CN115010983B - 一种超疏水改性柔性泡沫及其制备方法和应用 - Google Patents
一种超疏水改性柔性泡沫及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种超疏水改性柔性泡沫及其制备方法和应用,属于功能材料制备技术领域。本发明使用疏水改性浓乳液对柔性泡沫进行表面涂覆处理,使浓乳液在泡沫中被充分吸收,然后在加热条件下进行乳液聚合,在泡沫内部形成纳米孔径结构,最后经洗涤、干燥处理得到超疏水改性柔性泡沫,其中疏水改性浓乳液包括改性单体、引发剂、交联剂、乳化剂、低表面能改性剂和水。本发明制备的超疏水改性柔性泡沫具有优异的疏水亲油性能,工艺简单、反应条件温和、不含有毒有害溶剂、成本低且周期短,有望实现材料的宏量制备和市场化推广,实现材料在处理大面积水污染分离油水混合物中的应用。
Description
技术领域
本发明属于功能材料制备技术领域,具体涉及一种超疏水改性柔性泡沫及其制备方法和应用。
背景技术
油轮在作业、海底采油和石油化工过程中产生的含油污水给环境带来了毁灭性的灾难,例如,“Front Altair”号油轮因鱼雷***导致原油大量泄漏。因此,大力开发绿色、安全的油水分离材料如纤维、铜网、分子筛、海绵、梭织等,寻求一种有效分离油水混合物的技术是迫切需要的。其中,三维多孔柔性泡沫具有成本低、重量轻、环境友好、固有的微孔结构等优点,在大规模含油废水处理中具有广阔的应用前景。然而柔性泡沫本能的亲水亲油性会降低油水分离的效率,使泡沫成为可燃的二次污染物。因此,提高海绵油水混合物分离效率的前提是提高其选择性,如开发超疏水/超亲油柔性泡沫海绵。
虽然关于超疏水柔性泡沫改性的设计思路精巧,但是在实践中,大多三维多孔柔性泡沫的改性过程复杂,所用的试剂和相关的设备昂贵。同时改性过程会对环境有害,并且三维多孔柔性泡沫的孔径过大,导致不能有效的分离油水乳液,限制了大规模的工业应用。因此,开发简便、低成本和环保型改性柔性泡沫并将其广泛用于油水分离仍是一个挑战。
发明内容
本发明为解决上述现有技术存在的问题,首先提供了一种超疏水改性柔性泡沫的制备方法,包括如下步骤:使用疏水改性浓乳液对柔性泡沫进行表面涂覆处理,使浓乳液在泡沫中被充分吸收,然后在加热条件下进行乳液聚合,在泡沫内部形成纳米孔径结构,最后经洗涤、干燥处理得到超疏水改性柔性泡沫,其中所述疏水改性乳液包括改性单体、引发剂、交联剂、乳化剂、低表面能改性剂和水。
具体的,以重量份计,疏水改性浓乳液中改性单体和交联剂合计40-60份、引发剂1-5份、乳化剂10-30份、低表面能改性剂5-20份、水100-5000份。
优选的,其中改性单体和交联剂质量用量比为3:2。
为了使疏水改性浓乳液能够顺利充分进入泡沫内部,同时能够在泡沫内部经反应形成小于泡沫孔径的具有纳米级空隙结构的多孔材料,作为一种优选的实施方式,本发明在制备疏水改性浓乳液过程控制水相含量在74%到100%之间,其中水相含量指的是水在乳液中的质量百分比。
其中,疏水改性浓乳液的制备方法是将引发剂分散于去离子水中,得到含引发剂的溶液A,将改性单体、交联剂、乳化剂和低表面能改性剂混合均匀得到混合溶液B,将混合溶液A分散于溶液B中得到疏水改性浓乳液。
优选的,配制疏水改性浓乳液过程,混合溶液B与溶液A的重量份之比为1-40:35-1000。
由于本发明配置的浓乳液是油包水型,为了达到稳定均匀的乳液状态,作为一种优选的实施方式,需要将含有引发剂的溶液A少量多次滴加到溶液B中,且每次滴加需要油完全的把水包住后再进行下一次滴加,否则若没有完全包住水就进行下一次滴加,将形成不了稳定均匀浓乳液。
优选的,使用胶头滴管由慢到快、边滴加边搅拌将溶液A滴加到混合溶液B中制得疏水改性浓乳液。
