CN103980620B - 一种耐高温、难燃的输送带覆盖层胶料及其制备方法 - Google Patents

一种耐高温、难燃的输送带覆盖层胶料及其制备方法 Download PDF

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CN103980620B
CN103980620B CN201410197043.3A CN201410197043A CN103980620B CN 103980620 B CN103980620 B CN 103980620B CN 201410197043 A CN201410197043 A CN 201410197043A CN 103980620 B CN103980620 B CN 103980620B
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臧亚南
王艳秋
刘琼琼
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Dexin adhesive tape Technology Co., Ltd.
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Abstract

本发明公开了一种耐高温、难燃的输送带覆盖层胶料及其制备方法。所述胶料按质量份数计包括：三元乙丙橡胶50～90份、溴化丁基橡胶10～50份、改性纳米凹凸棒土5～40份、炭黑20～35份、无卤阻燃剂50～80份、硫化剂3～5.5份、防老剂3～5份、氧化锌3～5份、硬脂酸1～3份、古马隆5～15份。首先用硅烷偶联剂对纳米凹凸棒土进行改性处理，然后用三元乙丙橡胶、溴化丁基橡胶、改性纳米凹凸棒土制备母胶，最后将上述母胶在双辊开炼机上进行塑炼，然后加入氧化锌、硬脂酸、古马隆、防老剂、阻燃剂、炭黑、硫化剂进行混炼制得所述胶料。本发明胶料的加工性能、耐高温性能和阻燃性能均能达到或超过国家标准，产品及工艺具有良好的经济社会效益，具有推广应用前景。

