CN112574412A - 基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺及其制备方法 - Google Patents
基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺及其制备方法 Download PDFInfo
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- CN112574412A CN112574412A CN202011512763.6A CN202011512763A CN112574412A CN 112574412 A CN112574412 A CN 112574412A CN 202011512763 A CN202011512763 A CN 202011512763A CN 112574412 A CN112574412 A CN 112574412A
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- dianhydride
- acid dianhydride
- tetracarboxylic
- tetracarboxylic acid
- derivatives
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明公开了一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺及其制备方法,该聚酰亚胺由一种或两种二氨基三蝶烯与一种或两种四羧酸二酐聚合而成的共聚物,或由一种或两种二氨基三蝶烯衍生物与一种或两种四羧酸二酐聚合而成的共聚物;共聚物的聚合度取值范围为1~10000;该聚酰亚胺具有优异的气体分离性能,其制备成膜后可作为气体分离薄膜在沼气分离应用中能够有效从CH4和CO2的气体混合物中分离出CH4;由该种聚合物制备的膜材料可以在气体分离领域中有巨大的应用价值。例如,可以从空气中分别分理处N2和O2;在天然气的纯化过程中除去CO2,得到高纯度的CH4,在合成氨领域用于H2的回收。
Description
技术领域
本发明涉及气体分离膜技术领域,特别涉及一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺及其制备方法。
背景技术
21世纪,现代科技和工业的发展迅猛。工业上对于不同气体的需求量不断增加,也对气体分离领域有着越来越高的要求。其中,膜气体分离比传统的深冷分离、变压吸附等技术相比具有占地面积小、安装灵活等优点。
目前,气体分离膜材料面临的重大挑战是现有的商业化聚合物对气体透过率较低。刚性扭曲基元可以增加聚合物的比表面积,从而提高气体在聚合物膜材料种的透过率,而且刚性扭曲基元能够保持聚合物对气体较高的选择性。聚酰亚胺作为一种结构可设计的聚合物,在气体分离领域有良好的应用前景。大量文献报道将不同的刚性扭曲基元例如SBI、SBF、Trip和TB等结构引入聚酰亚胺结构中可以增加其气体透过率。
发明内容
本发明的目的是提供一种具有优异的气体分离性能的基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺。
本发明的另一目的是提供一种上述基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺的制备方法。
本发明的另一目的是提供一种采用上述基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺制备的气体分离膜。
为此,本发明技术方案如下:
一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺,其为由一种二氨基三蝶烯与一种四羧酸二酐聚合而成的共聚物,或由一种二氨基三蝶烯衍生物与一种四羧酸二酐聚合而成的共聚物。
该共聚物的化学反应方程式如下:
所述二氨基三蝶烯及其衍生物的化学结构式为:
其中,Ar是取代或者未取代的芳香族化合物,具体为苯、苯的衍生物、萘、萘的衍生物;X为Cl、Br或I;
