CN1147418A - 新的磺化聚酰亚胺气体分离膜 - Google Patents
新的磺化聚酰亚胺气体分离膜 Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 35
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- 125000003118 aryl group Chemical group 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
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- 239000002253 acid Substances 0.000 claims description 9
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- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
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- 238000000502 dialysis Methods 0.000 description 2
- KTTMEMZAHMGIFI-UHFFFAOYSA-L dilithium;5-amino-2-[2-(4-amino-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical class [Li+].[Li+].[O-]S(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S([O-])(=O)=O KTTMEMZAHMGIFI-UHFFFAOYSA-L 0.000 description 2
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- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
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- GCAIEATUVJFSMC-UHFFFAOYSA-N benzenetetracarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 230000008676 import Effects 0.000 description 1
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- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- B01D53/22—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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
Abstract
由表现出所需的气体分离特性、良好的成膜性和所需的溶解性的磺化聚酰亚胺制备气体分离膜的方法。
Description
本发明涉及磺化聚酰亚胺聚合物的制备及其作为气体和蒸气分离膜的用途。
已报导，具有刚性主链结构、强的链-链相互作用和高的玻璃化温度的聚酰亚胺在气体分离应用中展现出良好的气体分离和渗透性质。美国专利4705540、4717393、4717394、5042993和5074891公开了这类芳族聚酰亚胺气体分离膜。聚酰亚胺一般可溶解于质子惰性的溶剂如N，N-二甲基乙酰胺和N-甲基吡咯烷酮中。某些聚酰亚胺还可溶解于二氯甲烷和间-甲酚中。其溶解性质使得聚酰亚胺适用于不对称气体分离膜的制备，但不那么适合复合气体分离膜的制备，后者通常需要温和、高挥发性溶剂如低沸点溶剂。
在本领域也已公开了大量改性聚酰亚胺聚合物。美国专利4705540和4717394公开了结构上在所有和胺官能团相邻的位置均有烷基取代基的刚性聚酰亚胺可以形成具有优良气体渗透性的膜。美国专利5042993公开了表现出高气体分离系数的表面改性的聚酰亚胺膜。含羧基的改性的聚酰亚胺的制备描述于美国专利5076816中。
磺化聚酰亚胺的制备报告于美国专利4574144中。其中并没有述及这种材料作为分离膜的用途。I.V.Vasil’eva等在Vysokomol.Soyed.，A14，No.1，143-149(1972)还报告了用磺化二胺和1，2，4，5苯四酸二酐进行磺化聚酰亚胺的制备。这种聚合物还能溶于温和溶剂如简单醇中，其在膜方面的应用没有评价。因此，在本领域仍存在着制备具有改善的分离/渗透性质和改善的溶解性的聚酰亚胺的需要。
因此本发明的一个目的制备具有宽可溶性包括在温和的低沸点溶剂体系如制备复合膜中最常用的醇中的可溶性的改性聚酰亚胺。
本发明的另一目的是制备具有改良的气体渗透和分离性质的改性聚酰亚胺。
针对这些目的，下面将详细描述本发明的情况，其新的特征将在所附在权利要求书中特别指出。
