CN116462885B - 一种高吸油倍率酚醛树脂气凝胶材料的制备方法 - Google Patents
一种高吸油倍率酚醛树脂气凝胶材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种高吸油倍率酚醛树脂气凝胶材料的制备方法,本发明采用简单的水热法制备了酚醛树脂多孔,孔隙率达87.8%、水接触角为126.5°,对多种油剂具有良好的吸收能力且循环性能好。本发明利用酚醛树脂复合有机硅,同时提高材料的疏水性和多孔材料骨架稳定性,再经溶剂熏蒸进一步提高多孔材料的比表面积,从而提高了多孔材料的疏水性和吸收能力。
Description
技术领域
本发明属于多孔材料制备领域,具体涉及一种高吸油倍率酚醛树脂多孔材料的制备方法。
背景技术
在石油的开采、运输和贮存的过程中经常会发生石油泄漏事件,造成海洋生态环境的巨大破坏,含油污水处理已经成为目前世界上亟待解决的环境问题之一。为缓解溢油事件对海洋环境的影响,人们提出了焚烧、机械回收、吸附材料吸收以及生物降解等方法,在实际溢油事故处理中,吸附法具有极大的优势,使用吸附材料一直被认为是最有效的方法。目前的常见的吸附材料包括无纺布、吸油毡、海绵、麻袋、活性炭等,但仍然存在饱和吸油倍率低下等问题。
CN111111625A采用静电纺丝技术并结合表面修饰技术(浸渍)制备微纳米纤维气凝胶用于吸油,纳米纤维具有直径小,孔隙率高,比表面积大等优点,制成纳米纤维气凝胶,其具有整体密度小,孔隙率高等优点。但利用静电纺丝技术产量低、成本高,不利于大规模生产。
历史上第一个有机气凝胶是美国Lawerence Livemore国家实验室以小分子的间苯二酚和甲醛为原料,采用溶胶-凝胶法制备的酚醛有机气凝胶。目前,酚醛有机气凝胶的研究开展较早,研究较为充分,制备技术也比较成熟;且酚醛树脂具有优异的耐腐蚀性能,因此其气凝胶广泛应用于分离材料领域。但由于酚醛树脂湿凝胶为了防止气凝胶内部聚合物网络骨架的坍塌和体积的收缩,必须采用超临界干燥、冷冻干燥等特殊技术手段才能得到骨架稳定、收缩率较低、孔结构完好的有机气凝胶,这些无疑大大地限制了有机气凝胶的大规模生产与应用,也使得整个溶胶-凝胶制备过程复杂化,成本显著增加。
发明内容
基于上述技术现状,本发明提供一种高吸油倍率酚醛树脂多孔材料的制备方法,包括以下步骤:
S1-制备酚醛树脂/有机硅复合多孔材料
在酸性或碱性溶液中,混合苯酚、甲醛、氨基硅烷和十六烷基三甲基溴化铵,加热搅拌1h后将溶液转移至模具中,在不同温度下恒温陈化后干燥得到多孔材料。
所述氨基硅烷为氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、氨丙基乙基二甲氧基硅烷中的一种。
S2-溶剂熏蒸
为了进一步提高气凝胶中纤维的比表面积,对多孔材料进行溶剂熏蒸后处理。
本发明中制备气凝胶的原材料易得且成本低、利用水热法制备气凝胶方法简单,大大降低了制造成本。
步骤S1中,甲醛能与氨基、苯酚的邻、对位发生反应,同时Si-O-R能够在酸/碱催化下交联形成Si-O-Si的结构,从而形成多样的交联结构,该结构能够改善湿凝胶干燥过程中内部聚合物网络骨架的坍塌和体积的收缩,从而使得其可利用普通的干燥方法即可制备得到结构稳定的多孔材料。
苯酚离子化后通过静电吸引堆积在十六烷基三甲基溴化铵胶束的界面处,从而降低胶束的表面电荷密度,从而导致现有胶束的平均曲率变小,有利于形成细长的蠕虫状的胶束。随着缩合的进行,低聚物倾向于插入蠕虫状胶束的疏水端以降低表面能,最终得到酚醛树脂基纳米纤维(尤磊.可控润湿性块状纳米纤维聚合物/碳材料的制备及其应用[D].河南大学,2020.DOI:10.27114/d.cnki.ghnau.2020.002048.)。
本发明具有如下优点和有益效果:
本发明采用简单的水热法制备了酚醛树脂多孔,孔隙率达87.8%、水接触角为126.5°,对多种油剂具有良好的吸收能力且循环性能好。本发明利用酚醛树脂复合有机硅,同时提高材料的疏水性和多孔材料骨架稳定性,再经溶剂熏蒸进一步提高多孔材料的比表面积,从而提高了多孔材料的疏水性和吸收能力。
