CN115999379A - A polyamide-imide hollow fiber gas separation membrane, preparation method and application - Google Patents
A polyamide-imide hollow fiber gas separation membrane, preparation method and application Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
技术领域technical field
本发明属于高分子膜法分离技术领域,具体涉及一种聚酰胺酰亚胺中空纤维气体分离膜、制备方法及应用。所述气体分离膜为一种兼具良好溶解性与机械强度的聚酰胺酰亚胺中空纤维气体分离膜。本发明涉及芳香族聚酰胺酰亚胺的制造和使用。本发明也涉及一种非对称结构中空纤维气体分离膜,该气体分离膜渗透性能较好,抗CO2塑化能力强,兼具良好溶解性与较高机械性能。本发明还涉及一种CO2气体分离方法,使用前述气体分离膜。The invention belongs to the technical field of polymer membrane method separation, and in particular relates to a polyamide-imide hollow fiber gas separation membrane, a preparation method and an application. The gas separation membrane is a polyamide-imide hollow fiber gas separation membrane with good solubility and mechanical strength. This invention relates to the manufacture and use of aromatic polyamideimides. The invention also relates to a hollow fiber gas separation membrane with an asymmetric structure. The gas separation membrane has good permeability, strong resistance to CO2 plasticization, good solubility and high mechanical performance. The present invention also relates to a CO2 gas separation method using the aforementioned gas separation membrane.
背景技术Background technique
随着全球变暖问题日益严重,如何减少CO2的排放成为环保方面的重要问题。而CO2化石燃料燃烧产生,如何净化烟气中的CO2成为控制CO2排放的关键。With the increasingly serious problem of global warming, how to reduce CO 2 emissions has become an important issue in environmental protection. As CO 2 is produced by fossil fuel combustion, how to purify the CO 2 in flue gas becomes the key to control CO 2 emission.
沼气主要成分为甲烷,但二氧化碳杂质的存在会降低朝气热值,增大运输成本,限制沼气应用(International Journal of Hydrogen Energy,2021,46(11):21318-21337)。The main component of biogas is methane, but the presence of carbon dioxide impurities will reduce the calorific value of the gas, increase transportation costs, and limit the application of biogas (International Journal of Hydrogen Energy, 2021, 46(11): 21318-21337).
上述两个问题的关键都在于二氧化碳的分离。近年来,膜技术在CO2分离领域发挥着越来越重要的作用。因不涉及相变,膜法分离二氧化碳所需能耗较低,可以有效满足日益增长的二氧化碳气体分离要求(ChemicalEngineering Journal,2021,411:128468)。The key to both of the above problems is the separation of carbon dioxide. In recent years, membrane technology has played an increasingly important role in the field of CO2 separation. Because no phase change is involved, the membrane method requires low energy consumption for the separation of carbon dioxide, which can effectively meet the growing demand for carbon dioxide gas separation (Chemical Engineering Journal, 2021, 411: 128468).
近年来,聚酰亚胺,特别是基于6FDA-DABA体系的聚酰亚胺气体分离膜因其较高的选择性,较好的热稳定和化学稳定性,在甲烷与二氧化碳分离领域受到广泛的研究与应用。但6FDA-DABA体系的聚酰亚胺分子量低,机械性能差,严重限制了其在中空纤维膜领域的应用。In recent years, polyimide, especially the polyimide gas separation membrane based on the 6FDA-DABA system, has been widely used in the field of methane and carbon dioxide separation due to its high selectivity, good thermal stability and chemical stability. Research and Application. However, the polyimide of the 6FDA-DABA system has low molecular weight and poor mechanical properties, which severely limit its application in the field of hollow fiber membranes.
通过引入芳香性高结晶性的二酐与二胺单体可以解决上述问题。但是,引入高刚性二胺单体同时也会降低聚合物的溶解性,只能通过酚类溶剂溶解聚合物,限制了聚酰亚胺中空纤维膜的应用范围。The above problems can be solved by introducing aromatic and highly crystalline dianhydride and diamine monomers. However, the introduction of highly rigid diamine monomers will also reduce the solubility of the polymer, and the polymer can only be dissolved by phenolic solvents, which limits the application range of polyimide hollow fiber membranes.
本发明通过加入酰氯单体制备出兼具良好溶解性与高机械强度的聚酰胺酰亚胺气体分离膜,解决了高机械强度聚酰亚胺溶解性差的问题。The invention prepares the polyamide-imide gas separation membrane with both good solubility and high mechanical strength by adding acid chloride monomer, and solves the problem of poor solubility of high mechanical strength polyimide.
聚酰胺酰亚胺(PAI)既具有聚酰胺的优良机械性能,又具有聚酰亚胺的高热稳定性和耐溶剂性。Suat Hong Goh研究团队证明了再相同操作条件下,聚酰胺酰亚胺的水蒸气分离能力远强于聚酰胺与聚酰亚胺(Journal ofMembraneScience,2021,318(1-2):217-226)。目前T通过聚酰胺酰亚胺制备气体分离膜的研究较少。Polyamide-imide (PAI) has both the excellent mechanical properties of polyamide and the high thermal stability and solvent resistance of polyimide. The research team of Suat Hong Goh proved that under the same operating conditions, the water vapor separation ability of polyamide-imide is much stronger than that of polyamide and polyimide (Journal of Membrane Science, 2021, 318(1-2): 217-226) . At present, there are few studies on the preparation of gas separation membranes by polyamide-imide.
为了满足工业和生活实际应用要求,合成兼具高渗透性、高选择性、抗塑化以及机械性能优异等性能的用于CO2分离的中空纤维气体分离膜。本发明制备了聚酰胺酰亚胺气体分离膜。这种气体分离膜具有良好的分离选择性,高机械强度和优异的抗塑化能力。In order to meet the requirements of industrial and practical applications in life, a hollow fiber gas separation membrane for CO2 separation is synthesized with high permeability, high selectivity, anti-plasticization and excellent mechanical properties. The invention prepares the polyamide-imide gas separation membrane. This gas separation membrane has good separation selectivity, high mechanical strength and excellent resistance to plasticization.
发明内容Contents of the invention
本发明公开了一种聚酰胺酰亚胺中空纤维气体分离膜、制备方法及应用。所述应用为一种兼具良好溶解性与机械性能的抗塑化中空纤维气体分离膜在烟气与沼气脱CO2中的应用。本发明通过在结晶性高的聚酰亚胺体系中引入溶解性好的酰氯基团,制成聚酰胺酰亚胺气体分离膜。该气体分离膜机械性能优异,CO2/CH4选择性高,在烟气与沼气脱CO2领域有着重要作用。The invention discloses a polyamide-imide hollow fiber gas separation membrane, a preparation method and an application. The application is an application of a plasticization-resistant hollow fiber gas separation membrane with good solubility and mechanical properties in the removal of CO 2 from flue gas and biogas. In the invention, the polyamide-imide gas separation membrane is prepared by introducing an acid chloride group with good solubility into the polyimide system with high crystallinity. The gas separation membrane has excellent mechanical properties and high CO 2 /CH 4 selectivity, and plays an important role in the field of CO 2 removal from flue gas and biogas.
