CN113480776A - 一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法 - Google Patents
一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法 Download PDFInfo
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Abstract
本发明公开了一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,涉及胶乳多孔材料制备技术领域。本发明采用乳液共混方法,将环氧化天然胶乳、氧化石墨烯水分散液、PVA溶液、硫磺分散体等通过乳液共混复合后,倒置于模板中,采用冷冻干燥挥发掉水分,60℃硫化后得到三维多孔复合材料。本发明创新的以水作为溶剂和致孔剂,制备工艺简单、经济,制备过程中未用到任何乳化发泡剂,制备方法无毒无污染,环境友好。由于多孔材料以橡胶为主体具有优异的弹性,PVA作为增强体,提高了三维多孔材料力学强度,氧化石墨烯作为物理交联剂辅助交联,进一步提高了多孔材料优异的机械性能。
Description
技术领域
本发明属于环氧化天然胶多孔材料制备技术领域,特别是涉及一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法。
背景技术
环氧化天然胶多孔材料是一种低密度的多孔开放式材料。环氧化天然胶多孔材料柔软且具高弹性,缓冲性能好,材料天然绿色环保,适合各种体质人群。
目前,邓禄普法是环氧化天然胶多孔材料最常用的方法,其过程包括胶乳的配制、起泡、胶凝、定型、硫化、洗涤、干燥等工艺。如中国专利CN105599311B公开了一种基于增材制造技术制备硅橡胶多孔材料的方法,克服一般基于溶析成孔和化学发泡原理的模压和注射成型方法的不足,获得通过常用方法无法制备的具有特定泡孔结构的硅橡胶多孔材料,还如中国专利CN107599296A、CN110205101A、CN110843292A、CN105599311A等等诸如此类,均公开一种制备多孔材料的方法,目前广泛应用在床垫、坐垫和枕头等高级制品中,在隔音隔热领域也被广泛使用,深受广大消费者喜爱。
而对于冷冻干燥法制备胶乳多孔材料鲜有人提及,由于在冷冻过程中,冰晶取向生长在制备胶乳多孔材料过程中会极大影响多孔材料成品的泡孔结构,有人试图采用低温瞬间冷冻方式,实现冷冻目的的同时阻止结晶取向,但是温度过低会消耗大量的能源,且有潜在的操作风险,因此控制冰晶的生长也是一个复杂的过程。
发明内容
本发明的目的在于提供一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,通过水作为溶剂同时作为致孔剂,一举多用,未使用任何发泡剂或者表面活性剂,使用冷冻结合玻璃棒搅拌的方式在实现冷冻目的的同时避免冷冻结晶取向而破坏三维多孔材料结构。
为解决上述技术问题,本发明是通过以下技术方案实现的:
本发明为一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,包括以下步骤:
步骤SS01:将各原材料使用混合液搅拌结合超声方法混合均匀,获得混合溶液;
步骤SS02:使用冰箱冷冻结合玻璃棒搅拌方式冷冻混合溶液并破坏取向结晶,使用冷冻结合玻璃棒搅拌的方式在实现冷冻目的的同时避免冷冻结晶取向而破坏三维多孔材料结构;
步骤SS03:使用冷冻干燥方式去除溶剂并保证材料的多孔结构,最终高温固化后制得成品复合胶乳三维多孔材料;
所述步骤SS01中制得混合溶液的原材料为:环氧化天然胶乳、氧化石墨烯水分散液、PVA溶液、硫磺分散体、ZnO分散体、促进剂分散体,采用的都是分散体,更能均匀的共混到材料中。