附图说明
图1为实施例1的多孔材料的FT-IR。
图2为实施例3、实施例5多孔材料的SEM图。
图3为实施例5的对油的吸收能力柱状图。
图4为实施例5的对甲苯吸收循环能力示意图。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
S1-制备酚醛树脂/有机硅复合多孔材料
在酸性或碱性溶液中,混合苯酚、氨基硅烷、十六烷基三甲基溴化铵,升温至60℃,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中,在不同温度下陈化72h,最后置于60~80℃烘箱中干燥至恒重,即得到多孔材料。
所述的酸性溶液为往溶剂中加入草酸、盐酸、硫酸中的一种;
所述碱性溶液为往往溶剂中加入氢氧化钠、氨水中的一种;
所述溶液为水、乙醇中的一种。
所述陈化温度为180~250℃。
所述氨基硅烷为氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、氨丙基乙基二甲氧基硅烷中的一种。
S2-溶剂熏蒸
5L的干燥器内加入300ml溶剂,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上。将干燥器放入恒温箱中,设定一定温度(RT~50℃),熏蒸时间为1~2天。熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h。
所述溶剂为丙酮、DCM、甲醇中的一种。
实施例1
称取苯酚、氨丙基三乙氧基硅烷、十六烷基三甲基溴化铵溶于乙醇溶液中,加入2mol/L的HCl溶液,调节溶液的pH为4~5,升温至60℃回流,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中,在180℃温度下陈化72h,最后置于60℃烘箱中干燥至恒重,即得到气凝胶。所述苯酚、氨基硅烷、十六烷基三甲基溴化铵、甲醛的投料摩尔比为1:0.2:0.2:1,所述苯酚在乙醇中的浓度为0.05g/mL。
在5L的干燥器内加入300ml丙酮,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上。将干燥器放入恒温箱中,设定一定温度(40℃),熏蒸时间为1天。熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h。
实施例2
称取苯酚、氨丙基三乙氧基硅烷、十六烷基三甲基溴化铵溶于乙醇溶液中,加入氨水(25~28wt%),调节溶液的pH为8左右,升温至60℃回流,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中,在180℃温度下陈化72h,最后置于60℃烘箱中干燥至恒重,即得到多孔材料。所述苯酚、氨基硅烷、十六烷基三甲基溴化铵、甲醛的投料摩尔比为1:0.2:0.2:1,所述苯酚在乙醇中的浓度为0.05g/mL。
在5L的干燥器内加入300ml丙酮,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上。将干燥器放入恒温箱中,设定一定温度(40℃),熏蒸时间为1天。熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h。
实施例3
取苯酚、氨丙基三乙氧基硅烷、十六烷基三甲基溴化铵溶于乙醇溶液中,加入2mol/L的HCl溶液,调节溶液的pH为4~5,升温至60℃回流,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中,在220℃温度下陈化72h,最后置于60℃烘箱中干燥至恒重,即得到多孔材料。所述苯酚、氨基硅烷、十六烷基三甲基溴化铵、甲醛的投料摩尔比为1:0.2:0.2:1,所述苯酚在乙醇中的浓度为0.05g/mL。