所述四羧酸二酐包括但不仅限于4,4'-联苯四甲酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、乙二胺四乙酸二酐、1,2,3,4-环丁烷四甲酸二酐、3,4,9,10-苝四甲酸二酐、3,3',4,4'-二苯酮四甲酸二酐、均苯四甲酸二酐、1,2,4,5-环己烷四甲酸二酐、萘-1,4,5,8-四羧酸二酐、1,2,4,5-环己烷四甲酸二酐、1,6,7,12-四氯苝-3,4,9,10-四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,6,7,12-四氯四芳基四羧酸二酐、3-甲基戊二酐、meso-丁烷-1,2,3,4-四甲酸二酐、2-溴萘-1,4,5,8-四羧酸1,8,4,5-二酐、1,2,3,4-环戊烷四羧酸二酐、二乙烯基三胺基五乙酸二酐、2,6-二溴萘-1,4,5,8-四甲酸二酐、1,6,2,3-二酐-β-D-吡喃甘露糖、3,3',4,4'-二苯基磺酰基四甲酸二酐、二溴均苯四甲酸二酐、二环己基-3,4,3',4'-四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-环丁烷四羧酸二酐、三环[6.4.0.0(2,7)]十二烷-1,8,2,7-四羧酸二酐、二乙烯基三胺基五乙酸二酐、3-甲基戊二酐、3-(叔-丁基二甲基硅氧基)戊二酐、二萘嵌苯-3,4,9,10-四甲酸二酐、双酚A二酐、六氟二酐(6FDA)、SBIDA、N,N,N',N'-四(对氨基苯基)对苯二胺(TPDA)、螺芴二酐(SBFDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、二乙基蒽二酐(EA-DA)。
一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺,其为由一种或两种二氨基三蝶烯与两种四羧酸二酐聚合而成的共聚物,或由一种或两种二氨基三蝶烯衍生物与两种四羧酸二酐聚合而成的共聚物。
该共聚物的其中一种情况的化学反应方程式如下:
所述二氨基三蝶烯及其衍生物的化学结构式为:
其中,Ar是取代或者未取代的芳香族化合物,具体为苯、苯的衍生物、萘、萘的衍生物;X为Cl、Br或I;
所述四羧酸二酐包括但不仅限于4,4'-联苯四甲酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、乙二胺四乙酸二酐、1,2,3,4-环丁烷四甲酸二酐、3,4,9,10-苝四甲酸二酐、3,3',4,4'-二苯酮四甲酸二酐、均苯四甲酸二酐、1,2,4,5-环己烷四甲酸二酐、萘-1,4,5,8-四羧酸二酐、1,2,4,5-环己烷四甲酸二酐、1,6,7,12-四氯苝-3,4,9,10-四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,6,7,12-四氯四芳基四羧酸二酐、3-甲基戊二酐、meso-丁烷-1,2,3,4-四甲酸二酐、2-溴萘-1,4,5,8-四羧酸1,8,4,5-二酐、1,2,3,4-环戊烷四羧酸二酐、二乙烯基三胺基五乙酸二酐、2,6-二溴萘-1,4,5,8-四甲酸二酐、1,6,2,3-二酐-β-D-吡喃甘露糖、3,3',4,4'-二苯基磺酰基四甲酸二酐、二溴均苯四甲酸二酐、二环己基-3,4,3',4'-四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-环丁烷四羧酸二酐、三环[6.4.0.0(2,7)]十二烷-1,8,2,7-四羧酸二酐、二乙烯基三胺基五乙酸二酐、3-甲基戊二酐、3-(叔-丁基二甲基硅氧基)戊二酐、二萘嵌苯-3,4,9,10-四甲酸二酐、双酚A二酐、六氟二酐(6FDA)、SBIDA、N,N,N',N'-四(对氨基苯基)对苯二胺(TPDA)、螺芴二酐(SBFDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、二乙基蒽二酐(EA-DA)。
一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺的制备方法,其具体步骤为:将等摩尔的二氨基三蝶烯或其衍生物与四羧酸二酐溶于间甲酚中,并向反应溶液中加入异喹啉作为催化剂,引发共聚反应;反应结束后,将所得共聚物在乙醇中析出,并经过索氏提取除去聚合物中混有的间甲酚,得到聚酰亚胺。
优选,共聚反应的条件为:反应温度为80~180℃,反应时间为1~24h。
一种采用上述基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺制备而成的气体分离膜。其中,所述气体分离膜为均质膜或非均质膜;所述非均质膜包括中空纤维膜和复合膜的活性分离皮层。
