CN111499937B - 一种白炭黑配方橡胶连续混炼方法和装置 - Google Patents

一种白炭黑配方橡胶连续混炼方法和装置 Download PDF

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CN111499937B
CN111499937B CN202010293041.XA CN202010293041A CN111499937B CN 111499937 B CN111499937 B CN 111499937B CN 202010293041 A CN202010293041 A CN 202010293041A CN 111499937 B CN111499937 B CN 111499937B
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mixing
carbon black
white carbon
rubber
machine
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CN111499937A (zh
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边慧光
朱东林
汪传生
肖瑶
宋凤鹏
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Qingdao University of Science and Technology
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    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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Abstract

本发明属于橡胶制备技术领域，具体涉及一种白炭黑配方橡胶连续混炼方法和装置，将湿法混炼工艺与连续混炼进行结合，基于白炭黑配方橡胶连续混炼装置实现，将配方中所有填料和小料通过预处理方式与胶乳结合，然后通过高温雾化法制备包含配方物料的复合材料，最终通过高温/低温组合连续混炼机进行补充混炼，制备的白炭黑橡胶不仅物理性能和动态力学性能较常规干法混炼的炭黑橡胶有显著提高，而且生产周期也得到了缩短，并使填料在天然橡胶中达到了微观分散的效果；其没有使用酸，减少了污染，避免了酸性残留对橡胶性能的影响，能够缩短生产周期，并使填料在天然橡胶中达到均匀分布和分散，提升橡胶性能。

