CN114377558A - 改性聚丙烯腈水处理膜及其制备方法与应用 - Google Patents
改性聚丙烯腈水处理膜及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种改性聚丙烯腈水处理膜及其制备方法与应用。所述方法先将丙烯酸羟乙酯、甲基丙烯酸氧杂环丁烷酯、偶氮二异丁腈溶于N,N二甲基甲酰胺中,聚合反应形成丙烯酸羟乙酯和甲基丙烯酸氧杂环丁烷酯的梯度聚合物,再将梯度聚合物溶于甲醇中自组装形成胶束,最后将梯度聚合物胶束、促进剂和光引发剂混合后倒入固定好的基膜表面,紫外光照射,得到改性聚丙烯腈水处理膜。本发明采用阳离子开环聚合的方法,引入含有侧链有羟基的梯度聚合物,能够有效改善基膜的综合性能,提高膜的亲水性及抗污效果。
Description
技术领域
本发明属于水处理膜技术领域,涉及一种改性聚丙烯腈水处理膜及其制备方法与应用。
背景技术
工业水污染具有成分复杂、有毒有害等特点,给人体健康带来重大伤害。膜技术具有选择性强、操作过程简单、适用范围广、处理效果好等特点,正逐渐成为水处理领域的核心技术。但膜技术在处理工业水时,存在膜污染问题,其抗污性能差,缩短了使用寿命,同时重复使用次数低,导致处理成本变高,限制了膜技术的广泛应用。因此,如何防止膜污染或减缓膜污染过程,是目前应用研究的方向。
根据膜孔径的不同,可分为微滤膜、超滤膜、纳滤膜和反渗透膜。膜污染主要来自废水中的大分子有机物、腐殖质、碳氢化合物、细菌、悬浮污泥和无机物等。造成膜污染的主要原因分为两个方面:从内部角度来看,膜污染过程是膜和污染物、污染物和污染物之间的复杂相互作用,膜分离时,可能由于溶质分子堵塞膜孔造成污染、溶质分子被阻挡在膜内造成污染、溶质吸附在膜上造成污染、膜较为疏水;从外部角度来看,操作压力、流速等因素对膜污染有影响,适当的调节这些因素也可以降低膜污染。由于膜自身强度和结构因素,膜清洗不能太频繁,但为了保持稳定的通量,有时需要使用更大操作压力或频繁的化学清洗,这不可避免的降低了膜的使用寿命。因此开发一种抗污性能好的膜,是解决膜污染的关键。
提高膜的抗污性能的办法主要包括共混改性、共聚改性、表面涂覆和表面接枝改性。共混改性是将改性材料与膜材料共溶于同一溶剂中,形成刮膜液,然后制成膜。共聚改性是将亲水单体与疏水单体共聚得到的两亲性共聚物作为膜的改性剂。表面涂覆是在膜的表面通过浸涂或者旋涂等方式将改性液涂覆在膜的表面。表面接枝改性是直接在膜表面接枝亲水聚合物。
Ran等用RAFT法制备了乙烯基吡咯烷酮和甲基丙烯酸甲酯三嵌段聚合物(PVP-PMMA-PVP)。将三嵌段聚合物与聚醚砜共混后通过液-液相分离技术得到改性膜,其抗污性强(Ran F,Nie S,Zhao W,et al.Biocompatibility of modified polyethersulfonemembranes by blending an amphiphilic triblock co-polymer of poly(vinylpyrrolidone)-b-poly(methyl methacrylate)-b-poly(vinyl pyrrolidone).[J].ActaBiomaterialia,2011,7(9):3370-3381.)。Fang等利用聚乙二醇甲基丙烯酸酯和甲基丙烯酸甲酯的自由基聚合,合成接枝聚合物PEG-g-PMMA。