CN109153783B - 高渗透性聚酰亚胺膜:通过uv处理,气体选择性提高 - Google Patents
高渗透性聚酰亚胺膜:通过uv处理,气体选择性提高 Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 76
- 239000004642 Polyimide Substances 0.000 claims abstract description 68
- 239000007789 gas Substances 0.000 claims abstract description 53
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 14
- 229920006254 polymer film Polymers 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920005597 polymer membrane Polymers 0.000 claims description 9
- UFFBMTHBGFGIHF-UHFFFAOYSA-N (2,6-Me2C6H3)NH2 Natural products CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 14
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000001294 propane Substances 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 238000000926 separation method Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HHAVHBDPWSUKHZ-UHFFFAOYSA-N propan-2-ol;propan-2-one Chemical compound CC(C)O.CC(C)=O HHAVHBDPWSUKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- AIIPIXSXYANFAP-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1=CC(C)(N)C(N)C(C)=C1 AIIPIXSXYANFAP-UHFFFAOYSA-N 0.000 description 1
- -1 3 equivalents) Chemical compound 0.000 description 1
- QUACYTKJOFAODG-UHFFFAOYSA-N 4-[(4-amino-2,6-dimethylphenyl)methyl]-3,5-dimethylaniline Chemical compound CC1=CC(N)=CC(C)=C1CC1=C(C)C=C(N)C=C1C QUACYTKJOFAODG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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Abstract
提供聚酰亚胺膜,其提供极高的渗透性。聚酰亚胺不包含羰基或磺酰基官能团。这些膜用于分离气体,包括分离气体对,气体对包括二氧化碳/甲烷、氢气/甲烷和丙烯/丙烷以及其它气体混合物。膜选择性可以通过暴露于UV光而调整。
Description
优先权声明
该申请要求2014年9月26日提交的美国申请No.14/497,353的优先权,通过引用并入其全部内容。
发明背景
最常用于商业气体分离应用的膜为不对称聚合物膜且具有薄的无孔选择性皮层(其进行分离)。分离基于溶液-扩散机制。该机制包括渗透气体与膜聚合物的分子级相互作用。根据该溶液/扩散模型,分离给定气体对的膜性能通过两个参数测定:渗透系数(PA)和选择性(αA/B)。PA为气体通量与膜的选择性皮层厚度的乘积除以横跨膜的压差。αA/B为两种气体的渗透系数的比(αA/B=PA/PB),其中PA为更具渗透性的气体的渗透性,PB为较不具渗透性的气体的渗透性。气体可由于高溶解度系数、高扩散系数、或者由于两个系数都高而具有高渗透系数。一般而言,随着气体的分子尺寸增加,扩散系数降低而溶解度系数提高。在高性能聚合物膜中,需要高渗透性和选择性,因为较高的渗透性降低处理给定体积气体所需的膜面积尺寸,从而降低膜装置的资本成本,并且因为较高的选择性导致较高纯度的产物气体。这些新膜具有高的渗透性,且一些这些膜的选择性可借助在UV光的存在下交联而调整。