为实现上述目的,本发明采用的技术方案为:To achieve the above object, the technical solution adopted in the present invention is:
本发明的聚酰亚胺气体分离膜,所述气体分离膜由聚酰胺酰亚胺聚合物制成,所述聚酰胺酰亚胺聚合物具有通式Ⅰ所示结构:The polyimide gas separation membrane of the present invention, the gas separation membrane is made of polyamide-imide polymer, and the polyamide-imide polymer has the structure shown in general formula I:
其中,n表示聚合物不同组分的聚合度,n为50-200的整数,x,y,z分别为0-100的整数,x+y+z=100(可选的,x、y和z均不为0);聚合物的重均分子量为100000-300000。例如,n为50、55、60、65、70、75、80、85、90、95、100、105、110、115、120、125、130、135、140、145、150、155、160、165、170、175、180、185、190、195或200。例如x为0、5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100。例如y为0、5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100。例如z为0、5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100。Wherein, n represents the degree of polymerization of different components of the polymer, n is an integer of 50-200, x, y, and z are respectively an integer of 0-100, and x+y+z=100 (optional, x, y and z is not 0); the weight average molecular weight of the polymer is 100000-300000. For example, n is 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195 or 200. For example, x is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100. For example, y is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100. For example, z is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100.
进一步地,聚合物的重均分子量为100000-300000,例如,聚合物的重均分子量为100000、110000、120000、130000、140000、150000、160000、170000、180000、190000、200000、210000、220000、230000、240000、250000、260000、270000、280000、290000或300000。Further, the weight average molecular weight of the polymer is 100000-300000, for example, the weight average molecular weight of the polymer is 100000, 110000, 120000, 130000, 140000, 150000, 160000, 170000, 180000, 190000, 200000, 210000, 220000 、230000 , 240000, 250000, 260000, 270000, 280000, 290000, or 300000.
通式(Ⅰ)中的R1包含以下结构的一种或多种:R in general formula (I) contains one or more of the following structures:
R2基团包含以下结构中的任意一种或多种:The R2 group contains any one or more of the following structures:
R3基团为以下基团的一种或几种:The R3 group is one or more of the following groups:
所述的聚酰胺酰亚胺中空纤维气体分离膜为一种兼具良好溶解性与机械强度的聚酰胺酰亚胺中空纤维气体分离膜,所述气体分离膜的制备方法中,将酰氯单体参与共聚,提高聚合物的溶解度,保障聚合反应成功进行。The polyamide-imide hollow fiber gas separation membrane is a polyamide-imide hollow fiber gas separation membrane with good solubility and mechanical strength. In the preparation method of the gas separation membrane, the acid chloride monomer Participate in copolymerization, improve the solubility of the polymer, and ensure the successful progress of the polymerization reaction.
如上所述的聚酰胺酰亚胺中空纤维气体分离膜的制备方法,采用两步法制备,首先合成聚酰胺与聚酰亚胺共聚物,将共聚物用于纺丝,之后对制得的中空纤维膜进行热处理,得到聚酰胺与聚酰亚胺共聚物中空纤维膜。The preparation method of the polyamide-imide hollow fiber gas separation membrane as mentioned above is prepared by a two-step method. First, a polyamide and a polyimide copolymer are synthesized, and the copolymer is used for spinning, and then the prepared hollow fiber The fiber membrane is heat-treated to obtain a polyamide-polyimide copolymer hollow fiber membrane.
进一步地,如上所述的制备方法,包括如下步骤:Further, the above-mentioned preparation method includes the following steps:
(1).在-10~-15℃条件下,将DABA,6FDA,结晶性二胺单体与结晶性二酐单体,酰氯单体溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为二胺单体:酰氯单体+二酐单体=1~1.1:1~1.1,溶液固含量为15-20wt%,在-10~-15℃中搅拌溶解;其中,单体由DABA,6FDA,结晶性二胺单体与结晶性二酐单体,酰氯单体组成,结晶性二胺单体为单体A,结晶性二酐单体为单体B,酰氯单体为单体C;(1). Dissolve DABA, 6FDA, crystalline diamine monomer, crystalline dianhydride monomer, and acid chloride monomer in N,N-dimethylacetamide (DMAC) at -10~-15°C , the molar ratio of monomers is diamine monomer:acyl chloride monomer+dianhydride monomer=1~1.1:1~1.1, the solid content of the solution is 15-20wt%, and it is stirred and dissolved at -10~-15°C; Among them, the monomer is composed of DABA, 6FDA, crystalline diamine monomer, crystalline dianhydride monomer, and acid chloride monomer. The crystalline diamine monomer is monomer A, and the crystalline dianhydride monomer is monomer B. The acid chloride monomer is monomer C;
(2).待单体完全溶于溶剂后,提高搅拌转速,聚合反应开始后,聚合物粘度上升,呈现凝胶状态;此时继续加入DMAC不断稀释溶液固含量,使固体重新溶解继续进行聚合反应,不断逐步加入DMAC,直到溶液整体不再呈现凝胶态,此时溶液固含量在5-8wt%;反应体系中二胺和二酐的摩尔比保持在1~1.1:1~1.1;(2). After the monomer is completely dissolved in the solvent, increase the stirring speed. After the polymerization reaction starts, the viscosity of the polymer increases and becomes a gel state; at this time, continue to add DMAC to continuously dilute the solid content of the solution to redissolve the solid and continue polymerization For reaction, add DMAC step by step until the solution is no longer in a gel state. At this time, the solid content of the solution is 5-8wt%; the molar ratio of diamine and dianhydride in the reaction system is kept at 1-1.1:1-1.1;
其中,所述单体A选自如下化合物中的任意一种或多种:Wherein, the monomer A is selected from any one or more of the following compounds:
2,2’-二(三氟甲基)二氨基联苯,2,2’,5,5’-四氯二苯胺,对二氨基联苯,4,4’-二氨基-2,2’-二甲基-1,1’-联苯,4,4’-二氨基-3,3’-二甲基联苯,2,3,5,6-四甲基-1,4-苯二胺,3,6-二氨基咔唑,3,6-二氨基-9-乙基咔唑,盐酸-4,6-二脒基-2-苯基吲哚,4,4’-二氨基二苯硫醚;2,2'-bis(trifluoromethyl)diaminobenzidine, 2,2',5,5'-tetrachlorodiphenylamine, p-diaminobenzidine, 4,4'-diamino-2,2' -Dimethyl-1,1'-biphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 2,3,5,6-tetramethyl-1,4-benzenediphenyl Amine, 3,6-diaminocarbazole, 3,6-diamino-9-ethylcarbazole, 4,6-diamidino-2-phenylindole hydrochloride, 4,4'-diaminodi Phenyl sulfide;
所述单体B选自如下化合物中的任意一种或多种:The monomer B is selected from any one or more of the following compounds:
所述单体C选自如下化合物中的任意一种或多种:The monomer C is selected from any one or more of the following compounds:
(3).溶液稀释后呈无色清澈透明状态,反应14~18h;升至室温,加入吡啶与乙酸酐化学关环,继续反应20~24h;控制溶液粘度,在100℃时,粘度在150~200泊;(3). After the solution is diluted, it is in a colorless, clear and transparent state. React for 14-18 hours; rise to room temperature, add pyridine and acetic anhydride to chemically close the ring, and continue the reaction for 20-24 hours; control the viscosity of the solution. At 100 ° C, the viscosity is 150 ~200 poises;
(4).控制溶液的旋转粘度,将所得聚合物溶液过滤,然后通过中空纤维膜纺丝喷嘴挤压,并且使挤压的中空纤维体通过N2气氛,随后在乙醇水溶液的凝结浴中、在-10~-5℃的温度下进行相转化制成湿纤维;将湿纤维在50~60℃温度下的乙醇中浸渍2~3小时,之后在65~75℃温度下的异辛烷中浸渍3~5小时以去除纤维中的溶剂;在100~120℃的温度下彻底干燥,之后在320-350℃下进行热处理,处理时间15~20h,得到成品中空纤维膜。(4). Control the rotational viscosity of the solution, filter the obtained polymer solution, then extrude through the hollow fiber membrane spinning nozzle, and make the extruded hollow fiber body pass through the N2 atmosphere, then in the coagulation bath of ethanol aqueous solution, Perform phase inversion at a temperature of -10 to -5°C to make wet fibers; soak the wet fibers in ethanol at a temperature of 50 to 60°C for 2 to 3 hours, and then in isooctane at a temperature of 65 to 75°C Immerse for 3-5 hours to remove the solvent in the fibers; thoroughly dry at a temperature of 100-120°C, and then heat-treat at 320-350°C for 15-20 hours to obtain a finished hollow fiber membrane.
具体地,本发明如上所述的聚酰胺酰亚胺中空纤维气体分离膜的制备方法,包括如下步骤:Specifically, the preparation method of the polyamide-imide hollow fiber gas separation membrane as described above of the present invention comprises the following steps:
(1).在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将单体DABA(3,5-二氨基苯甲酸),6FDA(六氟二酐),高结晶性二胺单体(单体A)与高结晶性二酐单体(单体B),酰氯单体(单体C)溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为二胺单体:酰氯单体+二酐单体=1:1,溶液固含量为15-20wt%,在-10℃中搅拌溶解。(1). Under the condition of -10°C, firstly purging in N 2 atmosphere for about 10 minutes, then monomer DABA (3,5-diaminobenzoic acid), 6FDA (hexafluorodianhydride), high crystallinity Diamine monomer (monomer A) and highly crystalline dianhydride monomer (monomer B), acid chloride monomer (monomer C) dissolved in N,N-dimethylacetamide (DMAC), the monomer The molar ratio is diamine monomer: acid chloride monomer + dianhydride monomer = 1:1, the solid content of the solution is 15-20wt%, and it is stirred and dissolved at -10°C.
(2).待单体完全溶于溶剂后,提高搅拌转速,聚合反应开始后,聚合物粘度上升,呈现凝胶状态。此时继续加入DMAC不断稀释溶液固含量,使固体重新溶解继续进行聚合反应,不断逐步加入DMAC,直到溶液整体不再呈现凝胶态,此时溶液固含量在5-8wt%。反应体系中二胺和二酐的摩尔比保持在1:1。(2). After the monomer is completely dissolved in the solvent, increase the stirring speed. After the polymerization reaction starts, the viscosity of the polymer increases and becomes a gel state. At this time, continue to add DMAC to continuously dilute the solid content of the solution to redissolve the solid to continue the polymerization reaction. Continuously add DMAC step by step until the whole solution no longer presents a gel state. At this time, the solid content of the solution is 5-8wt%. The molar ratio of diamine and dianhydride in the reaction system was kept at 1:1.
上述制备方法中,所述单体A选自如下化合物中的任意一种或多种:In the above preparation method, the monomer A is selected from any one or more of the following compounds:
2,2’-二(三氟甲基)二氨基联苯,2,2’,5,5’-四氯二苯胺,对二氨基联苯,4,4’-二氨基-2,2’-二甲基-1,1’-联苯,4,4’-二氨基-3,3’-二甲基联苯,2,3,5,6-四甲基-1,4-苯二胺,3,6-二氨基咔唑,3,6-二氨基-9-乙基咔唑,盐酸-4,6-二脒基-2-苯基吲哚,4,4’-二氨基二苯硫醚。2,2'-bis(trifluoromethyl)diaminobenzidine, 2,2',5,5'-tetrachlorodiphenylamine, p-diaminobenzidine, 4,4'-diamino-2,2' -Dimethyl-1,1'-biphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 2,3,5,6-tetramethyl-1,4-benzenediphenyl Amine, 3,6-diaminocarbazole, 3,6-diamino-9-ethylcarbazole, 4,6-diamidino-2-phenylindole hydrochloride, 4,4'-diaminodi Phenyl sulfide.
所述单体B选自如下化合物中的任意一种或多种:所述单体B选自如下化合物中的任意一种或多种:The monomer B is selected from any one or more of the following compounds: the monomer B is selected from any one or more of the following compounds:
所述单体C选自如下化合物中的任意一种或多种:The monomer C is selected from any one or more of the following compounds:
(3).溶液稀释后呈无色清澈透明状态,反应14h。升至室温,加入吡啶与乙酸酐化学关环,继续反应24h。控制溶液粘度,在100℃时,粘度在200泊左右。(3). After dilution, the solution was in a colorless, clear and transparent state, and reacted for 14 hours. Rise to room temperature, add pyridine and acetic anhydride to chemically close the ring, and continue the reaction for 24h. Control the solution viscosity, at 100°C, the viscosity is around 200 poise.
