CN111389381A - 一种近红外低温脱附型智能吸附材料及其制备方法和应用 - Google Patents
一种近红外低温脱附型智能吸附材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种近红外低温脱附型智能吸附材料及其制备方法和应用。所述材料是通过在羧基化纤维素纳米纤维基体上化学接枝阶梯式双温度刺激响应的聚乙烯亚胺,制备阶梯式双温度刺激响应性智能纳米纤维,再与具有近红外刺激响应性的光敏剂复合,制备阶梯式双温度/近红外刺激响应性智能纳米纤维,采用交联剂直接将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺一步交联复合得到。该材料具有阶梯式双温度/近红外刺激响应性、高氨基密度(大于14mmol/g)和纳米空腔。
Description
技术领域
本发明属于生物质纤维改性技术领域,具体涉及一种近红外低温脱附型智能吸附材料及其制备方法和应用。
背景技术
目前,酸性气体的捕集方法主要包括吸收法、膜分离法、吸附法和深度冷凝法。其中,吸收法可以实现大量酸性气体的高效分离,且净化度和回收率高,但其再生能耗大、对设备腐蚀严重;膜分离是利用高分子聚合物对不同气体的相对渗透率不同而分离,其设备简单、操作方便、能耗低,但难以得到高纯度的酸性气体且膜材料再生能力差,限制了其大规模工业化应用;深度冷凝法是对原料气体进行多次压缩和冷却使其液化,但仅适用于高浓度的酸性气体;吸附法是基于多孔材料表面活性点选择性地捕集分离酸性气体,具有操作灵活性且操作成本较低的优点,但传统酸性气体吸附材料面临难以兼具高吸附容量和低再生温度的问题。
发明内容
本发明的目的在于提供一种近红外低温脱附型智能吸附材料及其制备方法,该材料具有阶梯式双温度/近红外刺激响应性、高氨基密度和纳米空腔,使得材料兼具高酸性气体吸附容量和低再生温度性能,在近红外作用下实现低温脱附再生。
本发明的上述目的通过以下技术方案予以实现:
一种近红外低温脱附型智能吸附材料,是通过在羧基化纤维素纳米纤维基体上化学接枝阶梯式双温度刺激响应的聚乙烯亚胺,制备阶梯式双温度刺激响应性智能纳米纤维,再与具有近红外刺激响应性的光敏剂复合,制备阶梯式双温度/近红外刺激响应性智能纳米纤维,采用交联剂直接将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺一步交联复合得到;所述近红外低温脱附型智能吸附材料的阶梯式双温度响应是具有两个温度阶段的刺激响应性,其低临界溶解温度分别在30-37℃和40-50℃范围;
所述阶梯式双温度刺激响应的聚乙烯亚胺是由N-异丙基丙烯酰胺和甲基丙烯酸二甲氨基乙酯分别修饰聚乙烯亚胺后,按比例混合均匀得到;所述羧基化纤维素纳米纤维是由纸浆纤维经过高碘酸钠氧化和TEMPO氧化制备得到,羧基化纤维素纳米纤维上具有大量的羧基基团;所述具有近红外刺激响应性的光敏剂为聚多巴胺,是在超声作用下,多巴胺聚合成聚多巴胺的同时与阶梯式双温度刺激响应性智能纳米纤维复合成阶梯式双温度/近红外刺激响应性智能纳米纤维,形成互穿网络结构的复合结构;所述超支化聚胺由胺化试剂与丙烯酸甲酯发生迈克尔加成反应和自缩聚反应得到;所述交联剂为环氧氯丙烷。
优选地,所述纸浆纤维为漂白纸浆纤维,纸浆纤维为蔗渣浆纤维、桉木浆纤维、竹浆纤维、马尾松浆纤维、麦草浆纤维中的一种或多种混合。
所述近红外低温脱附型智能吸附材料的制备方法,包括以下制备步骤:
S1.羧基化纤维素纳米纤维的制备:采用高碘酸钠将纸浆纤维的纤维素结构单元的C2和C3上的羟基选择性氧化为醛基,制备双醛纤维;然后采用TEMPO试剂将双醛纤维的纤维素结构单元的C2、C3上的醛基和C6上的羟基氧化为羧基,通过控制反应条件来调控氧化程度,制备羧基化纤维素纳米纤维;
