CN106146858B - 一种四丙氟橡胶组合物 - Google Patents

一种四丙氟橡胶组合物 Download PDF

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CN106146858B
CN106146858B CN201610522832.9A CN201610522832A CN106146858B CN 106146858 B CN106146858 B CN 106146858B CN 201610522832 A CN201610522832 A CN 201610522832A CN 106146858 B CN106146858 B CN 106146858B
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fluorine rubber
tetrapropanate fluorine
crosslinking agent
tetrapropanate
divinylbenzene
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CN106146858A (zh
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丛川波
孟晓宇
周琼
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China University of Petroleum Beijing
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
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Abstract

本发明涉及一种四丙氟橡胶组合物，该组合物以四丙氟橡胶为主体材料，以有机过氧化物为交联剂，以多功能交联微球为助交联剂，所述微球是二乙烯基苯均聚物微球，或二乙烯基苯与苯乙烯、丙烯酸酯、乙烯基吡啶三种的一种或是两种的共聚物微球，或以上述共聚物为核，二乙烯基苯为壳的核壳型交联微球，其直径50nm‑100μm，该微球不仅可使四丙氟橡胶交联，还可以改善橡胶的加工流动性。

Description

一种四丙氟橡胶组合物
技术领域
本发明涉及高分子材料的一种新交联方法，具体地说，发明了一类含有二乙烯苯的聚合物微球，可用于交联四丙氟橡胶，获得性能优异的四丙氟硫化胶。
背景技术
四丙氟橡胶是用途范围较广的极性橡胶，可应用于含油水的高温环境中。四丙氟橡胶在硫化过程中，不仅需要主硫化剂，还必须加入助硫化剂，所以其硫化体系是由过氧化物和助硫化剂组成，过氧化物一般为过氧化二异丙苯(DCP)、双叔丁基过氧化二异丙苯(BIBP)和过氧化苯甲酰(BPO)等一些过氧化物，而传统的助硫化剂主要为烯丙基异三聚氰酸酯(TAIC)、三聚氰酸三烯丙酯(TAC)和聚丁二烯，最近也推出了新型的助交联剂，如八乙烯基倍半硅氧烷(OVPOSS)，新型交联剂与传统的交联剂相比，用OVPOSS作为助交联剂获得的硫化胶在苛刻环境中具有更好的稳定性。对比这几种助交联剂，我们发现分子上连有乙烯基的化合物可以成为助交联剂。本发明采用二乙烯基苯做为单体采用乳液法或悬浮法共聚或是均聚形成不同尺寸的聚合物微球，该类微球表面带有乙烯基基团，该基团的性质类似于OVPOSS和TAIC中的双键，可用来作为助交联剂硫化四丙氟橡胶，制备出的特种的硫化胶在苛刻环境中具有较高的稳定性。
发明内容
本发明涉及一种交联四丙氟橡胶的新方法，具体地说，通过乳液聚合或是悬浮聚合合成不同粒径尺寸聚合物微球，该微球表面带有乙烯基团，可用来交联四丙氟橡胶。
本发明其特征是，该组合物以四丙氟橡胶为主体材料，以有机过氧化物为交联剂，以炭黑为增强填料，以含二乙烯基苯微球为助交联剂，以硬脂酸或其盐为加工助剂，其组成，以四丙氟橡胶为100重量份计，包括：
其中使用的四丙氟橡胶的氟含量为54.8～58.3％，该类氟橡胶的高分子主链主要是由C-F键组成，在苛刻环境中具有比较高的稳定性，具体产品如，日本旭硝子公司的和上海叁爱富(3F)公司生产的四丙氟橡胶。这类橡胶的分子链上没有双键，必须采用活性较高的过氧化物和助交联剂来进行硫化，有机过氧化物为DCP、BIBP和BPO，用量以四丙氟橡胶为100重量份计，宜为1-6重量份，用量过多，形成过度交联，均会对最终产品的性能产生不利影响，并且过氧化物分解的残余物会影响四丙氟橡胶的性能，因此过氧化物有用量不易过多。一般助硫化剂采用TAIC或TAC，这两种化合物中存在不稳定的基团在苛刻环境中会发生分解反应，而降低了四丙氟橡胶在酸性环境中的使用价值。本发明采用在更为稳定的含二乙烯基苯(DVB)微球为助交联剂，提高了四丙氟橡胶在酸性条件下的稳定性，同时也提高了四丙氟橡胶的加工流动性性能。采用的含有二乙烯基苯微球，主要是通过乳液聚合和悬浮聚合制备的，该微球可是DVB单独的共聚物微球，也可是DVB与苯乙烯、丙烯酸酯、乙烯基吡啶三种的一种或是两种的共聚物微球，还可以是以苯乙烯、丙烯酸酯、乙烯基吡啶的聚合物为核，DVB为壳的核壳型交联微球，该类微球的共同特点就是微球表面具有乙烯基团，可与四丙氟橡胶形成交联网络。根据不同的聚合方法，该类微球的直径范围为50nm-100μm，根据四丙氟橡胶的不同的交联密度和硬度的要求，该类微球的用量为2-20份。发明的配方中的防老剂为2-巯基苯并咪唑和2，2，4-三甲基-1，2-二氢化喹啉的复合体系，其用量各为0.5-2份。为了获得合适的硬度和较高的拉伸强度、断裂伸长率，本发明采用不同粒径的碳黑或是其他填料进行补强，以满足不同的需求。
具体实施方式
1.不同类型的交联微球
表1
a交联微球的直径为500nm，用量为10份
表2
b无法交联
2.交联微球直径的影响
表3
c交联微球的用量为10份
表4
3.交联微球用量变化
表3
c交联微球的用量为10份
表4

Claims (5)

1.一种四丙氟橡胶组合物，其特征是，该组合物以四丙氟橡胶为主体材料，以有机过氧化物为交联剂，以含有聚二乙烯苯的微球为助交联剂，以硬质炭黑为增强填料，以四丙氟橡胶为100重量份计，包括：
四丙氟橡胶 100
防老剂 1-4
硬脂酸盐 1-2
有机过氧化物 1-6
增强填料 15-80
助交联剂 2-20 ；
所述的助交联剂为表面带有乙烯基团的交联微球，其成份是二乙烯基苯均聚物微球；或是二乙烯基苯与苯乙烯、丙烯酸酯、乙烯基吡啶三种的一种或是两种的共聚物微球；或是以上述共聚物为核，二乙烯基苯为壳的核壳型交联微球。
2.根据权利要求1所述的四丙氟橡胶组合物，其特征是，所述四丙氟橡胶的氟含量为54.8~58.3wt%。
3.根据权利要求1所述的四丙氟橡胶组合物，其特征是，所述的增强填料为硬质炭黑N330和/或N550。
4.根据权利要求1所述的四丙氟橡胶组合物，其特征是，所述的有机过氧化物是过氧化二异丙苯（DCP）、双叔丁基过氧化二异丙基苯（BIBP）和过氧化苯甲酰（BPO）中的一种或多种的并用。
5.根据权利要求1-4任一项所述的四丙氟橡胶组合物，其特征是，所述助交联剂的微球直径范围为50nm-100μm。
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