CN103756170B - 一种子午线轮胎气密层胶及其制备方法 - Google Patents

一种子午线轮胎气密层胶及其制备方法 Download PDF

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CN103756170B
CN103756170B CN201310749408.4A CN201310749408A CN103756170B CN 103756170 B CN103756170 B CN 103756170B CN 201310749408 A CN201310749408 A CN 201310749408A CN 103756170 B CN103756170 B CN 103756170B
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李春鹏
吴文雷
樊其艳
姚刚
成鲁南
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Chambroad Chemical Industry Research Institute Co Ltd
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Abstract

本发明公开了一种高分散ZnO母胶粒的子午线轮胎气密层胶及其制备方法,涉及一种橡胶及制备方法,主要以溴化丁基橡胶为原料,具体配方如下:溴化丁基橡胶100份,炭黑N660?45~60份,均匀剂40MFS2~4份,203树脂2~5份,氧化锌母胶粒3~5份,硫磺0.5~1份,促进剂MBTS1.5~2份,硬脂酸2~5份,氧化镁0.15~0.5份,环烷矿基物油8~10份;其中,氧化锌母胶粒由氧化锌粉与三元乙丙橡胶、顺丁橡胶、环烷矿物油及硬脂酸锌捏炼配合后采用冷喂料造粒制成。采用本发明,子午线轮胎气密层胶胶料的拉伸强度、定伸强度、耐老化性能及曲挠与耐疲劳性能等显著提高。