S2.阶梯式双温度刺激响应的聚乙烯亚胺的制备:采用N-异丙基丙烯酰胺、甲基丙烯酸二甲氨基乙酯分别与聚乙烯亚胺发生迈克尔加成反应后,按比例混合均匀,使改性后的聚乙烯亚胺具有阶梯式双温度刺激响应性;
S3.阶梯式双温度刺激响应性智能纳米纤维的制备:羧基化纤维素纳米纤维与阶梯式双温度刺激响应的聚乙烯亚胺在高温下发生酰胺化反应;
S4.阶梯式双温度/近红外刺激响应性智能纳米纤维的制备:阶梯式双温度刺激响应性智能纳米纤维与多巴胺混合分散均匀后,在超声作用下,多巴胺聚合成聚多巴胺的同时与阶梯式双温度刺激响应性智能纳米纤维复合,形成互穿网络结构的复合结构,通过离心、冷冻干燥得到阶梯式双温度/近红外刺激响应性智能纳米纤维;
S5.超支化聚胺的制备:采用胺化试剂与丙烯酸甲酯发生迈克尔加成反应生成超支化聚胺前驱体,超支化聚胺前驱体发生自缩聚反应制得超支化聚胺;
S6.采用交联剂一步交联:将步骤S4制得的阶梯式双温度/近红外刺激响应性智能纳米纤维与步骤S5制得的超支化聚胺在碱性溶液中混合均匀,在搅拌条件下加入环氧氯丙烷交联剂,混合液直接被交联成固体颗粒,制得所述的近红外低温脱附型智能吸附材料。
进一步地,所述步骤S1的具体操作为:向纸浆纤维中加入邻苯二甲酸氢钾缓冲液,然后加入高碘酸钠,在30~40℃条件下,搅拌反应3.5~4.5h,最后加入乙二醇终止反应,洗涤,干燥,得到双醛纤维;所述纸浆纤维与高碘酸钠的质量比为4:2~3;向双醛纤维中加入磷酸钠缓冲溶液,在55~65℃条件下搅拌均匀,然后加入TEMPO,再加入次氯酸钠溶液,然后加入亚氯酸钠,氧化15~17h,加入乙醇来淬灭,洗涤、干燥,得到羧基化纤维素纳米纤维;所述双醛纤维与TEMPO的质量比为400:6~7。
进一步地,所述步骤S2的具体操作为:在55~65℃、磁力搅拌条件下,将浓度为0.15~0.25g/mL的聚乙烯亚胺水溶液按体积比为1:3滴加到浓度为0.03~0.09g/mL的N-异丙基丙烯酰胺水溶液中,反应22~26小时后,用液氮淬灭,得到的溶液用MWCO500D透析袋在水中透析22~26h,然后冷冻干燥得到N-异丙基丙烯酰胺修饰的聚乙烯亚胺,通过调控N-异丙基丙烯酰胺的加入量来调控低温段的低临界溶解温度介于30-37℃之间;在55~65℃、磁力搅拌条件下,将浓度为0.06~0.07g/mL的聚乙烯亚胺水溶液按体积比为1:1滴加到浓度为0.05~0.10g/mL的甲基丙烯酸二甲氨基乙酯水溶液中,反应22~26小时后,用液氮淬灭,得到的溶液用MWCO500D透析袋在水中透析22~26h,然后冷冻干燥得到甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺,通过调控甲基丙烯酸二甲氨基乙酯的加入量来调控高温段的低临界溶解温度介于40-50℃之间,将甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺和N-异丙基丙烯酰胺修饰的聚乙烯亚胺按等质量比例混合,得到阶梯式双温度刺激响应的聚乙烯亚胺。
进一步地,所述步骤S3的具体操作为:将阶梯式双温度刺激响应的聚乙烯亚胺和羧基化纤维素纳米纤维按质量比为1~2.7:1分散在水中,超声处理后,在100℃下反应9~10h,然后离心沉淀,直至上清液为中性,将沉淀冷冻干燥,得到阶梯式双温度刺激响应性智能纳米纤维。
进一步地,所述步骤S4的具体操作为:将氨水加入到乙醇和水的混合溶液中得到乙醇/水/氨水混合溶液,搅拌均匀,将盐酸多巴胺粉末溶于水中,再将阶梯式双温度刺激响应性智能纳米纤维与多巴胺水溶液混合于乙醇/水/氨水混合溶液中,在超声作用下,避光搅拌反应5~8h,反应结束后水洗,再次分散于水中,将混合物离心,冷冻干燥;所述盐酸多巴胺与阶梯式双温度刺激响应性智能纳米纤维的质量比为0.2~0.8:1。
