CN104558710A - 一种用于轮胎三角胶的橡胶材料的制备方法 - Google Patents
一种用于轮胎三角胶的橡胶材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于轮胎三角胶的橡胶材料的制备方法，属于橡胶材料技术领域。主要方法包括有：改性丙烯酸树脂的制备、聚氨酯预聚体的制备、改性聚氨酯的制备的步骤，然后将改性聚氨酯、天然橡胶、石墨、炭黑、石蜡油、防老剂、硫磺、硫化促进剂混炼均匀，再经硫化得到橡胶材料。发明通过采用丙烯酸对聚氨酯进行改性，提高了橡胶材料的物理性能。
Description
技术领域
本发明涉及一种用于轮胎三角胶的橡胶材料的制备方法，属于橡胶材料技术领域。
背景技术
子午线轮胎的应力最大区域是胎肩和胎圈区，尤其在超载比较严重时，胎圈除承受着内压应力、制动力矩、 侧滑和离心力以及轮辋过盈力等， 还由于胎体帘线子午排列，帘布层数少， 胎体柔软，致使轮胎在行驶过程中一直处于反复曲挠状态之中，在这样的应力状态下，钢丝圈胎圈受力很大， 使得胎体帘布端点部位容易产生脱离，由于胎侧柔软，在行驶时尤其是高速行驶时会增加不稳定性，因此胎圈部位必须大大增强。三角形状芯胶 ( 简称三角胶 ) 是胎圈部位重要的部件，位于钢丝圈上端，起着填充、定位、承受应力的作用，不但对改善子午线轮胎侧向刚性分布起重要作用， 同时与胎侧区刚柔过渡要均匀和屈挠性好。
轿车轮胎三角胶的硬度较高，其配方常采用较高用量的炭黑、补强树脂或/和硫黄配合，从而造成胶料塑性低、柔软性差、加工困难，成型反包时难以压倒贴合而出现窝气现象；为改善工艺粘合性能而添加增粘树脂(熔点一般为90～140℃)会明显降低胶料物理性能、老化后性能，升高生热，增大部件挺性，使成品轮胎胎圈产生气泡；添加较多增塑剂则会明显降低胶料硬度或导致性能劣化。
专利CN102199314A公开了一种改进粘合体系的轮胎三角胶组合物及其制备方法。改进粘合体系的轮胎三角胶组合物,以下的组分按重量份数混炼构成：天然橡胶70～100、丁苯橡胶0～30、炭黑55～75、间苯二酚1.0～4.0、癸酸钴0.2～3.0、亚甲基给予体粘合剂3～8、白炭黑0～20、硫化剂和硫化促进剂3～8；其它加工助剂。但是这种橡胶在使用过程中存在有硬度、弹性不高的问题。
发明内容
本发明所要解决的技术问题是：用于轮胎三角胶的橡胶材料的硬度、弹性不高，对其组分进行了改进。
技术方案：
一种用于轮胎三角胶的橡胶材料的制备方法，包括如下步骤：
第1步、改性丙烯酸树脂的制备，按重量份计，将苯乙烯2～4份、丙烯酸1～2份、醋酸乙烯酯0.5～1份、甲基丙烯酸二甲氨基乙酯0.5～1份、引发剂0.2～0.4份混合均匀，得到单体混合物；把有机溶剂10～20份投入反应釜，升温回流并保持10～20分钟；滴加单体混合物，滴加完毕后，在回流状态下保持1.5～2.5小时；再在反应釜中加入引发剂0.2～0.4份，并在回流状态下保持1.5～2.5小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯12～14份、十八碳二元脂肪酸3～4份和聚丁二烯二醇15～20份，升温60～80℃进行反应1～3h；然后加入扩链剂1～2份，再进行反应1～3h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸1～2份、琼脂1.2～1.5份、偶联剂1～2份、聚乙烯醇2～2.4份混合均匀，升温60～80℃后，保温2～3h，即可；
第4步、将改性聚氨酯、天然橡胶200～240份、石墨3～5份、炭黑30～60份、石蜡油10～25份、防老剂1～3份、硫磺3～5份、硫化促进剂1～3份混合均匀，混炼均匀，再经硫化得到橡胶材料。
