CN114369200B - 一种脱水滤膜的改性方法及其应用 - Google Patents
一种脱水滤膜的改性方法及其应用 Download PDFInfo
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- CN114369200B CN114369200B CN202111662152.4A CN202111662152A CN114369200B CN 114369200 B CN114369200 B CN 114369200B CN 202111662152 A CN202111662152 A CN 202111662152A CN 114369200 B CN114369200 B CN 114369200B
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- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims description 5
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- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004432 carbon atom Chemical group C* 0.000 claims 3
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Classifications
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
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Abstract
本发明公开了一种脱水滤膜的改性方法及其应用,将两性离子单体A、烯基聚乙二醇单体B和(甲基)丙烯酰胺,在空气氛围、室温下合成亲水嵌段共聚物,然后通过化学键合方式将其接枝在不同基质的脱水滤膜,既可以提高膜层表面的亲水性,又可弥补膜层易剥落的缺陷,使其具有优异的抗污染和稳定性能。本发明中嵌段共聚物通过化学键合的方式接枝到脱水膜上,涂层在强酸、强碱及复杂的有机环境中表现出优异的稳定性,该方法解决了聚合物长链断裂导致涂层剥离、脱落等问题。使用本发明改性的脱水膜具有优异的油水分离能力,有机物中水的脱除率可达99.9%以上,尤其适用于有机胺的脱水工艺。
Description
技术领域:
本发明属于油水分离膜的改性制备与应用技术领域,具体是涉及一种亲水嵌段共聚物、制作脱水滤膜的方法,及其在有机胺脱水中的应用。
技术背景:
膜分离技术与传统工业中的分离技术相比,具有能耗低、污染少、易于实现连续分离、易于与其它分离过程耦合、使用条件温和、易于放大等优点,在化工、食品、医药、环保、冶金等工业领域得到越来越广泛的应用。迄今为止,有多种类型的膜被应用于油水分离技术中。
由于传统的网膜抗污效果差,分离效率低,尤其在有机胺和水的分离应用上该缺陷表现更为明显,因此对其进行亲水改性。
通用网膜表面改性的方法有物理吸附、多巴胺介导改性等,但是物理吸附的涂层由于没有共价键合的作用,吸引力较差,涂层易整块脱落。多巴胺介导改性涂层虽在酸性、中性条件下稳定存在,但是在碱性条件中,多巴胺介导层和基材表面分离,影响膜的分离效率。
传统ATRP反应操作复杂、需密闭体系,需要惰性气体保护,反应温度需要极低温或极高温,并且催化剂、引发剂用量大,难去除,加速聚合物的老化,影响涂层性能。在对网膜进行亲水改性时,残余催化剂影响亲水涂层的机械性能,影响膜的分离效果。
将两性离子聚合物grft-from方式接枝到基材表面,虽接枝位阻较小,得到的聚合物涂层较致密,但是聚合物链段过长,存在断裂、翻转等问题,导致涂层的剥离、脱落,影响膜的分离能力。
发明内容:
本发明的目的之一是提供一种含两性离子单体的亲水嵌段共聚物,共聚物制备方法工艺简单,各功能基团比例可灵活调控。
