CN110898680B - 一种聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法 - Google Patents
一种聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种可实现对复杂成分截留和降解的、大大提高水处理深度和效率的聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法,包含如下步骤:1)、聚多巴胺改性膜的制备,2)、聚噻吩衍生物单体的制备,3)、聚噻吩敏化TiO2复合催化剂的制备,4)、酰胺功能纳滤膜的制备。其通过多巴胺自聚改性基膜,特别是疏水性基膜的亲水性和二次反应能力;通过共轭聚噻吩衍生物敏化TiO2,利用聚噻吩的共轭大π键提高TiO2的光利用率和催化活性;通过聚噻吩衍生物的水溶性设计实现与均苯三甲酰氯在改性基膜上界面共聚纳滤层。
Description
技术领域
本发明属于膜材料改性技术领域。涉及到利用多巴胺对膜表面改性以提高材料的亲水性和二次反应能力,利用导电聚合物敏化TiO2制备高活性光催化剂,利用聚噻吩衍生物的水溶性设计界面共聚纳滤层,以实现光催降解、分离多功能膜的一体化构建。该方法制得的分离膜可用于复杂成分印染废水的高效深度处理。
背景技术
工业染料废水的主要来源于纺织、印染和染料生产过程中的硝化、还原、氧化、氯化、缩合、偶合等反应产生的大量含染料废水的母液。染料废水中含有酚类、芳香族硝基化合物、芳香族胺基化合物、苯、萘、蒽、醌类化合物、有机联苯等多苯环取代化合物等,同时还含有NaCl、Na2SO4、Na2S等无机盐类化合物及铬、锰、铜等重金属离子。染料废水组分复杂、水质变化范围大、有机污染物浓度高、可生化性差,很难用常规的水处理技术和方法进行有效处理。高效处理染料废水成为目前环境科学领域研究的重点之一。
TiO2多相光催化技术,是目前降解有机污染物最有发展前景的环境污染治理手段之一。在波长小于387 nm的紫外光照射下,TiO2中的电子受激发发生跃迁,形成带负电的光生电子(e-)和带正点的光生空穴(h+)。e-和 h+分别就具有强还原性和强氧化性,通过与水中或溶解氧发生作用生成具有强氧化性的.OH自由基。.OH自由基是目前已知的氧化能力最强的物种之一,能氧化分解大多数的有机污染物,甚至部分无机污染物,并将其最终降解为二氧化碳和水等物质。研究表明,TiO2可以无选择性地氧化分解数百种有机污染物,甚至包括多种无机污染物。但其应用前景受到光吸收范围窄和光生电子-空穴易再复合导致光催效率低两个缺陷的制约。克服这两大缺陷,提高光催活性,是TiO2催化研究的一个热点。
膜分离是新兴的高效分离技术,其中纳滤膜是一种介于超滤和反渗透之间的以压差为驱动力的膜技术,其分离特征除了因具有纳米级微孔而具备的筛分效应外,还因为纳滤膜上存在带电基团而引起的电荷效应,通过静电作用实现不同价态无机盐离子的分离。纳滤膜材料的化学性质直接决定了膜的分离性能,需具备良好的成膜性、稳定性和抗污染等特点,因此需要对膜表面进行分子设计和构建,实现膜的高效分离。
为实现对染料废水中有机污染物和无机盐离子的高效深度处理,本项目基于分子结构设计,构筑了一种以带有可提高TiO2光催活性的共轭聚噻吩基酰胺复合纳滤层、通过仿生粘附材料聚多巴胺提高基膜和纳滤层的界面粘结力的多功能复合纳滤膜,实现高效光催和分离的联用,同时处理印染废水中的有机污染物和无机盐离子,具有重要意义。
发明内容