进一步地,所述步骤S5的具体操作为:将胺化试剂按体积比为9~10:5溶解于无水甲醇中,将丙烯酸甲酯按体积比为2~3:5溶解于无水甲醇中,向胺化试剂溶液中通入氮气,在0℃、搅拌条件下,将丙烯酸甲酯溶液按体积比为1:1滴加到胺化试剂溶液中,然后在常温下反应18~24h,得到超支化聚胺前驱体,将超支化聚胺前驱体在60~70℃条件下蒸发0.5~1.5h,再将温度依次升至100℃、140℃各反应2~3h,制得超支化聚胺;所述胺化试剂为二乙烯三胺、三乙烯四胺或四乙烯五胺。
进一步地,所述步骤S6的具体操作为:将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺按质量比为1:1~7的比例混合,然后分散于1~4wt%的NaOH水溶液中,在搅拌速度为100~800r/min的条件下,加入环氧氯丙烷,交联反应10~30min,制得所述的近红外低温脱附型智能吸附材料;所述阶梯式双温度/近红外刺激响应性智能纳米纤维与环氧氯丙烷的质量比为1:0.3~0.8,所述阶梯式双温度/近红外刺激响应性智能纳米纤维与NaOH水溶液的质量/体积比为1g:100~300mL。
所述的近红外低温脱附型智能吸附材料可应用于酸性气体捕集方面,所述酸性气体为二氧化碳、二氧化硫或硫化氢,材料饱和吸附酸性气体后,在近红外作用下实现低温脱附再生,即采用808nm近红外间隔照射材料,使材料的温度达到37℃维持5~10min,再提高温度至50℃维持5~10min,即可实现材料的脱附再生,再生率率大于95%。
本发明具有以下有益效果:
⑴本发明制备的近红外低温脱附型智能吸附材料具有阶梯式双温度/近红外刺激响应性,材料的阶梯式双温度刺激响应降低材料吸附酸性气体后的再生温度;该材料具有高氨基密度(大于14mmol/g)和纳米空腔,促进了酸性气体吸附(吸附容量大于7mmol/g),并可通过近红外刺激响应实现近红外脱附再生(再生率大于95%),近红外作用下材料的温度55~65℃,再生温度较低,使材料兼具高酸性气体吸附容量和低再生温度性能,克服传统酸性气体吸附材料难以兼具高酸性气体吸附容量和低再生温度的问题。
⑵本发明在材料上构建阶梯式双温度和近红外刺激响应性,提供近红外刺激响应的聚多巴胺与阶梯式双温度刺激响应性智能纳米纤维在制备过程中,形成互穿网络结构,结构稳定。通过双温度刺激和近红外刺激响应的协同作用,利用近红外作用使材料温度逐步升高,并阶梯式的触发双温度刺激响应,使得材料发生两次分子链收缩,以及由亲水态向疏水、更疏水态的阶梯式转变,促进酸性气体从饱和吸附后的材料中逐步解吸出来,实现完全脱附再生。本发明构建了近红外低温脱附的新型脱附方式,实现了材料的原位低温再生。
⑶饱和吸附酸性气体的材料,在解吸时,由于温敏作用,分子链收缩,会促进气体的脱附,本发明采用阶梯式双温度刺激,使材料的分子链逐步收缩,利于酸性气体逐步释放。
⑷本发明创新性的构建近红外触发双温敏开关的脱附方式,是一种新型的低温脱附方式,是通过直接照射材料而获得的热量,是一种“由内而外”的脱附方式,相比于传统“由外而内”的水浴加热的高温脱附方式,是一种更加节能的脱附方式。
具体实施方式
实施例1
S1.羧基化纤维素纳米纤维的制备:取4g绝干蔗渣浆纤维于锥形瓶中,加入200mL的邻苯二甲酸氢钾缓冲液(0.05M,pH=3),再加入2.0g高碘酸钠,用锡纸包裹后30℃条件下,搅拌4.5h,最后加入10mL乙二醇终止反应,将产物抽滤洗涤,干燥,得到双醛纤维。向2g双醛纤维中加入180mL的磷酸钠缓冲溶液(0.05M,pH=6.8),并将悬浮液在500rmp和55℃条件下密封的烧瓶中搅拌,然后加入0.030g TEMPO,再加入1.69M、1.183mL次氯酸钠溶液,最后加入2.1307g亚氯酸钠,氧化17h,加入5mL乙醇来淬灭,洗涤、干燥,得到羧基化纤维素纳米纤维。
