胶条，配方见下表4。
表4一种轮胎自修复胶条的配方
Figure GDA0002816215300000091
Figure GDA0002816215300000101
(1)A层制备：反应釜中加入环烷油、抗氧剂2246、抗紫外线剂770，240℃高温反应2h，然后加入EVA，搅拌4h后出料，然后用涂布机做成厚度为2mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到240℃，投入环烷油，橡胶和EVA，搅拌4h后加入抗氧剂1010、松香树脂和填料，再搅拌反应4h后，放料经过模头进行涂布，两面用PE膜，复合成厚度为1mm，宽度为1.2m的双面胶待用。
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂1010混合并在240℃下搅拌4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面PE膜的C层和A层复合成5mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
实施例5
本发明的一种轮胎自修复胶条，配方见下表5。
表5一种轮胎自修复胶条的配方
Figure GDA0002816215300000111
(1)A层制备：反应釜中加入环烷油、抗氧剂2246、抗紫外线剂770，240℃高温反应2h，然后加入EVA，搅拌4h后出料，然后用涂布机做成厚度为2mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到240℃，投入环烷油，橡胶和EVA，搅拌4h后加入抗氧剂1010、松香树脂和填料，再搅拌反应4h后，放料经过模头进行涂布，两面用PE膜，复合成厚度为1mm，宽度为1.2m的双面胶待用。
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂1010混合并在240℃下搅拌4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面PE膜的C层和A层复合成5mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
测试例
气体阻隔性能测试主要采用气体阻隔性测试仪测定。基于压差法的测试原理，在25℃，将试样放置于高压、低压之间，气体就会从高浓度一侧向低浓度渗透，通过检测低压方单位时间、单位面积透过试样的气体体积，表征提起阻隔性能。
拉伸实验依据GB/T528-2009《硫化橡胶或热塑性橡胶拉伸应力应变性能的测定》，拉伸速率为500mm/min、温度25℃、相对湿度50％。
回弹率测试为将胶条弯曲后，测试1min后回弹率。
试样：实施例1-5制备的轮胎自修复胶条，对照例1为实施例5中的橡胶改成天然橡胶，其余不变，对照例2为实施例5中的橡胶为仅为溴化丁基橡胶，对照例3实施例5中的填料仅为炭黑。将所制备的胶条经硫化剂硫化处理后进行实验，实验数据如下表6。
表6性能测试
Figure GDA0002816215300000131
天然橡胶的透气性是溴化丁基橡胶的5-10倍，但从对照例1和对照例2可以看出，本发明提供的制备方案有效弥补了天然橡胶透气性高的问题，将实施例1与实施例2进行比较，可以看出当橡胶中天然橡胶占83％与50％的时候，透气性差别进一步缩小。通过增加树脂含量以及改变填料比例以及改变热塑性弹性体的方式，从实施例5可以看出，本发明制备的胶条即使橡胶中天然橡胶占比83％，仍具有相当低的透气性。将实施例3与实施例4比较可以看出当填料中纳米碳酸钙:高岭土:炭黑为5:3:1，无论从透气性还是机械性能都更优。将实施例4与实施例5比较，可以发现当热塑性弹性体为EVA和SEBS，且两者重量比为7:1时，效果更好。
将实施例5制备的轮胎自修复胶条安装于轮胎气密层内侧，用钉子将轮胎扎一孔眼，然后拔出，隔一段时间进行压力测定，其中以未扎钉子的轮胎作为对照，结果如下表7。
表7轮胎压力
轮胎压力MPa 10天 30天 50天 80天 100天 120天
实施例 0.201 0.201 0.201 0.199 0.199 0.199
对照组 0.201 0.201 0.201 0.201 0.200 0.200
从表7可以看出，安装本发明制备的轮胎自修复胶条，即使遇到刺穿轮胎也基本不漏气。

Claims (9)

1.一种轮胎自修复胶条，其特征在于，从外到内共四层，分别为A层防穿透层、B层弹力层、C层抗压层、D层防护层，其中，所述A层组成成分按重量计为热塑性弹性体22-36份、软化剂50-75份、抗氧剂2-4份、抗紫外线剂770 1-2份；所述B层组成成分按重量计为聚酰胺树脂20-32份、聚醚酯纤维18-25份、填料5-10份、偶联剂2-4份、抗氧剂1-2份、橡胶10-15份；所述C层组成成分按重量计为橡胶11-16份、热塑性弹性体14-20份、树脂15-21份、软化剂40-55份、填料6-9份、抗氧剂1-3份；D层为离型纸或者PE膜。
2.根据权利要求1所述的轮胎自修复胶条，其特征在于，所述橡胶为溴化丁基橡胶与天然橡胶的混合物，其中溴化丁基橡胶与天然橡胶的重量比为(0.2-1):1。
3.根据权利要求1所述的轮胎自修复胶条，其特征在于，所述填料为纳米碳酸钙、高岭土、炭黑的组合物，其中，纳米碳酸钙、高岭土、炭黑的重量比为5:3:(1-2)。
4.根据权利要求1所述的轮胎自修复胶条，其特征在于，所述热塑性弹性体为SBS、SIS、SEBS、SEPS、EVA、APAO中的一种或多种混合。
5.根据权利要求1所述的轮胎自修复胶条，其特征在于，所述树脂为C5树脂、C5加氢树脂，C9树脂，C9加氢树脂，松香树脂、萜烯树脂、萜烯酚醛树脂中的一种或多种混合。
6.根据权利要求1所述的轮胎自修复胶条，其特征在于，所述软化剂为环烷油、白油、聚异丁烯、增塑剂DOA、DOS中的一种或多种混合。
7.根据权利要求1所述的轮胎自修复胶条，其特征在于，所述抗氧剂为抗氧剂2246、1010、16、264、770中的一种或多种混合。
8.根据权利要求1-7任意一项所述的轮胎自修复胶条的制备方法，其特征在于，包括下述步骤：
(1)A层制备：反应釜中加入软化剂、抗氧剂、抗紫外线剂770，220-250℃高温反应2-4h，然后加入热塑性弹性体，搅拌2-4h后出料，然后用涂布机做成厚度为1mm～3mm的厚度，宽度为1.2米的卷材待用；
(2)C层制备：反应釜加温到220-250℃，投入软化剂，橡胶和热塑性弹性体，搅拌3-5h后加入抗氧剂、树脂和填料，再搅拌反应2-4h后，放料经过模头进行涂布，两面用D层粘贴，复合成厚度为0.5～1mm，宽度为1.2m的双面胶待用；
(3)B层制备：将聚酰胺树脂、聚醚酯纤维、填料、偶联剂、抗氧剂混合并在220～250℃下搅拌2-4h，对共聚物改性，得到改性后的聚酰胺热熔胶，然后再加入橡胶，加入密炼机密炼1h；
(4)密炼后的B层用螺杆挤出机进行挤出，并跟去除一面D层的C层和A层复合成3～6mm的厚度，1.2米宽度的薄片，得轮胎自修复胶条。
9.一种自修复安全轮胎，包括胎面、胎肩、胎侧、束带层、内衬层、气密层、趾口，其特征在于，还包括如权利要求1所述的轮胎自修复胶条，该自修复胶条使用在轮胎生产的成型工序阶段，去除D层保护膜之后，由C层粘贴于轮胎最内侧的气密层内侧，经过轮胎成型机成型之后与轮胎胚体一起硫化成轮胎成品。
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