CN115536898A - 一种双网络聚乙烯醇缩丁醛海绵及其制备方法与应用 - Google Patents
一种双网络聚乙烯醇缩丁醛海绵及其制备方法与应用 Download PDFInfo
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- CN115536898A CN115536898A CN202211167474.6A CN202211167474A CN115536898A CN 115536898 A CN115536898 A CN 115536898A CN 202211167474 A CN202211167474 A CN 202211167474A CN 115536898 A CN115536898 A CN 115536898A
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Abstract
本发明公开了一种双网络聚乙烯醇缩丁醛海绵及其制备方法与应用。在高温和酸性条件下,聚乙烯醇与丁醛缩合形成交联网络结构,同时含磺酸基或羧基的烯烃不饱和单体经引发原位聚合形成聚合物网络贯穿于缩醛网络结构中,从而得到具有互穿双网络结构的聚乙烯醇缩丁醛海绵。本发明制备得的双网络聚乙烯醇缩丁醛海绵避免了使用较高毒性的甲醛,干态浸润速率快,力学性能优异,在保持海绵自身吸附能力的基础上显著提高了对阳离子型染料的吸附性能,且可通过脱附剂解吸循环使用;在吸附废水中的阳离子型染料领域具有较好的应用前景。
Description
技术领域
本发明属于高分子材料改性合成领域,涉及聚乙烯醇缩丁醛海绵的制备,特别涉及一种双网络聚乙烯醇缩丁醛海绵及其制备方法与应用。
背景技术
染料是主要的水体污染源之一,在众多污水处理方法中,吸附法因其简单、经济、高效和极少造成二次污染的特点而成为最具吸引力的污水处理方法。海绵因其丰富的开孔结构和较大的比表面积而具有一定的吸附能力,成为备受关注的吸附材料。聚乙烯醇缩甲醛海绵干态质硬,耐磨性好,力学强度高,且具有良好的水亲和力,吸水能力较强,湿时柔软有弹性,在污水处理方面具有较好的应用前景。但是,甲醛的毒性高,对环境和人体均造成较大的负担。相较于甲醛,丁醛的毒性较低,活性更高,并且韧性更好,因此用丁醛替代甲醛,不仅能提高海绵制备的效率,而且能在一定程度上降低环境和人体所受到的伤害。
并且,单纯的缩醛海绵吸附选择性低,且吸附能力不强。为了获得更优异的吸附性能,同时对于某些特定的有机化合物有更高的吸附选择性,可以在缩醛海绵上引入特殊官能团,比如氨基、羟基、羧基或磺酸基等,来对具有较大比表面积的普通海绵进行改性。专利CN114621493A《一种聚乙烯醇海绵生产方法》将聚乙烯醇缩醛树脂溶解在酒精水溶液中配制成聚乙烯醇缩醛树脂胶,并在其中添加有机或无机填料如海藻酸钠、聚丙烯酸钠、羟基磷灰石、硅藻土等,对聚乙烯醇缩醛树脂进行改性,填料在聚乙烯醇缩醛树脂胶中以溶解形式或分散形式存在,发泡成型后获得不同物化性能的聚乙烯醇海绵制品。专利CN114453024A《一种胺化木质素改性聚乙烯醇海绵载银材料及其制备方法和应用》在制备聚乙烯醇缩甲醛海绵的过程中,在反应液中分散胺化木质素和银离子,制备得到分散有胺化木质素的聚乙烯醇缩甲醛海绵半成品,同时对聚乙烯醇缩甲醛海绵半成品进行还原处理,得到胺化木质素改性聚乙烯醇缩甲醛海绵载银材料。专利CN110193358A《含氨基改性石墨烯的复合海绵及其制备方法和用途》将氨基改性石墨烯配置成浸泡溶液,将海绵浸入该浸泡溶液中,使氨基改性石墨烯充分吸附在海绵上,得到含氨基改性石墨烯的复合海绵。然而上述改性方法主要是共混,得到的海绵性能不够稳定,在一些强极性介质或者高温、高剪切条件下很容易脱附而降低吸附性能。