该基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺具有优异的气体分离性能,具体来说,其对He、H2、O2、CO2四种气体透过率很高,而对N2、CH4的气体透过率很低;因此,将该聚酰亚胺制备成膜后可作为气体分离薄膜在沼气分离应用中能够有效从CH4和CO2的气体混合物中分离出CH4;由该种聚合物制备的膜材料可以在气体分离领域中有巨大的应用价值。例如,可以从空气中分别分理处N2和O2;在天然气的纯化过程中除去CO2,得到高纯度的CH4,在合成氨领域用于H2的回收。
附图说明
图1为本发明的实施例1中制备得到的2,7-二氨基三蝶烯产品;
图2为本发明的实施例2中制备得到的2,7-二氨基三蝶烯-6FDA聚酰亚胺薄膜置于图案上的对比示意图。
具体实施方式
下面结合附图及具体实施例对本发明做进一步的说明,但下述实施例绝非对本发明有任何限制。
实施例1
取10.0g三蝶烯和8.6g硝酸钾加入至500mL的圆底烧瓶中,然后加入200mL的乙腈,然后加入20mL的三氟乙酸酐,室温下反应12h。反应结束后,将所得溶液滴加至去离子水中析出固体,过滤得到硝基化产物;
取上述硝基化产物10g加入至300mL无水乙醇中,开启冷却回流;而后加入15mL的80%的水合肼和1500mg的靶炭催化剂,升温至120℃回流反应2h;
反应结束后,利用硅藻土过滤并收集滤液,然后加入200mL的去离子水搅拌产生沉淀,放置在冰箱中重结晶,过滤,真空烘箱80℃烘干;
采用体积比为3:1石油醚和乙酸乙酯的混合液作为调节展开剂,对所得烘干固体通过层析柱进行提纯,分别分离得到纯净的的2,7-二氨基三蝶烯和2,6-二氨基三蝶烯。
经测试,该2,7-二氨基三蝶烯:熔点(mp):251℃;TLC:Ethyl acetate/Petroliumether=1/1,Rf=0.3;核磁氢谱(1H NMR,400MHz,DMSO-d6):δ7.31(m,1H),7.24(m,1H),6.95(d,2H,J=7.72Hz),6.93(m,2H),6.64(d,2H,J=1.68Hz),6.11(dd,2H,J1=7.72Hz,J2=2Hz),5.11(s,1H),5.14(s,1H),4.82(s,4H);核磁碳谱(13C NMR,100MHz,DMSO-d6):δ147.73,146.56,146.17,146.06,134.32,125.02,124.54,123.66,122.85,111.03,109.29,53.77,51.45;红外光谱(FT-IR,wavenumber,cm-1):3460,3373,3205(m,N-H不对称伸缩振动),2939(s,C-H不对称伸缩振动),1618(s,N-H对称伸缩振动),1600(s,芳环C=C振动),1480,1456,1350(芳环C-H振动);高分辨质谱:[C20H17N2]+:理论值285.1386;测量值285.1400;元素分析:C21H22N2,理论量:C,84.48;H,5.67;N,9.85;测量值:C,84.43;H,5.81;N,9.85。可见,合成结果与设想一致。
实施例2
2,7-二氨基三蝶烯-6FDA聚酰亚胺的制备:
将实施例1制备的2,7-二氨基三蝶烯二氨284mg和六氟二酐444.2mg溶于1.2mL间甲酚中,然后向溶液中加入一滴(0.05mL)异喹啉作为催化剂,并升温至160℃,反应2h;反应结束后,将所得聚合物在乙醇溶液中析出,并经过索氏提取出去间甲酚,得到2,7二氨基三蝶烯-6FDA聚酰亚胺。
对2,7二氨基三蝶烯-6FDA聚酰亚胺进行核磁氢谱(1H NMR,400MHz,CDCl3)测试,测试结果为:δ7.96(d,2H,J=8.00Hz),7.88(s,2H),7.80(d,2H,J=7.60Hz),7.53(d,2H,J=8.00Hz),7.452(s,2H),7.41(m,2H),7.05(m,4H),5.53(d,2H,J=12.8Hz)。可见,合成结果与设想一致。
实施例3
2,7-二氨基三蝶烯-6FDA:2,6-二氨基三蝶烯-6FD(1:1)聚酰亚胺的制备:
将实施例1制备的2,7二氨基三蝶烯二氨142mg,2,6二氨基三蝶烯二氨142mg以及六氟二酐444.2mg溶于1.2mL间甲酚中,然后向溶液中加入一滴(0.05mL)异喹啉作为催化剂,并升温至160℃,反应2h;反应结束后,将得到的聚合物在乙醇溶液中析出,并经过索氏提取出去间甲酚,得到2,7-二氨基三蝶烯-6FDA:2,6-二氨基三蝶烯-6FD聚酰亚胺。