优选的,搅拌速度控制在3500-8000转/分钟。
其中,改性单体为苯乙酰胺、苯乙烯、丙烯腈、甲基丙烯酸甲酯、醋酸乙烯酯和丙烯酸丁酯中的一种。
其中,低表面能改性剂为γ-氨丙基三乙氧基硅烷、聚二甲基硅氧烷、硬脂酸、硬脂酸钙、十二烷基硫醇和乙烯基三乙氧基硅烷中的一种。
其中,引发剂为过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异丁酸二甲酯、过硫酸铵/亚硫酸氢钠复合体系中的一种。
其中,交联剂为二乙烯基苯、乙二醇二甲基丙烯酸酯、双季戊四醇五丙烯酸酯和N,N-亚甲基双丙烯酰胺中的一种。
其中,乳化剂为Tween80、Span80、十六烷基氯化铵、N-十二烷基二甲胺和十二烷基磺酸钠中的一种。
其中,柔性泡沫为聚氨酯泡沫、酚醛泡沫、聚酰亚胺泡沫、三聚氰胺泡沫、聚乙烯泡沫和橡胶泡沫中的一种。
优选的,取1000-4000重量份的疏水改性浓乳液均匀涂覆在5-50重量份的柔性泡沫表面。
优选的,表面涂覆处理后,采用减压抽滤方式使浓乳液在泡沫中被充分吸收。
优选的,在0.02-0.1MPa条件下减压抽滤。
其中,乳液聚合具体为在25-80℃反应4-24h。
其中,干燥处理具体为在40-100℃鼓风干燥8-24h。
在25-80℃条件下反应是浓乳液的固化成形,浓乳液固化成形后泡沫表面还有少量未反应或者多余的其他药品,反应完后需要用无水乙醇浸泡去除杂质,再放置于40-100℃鼓风干燥去除无水乙醇得到最后的产物。
作为优选的,浓乳液在泡沫中被充分吸收后,将反应体系密封后置于油浴、水浴或者烘箱中进行反应,然后取出洗涤干燥。本发明为了更好的将浓乳液引进泡沫的多孔结构中,将涂覆浓乳液的泡沫密封后再反应时,能够尽可能将全部的浓乳液保留在泡沫结构中,若是在空气中直接加热反应,在反应过程中可能会有一部分浓乳液水相分离,从而影响产物的多孔结构和后续的油水分离性能。
本发明对于柔性泡沫的选择没有特殊要求,市售即可,但为了获得更好的效果,优先选择具有高孔隙率、开孔结构的泡沫材料产品。
本发明进一步公开了采用上述制备方法制备得到的超疏水改性柔性泡沫,以及在油水分离中的应用。
本发明超疏水改性柔性泡沫在油水分离中的一种应用,具体为可直接用于对油水乳液的分离。
本发明具有如下的优点和有益效果:
本发明的超疏水改性的柔性泡沫,制备工艺简单、化学反应条件温和、所需周期短、成本低且对环境无污染,符合绿色环保可持续发展的理念,有望实现材料的宏量制备和市场化推广;
本发明所制备的超疏水改性柔性泡沫具有优异的疏水亲油性能,可通过重力方式连续、高效分离不相容油水混合体系、微纳级油水乳液混合物,有望实现材料在处理大面积水污染中的应用;
本发明通过乳液聚合反应将浓乳液的微观多孔结构引入到柔性泡沫,基于尺寸筛分效应,使得改性过后的柔性泡沫的孔径从原始的100~1000微米降低至100纳米~10微米,从而实现表面活性剂稳定的油包水乳液分离。
附图说明
图1为改性前柔性泡沫(a)、实施例1超疏水改性柔性泡沫低倍数(b)、实施例1超疏水改性柔性泡沫高倍数(c)的扫描电子显微镜图;
图2为改性前柔性泡沫(a)、实施例1超疏水改性柔性泡沫(b)(c)的静态接触角;
图3为实施例1超疏水改性柔性泡沫的宏观润湿性能测试;
图4为实施例1超疏水改性柔性泡沫分别对石油醚/水混合物(a)、三氯甲烷/水混合物(b)进行油水分离测试;
图5为实施例1超疏水改性柔性泡沫在重力作用下实现表面活性剂稳定的甲苯包水乳液分离测试。
具体实施方式