发明概述
本发明提供具有下式的聚酰亚胺聚合物和聚酰亚胺膜:
其中m和n独立地为10-500的整数且比为1:10-10:1。
在本发明一些实施方案中,该聚酰亚胺膜为UV处理的。
本发明进一步提供从气体混合物中分离至少一种气体的方法,包括提供具有下式的UV处理的聚酰亚胺聚合物膜
其中m和n独立地为10-500的整数且比为1:10-10:1;使气体混合物接触UV处理的芳族聚酰亚胺膜的一侧以导致至少一种气体渗透所述膜;从聚酰亚胺膜的相反侧除去包含一部分渗透所述膜的所述至少一种气体的渗透气体组合物。
发明详述
本发明涉及聚酰亚胺气体分离膜,更特别地涉及具有高渗透性的新一类聚酰亚胺膜。具体而言,公开了大大超过商业聚酰亚胺膜的固有渗透性的具有高于430Barrer CO2和H2渗透性的改进聚酰亚胺膜。渗透性类似于U.S.Patent 8,613,362 B2中公开的热处理聚酰亚胺。然而,在这种情况下不要求热处理(其在制备膜中可能是有问题的)来实现这种高渗透性。
尽管本发明所述这些高渗透性聚酰亚胺的气体分离选择性是低的,但是它可以通过UV处理而显著提高。实际上,用UV处理可以实现对于CO2/CH4分离的高渗透性和选择性,如用于这些聚酰亚胺的膜致密膜的纯气体试验所证实的。对UV光的敏感还存在于薄膜复合膜中,其中所公开的聚酰亚胺为选择性层。Hayes的美国专利4,717,393和Liu等人的美国专利7,485,173公开了光化学交联芳族聚酰亚胺。在这些情况下,要求用UV光可交联的官能团,如羰基或磺酰基。然而,本发明所述高渗透性聚酰亚胺不包含用UV光可交联的官能团。
本发明公开的聚酰亚胺不包含这些羰基或磺酰基官能团。美国专利5,409,524记载了改进聚合物膜如聚砜、聚碳酸酯和聚苯乙烯膜的选择性的方法,不通过UV处理羰基或磺酰基,但要求将该膜加热至60-300℃的温度。此外,该专利中没有公开聚酰亚胺的UV和热处理。然而,UV处理期间不要求加热以实现本发明所述聚酰亚胺的高选择性。US 2006/0177740 Al公开了衍生自苯均四酸二酐(PMDA)和3,3’,5,5’-四甲基-4,4’-亚甲基二苯胺(TMMDA)的聚合物。该公开不包括含有2,4,6-三甲基-苯二胺(TMPDA)的聚合物。而且,该聚合物用于电池应用的聚酰亚胺基体电解质且不认为用作聚合物膜。
根据本发明制备的膜具有以下式。
其中m和n独立地为10-500的整数且比为1:10-10:1。
本发明涉及苯均四酸二酐(PMDA)与2,4,6-三甲基-1,3-苯二胺(TMPDA)和4,4’-亚甲基双(2,6-甲基苯胺)(TMMDA)在极性溶剂如二甲基乙酰胺(DMAc)或(NMP)溶剂中缩合反应以形成本发明所述聚酰亚胺。本发明所述缩合反应为两步骤反应,包括形成聚酰胺酸,之后溶液化学酰亚胺化过程。对于溶液化学酰亚胺化反应,乙酸酐用作脱水剂,吡啶用作酰亚胺化催化剂。典型的反应时间为在22℃下20小时。在第二步骤中,加入乙酸酐,之后加入吡啶,并将混合物加热至95℃2小时,然后冷却至室温。所得混合物然后用于制备聚酰亚胺膜,聚酰亚胺膜然后又用UV辐射处理以产生具有改进性能的聚酰亚胺膜。
实施例1:
合成聚酰亚胺1:聚(PMDA-TMPDA-TMMDA)(m=2,n=1)
由苯均四酸二酐(PMDA,3当量)、2,4,6-三甲基-1,3-苯二胺(TMPDA,2当量)和4,4’-亚甲基双(2,6-甲基苯胺)(TMMDA,1当量)在N,N-二甲基乙酰胺(DMAc)极性溶剂中通过包括形成聚酰胺酸、之后溶液化学酰亚胺化过程的两步骤方法合成芳族聚(苯均四酸二酐-2,4,6-三甲基-1,3-苯二胺-4,4’-亚甲基双(2,6-甲基苯胺))聚酰亚胺(聚(PMDA-TMPDA-TMMDA))。对于溶液化学酰亚胺化反应,乙酸用作脱水剂,吡啶用作酰亚胺化催化剂。
例如,在连接有机械搅拌器和回流冷凝器且具有氮气入口的干2L三颈圆底烧瓶中装入TMPDA(17.0g,2.00当量)、TMMDA(20.0g,1.00当量)和无水DMAc(380g),并剧烈搅拌该溶液。加入二酐PMDA(44.9g,3.00当量)。缓慢加入另外的DMAc(130g)。将反应容器用隔膜密封并在22℃下搅拌20小时。经5分钟将乙酸酐(43.2g)缓慢加入该粘性反应混合物中,之后一次性加入所有的吡啶(66.5g)。将反应加热至95℃2.5小时,然后冷却至室温。反应混合物沉淀至异丙醇:丙酮(1:1)溶液中以形成白色细纤维。在真空炉中在100℃下加热该白色固体两天。以几乎定量的收率分离聚合物。
实施例2:
合成聚酰亚胺2:聚(PMDA-TMPDA-TMMDA)(m=1,n=1)