进一步地,所述步骤SS01中各原材料所占的重量份为:环氧化天然胶乳20-25份、氧化石墨烯水分散液64~68份、PVA溶液5.76~6.8份、硫磺分散体1~1.5份、ZnO分散体1~1.5份、促进剂分散体0.5~0.75份。
进一步地,所述步骤SS01获得混合溶液的方法为:
步骤S011:称取一定质量PVA在三口烧瓶中,加入6倍于PVA质量的去离子水,将三口烧瓶置于90℃水浴锅中,使用电动搅拌器搅拌30min溶解,得到PVA溶液;
步骤S012:称取0.1g的氧化石墨烯,使用细胞粉碎机超声分散在15mL的去离子水中得到氧化石墨烯的悬浮液;
步骤S013:称取5.2g环氧化天然胶乳,在搅拌条件下,使用滴管将1.4g的PVA溶液缓慢滴加到环氧化天然胶乳中,继续搅拌10min,得到混合均匀的混合液A;
步骤S014:将步骤S012制得的氧化石墨烯悬浮液缓慢滴加到混合液A中,搅拌50min,得到混合均匀的混合液B;
步骤S015:将0.3g的硫磺分散体、0.3g的ZnO分散体、0.15g的促进剂分散体分别滴加到混合液B中,继续搅拌10min得到最终混合溶液。
进一步地,所述步骤S013中,5.2g的环氧化天然胶乳中含有2g干胶,1.4g的PVA溶液中含有0.2g的PVA。
进一步地,0.3g硫磺分散体中含有0.15g硫磺,0.1g的ZnO分散体中含有0.05g的ZnO,0.1g促进剂分散体中含有0.05g促进剂。
进一步地,所述步骤SS02中使用冰箱冷冻时,冰箱温度为-20℃。
进一步地,所述步骤SS02中冷冻混合溶液并破坏取向结晶的方法为:
步骤S021:将混合溶液倒置在模具中,放到冰箱中冷冻;
步骤S022:每冷冻十分钟后拿出,使用玻璃棒搅拌,破坏冰晶取向生长,如此反复三次,直至冻结。
进一步地,所述步骤SS03中使用冷冻干燥、高温固化的方式制得成品复合胶乳三维多孔材的方法为:
步骤S031:将步骤SS02中获得的冷冻后的样品置于冷冻干燥机中冷冻干燥48h;
步骤S032:将冷冻干燥后的样品置于烘箱中在60℃下固化12h得到最终成品。
进一步地,还包括:所述的方法制备的三维多孔材料作为具有柔软性和弹性相变储能材料的应用。
进一步地,所述的方法制备的三维多孔材料应用于床垫、枕头、坐垫。
本发明具有以下有益效果:
1.本发明采用乳液共混方式,能保证环氧化天然胶乳和PVA溶液更好的混合在一起,此外,硫磺、ZnO和促进剂采用的都是分散体,更能均匀的共混到材料中。
2.本发明采用GO作为补强材料,GO上含有大量含氧基团,ENR上含有大量的极性环氧基团,PVA上含有大量的羟基,GO可以与ENR和PVA产生强烈的相互作用,实现物理交联,提高三维多孔材料的机械性能,GO本身可以良好的分散在水相中,环氧化天然胶乳和PVA都是以水为溶剂,进一步的,GO可以更好的均匀分散在基体中。
3.本发明未使用任何发泡剂或者表面活性剂,水作为溶剂同时作为致孔剂,一举多用;制备工艺简单,安全无风险,环境友好,成本低,适合大规模生产。
4.本发明创新的使用冷冻结合玻璃棒搅拌的方式在实现冷冻目的的同时避免冷冻结晶取向而破坏三维多孔材料结构。
当然,实施本发明的任一产品并不一定需要同时达到以上所述的所有优点。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为三维多孔材料表面体视显微镜图,其中,(a)为未经破坏结晶三维多孔材料;(b)为破坏结晶取向后的三维多孔材料;
图2为三维多孔材料内部扫描电子显微镜图,其中,(a)为未经破坏结晶三维多孔材料;(b)为破坏结晶取向后的三维多孔材料;
图3为破坏结晶取向后三维多孔材料压缩应力应变曲线。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,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它实施例,都属于本发明保护的范围。
实施例1:
一种乳液共混协同冷冻干燥法制备环氧化天然胶乳三维多孔材料的方法,具体包括以下步骤:
步骤1、称取一定质量PVA(聚乙烯醇)在三口烧瓶中,加入6倍于PVA质量的去离子水,使用电动搅拌器在90℃水浴锅中搅拌30min溶解,得到PVA溶液;
步骤2、称取0.1g的GO(氧化石墨烯),使用细胞粉碎机超声分散在15mL的去离子水中得到GO的悬浮液;
步骤3、称取5.2g环氧化天然胶乳,使用滴管将1.4g的PVA溶液缓慢滴加到搅拌的环氧化天然胶乳中,搅拌10min,得到混合均匀的混合液A;
步骤4、将上述的GO悬浮液缓慢滴加到混合液A中,搅拌50min,得到混合均匀的混合液B;
步骤5、将0.3g的硫磺分散体、0.3g ZnO分散体、0.15g促进剂分别滴加到上述混合液B中,继续搅拌10min得到最终混合液C;
步骤6、将所述的混合液C倒置在模具中,放到冰箱中冷冻;
步骤7、每冷冻十分钟后拿出,使用玻璃棒搅拌,破坏冰晶取向生长,如此反复三次,直至冻结;
步骤8、将上述冷冻后的样品置于冷冻干燥机中冷冻干燥48h;
步骤9、将冷冻干燥后的样品置于烘箱中在60℃下固化12h得到最终成品。
制备工艺简单、经济,制备过程中未用到任何乳化发泡剂,制备方法无毒无污染,环境友好。
对照组1:
一种制备三维多孔材料的方法,具体包括以下步骤:
步骤1、称取一定质量PVA(聚乙烯醇)在三口烧瓶中,加入6倍于PVA(聚乙烯醇)质量的去离子水,使用电动搅拌器在90℃水浴锅中搅拌30min溶解,得到PVA(聚乙烯醇)溶液;
步骤2、称取0.1g的GO(氧化石墨烯),使用细胞粉碎机超声分散在15mL的去离子水中得到GO(氧化石墨烯)的悬浮液;
步骤3、称取5.2g环氧化天然胶乳,使用滴管将1.4g的PVA(聚乙烯醇)溶液缓慢滴加到搅拌的环氧化天然胶乳中,搅拌10min,得到混合均匀的混合液A;
步骤4、将上述的GO(氧化石墨烯)悬浮液缓慢滴加到混合液A中,搅拌50min,得到混合均匀的混合液B;
步骤5、将0.3g的硫磺分散体、0.3g ZnO分散体、0.15g促进剂分别滴加到上述混合液B中,继续搅拌10min得到最终混合液C;
步骤6、将所述的混合液C倒置在模具中,放到冰箱中冷冻;
步骤7、将上述冷冻后的样品置于冷冻干燥机中冷冻干燥48h;
步骤8、将冷冻干燥后的样品置于烘箱中在60℃下固化12h得到最终成品。
实验方式:
1.关于复合环氧化天然胶和聚乙烯醇三维多孔材料表面结构:通过体式显微镜观察样品表面结构特征,对比冷冻过程中破坏结晶结构和未破坏结晶结构样品的区别。
具体的:使用体式显微镜对实施例1和对照组1进行观察样品表面结构。
2.关于复合环氧化天然胶和聚乙烯醇三维多孔材料内部结构,观察样品内部结构特征,对比冷冻过程中破坏结晶结构和未破坏结晶结构样品的区别。
具体的:使用扫描电子显微镜对实施例1和对照组1内部结构进行观察。
3.关于复合环氧化天然胶和聚乙烯醇三维多孔材料,检测破坏结晶结构的样品压缩和回弹的力学性能。
实验结果:
1.通过图1可以看出:破坏结晶结构后样品表面均匀,未出现因取向导致的结构破坏,而冷冻阶段未破坏结晶结构的样品出现了明显的缝隙。
2.通过图2的扫描电子显微镜图示可以看出:所有样品表现出多孔结构,破坏结晶后的样品内部结构均匀,未破坏结晶的样品出现明显的结晶缝隙。
3.通过图3可以看出:样品经过100次的循环测试,样品拥有良好的压缩稳定性。
在本说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节,也不限制该发明仅为所述的具体实施方式。显然,根据本说明书的内容,可作很多的修改和变化。本说明书选取并具体描述这些实施例,是为了更好地解释本发明的原理和实际应用,从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。
Claims (10)
1.一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,包括以下步骤:
步骤SS01:将各原材料使用混合液搅拌结合超声方法混合均匀,获得混合溶液;