(4).用500目的金属丝网将一种聚酰亚胺溶液过滤,然后通过中空纤维膜纺丝喷嘴挤压,并且使挤压的中空纤维体通过N2气氛,随后在特定固含量(25wt%)乙醇水溶液的凝结浴中、在-5℃的温度下进行相转化制成湿纤维。将湿纤维在50℃温度下的乙醇中浸渍2小时,之后在70℃温度下的异辛烷中浸渍3小时以去除纤维中的溶剂。在100℃的温度下彻底干燥,之后在特定温度(320-350℃)下进行热处理,处理时间随温度提高从320℃20h到350℃1h得到成品中空纤维膜。(4). A polyimide solution is filtered with a 500-mesh wire mesh, then extruded through a hollow fiber membrane spinning nozzle, and the hollow fiber body of the extrusion is passed through N Atmosphere, then at a specific solid content ( 25wt%) ethanol aqueous coagulation bath at a temperature of -5°C to perform phase inversion to produce wet fibers. The wet fibers were immersed in ethanol at a temperature of 50°C for 2 hours, and then immersed in isooctane at a temperature of 70°C for 3 hours to remove the solvent in the fibers. Thoroughly dry at a temperature of 100°C, and then conduct heat treatment at a specific temperature (320-350°C). The treatment time increases from 320°C for 20 hours to 350°C for 1 hour to obtain a finished hollow fiber membrane.
本发明实施例中中空纤维膜的CO2通量与选择性的测定方法:The CO of the hollow fiber membrane in the embodiment of the present invention flux and selectivity assay method:
用大约10根中空纤维膜、一根不锈钢管和一种环氧树脂基粘合剂制成一种有效长度为20mm的透过性能评价元件,将该元件插入一个不锈钢容器中,以制成一个铅笔状组件。控制温度恒定为35℃,将纯CO2气体以固定的速率输入到该铅笔状组件的中空纤维的外部,以中空纤维膜元件以前的气体为上游气,通过元件的气体为下游气。控制上游气压不变,测量下游气压随时间的变化。通过公式计算得到CO2的渗透通量;以同样方式测试CH4的渗透通量。将二者相比得到CO2/CH4的选择性。About 10 hollow fiber membranes, a stainless steel tube and an epoxy resin-based adhesive are used to make a permeation performance evaluation element with an effective length of 20mm, and insert the element into a stainless steel container to make a Pencil-like components. Control the temperature to be constant at 35°C, input pure CO2 gas to the outside of the hollow fiber of the pencil-shaped module at a fixed rate, take the gas before the hollow fiber membrane element as the upstream gas, and the gas passing through the element as the downstream gas. Control the upstream air pressure to be constant, and measure the change of downstream air pressure with time. The permeation flux of CO 2 was calculated by the formula; the permeation flux of CH 4 was tested in the same way. Comparing the two yields the CO2 / CH4 selectivity.
将上述方法中的纯气体改为50%CH4含量的CH4/CO2混合气,以同样方法测试,得到混合气体通量,测定混合气体中两种气体的比例,即可得到混合气体中CO2/CH4的选择性。Change the pure gas in the above method to CH4 / CO2 mixed gas with 50% CH4 content, test in the same way to get the flux of the mixed gas, and measure the ratio of the two gases in the mixed gas to get the CO 2 /CH 4 selectivity.
本发明中的粘度为转动粘度。The viscosity in the present invention is rotational viscosity.
转动粘度(即旋转粘度)的测量:Measurement of rotational viscosity (ie rotational viscosity):
在100℃的温度下,使用转动粘度计(德国proRheo R180旋转粘度测试仪)(转子剪切速率:1.75/秒)来测量聚酰胺溶液的转动粘度。At a temperature of 100° C., the rotational viscosity of the polyamide solution was measured using a rotational viscometer (proRheo R180 rotational viscosity tester, Germany) (rotor shear rate: 1.75/sec).
本发明提供的由聚酰胺酰亚胺制得的中空纤维气体分离膜的应用,包括如下方面:The application of the hollow fiber gas separation membrane made by polyamide-imide provided by the invention comprises the following aspects:
由聚酰胺酰亚胺制得的中空纤维气体分离膜应用于工业等高污染烟气以及沼气的CO2脱除中。Hollow fiber gas separation membranes made of polyamideimide are used in the removal of CO2 from highly polluted flue gas and biogas such as in industry.
将大约1000-10000根长度适中的由本发明方法制备的中空纤维膜捆扎起来;将纤维束的两侧通过树脂固定在管板中,在纤维两端的一端处开口,保持进气,以该方法完成膜组件的组装。之后将膜组件连入装有混合气体进口、渗透气体的出口和非渗透气体出口的容器中,这样,连接中空纤维膜内部的空间与连接中空纤维膜外部的空间隔离。在这样的气体分离膜组件中,混合气体从混合气体导入口向中空纤维膜的内部或与外部连通的空间输入,但不限于此。当混合气体与中空纤维膜接触时,混合气体中所含的特定气体成分会选择性地透过膜。透过性气体从渗透性气体出口排出,未透过膜的非透过性气体从非透过性气体出口排出。以这种方式实现气体分离。通过此方式制备气体分离膜组件的元件。Bundle up about 1000-10000 hollow fiber membranes of moderate length prepared by the method of the present invention; fix both sides of the fiber bundles in the tube sheet through resin, open at one end of the fiber ends, and keep air intake, and complete in this way Assembly of membrane modules. The membrane module is then connected into a container equipped with a mixed gas inlet, a permeate gas outlet and a non-permeate gas outlet, so that the space connected to the inside of the hollow fiber membrane is isolated from the space connected to the outside of the hollow fiber membrane. In such a gas separation membrane module, the mixed gas is supplied from the mixed gas inlet to the inside of the hollow fiber membrane or a space communicating with the outside, but the present invention is not limited thereto. When the mixed gas comes into contact with the hollow fiber membrane, specific gas components contained in the mixed gas selectively permeate the membrane. The permeable gas is discharged from the permeable gas outlet, and the non-permeable gas that has not permeated the membrane is discharged from the non-permeable gas outlet. In this way gas separation is achieved. Elements of a gas separation membrane module are prepared in this way.
将元件插入不锈钢容器中制成膜分离组件在300psi压力下将待分离的烟气或沼气物料通入中空纤维气体分离膜外侧,在产品气出口得到脱CO2后的烟气或沼气。The element is inserted into a stainless steel container to make a membrane separation module. Under 300psi pressure, the flue gas or biogas material to be separated is passed to the outside of the hollow fiber gas separation membrane, and the flue gas or biogas after CO 2 removal is obtained at the product gas outlet.