本发明的磺化聚酰亚胺聚合物展现出改善的可溶性，是良好的成膜材料并表现出改善的分离性质。这种磺化的聚酰亚胺对不对称和复合气体分离膜的制备特别有用。
本发明涉及用于下面通式的磺化聚酰亚胺进行气体分离膜的制造：
Ar1和Ar2是有机基团，所述Ar1和Ar2基团的至少约80％、最好至少约90％以上是芳族基团，包括其中所述的Ar1和Ar2基团基本上全为芳香族基团的情况，其聚酰亚胺主链中芳香环的至少一部分、最好至少5％含有磺酸基。芳族基团应理解为含至少一个芳香环的有机基团。所述磺酸基被定义为磺酸基-SO3H、成盐的磺酸基-SO3M、或磺酸酯基-SO2OR1。M是有机碱，铵离子，碱金属离子如K+、Na+或Li+(优选Li+)，碱土或过渡金属离子。R1是少于6个碳原子的烷基或芳基，优选甲基或乙基。大多数情况下，磺酸基与双官能的氨基Ar2相连。在优选的实施方案中，Ar1是由下面结构代表的芳族二酐基：式中x是-CH2-，
和z是
-O-，-S-，
-CH2-，-CHOH-，
或
和R1是脂族基，优选CH3或C2H5；n等于1至6。在一些实施方案中Ar1可以是这些基团的混合物。
Ar2是具有下式的芳族二胺部分：
式中R是SO3H、SO3M或SO2OR′基，R2是H、CH3、SO3H、SO3M、SO2OR、CF3、卤素或其混合物，其中至少一个R2为磺酸基。R和M见上面的定义。Y不存在，或者是-CH＝CH-，
-O-，-S-，
-CH2-，
R、R1和n和上面的定义相同。
本发明的磺化聚酰亚胺可通过几种方法合成。一种方法包括二酐和二胺的缩聚，其中单体单元的一个含磺酸、磺酸盐或磺酸酯等。另一方法包括芳族聚酰亚胺前体的直接磺化。
在本领域中聚酰亚胺的制备是为人熟知的。聚酰亚胺一般通过二步法制备，第一步为二酐和二胺反应制备出聚酰胺酸，第二步再将聚酰胺酸转化成聚酰亚胺。可用众多种的二酐和二胺来制备适用于本发明的聚酰亚胺。可被用于二酐和二胺反应的适合溶剂公开于美国专利3179634中。最好所述溶剂是二甲基乙酰胺、二甲基甲酰胺或二甲基亚砜。在聚酰胺酸通过二胺和二酐反应制备出来后，使用热转化法或化学转化法将聚酰胺酸转化成聚酰亚胺。如果需要转化成可溶的聚酰亚，最好在作为催化剂的三乙胺的存在下使用乙酸酐来将聚酰胺酸化学转化成聚酰亚胺。得到的聚酰亚胺通过适合的溶剂沉淀，并回收和干燥。本发明的磺化聚酰亚胺可遵循上述方法用二酐和含磺酸、磺酸盐或磺酸酯基的二胺单体来制备。带磺酸基的二胺单体的使用是特别优选的。在一优选的实施方案中，2，2-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和用磺酸基如4，4’-二氨基茋-2，2’-二磺酸的锂盐取代的芳族二胺反应。含磺酸基的共聚酰亚胺还可用二种或多种含磺酸基的二胺的混合物制备。在一实施例中， 2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和由4，4’-二氨基基茋-2，2’-二磺酸的锂盐和4，4’-二氨基-2，2’-二苯基二磺酸的锂盐组成的芳族二胺的混合物反应。磺化共聚酰亚胺还可通过刚性芳族二酐和磺化与未磺化的二胺的混合物的缩聚来制备。本发明的磺化聚酰亚胺的可溶性特征和气体渗透/分离性质可通过选择适合的单体和其结合方式来控制。
本发明的聚酰亚胺还通过使用磺化剂如氯磺酸、三氧化硫和三氧化硫复合物将特定的芳族聚酰亚胺前体直接磺化来制备。一般来说，这种磺化可通过将聚酰亚胺的溶液或悬浮液和磺化剂在一惰性溶剂体系中简单掺和来进行。制备本发明的磺化聚酰亚胺的可采用的磺化方法可参见E.E.Gilbert的“Sulfonation and Related Reactions”R.E.Krieger Publishing Co，Huntington，NY(1977)和H.Cerfontain的“Mechanistic Aspects of Aromatic Sulfonation and Desulfonation”Interscience Publishers，NY(1968)。本领域大家都知道在吸电子基团的存在下，芳环可被基本上失活而不能直接磺化。因此并不是所有在聚酰亚胺前体中的芳环均是同样易于磺化的。二胺单体单元的芳环的一般较易直接磺化。对本领域技术人员来说得容易选择带含反应性芳环架构的聚酰亚胺前体来通过直接磺化制备本发明的磺化聚合物，诸如用G.E.Plastics生产的商标为Ultem的商品2，2’-二(3，4’-二羧基苯基)六氟丙烷二酐(6FDA)和2，4，6-三甲基苯二胺或聚醚酰亚胺制备的聚酰亚胺的磺化。
优选的制备本发明的磺化聚酰亚胺的磺化方法包括和氯磺酸、三氧化硫或三氧化硫/三乙基磷酸盐复合物反应，其中该反应在低温下进行以限制聚合物降解。