S2.阶梯式双温度刺激响应的聚乙烯亚胺的制备:将1.5g聚乙烯亚胺溶于10mL水中,0.9gN-异丙基丙烯酰胺溶于30mL水中。在55℃、磁力搅拌条件下,将10mL聚乙烯亚胺水溶液滴加到30mL N-异丙基丙烯酰胺水溶液中,反应22小时后,用液氮淬灭。所有获得的溶液用MWCO500D透析袋在水中透析22h,然后冷冻干燥得到N-异丙基丙烯酰胺修饰的聚乙烯亚胺,通过调控N-异丙基丙烯酰胺的加入量调控低温段的低临界溶解温度(LCST)介于30~37℃之间。将1.8g聚乙烯亚胺溶于30mL水中,1.5g甲基丙烯酸二甲氨基乙酯溶于30mL水中,在55℃、磁力搅拌条件下,将30mL聚乙烯亚胺水溶液滴加到30mL甲基丙烯酸二甲氨基乙酯水溶液中,反应22小时后,用液氮淬灭,所有获得的溶液用MWCO500D透析袋在水中透析22h,然后冷冻干燥得到甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺,通过调控甲基丙烯酸二甲氨基乙酯的加入量调控高温段的低临界溶解温度(LCST)介于40-50℃之间。甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺和N-异丙基丙烯酰胺修饰的聚乙烯亚胺按等质量比例混合,得到阶梯式双温度刺激响应的聚乙烯亚胺。
S3.阶梯式双温度刺激响应性智能纳米纤维的制备:将1.0g阶梯式双温度刺激响应的聚乙烯亚胺与1.0g羧基化生物质纤维分散在25mL水中,超声处理(300W)30min后,在100℃下反应9h,然后离心沉淀(4800r/min,10min),直至上清液为中性,将沉淀冷冻干燥,得到阶梯式双温度刺激响应性智能纳米纤维。
S4.阶梯式双温度/近红外刺激响应性智能纳米纤维的制备:将2mL、30wt%氨水加入到40mL乙醇和90mL水的混合溶液中得到乙醇/水/氨水混合溶液,搅拌30min,将0.2g盐酸多巴胺粉末溶于30mL水中,再将1.0g阶梯式双温度刺激响应性智能纳米纤维与多巴胺水溶液混合于乙醇/水/氨水混合溶液中,在超声(300W)作用下,避光搅拌反应5h,反应结束后水洗数次,再次分散于水中,将混合物离心(4800r/min、10min),冷冻干燥。
S5.超支化聚胺的制备:将二乙烯三胺按体积比为9:5溶解于无水甲醇中,丙烯酸甲酯将按体积比为2:5溶解于无水甲醇中,向二乙烯三胺溶液中通入氮气,在0℃、搅拌条件下,将丙烯酸甲酯溶液按体积比为1:1滴加到二乙烯三胺溶液中,然后在常温下反应18h,得到超支化聚胺前驱体,将超支化聚胺前驱体在70℃条件下蒸发0.5h,再将温度依次升至100℃、140℃各反应2h,制得超支化聚胺。
S6.采用交联剂一步交联:将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺按质量比为1:1的比例混合,然后分散于4wt%的NaOH水溶液中(阶梯式双温度/近红外刺激响应性智能纳米纤维与NaOH水溶液的质量/体积比为1g:100mL),在搅拌速度为100r/min的条件下,加入环氧氯丙烷(阶梯式双温度/近红外刺激响应性智能纳米纤维与环氧氯丙烷的质量比为1:0.3),交联反应10min,制得所述的近红外低温脱附型智能吸附材料。
实施例2
S1.羧基化纤维素纳米纤维的制备:取4g绝干蔗渣浆纤维于锥形瓶中,加入200mL的邻苯二甲酸氢钾缓冲液(0.05M,pH=3),再加入2.4g高碘酸钠,用锡纸包裹后35℃条件下,搅拌4h,最后加入10mL乙二醇终止反应,将产物抽滤洗涤,干燥,得到双醛纤维。向2g双醛纤维中加入180mL的磷酸钠缓冲溶液(0.05M,pH=6.8)中,并将悬浮液在500rmp和60℃条件下密封的烧瓶中搅拌,然后加入0.032g TEMPO,加入1.69M、1.183mL次氯酸钠溶液,再加入2.1307g亚氯酸钠,氧化16h,加入5mL乙醇来淬灭,洗涤、干燥,得到羧基化纤维素纳米纤维。