Description

一种白炭黑配方橡胶连续混炼方法和装置
技术领域：
本发明属于橡胶制备技术领域，具体涉及一种白炭黑配方橡胶连续混炼方法和装置，能够缩短生产周期，并使填料在天然橡胶中达到均匀分布和分散，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情况决定橡胶制品的性能和使用寿命，所以如何提高填料及助剂在橡胶基体中分散和分布以及能够实现连续混炼一直备受行业广泛关注。
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。例如：中国专利201710409066.X公开的一种提高含白炭黑混炼胶分散度的炼胶方法包括以下步骤：步骤1，检查密炼机上顶栓下压底位置，将上顶栓提升到高位，将天然橡胶、普通乳聚丁苯橡胶、顺丁橡胶、氧化锌、硬脂酸、偶联剂、粘合剂、白炭黑、炭黑N220在0秒时投入密炼机；步骤2，启动密炼机的高速剪切，同时对投入的物料进行加压剪切搅拌55秒；作业过程中，控制密炼机冷却循环水温在30～40℃；步骤3，当上顶栓刚下压到底，提起上顶栓后加入软化剂，同时对上顶栓上表面进行吹扫动作；步骤4，再加压混炼35秒，温度在145℃；步骤5，提起上顶栓进行排胶，从密炼室提出的混炼胶通过压片机进行压片冷却。
虽然新的混炼技术能提高混炼效率和质量，但由于橡胶的本质特性仍然使得填料在混炼胶的分散等级达不到人们的期望，尤其是传统混炼工艺制备的炭黑/天然橡胶复合材料，其主要由于炭黑表面基团和结构特性，导致传统混炼时无法填充高份数炭黑和在混炼时容易填料发生团聚；其次，目前的连续混炼技术对胶料有较多的要求，多适用于粒(粉)状预制母胶的混炼，还存在胶料与配合剂配比难以保证等现象；最后，现有连续混炼技术和设备生产过程仍存在间歇性，将会对连续混炼效率打折扣。
为了突破混炼工艺的桎梏，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201410462751.5公开的一种白炭黑湿法混炼胶的制备方法包括下列步骤：1)、橡胶溶液的化学和物理处理在搅拌下，于橡胶溶液中加入极性单体与之反应，使橡胶大分子主链上引入极性单体具有自乳化功能，反应温度在70～120℃，时间5～60分钟，极性单体质量分数为橡胶质量的0.5～5％，然后加入适量的水，维持温度在35～50℃；形成均相稳定的乳液或溶液稳定物料；所述极性单体为含酯基的丙烯酸酯、含氮的丙烯酰氨、含羧基的烯烃酸酐、含硅氧烷基的有机硅类化合物或过氧化合物；所述橡胶溶液为合成橡胶溶液；而后进行物理处理，在搅拌下，加入终止剂及抗氧剂，调节控制其粘度为15000～50000cp，再加入环保增塑油，准确控制其聚合物浓度，维持温度在50～60℃，成为均相乳液或溶液稳定物料；2)、白炭黑表面化学和物理改性处理将微米级至纳米级的白炭黑分散液加入搅拌釜中，然后加入含硫基、氨基、酰氧基、缩水甘油醚基或乙烯基的有机硅化合物的一种或以任何比例的两种以上的混合物对白炭黑分子表面进行改性反应，使其具有亲油性，加入量为白炭黑质量的1～5％，温度在室温～100℃，反应时间30～150分钟；物理处理是指机械杂质去除和大目数网过滤在搅拌釜中，后用去离子水来调节使固含量稳定在10～40wt％，并调节PH值在7±0.5，最终成为均相乳液；3)、混合乳液的制备和均化将各种所需填料及助剂，按其性质，分别加入到经上述步骤1)、2)、的均相乳液或溶液中，其中填料和亲水化合物加入到白炭黑均相乳液中；油性化合物和烃类化合物加入到橡胶均相乳液或溶液稳定物料中，其固含量为5～50wt％之间，分别得到两种掺混配置好的橡胶乳液或溶液和白炭黑均相乳液；将上述已经掺混配置好的橡胶乳液或溶液，送入由一个变速搅拌釜和变速乳液循环泵组成胶乳均化系统中进行均化，在开启搅拌和泵循环条件下，以一定流速将掺混配置好的白炭黑乳液加入搅拌釜中先进行掺混，再以不同的搅拌速度和泵循环量进行均化，制得稳定均一的橡胶与白炭黑混合乳液；4)、脱除混合乳液中的溶剂和水份A)将步骤3)、的混合乳液用泵喷入橡胶凝聚系统，用水蒸汽共沸脱除溶剂，后经振动筛与水分离，再经挤压脱水和膨胀干燥，制得含水量1wt％以下，挥发分小于0.5wt％的白炭黑湿法混炼胶；或B)将步骤3)、的混合乳液用一种封闭的双辊筒压炼机，同时脱除溶剂和水份，制得含水量小于1wt％，挥发分小于0.5wt％的白炭黑湿法混炼胶；或C)将步骤3)、的混合乳液在惰性气体保护下送入专用双螺杆机组中，同时脱除溶剂和水，再将挤出物压块成型，制得白炭黑湿法混炼胶，其中双螺杆机组主要参数为：长/径比为60～100，转速50～500rpm；所述惰性气体压力为0.3Mpa～3Mpa。
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，但是目前湿法工艺仍然采用成熟的强酸絮凝方式，酸性残留不仅对胶料制品产生影响，而且对设备以及操作人员身体健康都有危害，绿色环保性不强；后续混炼工艺还仍然使用传统的混炼工艺，即沿用密炼机多段式混炼方，生产连续性不强、自动化程度不高以及存在高能耗等。因此，研发一种针对高填充份数白炭黑配方、以湿法工艺为基础和高效环保的连续混炼方法和装置，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存在的缺点，研发设计一种炭黑配方橡胶连续混炼方法和装置，具有连续化生产程度高、节能环保以及填料高填充和高分散的优势。
为了实现上述目的，本发明涉及的一种白炭黑配方橡胶连续混炼方法是基于白炭黑配方橡胶连续混炼装置实现的，其工艺过程包括制备白炭黑浆料、制备助剂水溶液、制备助剂/炭黑母炼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质量百分比浓度为25wt％的白炭黑水溶液，以1000Hz的频率超声10min，研磨0-6h，备用；
(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)和去离子水配成质量百分比浓度为25wt％的助剂水溶液，研磨0-6h，备用；
