CN111363148A - 一种联二萘基网络型聚酰亚胺树脂与薄膜的制备方法及在气体分离中的应用 - Google Patents
一种联二萘基网络型聚酰亚胺树脂与薄膜的制备方法及在气体分离中的应用 Download PDFInfo
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- polyimide resin
- binaphthyl
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Abstract
本发明提供了一种联二萘基网络型聚酰亚胺树脂与薄膜的制备方法及在气体分离中的应用,主要用于H2、O2、CO2、N2、CH4等小分子气体的分离纯化。该类聚酰亚胺酸树脂是以1,1'‑联二萘酚为原料,经硝化生成7,7'‑二硝基‑1,1'‑联二萘酚,然后,在碱性条件下与2‑氯‑5‑硝基三氟甲苯进行醚化反应,经钯碳氢化还原生成四胺化合物,在低温下,再与二酐进行缩聚反应生成聚酰胺酸树脂。该类树脂可采用溶液加工方法,可简单方便地制备成聚酰胺酸树脂薄膜,再进一步加热进行亚胺化,即可制得聚酰亚胺薄膜。所得薄膜可用于气体分离,具有良好的气体渗透性能与选择性能。
Description
技术领域
本发明属于化工技术领域,涉及一种兼顾优异透气性和选择性的联二萘基网络型聚酰亚胺树脂的合成、薄膜的制备方法和用途,适用于H2回收、天然气中CO2的去除,空气中O2富集以及烟气中CO2脱除等领域。
背景技术
随着环境污染、能源和资源危机,气体分离膜技术以其卓越的性能已引起国际的高度重视。该技术是利用特定的气体分离膜对混合气体进行分离纯化的一种新型绿色化工分离技术,属于无相变的物理分离过程,具有流程工艺简单,耗能低,效率高等优点,已广泛应用于H2回收、天然气中CO2的去除,空气中O2富集以及烟气中CO2脱除等众多领域。
气体分离膜技术中的膜是连接两相之间的不连续区间,可以是固态的或液态的,而被分隔开的流体相物质可以是液态的或气态的。因此,膜分离是利用膜材料的选择分离性实现原料不同组分的分离、纯化、浓缩的过程。毫无疑问,膜材料的性质直接影响气体分离过程的渗透选择效率。常见的高分子聚合物膜材料有醋酸纤维素、聚砜、聚三甲基硅-1-丙炔、聚二甲基硅氧烷、芳香族聚酰亚胺等。
早在1980年商业化的醋酸纤维素膜就被用来分离天然气中的酸性气体二氧化碳。随后,在聚砜的非对称性膜表面涂覆一层硅橡胶的商业化Prism膜被用来纯化氢气。后来,主链重复单元中含有酰亚胺环的聚酰亚胺大分子因其结构可控、气体渗透选择性佳,机械强度高,备受气体分离领域青睐。比如其玻璃化转变温度常大于250℃,热降解温度大多高于450℃。2004年,Budd和McKeown等首次采用具有螺环结构的单体与四氟对苯二腈在催化剂碳酸钾的作用下,发生亲核取代反应,成功制备出自具微孔高分子材料。它具有的刚性扭转结构,可有效阻止分子链之间的堆积,从而使得聚合物自身具有很高的自由体积和比表面积,表现优异的气体渗透性能。自此以后,类似的刚性扭转结构,如螺二茚满(SBI)、EA、三碟烯(Trip)、螺二芴(SBF)、特勒格碱基(TB)等被相继报道。
