CN107200972A - 一种氟橡胶微孔发泡材料及其制备方法 - Google Patents

一种氟橡胶微孔发泡材料及其制备方法 Download PDF

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CN107200972A
CN107200972A CN201610150782.6A CN201610150782A CN107200972A CN 107200972 A CN107200972 A CN 107200972A CN 201610150782 A CN201610150782 A CN 201610150782A CN 107200972 A CN107200972 A CN 107200972A
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fluorubber
parts
foam material
microcellular foam
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张振秀
张昕
姜秀波
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Qingdao University of Science and Technology
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Abstract

本发明提供一种氟橡胶微孔发泡材料及其制备方法，其配方包括氟橡胶100份，填料0-100份，吸酸剂5-20份，加工助剂1-2份，改性剂0-3份，硫化剂1-3份；促进剂0-5份，并以上述配方提供了制备方法，通过微孔发泡工艺，制备得到不同性能的发泡材料，且无毒环保。本发明主要用于制作耐高温、耐油、耐介质的胶管、胶布、隔膜、密封件等；可用于电子零件、电气配件、各种包装材料及耐热性垫片材料等。

Description

一种氟橡胶微孔发泡材料及其制备方法
技术领域
本发明属于高分子材料领域，具体涉及一种氟橡胶微孔发泡材料及其制备方法。
背景技术
氟橡胶是分子结构中含有氟原子的合成橡胶，简称FR。氟橡胶有许多品种，通常以共聚物中含氟单元的氟原子数目来表示。它具有高度的化学稳定性，是目前所有弹性体中耐介质性能最好的一种；氟橡胶的耐高温性能和硅橡胶一样，可以说是目前弹性体中最好的。氟橡胶具有极好的耐天候老化性能，耐臭氧性能，在臭氧浓度为0.01％的空气中经45天作用没有明显龟裂；真空性能极佳；具有优良的物理机械性能；以及较好的电性能，可作为较好的电绝缘材料；透气性小，氟橡胶对气体的溶解度比较大，但扩散速度却比较小，所以总体表现出来的透气性也小；但氟橡胶的耐辐射性能较差，低温性能不好，这是由于其本身的化学结构所致。
氟橡胶的品种很多，26型氟橡胶是最常用的氟橡胶品种，26型氟橡胶拥有最好的耐热性，在200℃的高温下，使用寿命达10000h以上，在250℃下可长期使用，即使在300℃也可短时间使用。23型氟橡胶具有优越的耐发烟硝酸和耐化学药品等的性能。但其缺点是加工困难，价格高，限制了它的发展。四丙氟橡胶是日本旭硝子公司1960年开始研制的，因分子链中含有四氟乙烯基团，在一般氟橡胶性能的基础上，其加工性能比其他型号的氟橡胶要好，玻璃化温度在2℃左右，最高使用温度230℃，是取代23型氟橡胶的一种新品种。氟化磷腈橡胶由美国首次研制成功该产品具有优良的耐油、耐燃、耐水解性，低温柔软性以及宽广的温度使用范围(-55℃～180℃)，特别适用于航空航天等军事工业部门。亚硝基氟橡胶由于碳原子全部被氟化，而拥有了比其他氟橡胶更好的化学稳定性，其分子中不含C-H键，卤素含量大，高温裂解产生的气体(COF2和CF＝NCF2)能熄灭火焰，故亚硝基氟橡胶是现有橡胶中唯一不燃烧的橡胶。全氟醚橡胶 以四氟乙烯、全氟甲基乙烯基醚和通式为CF2＝CF-ORfX(式中X为-COOR、-CN、-OC6H5)的取代全氟乙烯醚所组成的三元共聚物。耐热性能很好，在288℃的高温下可长期使用，可以承受醚类、酮类、酯类、溶剂、氧化剂、燃油、酸碱类等几乎一切化学试剂的侵蚀。全氟醚橡胶绝大多数作为密封件应用于航空航天、石油化工和原子能等工业部门，可以在火箭发动机的燃料、氧化剂、四氧化二氮、肼、发烟硝酸及氟里昂等介质中正常使用。
由于氟橡胶具有耐高温、耐油、耐高真空及耐酸碱、耐多种化学药品的特点，已应用于现代航空、导弹、火箭、宇宙航行、舰艇、原子能等尖端技术及汽车、造船、化学、石油、电讯、仪器、机械等工业领域。
目前，工业生产中有许多氟橡胶的产品，但是对于氟橡胶发泡产品的研制还较少，目前仅有日本一家公司推出了其氟橡胶发泡产品，而在国内还没有类似产品出现，目前也没有文献报道成熟的氟橡胶发泡的配方及工艺。因此，本专利对于如此优良性能的氟橡胶发泡产品的推广应用具有重要的意义。
发明内容