由PMDA(2当量)、TMPDA(1当量)和TMMDA(1当量)在DMAc极性溶剂中通过包括形成聚酰胺酸、之后溶液化学酰亚胺化过程的两步骤方法合成芳族聚(苯均四酸二酐-2,4,6-三甲基-1,3-苯二胺-4,4’-亚甲基双(2,6-甲基苯胺))聚酰亚胺(聚(PMDA-TMPDA-TMMDA))。对于溶液化学酰亚胺化反应,乙酸用作脱水剂,吡啶用作酰亚胺化催化剂。
例如,在连接有机械搅拌器和回流冷凝器且具有氮气入口的干2L三颈圆底烧瓶中装入TMPDA(30.0g,1.00当量)、TMMDA(50.8g,1.00当量)和无水DMAc(775g),并剧烈搅拌该溶液。加入二酐PMDA(89.8g,2.00当量)。缓慢加入另外的DMAc(130g)。将反应用隔膜密封并在22℃下搅拌20小时。经5分钟将乙酸酐(86.4g)缓慢加入该粘性反应混合物中,之后一次性加入所有的吡啶(133g)。将反应加热至95℃2.5小时,然后冷却至室温。反应混合物沉淀至异丙醇:丙酮(1:1)溶液中以形成白色细纤维。在真空炉中在100℃下加热该白色固体两天。以几乎定量的收率分离聚合物。
实施例3:
制备聚(PMDA-TMPDA-TMMDA)聚酰亚胺聚合物膜
如下制备聚酰亚胺膜致密膜:将芳族聚(PMDA-TMPDA-TMMDA)聚酰亚胺溶于N-甲基吡咯烷酮(NMP,18%聚合物)中。过滤掺杂的聚酰亚胺,脱气一夜并用具有20mil的刀片间隙的刮刀涂到干净玻璃板上。将玻璃板上的膜加热至60℃保持6小时并在真空炉中在180℃下干燥48小时。在50℃下在689kPa(100psig)的纯气体进料压力下测试膜的CO2/CH4和H2/CH4分离。使膜在50℃下在254nm下在2cm下进行UV处理10分钟,随后再次在纯气体压力下测试。结果显示于表1中。
表1:用于CO2/CH4和H2/CH4分离a的聚(PMDA-TMPDA-TMMDA)的纯气体渗透测试结果
膜<sup>b</sup> | P<sub>CO2</sub>(Barrer) | P<sub>H2</sub>(Barrer) | α<sub>CO2/CH4</sub> | α<sub>H2/CH4</sub> |
聚酰亚胺-1 | 434.6 | 434.7 | 11.8 | 11.8 |
聚酰亚胺-1-UV 10分钟 | 114.6 | 342.8 | 33.7 | 100.8 |
聚酰亚胺-2 | 436.3 | 483.0 | 10.4 | 11.5 |
聚酰亚胺-2-UV 10分钟 | 117.7 | 365.0 | 45.3 | 140.4 |
a在50℃和690kPa(100psig)下测试PCO2、PCH4和PH2;
1Barrer=10-10cm3(STP)·cm/cm2·sec·cmHg
b聚酰亚胺1:PMDA:TMPDA:TMMDA(3:2:1);
聚酰亚胺2:PMDA-TMPDA:TMMDA(2:1:1).
实施例4:
制备聚(PMDA-TMPDA-TMMDA)聚酰亚胺薄-膜复合(TFC)膜
通过将0.8g实施例1中合成的聚酰亚胺1聚合物溶于由19.6g1,2,3-三氯-丙烷和19.6g二氯甲烷组成的溶剂混合物中而制备2wt%的聚酰亚胺1聚合物溶液。使用1微米级的过滤器过滤该溶液以除去任何不溶杂质并脱气一夜。在纯水浴的表面引入一滴聚酰亚胺1聚合物溶液。聚酰亚胺1溶液在水表面上展开同时溶剂蒸发以在水的表面上形成薄的聚合物膜。然后将水表面上的薄聚合物膜层压在低选择性、高渗透性多孔聚(醚砜)载体膜的表面上。在传统炉中在70℃下干燥所得TFC膜1小时。
实施例5:聚酰亚胺1TFC膜的UV处理
通过使膜经受一定距离的UV灯一定时间而制备UV处理的TFC聚酰亚胺1聚合物膜,时间基于所需分离性能选择。例如,由实施例3中得到的TFC聚酰亚胺1通过使用由UV灯产生的254nm波长UV光而暴露于UV辐射而制备一种UV处理的TFC聚酰亚胺1膜,膜表面距UV灯10cm(3.94英寸)且辐射时间为10分钟。用RTV615A/615B硅橡胶溶液滴涂TFC聚酰亚胺1膜的聚酰亚胺1层的表面。将该涂覆膜在通风橱内部在室温下干燥30分钟,然后在传统炉中在70℃下干燥1小时。
表2:聚酰亚胺1TFC膜用于的CO2/CH4混合气体渗透试验结果
膜 | P<sub>CO2</sub>/L(GPU) | α<sub>CO2/CH4</sub> |
聚酰亚胺1-TFC | 178 | 7.0 |
聚酰亚胺1-TFC-UV10分钟-2%RTV | 13.4 | 15.8 |
条件:在50℃,6895kPa(1000psig),10%CO2/90%CH4下试验;
具体实施方案
以下联系具体实施方案描述,应理解该描述意欲阐述本发明而不限制本说明书和权利要求书的范围。
本发明第一实施方案为具有下式的聚酰亚胺聚合物