以上的各种刚性结构单元有一个共同点,就是重复单元的功能结构的二面角是固定不能扭转的,可构建固定的微孔,营造高自由体积,使得这类材料具有较大的气体渗透系数。但是,该类材料的刚性扭转结构在形成连续微孔的同时,不易对聚合物微孔孔径及其分布进行有效调控,往往较难满足实际气体的分离需求。
2019年,Guy Koeckelberghs等通过引入不同的烷基桥接联二萘酚的两个萘环而设计合成了一类新的可以改变联二萘结构中两个萘环扭转角度的聚酰亚胺微孔材料。研究结果表明,柔性烷基桥接单元对材料内自由体积具有一定的调控作用,不同烷基桥联的联二萘型材料的气体分离性能差别却很小。
发明内容
本发明目的是解决现有气体分离膜材料不易对聚合物微孔孔径及其分布进行有效调控,较难满足实际气体分离需求的问题,提供一种联二萘基网络型聚酰亚胺树脂与薄膜的制备方法以及在气体分离中的应用。
本发明设计合成了一类以联二萘为骨架的新型网络型聚酰亚胺树脂,以期通过调控单体结构来改善聚合物材料的气体分离性能。本发明同时提出一种网络型聚酰亚胺树脂薄膜的制备方法,解决了网络型聚酰亚胺树脂成膜问题,所述聚酰亚胺薄膜有效提高了气体分离性能。
本发明技术方案
本发明所提供的联二萘基网络型聚酰亚胺树脂具有如下的结构通式:
本发明的一系列联二萘基网络型聚酰亚胺树脂,优选的几个特征方案中,Ar含义为以下结构式中的一种:
本发明所述联二萘基网络型聚酰亚胺树脂合成路线为:
上述合成路线中Ar含义与前文所述相同。
联二萘基网络型聚酰亚胺树脂及其薄膜的制备方法:
第1步、联二萘基网络型聚酰亚胺树脂的制备
通过四胺的活性官能团氨基(-NH2)与二酐的酐基(-CO-O-CO-)按等摩尔比进行投料,在低温-40~-60℃下缩聚反应1~6h制备得到,具体步骤如下:
(1)1,1'-联二萘酚经硝化后,生成7,7'-二硝基-1,1'-联二萘酚(化合物1),在(碳酸钾)碱性条件下,与2-氯-5-硝基三氟甲苯反应,生成化合物2,再通过钯-碳加氢还原反应即可得到联二萘四胺(化合物3)。
(2)合成的联二萘四胺单体与多种市售二酐(如6FDA或PMDA等)在低温下进行缩聚反应,即可制备联二萘基网络型聚酰胺酸树脂溶液。
第2步、联二萘基网络型聚酰亚胺薄膜的制备
在第1步制备的树脂溶液未形成凝胶前,通过溶液加工方法制备液膜,该液膜在室温下凝胶固化,再在30~80℃真空条件下缓慢脱除溶剂,形成联二萘基网络型聚酰胺酸薄膜,最后,通过化学或热亚胺化(以0.5~2℃/min的升温速率加热到温度250~350℃,并在该温度下保持1~5h)制备成联二萘基网络型聚酰亚胺薄膜。
本发明制备的联二萘基网络型聚酰亚胺树脂薄膜可用于气体分离,该气体分离可用于H2回收、天然气中酸性气体CO2的去除、助燃烧空气中O2富集等领域。
本发明的优点和有益效果:
本发明采用芳基结构修饰联二萘酚,合成了芳醚基联二萘的聚酰亚胺材料,由于芳基结构的立体位阻较大,促使联二萘两个萘环间二面角增大,材料表现出优异的气体渗透性和选择性。由于芳基及其侧链结构的可调性,结合两个萘环间自由旋转的C-C键特性,可以对两个萘环的扭转角度进行调节,进而调控聚合物微孔结构,改善膜材料的分离性能。此外,网络状微孔聚合物材料的内部具有丰富的自由体积,其刚性扭转骨架结构能有效阻止分子链之间的有效堆积,表现高的比表面积和丰富的微孔结构;高度互联的共价键,构筑了稳定的立体网络结构,增强了微孔机械强度,防止孔道物理塌陷,减缓物理老化。
