CN111171390A - 一种白炭黑/天然橡胶复合材料制备方法 - Google Patents
一种白炭黑/天然橡胶复合材料制备方法 Download PDFInfo
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Abstract
本发明属于天然橡胶湿法混炼技术领域，涉及一种白炭黑/天然橡胶复合材料制备方法，利用湿法混炼工艺，通过机械研磨将白炭黑制备成均匀的分散溶液，与天然胶乳混合后，慢速搅拌使天然胶乳和白炭黑充分接触，利用高温雾化法产生的正电荷将带有负电荷的天然胶乳絮凝，并使白炭黑包裹其中，脱水烘干后制得白炭黑/天然橡胶复合材料，其创新点在于：第一，将配方中的除填料和胶乳外的其他橡胶助剂一起加入，实现配方中物料的预混，便于后期加工减少混炼时间和混炼时产生的粉尘污染；第二，加工方式连续化，将制备好的母胶投入到连续混炼机，可实现连续生产。
Description
技术领域：
本发明属于天然橡胶湿法混炼技术领域，涉及一种白炭黑/天然橡胶复合材料连续制备方法，具有绿色环保和耗能低的优势，能够缩短生产周期，并使白炭黑在天然橡胶中达到微观分散，提升橡胶性能。
背景技术：
混炼是橡胶产品加工过程中最为关键的工序，目的是将配方内的橡胶助剂与橡胶充分混合，并使橡胶助剂尽可能的分散均匀，与其说混炼结果的好坏直接决定着橡胶制品的性能和使用寿命，不如说橡胶助剂在橡胶中的分散和分布程度决定橡胶制品的性能和使用寿命，所以如何提高橡胶助剂在橡胶中的分散程度一直备受行业的广泛关注。
目前，橡胶工业中的传统混炼方式是沿用密炼机多段式混炼方法，但是由于橡胶具有粘弹性与其他高聚物不同，导致橡胶在混炼过程中因被不断地剪切而温升较快，为防止胶料焦烧影响橡胶加工安全，混炼过程非常短暂，导致橡胶助剂在橡胶中的分散很难达到理想状态；为了提高混炼效率，橡胶行业开发出新的混炼方法和工艺，包括低温一次法、串联式混炼和连续混炼等，虽然新的混炼技术能提高混炼效率和质量，由于橡胶的本质特性的仍然使得填料在混炼胶的分散等级达不到人们所期望的，尤其是传统混炼制备的白炭黑/天然橡胶复合材料。白炭黑是白色粉末状X-射线无定形硅酸和硅酸盐产品的总称，主要是指沉淀二氧化硅、气相二氧化硅和超细二氧化硅凝胶，也包括粉末状合成硅酸铝和硅酸钙等，白炭黑是多孔性物质，具有耐高温、不燃、无味、无嗅、具有很好的电绝缘性。白炭黑作为橡胶补强助剂的一种，与传统的炭黑补强助剂相媲美，并且由于本身特性能进一步解决橡胶轮胎中的“魔三角”问题。天然橡胶是应用最广的通用橡胶，具有优良的回弹性、绝缘性、隔水性及可塑性等特性，并且，经过适当处理后还具有耐油、耐酸、耐碱、耐热、耐寒、耐压、耐磨等宝贵性质，所以，具有广泛用途。例如日常生活中使用的雨鞋、暖水袋、松紧带；医疗卫生行业所用的外科医生手套、输血管、避孕套；交通运输上使用的各种轮胎；工业上使用的传送带、运输带、耐酸和耐碱手套；农业上使用的排灌胶管、氨水袋；气象测量用的探空气球；科学试验用的密封、防震设备；国防上使用的飞机、坦克、大炮、防毒面具；甚至连火箭、人造地球卫星和宇宙飞船等高精尖科学技术产品都离不开天然橡胶。随着天然橡胶广泛应用于交通运输、军工和航天等领域，天然橡胶与煤炭，钢铁，石油并称为四大工业原料。天然橡胶是天然胶乳经过收集、凝固、清洗和干燥等步骤制备而成，其中凝固工艺是形成天然橡胶的重要步骤。
为了突破传统机械混炼的桎梏，湿法混炼工艺应运而生，将制备成浆料的橡胶助剂与天然胶乳混合搅拌、絮凝干燥，制备成母胶进行混炼，其液态混合的优势能大大提高橡胶混炼质量。例如：中国专利201110064299.3公开的一种湿法混炼天然橡胶料的制备方法包括：A、配制浆料，浆料由白炭黑干料、去离子水、偶联剂和表面活性剂构成，配制程序是：1、将15-40％白炭黑干料浸泡在60-85％的去离子水中，浸泡时间为3-6小时；2、加入白炭黑干料含量的1-10％偶联剂、0.2-5％表面活性剂，机械搅拌使白炭黑干料、偶联剂和表面活性剂混合均匀，制成白炭黑浆料；B、研磨用研磨机将上述浆料研磨至沉降量小于80mg/L的白炭黑水分散体；C、制取胶乳混合液：1、取干胶含量为15-60％的天然橡胶的田间胶乳或经离心浓缩的天然胶乳；2、将制备好的白炭黑水分散体