所述的第1步中，有机溶剂是甲苯或醋酸丁酯。
所述的第1步中，引发剂是过氧化二苯甲酰或偶氮二异丁氰。
所述的第2步中，扩链剂为l,4-丁二醇、新戊二醇、乙二醇、一缩二乙二醇、甘油、顺丁烯二酸酐、三羟甲基丙烷、乙二胺、二乙烯三胺、三乙烯四胺或二羟甲基丙酸中的一种或几种的混合物。
所述的第3步中，偶联剂是硅烷偶联剂KH -550、KH-560、KH-570中的一种。
所述的第4步中，硫化温度是150～170℃，时间20～40min，压力8～12 MPa。
所述的第4步中，硫化促进剂是指促进剂M或者促进剂DM。
有益效果
本发明通过采用丙烯酸对聚氨酯进行改性，提高了橡胶材料的物理性能。
具体实施方式
实施例
1
第1步、改性丙烯酸树脂的制备，将苯乙烯2Kg、丙烯酸1Kg、醋酸乙烯酯0.5Kg、甲基丙烯酸二甲氨基乙酯0.5Kg、过氧化二苯甲酰0.2Kg混合均匀，得到单体混合物；把甲苯10Kg投入反应釜，升温回流并保持10分钟；滴加单体混合物，滴加完毕后，在回流状态下保持1.5小时；再在反应釜中加入过氧化二苯甲酰0.2Kg，并在回流状态下保持1.5小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯12Kg、十八碳二元脂肪酸3Kg和聚丁二烯二醇15Kg，升温60℃进行反应1h；然后加入l,4-丁二醇1Kg，再进行反应1h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸1Kg、琼脂1.2Kg、KH-560偶联剂1Kg、聚乙烯醇2Kg混合均匀，升温60℃后，保温2h，即可；
第4步、将改性聚氨酯、天然橡胶200Kg、石墨3Kg、炭黑30Kg、石蜡油10Kg、防老剂1Kg、硫磺3Kg、硫化促进剂M 1Kg混合均匀，混炼均匀，再经硫化得到橡胶材料，硫化温度是150℃，时间20min，压力8MPa。
实施例
2
第1步、改性丙烯酸树脂的制备，将苯乙烯4Kg、丙烯酸2Kg、醋酸乙烯酯1Kg、甲基丙烯酸二甲氨基乙酯1Kg、过氧化二苯甲酰0.4Kg混合均匀，得到单体混合物；把甲苯20Kg投入反应釜，升温回流并保持20分钟；滴加单体混合物，滴加完毕后，在回流状态下保持2.5小时；再在反应釜中加入过氧化二苯甲酰0.4Kg，并在回流状态下保持2.5小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯14Kg、十八碳二元脂肪酸4Kg和聚丁二烯二醇20Kg，升温80℃进行反应3h；然后加入l,4-丁二醇2Kg，再进行反应3h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸2Kg、琼脂1.5Kg、KH-560偶联剂2Kg、聚乙烯醇2.4Kg混合均匀，升温80℃后，保温3h，即可；
第4步、将改性聚氨酯、天然橡胶240Kg、石墨5Kg、炭黑60Kg、石蜡油25Kg、防老剂3Kg、硫磺5Kg、硫化促进剂M 3Kg混合均匀，混炼均匀，再经硫化得到橡胶材料，硫化温度是170℃，时间40min，压力12 MPa。
实施例
3
第1步、改性丙烯酸树脂的制备，将苯乙烯3Kg、丙烯酸2Kg、醋酸乙烯酯0.7Kg、甲基丙烯酸二甲氨基乙酯0.8Kg、过氧化二苯甲酰0.3Kg混合均匀，得到单体混合物；把甲苯15Kg投入反应釜，升温回流并保持15分钟；滴加单体混合物，滴加完毕后，在回流状态下保持2小时；再在反应釜中加入过氧化二苯甲酰0.3Kg，并在回流状态下保持2小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯13Kg、十八碳二元脂肪酸4Kg和聚丁二烯二醇17Kg，升温70℃进行反应2h；然后加入l,4-丁二醇1Kg，再进行反应2h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸2Kg、琼脂1.3Kg、KH-560偶联剂1Kg、聚乙烯醇2.3Kg混合均匀，升温70℃后，保温2h，即可；