Description

一种子午线轮胎气密层胶及其制备方法
技术领域
本发明涉及一种橡胶及制备方法,特别涉及一种子午线轮胎气密层胶及其制备方法。
背景技术
随着国内高速公路的快速发展,子午线轮胎已经逐渐替代了传统的斜交轮胎,成为轮胎中的一种重要产品。目前,无内胎化正成为轮胎工业一大发展趋势,而气密层胶,作为子午线轮胎的主要产品部件,是影响无内胎轮胎气密性能的重要因素。气密层胶料要求具有较高的硫化程度,较好的耐疲劳性能,较高的拉伸强度和撕裂强度,与气密层相邻构件中的通用橡胶粘合性能好。目前,典型的轮胎气密层硫磺硫化体系包括:硫磺、氧化锌和促进剂。其中,粉末状的氧化锌分散不好,不利于加工成型,同时影响密封层胶的性能。
高分散氧化锌母胶粒(氧化锌-80)是随我国子午线轮胎生产线引进而引入的特种橡胶助剂,是把聚合物橡胶载体与粉体助剂氧化锌按照比例均匀复配造粒的高分散性高活性硫化活性剂。加入该种氧化锌母胶粒可以改善:(1)、氧化锌与溴化丁基橡胶的分散性;(2)、可以实现精确计量,保证硫化胶的质量;(3)便于运输和存储;(4)防止操作人员职业病危害;(5)提高橡胶与助剂之间的相容性,在橡胶中分散的更好,因此易于在橡胶中均匀分散,从而起到节能环保的效果,但是现有的氧化锌母胶粒一般仅仅由载体橡胶和氧化锌粉按照比例混合加工制成,加工性能一般,制造成本高。
发明内容
针对上述问题,本发明提供了一种高分散氧化锌母胶粒子午线轮胎气密层胶及其制备方法,改善子午线轮胎气密层胶混炼过程中氧化锌的计量不准、分散不均的状况,改善了操作环境与工作效率,进而显著提高胶料的拉伸强度、定伸强度、耐老化性能及曲挠与耐疲劳等性能。
本发明所述的气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66045~60份,均匀剂40MFS2~4份,203树脂2~5份,氧化锌母胶粒3~5份,硫磺0.5~1份,促进剂MBTS1.5~2份,硬脂酸2~5份,氧化镁0.15~0.5份,环烷基矿物油8~10份。
其中,溴化丁基橡胶是制备气密层胶的基体橡胶;其余为助剂。其中,炭黑N660用于补强溴化丁基橡胶;均匀剂40MSF用于分散炭黑N660;203树脂为增粘剂,提高了气密层胶与相邻构件中的通用橡胶粘合性能;氧化锌母胶粒、硫磺、促进剂MBTS、硬脂酸以及氧化镁可以使橡胶发生交联硫化,产生强度;环烷基矿物油改变橡胶的门尼粘度,使橡胶更易于加工。
经过发明人长期试验摸索发现,该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66060份,均匀剂40MFS4份,203树脂2份,氧化锌母胶粒3份,硫磺0.5份,促进剂MBTS1.5份,硬脂酸2份,氧化镁0.15份,环烷基矿物油8份时,效果最好。
本发明中,所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉65~80份,载体橡胶14~20份,环烷基矿物油3~6份;硬脂酸锌3~5份。
其中,所述的载体橡胶为三元乙丙橡胶与顺丁橡胶,两者可以以任意比例混合;环烷基矿物油是软化剂,用于降低母胶粒的门尼粘度;硬脂酸锌是润滑剂,改善氧化锌母胶粒挤出时效果,同时软化橡胶。
本发明中,由于采用了环烷基矿物油,降低了氧化锌母胶粒的粘度,易于后期加工;同时,与现有技术相比,本发明中,由于采用了环烷基矿物油,在载体橡胶用量减少的情况下,氧化锌粉也能够与载体橡胶充分的混合均匀,取得较好的实验效果,降低了成本。
经过发明人长期试验摸索发现,所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉80份,载体橡胶14份,环烷基矿物油3份;硬脂酸锌3份时,效果最好。
本发明还提供了所述子午线轮胎气密层胶的制备方法,其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为85~115℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度115-125℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中6~8h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
上述制备过程中,一段混炼胶排出密炼机后应置于空气中6~8h,待其完全干燥、冷却,主要保证其中的助剂进一步分散,以利于后续加工。由于加工温度太高造成橡胶软化,温度太低不利于助剂分散,因此上述制备过程中应严格控制其温度。
现有技术中,为了易于加工,往往需要对溴化丁基橡胶进行塑炼,在塑炼过程中由于带进空气,会形成诸多小胶粒,影响最终产品性能。而本发明中,由于采用了高分散氧化锌母胶粒以及环烷基矿物油,改善了溴化丁基橡胶的加工性能,从而使得溴化丁基橡胶在加工过程中不需要进行塑炼,避免了上述问题的发生,保证了最终产品性能。
本发明中,所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料。
现有技术中,为了保证载体橡胶具有较好的加工性能,易于后期造粒出料,氧化锌母胶粒前期制备过程中,往往采用较高的加工温度使其软化。但是,发明人发现,由于氧化锌粉硬度大,比重大,在制备过程中与载体橡胶之间存在较大摩擦。由于摩擦生热,从而在加工过程中,物料表面会携带有一定的温度,因此,在输送至挤出机时,无需采用热喂料,即可实现造粒出料。
由于加工过程中设备转数过高,会导致胶料温度过高,不利于后续的加工,同时,对氧化锌母胶粒表面和性能有一定影响,所以,本发明所述氧化锌母胶粒的制备过程中,所述开炼机的转速为24r/min。所述密炼机的转速为110r/min-190r/min,温度为45~75℃。捏炼机的转速为75r/min~110r/min。单螺杆冷喂料挤出机机头温度为45~60℃。
综上所述,本发明通过在气密层胶混炼过程中采用氧化锌母胶粒对其进行分散,改善了子午线轮胎气密层胶混炼过程中氧化锌的计量不准、分散不均的问题,改善了操作环境,提高了工作效率,进而显著提高胶料的拉伸强度、定伸强度、耐老化性能及曲挠与耐疲劳等性能。氧化锌母胶粒制备过程中采用环烷基矿物油以及冷喂料挤出加工工艺,降低了生产成本,降低了加工温度,节约能源,无三废排放,具有清洁高效、节能环保的优势。
具体实施方式:
实施例1
一种子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66060份,均匀剂40MFS4份,203树脂2份,氧化锌母胶粒3份,硫磺0.5份,促进剂MBTS1.5份,硬脂酸2份,氧化镁0.15份,环烷基矿物油8份。
所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉80份,载体橡胶14份,环烷基矿物油3份;硬脂酸锌3份。
所述的子午线轮胎气密层胶的制备方法,其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为85℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度115℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中8h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
其中,所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀,所述开炼机的转速为24r/min;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼,所述密炼机的转速为110r/min,温度为75℃;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料;所述捏炼机的转速为110r/min;所述单螺杆冷喂料挤出机机头温度为60℃。
本实施例采用的溴化丁基橡胶型号为BIIR2222。
