CN107200937A - 一种丁基橡胶微孔发泡材料及其制备方法 - Google Patents
一种丁基橡胶微孔发泡材料及其制备方法 Download PDFInfo
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- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 35
- 239000006261 foam material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005187 foaming Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 10
- 239000005060 rubber Substances 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 7
- 230000000994 depressogenic effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000036772 blood pressure Effects 0.000 claims description 3
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- YOEWQQVKRJEPAE-UHFFFAOYSA-L succinylcholine chloride (anhydrous) Chemical class [Cl-].[Cl-].C[N+](C)(C)CCOC(=O)CCC(=O)OCC[N+](C)(C)C YOEWQQVKRJEPAE-UHFFFAOYSA-L 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
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- 229920005556 chlorobutyl Polymers 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000013016 damping Methods 0.000 abstract description 4
- 238000004500 asepsis Methods 0.000 abstract description 3
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- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 ageing-resistant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
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- 125000004968 halobutyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
本发明公开了一种丁基橡胶微孔发泡材料及其制备方法,其配方如下:丁基橡胶100份,填料0‑100,硫化剂0.1‑2份,活化剂0‑8份,防老剂0‑5份;并以上述配方提供了制备方法。本发明具有较好的吸震、减震、隔声等性能,且超临界发泡材料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。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种丁基橡胶微孔发泡材料及其制备方法。
背景技术
丁基橡胶是异丁烯与少量的硫化点单体异戊二烯的共聚物。卤化丁基是氯化或溴化的丁基,卤化丁基橡胶的需求量约占丁基橡胶总需求量的60%左右。丁基橡胶属于碳链饱和非极性橡胶,化学性质稳定,但由于密集的侧甲基使丁基橡胶的稳定性增加,丁基橡胶的耐老化性、耐水性、耐化学介质性、低温性能都较优异。丁基橡胶密集的侧甲基使大分子内旋转困难使得其在广泛的温度范围内弹性都是最低的;丁基橡胶的高阻尼性使其有着良好的吸声减震性;在通用橡胶中,IIR具有最好的气密,渗透率低则气密性高,好的气密性适合于制造如内胎、药用瓶塞等产品。
对IIR进行卤化可以得到氯化丁基橡胶和溴化丁基橡胶。经过卤化后的丁基橡胶硫化速度加快,黏着性提高,共混性得到改善。卤化丁基橡胶有着丁基橡胶的显著的优点,并且卤化丁基橡胶的耐老化性、耐候性都有显著提高。