对2,7-二氨基三蝶烯-6FDA:2,6-二氨基三蝶烯-6FD聚酰亚胺进行核磁氢谱(1HNMR,400MHz,CDCl3)测试,测试结果为:δ7.98(d,2H,J=5.2Hz),7.88(s,2H),7.83(s,2H),7.53(d,2H,J=7.6Hz),7.43(d,4H,J=14.6Hz),7.04(m,4H),5.52(t,2H)。可见,合成结果与设想一致。
实施例4
13,14-二氟-2,7-二氨基三蝶烯-6FDA:13,14-二氟-2,7-二氨基三蝶烯-6FDA聚酰亚胺的制备:
13,14-二氟-2,7二氨基三蝶烯二氨160mg,13,14-二氟-2,6二氨基三蝶烯二氨160mg和六氟二酐444.2mg溶于1.2mL间甲酚中,然后向溶液中加入一滴(0.05mL)异喹啉作为催化剂,并升温至160℃,反应2h;反应结束后,将所得到的聚合物在乙醇溶液中析出,并经过索氏提取出去间甲酚,得到13,14-二氟-2,7-二氨基三蝶烯-6FDA:13,14-二氟-2,7-二氨基三蝶烯-6FDA聚酰亚胺。
对13,14-二氟-2,7-二氨基三蝶烯-6FDA:13,14-二氟-2,7-二氨基三蝶烯-6FDA聚酰亚胺进行核磁氢谱(1H NMR,400MHz,CDCl3)测试,测试结果为:δ7.98(s,2H),7.86(d,4H,J=11.1Hz),7.53(d,2H,J=6.6Hz),7.46(s,2H),7.21(s,2H),7.10(d,2H,J=8.0Hz),5.48(t,2H)。可见,合成结果与设想一致。
实施例5
2,7二氨基三蝶烯-6FDA:2,7二氨基三蝶烯-PMDA(1:1)聚酰亚胺的制备:
2,7二氨基三蝶烯二氨284mg、六氟二酐222mg和PMDA109 mg溶于1.2mL间甲酚中,然后向溶液中加入一滴异喹啉(0.05mL)作为催化剂,并升温至170℃,反应3h;反应结束后,将所得聚合物在乙醇溶液中析出,并经过索氏提取出去间甲酚,得到2,7二氨基三蝶烯-6FDA:2,7二氨基三蝶烯-PMDA(1:1)聚酰亚胺。
对2,7二氨基三蝶烯-6FDA:2,7二氨基三蝶烯-PMDA(1:1)进行核磁氢谱(1H NMR,400MHz,CDCl3)测试,测试结果为:δ8.75(s,2H)7.96(d,2H,J=8.00Hz),7.88(s,2H),7.80(d,2H,J=7.60Hz),7.53(d,4H,J=8.00Hz),7.452(s,4H),7.41(m,4H),7.05(m,8H),5.53(d,4H,J=12.8Hz)
从上述5个实施例中可以看出,本申请提出的基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺可以成功实现制备,得到新型的聚酰亚胺材料。
实施例6
对实施例2制备的2,7二氨基三蝶烯-6FDA聚酰亚胺进行气体分离性能的测试:取0.2g 2,7二氨基三蝶烯-6FDA聚酰亚胺溶于10mL氯仿中,通过溶剂挥发的方式制得厚度均匀的聚酰亚胺薄膜。
该聚酰亚胺薄膜的气体透过率如下表1所示。
表1:
实施例7
对实施例3制备的2,7二氨基三蝶烯-6FDA:2,6二氨基三蝶烯-6FDA(1:1)聚酰亚胺进行气体分离性能的测试:取0.2g 2,7二氨基三蝶烯-6FDA:2,6二氨基三蝶烯-6FDA(1:1)聚酰亚胺溶于10mL氯仿中,通过溶剂挥发的方式制得厚度均匀的聚酰亚胺薄膜。
该聚酰亚胺薄膜的气体透过率如下表2所示。
表2:
从表1和表2的测试结果可以看出,上述两种聚酰亚胺薄膜薄膜对He、H2、O2、CO2四种气体透过率很高,而对N2、CH4的气体透过率很低;因此,可以预见地,该气体分离薄膜在沼气分离应用中能够有效从CH4和CO2的气体混合物中分离出CH4;由该种聚合物制备的膜材料可以在气体分离领域中有巨大的应用价值。例如,可以从空气中分别分理处N2和O2;在天然气的纯化过程中除去CO2,得到高纯度的CH4,在合成氨领域用于H2的回收。
Claims (6)
1.一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺,其特征在于,其为由一种二氨基三蝶烯与一种四羧酸二酐聚合而成的共聚物,或由一种二氨基三蝶烯衍生物与一种四羧酸二酐聚合而成的共聚物;其中,共聚物的聚合度取值范围为1~10000;
所述二氨基三蝶烯及其衍生物的化学结构式为:
其中,Ar为苯、苯的衍生物、萘或萘的衍生物;X为Cl、Br或I;