本发明公开了一种可实现对复杂成分截留和降解的、大大提高水处理深度和效率的聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法。其通过多巴胺自聚改性基膜,特别是疏水性基膜的亲水性和二次反应能力;通过共轭聚噻吩衍生物敏化TiO2,利用聚噻吩的共轭大π键提高TiO2的光利用率和催化活性;通过聚噻吩的水溶性衍生物设计实现与均苯三甲酰氯在改性基膜上界面共聚纳滤层。
为实现上述目的,本发明采用以下技术方案:一种聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法,包含如下步骤:
1)、聚多巴胺改性膜的制备:
a)、基膜预处理:取基膜浸于无水乙醇中超声清洗1-5h除去表面油剂及杂质,取出后用蒸馏水清洗,晾干备用;
b)、利用多巴胺对预处理的基膜进行改性:改性取100mL质量浓度为0.5-5g/L的多巴胺溶液,加入Tris-HCl缓冲液并调节至pH为8-9,将预处理后的改性膜浸泡于多巴胺溶液中于15-40℃恒温振荡12-30h取出,冲洗晾干得聚多巴胺改性膜;
2)、聚噻吩衍生物单体的制备:
a)、3-溴甲基噻吩(a)的制备方法为,在氮气保护下,将3-噻吩甲醇与PBr3按1:1比例分别加入到氯仿中搅拌均匀中,室温下反应,结束后加入冰水结束反应;
b)、噻吩-3-亚甲基-亚磷酸二乙酯(b)的制备方法为,将3-溴甲基噻吩与亚磷酸三乙酯按1:1~1:1.5的摩尔比混合,在140~180℃温度下回流反应,经4~6h后反应完毕;
c)、3-(N-Boc-4-哌啶亚甲基)-噻吩(c)的制备方法:在氮气保护下,将氢化钠/四氢呋喃悬浮液滴加在噻吩-3-亚甲基-亚磷酸二乙酯(b)中,氢化钠与噻吩-3-亚甲基-亚磷酸二乙酯(b)的摩尔比为1:1~3:1,在冰水浴中滴加与噻吩-3-亚甲基-亚磷酸二乙酯(b)等摩尔比的N-Boc-4-哌啶酮,冰水反应12~24h;
d)、3-(4-哌啶亚甲基)-噻吩(d)的制备方法:将3-(N-Boc-4-哌啶亚甲基)-噻吩(c)与无水甲酸按体积比1:10~1:20混合,在40~80℃下反应12~24h;
其共轭聚噻吩衍生物单体3-(4-哌啶亚甲基)-噻吩的合成路线为:
3)、聚噻吩敏化TiO2复合催化剂的制备:将单体3-(4-哌啶亚甲基)-噻吩与TiO2氯仿悬浮液按质量比为2:1~1:1慢慢滴加与单体等质量的无水三氯化铁氯仿溶液中,氮气保护下搅拌12~24h,反应结束后加入等体积甲醇淬灭反应,过滤并用加有1:20~1:100体积比的水合肼/甲醇溶液洗涤;
4)、酰胺功能纳滤膜的制备:以均苯三甲酰氯的正己烷溶液作为有机相,聚噻吩敏化TiO2复合催化剂的水分散液配成水相,将聚多巴胺改性基膜先后浸泡于水相和有机相,反应结束后形成在基膜表面形成聚酰胺功能纳滤皮层,从而制得聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜。
进一步改进的是:所述TiO2负载聚噻吩衍生物与均苯三甲酰氯制备酰胺功能纳滤层的反应历程如下:
进一步改进的是:所述TiO2负载聚噻吩衍生物与均苯三甲酰氯制备酰胺功能纳滤层的具体制作方法包括:
1)、配制2~5w/v% TiO2负载聚噻吩衍生物/水分散液和浓度为3~8w/v%的三乙胺缚酸剂,以及0.1~0.2w/v%的均苯三甲酰氯正己烷有机相;
2)、将多巴胺改性聚丙烯腈基膜平整的固定在制备好的模具之间,将表面多余的水分轻轻吹干,用固定夹夹住,在基膜表面加入适量TiO2负载聚噻吩衍生物/水分散液和三乙胺中,浸泡3~6min后将基膜表面多余的水分倒出去,表面残余的水分放在通风橱中自然晾干;
3)、在晾干的基膜上表面加入适量的0.15w/v%的均苯三甲酰氯/正己烷有机溶液,浸泡1min后将基膜表面的有机溶液倒出去,然后立即将基膜放入40~60℃的烘箱中继续进行聚合5~20min,制得聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜。