本发明的有益结果是:Beneficial result of the present invention is:
(1)兼具良好溶解性与高机械性能的聚酰胺酰亚胺中空纤维气体分离膜。是一种CO2/CH4选择性高,抗CO2塑化能力优异气体分离膜;(1) Polyamide-imide hollow fiber gas separation membrane with good solubility and high mechanical properties. It is a gas separation membrane with high CO 2 /CH 4 selectivity and excellent resistance to CO 2 plasticization;
(2)制备的聚合物具有良好的溶解性和成膜性能,能在室温下溶解于NMP、DMF、DMAc、DMSO的一种或多种极性溶剂中;(2) The prepared polymer has good solubility and film-forming properties, and can be dissolved in one or more polar solvents of NMP, DMF, DMAc, DMSO at room temperature;
(3)得到的中空纤维气体分离膜具有良好的热稳定性和机械性能,玻璃化转变温度能达到350℃左右,拉伸强度能达到12MPa以上;(3) The obtained hollow fiber gas separation membrane has good thermal stability and mechanical properties, the glass transition temperature can reach about 350°C, and the tensile strength can reach above 12MPa;
(4)该气体分离膜应用于沼气与烟气的脱CO2上,具有优良气体选择性和渗透通量;(4) The gas separation membrane is applied to the removal of CO2 from biogas and flue gas, and has excellent gas selectivity and permeation flux;
(5)该气体分离膜应用于CO2分离膜上,在500psi压力下,经纯CO2气体处理100h后,渗透性降低15%左右,并未出现塑化现象,说明该气体分离膜可以在高进料压力下长期稳定运行。(5) The gas separation membrane is applied to the CO2 separation membrane. Under the pressure of 500psi, after being treated with pure CO2 gas for 100h, the permeability is reduced by about 15%, and there is no plasticization phenomenon, indicating that the gas separation membrane can be used in Long-term stable operation under high feed pressure.
附图说明Description of drawings
图1为实施例一制备的聚合物膜在纯气体条件,不同进料压力下的渗透通量与选择性变化图。Fig. 1 is a graph showing the permeation flux and selectivity changes of the polymer membrane prepared in Example 1 under pure gas conditions and different feed pressures.
图2为实施例四制备的聚合物膜在的热重曲线。Fig. 2 is the thermogravimetric curve of the polymer film prepared in Example 4.
图3为实施例四制备的聚合物膜与对比例的拉伸强度曲线。Fig. 3 is the tensile strength curve of the polymer film prepared in Example 4 and the comparative example.
图4为实施例四所制备聚合物的溶解情况。Fig. 4 is the dissolution situation of the polymer prepared in embodiment four.
具体实施方式Detailed ways
下面通过具体实施例对本发明的技术方案进行详细说明,但应该明确提出这些实施例用于举例说明,但是不解释为限制本发明的范围。The technical solutions of the present invention will be described in detail below through specific examples, but these examples should be clearly set forth for illustration, but are not interpreted as limiting the scope of the present invention.
实施例一:Embodiment one:
(1).在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,3,3’,4,4’-联苯四甲酸二酐(BPDA),2,2’-二(三氟甲基)二氨基联苯(TFDB)溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为TFDB:DABA:6FDA:BPDA:TPC=4:6:2:2:6,溶液固含量为20wt%,在-10℃条件下搅拌溶解。(1). Under the condition of -10°C, first purging in N 2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 3,3',4,4'-biphenyl Tetracarboxylic dianhydride (BPDA), 2,2'-bis(trifluoromethyl)diaminobiphenyl (TFDB) dissolved in N,N-dimethylacetamide (DMAC), the molar ratio of monomers is TFDB : DABA: 6FDA: BPDA: TPC = 4: 6: 2: 2: 6, the solid content of the solution is 20wt%, stirred and dissolved at -10°C.
(2).待单体完全溶于溶剂后,提高搅拌转速,聚合反应开始后,聚合物粘度快速上升,呈现凝胶状态。此时继续加入DMAC不断稀释溶液固含量,使固体重新溶解继续进行聚合反应,不断逐步加入DMAC,直到溶液整体不再呈现凝胶态,此时溶液固含量在8wt%。(2). After the monomer is completely dissolved in the solvent, increase the stirring speed. After the polymerization reaction starts, the viscosity of the polymer rises rapidly and becomes a gel state. At this time, continue to add DMAC to continuously dilute the solid content of the solution to redissolve the solid to continue the polymerization reaction. Continuously add DMAC step by step until the solution as a whole no longer presents a gel state. At this time, the solid content of the solution is 8 wt%.
(3).溶液稀释后呈无色清澈透明状态,反应14h。升至室温,加入二酐单体总摩尔数1.1倍的吡啶与二酐单体总摩尔数10倍的乙酸酐化学关环,继续反应24h。控制溶液粘度,在100℃时,粘度在200泊左右。得到聚合物,聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。(3). After dilution, the solution was in a colorless, clear and transparent state, and reacted for 14 hours. Rise to room temperature, add pyridine with 1.1 times the total moles of dianhydride monomers and acetic anhydride with 10 times the total moles of dianhydride monomers for chemical ring closure, and continue the reaction for 24 hours. Control the solution viscosity, at 100°C, the viscosity is around 200 poise. The obtained polymer has a weight average molecular weight of about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
(4).用500目的金属丝网将所得聚合物溶液过滤,然后通过中空纤维膜纺丝喷嘴(1000μm圆形孔径,300μm圆形孔缝宽,350μm中心孔直径)挤压,并且使挤压的中空纤维体通过N2气氛,随后在特定固含量(25%)乙醇水溶液的凝结浴中、在-5℃的温度下进行相转化制成湿纤维。将湿纤维在50℃温度下的乙醇中浸渍2小时,之后在70℃温度下的异辛烷中浸渍3小时以去除纤维中的溶剂。在100℃的温度下彻底干燥,之后在特定温度(350℃)下进行热处理,处理10h制得约500μm的外径尺寸,约400μm的内径尺寸,约70μm的膜厚度的中空纤维膜。(4). The gained polymer solution is filtered with a 500-mesh wire mesh, then extruded through a hollow fiber membrane spinning nozzle (1000 μm circular aperture, 300 μm circular aperture slit width, 350 μm center hole diameter), and the extrusion The hollow fiber body was passed through N2 atmosphere, followed by phase inversion in a coagulation bath of ethanol aqueous solution with a specific solid content (25%) at a temperature of -5 °C to make a wet fiber. The wet fibers were immersed in ethanol at a temperature of 50°C for 2 hours, and then immersed in isooctane at a temperature of 70°C for 3 hours to remove the solvent in the fibers. Thoroughly dry at a temperature of 100°C, and then perform heat treatment at a specific temperature (350°C) for 10 hours to obtain a hollow fiber membrane with an outer diameter of about 500 μm, an inner diameter of about 400 μm, and a membrane thickness of about 70 μm.