在一般的磺化过程中，聚酰亚胺聚合物被溶解在惰性溶剂如二氯甲烷或氯仿中，反应混合物被冷却至10℃以下，最好是5℃以下，在剧烈搅拌下磺化剂被缓慢加入。所述聚酰亚胺可以受暴露于强酸或碱的影响，其中可能发生严重的降解和分子量的下降。业已发现如果所述反应在严格的无水条件下进行，并且在没有分离磺酸形态中间体的情况下将磺化聚酰亚胺产物在原处转化成盐形式。那么在磺化过程中聚酰亚胺的降解可被限制。盐形式的转化在磺化过程的最终进行，优选在降温条件下进行，最优选在5℃以下进行。所述中和通过导入适当的碱在剧烈搅拌下进行，碱的例子有有机碱、金属氢氧化物或金属氢氧化物与盐的混合物。碱的加入在pH达到约为7时中止。业已出乎意料地发现在这种中和条件下，聚合物降解的程度最大程度地受到限制。如此制备的成盐的磺化聚酰亚胺可经纯化并用于制备气体分离膜。通过在膜制备前或在最终的膜件中进行离子交换，这种成盐的磺化聚酰亚胺也可再转化成其它所需的反离子形式。
磺化聚酰亚胺的可溶性特征取决于取代的程度和反离子的性质。以离子交换容量IEC衡量的磺酸基的浓度可从低至0.1meq/g至高于3meq/g而各不同。优选的范围是0.5～3meq/gH+形式的干树脂。优选的反离子是碱金属和有机单官能的胺。最优选的反离子是锂离子。高浓度磺酸基的存在使得本发明的聚酰亚胺可溶于溶剂系统如酮类、氧代醇类、和脂族醇类及其与水的混合物。
聚酰亚胺的气体渗透系数通常随着结构上刚性的二酐和环取代的二胺的使用而升高。刚性键和旋转阻碍基团的存在可提高气体渗透系数和气体分离系数。聚酰亚胺结构中磺酸基的导入提供了这种大体积的旋转阻碍侧基。这些基团也使聚合物的可溶性更好。在聚酰亚胺架构中磺酸基的高浓度能降低气体渗透系数但导致气体分离系数的提高。
按照本发明地制备的聚酰亚胺的气体渗透系数和气体分离系数通过使用平板膜来测量定。通过在玻璃板上进行溶解于甲醇或二甲基甲酰胺中的聚合物的溶液浇铸并紧接着空气干燥来制备所述膜。将空气干燥后的膜从玻璃板剥离并在70℃的真空烘箱中干燥一星期。将1至3密尔厚的干燥膜夹于具有2.54cm直径暴露面积的二铝箔之间，置于渗透池中并用环氧树脂密封。池的下流侧抽真空到约2×10-2mmHg，渗透物原料气从上流侧导入。在下游侧渗透气的压力用MKS-Baratihon压力传感器测定。渗透系数P按照下式的稳态气体渗透率来计算：
P＝C×V×L×dp/dt×1/h
C＝常数
V＝收集器体积
L＝膜厚度
h＝上游压力
dp/dt＝稳态线斜率
所述渗透率系数P以Barrer单位(1 Barrer＝10-10×cm3/cm2cmHg Sec)报告。为测定特性粘度，测定了在三个不同浓度(0.40、0.27和0.20g/dl)下的比浓粘度和特性粘度。所述测量于25℃在乌氏粘度计上进行。在0.5N高氯酸锂二甲基甲酰胺溶剂混合物中测定了磺化样品的特性粘度。
实施例1
用2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和4，4’-二氨基茋-2，2’-二磺酸锂盐制备聚酰亚胺：将12.9g(0.0338摩尔)的4，4’-二氨基茋-2，2’-二磺酸锂盐在室温下在干氩气氛中溶于87ml二甲基亚砜(在使用前在减压下用氢氧化钠丸粒干燥和蒸馏并通过4A分子筛贮存)中。将该溶液冷却至20℃，用大约半小时周期以每次3g加入15.3g(0.0338摩尔)6FDA。添加过程中不断搅拌反应混合物并将温度保持在约20℃左右。完成添加6FDA后，得到非常粘的溶液。将200mlDMSO加入以降低粘度。将溶液冷却至20℃后逐滴加入新鲜蒸馏的乙酸酐30ml，接着加入4.9ml新鲜蒸馏的三乙胺。将该溶液在室温下搅拌28小时后一边剧烈搅拌一边加入100ml丙酮以将产物沉淀。将沉淀的聚合物过滤并用丙酮洗涤。将聚合物先在室温下干燥后接着在170℃直空烘箱干燥至恒重。这样制备的聚酰亚胺的特性粘度是1.10dl/g。
实施例2
用2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和4，4’-二氨基茋-2，2’-二磺酸锂盐制备聚酰亚胺：按照实施例1中所列的程序，用下列材料制备聚酰亚胺：12.0g(0.0338摩尔)4，4’-二氨基-2，2’-二苯基二磺酸锂盐；15.3g(0.0338摩尔)6FDA；87ml二甲基亚砜(按实施例1中所述方法处理)。该聚酰亚胺的特性粘度是0.63dl/g。
实施例3
用2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和4，4’-二氨基芪-2，2’-二磺酸锂盐与2，4，6-三甲基苯二胺的混合物(50/50)制备共聚酰亚胺。将6.46g(0.0169摩尔)4，4’-二氨基芪-2，2’-二磺酸锂盐和2.54g(0.0169摩尔)2，4，6-三甲基苯二胺在室温下干氩气氛中溶解于180ml二甲基亚砜(在减压下用氢氧化钠丸粒干燥和蒸馏并在4A分子筛存在下贮存)中。将该溶液冷却至20℃，并用约半小时的时间周期以每次3g的量将15.3g(0.0338摩尔)6FDA加入。加入时不断搅拌反应混合物并将温度保持在20℃左右。加入过程完成后，将该溶液在室温下搅拌二天。将30ml新鲜蒸馏的乙酐逐滴加入到反应混合物中后，加入4.9ml新鲜蒸馏的三乙胺。将该溶液在室温下搅拌28小时并将所述聚合物沉淀到甲苯/甲乙酮(5/1)混合物中。回收所述聚合物并将其重新溶解于甲醇中。通过旋转蒸发回收最终产物。这种共聚酰亚胺的特性粘度为0.36dl/g。
实施例4
