CN113461933B - 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 - Google Patents
聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 Download PDFInfo
- Publication number
- CN113461933B CN113461933B CN202110609091.9A CN202110609091A CN113461933B CN 113461933 B CN113461933 B CN 113461933B CN 202110609091 A CN202110609091 A CN 202110609091A CN 113461933 B CN113461933 B CN 113461933B
- Authority
- CN
- China
- Prior art keywords
- reactive monomer
- ionic liquid
- polymer self
- supporting nano
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/54—Polyureas; Polyurethanes
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- 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
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
本发明公开了一种聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用,制备方法包括以下步骤:(1)将反应性单体a的离子液体溶液均匀涂布在连续向前运动的平整的传输机构上,形成稳定均匀的反应性单体a的离子液体溶液涂层;(2)将步骤(1)中的反应性单体a的离子液体溶液涂层与溶有反应性单体b的非极性溶液接触,发生界面聚合反应,合成聚合物自支撑纳米薄膜;(3)将步骤(2)中的聚合物自支撑纳米薄膜用水洗涤,其自动从传输机构上脱落,经干燥热处理后,即获得所述的聚合物自支撑纳米薄膜。本发明的制备方法极大地拓展了反应物的可选种类,使非水溶性的具有特殊结构的反应物能够应用于聚合物薄膜的界面合成中。
Description
技术领域
本发明涉及膜制备领域,尤其涉及一种聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用。
背景技术
聚合物自支撑纳米薄膜广泛应用于分离纯化、能源再生、材料保护以及电子器件等领域。界面聚合因其快速高效、条件温和而成为制备自支撑聚合物纳米薄膜的重要方法。
界面聚合是指两种高反应活性物质分别溶于两个互不相溶的溶剂中,并在界面处发生聚合反应,形成聚合物纳米薄膜。
常规的界面聚合反应发生在油/水界面上(例如专利文献US4277344和US4259183),其中一种高反应活性物质必为水溶性,但大多数有机物都难溶于水,因此常规的油/水界面聚合限制了反应物的选用,不利于任务专化聚合物纳米薄膜的开发。其次,油/水界面聚合反应速率极高,难以控制,且水作为一种活泼的质子性溶剂,易于与油相中的高活性反应物发生副反应,导致所得薄膜存在缺陷。由此可见,水虽然易于与有机溶剂形成界面,但水的存在却不利于界面聚合反应。因此,十分有必要开发一种无水、可控且普适的界面聚合体系。
与水不同,离子液体是一种完全由阴阳离子组成的有机熔融盐,大多在室温下呈液态。与传统有机溶剂相比,离子液体具有不挥发、不易燃、化学和热稳定性高、溶解能力强、结构可调控、电化学窗口宽等优点,被誉为一种新型的“绿色溶剂”,在化学合成领域有着广泛的应用。
由于内部相互作用的巨大差异,许多离子液体能够与烷烃或苯及其衍生物形成界面,使用离子液体/有机溶剂体系开展界面聚合反应,能够拓展单体选用范围,按不同应用需求筛选反应物,合成不同种类和功能的纳米薄膜,同时可以减少反应物水解等副反应,提高薄膜质量。特别地,离子液体的高粘度以及可设计性使其能够在各种基材表面形成稳定均匀的溶液涂层,为可控界面聚合制备聚合物纳米薄膜奠定基础。
目前尚无基于离子液体/有机溶剂体系开展界面聚合制备聚合物纳米薄膜的专利和论文报导。
发明内容
