CN107325404A - 一种疏水及耐热型热塑性弹性体及其制备方法 - Google Patents

一种疏水及耐热型热塑性弹性体及其制备方法 Download PDF

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CN107325404A
CN107325404A CN201710602177.2A CN201710602177A CN107325404A CN 107325404 A CN107325404 A CN 107325404A CN 201710602177 A CN201710602177 A CN 201710602177A CN 107325404 A CN107325404 A CN 107325404A
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肖雅
王彦君
史新妍
肖建斌
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Ji'nan Ruifeng Macromolecule New Material Co Ltd
Qingdao University of Science and Technology
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Qingdao University of Science and Technology
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Abstract

本发明涉及一种疏水及耐热型热塑性弹性体及其制备方法,采用聚丙烯(PP)为基体材料,将甲基乙烯基硅橡胶(MVQ)与聚乙烯‑辛烯弹性体(POE)经过动态硫化制备成热塑性弹性体,再采用双螺杆挤出机将PP与此种热塑性弹性体共混改性,并添加200目聚四氟乙烯微粉,制备出了具有自清洁性、力学性能优异、耐高温的新型热塑性材料,可循环使用。

Description

一种疏水及耐热型热塑性弹性体及其制备方法
技术领域
本发明涉及一种疏水及耐热型热塑性弹性体及其制备方法,将POE与MVQ动态硫化制成热塑性弹性体(PMTPV),采用PP作为基体材料,与PMTPV共混,并添加聚四氟乙烯微粉,得到一种疏水及耐热型热塑性弹性体,其为动态硫化热塑性弹性体,具有自清洁性,优异的力学性能,耐热性,可循环利用等特点;该材料可用于电线电缆、装饰材料及一些公共设施材料。
背景技术
热塑性动态硫化弹性体是橡胶在熔融的塑料相中动态硫化,同时被剪切成了微米级的硫化粒子,分散在塑料相中,从而形成海--岛结构的橡塑两相体系。既具有塑料可热塑加工、可循环利用等性能优势,又具有橡胶的回弹性。
聚丙烯是由丙烯聚合而制得的一种热塑性树脂。结晶度高,结构规整,因而具有优良的力学性能。另外,聚丙烯也具有良好的耐热性、化学稳定性以及电绝缘性能。
硅橡胶作为一种兼具有机和无机性质的高分子材料,与一般的有机橡胶相比,具有优异的耐高温、耐侯、耐老化、低压缩永久变形、低表面张力和电绝缘性能。
POE是由乙烯和辛稀共聚而成,具有塑料和橡胶的双重特性。一方面具有窄的相对分子量分布和短支链,使其具有优异的物理机械性能;另一方面,POE的结构与三元乙丙橡胶类似,具有较高的拉伸强度和拉断伸长率。
聚四氟乙烯微粉(PTFE),又称聚四氟乙烯超细粉,为白色微粉状树脂,其分子量一般为常用高分子量PTFE的百分之一,粒径平均为1-20μm,不仅保持PTFE原有的优异性能,还具有结晶度高、分散性好,易于均匀与其他材料混合的优点,因此广泛应用于合成材料的共混改性,可以明显提高基材的润滑性、耐磨性、不粘性和阻燃性。微粉的耐候性、耐化学药品性、滑动性、不粘性完全与高分子量PTFE相同。此外微粉还可以作为润滑油、涂料等添加剂。PTFE由于其表面能极低、润湿性极差和化学惰性强、有良好的机械性能、电性能、使用温度范围宽(-20℃-+260℃),在高分子材料应用中逐渐引起重视。
冬季雨雪天气时,电线电缆上容易形成冰挂,影响了电力设备的正常使用,甚至损坏了电力设备,这是由于电缆材料与水的接触角小,材料的表面张力大,亲水性好。降低材料的临界表面张力可以减轻甚至避免这一现象的发生。
自清洁材料时指在自然条件下能够保持自身清洁的材料。在家装材料中抗污,易清洁的材料是非常受欢迎的。这就要求材料与水的接触角大,表面张力小,具有疏水性。降低材料的表面张力可以使装饰材料具有自清洁性。
在CN102746573A,CN104177692A,CN102731901A等文献中也提到了采用PP、POE、MVQ等材料制备的弹性体,但基本都采用简单的机械混合,难以解决几种材料之间的相容性,同时对交联硅橡胶的过氧化物会降解聚丙烯的问题都没有提及,更无方法解决。
本材料将PP、POE、MVQ共混动态硫化,并添加聚四氟乙烯微粉,制备出具有较低临界表面张力,优异力学性能和耐热性的动态硫化热塑性弹性体。一方面是具有自清洁性且可循环利用的热塑性材料;另一方面改善了材料的耐热性,使其应用范围拓宽。
发明内容
本发明涉及一种疏水及耐热型热塑性弹性体及其制备方法。其特征在于:采用聚丙烯(PP)为基体材料,将甲基乙烯基硅橡胶(MVQ)与聚乙烯-辛烯弹性体(POE)经过动态硫化制备成热塑性弹性体,再采用双螺杆挤出机将聚丙烯与此种热塑性弹性体共混改性。先用POE与MVQ制备成动态硫化热塑性弹性体(PMTPV),再与PP共混,既能改善PP与MVQ的相容性,又解决了过氧化物硫化剂降解PP的问题。