对丁基橡胶和卤化丁基橡胶进行超临界发泡得到的发泡材料,将会保留它们原有的特殊性质,而且发泡材料还有质轻、原材料使用少等特点,降低了生产成本,节约材料。对于生产和生活中的使用是不可或缺的。
发明内容
本发明的目的是提供一种丁基橡胶微孔发泡材料及其制备方法,本发明具有较好的耐老化性、吸震、电绝缘等性能,且超临界发泡材料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。
一种丁基橡胶微孔发泡材料,其配方如下:丁基橡胶100份,填料0-100,硫化剂0.1-2份,活化剂0-8份,防老剂0-5份。
丁基橡胶包括丁基橡胶IIR、氯化丁基橡胶CIIR、溴化丁基BIIR。
填料为炭黑、白炭黑、滑石粉、高岭土中的一种或多种。
硫化剂为硫黄(S)、过氧化二异丙苯(DCP)中的一种或多种。
活化剂为中的硬脂酸(SA)、氧化镁(MgO)中的一种或多种。
防老剂为2,2,4-三甲基1,2-二氢化喹(RD)、N-苯基-N`-环己基对苯二胺(4010)、ODA中的任一种。
一种丁基橡胶微孔发泡材料的制备方法,其步骤如下:
1)混炼胶制备
(1)按重量分别称取所需生胶、填料等;(2)密炼机温度设置为70-120℃,转速为45-60r/min,将生胶、填料、硫化剂、活性剂和防老剂依次投入密炼机中,混炼均匀,控制排胶温度低于120℃;(3)混炼胶排胶、压片、冷却停放12h;
2)预硫化
(1)挤出成型预硫化
将混炼胶放入130-190℃的进行预硫化,预硫化时间为1min-15min,硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
(2)模压成型预硫化
将混炼胶放入所需模具中,热压机压力为8-20MPa,温度140-190℃,预硫化时间为1-12min,之后将胶料从模具中拿出,得到预硫化材料。
3)超临界发泡
预硫化好的样品放入高压反应釜中,通入超临界流体并升温、加压使其变为超临界状态,当超临界流体在预硫化物胶中达到饱和后,采用快速降压法、或快速升温法,制得微孔材料。其中超临界流体为CO2,N2中的一种或两种气体的混合气体。
升温法:将预硫化材料装入高压釜内,先用少量CO2吹洗2-3min,然后密封,反 应釜温度为25-140℃,用超临界注气系统将超临界流体注入高压釜内,使压力达到8-60MPa,恒压饱和0.5-24h。然后迅速卸压至常压,最后在100-220℃温度的平板硫化机(或烘箱中)加热样品一定时间使之发泡后放入水中冷却,得到发泡材料。
降压法:将预硫化材料装入高压釜内,先用少量CO2吹洗2-3min,然后密封,反应釜温度为25-140℃,用超临界注气系统将超临界流体注入高压釜内,使压力达到5-60MPa,恒压饱和0.5-24h。然后迅速卸压至常压,卸压时间为5-80s,得到发泡材料。
4)二次硫化、定型;
将预硫化微发泡材料放入另一烘道中二次硫化、定型,其中烘道温度为120-180℃,硫化时间为10-60min,硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
与现有技术相比,本发明具有以下有益效果:
丁基橡胶包括卤化丁基橡胶 ,其最突出的是气密性和水密性,它还能耐热、耐臭氧、耐老化、耐化学药品,并有吸震、电绝缘性能。对阳光及臭氧具良好的抵抗性,可暴露于动物或植物油或是可氧化的化学物中。主要用于制造各种内胎、蒸汽管、水胎、水坝底层以及垫圈等各种橡胶制品。其发泡材料同样具有较好的耐老化性、吸震、电绝缘等性能,且超临界发泡材料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。
本发明提供的发泡体材料可用于汽车工业领域,用于密封,减震,耐油、发动机组件等器件;可用于精密机械、医疗器具、家具、玻璃等的运输用缓冲材料;各种机械设备的防噪音密封材料、住宅隔音墙密封材料、各种电器的防水防潮密封材料;可用于航空航天,轨道交通等领域。
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;
图4本发明制备方法中,实施例4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:
一种丁基橡胶微孔发泡材料的制备方法,其步骤如下:
1)混炼胶制备
(1)按重量分别称取所需生胶、填料等;(2)密炼机温度设置为70-120℃,转速为45-60r/min,将生胶、填料、硫化剂、活性剂和防老剂依次投入密炼机中,混炼均匀,控制排胶温度低于120℃;(3)混炼胶排胶、压片、冷却停放12h;
2)预硫化
(1)挤出成型预硫化