Pan等[Pan,Y.;Liu,Z.;Wang,W.;Peng,C.;Shi,K.;Ji,X.,Highlyefficient macroporous adsorbents for toxic metal ions in water systems basedon polyvinyl alcohol-formaldehyde sponges.Journal of Materials Chemistry A2016,4(7),2537-2549]研究了聚(丙烯酰胺-丙烯酸)接枝的聚乙烯醇缩甲醛海绵,将制备的聚乙烯醇缩甲醛海绵浸泡在含硝酸铈铵和丙烯酰胺的反应液中,通过氧化还原在海绵上接枝丙烯酰胺,进一步在碱性条件下,将丙烯酰胺水解转化为羧酸钠。这种方法是先制备海绵,然后在海绵表面进行改性,分步操作,过程复杂,周期长,而且改性容易停留在表面。
发明内容
本发明的首要目的在于提供一种双网络聚乙烯醇缩丁醛海绵及其制备方法,解决了现有技术中海绵吸附能力不足,改性操作复杂的问题。
本申请的另一目的在于提供上述双网络聚乙烯醇缩丁醛海绵在吸附废水中阳离子型染料的应用,显著提高了对阳离子型染料的吸附性能。
本发明提出一种双网络聚乙烯醇缩丁醛海绵的制备方法,在聚乙烯醇缩丁醛的反应液中加入含磺酸基或羧基的烯烃类不饱和单体,一步发泡,在高温和酸性条件下,聚乙烯醇与丁醛缩合形成交联网络结构,同时含磺酸基或羧基的烯烃不饱和单体经引发原位聚合形成聚合物网络贯穿于缩醛网络结构中,从而得到具有互穿双网络结构的聚乙烯醇缩丁醛海绵。该制备过程简单,海绵性能稳定。
本发明的目的通过以下技术方案实现。
一种双网络聚乙烯醇缩丁醛海绵的制备方法,包括以下步骤:
(1)向聚合度为1700-2400、醇解度为88mol%-99mol%的聚乙烯醇中加入蒸馏水,升温至95℃水浴加热搅拌1-2小时,得到聚乙烯醇水溶液;
(2)将含磺酸基或羧基的烯烃不饱和单体和引发剂用蒸馏水溶解,得到澄清的混合物溶液;
(3)将步骤(2)中得到的混合物溶液和步骤(1)中得到的聚乙烯醇水溶液混合均匀;
(4)加入正丁醛、戊二醛、增塑剂、表面活性剂和稳泡剂,搅拌使其混合均匀;
(5)将步骤(4)中的混合物溶液高速分散,使其发泡,得到混合物泡沫;
(6)加入稀硫酸溶液混合均匀,注入模具,烘箱固化3-4小时,结束后将泡沫取出洗净,即得到双网络聚乙烯醇缩丁醛海绵。
进一步地,步骤(1)所述的聚乙烯醇水溶液的质量浓度为5%-16.67%,优选为14.28%。
进一步地,步骤(2)所述的含磺酸基或羧基的烯烃不饱和单体为2-丙烯酰胺-2-甲基丙磺酸、2-丙烯酰胺-2-甲基丙磺酸钠、对苯乙烯磺酸钠、丙烯酸、衣康酸中的一种或多种。
进一步地,步骤(2)所述的引发剂为过硫酸钾、过硫酸铵和偶氮二异丁基脒中的一种或多种。
进一步地,步骤(4)所述的表面活性剂为OP-10、吐温80、司盘80、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种。
进一步地,步骤(4)所述的稳泡剂为十二烷基二甲基氧化铵、烷基醇胺、硅树脂聚醚乳液、硅油、L-580中的一种或多种。
进一步地,上述步骤中各反应物的配比为:
含磺酸基或羧基的烯烃不饱和单体的用量为聚乙烯醇质量的11.11%-55.55%,优选为44.44%;
引发剂的用量为含磺酸基或羧基的烯烃不饱和单体质量的0.4%-1%,优选为0.6%;
正丁醛的用量为聚乙烯醇质量的45.79%-91.59%,优选为82.43%;
戊二醛的用量为聚乙烯醇质量的1%-5%,优选为2.5%;
增塑剂的用量为聚乙烯醇质量的10%-50%,优选为23.4%;
表面活性剂的用量为聚乙烯醇质量的7%-14%,优选为10.5%;
稳泡剂的用量为聚乙烯醇质量的0.2%-1%,优选为0.2%;