本发明的目的是提供一种氟橡胶微孔发泡材料及其制备方法，通过微孔发泡工艺可以通过调整配方或者工艺，制备得到不同性能的发泡材料，且无毒环保，本发明主要用于制作耐高温、耐油、耐介质的胶管、胶布、隔膜、密封件等；可用于电子零件、电气配件、各种包装材料及耐热性垫片材料等。
一种氟橡胶微孔发泡材料，其特征在于，其配方如下：氟橡胶100份，填料0-100份，吸酸剂5-20份，加工助剂1-2份，改性剂0-3份，硫化剂1-3份；促进剂0-5份。
其中，氟橡胶包括氟橡胶26、四丙氟橡胶、全氟醚橡胶。
其中，填料为喷雾炭黑、沉淀法白炭黑、硅酸钙、超细硫酸钡、碳纤维中的一种或多种。
其中，吸酸剂为氧化镁、氧化锌、氧化铅、氢氧化钙中的一种或多种混合。
其中，加工助剂为硬脂酸锌、硬脂酸钠、氟蜡、低分子量聚乙烯中的任一种。
其中，硫化剂包括有机二胺类，双酚类，有机过氧化物类，高能辐射类中的任一类。其中，有机二胺类硫化剂包括六亚甲基二胺氨基甲酸盐(1#硫化剂)、N,N-二次肉桂基-1,6-己二胺(3#硫化剂)中的任一种；双酚类硫化剂为2,2-双-(4-羟苯基)六氟丙烷(双酚AF)与三苯基氯化磷(BPP)联用；有机过氧化物类硫化剂包括过氧化二异丙苯(DCP)、过氧化苯甲酰(BPO)、2,5-二甲基-2,5-双(叔丁基过氧基)己烷(双二五)中的任一种；高能辐射硫化则由电子加速器发射β射线或者γ射线来完成。
其中，交联助剂为N,N’-间苯基双马来酰亚胺(MPBM)、三烯丙基异三聚氰酸酯(TAIC)中的一种。
一种氟橡胶微孔发泡材料的制备方法，其特征在于，其步骤如下：
1)混炼胶制备
(1)密炼机温度设置为60-90℃，转速为40-60rpm，先将氟橡胶投入密炼机中，塑炼60s，提压砣，投入加工助剂和吸酸剂，混炼90s，提压砣，投入填料、改性剂，继续混炼90s，然后排胶、下片，得到氟橡胶母胶；
(2)将开炼机辊温升至40-50℃，辊距调至2mm，将母胶投入开炼机中，捏合3-4min，之后加入硫化剂、促进剂，薄通3-4次，打三角包3次，并90°调头，最后调整辊距至8-10mm左右下片，冷却至室温，放24h待用。
2)预硫化
模压预硫化：将混炼胶放入模具中，热压机压力为5-20MPa，温度120-180℃，预硫化时间为5-30min，之后将胶料从模具中拿出，得到预硫化胶。
还可通过高能辐射交联对氟橡胶进行预硫化。
3)微孔发泡
预硫化好的样品放入高压反应釜中，通入物理发泡剂并升温、加压，当物理发泡剂 在预硫化物胶中达到饱和后，泄压，冷却后去出样品，得到微孔材料。其中物理发泡剂为CO2，N2、丁烷、戊烷中的一种或几种气体混合。
4)二次硫化
将微发泡材料放入烘箱中二次硫化，其中温度为180-250℃，时间为10-24h，硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
其中，步骤3)微孔发泡过程中，反应釜温度为100-150℃，压力为5-30Mpa，饱和时间为2-10h，泄压时间为10-200s。
与现有技术相比，本发明具有以下有益效果：
氟橡胶(FPM)是主链或侧链的碳原子上连接有氟原子的一种合成高分子弹性体，它具有很多其它橡胶不可比拟的优异性能，具有优良的耐热性、耐溶剂性、耐酸、碱、酒精，以及良好的耐油性、耐候性和抗臭氧性能。主要用于制作耐高温、耐油、耐介质的胶管、胶布、隔膜、密封件等；在航空、石油、化工、汽车等领域有广泛的应用前景。
附图说明
图1本发明制备方法中，实施例1的扫描电镜图；
图2本发明制备方法中，实施例2的扫描电镜图；
图3本发明制备方法中，实施例3的扫描电镜图。
具体实施方式
下面结合实施例对本发明做进一步描述：
1)混炼胶制备
(1)密炼机温度设置为60-90℃，转速为40-60rpm，先将氟橡胶投入密炼机中，塑炼60s，提压砣，投入加工助剂和吸酸剂，混炼90s，提压砣，投入填料、改性剂，继续混炼90s，然后排胶、下片，得到氟橡胶母胶；
(2)将开炼机辊温升至40-50℃，辊距调至2mm，将母胶投入开炼机中，捏合 3-4min，之后加入硫化剂、促进剂，薄通3-4次，打三角包3次，并90°调头，最后调整辊距至8-10mm左右下片，冷却至室温，放24h待用。
2)预硫化
模压预硫化：将混炼胶放入模具中，热压机压力为5-20MPa，温度120-180℃，预硫化时间为5-30min，之后将胶料从模具中拿出，得到预硫化胶。
还可通过高能辐射交联对氟橡胶进行预硫化。
3)微孔发泡
预硫化好的样品放入高压反应釜中，通入物理发泡剂并升温、加压，当物理发泡剂在预硫化物胶中达到饱和后，泄压，冷却后去出样品，得到微孔材料。其中物理发泡剂为CO2，N2、丁烷、戊烷中的一种或几种气体混合。
4)二次硫化
将微发泡材料放入烘箱中二次硫化，其中温度为180-250℃，时间为10-24h，硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
实施例1至实施例4的具体配方、工艺条件见下表。
以上所述仅为本发明的实施例，并不限制本发明，凡采用等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。