所得到中空纤维气体分离膜应用于烟气与沼气脱CO2中。The obtained hollow fiber gas separation membrane is applied to CO 2 removal from flue gas and biogas.
将大约105根长度适中的由本发明方法制备的中空纤维膜捆扎起来;这些中空纤维紧密堆积(填充率约为50%),将纤维束的两侧两端嵌入热固性聚合物环氧树脂中,固定在管板里,在纤维两端的一端处开口,保持进气,以该方法完成膜组件的组装。之后将膜组件连入装有混合气体进口、渗透气体的出口和非渗透气体出口的容器中,这样,连接中空纤维膜内部的空间与连接中空纤维膜外部的空间隔离。在这样的气体分离膜组件中,混合气体从混合气体导入口向中空纤维膜的内部或与外部连通的空间输入,但不限于此。当混合气体与中空纤维膜接触时,混合气体中所含的特定气体成分会选择性地透过膜。透过性气体从渗透性气体出口排出,未透过膜的非透过性气体从非透过性气体出口排出。以这种方式制得气体分离元件。About 105 moderate length hollow fiber membranes prepared by the method of the present invention are bundled; these hollow fibers are tightly packed (fill rate is about 50%), both ends of the fiber bundle are embedded in thermosetting polymer epoxy resin, fixed In the tube sheet, there is an opening at one end of the two ends of the fiber to keep the air in, and the assembly of the membrane module is completed in this way. The membrane module is then connected into a container equipped with a mixed gas inlet, a permeate gas outlet and a non-permeate gas outlet, so that the space connected to the inside of the hollow fiber membrane is isolated from the space connected to the outside of the hollow fiber membrane. In such a gas separation membrane module, the mixed gas is supplied from the mixed gas inlet to the inside of the hollow fiber membrane or a space communicating with the outside, but the present invention is not limited thereto. When the mixed gas comes into contact with the hollow fiber membrane, specific gas components contained in the mixed gas selectively permeate the membrane. The permeable gas is discharged from the permeable gas outlet, and the non-permeable gas that has not permeated the membrane is discharged from the non-permeable gas outlet. In this way a gas separation element is produced.
将元件插入不锈钢容器中制成膜分离组件在300psi压力下将待分离的烟气或沼气物料通入中空纤维气体分离膜外部孔侧,在产品气出口得到脱CO2后的烟气或沼气。The element is inserted into a stainless steel container to make a membrane separation module. Under the pressure of 300psi, the flue gas or biogas material to be separated is passed into the outer hole side of the hollow fiber gas separation membrane, and the flue gas or biogas after CO 2 removal is obtained at the product gas outlet.
实施例二:Embodiment two:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA(3,5-二氨基苯甲酸),对苯二甲酰氯(TPC),6FDA,3,3’,4,4’-联苯四甲酸二酐(BPDA),2,2’-二(三氟甲基)二氨基联苯(TFDB)溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为TFDB:DABA:BPDA:6FDA:TPC=3:7:2:2:6,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, first purging in N 2 atmosphere for about 10 minutes, then DABA (3,5-diaminobenzoic acid), terephthaloyl chloride (TPC), 6FDA, 3,3',4 , 4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis(trifluoromethyl)diaminobiphenyl (TFDB) dissolved in N,N-dimethylacetamide (DMAC), mono The molar ratio of the body is TFDB: DABA: BPDA: 6FDA: TPC = 3: 7: 2: 2: 6, the solid content of the solution is 20wt%, and it is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例三:Embodiment three:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,2,2’,5,5’-四氯二苯胺溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为2,2’,5,5’-四氯二苯胺:DABA:6FDA:TPC=4:6:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purged under N2 atmosphere for about 10 minutes, then dissolved DABA, terephthaloyl chloride (TPC), 6FDA, 2,2',5,5'-tetrachlorodiphenylamine in In N,N-dimethylacetamide (DMAC), the molar ratio of monomers is 2,2',5,5'-tetrachlorodiphenylamine:DABA:6FDA:TPC=4:6:3:7, the solution The solid content is 20wt%, and it is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例四:Embodiment four:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,2,2’,5,5’-四氯二苯胺溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为2,2’,5,5’-四氯二苯胺:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purged under N2 atmosphere for about 10 minutes, then dissolved DABA, terephthaloyl chloride (TPC), 6FDA, 2,2',5,5'-tetrachlorodiphenylamine in In N,N-dimethylacetamide (DMAC), the molar ratio of monomers is 2,2',5,5'-tetrachlorodiphenylamine:DABA:6FDA:TPC=3:7:3:7, the solution The solid content is 20wt%, and it is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例五:Embodiment five:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,对二氨基联苯溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为二氨基联苯溶解:DABA:6FDA:TPC=4:6:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purging in N 2 atmosphere for about 10 minutes, then dissolve DABA, terephthaloyl chloride (TPC), 6FDA, p-diaminobenzidine in N,N-dimethylacetamide In (DMAC), the molar ratio of the monomers is diaminobiphenyl dissolved: DABA: 6FDA: TPC = 4: 6: 3: 7, the solid content of the solution is 20wt%, and the solution is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例六:Embodiment six:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,对二氨基联苯溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为对二氨基联苯:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purging in N 2 atmosphere for about 10 minutes, then dissolve DABA, terephthaloyl chloride (TPC), 6FDA, p-diaminobenzidine in N,N-dimethylacetamide In (DMAC), the molar ratio of the monomers is p-diaminobiphenyl:DABA:6FDA:TPC=3:7:3:7, the solid content of the solution is 20wt%, and it is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例七:Embodiment seven:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,1,2,4,5-均苯四甲酸二酐(PMDA),对苯二甲酰氯(TPC),6FDA,4,4’-二氨基-2,2’-二甲基-1,1’-联苯溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为4,4’-二氨基-2,2’-二甲基-1,1’-联苯:DABA:6FDA:PMDA:TPC=4:6:2:2:6,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, first purging in N 2 atmosphere for about 10 minutes, then DABA, 1,2,4,5-pyromellitic dianhydride (PMDA), terephthaloyl chloride (TPC), 6FDA, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl dissolved in N,N-dimethylacetamide (DMAC), the molar ratio of the monomer is 4, 4'-diamino-2,2'-dimethyl-1,1'-biphenyl: DABA: 6FDA: PMDA: TPC = 4: 6: 2: 2: 6, the solid content of the solution is 20wt%, in- Stir to dissolve at 10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例八:Embodiment eight:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,4,4’-二氨基-2,2’-二甲基-1,1’-联苯溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为4,4’-二氨基-2,2’-二甲基-1,1’-联苯:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purging under N2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 4,4'-diamino-2,2'-dimethyl -1,1'-biphenyl dissolved in N,N-dimethylacetamide (DMAC), the molar ratio of monomers is 4,4'-diamino-2,2'-dimethyl-1,1 '-biphenyl: DABA: 6FDA: TPC = 3:7:3:7, the solid content of the solution is 20wt%, and the solution is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例九:Embodiment nine:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,4,4’-二氨基-3,3’-二甲基联苯溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为4,4’-二氨基-3,3’-二甲基联苯:DABA:6FDA:TPC=4:6:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purging under N2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 4,4'-diamino-3,3'-dimethyl Biphenyl is dissolved in N,N-dimethylacetamide (DMAC), and the molar ratio of monomers is 4,4'-diamino-3,3'-dimethylbiphenyl: DABA: 6FDA: TPC = 4 :6:3:7, the solid content