(3)制备助剂/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质量份质量百分比浓度为60wt％的NRL(天然胶乳)混合，装入储存罐后泵送至搅拌罐进行搅拌形成混合溶液，搅拌频率为10Hz，通过喷射雾化形式将混合溶液絮凝干燥，喷射压力为1.2MPa，干燥温度为110-160℃，得到助剂/白炭黑母胶；
(4)连续混炼：将步骤(3)制备的助剂/白炭黑母胶投入第一阶段混炼机中进行混炼，混炼温度为130℃，转速为35r/min，混炼5-8分钟后，加入1.2质量份促进剂(CZ)和1质量份硫磺(S)投入第二阶段混炼机中混炼，混炼温度为115℃，转速为35r/min，混炼5-8分钟后，得到白炭黑配方橡胶。
本发明与现有技术相比，将湿法混炼工艺与连续混炼进行结合，基于白炭黑配方橡胶连续混炼装置实现，将配方中所有填料和小料通过预处理方式与胶乳结合，然后通过高温雾化法制备包含配方物料的复合材料，最终通过高温/低温组合连续混炼机进行补充混炼，制备的白炭黑橡胶不仅物理性能和动态力学性能较常规干法混炼的炭黑橡胶有显著提高，而且生产周期也得到了缩短，并使填料在天然橡胶中达到了微观分散的效果；其没有使用酸，减少了污染，避免了酸性残留对橡胶性能的影响，能够缩短生产周期，并使填料在天然橡胶中达到均匀分布和分散，提升橡胶性能。
附图说明：
图1为本发明涉及的白炭黑配方橡胶连续混炼装置的主体结构原理示意图。
图2为本发明涉及的机筒的剖面结构原理示意图。
图3为本发明涉及的机头的主体结构原理示意图。
图4为本发明涉及的混炼转子的主体结构原理示意图。
图5为本发明涉及的混炼转子的剖面结构原理示意图。
图6为本发明涉及的机筒流道的排布示意图。
具体实施方式：
下面通过实施例并结合附图做进一步说明。
实施例1：
本实施例涉及的一种白炭黑配方橡胶连续混炼方法是基于白炭黑配方橡胶连续混炼装置实现的，其工艺过程包括制备白炭黑浆料、制备助剂水溶液、制备助剂/炭黑母炼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质量百分比浓度为25wt％的白炭黑水溶液，以1000Hz的频率超声10min，研磨4h，备用；
(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)和去离子水配成质量百分比浓度为25wt％的助剂水溶液，研磨4h，备用；
(3)制备助剂/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质量份质量百分比浓度为60wt％的NRL(天然胶乳)混合，装入储存罐后泵送至搅拌罐进行搅拌形成混合溶液，搅拌频率为10Hz，通过喷射雾化形式将混合溶液絮凝干燥，喷射压力为1.2MPa，干燥温度为135℃，得到助剂/白炭黑母胶；
(4)连续混炼：将步骤(3)制备的助剂/白炭黑母胶投入第一阶段混炼机中进行混炼，混炼温度为130℃，转速为35r/min，混炼5-8分钟后，加入1.2质量份促进剂(CZ)和1质量份硫磺(S)投入第二阶段混炼机中混炼，混炼温度为115℃，转速为35r/min，混炼5-8分钟后，得到白炭黑配方橡胶。
本实施例涉及的白炭黑配方橡胶连续混炼装置的主体结构包括储存罐1、研磨机2、搅拌罐3、泵4、搅拌器5、喷枪6、高温雾化罐7、一号失重称8、二号失重称9、第一阶段混炼机10、三号失重称11和第二阶段混炼机12；两台独立设置的储存罐1分别与研磨机2连接，研磨机2与搅拌罐3管道式连接，研磨机2与搅拌罐3之间设置有泵4，搅拌罐3内设置有搅拌器5，搅拌罐3的出口端与喷枪6连接，喷枪6伸入高温雾化罐7内，高温雾化罐7的下方设置有一号失重称8和二号失重称9，一号失重称8和二号失重称9的下方设置有第一阶段混炼机10，第一阶段混炼机10一侧设置有三号失重称11，第一阶段混炼机10和三号失重称11的下方设置有第二阶段混炼机12。
本实施例涉及的第一阶段混炼机10和第二阶段混炼机12的主体结构相同，均包括电机100、机筒101、机头102和混炼转子103；电机100与机筒101连接，机筒101与机头102螺栓式连接，机筒101内设置有双螺杆结构的混炼转子103。
本实施例涉及的研磨机2为球磨机或砂磨机，对物料进行研磨和混合；喷枪6为口径直径为0.5-5mm的气动喷枪；电机100为单入双输出结构的减速电机；机筒101采用两段或三段式结构，机筒101之间螺栓式连接，每段机筒101的内壁均开设有供温控介质循环的机筒流道104，每段机筒101的温度根据工艺要求设定；机头102的内壁开设有供温控介质循环的机头流道105，机头102的胶料挤出口呈倒锥形；温控介质为导热油，温控范围0-200℃，精确度为±0.5℃；混炼转子103为双螺杆混炼转子，具有啮合、剪切和输送胶料作用。
本实施例制备的白炭黑配方橡胶的机械性能与常规干法和湿法制备的白炭黑配方橡胶的机械性能的对比结果如下表：
序号 测试项目 干法 湿法 本实施例
1 硬度(邵氏A) 66 69 67
2 10％定伸(Mpa) 0.7 0.84 0.83
3 50％定伸(Mpa) 1.12 1.45 1.508
5 100％定伸(Mpa) 1.48 2.11 2.298
5 200％定伸(Mpa) 2.67 4.31 5.918
6 300％定伸(Mpa) 4.77 7.58 11.542
7 M300％/M100％ 3.22 3.59 5.02
8 M300％/M50％ 4.26 5.23 7.65
9 拉伸强度(Mpa) 20.28 25.87 28.514
10 扯断伸长率(％) 720.65 722.27 569.32
11 撕裂强度(Mpa) 77.76 94.42 125.80
，可知：本实施例制备的白炭黑配方橡胶的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，综合性能高；从定伸应力M300％/M100％的比值来看：本实施例制备的白炭黑配方橡胶的补强效果最好，能够使白炭黑纳米颗粒在天然橡胶基体中分散均匀。