第4步、将改性聚氨酯、天然橡胶220Kg、石墨4Kg、炭黑50Kg、石蜡油20Kg、防老剂2Kg、硫磺4Kg、硫化促进剂M 2Kg混合均匀，混炼均匀，再经硫化得到橡胶材料，硫化温度是160℃，时间30min，压力10 MPa。
对照例
1
与实施例3的区别在于：第1步中未加入醋酸乙烯酯。
第1步、改性丙烯酸树脂的制备，将苯乙烯3Kg、丙烯酸2Kg、甲基丙烯酸二甲氨基乙酯0.8Kg、过氧化二苯甲酰0.3Kg混合均匀，得到单体混合物；把甲苯15Kg投入反应釜，升温回流并保持15分钟；滴加单体混合物，滴加完毕后，在回流状态下保持2小时；再在反应釜中加入过氧化二苯甲酰0.3Kg，并在回流状态下保持2小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯13Kg、十八碳二元脂肪酸4Kg和聚丁二烯二醇17Kg，升温70℃进行反应2h；然后加入l,4-丁二醇1Kg，再进行反应2h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸2Kg、琼脂1.3Kg、KH-560偶联剂1Kg、聚乙烯醇2.3Kg混合均匀，升温70℃后，保温2h，即可；
第4步、将改性聚氨酯、天然橡胶220Kg、石墨4Kg、炭黑50Kg、石蜡油20Kg、防老剂2Kg、硫磺4Kg、硫化促进剂M 2Kg混合均匀，混炼均匀，再经硫化得到橡胶材料，硫化温度是160℃，时间30min，压力10 MPa。
对照例
2
与实施例3的区别在于：第1步中未加入甲基丙烯酸二甲氨基乙酯。
第1步、改性丙烯酸树脂的制备，将苯乙烯3Kg、丙烯酸2Kg、醋酸乙烯酯0.7Kg、过氧化二苯甲酰0.3Kg混合均匀，得到单体混合物；把甲苯15Kg投入反应釜，升温回流并保持15分钟；滴加单体混合物，滴加完毕后，在回流状态下保持2小时；再在反应釜中加入过氧化二苯甲酰0.3Kg，并在回流状态下保持2小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯13Kg、十八碳二元脂肪酸4Kg和聚丁二烯二醇17Kg，升温70℃进行反应2h；然后加入l,4-丁二醇1Kg，再进行反应2h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸2Kg、琼脂1.3Kg、KH-560偶联剂1Kg、聚乙烯醇2.3Kg混合均匀，升温70℃后，保温2h，即可；
第4步、将改性聚氨酯、天然橡胶220Kg、石墨4Kg、炭黑50Kg、石蜡油20Kg、防老剂2Kg、硫磺4Kg、硫化促进剂M 2Kg混合均匀，混炼均匀，再经硫化得到橡胶材料，硫化温度是160℃，时间30min，压力10 MPa。
对照例
3
与实施例3的区别在于：聚氨酯未经过改性丙烯酸改性。
第1步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯13Kg、十八碳二元脂肪酸4Kg和聚丁二烯二醇17Kg，升温70℃进行反应2h；然后加入l,4-丁二醇1Kg，再进行反应2h，过滤后，将固态物烘干即可；
第2步、改性聚氨酯的制备：将聚氨酯预聚体、聚乳酸2Kg、琼脂1.3Kg、KH-560偶联剂1Kg、聚乙烯醇2.3Kg混合均匀，升温70℃后，保温2h，即可；