本发明以联二萘为母核的四胺,采用低温缩聚方法,制备网络型聚酰亚胺材料及其气体分离膜,该薄膜制备工艺简单、便于产业化,并且该膜具有很好的气体渗透性和选择性。适用于H2回收、天然气中CO2的去除,空气中O2富集以及烟气中CO2脱除。
附图说明
图1为本发明联二萘基网络型聚酰亚胺树脂薄膜的O2/N2气体分离特性图。
图2为本发明联二萘基网络型聚酰亚胺树脂薄膜的CO2/CH4气体分离特性图。
具体实施方式
下面结合附图通过具体实施例对本发明进一步阐述,所举之例不限制本发明的保护范围。
本发明所述的气体分离膜的制备方法主要包括以下步骤:联二萘四胺单体的制备、联二萘基网络型聚酰胺酸树脂的制备以及联二萘基网络型聚酰亚胺树脂薄膜的制备。具体制备步骤如下:
(1)7,7'-二硝基-1,1'-联二萘酚(化合物1)的制备
准备一个单口圆底烧瓶,加一定量的乙酸与1,1'-联二萘酚,剧烈搅拌10分钟。然后向反应溶液中缓慢滴加发烟硝酸(98%),在室温下搅拌1h,在此期间溶液颜色从白色变为黑色,最后变为绿色。将混合物倒入冰水中搅拌10min,过滤,干燥,即可得到化合物1。
(2)四硝基联二萘(化合物2)的制备
将化合物1、K2CO3和无水DMF加入干燥三颈圆底烧瓶中,在室温下搅拌30分钟,直到得到均匀的溶液。然后,将2-氯-5-硝基三氟甲苯缓慢加入烧瓶中,并在100℃下剧烈搅拌24h。反应完成后,将混合物倒入冰水溶液中,然后过滤,干燥,得白色固体化合物2。
(3)联二萘四胺(化合物3)的制备
将化合物2溶于DMF中,并且加入10%的Pd/C。氮气吹扫三次后,在室温下,2bar氢气气氛下搅拌反应24h,混合物经硅藻土过滤,滤液倒入10wt%碳酸钾水溶液中。将沉淀的固体过滤,并在40℃真空环境中干燥,即可获得白色固体化合物3。
(4)联二萘基网络型聚酰亚胺树脂薄膜的制备
联二萘四胺(化合物3)的活性官能团氨基(-NH2)与二酐(6FDA,PMDA等)的酐基(-CO-O-CO-)按等摩尔比投料,在适当低温下反应,可得到聚酰胺酸树脂。在该聚酰胺酸树脂未形成凝胶前,倒入玻璃器皿,在一定温度下脱除溶剂,即可得到联二萘基网络型聚酰胺酸薄膜。最后,在一定温度下热亚胺化即可制备对应的联二萘基网络型聚酰亚胺树脂薄膜。
(5)联二萘基网络型聚酰亚胺树脂薄膜的应用
本发明所述的联二萘基网络型聚酰亚胺树脂可用于气体分离膜的制备,该气体分离膜可用于H2回收、天然气中酸性气体CO2的去除、助燃烧空气中O2富集等领域。
实施例1:联二萘基网络型聚酰亚胺树脂XS18的制备
(1)7,7'-二硝基-1,1'-联二萘酚(化合物1)的制备
向25ml的单口圆底烧瓶中加入1,1'-联萘酚(1.0g,3.49mmol)、乙酸(15mL),在室温下搅拌10min后,在0℃下向溶液中缓慢滴加发烟硝酸(98%,0.62mL,15.24mmol)。然后在室温下将所得混合物搅拌1h,在此期间溶液颜色从白色变为黑色,最后变为绿色。将混合物倒入冰水(500ml)中搅拌10min,过滤,干燥即可得到绿色粉末(化合物1),收率78%。
(2)四硝基联二萘(化合物2)的制备
向500ml三口圆底烧瓶中加入化合物1(7.00g,18.61mmol)、K2CO3(3.85g,27.92mmol)和无水DMF(200mL),在室温下搅拌30分钟,直到得到均匀的溶液。将2-氯-5-硝基三氟甲苯(8.79g,39.09mmol)加入烧瓶中,在100℃下剧烈搅拌24h。反应完成后,将混合物在冰水溶液中沉淀,然后过滤,用乙酸乙酯反复洗涤,干燥即可得到白色固体粉末(9.77g,产率=92.8%)。