S2.阶梯式双温度刺激响应的聚乙烯亚胺的制备:将2.0g聚乙烯亚胺溶于10mL水中,1.8gN-异丙基丙烯酰胺溶于30mL水中。在60℃、磁力搅拌条件下,将10mL聚乙烯亚胺水溶液滴加到30mL N-异丙基丙烯酰胺水溶液中,反应24小时后,用液氮淬灭。所有获得的溶液用MWCO500D透析袋在水中透析24h,然后冷冻干燥得到N-异丙基丙烯酰胺修饰的聚乙烯亚胺,通过调控N-异丙基丙烯酰胺的加入量调控低温段的低临界溶解温度(LCST)介于30~37℃之间。将2.0g聚乙烯亚胺溶于30mL水中,2.4g甲基丙烯酸二甲氨基乙酯溶于30mL水中,在60℃、磁力搅拌条件下,将30mL聚乙烯亚胺水溶液滴加到30mL甲基丙烯酸二甲氨基乙酯水溶液中,反应24小时后,用液氮淬灭,所有获得的溶液用MWCO500D透析袋在水中透析24h,然后冷冻干燥得到甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺,通过调控甲基丙烯酸二甲氨基乙酯的加入量调控高温段的低临界溶解温度(LCST)介于40-50℃之间。甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺修饰和N-异丙基丙烯酰胺修饰的聚乙烯亚胺按等质量比例混合,得到阶梯式双温度刺激响应的聚乙烯亚胺。
S3.阶梯式双温度刺激响应性智能纳米纤维的制备:将2.0g阶梯式双温度刺激响应的聚乙烯亚胺与1.0g羧基化生物质纤维分散在35mL水中,超声处理(300W)30min后,在100℃下反应9.6h,然后离心沉淀(4800r/min,10min),直至上清液为中性,将沉淀冷冻干燥,得到阶梯式双温度刺激响应性智能纳米纤维。
S4.阶梯式双温度/近红外刺激响应性智能纳米纤维的制备:将2mL、30wt%氨水加入到40mL乙醇和90mL水的混合溶液中得到乙醇/水/氨水混合溶液,搅拌30min,将0.6g盐酸多巴胺粉末溶于30mL水中,再将1.0g阶梯式双温度刺激响应性智能纳米纤维与多巴胺水溶液混合于乙醇/水/氨水混合溶液中,在超声(300W)作用下,避光搅拌反应7h,反应结束后水洗数次,再次分散于水中,将混合物离心(4800r/min、10min),冷冻干燥。
S5.超支化聚胺的制备:将三乙烯四胺按体积比为9.6:5溶解于无水甲醇中,丙烯酸甲酯将按体积比为2.7:5溶解于无水甲醇中,向三乙烯四胺溶液中通入氮气,在0℃、搅拌条件下,将丙烯酸甲酯溶液按体积比为1:1滴加到三乙烯四胺溶液中,然后在常温下反应22h,得到超支化聚胺前驱体,将超支化聚胺前驱体在65℃条件下蒸发1.0h,再将温度依次升至100℃、140℃各反应2.5h,制得超支化聚胺。
S6.采用交联剂一步交联:将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺按质量比为1:5的比例混合,然后分散于3wt%的NaOH水溶液中(阶梯式双温度/近红外刺激响应性智能纳米纤维与NaOH水溶液的质量/体积比为1g:240mL),在搅拌速度为500r/min的条件下,加入环氧氯丙烷(阶梯式双温度/近红外刺激响应性智能纳米纤维与环氧氯丙烷的质量比为1:0.6),交联反应25min,制得所述的近红外低温脱附型智能吸附材料。
实施例3
S1.羧基化纤维素纳米纤维的制备:取4g绝干蔗渣浆纤维于锥形瓶中,加入200mL的邻苯二甲酸氢钾缓冲液(0.05M,pH=3),再加入3.0g高碘酸钠,用锡纸包裹后40℃条件下,搅拌3.5h,最后加入10mL乙二醇终止反应,将产物抽滤洗涤,干燥,得到双醛纤维。向2g双醛纤维中加入180mL的磷酸钠缓冲溶液(0.05M,pH=6.8)中,并将悬浮液在500rmp和65℃条件下密封的烧瓶中搅拌,然后加入0.035g TEMPO,加入1.69M、1.183mL次氯酸钠溶液,再加入2.1307g亚氯酸钠,氧化15h,加入5mL乙醇来淬灭,洗涤、干燥,得到羧基化纤维素纳米纤维。