进一步改进的是:所述的基膜按材料包括有机膜、无机膜、有机无机杂化膜以及膜组合。
有益效果:
本发明的效果和益处是基于多巴胺分子对材料表面的超强黏附行为,并引入活性基团提高二次反应活性。在纳滤膜的制备过程中,由于复合基膜和复合皮层选用不同材料,二者表面张力的差异会影响复合膜的结构稳定性,通过使用特殊功能的粘合剂能增加界面相互作用。聚多巴胺仿生粘附的自聚-复合技术能与基膜材料表面建立相互作用,与基膜连接紧密。聚合后的聚多巴胺仍具有邻苯二酚等活性官能团,可以进行二次反应,实现膜表面的进一步功能化。通过界面聚合在改性膜表面形成纳滤层,从而制备具有一体结构的高强度复合纳滤膜。
本发明对聚噻吩和TiO2进行复合,TiO2表现出电子授体性质,在可见光下电子由聚噻吩转移到TiO2的导带,而TiO2价带上的电子转移到聚噻吩上,减少电子、空穴的复合几率,同时聚噻吩的存在,拓宽了复合体系的光谱响应范围,大大提升了光催化剂的催化性能。以均苯三甲酰氯(TMC)作为油相单体,设计能与TMC进行界面聚合的带胺基氢的水性单体侧链带胺基氢的水溶性聚噻吩衍生物(PT),采用界面聚合法制备以水溶性PT和均苯三甲酰氯(TMC)为单体的聚酰胺类功能阻隔层,从而实现纳滤膜的构建。
本发明将带有光催功能的纳滤膜作为印染废水的深度处理,既可以浓缩染料进行光催降解,又可以达到脱盐的目的,在高效深度处理印染废水领域有良好的应用前景。
附图说明
图1为复合膜材料模拟太阳光降解罗丹明B染料的实施效果图。
具体实施方式
实施例1
一种聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法,包含如下步骤:
(1)聚多巴胺改性聚丙烯腈膜的制备:
取聚丙烯腈膜浸于无水乙醇中超声清洗1h除去表面油剂及杂质,取出后用蒸馏水清洗,晾干备用,取100mL质量浓度为0.5g/L的多巴胺溶液,加入Tris-HCl缓冲液并调节至pH为8,取预处理后的改性膜浸泡于多巴胺溶液中于15℃恒温振荡12-30h取出,冲洗晾干得PDA改性膜;
(2)聚噻吩衍生物单体的制备
3-溴甲基噻吩(a)的合成:在氮气保护下,将3-噻吩甲醇(22.8g,0.20mol)和PBr3(54.0g,0.20mol)分别加入到50mL氯仿中搅拌均匀中,室温下反应12h后用冰水淬灭反应,分液得无色液体28.3g。
噻吩-3-亚甲基-亚磷酸二乙酯(b)的合成:将a(8.85g,50mmol)与亚磷酸三乙酯(10.00g,60mmol),在160℃回流反应,6h后反应完毕。得无色液体10.33g。
3-(N-Boc-4-哌啶亚甲基)-噻吩(c)的合成:在氮气保护下,将10mL氢化钠(0.60g,25.00mmol)/四氢呋喃悬浮液中滴加(b)(2.34g,10.00mmol),冰水冷却,然后滴加N-Boc-4-哌啶酮(1.97g,10.00mmol),冰水浴中下反应过夜,经萃取提纯得1.97g淡黄色的产品。
3-(4-哌啶亚甲基)-噻吩(d)的合成:将(c)(1.50g,6.00mmol)和15mL无水甲酸混合,在50℃下反应24h。反应完毕后,蒸出溶剂,得到0.8g淡黄色产品。其共轭聚噻吩衍生物单体3-(4-哌啶亚甲基)-噻吩的合成路线为:
(3)、聚噻吩敏化TiO2复合催化剂的制备:称取无水三氯化铁(0.45g,2.8mmol)和20mL无水氯仿,氮气保护下搅拌30min,将聚噻吩衍生物单体与0.4gTiO2氯仿悬浮液慢慢滴加到上述反应液中,搅拌反应24h。反应结束后加入25mL甲醇淬灭其反应,过滤得到滤饼,再用加有1mL水合肼的甲醇(50mL)溶液来洗涤滤饼,洗涤12h后过滤并旋蒸掉溶剂。用加有四丁基氯化铵的THF和甲醇(THF:甲醇=5:1)重复洗涤6次,再用索氏提取器去除其中的杂质和低聚物,最后得到产品0.22g。