实施例2
一种子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66045份,均匀剂40MFS4份,203树脂5份,氧化锌母胶粒4份,硫磺0.6份,促进剂MBTS1.8份,硬脂酸3份,氧化镁0.5份,环烷矿基物油9份。
所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉65份,载体橡胶17份,环烷基矿物油6份;硬脂酸锌4份。
所述的子午线轮胎气密层胶的制备方法,其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为95℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度125℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中6h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
其中,所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀,所述开炼机的转速为24r/min;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼,所述密炼机的转速为120r/min,温度为45℃;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料;所述捏炼机的转速为75r/min;所述单螺杆冷喂料挤出机机头温度为50℃。
本实施例采用的溴化丁基橡胶型号为SBB6222。
实施例3
一种子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66055份,均匀剂40MFS2份,203树脂3份,氧化锌母胶粒5份,硫磺1份,促进剂MBTS1.7份,硬脂酸5份,氧化镁0.1份,环烷矿基物油9.5份。
所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉75份,载体橡胶20份,环烷基矿物油4.5份;硬脂酸锌5份。
所述的子午线轮胎气密层胶的制备方法,其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为105℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度120℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中7h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
其中,所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀,所述开炼机的转速为24r/min;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼,所述密炼机的转速为150r/min,温度为55℃;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料;所述捏炼机的转速为95r/min;所述单螺杆冷喂料挤出机机头温度为55℃。
本实施例采用的溴化丁基橡胶型号为BIIR2235。
实施例4
一种子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66050份,均匀剂40MFS3份,203树脂5份,氧化锌母胶粒3.5份,硫磺0.7份,促进剂MBTS2份,硬脂酸4份,氧化镁0.12份,环烷矿基物油10份。
所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉70份,载体橡胶16份,环烷基矿物油4份;硬脂酸锌4.5份。
所述的子午线轮胎气密层胶的制备方法,其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为115℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度117℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中6.5h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
其中,所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀,所述开炼机的转速为24r/min;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼,所述密炼机的转速为190r/min,温度为65℃;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料;所述捏炼机的转速为105r/min;所述单螺杆冷喂料挤出机机头温度为60℃。
本实施例采用的溴化丁基橡胶型号为MD86-6。
实施例5
一种子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66060份,均匀剂40MFS3.5份,203树脂4份,氧化锌母胶粒4.5份,硫磺0.8份,促进剂MBTS1.6份,硬脂酸3.5份,氧化镁0.14份,环烷矿基物油8.5份。
所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉77份,载体橡胶18份,环烷基矿物油5份;硬脂酸锌3.5份。
所述的子午线轮胎气密层胶的制备方法,其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为100℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度122℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中7.5h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
其中,所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀,所述开炼机的转速为24r/min;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼,所述密炼机的转速为170r/min,温度为60℃;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料;所述捏炼机的转速为85r/min;所述单螺杆冷喂料挤出机机头温度为45℃。
本实施例采用的溴化丁基橡胶型号为BIIR2222。
表1本发明与现有技术所得气密层胶技术参数对比
实施例1 实施例2 实施例3 实施例4 实施例5 现有技术
混炼胶门尼 53 49 62 58 57 56
T5(135℃)/min 14 14.9 16.6 19.2 18.3 14
t90(160℃)/min 29.9 27.7 24.2 21.3 25.6 32
生胶强度/MPa(100%模量) 0.27 0.33 0.32 0.37 0.35 0.27
硬度 57 54 60 61 60 55
100%定伸应力/MPa 1.3 1.4 1.2 1.3 1.4 1.3
300%定伸应力/MPa 4.3 3.9 3.7 3.9 4.2 3.3
拉伸强度/MPa 9.3 7.7 9.1 9.0 9.2 8.1
扯断伸长率/% 721 683 812 727 801 621
松驰(75%)时间/min 1.5 1.5 2.4 2.0 2.2 1.3
由表1看出,本发明所述气密层胶,胶料的拉伸强度、定伸强度、耐老化性能及曲挠与耐疲劳性能等显著提高。