S2.阶梯式双温度刺激响应的聚乙烯亚胺的制备:将2.5g聚乙烯亚胺溶于10mL水中,2.7gN-异丙基丙烯酰胺溶于30mL水中。在65℃、磁力搅拌条件下,将10mL聚乙烯亚胺水溶液滴加到30mL N-异丙基丙烯酰胺水溶液中,反应26小时后,用液氮淬灭。所有获得的溶液用MWCO500D透析袋在水中透析26h,然后冷冻干燥得到N-异丙基丙烯酰胺修饰的聚乙烯亚胺,通过调控N-异丙基丙烯酰胺的加入量调控低温段的低临界溶解温度(LCST)介于30~37℃之间。将2.1g聚乙烯亚胺溶于30mL水中,3.0g甲基丙烯酸二甲氨基乙酯溶于30mL水中,在65℃、磁力搅拌条件下,将30mL聚乙烯亚胺水溶液滴加到30mL甲基丙烯酸二甲氨基乙酯水溶液中,反应26小时后,用液氮淬灭,所有获得的溶液用MWCO500D透析袋在水中透析26h,然后冷冻干燥得到甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺,通过调控甲基丙烯酸二甲氨基乙酯的加入量调控高温段的低临界溶解温度(LCST)介于40-50℃之间。甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺修饰和N-异丙基丙烯酰胺修饰的聚乙烯亚胺按等质量比例混合,得到阶梯式双温度刺激响应的聚乙烯亚胺。
S3.阶梯式双温度刺激响应性智能纳米纤维的制备:将2.7g阶梯式双温度刺激响应的聚乙烯亚胺与1.0g羧基化生物质纤维分散在50mL水中,超声处理(300W)30min后,在100℃下反应10h,然后离心沉淀(4800r/min,10min),直至上清液为中性,将沉淀冷冻干燥,得到阶梯式双温度刺激响应性智能纳米纤维。
S4.阶梯式双温度/近红外刺激响应性智能纳米纤维的制备:将2mL、30wt%氨水加入到40mL乙醇和90mL水的混合溶液中得到乙醇/水/氨水混合溶液,搅拌30min,将0.8g盐酸多巴胺粉末溶于30mL水中,再将1.0g阶梯式双温度刺激响应性智能纳米纤维与多巴胺水溶液混合于乙醇/水/氨水混合溶液中,在超声(300W)作用下,避光搅拌反应8h,反应结束后水洗数次,再次分散于水中,将混合物离心(4800r/min、10min),冷冻干燥。
S5.超支化聚胺的制备:将四乙烯五胺按体积比为10:5溶解于无水甲醇中,丙烯酸甲酯将按体积比为3:5溶解于无水甲醇中,向四乙烯五胺溶液中通入氮气,在0℃、搅拌条件下,将丙烯酸甲酯溶液按体积比为1:1滴加到四乙烯五胺溶液中,然后在常温下反应24h,得到超支化聚胺前驱体,将超支化聚胺前驱体在60℃条件下蒸发1.5h,再将温度依次升至100℃、140℃各反应3h,制得超支化聚胺。
S6.采用交联剂一步交联:将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺按质量比为1:7的比例混合,然后分散于1wt%的NaOH水溶液中(阶梯式双温度/近红外刺激响应性智能纳米纤维与NaOH水溶液的质量/体积比为1g:300mL),在搅拌速度为800r/min的条件下,加入环氧氯丙烷(阶梯式双温度/近红外刺激响应性智能纳米纤维与环氧氯丙烷的质量比为1:0.8),交联反应30min,制得所述的近红外低温脱附型智能吸附材料。
实施例1、2、3所制备的近红外低温脱附型智能吸附材料的性能表征
①将实施例1、2、3制备的近红外低温脱附型智能吸附材料进行双温度刺激响应性能测试,测试结果均表现出良好的双温度刺激响应性能,材料在25℃条件下表现出亲水性能(水接触角小于30°),当温度升高至30-37℃时,材料表现出疏水性能(水接触角大于106°),当温度继续升高至40~50℃时,材料的疏水性能进一步提高(水接触角大于125°)。
②将实施例1、2、3制备的近红外低温脱附型智能吸附材料进行酸性气体吸/脱附性能测试,测试结果均表现出优异的酸性气体吸/脱附性能,在湿态下对二氧化碳、二氧化硫、硫化氢气体的吸附容量大于7mmol/g,材料饱和吸附酸性气体后,可实现近红外脱附再生,采用808nm近红外间隔照射材料,使材料的温度达到37℃维持5~10min,再提高温度至50℃维持5~10min,即可实现材料的脱附再生,再生率大于95%。材料兼具高酸性气体吸附容量和低再生温度性能;该材料也可用于对沼气中酸性气体的吸附并纯化沼气,纯化后沼气中甲烷含量大于98%。