稀硫酸溶液的用量为聚乙烯醇质量的5%-20%,优选为7%。
进一步地,步骤(6)所述固化的温度为50-80℃,优选为55℃。
一种双网络聚乙烯醇缩丁醛海绵,通过上述制备方法制备得到。
根据本发明所述方法制备得到的双网络聚乙烯醇缩丁醛海绵,可将其应用于废水中染料的吸附。优选地,在含阳离子型染料的废水中的应用。
进一步地,所述的阳离子型染料为杂化偶氮型阳离子型染料、三芳甲烷型阳离子型染料、嗪型阳离子型染料、多甲川型阳离子型染料和偶氮甲川型阳离子型染料等中的至少一种;优选为亚甲基蓝染料溶液(MB)、罗丹明B染料溶液(RhB)和孔雀石绿染料溶液(MG)。
本发明制备的双网络聚乙烯醇缩丁醛海绵可在吸附阳离子型染料后使用脱附剂洗脱,然后用蒸馏水清洗,干燥即可循环利用。
本发明相对于现有技术具有如下的优点及有益效果:
(1)本发明的原料易得,来源广泛,操作过程简单。
(2)在高温和酸性条件下,聚乙烯醇与丁醛缩合形成交联网络结构,同时含磺酸基或羧基的烯烃不饱和单体经引发原位聚合形成聚合物网络贯穿于缩醛网络结构中,形成的互穿双网络结构比普通缩醛海绵形成的单层缩醛网络交联更加紧密,制备得到的海绵韧性更好,力学性能更加优异。此外,互穿使得海绵在保持原缩醛结构固有特性的同时,又获得含磺酸基或羧基的聚合物的独特性能,能够通过磺酸基或羧基与阳离子型染料之间的静电相互作用实现对于阳离子型染料的选择性吸附。
(3)本发明制得的具有互穿双网络结构的聚乙烯醇缩丁醛海绵避免了使用较高毒性的甲醛,且通过原位聚合的方法将强吸水吸附性分子链交错贯穿于缩醛网络中,加快了其干态浸润速率。
(4)本发明制得的双网络聚乙烯醇缩丁醛海绵在保持海绵自身吸附能力的基础上显著提高了对阳离子型染料的吸附性能。另外,本发明制得的双网络聚乙烯缩丁醛海绵可通过脱附剂解吸循环使用,循环性能好。
附图说明
图1为实施例2中制备的双网络聚乙烯醇缩丁醛海绵的内部形貌扫描电子显微镜照片。
图2为实施例2中制备的双网络聚乙烯醇缩丁海绵的表面水渗透动态图。
图3为实施例2中制备的双网络聚乙醇缩丁醛海绵湿态下的应力-应变曲线。
图4为实施例2中制备的双网络聚乙烯醇缩丁醛海绵分别对于亚甲基蓝染料溶液、罗丹明B染料溶液以及孔雀石绿染料溶液的吸附效果图。
具体实施方式
为了更好地理解本发明,下面结合实施例和附图对本发明做出进一步的阐述,但需说明的是,实施例并不构成对本发明的限定。
以下实施例中使用的试剂均可以从商业渠道获得。
实施例1
(1)在4g聚合度为2400、醇解度为99%的聚乙烯醇2499中加入76mL蒸馏水,升温至95℃水浴加热搅拌1小时,得到聚乙烯醇水溶液;
(2)将0.4444g丙烯酸、0.4444g 2-丙烯酰胺-2-甲基丙磺酸钠和0.0036g过硫酸铵溶解于蒸馏水中,得到澄清的混合物溶液;
(3)将步骤(2)中得到的混合物溶液和步骤(1)中得到的聚乙烯醇水溶液混合均匀;
(4)加入1.8316g正丁醛、0.04g戊二醛、0.4g增塑剂、0.56g表面活性剂(OP-10、十二烷基硫酸钠和十二烷基苯磺酸钠)、以及0.024g稳泡剂(十二烷基二甲基氧化铵和L-580),搅拌使其混合均匀;
(5)将步骤(4)中的混合物溶液高速分散,使其发泡,得到混合物泡沫;
(6)加入0.2g稀硫酸溶液混合均匀,注入模具,烘箱80℃固化3小时,结束后将泡沫取出洗净,即得到双网络聚乙烯醇缩丁醛海绵。
实施例2
(1)在4g聚合度为1700、醇解度为99%的聚乙烯醇1799中加入24.01mL蒸馏水,升温至95℃水浴加热搅拌2小时,得到聚乙烯醇水溶液;
(2)将1.7776g 2-丙烯酰胺-2-甲基丙磺酸钠和0.01067g过硫酸钾溶解于蒸馏水中,得到澄清的混合物溶液;
(3)将步骤(2)中得到的混合物溶液和步骤(1)中得到的聚乙烯醇水溶液混合均匀;