(3)联二萘四胺(化合物3)的制备
向500ml圆底烧瓶中加入化合物2(8.80g,11.66mmol)、DMF(200ml)和10%的Pd/C(0.5g)。氮气吹扫三次后,在室温下,在2bar氢气气氛下搅拌反应24h,混合物经硅藻土过滤,滤液倒入800ml的10wt%碳酸钾水溶液中。将沉淀的固体过滤,并在40℃真空环境中干燥12h,即可获得白色固体粉末(化合物3,7.26g,产率=98.1%)。
(4)联二萘基网络型聚酰亚胺树脂XS18的制备
通过四胺单体(化合物3)和PMDA的缩聚反应制备联二萘基网络型聚酰亚胺树脂XS18。具体地说,将联二萘四胺单体(化合物3)(0.20g,0.32mmol)加入装有搅拌器的干燥烧瓶中,用真空泵将烧瓶脱气10min,然后在氩气保护下将DMF(10ml)加入烧瓶中,在-50℃下搅拌15min,直至得到均匀的溶液。然后,将7ml的DMF与PMDA(0.14g,0.63mmol)的混合溶液通过注射器缓慢加入,在低温下再剧烈搅拌4h,即可得到联二萘基网络型聚酰胺酸树脂。通过300℃热亚胺化即可制备联二萘基网络型聚酰亚胺树脂XS18。
实施例2:联二萘基网络型聚酰亚胺树脂XS19制备
(1)7,7'-二硝基-1,1'-联二萘酚(化合物1)的制备
向25ml的单口圆底烧瓶中加入1,1'-联萘酚(1.0g,3.49mmol)、乙酸(15mL),在室温下搅拌10min后,在0℃下向溶液中缓慢滴加发烟硝酸(98%,0.62mL,15.24mmol)。然后在室温下将所得混合物搅拌1h,在此期间溶液颜色从白色变为黑色,最后变为绿色。将混合物倒入冰水(500ml)中搅拌10min,过滤,干燥即可得到绿色粉末(化合物1),收率78%。
(2)四硝基联二萘(化合物2)的制备
向500ml三口圆底烧瓶中加入化合物1(7.00g,18.61mmol)、K2CO3(3.85g,27.92mmol)和无水DMF(200mL),在室温下搅拌30分钟,直到得到均匀的溶液。将2-氯-5-硝基三氟甲苯(8.79g,39.09mmol)加入烧瓶中,在100℃下剧烈搅拌24h。反应完成后,将混合物在冰水溶液中沉淀,然后过滤,用乙酸乙酯反复洗涤,干燥即可得到白色固体粉末(9.77g,产率=92.8%)。
(3)联二萘四胺(化合物3)的制备
向500ml圆底烧瓶中加入化合物2(8.79g,11.66mmol)、DMF(200ml)和10%的Pd/C(0.5g)。氮气吹扫三次后,在室温下,在2bar氢气气氛下搅拌反应24h,混合物经硅藻土过滤,滤液倒入800ml的10wt%碳酸钾水溶液中。将沉淀的固体过滤,并在40℃真空环境中干燥12h,即可获得白色固体粉末(化合物3,7.26g,产率=98.1%)。
(4)联二萘基网络型聚酰亚胺树脂XS19的制备
通过四胺单体和6FDA的缩聚反应制备联二萘基网络型聚酰亚胺树脂XS19。具体地说,将联二萘四胺单体(化合物3)(0.20g,0.32mmol)加入装有搅拌器的干燥烧瓶中,用真空泵将烧瓶脱气10min,然后在氩气保护下将DMF(10ml)加入烧瓶中,在-50℃下搅拌15min,直至得到均匀的溶液。然后,将7ml的DMF与6FDA(0.28g,0.63mmol)的混合溶液通过注射器缓慢加入,在低温下再剧烈搅拌4h,即可得到联二萘基网络型聚酰胺酸树脂。通过300℃热亚胺化即可制备联二萘基网络型聚酰亚胺树脂XS19。