Claims (10)
1.一种近红外低温脱附型智能吸附材料,其特征在于,在羧基化纤维素纳米纤维基体上化学接枝阶梯式双温度刺激响应的聚乙烯亚胺,制备阶梯式双温度刺激响应性智能纳米纤维,再与具有近红外刺激响应性的光敏剂复合,制备阶梯式双温度/近红外刺激响应性智能纳米纤维,采用交联剂直接将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺一步交联复合得到;所述的近红外低温脱附型智能吸附材料的阶梯式双温度响应是具有两个温度阶段的刺激响应性,其低临界溶解温度分别在30-37℃和40-50℃范围;
所述阶梯式双温度刺激响应的聚乙烯亚胺是由N-异丙基丙烯酰胺和甲基丙烯酸二甲氨基乙酯分别修饰聚乙烯亚胺后,按比例混合均匀得到;所述羧基化纤维素纳米纤维是由纸浆纤维经过高碘酸钠氧化和TEMPO氧化制备得到,羧基化纤维素纳米纤维上具有大量的羧基基团;所述具有近红外刺激响应性的光敏剂为聚多巴胺,是在超声作用下,多巴胺聚合成聚多巴胺的同时与阶梯式双温度刺激响应性智能纳米纤维复合成阶梯式双温度/近红外刺激响应性智能纳米纤维,形成互穿网络结构的复合结构;所述超支化聚胺由胺化试剂与丙烯酸甲酯发生迈克尔加成反应和自缩聚反应得到;所述交联剂为环氧氯丙烷。
2.根据权利要求1所述的一种近红外低温脱附型智能吸附材料,其特征在于,所述纸浆纤维为漂白纸浆纤维,纸浆纤维为蔗渣浆纤维、桉木浆纤维、竹浆纤维、马尾松浆纤维、麦草浆纤维中的一种或多种混合。
3.一种近红外低温脱附型智能吸附材料的制备方法,其特征在于,包括以下制备步骤:
S1.羧基化纤维素纳米纤维的制备:采用高碘酸钠将纸浆纤维的纤维素结构单元的C2和C3上的羟基选择性氧化为醛基,制备双醛纤维;然后采用TEMPO试剂将双醛纤维的纤维素结构单元的C2、C3上的醛基和C6上的羟基氧化为羧基,通过控制反应条件来调控氧化程度,制备羧基化纤维素纳米纤维;
S2.阶梯式双温度刺激响应的聚乙烯亚胺的制备:采用N-异丙基丙烯酰胺、甲基丙烯酸二甲氨基乙酯分别与聚乙烯亚胺发生迈克尔加成反应后,按比例混合均匀,使改性后的聚乙烯亚胺具有阶梯式双温度刺激响应性;
S3.阶梯式双温度刺激响应性智能纳米纤维的制备:羧基化纤维素纳米纤维与阶梯式双温度刺激响应的聚乙烯亚胺在高温下发生酰胺化反应;
S4.阶梯式双温度/近红外刺激响应性智能纳米纤维的制备:阶梯式双温度刺激响应性智能纳米纤维与多巴胺混合分散均匀后,在超声作用下,多巴胺聚合成聚多巴胺的同时与阶梯式双温度刺激响应性智能纳米纤维复合,形成互穿网络结构的复合结构,通过离心、冷冻干燥得到阶梯式双温度/近红外刺激响应性智能纳米纤维;
S5.超支化聚胺的制备:采用胺化试剂与丙烯酸甲酯发生迈克尔加成反应生成超支化聚胺前驱体,超支化聚胺前驱体发生自缩聚反应制得超支化聚胺;
S6.采用交联剂一步交联:将步骤S4制得的阶梯式双温度/近红外刺激响应性智能纳米纤维与步骤S5制得的超支化聚胺在碱性溶液中混合均匀,在搅拌条件下加入环氧氯丙烷交联剂,混合液直接被交联成固体颗粒,制得所述的近红外低温脱附型智能吸附材料。
4.根据权利要求3所述的制备方法,其特征在于,所述步骤S1的具体操作为:向纸浆纤维中加入邻苯二甲酸氢钾缓冲液,然后加入高碘酸钠,在30~40℃条件下,搅拌反应3.5~4.5h,最后加入乙二醇终止反应,洗涤,干燥,得到双醛纤维;所述纸浆纤维与高碘酸钠的质量比为4:2~3;向双醛纤维中加入磷酸钠缓冲溶液,在55~65℃条件下搅拌均匀,然后加入TEMPO,再加入次氯酸钠溶液,然后加入亚氯酸钠,氧化15~17h,加入乙醇来淬灭,洗涤、干燥,得到羧基化纤维素纳米纤维;所述双醛纤维与TEMPO的质量比为400:6~7。