(4)加入3.2972g正丁醛、0.1g戊二醛、0.936g增塑剂、0.42g表面活性剂(吐温80、十二烷基硫酸钠和十二烷基苯磺酸钠)、以及0.008g稳泡剂(硅油和L-580),搅拌使其混合均匀;
(5)将步骤(4)中的混合物溶液高速分散,使其发泡,得到混合物泡沫;
(6)加入0.28g稀硫酸溶液混合均匀,注入模具,烘箱55℃固化3小时,结束后将泡沫取出洗净,即得到双网络聚乙烯醇缩丁醛海绵。
图1为实施例2中制备的双网络聚乙烯醇缩丁醛海绵的内部形貌扫描电子显微镜照片,右上角为放大50倍的图,由图1可以看出,该海绵孔径均匀,且开孔较多,孔径在0.1mm的居多。
图2为实施例2中制备的双网络聚乙烯醇缩丁海绵的表面水渗透动态图,由图2可以看出,该海绵表面水渗透速率很快,仅需3秒。
图3为实施例2中制备的双网络聚乙醇缩丁醛海绵湿态下的应力-应变曲线,由图3可以看出该海绵的力学性能优异,拉伸强度达到了0.3666MPa,拉伸断裂伸长率达到138.341%。
实施例3
(1)在4g聚合度为1700、醇解度为88%的聚乙烯醇1788中加入20mL蒸馏水,升温至95℃水浴加热搅拌2小时,得到聚乙烯醇水溶液;
(2)将1.111g 2-丙烯酰胺-2-甲基丙磺酸、1.111g对苯乙烯磺酸钠和0.02g过硫酸钾溶解于蒸馏水中,得到澄清的混合物溶液;
(3)将步骤(2)中得到的混合物溶液和步骤(1)中得到的聚乙烯醇水溶液混合均匀;
(4)加入3.6636g正丁醛、0.2g戊二醛、2g增塑剂、0.56g表面活性剂(司盘80、十二烷基硫酸钠和十二烷基苯磺酸钠)、以及0.04g稳泡剂(烷基烯醇、硅树脂聚醚乳液和L-580),搅拌使其混合均匀;
(5)将步骤(4)中的混合物溶液高速分散,使其发泡,得到混合物泡沫;
(6)加入0.8g稀硫酸溶液混合均匀,注入模具,烘箱50℃固化4小时,结束后将泡沫取出洗净,即得到双网络聚乙烯醇缩丁醛海绵。
实施例4
取6份质量约为0.2g的按实施例2最优实验方案制备的双网络聚乙烯醇缩丁醛海绵分别放入含有亚甲基蓝(MB)的浓度为10mg/L、30mg/L、50mg/L、70mg/L、100mg/L的染料溶液,分别在室温条件下震荡4h,测试该海绵对亚甲基蓝(MB)的吸附性能。
实施例5
取6份质量约为0.2g的按实施例2最优实验方案制备的双网络聚乙烯醇缩丁醛海绵分别放入含有罗丹明B(RhB)的浓度为10mg/L、30mg/L、50mg/L、70mg/L、100mg/L的染料溶液,分别在室温条件下震荡4h,测试该海绵对罗丹明B(RhB)的吸附性能。
实施例6
取6份质量约为0.2g的按实施例2最优实验方案制备的双网络聚乙烯醇缩丁醛海绵分别放入含有孔雀石绿(MG)的浓度为10mg/L、30mg/L、50mg/L、70mg/L、100mg/L的染料溶液,分别在室温条件下震荡4h,测试该海绵对孔雀石绿(MG)的吸附性能。
图4为实施例2中制备的双网络聚乙烯醇缩丁醛海绵分别对于亚甲基蓝染料溶液、罗丹明B染料溶液以及孔雀石绿染料溶液的吸附效果图。通过公式Ce/qe=1/bqm+Ce/qm计算得到海绵的最大吸附量,其中Ce(mg/L)为吸附平衡溶液中的染料浓度,qe(mg/g)为平衡时海绵的吸附量,qm为海绵最大吸附量。经计算,该海绵对亚甲基蓝(MB)的最大吸附量为181.82mg/g;该海绵对罗丹明B(RhB)的最大吸附量为80.64mg/g;该海绵对孔雀石绿(MG)的最大吸附量为81.97mg/g。
实施例7
取质量约为0.2g的按实施例2最优实验方案制备的双网络聚乙烯醇缩丁醛海绵置于容器中,加入含有亚甲基蓝100mg/L的染料溶液,在室温条件下震荡4h,将负载亚甲基蓝的海绵用水冲洗后,加入NH4OH/NH4Cl(pH=10)溶液进行解吸附,解吸附率可达到98%,并可重复利用。