在5L的干燥器内加入300ml丙酮,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上。将干燥器放入恒温箱中,设定一定温度(40℃),熏蒸时间为1天。熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h。
实施例4
取苯酚、氨丙基三乙氧基硅烷、十六烷基三甲基溴化铵溶于乙醇溶液中,加入2mol/L的HCl溶液,调节溶液的pH为4~5,升温至60℃回流,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中,在250℃温度下陈化72h,最后置于60℃烘箱中干燥至恒重,即得到多孔材料。所述苯酚、氨基硅烷、十六烷基三甲基溴化铵、甲醛的投料摩尔比为1:0.2:0.2:1,所述苯酚在乙醇中的浓度为0.05g/mL。
在5L的干燥器内加入300ml丙酮,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上。将干燥器放入恒温箱中,设定一定温度(40℃),熏蒸时间为1天。熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h。
实施例5
取苯酚、氨丙基乙基二甲氧基硅烷、十六烷基三甲基溴化铵溶于乙醇溶液中,加入2mol/L的HCl溶液,调节溶液的pH为4~5,升温至60℃回流,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中,在220℃温度下陈化72h,最后置于60℃烘箱中干燥至恒重,即得到多孔材料。所述苯酚、氨基硅烷、十六烷基三甲基溴化铵、甲醛的投料摩尔比为1:0.2:0.2:1,所述苯酚在乙醇中的浓度为0.05g/mL。
在5L的干燥器内加入300ml丙酮,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上。将干燥器放入恒温箱中,设定一定温度(40℃),熏蒸时间为1天。熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h。
实施例6
采用甲醇对实施例5多孔材料进行熏蒸,熏蒸温度为60℃,熏蒸时间为1天。
对比例1
称取54.5mmol苯酚和11mL 37wt%甲醛水溶液加入140mL乙醇中,加热升温至40℃,在快速搅拌下向体系加入3mL 50%的NaOH水溶液,搅拌均匀后置于密闭容器中,保温在40℃进行凝胶24h,然后常温下陈化72h,倒入模具中,置于50℃烘箱中干燥至恒重。
对上述制备的多孔材料进行如下性能测试:
(1)FT-IR结构分析
实施例1制备的凝胶与对比例1制备的凝胶的红外谱图参阅附图1,从图中可以看出,实施例1凝胶在1147cm-1、1080cm-1出现了Si-O-Si的特征峰,而在1226cm-1对应的为酚醛树脂中的酚羟基数量减少甚至消失,说明酚醛树脂与有机硅之间进行了化学键联。
(2)表观密度分析:根据多孔材料的体积与质量,根据以下计算其表观密度:
式中,ρ为多孔材料的表观密度,mg/cm3;w和v分别为多孔材料的质量(mg)和体积(cm3)。
(3)孔结构特征分析:通过美国康塔Poremaster GT60全自动孔隙度压汞分析仪测定,采用连续扫描模式,室温测试。
(4)接触角测量
将多孔材料平整地粘在载玻片上,在表面滴一滴10μL纯水液滴,采用JC2000D型接触角测试仪进行测试。
(5)油吸收能力和循环测试
在室温下用重量法测定材料对油的吸收能力。测试油类包括:乙醇、正己烷、甲苯、二氯甲烷、石油醚、丙酮、植物油。首先对干燥后的多孔材料进行称重(M0)然后浸入溶剂中,直至饱和,再次称重(M1)。并通过以下公式计算吸油能力:
随后,通过机械挤压将油回收,对挤压后的材料称重,进行多次循环试验。
表1:多孔材料性能测试结果
体积收缩率是根据干燥后溶剂熏蒸前的多孔材料的体积与模具体积计算得到。