本发明的另一目的在于提供一种亲水嵌段共聚物改性常规膜的涂层,以提高膜的亲水性、分离选择性、结构稳定性和耐碱性等,并进行有机胺的脱水应用。
本发明是通过下述技术方案来实现的。
本发明所述的一种亲水嵌段共聚物,结构式如(1)所示:
其中,A为1~10个含碳原子链连接的两性离子单体,包括磷酰胆碱、羧酸甜菜碱或磺酸甜菜碱;
B为1~10个含碳原子链连接的烯基聚乙二醇单体,且单体含有羧基、酯基或酰氯基团。
x,y,z为(甲基)丙烯酰胺单体聚合度,为1~60的整数。
本发明还涉及上述亲水嵌段共聚物的制备方法,包括如下步骤:
步骤a:按照质量比为(1~50):(1~50):(1~50)分别将1~10个含碳原子链连接的两性离子单体A、1~10个含碳原子链连接的烯基聚乙二醇单体B和(甲基)丙烯酰胺类单体溶于溶剂中,得到单体混合液;
其中,(甲基)丙烯酰胺单体与溶剂的质量比优选为1:4~1:20;
步骤b:加入引发剂、催化剂和还原剂,在25~70℃下进行聚合反应3~12h,纯化后,得到亲水嵌段共聚物;
其中,优选地,引发剂是(甲基)丙烯酰胺单体质量的0.1%~1.0%,催化剂是(甲基)丙烯酰胺单体质量的0.01%~0.1%,还原剂是(甲基)丙烯酰胺单体质量的0.05%~1%。
进一步,所述含碳原子链连接的两性离子A为2-甲基丙烯酰氧乙基磷酰胆碱(CAS:67881-98-5)、3-[N,N-二甲基-[2-(2-甲基丙-2-烯酰氧基)乙基]铵]丙烷-1-磺酸内盐(CAS:3637-26-1)或N-(3-磺丙基)-N-甲基丙烯氧乙基-N,N-二甲基铵甜菜碱(默克化工技术有限公司)的至少一种;
所述含碳原子链连接的烯基聚乙二醇单体B为聚乙二醇二甲基丙烯酸酯(CAS:25852-47-5)、聚乙二醇甲基丙烯酸酯(CAS:25736-86-1)、聚乙二醇甲醚甲基丙烯酸酯(CAS:26915-72-0)中的至少一种;
所述(甲基)丙烯酰胺类单体为N-甲基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N-叔丁基丙烯酰胺,或其它烷基(碳原子数0~10)(甲基)丙烯酰胺的至少一种。
进一步,所用的溶剂为水、甲醇、乙醇、丙醇、无机盐水溶液中的至少一种。其中无机盐水溶液可以是氯化钠、氯化钾、硫酸钾、硫酸钠、硝酸钾、硝酸钠以及磷酸盐等的水溶液,盐溶液的质量浓度范围可以是0.5%~5%。
进一步,所述引发剂为2-溴异丁酸乙酯、2-溴异丁酰溴中的至少一种,
催化剂为CuX2/4,4-联吡啶(bpy)或CuL/4,4-联吡啶(bpy),其中X为Cl、Br,L为S、O,
还原剂为L-抗坏血酸。
本发明通过ARGET-ATRP的方法合成嵌段共聚物,该体系中优选使用微量高价铜Cu做催化剂,是为了降低体系对氧的的敏感性。在反应过程中,过量还原剂不仅将高价铜还原成低价,还负责清除氧和自由基抑制剂,从而促进整个反应的正向进行,因此该反应不需要无氧条件,可在敞口下、室温、催化剂用量为传统ATRP的百万甚至千万分之一的水溶液中进行,操作简单,普适性强。
本发明进一步提供一种利用前述方法制备的共聚物改性常规脱水膜涂层的方法,包括以下步骤:
步骤1:膜表面活性处理:将洗干净的网膜浸泡在食人鱼溶液(硫酸:双氧水=7:3)中,温度为45~90℃,反应时间为6~24h。
步骤2:亲水共聚物涂层构建:将活化后的网膜浸泡在含有EDC、NHS的共聚物溶液中,40~70℃反应12~48h,得到改性嵌段共聚物膜。
步骤1中,网膜用甲醇、乙醇、丙酮、洗洁精水的多种溶剂清洗;
网膜可以是不锈钢膜(SS)、聚偏氟乙烯膜(PVDF)、聚乙烯膜(PE)、乙酸纤维素膜(CA)、聚四氟乙烯膜(PTFE);
步骤2中,共聚物在溶液中的浓度为0.5~10mg/mL,溶剂为水、乙醇的一种或两种;
进一步,EDC表示1-乙基-(3-二甲基氨基丙基)碳酰二亚胺(CAS:1892-57-5),NHS表示N-羟基琥珀酰亚胺;
EDC在溶液中的浓度为0.01-0.2mg/mL,
NHS在溶液中的浓度为0.02~0.5mg/mL。