材料还采用PTFE,明显改善PP基材的润滑性,提高加工性能;由于其表面能极低、润湿性极差和化学惰性强,提高材料的表面疏水性能,制备出了具有自清洁性、力学性能优异、耐高温的新型热塑性材料,可循环使用。
具体的技术方案如下:一种疏水型阻燃新材料,其组成包含以下组分(wt.%表示):聚丙烯:30-40%、乙烯辛烯弹性体:20-30%、甲基乙烯基硅橡胶:20-30%、白炭黑:5-10%、硅烷偶联剂0.2-0.4%、过氧化物硫化剂TX29:0.2-0.4%、聚四氟乙烯微粉:1-3%。
反式异戊二烯的分子链具有反式有序性,是顺式异戊二烯的同分异构体,具有橡胶和塑料的双重特性,硫化交联后,其结晶软化成为柔软的弹性体;加入适量反式异戊二烯还可以提高材料的强度、耐磨性能,其加入量适合为5-10%。
进一步的,加入低分子量聚异戊二烯1-3%,作为增塑剂改善热塑性弹性体的加工流动性。
本发明的制备方法:
1)先将MVQ与白炭黑、硅烷偶联剂、过氧化物硫化剂在开炼机或密炼机中混炼均匀,制备MVQ母胶,下片备用;
2)将POE与MVQ母胶在密炼机或双螺杆挤出机中动态硫化制备成PMTPV,反应完全后下片冷却,造粒;
3)PP、PMTPV与聚四氟乙烯微粉混合均匀后投入双螺杆挤出机中挤出,切粒,即为本发明所制备的材料。
本发明解决其技术问题所采用的技术方案是:其包括如下步骤:
1)本材料选用MVQ改性PP,MVQ与烯烃类材料相比具有较低的表面张力和耐高低温性能,因此可以改善材料表面的疏水性和耐热性。
2)选用POE作为PP与MVQ的增容剂,既能改善PP与MVQ的相容性,同时POE又可作为PP的增韧剂,改善PP材料的柔韧性。
3)PTFE由于其表面能极低、润湿性极差和化学惰性强、加入能明显改善热塑性弹性体的加工流动性,改善材料表面的疏水性。
4)在加工工艺上,先用POE与加入过氧化物硫化剂的MVQ动态硫化制备成热塑性弹性体(PMTPV),再与PP共混。将过氧化物硫化剂在与PP共混之前反应完全,解决了过氧化物硫化剂降解PP的问题,提高了材料的力学性能和使用寿命。
本发明的技术效果:
采用本专利的制备方法,先将POE与MVQ共混,加入过氧化物硫化剂动态硫化制成热塑性弹性体(PMTPV),然后再与基体PP共混,既解决了聚丙烯与硅橡胶之间的相容性,同时又解决了过氧化物硫化剂降解PP的问题。在弹性体中加入聚四氟乙烯微粉,能够改善弹性体加工性能的同时,又能降低弹性体材料的临界表面张力,从而制备出一种具有低表面张力、自清洁性、力学性能优异和耐热性好的热塑性弹性体。
(1)采用动态硫化的方法将POE和MVQ进行交联剪切,制备了一种硅橡胶与烯烃弹性体预交联体系。
(2)将POE和MVQ的预交联体系与PP共混,改善了MVQ与PP的热力学相容性。
(3)交联MVQ的过氧化物硫化剂在与PP共混之前反应完全,解决了过氧化物硫化剂降解PP的问题。
(4)加入聚四氟乙烯微粉,能够改善弹性体加工性能,同时又能降低弹性体材料的临界表面张力,能极大改善热塑性弹性体的自清洁性和耐热性。
(5)制备的热塑性弹性体具有低的表面张力和疏水性能,该材料便于清洁,防止冰挂。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施方式一:
(1)先将MVQ与白炭黑、硅烷偶联剂、过氧化物硫化剂在开炼机上混炼均匀,制成MVQ母胶,下片备用;配比为100:20:1:1。
(2)将POE与上述MVQ母胶和聚四氟乙烯微粉在高温开炼机上混炼均匀,下片,切成胶条备用;共混比例为100:110:6,高温开炼机温度为90℃。
(3)将上述胶条用双螺杆挤出机挤出,动态硫化制成PMTPV;挤出机投料段温度135℃,塑化段温度140℃,挤出段温度145℃,机头温度140℃,螺杆转速为80rpm。
(4)将PP、PMTPV粒料混合均匀后,比例为:100:135;采用双螺杆挤机挤出造粒,挤出机投料段温度180℃,塑化段温度185℃,挤出段温度190℃,机头温度185℃,螺杆转速为50rpm,即制的本发明的材料。
实施方式二:
(1)先将MVQ与白炭黑、硅烷偶联剂、过氧化物硫化剂在开炼机上混炼均匀,下片备用;配比为100:25:1:1。
(2)将POE与上述MVQ母胶在密炼机中混炼均匀,在开炼机上下片,切成胶条,造粒备用;共混比例为100:120。
(3)将上述粒料用双螺杆挤出机挤出造粒,动态硫化制成PMTPV;挤出机投料段温度135℃,塑化段温度140℃,挤出段温度145℃,机头温度140℃,螺杆转速为80rpm。
(4)将PP、PMTPV粒料和聚四氟乙烯微粉混合均匀后,比例为:100:140:5;采用双螺杆挤机挤出造粒,即制的本发明的材料。挤出机投料段温度180℃,塑化段温度185℃,挤出段温度190℃,机头温度185℃,螺杆转速为50rpm。
实施方式三:
(1)先将MVQ与白炭黑、硅烷偶联剂、过氧化物硫化剂在开炼机上混炼均匀,制成MVQ母胶,下片备用;配比为100:25:1:1。
(2)将POE与上述MVQ母胶和聚四氟乙烯微粉在高温开炼机上混炼均匀,下片,切成胶条备用;共混比例为100:130:6,高温开炼机温度为90℃。
(3)将上述胶条用双螺杆挤出机挤出,动态硫化制成PMTPV;挤出机投料段温度135℃,塑化段温度140℃,挤出段温度145℃,机头温度140℃,螺杆转速为80rpm。
(4)将PP、PMTPV粒料混合均匀后,比例为:100:145;采用双螺杆挤机挤出造粒,挤出机投料段温度180℃,塑化段温度185℃,挤出段温度190℃,机头温度185℃,螺杆转速为50rpm,即制的本发明的材料。
本发明材料具有如下技术参数:

Claims (5)

1.一种疏水及耐热型热塑性弹性体,其特征是:其组成以wt.%表示包含以下组分,聚丙烯:30-40%、乙烯辛烯弹性体:20-30%、甲基乙烯基硅橡胶:20-30%、白炭黑:5-10%、硅烷偶联剂0.2-0.4%、过氧化物硫化剂TX29:0.2-0.4%、聚四氟乙烯微粉:1-3%。
2.根据权利要求1的热塑性弹性体,其特征在于:采用PP作为基体材料,具有良好的力学性能和耐热性;采用MVQ,其具有良好的耐热性及疏水性;采用POE即乙烯辛烯弹性体,其结构与三元乙丙橡胶类似,可改善PP与MVQ的相容性。
3.权利要求1-2任一项所述热塑性弹性体的制备方法,包括如下步骤:先将POE与MVQ在密炼机或螺杆挤出机中加入过氧化物硫化剂动态硫化制成热塑性弹性体(称PMTPV),再将PMTPV与PP共混,一方面改善了PP与MVQ的相容性,使橡胶相颗粒更加均匀的分散于塑料相中,另一方面将过氧化物硫化剂在与PP共混之前反应完全,以免降解PP,影响材料力学性能和使用寿命。
4.根据权利要求3所述的制备方法,其特征在于:
1)先将MVQ与白炭黑、硅烷偶联剂、过氧化物硫化剂在开炼机或密炼机中混炼均匀,制备MVQ母胶,下片备用;
2)将POE与MVQ母胶在密炼机或双螺杆挤出机中动态硫化制备成PMTPV,反应完全后下片冷却,造粒;
3)PP、PMTPV与聚四氟乙烯微粉混合均匀后投入双螺杆挤出机中挤出。
5.权利要求1-2任一项所述热塑性弹性体的用途,用于电线电缆、装饰材料及公共设施材料。
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