(4)、酰胺功能纳滤膜的制备:以均苯三甲酰氯的正己烷溶液作为有机相,聚噻吩敏化TiO2复合催化剂的水分散液配成水相,将聚多巴胺改性基膜先后浸泡于水相和有机相,反应结束后形成在基膜表面形成聚酰胺功能纳滤皮层,从而制得聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜。
所述TiO2负载聚噻吩衍生物与均苯三甲酰氯制备酰胺功能纳滤层的反应历程如下:
所述TiO2负载聚噻吩衍生物与均苯三甲酰氯制备酰胺功能纳滤层的具体制作方法包括:
取第一步完成的多巴胺改性聚丙烯腈膜作为基膜,用超纯水浸泡过夜,配制2w/v%TiO2负载水溶性聚噻吩衍生物水溶液和浓度为3w/v%的缚酸剂(三乙胺),和0.15w/v%的均苯三甲酰氯正己烷有机相反应。
将多巴胺改性聚丙烯腈基膜平整的固定在制备好的模具之间,将表面多余的水分轻轻吹干,用固定夹夹住,在基膜表面加入适量TiO2负载水溶性聚噻吩衍生物的水溶液和3w/v%的三乙胺中,浸泡5min后将基膜表面多余的水分倒出去,表面残余的水分放在通风橱中自然晾干。
在晾干的基膜上表面加入适量的0.15w/v%的均苯三甲酰氯正己烷有机溶液,浸泡1min后将基膜表面的有机溶液倒出去,然后立即将基膜放入60℃的烘箱中继续进行聚合10min,制得聚丙烯腈基聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜。
具体实施结果测试方法如下:
①纯水通量测试:采用自制膜通量评价系统进行测定,在0.5MPa压力下,料液经膜过滤后返回进水槽,其水通量J(L·m-2·h-1)按下式计算
式中,V为透过液体积,L;A为膜的有效面积,m2;t为过滤时间,h。
②实验过程中在复合膜上使用盐溶液进行通量截留性能测试,将每次实验通过电导率仪测试出的原液以及在不同时间段中所取的滤出液的电导率,根据变化趋势,计算出截留率,按照公式计算复合膜对盐的截留率。
式中,R为截留率,C p 为滤出液的浓度,C f 是原液浓度。
③光催化性能测试:以阳离子染料罗丹明B(RhB)为目标物,以疝气灯模拟太阳光光源,测试膜的光催化性能。将待测膜置于装有相同体积(50mL)和相同浓度(10mg·L-1)罗丹明B溶液的表面皿中进行光照降解实验。每隔1h取出一定量的溶液进行吸光度测试,由标准曲线确定罗丹明B溶液。
实例1实施结果
表1 不同盐类型测定复合膜水通量和盐截留
盐类型 | Na<sub>2</sub>SO<sub>4</sub> | Mg<sub>2</sub>SO<sub>4</sub> | MgCl<sub>2</sub> | CaCl<sub>2</sub> | NaCl |
通量(L/m<sup>2</sup>h) | 52 | 40 | 50 | 51 | 78 |
截流率(%) | 95 | 78 | 58 | 68 | 28 |
如说明书附图1所示,其为复合膜材料模拟太阳光降解罗丹明B染料的实施效果图,图中的Na2SO4截留率非常高,NaCl保留率小于30%,硫酸钠的截留率大于硫酸镁,在该操作压力下,水通量较好,属于低能耗纳滤膜,可望具有较好的应用价值。在模拟太阳光照射的条件下,光照4 h之后,TiO2能够降解42%左右的罗丹明B分子,而聚噻吩衍生物改性TiO2复合膜的降解率为57%。
Claims (3)