本发明中,网膜活化的方法简单可行,对于常用网膜基本适用,通过化学键合将共聚物固定在材料表面,克服了grft-from接枝方式导致涂层易脱落等问题。
本发明的另一个方面,还提供了上述改性嵌段共聚物膜在有机物脱水中的应用,优选地,所述有机物脱水的体系为有机胺——水混合物;
进一步,有机胺例如三乙胺、三甲胺、等脂肪胺,苯胺、MDA、TDA等芳香胺,以及醇胺类、酰胺类、脂环胺类、萘系胺类等其它有机胺。
本发明的有益效果在于:
所述两性离子具有强亲水性,其表面带有等量的正、负电荷,呈电中性,可以与水分子结合,形成牢固的水合层,避免材料与蛋白质分子及其他生物分子直接接触,从而表现出良好的抗生物污染能力。聚乙二醇是同时具有亲水及亲油性质的两亲性聚合物,且随着聚乙二醇表面密度加大以及链长的增长,其表面吸附的蛋白质会明显减少随着聚乙二醇表面密度加大以及链长的增长,其表面吸附的蛋白质会明显减少,从而赋予材料极强的亲水性能及抗污性能。
烯基-聚乙二醇单体在聚合物中作为固定链段存在,固定链上羧基、酯基、酰氯等与膜表面羟基发生化学反应,从而使共聚物涂层通过化学键合方式稳定存在与膜材料表面。最终制备的膜可以增加膜层亲水性、提高膜的分离选择性,膜的结构稳定性好,耐碱性好。
具体实施方式:
为准确描述该发明的目的、技术方案和优点,以下通过实施例更清楚、完成的表述本发明的技术方案。所描述的实施例仅仅是本发明一部分,而并非全部。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例中部分原料来源:
两性离子单体A:
2-甲基丙烯酰氧乙基磷酰胆碱(CAS:67881-98-5)、
3-[N,N-二甲基-[2-(2-甲基丙-2-烯酰氧基)乙基]铵]丙烷-1-磺酸内盐(CAS:3637-26-1)
N-(3-磺丙基)-N-甲基丙烯氧乙基-N,N-二甲基铵甜菜碱(默克化工技术有限公司)
烯基聚乙二醇单体B:
聚乙二醇二甲基丙烯酸酯(上海吉至生化科技有限公司);
聚乙二醇甲基丙烯酸酯(上海吉至生化科技有限公司);
聚乙二醇甲醚甲基丙烯酸酯(贝斯特试剂);
性能测试方法:
接触角测试:水滴角测量仪测定,测试分析用蒸馏水样品的表面张力值,测试温度条件为25℃,标准值为71.97mN/m,测试结果均值为71.69mN/m;将测试样品剪切长条小块并采用夹具固定;测试每个样品的多点位置接触角值;最后软件进行数据处理。
膜通量:渗透测试:在0.1MPa压力下,温度25℃,使用25cm*25cm的脱水膜,过滤高纯水1h,每间隔10min所得的平均通量。
实施例1:合成嵌段共聚物-SS膜并将其应用于水/二氨基甲苯的分离
1、亲水嵌段共聚物的合成:将10g单体2-甲基丙烯酰氧乙基磷酰胆碱、10g N-甲基甲基丙烯酰胺单体、1g聚乙二醇二甲基丙烯酸酯(上海吉至生化科技有限公司)于锥形瓶中,加入100mL乙醇水溶液(乙醇水混合比为5:95)溶液,加入基于N-甲基甲基丙烯酰胺单体质量0.01%的CuBr2/bpy、0.1%2-溴异丁酰溴、0.5%%抗坏血酸,25℃下搅拌6h。反应完成后,将产物装进截留分子量为3500的透析袋中,先用乙醇透析两次,约3~4h,然后换成蒸馏水透析48h,期间不断更换蒸馏水。最后进行冷冻干燥,得到白色的固体产物。
2、网膜的表面活化过程:将洗干净的10cm×10cm SS膜浸泡在食人鱼溶液(硫酸:双氧水=7:3)中70℃反应12h,取出,用大量蒸馏水冲洗片基表面后真空干燥。
3、亲水涂层的制备:将活化后的网膜浸泡在共聚物浓度为2mg/mL、EDC浓度为0.1mg/mL、NHS浓度为0.3mg/mL的水溶液中,在60℃反应48h,取出,用大量水冲洗干净后真空干燥。改性后膜表面静态接触角约在100ms可到达0°。
4、测试改性脱水膜的分离性能:操作温度为120℃,60wt%TDA/水进行渗透蒸发分离,连续分离24h后,改性膜的通量由实验前的3.66kg/m2*h降低到实验后的2.95kg/m2*h,水含量可由40%脱除至2.0%。
实施例2:合成嵌段共聚物-PVDF膜并将其应用于水/二氨基甲苯的分离