将混炼胶放入140-190℃的进行预硫化,预硫化时间为1min-15min,硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
(2)模压成型预硫化
将混炼胶放入所需模具中,热压机压力为8-12MPa,温度140-190℃,预硫化时间为1-12min,之后将胶料从模具中拿出,得到预硫化材料。
3)超临界发泡
预硫化好的样品放入高压反应釜中,通入超临界流体并升温、加压使其变为超临界状态,当超临界流体在预硫化物胶中达到饱和后,采用快速降压法、或快速升温法,制得微孔材料。其中超临界流体为CO2,N2中的一种或两种气体的混合气体。
升温法:将预硫化材料装入高压釜内,先用少量CO2吹洗2-3min,然后密封,反应釜温度为25-140℃,用超临界注气系统将超临界流体注入高压釜内,使压力达到8-60MPa,恒压饱和0.5-24h。然后迅速卸压至常压,最后在120-200℃温度的平板硫化机(或 烘箱中)加热样品一定时间使之发泡后水中或空气中冷却,得到发泡材料。
降压法:将预硫化材料装入高压釜内,先用少量CO2吹洗2-3min,然后密封,反应釜温度为25-140℃,用超临界注气系统将超临界流体注入高压釜内,使压力达到5-60MPa,恒压饱和0.5-24h。然后迅速卸压至常压,卸压时间为5-80s,得到发泡材料。
4)二次硫化、定型;
将预硫化微发泡材料放入另一烘道中二次硫化、定型,其中烘道温度为120-180℃,硫化时间为10-60min,硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管前述实施例对本发明进行了详细的说明,本领域的普通技术人员依然可以对前述各实施例的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (6)
1.一种丁基橡胶微孔发泡材料,其特征在于,其配方如下:丁基橡胶100份,填料0-100份,硫化剂0.1-2份,活化剂0-8份,防老剂ODA0.5-2份。
2.根据权利要求书1所述的一种丁基橡胶微孔发泡材料,其特征在于,丁基橡胶包括丁基橡胶IIR、氯化丁基橡胶CIIR、溴化丁基橡胶BIIR。
3.根据权利要求书1所述的一种丁基橡胶微孔发泡材料,其特征在于,填料为炭黑、白炭黑、滑石粉、高岭土中的一种或多种。
4.根据权利要求书1所述的一种丁基橡胶微孔发泡材料,其特征在于,硫化剂为硫黄(S)、过氧化二异丙苯(DCP)、氧化锌中的一种或多种。
5.根据权利要求书1所述的一种丁基橡胶微孔发泡材料,其特征在于,活化剂为硬脂酸(SA)、氧化镁(MgO)中的一种或多种。
6.一种丁基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)按重量分别称取所需生胶、填料等;(2)密炼机温度设置为70-120℃,转速为45-60r/min,将生胶、填料、硫化剂、活性剂和防老剂依次投入密炼机中,混炼均匀,控制排胶温度低于120℃;(3)混炼胶排胶、压片、冷却停放12h;
2)预硫化
(1)挤出成型预硫化
将混炼胶放入130-190℃的进行预硫化,预硫化时间为1min-15min,硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
(2)模压成型预硫化
将混炼胶放入所需模具中,热压机压力为8-20MPa,温度140-190℃,预硫化时间为1-12min,之后将胶料从模具中拿出,得到预硫化材料。
3)超临界发泡
预硫化好的样品放入高压反应釜中,通入超临界流体并升温、加压使其变为超临界状态,当超临界流体在预硫化物胶中达到饱和后,采用快速降压法、或快速升温法,制得微孔材料。其中超临界流体为CO2,N2中的一种或两种气体的混合气体。
升温法:将预硫化材料装入高压釜内,先用少量CO2吹洗2-3min,然后密封,反应釜温度为25-140℃,用超临界注气系统将超临界流体注入高压釜内,使压力达到8-60MPa,恒压饱和0.5-24h。然后迅速卸压至常压,最后在120-200℃温度的油浴中(或烘箱中)加热样品一定时间使之发泡后放入水中冷却,得到发泡材料。
降压法:将预硫化材料装入高压釜内,先用少量CO2吹洗2-3min,然后密封,反应釜温度为40-140℃,用超临界注气系统将超临界流体注入高压釜内,使压力达到5-60MPa,恒压饱和0.5-4h。然后迅速卸压至常压,卸压时间为5-80s,得到发泡材料。
4)二次硫化、定型;
将预硫化微发泡材料放入另一烘道中二次硫化、定型,其中烘道温度为120-180℃,硫化时间为10-60min,硫化方式为热空气硫化、微波辐射交联或者红外辐射交联。
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