将接枝聚合物与聚氯乙烯共混改性,在不同溶剂(乙醇、水)中进行相分离成膜,发现水为凝固液时膜的亲水性更大,抗污染性更强(Li-Feng Fang,BK Zhu,LP Zhu,et al.Structures and antifouling properties ofpolyvinyl chloride/poly(methyl methacrylate)-graft-poly(ethylene glycol)blendmembranes formed in different coagulation media[J].Journal of MembraneScience,2017.)。然而,共混的改性剂与膜基材很难相容,而且操作复杂,不易于工业化大规模生产。表面接枝改性之后会对原始膜的表面形貌以及内部的结构产生影响,接枝浓度过高时,有可能出现分离膜堵塞的情况,且聚合物的分子量、多分散性的大小、聚合物的链长不易调控。
发明内容
本发明的目的在于提供一种改性聚丙烯腈水处理膜及其制备方法与应用。所述方法利用阳离子开环光聚合,在膜表面发生紫外光固化,从而形成表面交联层对分离膜表面进行亲水化改性,制得具有优异截留性能和抗污性能的水处理膜。
实现本发明目的的技术方案如下:
改性聚丙烯腈水处理膜的制备方法,包括如下步骤:
步骤1,聚合物的制备:将丙烯酸羟乙酯(HEA)、甲基丙烯酸氧杂环丁烷酯、偶氮二异丁腈(AIBN)溶于N,N二甲基甲酰胺(DMF)中,在氮气的氛围中,在80±5℃下聚合反应,反应结束后,透析、冻干得到丙烯酸羟乙酯和甲基丙烯酸氧杂环丁烷酯的梯度聚合物;
步骤2,胶束的自组装:将梯度聚合物溶于甲醇中,超声搅拌,自组装形成浓度为5~20mg/mL的胶束;
步骤3,膜的制备:以疏水聚丙烯腈(PAN)膜为基膜,将梯度聚合物胶束、促进剂3,4-环氧环己基甲酸-3’,4’-环氧环己基甲酯和光引发剂二苯基-(4-苯基硫)苯基锍六氟锑酸盐(PAG-201)混合,超声搅拌,倒入到固定好的基膜表面,紫外光照射2~5min,在膜表面发生交联,得到改性聚丙烯腈水处理膜。
优选的,步骤1中,聚合反应时间为18~24h。
优选的,步骤1中,甲基丙烯酸氧杂环丁烷酯、丙烯酸羟乙酯的质量比为1:6~12。
优选的,步骤1中,偶氮二异丁腈的投加量为甲基丙烯酸氧杂环丁烷酯和丙烯酸羟乙酯的总质量的2%。
优选的,步骤2中,超声搅拌时间为5分钟以上。
优选的,步骤3中,3,4-环氧环己基甲酸-3’,4’-环氧环己基甲酯的投加量为梯度聚合物质量的20%。
优选的,步骤3中,二苯基-(4-苯基硫)苯基锍六氟锑酸盐的投加量为梯度聚合物质量的5%。
优选的,步骤3中,紫外光功率为300W。
优选的,步骤3中,紫外光与膜的间距为50cm。
本发明中,在紫外光照下,阳离子光引发剂二苯基-(4-苯基硫)苯基锍六氟锑酸盐产生阳离子活性自由基,引发含氧杂环丁烷基团的聚合物发生开环光聚合,从而在膜表面形成一层固化膜。
与现有技术相比,本发明具有以下特点:
(1)本发明采用阳离子开环聚合的方法,整个固化过程非常迅速,可在几分钟甚至几十秒间快速完成,通过控制光照时间和聚合物浓度实现交联程度的调控。
(2)本发明制得的水处理膜,引入含有侧链有羟基的梯度聚合物,能够有效改善综合性能,提高膜的亲水性及抗污效果。
附图说明
图1为对比例1~3与实施例1中制备的水处理膜的染料截留效果对比图;
图2为对比例1~3与实施例1中制备的水处理膜的抗污性能效果对比图;
图3为对比例1~3与实施例1中制备的水处理膜的接触角对比图;
图4为对比例6~7与实施例1中制备的水处理膜的染料截留效果对比图;
图5为对比例6~7与实施例1中制备的水处理膜的抗污性能效果对比图。
具体实施方式