步骤SS02:使用冰箱冷冻结合玻璃棒搅拌方式冷冻混合溶液并破坏取向结晶;
步骤SS03:使用冷冻干燥方式去除溶剂并保证材料的多孔结构,最终高温固化后制得成品复合胶乳三维多孔材料;
所述步骤SS01中制得混合溶液的原材料为:环氧化天然胶乳、氧化石墨烯水分散液、PVA溶液、硫磺分散体、ZnO分散体、促进剂分散体。
2.根据权利要求1所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述步骤SS01中各原材料所占的重量份为:环氧化天然胶乳20-25份、氧化石墨烯水分散液64~68份、PVA溶液5.76~6.8份、硫磺分散体1~1.5份、ZnO分散体1~1.5份、促进剂分散体0.5~0.75份。
3.根据权利要求1所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述步骤SS01获得混合溶液的方法为:
步骤S011:称取一定质量PVA在三口烧瓶中,加入6倍于PVA质量的去离子水,将三口烧瓶置于90℃水浴锅中,使用电动搅拌器搅拌30min溶解,得到PVA溶液;
步骤S012:称取0.1g的氧化石墨烯,使用细胞粉碎机超声分散在15mL的去离子水中得到氧化石墨烯的悬浮液;
步骤S013:称取5.2g环氧化天然胶乳,在搅拌条件下,使用滴管将1.4g的PVA溶液缓慢滴加到环氧化天然胶乳中,继续搅拌10min,得到混合均匀的混合液A;
步骤S014:将步骤S012制得的氧化石墨烯悬浮液缓慢滴加到混合液A中,搅拌50min,得到混合均匀的混合液B;
步骤S015:将0.3g的硫磺分散体、0.3g的ZnO分散体、0.15g的促进剂分散体分别滴加到混合液B中,继续搅拌10min得到最终混合溶液。
4.根据权利要求3所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述步骤S013中,5.2g的环氧化天然胶乳中含有2g干胶,1.4g的PVA溶液中含有0.2g的PVA。
5.根据权利要求3所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,0.3g硫磺分散体中含有0.15g硫磺,0.1g的ZnO分散体中含有0.05g的ZnO,0.1g促进剂分散体中含有0.05g促进剂。
6.根据权利要求1所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述步骤SS02中使用冰箱冷冻时,冰箱温度为-20℃。
7.根据权利要求1所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述步骤SS02中冷冻混合溶液并破坏取向结晶的方法为:
步骤S021:将混合溶液倒置在模具中,放到冰箱中冷冻;
步骤S022:每冷冻十分钟后拿出,使用玻璃棒搅拌,破坏冰晶取向生长,如此反复三次,直至冻结。
8.根据权利要求1所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述步骤SS03中使用冷冻干燥、高温固化的方式制得成品复合胶乳三维多孔材的方法为:
步骤S031:将步骤SS02中获得的冷冻后的样品置于冷冻干燥机中冷冻干燥48h;
步骤S032:将冷冻干燥后的样品置于烘箱中在60℃下固化12h得到最终成品。
9.根据权利要求1~8任意一项所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,还包括:所述的方法制备的三维多孔材料作为具有柔软性和弹性相变储能材料的应用。
10.根据权利要求1~8所述的一种乳液共混协同冷冻干燥法制备橡胶基多孔材料的方法,其特征在于,所述的方法制备的三维多孔材料应用于床垫、枕头、坐垫。
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