1.一种聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法,包含如下步骤:
1)、聚多巴胺改性膜的制备:
a)、基膜预处理:取基膜浸于无水乙醇中超声清洗1-5h除去表面油剂及杂质,取出后用蒸馏水清洗,晾干备用;
b)、利用多巴胺对预处理的基膜进行改性:改性取100mL质量浓度为0.5-5g/L的多巴胺溶液,加入Tris-HCl缓冲液并调节至pH为8-9,将预处理后的改性膜浸泡于多巴胺溶液中于15-40℃恒温振荡12-30h取出,冲洗晾干得聚多巴胺改性膜;
2)、聚噻吩衍生物单体的制备:
a)、3-溴甲基噻吩(a)的制备方法:在氮气保护下,将3-噻吩甲醇与PBr3 按1:1比例分别加入到氯仿中搅拌均匀,室温下反应,结束后加入冰水结束反应;
b)、噻吩-3-亚甲基-亚磷酸二乙酯(b)的制备方法:将3-溴甲基噻吩与亚磷酸三乙酯按1:1~1:1.5的摩尔比混合,在140~180℃温度下回流反应,经4~6h后反应完毕;
c)、3-(N-Boc-4-哌啶亚甲基)-噻吩(c)的制备方法:在氮气保护下,将氢化钠/四氢呋喃悬浮液滴加在噻吩-3-亚甲基-亚磷酸二乙酯(b)中,氢化钠与噻吩-3-亚甲基-亚磷酸二乙酯(b)的摩尔比为1:1~3:1,在冰水浴中滴加与噻吩-3-亚甲基-亚磷酸二乙酯(b)等摩尔比的N-Boc-4-哌啶酮,冰水反应12~24h;
d)、3-(4-哌啶亚甲基)-噻吩(d)的制备方法:将3-(N-Boc-4-哌啶亚甲基)-噻吩(c)与无水甲酸按体积比1:10~1:20混合,在40~80℃下反应12~24h;
3)、聚噻吩敏化TiO2复合催化剂的制备:将单体3-(4-哌啶亚甲基)-噻吩与TiO2氯仿悬浮液按质量比为2:1~1:1慢慢滴加与单体等质量的无水三氯化铁氯仿溶液中,氮气保护下搅拌12~24h,反应结束后加入等体积甲醇淬灭反应,过滤并用加有1:20~1:100体积比的水合肼/甲醇溶液洗涤;
4)、酰胺功能纳滤膜的制备:以均苯三甲酰氯的正己烷溶液作为有机相,聚噻吩敏化TiO2复合催化剂的水分散液配成水相,将聚多巴胺改性基膜先后浸泡于水相和有机相,反应结束后在基膜表面形成聚酰胺功能纳滤皮层,从而制得聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜。
2.根据权利要求1所述的聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法,其特征在于: TiO2负载聚噻吩衍生物与均苯三甲酰氯制备酰胺功能纳滤层的具体制作方法具体包括:
1)、配制2~5w/v% TiO2负载聚噻吩衍生物/水分散液和浓度为3~8w/v%的三乙胺缚酸剂,以及0.1~0.2w/v%的均苯三甲酰氯正己烷有机相;
2)、将多巴胺改性基膜平整的固定在制备好的模具之间,将表面多余的水分轻轻吹干,用固定夹夹住,在基膜表面加入适量TiO2负载聚噻吩衍生物/水分散液和三乙胺中,浸泡3~6min后将基膜表面多余的水分倒出去,表面残余的水分放在通风橱中自然晾干;
3)、在晾干的基膜上表面加入适量的0.15w/v%的均苯三甲酰氯/正己烷有机溶液,浸泡1min后将基膜表面的有机溶液倒出去,然后立即将基膜放入40~60℃的烘箱中继续进行聚合5~20min,制得聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜。
3.根据权利要求1或2所述的聚噻吩敏化TiO2/聚多巴胺改性复合纳滤膜的制备方法,其特征在于:所述的基膜按材料包括有机膜或无机膜或有机无机杂化膜。
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