所述四羧酸二酐为4,4'-联苯四甲酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、乙二胺四乙酸二酐、1,2,3,4-环丁烷四甲酸二酐、3,4,9,10-苝四甲酸二酐、3,3',4,4'-二苯酮四甲酸二酐、均苯四甲酸二酐、1,2,4,5-环己烷四甲酸二酐、萘-1,4,5,8-四羧酸二酐、1,2,4,5-环己烷四甲酸二酐、1,6,7,12-四氯苝-3,4,9,10-四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,6,7,12-四氯四芳基四羧酸二酐、3-甲基戊二酐、meso-丁烷-1,2,3,4-四甲酸二酐、2-溴萘-1,4,5,8-四羧酸1,8,4,5-二酐、1,2,3,4-环戊烷四羧酸二酐、二乙烯基三胺基五乙酸二酐、2,6-二溴萘-1,4,5,8-四甲酸二酐、1,6,2,3-二酐-β-D-吡喃甘露糖、3,3',4,4'-二苯基磺酰基四甲酸二酐、二溴均苯四甲酸二酐、二环己基-3,4,3',4'-四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-环丁烷四羧酸二酐、三环[6.4.0.0(2,7)]十二烷-1,8,2,7-四羧酸二酐、二乙烯基三胺基五乙酸二酐、3-甲基戊二酐、3-(叔-丁基二甲基硅氧基)戊二酐、二萘嵌苯-3,4,9,10-四甲酸二酐、双酚A二酐、六氟二酐、SBIDA、N,N,N',N'-四(对氨基苯基)对苯二胺、螺芴二酐、3,3',4,4'-二苯甲酮四甲酸二酐或二乙基蒽二酐。
2.一种基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺,其特征在于,其为由一种或两种二氨基三蝶烯与两种四羧酸二酐聚合而成的共聚物,或由一种或两种二氨基三蝶烯衍生物与两种四羧酸二酐聚合而成的共聚物;其中,共聚物的聚合度取值范围为1~10000;
所述二氨基三蝶烯及其衍生物的化学结构式为:
其中,Ar为苯、苯的衍生物、萘或萘的衍生物;X为Cl、Br或I;
所述四羧酸二酐选自4,4'-联苯四甲酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、乙二胺四乙酸二酐、1,2,3,4-环丁烷四甲酸二酐、3,4,9,10-苝四甲酸二酐、3,3',4,4'-二苯酮四甲酸二酐、均苯四甲酸二酐、1,2,4,5-环己烷四甲酸二酐、萘-1,4,5,8-四羧酸二酐、1,2,4,5-环己烷四甲酸二酐、1,6,7,12-四氯苝-3,4,9,10-四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,6,7,12-四氯四芳基四羧酸二酐、3-甲基戊二酐、meso-丁烷-1,2,3,4-四甲酸二酐、2-溴萘-1,4,5,8-四羧酸1,8,4,5-二酐、1,2,3,4-环戊烷四羧酸二酐、二乙烯基三胺基五乙酸二酐、2,6-二溴萘-1,4,5,8-四甲酸二酐、1,6,2,3-二酐-β-D-吡喃甘露糖、3,3',4,4'-二苯基磺酰基四甲酸二酐、二溴均苯四甲酸二酐、二环己基-3,4,3',4'-四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-环丁烷四羧酸二酐、三环[6.4.0.0(2,7)]十二烷-1,8,2,7-四羧酸二酐、二乙烯基三胺基五乙酸二酐、3-甲基戊二酐、3-(叔-丁基二甲基硅氧基)戊二酐、二萘嵌苯-3,4,9,10-四甲酸二酐、双酚A二酐、六氟二酐、SBIDA、N,N,N',N'-四(对氨基苯基)对苯二胺、螺芴二酐、3,3',4,4'-二苯甲酮四甲酸二酐、二乙基蒽二酐。
3.一种根据权利要求1或2所述的基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺的制备方法,其特征在于,步骤如下:将等摩尔的二氨基三蝶烯或其衍生物与四羧酸二酐溶于间甲酚中,并向反应溶液中加入异喹啉作为催化剂,引发共聚反应;反应结束后,将所得共聚物在乙醇中析出,并经过索氏提取除去聚合物中混有的间甲酚,得到聚酰亚胺。
4.根据权利要求3所述的基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺的制备方法,其特征在于,共聚反应的条件为:反应温度为80~180℃,反应时间为1~24h。
5.一种采用如权利要求1或2所述的基于二氨基三蝶烯及其衍生物制备的气体分离用聚酰亚胺制备而成的气体分离膜。
6.根据权利要求5所述的气体分离膜,其特征在于,所述气体分离膜为均质膜或非均质膜。
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