用2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和4，4’-二氨基茋-2，2’-二磺酸锂盐与2，6-二氨基甲基的混合物(50/50)制备共聚酰亚胺。按照在实施例3中所列的步骤，用下列材料制备共聚酰亚胺：6.46g(0.0169摩尔)4，4’-二氨基茋-2，2’-二磺酸锂盐；2.06 g(0.0169摩尔)2，6-二氨基甲苯、15.3g(0.0338摩尔)6FDA；160ml二甲基亚砜(经实施例1中所述的处理)。该聚酰亚胺的特性粘度是0.48dl/g。
实施例5
用2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和4，4’-二氨基-2，2’-二磺酸锂盐2，4，6-三甲基苯二胺的混合物(50/50)制备共聚酰亚胺。按照在实施例3中所列的步骤，用下列材料制备共聚酰亚胺：6.02g(0.0169摩尔)4，4’-二氨基-2，2’-二苯基二磺酸锂盐；2.54g(0.0169摩尔)2，4，6-三甲基苯二胺；15.3g(0.0338摩尔)6FDA；95ml二甲基亚砜(经实施例1中所述的方法处理)。这种共聚酰亚胺的特性粘度是0.38dl/g。
实施例6
用2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)和2，4，6-三甲基苯二胺(VI)制备的聚酰亚胺的磺化：4g(0.072摩尔)聚酰亚胺溶于160ml二氯甲烷的溶液和1.23ml(0.029摩尔)三氧化硫溶于60ml三氯甲烷的溶液在剧烈搅拌的条件下同时加入到冷却至0℃的50ml二氯甲烷中。整个加入过程中溶液的温度维持在0℃。添加过程完成后，将反应混合物在25℃搅拌3小时。
然后再将反应混合物冷却至0℃，并将1.23g一水合氢氧化锂和2.45g氯化锂在200ml甲醇的溶液滴入到反应混合物中。通过按需要加入一水合氢氧化锂的甲醇溶液将反应混合物的pH调节到7。在室温下将该溶液搅拌二天。将该溶液旋转蒸发至干，残渣溶解于100ml甲醇中。用300ml水稀释该溶液后过滤。将该产品在6000-8000 MWCO(分子量级分)的渗析袋中渗析。在50℃将含水渗析液旋转蒸发，所回收的聚合物在45-50℃下真空干燥至恒重。该聚合物的特性粘度是10.77dl/g。H+式干聚合物的离子交换容量是1.40meq/g。
按上面实施例制备的本发明的磺化聚酰亚胺的气体渗透系数和气体分离系数提供于下面的表1中。
表1
| 聚合物实施例编号 | IV (1)dl/g | IEC(2) | 渗透性系数 | 分离系数 | ||||||
| PHe | PO2 | PN2 | PCH4 | PCO2 | O2/N2 | He/N2 | CO2/CH4 | |||
| 1 | 1.1 | 2.53 | 4.16 | 0.06 | 0.01 | - | - | 11 | 830 | - |
| 2 | 0.63 | 2.62 | 6.07 | 0.11 | 0.01 | - | - | 8.4 | 480 | - |
| 3 | 0.36 | 1.48 | 42.8 | 2.66 | 0.41 | 0.16 | 11.4 | 6.4 | 103 | 70 |
| 4 | 0.48 | 1.51 | 25.6 | 1.04 | 0.15 | 0.05 | 4.63 | 7.1 | 176 | 96 |
| 5 | 0.38 | 1.54 | 56.1 | 4.20 | 0.75 | 0.28 | 18.8 | 5.6 | 75 | 66 |
| 6 | 0.77 | 1.3 | 95.4 | 11.6 | 2.36 | 1.18 | 56.2 | 4.9 | 40 | 47 |
(1)特性温度，在0.05N LiClO4的DMF溶液中于25℃下测量。
(2)IEC即离子交换容量，meq/g H+式干聚合物。
(3)单位为Barrer单位，300℃时测量。
除了展现出所需的气体分离特性外，发现本发明的磺化聚酰亚胺具有良好的成膜性和高度所需的溶解性。结果，对于气体分离膜制备的用途来说，它们是高度有利的。
Claims (17)
1.由下面通式的芳族聚酰亚胺形成的气体分离膜：
式中Ar1和Ar2是有机基团，至少约80％的Ar1和Ar2基团是芳族基团，在所述聚酰亚胺中的所述芳族德国的一部分含有磺酸基。
2.权利要求1的气体分离膜，其中约90％以上的所述Ar1和Ar2基团是芳族基团。
3.权利要求2的气体分离膜，其中所述Ar1和Ar2基团基本上全是芳族基团。
4.权利要求1的气体分离膜，其中在所述聚酰亚胺中的所述芳族基团的至少5％含有磺酸基。
5.权利要求4的气体分离膜，其中所述磺酸基是磺酸基或其成盐形式。
6.权利要求5的气体分离膜，其中，所述磺酸基的浓度是0.15-3meq/gH+式干聚合物。
7.权利要求5的气体分离膜，其中，所述磺酸基成盐形式包含碱性阳离子或有机碱。
8.权利要求7的气体分离膜，其中，所述碱性阳离子是锂。
9.权利要求1的气体分离膜，其中所述芳族聚酰亚胺是2，2’-二(3，4-二羧基苯基)六氟丙烷二酐(6FDA)与至少一种含磺酸基的芳族二胺的产物。
10.权利要求9的气体分离膜，其中所述芳族二胺是4，4’-二氨基茋-2，2’-二磺酸或其盐，或4，4’-二氨基-2，2’-二苯基二磺酸或其盐。