of the solution is 20wt%, stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十:Embodiment ten:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,4,4’-二氨基-3,3’-二甲基联苯溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为4,4’-二氨基-3,3’-二甲基联苯:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purging under N2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 4,4'-diamino-3,3'-dimethyl Biphenyl is dissolved in N,N-dimethylacetamide (DMAC), and the molar ratio of monomers is 4,4'-diamino-3,3'-dimethylbiphenyl: DABA: 6FDA: TPC = 3 :7:3:7, the solid content of the solution is 20wt%, stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十一:Embodiment eleven:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,1,2,4,5-均苯四甲酸二酐(PMDA),2,3,5,6-四甲基-1,4-苯二胺溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为2,3,5,6-四甲基-1,4-苯二胺:DABA:6FDA:PMDA:TPC=4:6:2:2:6,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, first purging in N 2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 1,2,4,5-pyromellitic dianhydride (PMDA ), 2,3,5,6-tetramethyl-1,4-phenylenediamine dissolved in N,N-dimethylacetamide (DMAC), the molar ratio of monomers is 2,3,5,6 -Tetramethyl-1,4-phenylenediamine: DABA: 6FDA: PMDA: TPC = 4: 6: 2: 2: 6, the solution has a solid content of 20 wt%, and is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十二:Embodiment 12:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,2,3,5,6-四甲基-1,4-苯二胺溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为2,3,5,6-四甲基-1,4-苯二胺胺:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, first purging in N 2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 2,3,5,6-tetramethyl-1,4- Phenylenediamine is dissolved in N,N-dimethylacetamide (DMAC), and the molar ratio of monomers is 2,3,5,6-tetramethyl-1,4-phenylenediamine: DABA: 6FDA: TPC=3:7:3:7, the solid content of the solution is 20wt%, stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十三:Embodiment thirteen:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,3,6-二氨基咔唑溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为3,6-二氨基咔唑:DABA:6FDA:TPC=4:6:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purging under N2 atmosphere for about 10 minutes, then dissolving DABA, terephthaloyl chloride (TPC), 6FDA, 3,6-diaminocarbazole in N,N-dimethyl In DMAC, the molar ratio of monomers is 3,6-diaminocarbazole: DABA: 6FDA: TPC = 4: 6: 3: 7, the solid content of the solution is 20wt%, at -10°C Stir to dissolve. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十四:Embodiment 14:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,3,6-二氨基咔唑溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为3,6-二氨基咔唑溶:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purging under N2 atmosphere for about 10 minutes, then dissolving DABA, terephthaloyl chloride (TPC), 6FDA, 3,6-diaminocarbazole in N,N-dimethyl In DMAC, the molar ratio of the monomer is 3,6-diaminocarbazole solution: DABA: 6FDA: TPC = 3:7:3:7, the solid content of the solution is 20wt%, at -10°C Stir to dissolve. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十五:Embodiment fifteen:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,3,6-二氨基-9-乙基咔唑溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为3,6-二氨基-9-乙基咔唑:DABA:6FDA:TPC=4:6:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purged under N2 atmosphere for about 10 minutes, then dissolved DABA, terephthaloyl chloride (TPC), 6FDA, 3,6-diamino-9-ethylcarbazole in N , In N-dimethylacetamide (DMAC), the molar ratio of monomers is 3,6-diamino-9-ethylcarbazole: DABA: 6FDA: TPC = 4: 6: 3: 7, the solid content of the solution It was 20wt%, stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十六:Embodiment sixteen:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,3,3’,4,4’-联苯四甲酸二酐(BPDA),3,6-二氨基-9-乙基咔唑溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为3,6-二氨基-9-乙基咔唑:DABA:6FDA:BPDA:TPC=3:7:2:2:6,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purging under N2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,6-diamino-9-ethylcarbazole dissolved in N,N-dimethylacetamide (DMAC), the molar ratio of the monomer is 3,6-diamino-9-ethyl Carbazole: DABA: 6FDA: BPDA: TPC = 3: 7: 2: 2: 6, the solid content of the solution is 20 wt%, and the solution is stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十七:Embodiment seventeen:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,4,4’-二氨基二苯硫醚溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为4,4’-二氨基二苯硫醚:DABA:6FDA:TPC=4:6:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purging under N 2 atmosphere for about 10 minutes, then dissolve DABA, terephthaloyl chloride (TPC), 6FDA, 4,4'-diaminodiphenyl sulfide in N,N - In dimethylacetamide (DMAC), the molar ratio of monomers is 4,4'-diaminodiphenyl sulfide: DABA: 6FDA: TPC = 4: 6: 3: 7, and the solid content of the solution is 20 wt%, Stir to dissolve at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十八:Embodiment eighteen:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,4,4’-二氨基二苯硫醚溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为4,4’-二氨基二苯硫醚:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10℃, firstly purging under N 2 atmosphere for about 10 minutes, then dissolve DABA, terephthaloyl chloride (TPC), 6FDA, 4,4'-diaminodiphenyl sulfide in N,N - In dimethylacetamide (DMAC), the molar ratio of monomers is 4,4'-diaminodiphenyl sulfide: DABA: 6FDA: TPC = 3: 7: 3: 7, and the solid content of the solution is 20 wt%, Stir to dissolve at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例十九:Embodiment nineteen:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,1,2,4,5-均苯四甲酸二酐(PMDA),盐酸-4,6-二脒基-2-苯基吲哚溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为盐酸-4,6-二脒基-2-苯基吲哚:DABA:6FDA:PMDA:TPC=4:6:2:2:6,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, first purging in N 2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 1,2,4,5-pyromellitic dianhydride (PMDA ), hydrochloric acid-4,6-diamidino-2-phenylindole was dissolved in N,N-dimethylacetamide (DMAC), and the molar ratio of the monomer was hydrochloric acid-4,6-diamidino- 2-Phenylindole: DABA: 6FDA: PMDA: TPC=4:6:2:2:6, the solid content of the solution is 20wt%, stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
实施例二十:Embodiment 20:
在-10℃条件下,首先在N2氛围下吹扫10分钟左右,之后将DABA,对苯二甲酰氯(TPC),6FDA,盐酸-4,6-二脒基-2-苯基吲哚溶解于N,N-二甲基乙酰胺(DMAC)中,单体的摩尔比例为盐酸-4,6-二脒基-2-苯基吲哚:DABA:6FDA:TPC=3:7:3:7,溶液固含量为20wt%,在-10℃条件下搅拌溶解。其余实验步骤以及应用步骤同实施例一。聚合物重均分子量约250000。n表示所述聚合物不同组分的聚合度,n约为200。Under the condition of -10°C, firstly purging under N2 atmosphere for about 10 minutes, then DABA, terephthaloyl chloride (TPC), 6FDA, 4,6-diamidino-2-phenylindole hydrochloride Dissolved in N,N-dimethylacetamide (DMAC), the molar ratio of the monomer is hydrochloric acid-4,6-diamidino-2-phenylindole:DABA:6FDA:TPC=3:7:3 : 7, the solid content of the solution is 20wt%, stirred and dissolved at -10°C. The remaining experimental steps and application steps are the same as in Example 1. The weight average molecular weight of the polymer is about 250,000. n represents the degree of polymerization of the different components of the polymer, and n is about 200.