Claims (10)

1.一种子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66045~60份,均匀剂40MFS2~4份,203树脂2~5份,氧化锌母胶粒3~5份,硫磺0.5~1份,促进剂MBTS1.5~2份,硬脂酸2~5份,氧化镁0.15~0.5份,环烷基矿物油8~10份;
其具体制备步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为85~115℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度115-125℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中6~8h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
2.根据权利要求1所述的子午线轮胎气密层胶,其特征在于:该气密层胶的各组份按照重量份计,其配比为:溴化丁基橡胶100份,炭黑N66060份,均匀剂40MFS4份,203树脂2份,氧化锌母胶粒3份,硫磺0.5份,促进剂MBTS1.5份,硬脂酸2份,氧化镁0.15份,环烷基矿物油8份。
3.根据权利要求1或2所述的子午线轮胎气密层胶,其特征在于:所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉65~80份,载体橡胶14~20份,环烷基矿物油3~6份;硬脂酸锌3~5份。
4.根据权利要求3所述的子午线轮胎气密层胶,其特征在于:所述的氧化锌母胶粒各组份按照重量份计,其配比为:氧化锌粉80份,载体橡胶14份,环烷基矿物油3份;硬脂酸锌3份。
5.制备权利要求1所述的子午线轮胎气密层胶的方法,其特征在于:其具体步骤为:
(1)将溴化丁基橡胶、炭黑N660、203树脂以及硬脂酸按照比例投入密炼机,混合密炼,混炼温度为85~115℃;
(2)向上述密炼混合物中按照比例加入环烷基矿物油,混炼,温度115-125℃;
(3)将上述混合物继续混炼至140℃,排出密炼机,此胶称为一段混炼胶;
(4)将一段混炼胶置于空气中6~8h,待其完全干燥、冷却;
(5)将氧化锌母胶粒、硫磺、促进剂MBTS、氧化镁按照比例与一段混炼胶加入密炼机,混合密炼至105℃,排胶出料。
6.根据权利要求5所述的子午线轮胎气密层胶制备方法,其特征在于:所述的氧化锌母胶粒的具体制备步骤为:
(1)将载体橡胶及硬脂酸锌按照比例投入开炼机,塑炼均匀;
(2)将步骤(1)所得产物与氧化锌粉和环烷基矿物油按照比例投入密炼机,混合密炼;
(3)将步骤(2)中所得物料投至运输料斗,运至锥形双螺杆强制捏炼机,经捏炼后输送至单螺杆冷喂料挤出机,造粒出料。
7.根据权利要求6所述的子午线轮胎气密层胶制备方法,其特征在于:步骤(1)所述开炼机的转速为24r/min。
8.根据权利要求6所述的子午线轮胎气密层胶制备方法,其特征在于:步骤(2)所述密炼机的转速为110r/min~190r/min,温度为45-75℃。
9.根据权利要求6所述的子午线轮胎气密层胶制备方法,其特征在于:步骤(3)所述捏炼机的转速为75r/min~110r/min。
10.根据权利要求6所述的子午线轮胎气密层胶制备方法,其特征在于:步骤(3)所述单螺杆冷喂料挤出机机头温度为45~60℃。
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CN104943053A (zh) * 2015-06-01 2015-09-30 陈友寿 利用废旧轮胎橡胶注射生产汽车轮胎垫带的方法及其产品
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CN107828138A (zh) * 2017-12-12 2018-03-23 三角轮胎股份有限公司 巨型工程子午胎气密层用橡胶组合物及其制备方法
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