从表1分析可知,分析实施例1和2的多孔结构数据可知,酸催化交联下多孔材料的孔隙率和比表面积更大,因此密度较小。是因为在碱催化下,无论苯酚与甲醛的缩合还是氨基硅烷的自缩合,其反应速度更高,交联密度更大,而酸催化下交联反应的速度越慢且交联程度较低,所形成的凝胶的半径越小且均匀,因此孔隙更为均匀致密。
分析实施例3和实施例5,当氨基硅烷为氨丙基乙基二甲氧基硅烷时,多孔材料具有更高的比表面积,干燥后有更低的体积收缩率;这是由于2RO-Si-2R相比于R-Si-3OR(R为烷基)能够降低硅烷的缩合程度,使其干燥后刚度较低、韧性较高,从而使得收缩率较低,进一步导致密度较低。实施例5的比表面积比实施例3更大有两部分原因:一方面是由于当线型Si-O-Si的含量较高时,溶剂熏蒸对纤维表面产生皱褶更为有效,参阅附图2两者的SEM图谱;另一方面,当多孔材料的交联密度较低时(实施例5),凝胶半径较小且均匀,因此孔隙更为均匀致密,导致孔隙率较大,密度较低。
陈化温度越高,醚键进一步歧化以及NH和NH2的活性氢与甲醛键合,反应产生更多的亚甲基键,使得多孔材料的含氧基团减少,从附图1中可以看出,实施例1相比于对比例1酚羟基峰减少(酚羟基与Si-O-R反应)、2800~3000cm-1对应的CH2峰值增强,由此可见陈化温度越高多孔材料的疏水性越强。但另一方面温度越高交联过程更为迅速,导致交联密度高、孔隙率下降,多孔结构不利于疏水,因此从实施例1、3、4来看,综合两个因素影响,实施例3得到的多孔材料具有最高的水接触角。
多孔材料的疏水性能与其多孔结构和表面化学构成都有重大关系,孔隙率越高、多孔材料表面越粗糙,疏水性越强;受溶剂熏蒸后,多孔材料中的纤维表面产生皱褶,使其表面更粗糙,疏水性更强;采用2RO-Si-2R相比于R-Si-3OR(R为烷基)得到的多孔材料烷基量更多,疏水性更强。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,包括如下步骤:
S1-制备酚醛树脂/有机硅复合多孔材料
在酸性或碱性溶液中,混合苯酚、氨基硅烷、十六烷基三甲基溴化铵,升温至60℃,加入甲醛,搅拌反应1h;随后将反应液转移至聚四氟乙烯的水热釜中陈化72h,最后置于60~80℃烘箱中干燥至恒重,即得到多孔材料;
所述氨基硅烷为氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、氨丙基乙基二甲氧基硅烷中的一种;
S2-溶剂熏
在5L的干燥器内加入300ml溶剂,放入多孔陶瓷隔板,然后将真空干燥过的多孔材料放在陶瓷隔板上,将干燥器放入恒温箱中,设定温度为室温~50℃,熏蒸时间为1~2天;熏蒸完毕后,将样品取出,放入干燥箱中,室温下继续真空干燥24h;所述溶剂为丙酮、DCM、甲醇中的一种。
2.根据权利要求1所述一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,所述酸性溶液为往溶剂中加入草酸、盐酸、硫酸中的一种。
3.根据权利要求1所述的一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,所述碱性溶液为往溶剂中加入氢氧化钠、氨水中的一种。
4.根据权利要求1~3任一所述一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,S1所述溶液为水、乙醇中的一种。
5.根据权利要求1所述一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,所述陈化温度为180~250℃。
6.根据权利要求1或5任一所述一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,所述陈化温度为220℃。
7.根据权利要求1所述一种高吸油倍率酚醛树脂气凝胶材料的制备方法,其特征在于,所述氨基硅烷为氨丙基乙基二甲氧基硅烷。
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