其中m和n独立地为10-500的整数且比为1:10-10:1。本发明一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中m与n的比为1:5-5:1。本发明一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中聚酰亚胺膜包含具有上式的聚酰亚胺聚合物。本发明一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中聚酰亚胺聚合物为UV处理的。
本发明第二实施方案为从气体混合物中分离至少一种气体的方法,包括提供具有下式聚酰亚胺聚合物的UV处理的聚酰亚胺聚合物膜
其中m和n独立地为10-500的整数且比为1:10-10:1;使气体混合物与UV处理的聚酰亚胺聚合物膜的一侧接触以导致至少一种气体渗透过膜;从UV处理的聚酰亚胺聚合物膜相反侧除去包含一部分渗透过膜的至少一种气体的渗透气体组合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含二氧化碳和甲烷的混合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含氢气和甲烷的混合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含氦气和甲烷的混合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含至少一种挥发性有机化合物和至少一种大气气体的混合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含氮气和氢气的混合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含二氧化碳、氧气、氮气、水蒸气、硫化氢、氦气和甲烷的混合物。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中UV处理的聚酰亚胺聚合物膜包含强吸附至少一种气体的物种。本发明一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中气体混合物包含链烷烃和烯烃的混合物。
本发明第三实施方案为制备聚酰亚胺聚合物膜的方法,包括使苯均四酸二酐(PMDA)与2,4,6-三甲基-1,3-苯二胺(TMPDA)和4,4’-亚甲基双(2,6-甲基苯胺)(TMMDA)的混合物在极性溶剂中缩合反应以产生聚酰亚胺聚合物;然后由聚酰亚胺聚合物制备聚酰亚胺聚合物膜,并用UV辐射处理聚酰亚胺聚合物膜。本发明一个实施方案为从该段中第三实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中极性溶剂包含二甲基乙酰胺(DMAc)或(NMP)溶剂。本发明一个实施方案为从该段中第三实施方案开始的该段中先前实施方案中的一个、任何或者所有,其中缩合反应为两步骤反应,包括形成聚酰胺酸,之后溶液化学酰亚胺化过程。本发明一个实施方案为从该段中第三实施方案开始的该段中先前实施方案中的一个、任何或者所有,对于溶液化学酰亚胺化反应,乙酸酐用作脱水剂,吡啶用作酰亚胺化催化剂。
不进一步详细阐述,认为使用前述说明书,本领域技术人员能够最大程度地使用本发明并容易确定本发明的主要特征,而不偏离本发明精神和范围,对本发明作出各种改变和改进以适应各种应用和条件。所以,前述优选具体实施方案仅作为阐述目的,并不以任何方式限制公开的剩余部分,并意欲覆盖随附权利要求书范围内的各种改进和相当的配置。
在前文中,除非另外说明,所有温度以摄氏度表示,所有份和百分数以重量计。
Claims (7)
2.一种制备UV处理的聚酰亚胺聚合物膜的方法,包括:
a)使苯均四酸二酐(PMDA)与2,4,6-三甲基-1,3-苯二胺(TMPDA)和4,4’-亚甲基双(2,6-甲基苯胺)(TMMDA)的混合物在极性溶剂中缩合反应以产生聚酰亚胺聚合物;
b)然后由所述聚酰亚胺聚合物制备聚酰亚胺聚合物膜;和
c)用UV辐射处理所述聚酰亚胺聚合物膜。
5.根据权利要求4所述的方法,其中所述气体混合物选自由二氧化碳和甲烷的混合物;氢气和甲烷的混合物;氦气和甲烷的混合物;至少一种挥发性有机化合物和至少一种大气气体的混合物;氮气和氢气的混合物或链烷烃和烯烃的混合物组成的组。
6.根据权利要求4所述的方法,其中所述气体混合物包含二氧化碳、氧气、氮气、水蒸气、硫化氢、氦气和甲烷的混合物。
7.根据权利要求4所述的方法,其中所述UV处理的聚酰亚胺聚合物膜包含强吸附至少一种气体的物种。
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