加入到胶乳中，在常温下搅拌20-50分钟；3、胶乳和白炭黑的水分散体均匀混合成胶乳混合液；D、絮凝、洗胶和脱水：1、在经混合均匀后的混合液中加入混合液总量的:0.3-1％的醋酸，使其pH值为3-5，胶乳均匀絮凝并与白炭黑共沉；2、凝固后的胶料用清水将多余的醋酸洗除，经洗胶机进行洗胶和脱水；3、脱水后的胶料送至橡胶造粒机造粒，然后将胶料粒送入箱式干燥柜中进行干燥，温度为90-120℃，干燥时间为4-6小时；E、干燥完全后即为天然橡胶的混炼胶料；其对传统混炼技术进行了改进，在制取的胶乳溶液中加入醋酸絮凝，经洗胶机洗胶和脱水，再在干燥箱中干燥，干燥后即可得到天然橡胶的混炼胶料。研究发现湿法混炼工艺虽然能够改善填料的微观分散程度，但是由于絮凝干燥方式多为酸性絮凝等化学手段，所以会对橡胶制品的性能产生影响。酸性絮凝方法存在不可消除的缺陷，不仅会影响操作人员的身体健康，腐蚀设备，絮凝后的长时间烘干容易产生影响环境的酸性气体，如果强酸清洗不干净还会影响后续的硫化时间，并且，在酸性环境下胶料的硫化时间会产生滞后现象，容易引起过硫影响橡胶制品性能。因此，研发一种绿色连续化制备的复合材料制备方法，是有良好的社会和应用前景。
发明内容：
本发明的目的在于克服现有技术中湿法混炼过程存在的缺点，研发设计一种白炭黑/天然橡胶复合材料连续制备方法，避免酸的使用，能够减少污染的产生和酸性残留对橡胶性能的影响，绿色环保。
为了实现上述目的，本发明涉及的白炭黑/天然橡胶复合材料制备方法称为高温雾化法，工艺过程包括制备白炭黑水溶液、制备助剂水溶液、制备白炭黑母胶和连续混炼共四个步骤：
(1)制备白炭黑水溶液：在1号烧杯中加入40质量份SiO2(二氧化硅)、5质量份液态Si69(硅烷偶联剂)溶液和去离子水配制成25wt％的白炭黑水溶液，将白炭黑水溶液置于超声波震荡仪中以1000Hz的频率超声10min，然后将超声之后的溶液置于行星式球磨机进行4h的二次破碎研磨；
(2)制备助剂水溶液：在2号烧杯中加入20质量份SiO2(二氧化硅)、2质量份4020(防老剂)、2质量份SAD(硬脂酸)、2质量份ZnO(氧化锌)、1.3质量份DPG(二苯胍)和去离子水配成25wt％的助剂水溶液，将助剂水溶液置于行星式球磨机研磨4h；
(3)制备白炭黑母胶：将180g步骤(1)制备的白炭黑水溶液、109.2g步骤(2)制备的助剂水溶液与166.67质量份60wt％的NRL(天然胶乳)混合，分别装入储存罐中，通过泵将三种溶液抽到搅拌罐中，利用搅拌器进行混合，搅拌频率为10-20Hz，将混合好的溶液通过喷射雾化形式絮凝干燥，喷射压力为0.5-2.0MPa，干燥温度为110-160℃，得到含有助剂的白炭黑母胶；
(4)连续混炼：将(3)制备的白炭黑母胶投入双螺杆结构的连续混炼机中进行混炼，混炼温度为90-150℃，转速为0-50r/min，混炼3-20min，得到白炭黑/天然橡胶复合材料。
本发明与现有技术相比，利用湿法混炼工艺，通过机械研磨将白炭黑制备成均匀的分散溶液，与天然胶乳混合后，慢速搅拌使天然胶乳和白炭黑充分接触，利用高温雾化法产生的正电荷将带有负电荷的天然胶乳絮凝，并使白炭黑包裹其中，脱水烘干后制得白炭黑/天然橡胶复合材料，其制备的混炼胶质量均一，不仅物理性能和动态力学性能相比于传统的混炼工艺都有显著提高，而且生产周期也得到了缩短，并使白炭黑在天然橡胶中达到了微观分散的效果；其原理科学可靠，没有使用酸，减少了污染，避免了酸性残留对橡胶性能的影响；创新点在于：第一，将配方中的除填料和胶乳外的其他橡胶助剂一起加入，实现配方中物料的预混，便于后期加工减少混炼时间和混炼时产生的粉尘污染；第二，加工方式连续化，将制备好的母胶投入到连续混炼机，可实现连续生产。
附图说明：
图1为本发明涉及的工艺流程示意图。
具体实施方式：
下面通过实施例并结合附图对本发明作进一步说明。
实施例1：
本实施例涉及的白炭黑/天然橡胶复合材料制备方法为高温雾化法，工艺过程包括制备白炭黑水溶液、制备助剂水溶液、制备白炭黑母胶和连续混炼共四个步骤：
(1)制备白炭黑水溶液：在1号烧杯中加入40质量份SiO2(二氧化硅)、5质量份液态Si69(硅烷偶联剂)溶液和去离子水配制成25wt％的白炭黑水溶液，将白炭黑水溶液置于超声波震荡仪中以1000Hz的频率超声10min，然后将超声之后的溶液置于行星式球磨机进行4h的二次破碎研磨；