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 (10)
1.一种双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,包括以下步骤:
(1)向聚乙烯醇中加入蒸馏水,加热搅拌,得到聚乙烯醇水溶液;
(2)将含磺酸基或羧基的烯烃不饱和单体和引发剂用蒸馏水溶解,得到澄清的混合物溶液;
(3)将步骤(2)中得到的混合物溶液和步骤(1)中得到的聚乙烯醇水溶液混合均匀;
(4)加入正丁醛、戊二醛、增塑剂、表面活性剂和稳泡剂,搅拌使其混合均匀;
(5)将步骤(4)中的混合物溶液高速分散,使其发泡,得到混合物泡沫;
(6)加入稀硫酸溶液混合均匀,注入模具,烘箱固化,结束后将泡沫取出洗净,即得到双网络聚乙烯醇缩丁醛海绵。
2.根据权利要求1所述的双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,步骤(1)所述聚乙烯醇的聚合度为1700-2400、醇解度为88mol%-99mol%;步骤(1)所述加热搅拌为升温至95℃水浴加热搅拌1-2小时;步骤(1)所得聚乙烯醇水溶液的质量浓度为5%-16.67%。
3.根据权利要求1所述的双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,步骤(2)所述的含磺酸基或羧基的烯烃不饱和单体为2-丙烯酰胺-2-甲基丙磺酸、2-丙烯酰胺-2-甲基丙磺酸钠、对苯乙烯磺酸钠、丙烯酸、衣康酸中的一种或多种;步骤(2)所述的引发剂为过硫酸钾、过硫酸铵和偶氮二异丁基脒中的一种或多种。
4.根据权利要求1所述的双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,步骤(4)所述的表面活性剂为OP-10、吐温80、司盘80、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种。
5.根据权利要求1所述的双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,步骤(4)所述的稳泡剂为十二烷基二甲基氧化铵、烷基醇胺、硅树脂聚醚乳液、硅油、L-580中的一种或多种。
6.根据权利要求1所述的双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,各反应物配比为:
含磺酸基或羧基的烯烃不饱和单体的用量为聚乙烯醇质量的11.11%-55.55%;
引发剂的用量为含磺酸基或羧基的烯烃不饱和单体质量的0.4%-1%;
正丁醛的用量为聚乙烯醇质量的45.79%-91.59%;
戊二醛的用量为聚乙烯醇质量的1%-5%;
增塑剂的用量为聚乙烯醇质量的10%-50%;
表面活性剂的用量为聚乙烯醇质量的7%-14%;
稳泡剂的用量为聚乙烯醇质量的0.2%-1%;
稀硫酸溶液的用量为聚乙烯醇质量的5%-20%。
7.根据权利要求1所述的双网络聚乙烯醇缩丁醛海绵的制备方法,其特征在于,步骤(6)所述固化的温度为50-80℃,固化的时间为3-4小时。
8.一种由权利要求1-7任一项所述的制备方法制备得到的双网络聚乙烯醇缩丁醛海绵。
9.一种权利要求8所述的双网络聚乙烯醇缩丁醛海绵的应用,其特征在于,用于废水中阳离子型染料的吸附。
10.根据权利要求9所述的应用,其特征在于,所述的阳离子型染料为杂化偶氮型阳离子型染料、三芳甲烷型阳离子型染料、嗪型阳离子型染料、多甲川型阳离子型染料和偶氮甲川型阳离子型染料中的至少一种。
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