1、亲水嵌段共聚物的合成:将20gN-(3-磺丙基)-N-甲基丙烯氧乙基-N,N-二甲基铵甜菜碱,5g N-甲基甲基丙烯酰胺,1g聚乙二醇甲基丙烯酸酯(上海吉至生化科技有限公司)于锥形瓶中,加入100mL乙醇水溶液(乙醇水混合比为10:90)溶液,加入基于N-甲基甲基丙烯酰胺单体质量0.05%CuCl2/bpy、0.5%2-溴异丁酰溴、0.06%抗坏血酸,25℃下搅拌6h。反应完成后,将产物装进截留分子量为3500的透析袋中,以便除去未反应的单体,先用乙醇透析两次,约3~4h,然后换成蒸馏水透析48h,期间不断更换蒸馏水。最后进行冷冻干燥,得到白色的固体产物。
2、网膜的表面活化过程:将洗干净的10cm×10cm PVDF膜浸泡在食人鱼溶液(硫酸:双氧水=7:3)中70℃反应24h,取出,用大量蒸馏水冲洗片基表面后真空干燥。活化后网膜静态接触角为50±4.7°。
3、亲水涂层的制备:将活化后的网膜浸泡在共聚物浓度为0.5mg/mL、EDC浓度为0.1mg/mL、NHS浓度为0.5mg/mL的水溶液中,在70℃反应24h,取出,用大量水冲洗干净后真空干燥。改性后膜表面静态接触角约在80ms可到达0°。
4、测试改性脱水膜的分离性能:操作温度为120℃,99.8wt%TDA/水进行渗透蒸发分离。连续分离24h后,改性膜的通量由实验前的3.45kg/m2*h降低到实验后的3.06kg/m2*h,,水分可由0.2%脱除至0.05%。
实施例3:合成嵌段共聚物-PTFE膜并将其应用于水/苯胺的分离
1、亲水嵌段共聚物的合成:将20g3-[N,N-二甲基-[2-(2-甲基丙-2-烯酰氧基)乙基]铵]丙烷-1-磺酸内盐,2g N-异丙基甲基丙烯酰胺、2g聚乙二醇甲醚甲基丙烯酸酯(贝斯特试剂)于锥形瓶中,加入100mL乙醇、0.5%的NaCl水溶液混合溶剂(乙醇、NaCl溶液混合比为50:50),加入基于N-异丙基甲基丙烯酰胺单体质量0.01%CuS/bpy、0.3%-溴异丁酰溴、0.1%抗坏血酸,25℃下搅拌6h。反应完成后,将产物装进截留分子量为3500的透析袋中,先用乙醇透析两次,约3~4h,然后换成蒸馏水透析48h,期间不断更换蒸馏水。最后进行冷冻干燥,得到白色的固体产物。产物分子量约为10000,分子量分布为1.36。
2、网膜的表面活化过程:将洗干净的10cm×10cm PTFE膜浸泡在食人鱼溶液(硫酸:双氧水=7:3)中70℃反应12h后,取出,用大量蒸馏水冲洗片基表面后真空干燥。活化后网膜静态接触角为58±3.7°。
3、亲水涂层的制备:将活化后的网膜浸泡在共聚物浓度为5mg/mL、EDC浓度为0.05mg/mL、NHS浓度为0.2mg/mL的水溶液中,在50℃反应36h,取出,用大量水冲洗干净后真空干燥。改性后膜表面静态接触角约在70ms可到达0°。
4、测试改性脱水膜的分离性能:操作温度为50℃,70wt%苯胺/水进行渗透蒸发分离。连续分离24h后,改性膜的通量由实验前的3.33kg/m2*h降低到实验后的3.06kg/m2*h水含量可由30%脱除至2.0%。
实施例4:合成嵌段共聚物-PE膜并将其应用于水/苯胺的分离
1、亲水嵌段共聚物的合成:将20g2-甲基丙烯酰氧乙基磷酰胆碱、2g N-叔丁基丙烯酰胺、1g聚乙二醇甲基丙烯酸酯(上海吉至生化科技有限公司)于锥形瓶中,加入100mL乙醇/1%的KNO3水溶液(混合比为10:90),加入基于N-叔丁基丙烯酰胺单体质量0.06%CuBr2/bpy、0.4%2-溴异丁酸乙酯,0.2%抗坏血酸,50℃下搅拌6h。反应完成后,将产物装进截留分子量为3500的透析袋中,以便除去未反应的单体,先用乙醇透析两次,约3~4h,然后换成蒸馏水透析48h,期间不断更换蒸馏水。最后进行冷冻干燥,得到白色的固体产物。产物分子量约为18000,分子量分布为1.43。
2、网膜的表面活化过程:将洗干净的10cm×10cm PE膜浸泡在食人鱼溶液(硫酸:双氧水=7:3)中90℃反应24h,取出,用大量蒸馏水冲洗片基表面后真空干燥。活化后网膜静态接触角为38±2.9°。