(2)制备助剂水溶液：在2号烧杯中加入20质量份SiO2(二氧化硅)、2质量份4020(防老剂)、2质量份SAD(硬脂酸)、2质量份ZnO(氧化锌)、1.3质量份DPG(二苯胍)和去离子水配成25wt％的助剂水溶液，将助剂水溶液置于行星式球磨机研磨4h；
(3)制备白炭黑母胶：将180g步骤(1)制备的白炭黑水溶液、109.2g步骤(2)制备的助剂水溶液与166.67质量份60wt％的NRL(天然胶乳)混合，分别装入储存罐中，通过泵将三种溶液抽到搅拌罐中，利用搅拌器进行混合，搅拌频率为10Hz，将混合好的溶液通过喷射雾化形式絮凝干燥，喷射压力为1.2MPa，干燥温度为135℃，得到含有助剂的白炭黑母胶；
(4)连续混炼：将(3)制备的白炭黑母胶投入双螺杆结构的连续混炼机中进行混炼，混炼温度为130℃，转速为35r/min，混炼6min，得到白炭黑/天然橡胶复合材料。
实施例2：
本实施例涉及白炭黑/天然橡胶复合材料硫化胶料的综合性能测试，分别将使用烟片胶-干法、酸絮凝法-湿法和高温雾化法制备白炭黑/天然橡胶复合材料制备成胶料，其中，高温雾化法胶料的制备过程为：将步骤(4)制备的白炭黑/天然橡胶复合材料与1质量份S(硫)和1.2质量份CZ(N-环已基-2-苯并噻唑次磺酰胺)置于开炼机中薄通6次，得到胶料；对三份胶料分别进行机械性能测试，结果如下表：
根据拉伸强度和撕裂强度数据可知：高温雾化法制备的胶料在高形变下具有较高的强度，说明白炭黑—天然橡胶分子链网络结构多，作用力强，综合性能最高；根据定伸应力M300％/M100％的比值可知：高温雾化法制备的胶料的补强效果最好，能够使白炭黑纳米颗粒在天然橡胶基体中分散均匀。
Claims (1)
1.一种白炭黑/天然橡胶复合材料制备方法，其特征在于称为高温雾化法，工艺过程包括制备白炭黑水溶液、制备助剂水溶液、制备白炭黑母胶和连续混炼共四个步骤：
(1)制备白炭黑水溶液：在1号烧杯中加入40质量份SiO2、5质量份液态Si69溶液和去离子水配制成25wt％的白炭黑水溶液，将白炭黑水溶液置于超声波震荡仪中以1000Hz的频率超声10min，然后将超声之后的溶液置于行星式球磨机进行4h的二次破碎研磨；
(2)制备助剂水溶液：在2号烧杯中加入20质量份SiO2、2质量份4020、2质量份SAD、2质量份ZnO、1.3质量份DPG和去离子水配成25wt％的助剂水溶液，将助剂水溶液置于行星式球磨机研磨4h；
(3)制备白炭黑母胶：将180g步骤(1)制备的白炭黑水溶液、109.2g步骤(2)制备的助剂水溶液与166.67质量份60wt％的NRL混合，分别装入储存罐中，通过泵将三种溶液抽到搅拌罐中，利用搅拌器进行混合，搅拌频率为10-20Hz，将混合好的溶液通过喷射雾化形式絮凝干燥，喷射压力为0.5-2.0MPa，干燥温度为110-160℃，得到含有助剂的白炭黑母胶；
(4)连续混炼：将(3)制备的白炭黑母胶投入双螺杆结构的连续混炼机中进行混炼，混炼温度为90-150℃，转速为0-50r/min，混炼3-20min，得到白炭黑/天然橡胶复合材料。
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| CN111662488A (zh) * | 2020-07-16 | 2020-09-15 | 株洲安宝麟锋新材料有限公司 | 一种湿法混炼胶料的无酸制备方法 |
| CN113232187A (zh) * | 2021-04-27 | 2021-08-10 | 青岛科技大学广饶橡胶工业研究院 | 一种白炭黑与天然橡胶湿法混炼方法 |
| CN113232187B (zh) * | 2021-04-27 | 2022-08-19 | 青岛科技大学广饶橡胶工业研究院 | 一种白炭黑与天然橡胶湿法混炼方法 |
| CN115256685A (zh) * | 2022-06-22 | 2022-11-01 | 青岛黑猫新材料研究院有限公司 | 一种湿法混炼连续化脱水工艺 |
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