实施例3:联二萘基网络型聚酰亚胺树脂薄膜Film XS18
将实施例1制备的联二萘基网络型聚酰胺酸溶液精心倒入干燥、清洁的培养皿中,然后在60℃真空条件下缓慢脱出溶剂直至成膜,将所得膜剥离,随后在300℃下热亚胺化2h(以每分钟1℃的速率),即可得到联二萘基网络型聚酰亚胺树脂薄膜Film XS18。
实施例4:联二萘基网络型聚酰亚胺树脂薄膜Film XS19
将实施例2制备的联二萘基网络型聚酰胺酸溶液精心倒入干燥、清洁的培养皿中,然后在60℃真空条件下缓慢脱出溶剂直至成膜,将所得膜剥离,随后在300℃下热亚胺化2h(以每分钟1℃的速率),即可得到联二萘基网络型聚酰亚胺树脂薄膜Film XS19。
实施例5:联二萘基网络型聚酰亚胺树脂薄膜的气体分离特性测试
联二萘基网络型聚酰亚胺树脂薄膜的气体分离特性测试方法为“变体积法”:在302.15K、0.2MPa工作压力条件下,使用4.5cm2的聚酰亚胺薄膜分别测试H2、CO2、O2、N2和CH4的渗透性。该类薄膜测试结果如下:H2的渗透系数159.8~180.7Barrer;O2的渗透系数43.6~49.9Barrer,CO2的渗透系数216.4~229.6Barrer;H2/N2的选择性21.2~22.8,O2/N2的选择性5.8~6.2,CO2/N2的选择性27.0~30.9,CO2/CH4的选择性52.1~60.1。其中,联二萘基网络型聚酰亚胺树脂薄膜FilmXS19的气体渗透分离性能最佳:H2的渗透系数180.7Barrer,CO2的渗透系数229.6Barrer,O2的渗透系数49.9Barrer;O2/N2的选择性系数5.8,CO2/N2的选择性系数27.0,H2/N2的选择性系数21.2,CO2/CH4的选择性系数52.1。该类材料对O2/N2、CO2/CH4的气体分离展现出很好的渗透性和选择性,其分离特性均高于2008年Robeson上线,分别如图1和图2所示。
Claims (7)
3.权利要求1所述的联二萘基网络型聚酰亚胺树脂的制备方法,其特征在于,通过四胺的活性官能团氨基(-NH2)与二酐的酐基(-CO-O-CO-)按等摩尔比进行投料,在低温下缩聚反应制备得到。
4.如权利要求3所述的联二萘基网络型聚酰亚胺树脂的制备方法,其特征在于,所述的型聚酰亚胺树脂制备方法为低温合成法,在低温-40~-60℃下,向四胺溶液中缓慢加入含等摩尔量的二酐和DMF溶液,在该条件下剧烈搅拌1~6h,即得聚酰胺酸树脂溶液。
5.如权利要求3或4所述的联二萘基网络型聚酰亚胺树脂的制备方法,其特征在于,所述的二酐为6FDA或PMDA。
6.一种联二萘基网络型聚酰亚胺树脂薄膜的制备方法,其特征在于:将权利要求4中合成的聚酰胺酸树脂溶液,采用溶液加工方法制备薄膜,在30~80℃真空条件下缓慢脱除溶剂,然后以0.5~2℃/min的升温速率加热到温度250~350℃,并在该温度下保持1~5h,得到网络型聚酰亚胺树脂薄膜。
7.权利要求6所得联二萘基网络型聚酰亚胺树脂薄膜的用途,其特征在于:用于气体分离。
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