Claims (2)

1.一种白炭黑/橡胶连续混炼方法，其特征在于基于白炭黑配方橡胶连续混炼装置实现的，其工艺过程包括制备白炭黑浆料、制备助剂水溶液、制备助剂/炭黑母炼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质量百分比浓度为25wt%的白炭黑水溶液，以1000Hz的频率超声10min，研磨0-6h，备用；
（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和去离子水配成质量百分比浓度为25wt%的助剂水溶液，研磨0-6h，备用；
（3）制备助剂/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质量份质量百分比浓度为60wt%的NRL混合，装入储存罐后泵送至搅拌罐进行搅拌形成混合溶液，搅拌频率为10Hz，通过喷射雾化形式将混合溶液絮凝干燥，喷射压力为1.2MPa，干燥温度为110-160℃，得到助剂/白炭黑母胶；
（4）连续混炼：将步骤（3）制备的助剂/白炭黑母胶投入第一阶段混炼机中进行混炼，混炼温度为130℃，转速为35r/min，混炼5-8分钟后，加入1.2质量份促进剂和1质量份硫磺投入第二阶段混炼机中混炼，混炼温度为115℃，转速为35r/min，混炼5-8分钟后，得到白炭黑配方橡胶。
2.根据权利要求1所述的白炭黑/橡胶连续混炼方法，其特征在于，白炭黑/橡胶连续混炼装置的主体结构包括储存罐、研磨机、搅拌罐、泵、搅拌器、喷枪、高温雾化罐、一号失重称、二号失重称、第一阶段混炼机、三号失重称和第二阶段混炼机；两台独立设置的储存罐分别与研磨机连接，研磨机与搅拌罐管道式连接，研磨机与搅拌罐之间设置有泵，搅拌罐内设置有搅拌器，搅拌罐的出口端与喷枪连接，喷枪伸入高温雾化罐内，高温雾化罐的下方设置有一号失重称和二号失重称，一号失重称和二号失重称的下方设置有第一阶段混炼机，第一阶段混炼机一侧设置有三号失重称，第一阶段混炼机和三号失重称的下方设置有第二阶段混炼机；第一阶段混炼机和第二阶段混炼机的主体结构相同，均包括电机、机筒、机头和混炼转子；电机与机筒连接，机筒与机头螺栓式连接，机筒内设置有双螺杆结构的混炼转子；研磨机为球磨机或砂磨机，对物料进行研磨和混合；喷枪为口径直径为0.5-5mm的气动喷枪；电机为单入双输出结构的减速电机；机筒采用两段或三段式结构，机筒之间螺栓式连接，每段机筒的内壁均开设有供温控介质循环的机筒流道，每段机筒的温度根据工艺要求设定；机头的内壁开设有供温控介质循环的机头流道，机头的胶料挤出口呈倒锥形；温控介质为导热油，温控范围0-200℃，精确度为±0.5℃；混炼转子为双螺杆混炼转子，具有啮合、剪切和输送胶料作用。
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