对比例:Comparative example:
本例以6FDA-DABA体系聚合物作为对比例:在室温环境下,将DABA与6FDA溶解于对氯苯酚中,单体的摩尔比例为6FDA:DABA=1:1,溶液固含量为18wt%。其余实验步骤以及应用步骤同实施例一。This example uses the 6FDA-DABA system polymer as a comparative example: at room temperature, DABA and 6FDA are dissolved in p-chlorophenol, the molar ratio of the monomers is 6FDA:DABA=1:1, and the solid content of the solution is 18wt%. The remaining experimental steps and application steps are the same as in Example 1.
表1为全部实施例与对比例制备的聚合物膜性能的对比。表1显示了不同实施例与对比例的气体渗透性能。可以看出,与纯6FDA-DABA体系相比,加入酰氯单体和芳香性单体后,可以做到在维持选择性在较高水平的同时,气体分离膜的渗透通量大幅提高。Table 1 is a comparison of the properties of polymer films prepared in all examples and comparative examples. Table 1 shows the gas permeation properties of different examples and comparative examples. It can be seen that, compared with the pure 6FDA-DABA system, the permeation flux of the gas separation membrane can be greatly increased while maintaining the selectivity at a high level after adding the acid chloride monomer and the aromatic monomer.
图1为实施例一制备的聚合物膜在纯气体条件,不同进料压力下的渗透通量与选择性变化图。由图1可以看出,增加酰氯单体后的气体分离膜依然具有良好的抗塑化能力,在600psi进料压力下仍不会塑化,证明该膜可以在高进料压力下长期稳定运行。Fig. 1 is a graph showing the permeation flux and selectivity changes of the polymer membrane prepared in Example 1 under pure gas conditions and different feed pressures. It can be seen from Figure 1 that the gas separation membrane after adding acid chloride monomer still has good anti-plasticization ability, and it will not be plasticized under 600psi feed pressure, which proves that the membrane can operate stably for a long time under high feed pressure .
图2为实施例四制备的聚合物膜在的热重曲线。在图2的热重曲线中可清楚看到本发明的膜的耐高温性能,该膜在400℃以上才开始逐渐失重,说明本发明制得的膜可在400℃高温下保持稳定,可以满足几乎所有严苛的应用温度。Fig. 2 is the thermogravimetric curve of the polymer film prepared in Example 4. The high temperature resistance of the film of the present invention can be clearly seen in the thermogravimetric curve of Fig. 2, and the film begins to lose weight gradually above 400°C, indicating that the film prepared by the present invention can remain stable at a high temperature of 400°C and can meet Almost all severe application temperatures.
图3为实施例四制备的聚合物膜与对比例的拉伸强度曲线。图3说明加入酰氯后,膜的机械性能并未明显降低,可以保证绝大多数气体分离工况。Fig. 3 is the tensile strength curve of the polymer film prepared in Example 4 and the comparative example. Figure 3 shows that after the addition of acid chloride, the mechanical properties of the membrane are not significantly reduced, and most of the gas separation conditions can be guaranteed.
图4为实施例四所制备聚合物的溶解情况。图4展示了加入酰氯单体后聚合物的溶解情况,图中所用溶剂为DMAC,聚合物溶解性十分优异,避免了酚类溶剂的使用。Fig. 4 is the dissolution situation of the polymer prepared in embodiment four. Figure 4 shows the dissolution of the polymer after adding the acid chloride monomer. The solvent used in the figure is DMAC, and the solubility of the polymer is very good, avoiding the use of phenolic solvents.
实验过程中所用拉伸强度测试方法为国家标准:GB/T 1040.2-2006测试标准。所用测试仪器为CMT4502双柱落地电子万能试验机,生产厂家为上海捷沪仪器仪表有限公司。测试过程为单根中空纤维膜拉伸测试,测试中的拉伸速度为50mm/分钟。The tensile strength test method used in the experiment is the national standard: GB/T 1040.2-2006 test standard. The test instrument used is CMT4502 double-column floor-standing electronic universal testing machine, and the manufacturer is Shanghai Jiehu Instrument Co., Ltd. The test process is a tensile test of a single hollow fiber membrane, and the tensile speed in the test is 50 mm/min.
表1Table 1
本发明未详细阐述部分属于本领域技术人员的公知技术。以上所述的实施例仅是对本发明的优选实施方式进行描述,优选实施例并没有详尽叙述所有的细节,也不限制该发明仅为所述的具体实施方式。在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。Parts not described in detail in the present invention belong to the known techniques of those skilled in the art. The above-mentioned embodiments are only descriptions of the preferred implementations of the present invention, and the preferred embodiments do not exhaustively describe all the details, nor limit the invention to the described specific implementations. Without departing from the design spirit of the present invention, various modifications and improvements to the technical solution of the present invention by those skilled in the art shall fall within the scope of protection determined by the claims of the present invention.
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