5.根据权利要求3所述的制备方法,其特征在于,所述步骤S2的具体操作为:在55~65℃、磁力搅拌条件下,将浓度为0.15~0.25g/mL的聚乙烯亚胺水溶液按体积比为1:3滴加到浓度为0.03~0.09g/mL的N-异丙基丙烯酰胺水溶液中,反应22~26小时后,用液氮淬灭,得到的溶液用MWCO500D透析袋在水中透析22~26h,然后冷冻干燥得到N-异丙基丙烯酰胺修饰的聚乙烯亚胺,通过调控N-异丙基丙烯酰胺的加入量来调控低温段的低临界溶解温度介于30-37℃之间;在55~65℃、磁力搅拌条件下,将浓度为0.06~0.07g/mL的聚乙烯亚胺水溶液按体积比为1:1滴加到浓度为0.05~0.10g/mL的甲基丙烯酸二甲氨基乙酯水溶液中,反应22~26小时后,用液氮淬灭,得到的溶液用MWCO500D透析袋在水中透析22~26h,然后冷冻干燥得到甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺,通过调控甲基丙烯酸二甲氨基乙酯的加入量来调控高温段的低临界溶解温度介于40-50℃之间,将甲基丙烯酸二甲氨基乙酯修饰的聚乙烯亚胺和N-异丙基丙烯酰胺修饰的聚乙烯亚胺按等质量比例混合,得到阶梯式双温度刺激响应的聚乙烯亚胺。
6.根据权利要求3所述的制备方法,其特征在于,所述步骤S3的具体操作为:将阶梯式双温度刺激响应的聚乙烯亚胺和羧基化纤维素纳米纤维按质量比为1~2.7:1分散在水中,超声处理后,在100℃下反应9~10h,然后离心沉淀,直至上清液为中性,将沉淀冷冻干燥,得到阶梯式双温度刺激响应性智能纳米纤维。
7.根据权利要求3所述的制备方法,其特征在于,所述步骤S4的具体操作为:将氨水加入到乙醇和水的混合溶液中得到乙醇/水/氨水混合溶液,搅拌均匀,将盐酸多巴胺粉末溶于水中,再将阶梯式双温度刺激响应性智能纳米纤维与多巴胺水溶液混合于乙醇/水/氨水混合溶液中,在超声作用下,避光搅拌反应5~8h,反应结束后水洗,再次分散于水中,将混合物离心,冷冻干燥;所述盐酸多巴胺与阶梯式双温度刺激响应性智能纳米纤维的质量比为0.2~0.8:1。
8.根据权利要求3所述的制备方法,其特征在于,所述步骤S5的具体操作为:将胺化试剂按体积比为9~10:5溶解于无水甲醇中,将丙烯酸甲酯按体积比为2~3:5溶解于无水甲醇中,向胺化试剂溶液中通入氮气,在0℃、搅拌条件下,将丙烯酸甲酯溶液按体积比为1:1滴加到胺化试剂溶液中,然后在常温下反应18~24h,得到超支化聚胺前驱体,将超支化聚胺前驱体在60~70℃条件下蒸发0.5~1.5h,再将温度依次升至100℃、140℃各反应2~3h,制得超支化聚胺;所述胺化试剂为二乙烯三胺、三乙烯四胺或四乙烯五胺。
9.根据权利要求3所述的制备方法,其特征在于,所述步骤S6的具体操作为:将阶梯式双温度/近红外刺激响应性智能纳米纤维与超支化聚胺按质量比为1:1~7的比例混合,然后分散于1~4wt%的NaOH水溶液中,在搅拌速度为100~800r/min的条件下,加入环氧氯丙烷,交联反应10~30min,制得所述的近红外低温脱附型智能吸附材料;所述阶梯式双温度/近红外刺激响应性智能纳米纤维与环氧氯丙烷的质量比为1:0.3~0.8,所述阶梯式双温度/近红外刺激响应性智能纳米纤维与NaOH水溶液的质量/体积比为1g:100~300mL。
10.权利要求1~9任一项所述的近红外低温脱附型智能吸附材料在酸性气体捕集方面的应用,所述酸性气体为二氧化碳、二氧化硫或硫化氢,材料饱和吸附酸性气体后,在近红外作用下实现脱附再生,即采用808nm近红外间隔照射材料,使材料的温度达到37℃维持5~10min,再提高温度至50℃维持5~10min,即可实现材料的脱附再生,再生率率大于95%。
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