现有三维泡沫多孔材料的孔径大小不足以分离油水乳液,而在海上原油泄漏、工厂漏油等实际情况中大多都是一些油水乳液混合物,若不解决分离乳液的问题,三维泡沫多孔材料那么就不能实际应用。基于三维多孔商用柔性泡沫具有成本低、重量轻、环境友好等优点,以及现有泡沫表面改性技术需要复杂的工艺、昂贵的设备和试剂,本发明设计了一种简单、绿色、高效、低成本的超疏水改性柔性泡沫的制备方法,有望用于大规模含油废水的处理,尤其是表面活性剂稳定的油水乳液型废水或油气田采出液。本发明提供的一种超疏水改性柔性泡沫的制备方法,具体可按如下步骤进行:
(1)将1重量份引发剂分散于100-5000重量份去离子水中,得到含引发剂的溶液A;
(2)将50重量份改性单体和交联剂(改性单体与交联剂的比例为3:2)、10-30重量份乳化剂和5-20重量份低表面能改性剂分散后制得混合溶液B;
(3)使用胶头滴管由慢到快,边滴加边搅拌将溶液A滴加到混合溶液B中制得浓乳液C,使整个浓乳液C中水相含量大于等于74%,其中机械搅拌速度为3500-8000转/分钟;
(4)取1000-4000重量份的浓乳液C,均匀涂覆在5-50重量份的柔性泡沫表面,在0.02-0.1MPa条件下,采用减压抽滤方式,使浓乳液C完全的渗透到柔性泡沫多孔结构中;
(5)将渗透有浓乳液C的柔性泡沫密封后置于25-80℃的环境中反应4-24h,将产物先用无水乙醇清洗之后,再在40-100℃鼓风干燥8-24h,得到超疏水改性柔性泡沫。
本发明通过乳液聚合反应将浓乳液的微观多孔结构引入到柔性泡沫中,涉及原理如下:通过涂覆、减压抽滤等方式,将浓乳液充分进入到泡沫结构中,在加热条件下进行乳液聚合,改性完成后的泡沫结构应该是原始柔性泡沫的大孔结构里填满引入的小孔结构,原始柔性泡沫既亲水又亲油,而加入低表面能改性试剂赋予材料低表面能,通过增加粗糙度和减低表面能实现了柔性泡沫的超疏水改性,做到超疏水超亲油的特性。
为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。其中,下述实施例中使用的柔性泡沫采购自成都美讷敏新材料科技有限公司,其表观密度为6-12kg/m3,孔隙率为99%。
实施例1
本实施例一种超疏水改性三聚氰胺泡沫由以下步骤制备:
(1)将2重量份过硫酸钠引发剂分散于1500重量份去离子水中,得到含过硫酸钠的溶液A;
(2)将30重量份苯乙烯、20重量份二乙烯基苯、15重量份乳化剂Span80和5重量份聚二甲基硅氧烷混合得到溶液B;
(3)将溶液A使用胶头滴管由慢到快、边滴加边机械搅拌至混合溶液B中制得浓乳液C,机械搅拌速度为5000转/分钟;
(4)将1000重量份浓乳液C均匀涂覆在5重量份三聚氰胺柔性泡沫表面,随后通过减压抽滤的方式使浓乳液C完全渗透到柔性泡沫的多孔结构中,再将涂覆好的柔性泡沫密封后放置烘箱65℃反应8h,将产物先用无水乙醇清洗之后,再在50℃鼓风干燥12h,得到超疏水改性三聚氰胺泡沫。
实施例2
本实施例一种超疏水改性三聚氰胺泡沫由以下步骤制备:
(1)将3重量份过硫酸钠引发剂分散于3000重量份去离子水中,得到含过硫酸钠的溶液A;
(2)将30重量份苯乙酰胺、20重量份乙二醇二甲基丙烯酸酯、20重量份乳化剂Tween80和10重量份γ-氨丙基三乙氧基硅烷混合得到溶液B;
(3)将溶液A使用胶头滴管由慢到快、边滴加边机械搅拌至混合溶液B中制得浓乳液C,机械搅拌速度为3500转/分钟;
(4)将2000重量份浓乳液C均匀涂覆在6重量份柔性泡沫表面,随后通过减压抽滤的方式使浓乳液C完全渗透到三聚氰胺泡沫的多孔结构中,再将涂覆好的三聚氰胺泡沫密封后放置烘箱60℃反应6h,将产物先用无水乙醇清洗之后,再在60℃鼓风干燥10h,得到超疏水改性三聚氰胺泡沫。
实施例3
本实施例一种超疏水改性聚氨酯泡沫由以下步骤制备:
(1)将3重量份偶氮二异丁腈引发剂分散于3000重量份去离子水中,得到含偶氮二异丁腈的溶液A;
(2)将36重量份甲基丙烯酸甲酯、24重量份双季戊四醇五丙烯酸酯、25重量份乳化剂十六烷基氯化铵和12重量份硬脂酸混合得到溶液B;