11.权利要求1的气体分离膜，其中所述芳族聚酰亚胺是2，2’-二(3，4-二羧基苯基)六氟丙烷二酐与至少一种含磺酸基的芳族二胺和至少一种另外的芳族二胺的混合物的产物。
12.权利要求11的气体分离膜，其中所述的另外的二胺是2，4，6-三甲基苯二胺。
13.由磺化芳族聚酰亚胺构成的气体分离膜，其中所述聚酰亚胺由包括下列步骤的方法制备：
(a)将前体芳族聚酰亚胺溶于惰性溶剂中；
(b)将得到的聚酰亚胺溶液冷却至10℃以下；
(c)将磺化剂加入到所述聚酰亚胺溶液中进行溶解的聚酰亚胺的磺化；
(d)在不超出中性pH条件的前提下用碱中和磺化聚酰亚胺反应混合物；
(e)回收得到的磺化聚酰亚胺。
14.权利要求13的气体分离膜，其中所述芳族聚酰亚胺是2，2’-二(3，4-二羧基苯基)六氟丙烷二酐与芳族二胺的反应产物。
15.权利要求13的气体分离膜，其中所述芳族聚酰亚胺是聚醚酰亚胺。
16.权利要求13的气体分离膜，其中步骤(b)在低于5℃的温度下进行。
17.权利要求13的气体分离膜，其中步骤(d)在低于5℃的温度下进行。
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|---|---|---|---|---|
| CN101139501B (zh) * | 2007-10-11 | 2011-05-25 | 同济大学 | 一种聚酰亚胺耐高温水性分散体涂料及其制备方法和应用 |
| TWI568491B (zh) * | 2015-12-31 | 2017-02-01 | 財團法人工業技術研究院 | 過濾材料 |
| CN107376672A (zh) * | 2017-06-23 | 2017-11-24 | 江南大学 | 一种聚酰亚胺气体分离膜的绿色制备方法 |
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| FR2789912B1 (fr) * | 1999-02-18 | 2002-12-20 | Commissariat Energie Atomique | Procede et dispositif de separation a membranes semi-permeables en polyimides sulfones |
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| EP1086973A3 (en) * | 1999-09-24 | 2001-11-21 | Praxair Technology, Inc. | Polyimide gas separation membranes |
| EP1095695A3 (en) * | 1999-09-24 | 2001-11-21 | Praxair Technology, Inc. | Novel polyimide amic acid salts and polyimide membranes formed therefrom |
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| US6383258B1 (en) * | 2000-12-19 | 2002-05-07 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Copolyimide gas separation membranes |
| KR100415979B1 (ko) * | 2001-02-21 | 2004-01-24 | 한국과학기술연구원 | 계면활성제가 첨가된 고체고분자 전해질 촉진수송 분리막 |
| SG108269A1 (en) * | 2001-08-15 | 2005-01-28 | Inst Materials Research & Eng | Chemical modification of polyimides |
| US7018445B2 (en) * | 2002-12-02 | 2006-03-28 | L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Polyimide blends for gas separation membranes |
| US20050014432A1 (en) * | 2003-06-20 | 2005-01-20 | Jain Mukesh K. | Waterproof and high moisture vapor permeable fabric laminate |
| US20040259446A1 (en) * | 2003-06-20 | 2004-12-23 | Jain Mukesh K. | Chemical protective articles of apparel and enclosures |
| US7527673B2 (en) * | 2004-03-26 | 2009-05-05 | L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Polyimide based mixed matrix composite membranes |