Description

一种耐高温、难燃的输送带覆盖层胶料及其制备方法
技术领域
本发明属于橡胶产品技术领域，具体涉及一种包括改性纳米凹凸棒土/三元乙丙橡胶/溴化丁基橡胶复合母胶、炭黑、无卤阻燃剂等组分的耐高温、难燃的输送带覆盖层橡胶复合材料。
技术背景
输送带的结构包括上下橡胶覆盖层、骨架层和橡胶粘合层三个主要部分，其中覆盖层橡胶的性能是决定输送带使用寿命的关键，所以提高覆盖层橡胶的耐热性、阻燃性对于冶金、建材等行业显得十分重要。特别是冶金行业许多高炉的炉渣直接放在输送带上，温度很高同时带着火星，严重影响输送带的使用寿命。
提高输送带的耐高温性能主要采用耐高温的橡胶为基体，一般在180℃以下使用的T4型耐热输送带的覆盖胶多采用EPDM或者与其他橡胶如卤化丁基橡胶、硅橡胶、聚烯烃弹性体等组成的并用胶。所常用的补强剂采用白炭黑、煅烧陶土、层状硅酸盐等部分替代炭黑以提高其耐高温性能。提高输送带的阻燃性能方面，主要采用无卤阻燃剂替代卤系阻燃剂，以减少卤系阻燃剂燃烧时发烟量大、释放大量有毒有害气体的缺点。同时具有耐高温、阻燃性能的输送带覆盖层胶料，其添加的阻燃剂主要以无机氢氧化物为主。其优点是燃烧时不挥发、发烟量少、不产生有毒气体，但是无机阻燃剂的添加量过大且与高聚物基体的相容性不佳，影响输送带覆盖胶的物理机械性能。
纳米凹凸棒土是一种针状硅酸盐，具有原料来源丰富、价格低廉等优点。一定比例纳米凹凸棒土的加入，能提高复合材料的力学性能、耐高温性能和阻燃性能。
因此在采用无卤阻燃剂时，降低其用量，提高阻燃剂与高聚物基体的相容性是无卤阻燃材料研究的重点。
发明内容
本发明的任务就是提供新型耐高温、难燃输送带覆盖层胶料，选用的耐高温橡胶基体及与之相配伍的各种助剂能够具有优异的耐高温、难燃、粘合性能，提高输送带的使用寿命。
本发明解决上述问题的技术方案如下：
一种耐高温、难燃的输送带覆盖层胶料，胶料包括基体橡胶及各种助剂，以质量份数计胶料中各组份为：三元乙丙橡胶50～90份、溴化丁基橡胶10～50份、改性纳米凹凸棒土5～40份、炭黑20～35份、无卤阻燃剂50～80份、硫化剂3～5.5份、防老剂3～5份、氧化锌3～5份、硬脂酸1～3份、古马隆5～15份。
上述改性纳米凹凸棒土为硅烷偶联剂改性纳米凹凸棒土，纳米凹凸棒土具有原料来源丰富、价格低廉等优点。一定比例纳米凹凸棒土的加入，能提高复合材料的力学性能、耐高温性能和阻燃性能。另外，纳米凹凸棒土的加入也会提高复合材料的阻燃性能，纳米凹凸棒土的主要成分包括二氧化硅，也会在体系表面形成含硅保护层,起到绝热和屏蔽双重作用。
上述炭黑为N234、N220、N330中的一种或多种混合组成，中超耐磨炭黑(N234、N220)以及高耐磨炭黑(N330)能够保证复合材料具有良好的力学性能和耐磨性能。
上述无卤阻燃剂为聚磷酸铵、三异丙苯基磷酸酯、三聚氰胺、季戊四醇中的三种或四种任意重量比混合而成。采用的是经过热处理后的高聚合度聚磷酸铵(聚合度为1500)，其热稳定性好，阻燃性能持久，无毒抑烟，属于磷系阻燃剂。三异丙苯基磷酸酯常用作聚氯乙烯的阻燃增塑剂，也适用于橡胶输送带胶料的阻燃增塑，属于磷系阻燃剂。三聚氰胺是一种常用的氮系阻燃剂，含氮阻燃剂受热放出二氧化碳、氮气、氨气等不燃气体,这类阻燃剂还可用作其它阻燃剂如磷系阻燃剂的协效剂,在磷-氮协同体系中作为发泡剂。季戊四醇的加入，与磷系、氮系阻燃剂可形成膨胀型阻燃剂。添加膨胀型阻燃剂的聚合物燃烧时会在表面上形成一层均匀的炭质泡沫层，此炭层在凝聚相能起到隔热、隔氧、抑烟和防熔滴的作用。
上述硫化剂为过氧化物类和树脂类硫化剂混合而成。过氧化物类硫化剂采用的是过氧化二异丙苯(DCP)，树脂类硫化剂用的是溴化对特辛基酚醛硫化树脂(201树脂)，DCP的共交联剂用的是三烯丙基异三聚氰酸酯(TAIC)或N，N’-间苯撑双马来酰亚胺(HVA-2)。DCP和201树脂均能使三元乙丙橡胶和溴化丁基橡胶硫化，形成耐热性优良的交联键。本发明采用的硫化体系能使三元乙丙橡胶和溴化丁基橡胶硫化，形成耐热性优良的交联键。
上述防老剂为喹啉类防老剂和对苯二胺类防老剂混合而成。喹啉类防老剂为化学成分为2,2,4-三甲基-1,2-二氢化喹啉聚合体的防老剂RD和防老剂FR，相比于防老剂RD，防老剂FR的胺含量较低，对过氧化物交联剂影响很小。对苯二胺类防老剂为N-(1,3-二甲基)丁基-N'-苯基对苯二胺(防老剂4020)和N，N’-双(1,4-二甲基戊基)对苯二胺(防老剂4030)。
上述耐高温、难燃的输送带覆盖层胶料的制备方法，其特征在于包括以下步骤：
首先对纳米凹凸棒土进行改性处理，将硅烷偶联剂溶在无水乙醇中制成一定浓度的溶液，加入纳米凹凸棒土搅拌并加热，充分反应后冷却至室温，高速离心、洗涤、烘干，粉碎后即得改性样品。如将硅烷偶联剂(Si69)溶在无水乙醇中制成一定浓度的溶液，加入适量的纳米凹凸棒土搅拌并加热，充分反应后冷却至室温，高速离心、洗涤、烘干，粉碎后即可得改性纳米凹凸棒土。
其次进行母胶制备，调节双辊开炼机辊距至2mm，加入三元乙丙橡胶和溴化丁基橡胶，混炼均匀后加上述改性凹凸棒土进行混炼，最后将辊距调至0.1mm，薄通5～8次制备母胶。
最后进行胶料制备，调节双辊开炼机辊距至2mm，将上述母胶在双辊开炼机上进行塑炼，然后依次加入氧化锌、硬脂酸、古马隆、防老剂、阻燃剂进行混炼，随后再加入炭黑进行混炼，最后加入硫化剂混炼，再将辊距调至0.1mm，薄通5～8次制备三元乙丙橡胶复合材料。
上述制得的混炼胶料于160～180℃下硫化即可得到橡胶复合材料，如耐高温、难燃的输送带覆盖层。硫化后产品性能见实施例中表1。
本发明具有以下有益效果：
本发明将改性纳米凹凸棒土应用在耐热输送带覆盖层中，与单纯使用炭黑填料的输送带覆盖层胶料相比，成本低、污染小，改性纳米凹凸棒土的加入还可以提高胶料的耐高温性能。本发明所采用的无卤阻燃体系，总体用量较低，与橡胶基体的相容性较好，阻燃性能良好。本发明所采用的硫化体系能使三元乙丙橡胶和溴化丁基橡胶硫化，形成耐热性优良的交联键。
具体实施方式
实施例1：
将硅烷偶联剂(Si69)溶在无水乙醇中制成5％的溶液，加入适量的纳米凹凸棒土搅拌并加热，温度为80℃，充分反应4小时后冷却至室温，高速离心、洗涤、烘干，粉碎后即可得改性纳米凹凸棒土。
实施例2：
调节双辊开炼机辊距至2mm，加入90份(重量份，下同)三元乙丙橡胶和10份溴化丁基橡胶，混炼均匀后加入10份上述改性纳米凹凸棒土再进行混炼，最后将辊距调至0.1mm，薄通5～8次制备得到母胶。
实施例3：
调节双辊开炼机辊距至2mm，将110g上述母胶在双辊开炼机上进行塑炼，而后加入5g氧化锌、2g硬脂酸、10g古马隆、2g防老剂RD和2g防老剂4020、50g聚磷酸铵、10g三聚氰胺、10g季戊四醇进行混炼，而后加入15gN234和15gN330进行混炼，最后加入2gDCP、0.5gTAIC和2g201树脂混炼，最后将辊距调至0.1mm，薄通5～8次制备混炼胶。
实施例4：
调节双辊开炼机辊距至2mm，加入75g三元乙丙橡胶和25g溴化丁基橡胶，混炼均匀后加入20g上述改性凹凸棒土再进行混炼，最后将辊距调至0.1mm，薄通5～8次制备母胶。
调节双辊开炼机辊距至2mm，将120g母胶在双辊开炼机上进行塑炼，而后加入5g氧化锌、2g硬脂酸、10g古马隆、2g防老剂RD和2g防老剂4020、40g聚磷酸铵、16g三聚氰胺、10g季戊四醇加入混炼，而后加入15gN220和15gN330进行混炼，最后加入2gDCP、0.5gTAIC和2g201树脂混炼，最后将辊距调至0.1mm，薄通5～8次制备混炼胶。
实施例5：
调节双辊开炼机辊距至2mm，加入50g三元乙丙橡胶和50g溴化丁基橡胶，混炼均匀后加入20g上述改性凹凸棒土再进行混炼，最后将辊距调至0.1mm，薄通5～8次制备母胶。
调节双辊开炼机辊距至2mm，将120g母胶在双辊开炼机上进行塑炼，而后加入5g氧化锌、2g硬脂酸、10g古马隆、2g防老剂RD和2g防老剂4020、35g聚磷酸铵、16g三聚氰胺、10g季戊四醇、5g三异丙苯基磷酸酯加入混炼，而后加入15gN234和15gN330进行混炼，最后加入2gDCP、0.5gTAIC和3g201树脂混炼，最后将辊距调至0.1mm，薄通5～8次制备混炼胶。
实施例6：
将上述实施例3-5得到的混炼胶在170℃下硫化，得到橡胶复合材料并进行老化试验检测，其老化前后性能的检测结果见表1。
表1 耐高温、难燃的输送带覆盖层胶料相关检测数据
从表1性能可知，本发明所制备的耐高温、难燃输送带覆盖层胶料的老化前、后力学性能良好，均可达到耐高温输送带使用的基本要求，同时具有良好的阻燃性能。