(3)将溶液A使用胶头滴管由慢到快、边滴加边机械搅拌至混合溶液B中制得浓乳液C,机械搅拌速度为8000转/分钟;
(4)将1500重量份浓乳液C均匀涂覆在5重量份聚氨酯泡沫表面,随后通过减压抽滤的方式使浓乳液C完全渗透到聚氨酯泡沫的多孔结构中,再将涂覆好的聚氨酯泡沫密封后放置烘箱55℃反应5h,将产物先用无水乙醇清洗之后,再在70℃鼓风干燥8h,得到超疏水改性聚氨酯泡沫。
实施例4
本实施例一种超疏水改性聚乙烯泡沫由以下步骤制备:
(1)将3重量份偶氮二异丁酸二甲酯引发剂分散于2500重量份去离子水中,得到含偶氮二异丁酸二甲酯的溶液A;
(2)将40重量份丙烯酸丁酯、20重量份N,N-亚甲基双丙烯酰胺、15重量份乳化剂十二烷基磺酸钠和8重量份乙烯基三乙氧基硅烷混合得到溶液B;
(3)将溶液A使用胶头滴管由慢到快、边滴加边机械搅拌至混合溶液B中制得浓乳液C,机械搅拌速度为3500转/分钟;
(4)将3000重量份浓乳液C均匀涂覆在7重量份聚乙烯泡沫表面,随后通过减压抽滤的方式使浓乳液C完全渗透到聚乙烯泡沫的多孔结构中,再将涂覆好的聚乙烯泡沫密封后放置烘箱50℃反应6h,将产物先用无水乙醇清洗之后,再在80℃鼓风干燥8h,得到超疏水改性聚乙烯泡沫。
实施例5
本实施例一种超疏水改性酚醛泡沫由以下步骤制备:
(1)将5重量份过硫酸钾引发剂分散于2000重量份去离子水中,得到含过硫酸钾的溶液A;
(2)将30重量份丙烯腈、20重量份二乙烯基苯、25重量份乳化剂十六烷基氯化铵和10重量份聚二甲基硅氧烷混合得到溶液B;
(3)将溶液A使用胶头滴管由慢到快、边滴加边机械搅拌至混合溶液B中制得浓乳液C,机械搅拌速度为3500转/分钟;
(4)将4000份浓乳液C均匀涂覆在8重量份酚醛泡沫表面,随后通过减压抽滤的方式使浓乳液C完全渗透到酚醛泡沫的多孔结构中,再将涂覆好的酚醛泡沫密封后放置烘箱70℃反应8h,将产物先用无水乙醇清洗之后,再在70℃鼓风干燥12h,得到超疏水改性酚醛泡沫。
结构表征及性能测试例
1、扫描电子显微镜图(SEM)
采用JSM-7500F扫描电子显微镜对原始柔性泡沫、实施例一改性柔性泡沫形貌进行分析,加速电压为20.0KV,样品测试前,需进行表面喷金处理,结构表征如图1所示。从图中可以看到,原始柔性泡沫的孔径在几十、上百微米,实施例1改性后的柔性泡沫孔径在几十、上百纳米,相差100倍左右,本发明在柔性泡沫里引进了浓乳液的小孔结构,而对改性前原始柔性泡沫的骨架和孔径不影响,因此柔性泡沫在改性过后具有大孔里包含小孔的结构,整体上进一步减小了泡沫孔径,从而可以直接用于分离乳液。
2、静态接触角测试(WCA)
本次试验采用德国Dataphysics公司的OCA25型测试仪对原始柔性泡沫实施例一改性泡沫的表面进行静态水接触角测试,结果如图2所示。
3、宏观润湿性能
采用2.5ml的针管取少量的去离子水,对改性过后的柔性泡沫的表面进行宏观润湿性能测试,结果如图3所示。
4、宏观油水分离测试
使用油溶性颜料甲基橙对石油醚、红油O对三氯甲烷进行染色处理,使用水溶性颜料溴酚蓝对水进行染色处理。采用实施例一改性柔性泡沫分别对轻油/水混合物、重油/水混合物进行油水分离测试,结果如图4所示。
5、对实施例一改性柔性泡沫进行表面活性剂稳定的油水乳液分离测试
具体测试方法:(1)油水乳液制备:表面活性剂稳定的甲苯包水乳液被制备。在V水:V甲苯=1:99的条件下,加入1g/L Span 80表面活性剂,1500r/min搅拌1h,得到稳定的甲苯包水乳液;(2)油水乳液分离:将适量的实施例一制备的改性泡沫固定在漏斗颈部。