Claims (9)

1.一种氟橡胶微孔发泡材料，其特征在于，其配方如下：氟橡胶100份，填料0-100份，吸酸剂5-20份，加工助剂1-2份，改性剂0-3份，硫化剂1-3份；促进剂0-5份。
2.根据权利要求书1所述的一种氟橡胶微孔发泡材料，其特征在于，氟橡胶包括氟橡胶26、四丙氟橡胶、全氟醚橡胶。
3.根据权利要求书1所述的一种氟橡胶微孔发泡材料，其特征在于，填料为喷雾炭黑、沉淀法白炭黑、硅酸钙、超细硫酸钡、碳纤维中的一种或多种。
4.根据权利要求书1所述的一种氟橡胶微孔发泡材料，其特征在于，吸酸剂为氧化镁、氧化锌、氧化铅、氢氧化钙中的一种或多种混合。
5.根据权利要求书1所述的一种氟橡胶微孔发泡材料，其特征在于，加工助剂为硬脂酸锌、硬脂酸钠、氟蜡、低分子量聚乙烯中的任一种。
6.根据权利要求书1所述的一种氟橡胶微孔发泡材料，其特征在于，硫化剂包括有机二胺类，双酚类，有机过氧化物类，高能辐射类中的任一类。其中，有机二胺类硫化剂包括六亚甲基二胺氨基甲酸盐(1#硫化剂)、N,N-二次肉桂基-1,6-己二胺(3#硫化剂)中的任一种；双酚类硫化剂为2,2-双-(4-羟苯基)六氟丙烷(双酚AF)与三苯基氯化磷(BPP)联用；有机过氧化物类硫化剂包括过氧化二异丙苯(DCP)、过氧化苯甲酰(BPO)、2,5-二甲基-2,5-双(叔丁基过氧基)己烷(双二五)中的任一种；高能辐射硫化则由电子加速器发射β射线或者γ射线来完成。
7.根据权利要求书1所述的一种氟橡胶微孔发泡材料，其特征在于，交联助剂为N,N’-间苯基双马来酰亚胺(MPBM)、三烯丙基异三聚氰酸酯(TAIC)中的一种。
8.一种氟橡胶微孔发泡材料的制备方法，其特征在于，其步骤如下：
1)混炼胶制备
(1)密炼机温度设置为60-90℃，转速为40-60rpm，先将氟橡胶投入密炼机中，塑炼60s，提压砣，投入加工助剂和吸酸剂，混炼90s，提压砣，投入填料、改性剂，继续混炼90s，然后排胶、下片，得到氟橡胶母胶；
(2)将开炼机辊温升至40-50℃，辊距调至2mm，将母胶投入开炼机中，捏合3-4min，之后加入硫化剂、促进剂，薄通3-4次，打三角包3次，并90°调头，最后调整辊距至8-10mm左右下片，冷却至室温，放24h待用。
2)预硫化
模压预硫化：将混炼胶放入模具中，热压机压力为5-20MPa，温度120-180℃，预硫化时间为5-30min，之后将胶料从模具中拿出，得到预硫化胶。
还可通过高能辐射交联对氟橡胶进行预硫化。
3)微孔发泡
预硫化好的样品放入高压反应釜中，通入物理发泡剂并升温、加压使其变为超临界状态，当物理发泡剂在预硫化物胶中达到饱和后，泄压，冷却后去出样品，得到微孔材料。其中物理发泡剂为CO2，N2、丁烷、戊烷中的一种或几种混合。
4)二次硫化
将微发泡材料放入烘箱中二次硫化，其中温度为180-250℃，时间为10-24h，硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
9.根据权利要求书8所述的一种氟橡胶超临界发泡材料的制备方法，其特征在于，步骤3)超临界发泡过程中，反应釜温度为100-150℃，压力为5-60Mpa，饱和时间为2-10h，泄压时间为10-200s。
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CN109749316A (zh) * 2017-11-01 2019-05-14 中国石油化工股份有限公司 一种耐高温水环境的四丙氟橡胶组合物及制备方法
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