下面将结合具体实施例和附图对本发明作进行进一步描述,但本发明的范围不仅限于此。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。除非特别说明,本发明所用试剂和材料均为市购。
实施例1
(1)聚合物的制备:将30g丙烯酸羟乙酯(HEA),2.5g甲基丙烯酸氧杂环丁烷酯,0.65g的AIBN溶于60mLN,N-二甲基乙酰胺中,脱气15min,之后在氮气保护下,在80℃下反应24小时,反应结束,透析、冻干,得到丙烯酸羟乙酯和甲基丙烯酸氧杂环丁烷酯的梯度聚合物;
(2)胶束的自组装:将丙烯酸羟乙酯和甲基丙烯酸氧杂环丁烷酯的梯度聚合物0.1g溶于10mL甲醇中,超声搅拌5min,自发组装形成胶束;
(3)膜的制备:以疏水PAN膜为基膜,将步骤(2)得到的梯度聚合物胶束、0.02g(占聚合物质量的20%)促进剂3,4-环氧环己基甲酸-3’,4’-环氧环己基甲酯和0.005g(占聚合物质量的5%)的光引发剂二苯基-(4-苯基硫)苯基锍六氟锑酸盐(PAG-201)混合,超声搅拌,倒入到固定好的基膜表面,在300W紫外光下照射5min,在膜表面发生交联,得到改性聚丙烯腈水处理膜。
对比例1
本对比例的光照时间为1min,其他步骤同实施例1。
对比例2
本对比例的光照时间为2min,其他步骤同实施例1。
对比例3
本对比例的光照时间为8min,其他步骤同实施例1。
对实施例1和对比例1~3制得的水处理膜进行截留性能测试,测试方法如下:
在柠檬黄模拟的染料废水(50mg/L的柠檬黄溶液)中,以实施例1和对比例1~3制得的膜为水处理膜,定期取柠檬黄溶液,利用紫外分光光度计测定柠檬黄溶液在吸收波长428nm下的吸光度变化,并根据下式计算催化降解效率:
Removal Rate=(1-At/A0)×100%,
其中,A0表示初始亚柠檬黄溶液吸光度,At表示间隔时间t时的吸光度。
截留性能测试结果如图1所示,从图中可以看出,与对比例1~3相比,实施例1制备的膜表现出优异的柠檬黄染料截留性能,实施例1达到82%的截留率,相对于对比例1和2,染料截留效率大大提升。相比于对比例3,截留率接近,但是对比例3的截留通量下降明显,而实施例1的截留通量比对比例3高出很多。上述结果表明,光照一定时间,膜表面形成一层交联层,改变了膜表面孔径,截留性能得到大大提升,同时亲水性得到改善。同时由于交联层的存在,膜的抗污性能也得到很大提升。当光照时间变长,交联程度越高,膜表面形成的交联层越致密,水通量下降明显。
抗污性能测试实验:(1)在2bar的压力下对膜预压1小时,预压结束后,在1bar的压力下测量膜的纯水通量30分钟;(2)用1g/L的BSA溶液代替纯水,继续在相同压力下过滤污染物1小时;(3)将被污染的膜在纯水中浸泡30分钟,并反复进行冲洗。清洗干净后,在2bar的压力下再次对膜预压1小时,在1bar的压力下再次测试膜的纯水通量30分钟。
抗污测试结果如图2所示,从图中可以看出,与原始膜相比,在对BSA截留之后,实施例1与对比例1~3展现出较高的通量恢复。原始膜的通量恢复率约为67%,而改性的水处理膜的通量恢复皆可达到约100%。这说明在膜表面形成的交联层可以有效截留污染物,同时亲水性较好,抗污性能提升。
实施例1和对比例1~3制得的水处理膜的水接触角结果如图3所示,从图中可以看出,实施例1制得的膜的接触角相较于对比例1~3出现明显下降。
对比例4
本对比例中,甲基丙烯酸氧杂环丁烷酯、丙烯酸羟乙酯的质量比为1:6,其他步骤同实施例1的步骤(1)。
对比例5