第3步、将改性聚氨酯、天然橡胶220Kg、石墨4Kg、炭黑50Kg、石蜡油20Kg、防老剂2Kg、硫磺4Kg、硫化促进剂M 2Kg混合均匀，混炼均匀，再经硫化得到橡胶材料，硫化温度是160℃，时间30min，压力10 MPa。
性能试验
从表中可以看出，本发明提供的橡胶材料具有良好的物理性能。其中，实施例与对照例1相比可以看出，通过在丙烯酸中引入醋酸乙烯酯可以提高最终制得的橡胶材料的断裂伸长率；实施例与对照例2相比可以看出，通过在丙烯酸树脂中引入甲基丙烯酸二甲氨基乙酯，可以提高橡胶材料的撕裂强度和硬度；通过实施例与对照例3相比可以看出，通过丙烯酸对聚氨酯进行改性之后，可以提高橡胶材料的硬度和拉伸强度。
Claims (7)
1.一种用于轮胎三角胶的橡胶材料的制备方法，其特征在于，包括如下步骤：
第1步、改性丙烯酸树脂的制备，按重量份计，将苯乙烯2～4份、丙烯酸1～2份、醋酸乙烯酯0.5～1份、甲基丙烯酸二甲氨基乙酯0.5～1份、引发剂0.2～0.4份混合均匀，得到单体混合物；把有机溶剂10～20份投入反应釜，升温回流并保持10～20分钟；滴加单体混合物，滴加完毕后，在回流状态下保持1.5～2.5小时；再在反应釜中加入引发剂0.2～0.4份，并在回流状态下保持1.5～2.5小时，放冷，过滤后，将固态物烘干即可；
第2步、聚氨酯预聚体的制备：在反应釜中，加入异佛尔酮二异氰酸酯12～14份、十八碳二元脂肪酸3～4份和聚丁二烯二醇15～20份，升温60～80℃进行反应1～3h；然后加入扩链剂1～2份，再进行反应1～3h，过滤后，将固态物烘干即可；
第3步、改性聚氨酯的制备：将改性丙烯酸树脂、聚氨酯预聚体、聚乳酸1～2份、琼脂1.2～1.5份、偶联剂1～2份、聚乙烯醇2～2.4份混合均匀，升温60～80℃后，保温2～3h，即可；
第4步、将改性聚氨酯、天然橡胶200～240份、石墨3～5份、炭黑30～60份、石蜡油10～25份、防老剂1～3份、硫磺3～5份、硫化促进剂1～3份混合均匀，混炼均匀，再经硫化得到橡胶材料。
2.根据权利要求1所述的用于轮胎三角胶的橡胶材料的制备方法，其特征在于：所述的第1步中，有机溶剂是甲苯或醋酸丁酯。
3.根据权利要求1所述的用于轮胎三角胶的橡胶材料的制备方法，其特征在于：所述的第1步中，引发剂是过氧化二苯甲酰或偶氮二异丁氰。
4.根据权利要求1所述的用于轮胎三角胶的橡胶材料的制备方法，其特征在于：所述的第2步中，扩链剂为l,4-丁二醇、新戊二醇、乙二醇、一缩二乙二醇、甘油、顺丁烯二酸酐、三羟甲基丙烷、乙二胺、二乙烯三胺、三乙烯四胺或二羟甲基丙酸中的一种或几种的混合物。
5.根据权利要求1所述的用于轮胎三角胶的橡胶材料的制备方法，其特征在于：所述的第3步中，偶联剂是硅烷偶联剂KH
-550、KH-560、KH-570中的一种。
6.根据权利要求1所述的用于轮胎三角胶的橡胶材料的制备方法，其特征在于：所述的第4步中，硫化温度是150～170℃，时间20～40min，压力8～12 MPa。
7.根据权利要求1所述的用于轮胎三角胶的橡胶材料的制备方法，其特征在于：所述的第4步中，硫化促进剂是指促进剂M或者促进剂DM。
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| WO2019093304A1 (ja) * | 2017-11-07 | 2019-05-16 | Ｊｘｔｇエネルギー株式会社 | 天然ゴム組成物及び接着剤 |
| CN108034224A (zh) * | 2017-12-19 | 2018-05-15 | 滁州环球聚氨酯科技有限公司 | 一种叉车轮毂表面包覆的聚氨酯层制备方法 |
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