3、亲水涂层的制备:将活化后的网膜浸泡在共聚物浓度为10mg/mL、EDC浓度为0.2mg/mL、NHS浓度为0.3mg/mL的水溶液中,在70℃反应18h,取出,用大量水冲洗干净后真空干燥。改性后膜表面静态接触角约在60ms可到达0°。
4.测试改性脱水膜的分离性能:操作温度为120℃,99wt%苯胺/水进行渗透蒸发分离。连续分离24h后,改性膜的通量由实验前的3.73kg/m2*h降低到实验后的3.10kg/m2*h,水分可由1.0%脱除至0.16%。
对比例1未进行改性的PVDF膜应用于水/苯胺的分离
测试改性脱水膜的分离性能:操作温度为120℃,99wt%苯胺/水进行渗透蒸发分离。与实施例相同的渗透蒸发分离方式,连续分离24h后,改性膜的通量由实验前的3.73kg/m2*h降低到实验后的1.32kg/m2*h,膜表面出现严重污染,并且无法实现对1%的水进行深度分离(水分维持0.9%~1%)。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (12)
1.一种亲水嵌段共聚物的制备方法,其特征在于,包括如下步骤:
步骤a:分别将1~10个含碳原子链连接的两性离子单体A、1~10个含碳原子链连接的烯基聚乙二醇单体B和(甲基)丙烯酰胺类单体溶于溶剂中,得到单体混合液;
单体A为2-甲基丙烯酰氧乙基磷酰胆碱、3-[N,N-二甲基-[2-(2-甲基丙-2-烯酰氧基)乙基]铵]丙烷-1-磺酸内盐或N-(3-磺丙基)-N-甲基丙烯氧乙基-N,N-二甲基铵甜菜碱的至少一种;
单体B为聚乙二醇二甲基丙烯酸酯、聚乙二醇甲基丙烯酸酯、聚乙二醇甲醚甲基丙烯酸酯中的至少一种;
单体A、单体B、(甲基)丙烯酰胺类单体的质量比为1~50:1~50:1~50;
步骤b:加入引发剂、催化剂和还原剂,进行聚合反应,纯化后得到亲水嵌段共聚物;所述引发剂为2-溴异丁酸乙酯、2-溴异丁酰溴中的至少一种,催化剂选自CuX2/4,4-联吡啶或CuL/4,4-联吡啶,其中X为Cl、Br,L为S、O,还原剂为L-抗坏血酸。
2.根据权利要求1所述的方法,其中,步骤a中,所述(甲基)丙烯酰胺类单体为N-甲基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N-叔丁基丙烯酰胺,或其它碳原子数0~10的烷基的(甲基)丙烯酰胺的至少一种。
3.根据权利要求1所述的方法,其中,引发剂用量是(甲基)丙烯酰胺类单体质量的0.1%~1.0%,催化剂用量是(甲基)丙烯酰胺类单体质量的0.01%~0.1%,还原剂用量是(甲基)丙烯酰胺类单体质量的0.05%~1%。
4.根据权利要求1-3任一项所述的方法,其中,步骤b中,在25~70℃下进行聚合反应3~12h。
5.一种利用权利要求1-4任一项所述方法制备的共聚物制备改性嵌段共聚物膜的方法,包括以下步骤:
步骤1:膜表面活性处理:将洗干净的网膜浸泡在食人鱼溶液中;
步骤2:亲水共聚物涂层构建:将活化后的网膜浸泡在含有EDC、NHS的共聚物溶液中,反应,得到改性嵌段共聚物膜。
6.根据权利要求5所述的方法,其中,步骤1中,网膜选自不锈钢膜、聚偏氟乙烯膜、聚乙烯膜、乙酸纤维素膜、聚四氟乙烯膜。
7.根据权利要求6所述的方法,其中,步骤1中,网膜在食人鱼溶液中的浸泡温度为45~90℃,时间为6~24h。
8.根据权利要求5所述的方法,其中,步骤2中,溶液中,共聚物的浓度为0.5~10mg/mL,EDC的浓度为0.01-0.2mg/mL,NHS的浓度为0.02~0.5mg/mL。
9.根据权利要求5或8所述的方法,其中,步骤2中,反应条件为40~70℃反应12~48h。
10.根据权利要求5-9任一项所述的方法制备的改性嵌段共聚物膜在有机物脱水中的应用。
11.根据权利要求10所述的应用,所述有机物脱水的体系为有机胺-水混合物。
12.根据权利要求11所述的应用,所述有机胺选自三乙胺、三甲胺、苯胺、MDA、TDA、醇胺类、酰胺类、脂环胺类、萘系胺类。
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