在重力作用下,改性泡沫基于疏水亲油相反分子间作用力和尺寸筛分效应实现表面活性剂稳定的甲苯包水乳液分离,如图5(a)所示。使用无目镜倒置荧光数码显微镜对分离前后液体进行观察,分离前乳白色甲苯包水乳液中有许多液滴,如图5(d)所示,但分离后获得了一个透明的油相,分离后的滤液中没有观察到的液滴,如图5(c)所示。由于经改性后的泡沫的孔径大多在纳米级别,在分离油水乳液的时候,纳米级别的孔已经足以通过尺寸筛分作用实现分离,因而不需要通过压缩的方式来减小孔径就能达到较好的分离效果
对实施例2-5制备的的超疏水改性柔性泡沫进行上述结构表征和性能测试,结果均与实施例1类似,从而说明本发明制备的超疏水改性柔性泡沫具有优异的疏水亲油性能,可用于油水混合物的分离。
以上内容是结合具体/优选的实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。在不脱离本发明构思的前提下,其还可以对这些已描述的实施方式做出若干替代或变型,而这些替代或变型方式都应当视为属于本发明的保护范围。
Claims (7)
1.一种超疏水改性柔性泡沫的制备方法,其特征在于包括如下步骤:使用疏水改性浓乳液对柔性泡沫进行表面涂覆处理,使浓乳液在泡沫中被充分吸收,然后在加热条件下进行乳液聚合,在泡沫内部形成纳米孔径结构,最后经洗涤、干燥处理得到超疏水改性柔性泡沫,从而得到超疏水改性柔性泡沫,其中所述疏水改性浓乳液包括改性单体、引发剂、交联剂、乳化剂、低表面能改性剂和水;
所述疏水改性浓乳液的制备方法包括如下步骤:将引发剂分散于去离子水中,得到含引发剂的溶液A,将改性单体、交联剂、乳化剂和低表面能改性剂混合均匀得到混合溶液B,将混合溶液A分散于溶液B中得到疏水改性浓乳液;混合溶液B与溶液A的重量份之比为1-40:35-1000;
所述改性单体为苯乙酰胺、苯乙烯、丙烯腈、甲基丙烯酸甲酯、醋酸乙烯酯和丙烯酸丁酯中的一种;所述低表面能改性剂为γ-氨丙基三乙氧基硅烷、聚二甲基硅氧烷、硬脂酸、硬脂酸钙、十二烷基硫醇和乙烯基三乙氧基硅烷中的一种;
所述柔性泡沫为聚氨酯泡沫、酚醛泡沫、聚酰亚胺泡沫、三聚氰胺泡沫、聚乙烯泡沫和橡胶泡沫中的一种;取1000-4000重量份的疏水改性浓乳液均匀涂覆在5-50重量份的柔性泡沫表面。
2.根据权利要求1所述的超疏水改性柔性泡沫的制备方法,其特征在于:以重量份计,所述疏水改性浓乳液中改性单体和交联剂合计40-60份、引发剂1-5份、乳化剂10-30份、低表面能改性剂5-20份、水100-5000份;改性单体和交联剂质量用量比为3:2;所述疏水改性浓乳液的水相含量控制不小于74%。
3.根据权利要求1-2任一项所述的超疏水改性柔性泡沫的制备方法,其特征在于:所述引发剂为过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异丁酸二甲酯、过硫酸铵/亚硫酸氢钠复合体系中的一种;所述交联剂为二乙烯基苯、乙二醇二甲基丙烯酸酯、双季戊四醇五丙烯酸酯和N,N-亚甲基双丙烯酰胺中的一种。
4.根据权利要求3所述的超疏水改性柔性泡沫的制备方法,其特征在于:所述乳化剂为Tween80、Span80、十六烷基氯化铵、N-十二烷基二甲胺和十二烷基磺酸钠中的一种。
5.根据权利要求4所述的超疏水改性柔性泡沫的制备方法,其特征在于:表面涂覆处理后,采用减压抽滤方式使浓乳液在泡沫中被充分吸收;在0.02-0.1MPa条件下减压抽滤;乳液聚合在密封环境中进行;乳液聚合具体为在25-80℃反应4-24h;干燥处理具体为40-100℃鼓风干燥8-24h。
6.一种采用权利要求1-5任一项所述的超疏水改性柔性泡沫的制备方法制备得到的超疏水改性柔性泡沫。
7.一种根据权利要求6所述的超疏水改性柔性泡沫在油水分离中的应用。
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