| US20050268782A1 (en) * | 2004-03-26 | 2005-12-08 | Kulkarni Sudhir S | Novel polyimide based mixed matrix membranes |
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| US7803214B2 (en) * | 2006-07-21 | 2010-09-28 | Ube Industries, Ltd. | Asymmetric hollow-fiber gas separation membrane, gas separation method and gas separation membrane module |
| FR2904779B1 (fr) * | 2006-08-09 | 2008-10-31 | Inst Francais Du Petrole | Procede de separation par membrane d'une olefine contenue dans un melange d'hydrocarbures |
| US20140137734A1 (en) * | 2012-11-20 | 2014-05-22 | Uop Llc | Cross-linked polyimide membranes for separations |
| JP2015051407A (ja) * | 2013-09-09 | 2015-03-19 | 富士フイルム株式会社 | ガス分離複合膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 |
| JP2015083296A (ja) * | 2013-09-20 | 2015-04-30 | 富士フイルム株式会社 | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 |
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| KR102107517B1 (ko) * | 2018-01-22 | 2020-05-08 | 고려대학교 산학협력단 | 용매 후처리를 통한 고성능 박막 복합체 분리막의 제조 방법 |
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- 1996-06-28 CN CN96108864.8A patent/CN1147418A/zh active Pending
- 1996-06-28 EP EP96110538A patent/EP0750939A3/en not_active Withdrawn
- 1996-06-28 BR BR9602923A patent/BR9602923A/pt active Search and Examination
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1997
- 1997-11-12 US US08/968,943 patent/US5964925A/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139501B (zh) * | 2007-10-11 | 2011-05-25 | 同济大学 | 一种聚酰亚胺耐高温水性分散体涂料及其制备方法和应用 |
| TWI568491B (zh) * | 2015-12-31 | 2017-02-01 | 財團法人工業技術研究院 | 過濾材料 |
| US10124301B2 (en) | 2015-12-31 | 2018-11-13 | Industrial Technology Research Institute | Filtration material |
| CN107376672A (zh) * | 2017-06-23 | 2017-11-24 | 江南大学 | 一种聚酰亚胺气体分离膜的绿色制备方法 |
| CN107376672B (zh) * | 2017-06-23 | 2020-05-22 | 江南大学 | 一种聚酰亚胺气体分离膜的绿色制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US5618334A (en) | 1997-04-08 |
| BR9602923A (pt) | 1998-04-28 |
| US5964925A (en) | 1999-10-12 |
| JPH0910567A (ja) | 1997-01-14 |
| EP0750939A2 (en) | 1997-01-02 |
| EP0750939A3 (en) | 1997-07-02 |
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