本对比例中,甲基丙烯酸氧杂环丁烷酯、丙烯酸羟乙酯的质量比为1:10,其他步骤同实施例1的步骤(1)。
观察实施例1和对比例4、对比例5制得的梯度聚合物在水中和甲醇中的溶解速率,发现实施例1制得的梯度聚合物溶解速率远大于对比例4和对比例5,这是因为丙烯酸羟乙酯是亲水性化合物,而甲基丙烯酸氧杂环丁烷酯是相对疏水的化合物,这两种物质在聚合物合成过程中的比例对制得的聚合物亲水性有显著影响。当甲基丙烯酸氧杂环丁烷酯、丙烯酸羟乙酯的质量比为1:12时,聚合物的亲水性最强。
对比例6
本对比例,胶束的自组装过程中添加的梯度聚合物质量为0.05g,其他步骤同实施例1。
对比例7
本对比例,胶束的自组装过程中添加的梯度聚合物质量为0.2g,其他步骤同实施例1。
对实施例1和对比例6~7不同浓度胶束下制得的膜的截留性能与抗污性能进行测试,截留结果如图4所示,实施例1制得的膜表现出优异的柠檬黄染料截留性能,实施例1达到82%的截留率,相对于对比例6,染料截留效率提升较大;相比于对比例7,截留率接近,但是对比例1截留通量下降明显,而实施例1截留通量比对比例7高出很多。
实施例1和对比例6~7不同浓度胶束下制得的膜抗污测试结果如图5所示,从图中可以看出,在对BSA截留之后,实施例1与对比例6~7皆展现出来比较高的通量恢复。在膜表面受到紫外光照,亲水化改性之后,膜的通量恢复皆可达到约100%。这说明在膜表面形成的交联层,可以有效截留污染物,同时亲水性较好,抗污性能提升。
Claims (10)
1.改性聚丙烯腈水处理膜的制备方法,其特征在于,包括如下步骤:
步骤1,聚合物的制备:将丙烯酸羟乙酯、甲基丙烯酸氧杂环丁烷酯、偶氮二异丁腈溶于N,N二甲基甲酰胺中,在氮气的氛围中,在80±5℃下聚合反应,反应结束后,透析、冻干得到丙烯酸羟乙酯和甲基丙烯酸氧杂环丁烷酯的梯度聚合物;
步骤2,胶束的自组装:将梯度聚合物溶于甲醇中,超声搅拌,自组装形成浓度为5~20mg/mL的胶束;
步骤3,膜的制备:以疏水聚丙烯腈膜为基膜,将梯度聚合物胶束、促进剂3,4-环氧环己基甲酸-3’,4’-环氧环己基甲酯和光引发剂二苯基-(4-苯基硫)苯基锍六氟锑酸盐混合,超声搅拌,倒入固定好的基膜表面,紫外光照射2~5min,在膜表面发生交联,得到改性聚丙烯腈水处理膜。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,聚合反应时间为18~24h。
3.根据权利要求1所述的制备方法,其特征在于,步骤1中,甲基丙烯酸氧杂环丁烷酯、丙烯酸羟乙酯的质量比为1:6~12。
4.根据权利要求1所述的制备方法,其特征在于,步骤1中,偶氮二异丁腈的投加量为甲基丙烯酸氧杂环丁烷酯和丙烯酸羟乙酯的总质量的2%。
5.根据权利要求1所述的制备方法,其特征在于,步骤2中,超声搅拌时间为5分钟以上。
6.根据权利要求1所述的制备方法,其特征在于,步骤3中,3,4-环氧环己基甲酸-3’,4’-环氧环己基甲酯的投加量为梯度聚合物质量的20%。
7.根据权利要求1所述的制备方法,其特征在于,步骤3中,二苯基-(4-苯基硫)苯基锍六氟锑酸盐的投加量为梯度聚合物质量的5%。
8.根据权利要求1所述的制备方法,其特征在于,步骤3中,紫外光功率为300W,紫外光与膜的间距为50cm。
9.根据权利要求1至8任一所述的制备方法制得的改性聚丙烯腈水处理膜。
10.根据权利要求9所述的改性聚丙烯腈水处理膜在水处理中的应用。
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