Claims (6)

1.一种耐高温、难燃的输送带覆盖层胶料，胶料包括基体橡胶及各种助剂，其特征在于，以质量份数计胶料中各组份为：三元乙丙橡胶50~90份、溴化丁基橡胶10~50份、改性纳米凹凸棒土5~40份、炭黑20~35份、无卤阻燃剂50~80份、硫化剂3~5.5份、防老剂3~5份、氧化锌3~5份、硬脂酸1~3份、古马隆5~15份；
所述的无卤阻燃剂为聚磷酸铵、三异丙苯基磷酸酯、三聚氰胺、季戊四醇中的任三种或四种以其任意重量比混合而成；
所述的的硫化剂为过氧化物类和树脂类硫化剂任意重量比混合而成；
所述过氧化物类硫化剂为过氧化二异丙苯；
所述树脂类硫化剂为溴化对特辛基酚醛硫化树脂。
2.根据权利要求1所述的耐高温、难燃的输送带覆盖层胶料，其特征在于：所述改性纳米凹凸棒土为硅烷偶联剂改性纳米凹凸棒土。
3.根据权利要求1所述的耐高温、难燃的输送带覆盖层胶料，其特征在于：所述的炭黑为N234、N220、N330中的一种或多种混合组成。
4.根据权利要求1所述的耐高温、难燃的输送带覆盖层胶料，其特征在于：所述的聚磷酸铵是经过热处理后的高聚合度聚磷酸铵，所述聚磷酸铵的聚合度为1500。
5.根据权利要求1所述的耐高温、难燃的输送带覆盖层胶料，其特征在于：所述的的防老剂为喹啉类防老剂和对苯二胺类防老剂任意重量比混合而成。
6.一种如权利要求1所述的耐高温、难燃的输送带覆盖层胶料的制备方法，其特征在于：包括以下步骤：
首先对纳米凹凸棒土进行改性处理，将硅烷偶联剂溶在无水乙醇中制成5%的溶液，加入纳米凹凸棒土搅拌并加热至80℃，充分反应4小时后冷却至室温，高速离心、洗涤、烘干，粉碎后即得改性样品；
其次进行母胶制备，调节双辊开炼机辊距至2mm，加入三元乙丙橡胶和溴化丁基橡胶，混炼均匀后加上述改性纳米凹凸棒土进行混炼，最后将辊距调至0.1mm，薄通5~8次制备母胶；
最后进行胶料制备，调节双辊开炼机辊距至2mm，将上述母胶在双辊开炼机上进行塑炼，然后依次加入氧化锌、硬脂酸、古马隆、防老剂、阻燃剂进行混炼，随后再加入炭黑进行混炼，最后加入硫化剂混炼，再将辊距调至0.1mm，薄通5~8次制备三元乙丙橡胶复合材料。
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