本发明提供了一种聚合物自支撑纳米薄膜及其连续和宏量制备方法,该方法极大地拓展了反应物的可选种类,使非水溶性的具有特殊结构的反应物能够应用于聚合物薄膜的界面合成中。
本发明的技术方案如下:
一种聚合物自支撑纳米薄膜的连续和宏量制备方法,包括以下步骤:
(1)将反应性单体a的离子液体溶液均匀涂布在连续向前运动的平整的传输机构上,形成稳定均匀的反应性单体a的离子液体溶液涂层;
(2)将步骤(1)中的反应性单体a的离子液体溶液涂层与溶有反应性单体b的非极性溶液接触,引发界面聚合反应,合成聚合物自支撑纳米薄膜;
(3)将步骤(2)中的聚合物自支撑纳米薄膜用水洗涤,其自动从传输机构上脱落,经干燥热处理后,即获得所述的聚合物自支撑纳米薄膜。
步骤(2)中,反应性单体a的离子液体溶液涂层与溶有反应性单体b的非极性溶液接触的方式选自以下两种中的一种:
(A)将涂有反应性单体a的离子液体溶液涂层的传输机构浸入溶有反应性单体b的非极性溶液中;
(B)将溶有反应性单体b的非极性溶液喷涂至反应性单体a的离子液体溶液涂层表面。
所述的传输机构为传送带、辊筒等;材质为聚合物、玻璃、陶瓷、金属等。
优选的,所述的离子液体的熔点为-100℃~100℃;所述的离子液体的黏度为10cP~1000cP。
进一步优选的,所述离子液体的阳离子选自以下的一种或多种:烷基季铵离子、烷基季鏻离子、N,N'-二烷基取代咪唑鎓、N-烷基取代的吡啶鎓;阴离子选自以下的一种或多种:卤离子、四氯合铝酸根、六氟合铝酸根、四氟合硼酸根、六氟合磷酸根、硝酸根、高氯酸根、三氟乙酸根、三氟甲磺酸根离子、双三氟甲磺酰亚胺阴离子、对甲苯磺酸根、全氟丁酸根、全氟丁基磺酸根。
优选的,所述非极性溶液的溶剂为正烷烃、异构烷烃、环烷烃和芳烃中的至少一种。
进一步优选的,所述非极性溶液的溶剂为正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、石脑油、异构烷烃G、异构烷烃H、异构烷烃L、异构烷烃M、环戊烷、环己烷、环庚烷、环辛烷、苯、甲苯、1,2-二甲苯、1,3-二甲苯、1,4-二甲苯和1,3,5-三甲基苯中的至少一种。
优选的,所述反应性单体a为胺类化合物、醇类化合物、酚类化合物、过氧化氢、过硫酸盐和偶氮二异丁腈中的至少一种。
所述胺类化合物的分子结构中至少具有两个胺基。
所述胺类化合物为由以下化学式表示的化合物中的至少一种:
进一步优选的,所述胺类化合物为乙二胺、丁二胺、己二胺、辛二胺、癸二胺、哌嗪、1,3-环己二甲胺、二乙烯三胺、1,2-苯二胺、1,3-苯二胺、1,4-苯二胺、2,2'-双(4-氨基苯基)丙烷、2,2'-双(4-氨基苯基)六氟丙烷、四(4-氨苯基)甲烷、9,9'-双(4-氨基苯基)芴、四(4-氨基苯基)乙烯、4,4'-二氨基二苯砜、4,4'-双(4-氨基苯氧基)二苯砜、三(4-氨苯基)胺和1,3,5-三(4-氨苯基)苯中的至少一种。
所述醇类化合物或酚类化合物的分子结构中至少具有两个羟基。
优选的,所述醇类化合物或酚类化合物为由以下化学式表示的化合物中的至少一种:
优选的,所述的醇类化合物或酚类化合物为乙二醇、丁二醇、己二醇、辛二醇、癸二醇、丙三醇、1,2-苯二酚、1,3-苯二酚、1,4-苯二酚、9,9-双(4-羟基苯基)芴、2,6-二羟基蒽醌和5,5',6,6'-四羟基-3,3,3',3'-四甲基-1,1'-螺旋联吲哚中的至少一种。
所述反应性单体b为酰氯化合物、醛类化合物、异氰酸酯、吡咯、噻吩和苯胺中的至少一种。
所述酰氯化合物的分子结构中至少具有两个酰氯基团。
优选的,所述酰氯化合物为由以下化学式表示的化合物中的至少一种:
进一步优选的,所述酰氯化合物为间苯二甲酰氯、对苯二甲酰氯、1,2,4-苯三甲酰氯、1,3,5-苯三甲酰氯、1,2,4,5-苯四甲酰氯、4,4'-联苯二甲酰氯和3,5,3',5'-联苯四甲酰氯中的至少一种。
所述醛类化合物的分子结构中至少具有两个醛基。
优选的,所述醛类化合物为由以下化学式表示的化合物中的至少一种:
进一步的,所述醛类化合物为间苯二甲醛、对苯二甲醛、1,2,4-苯三甲醛、1,3,5-苯三醛、2,4,6-三羟基-1,3,5-苯三甲醛、2,4,6-三甲基-1,3,5-苯三甲醛、1,2,4,5-苯四甲醛、4,4'-联苯二甲醛和3,5,3',5'-联苯四甲醛中的至少一种。
所述异氰酸酯的分子结构中至少具有两个异氰酸酯基。
进一步的,所述异氰酸酯为甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯和3,3'-二甲基-4,4'-联苯二异氰酸酯中的至少一种。
所述反应性单体a的离子液体溶液中,反应性单体a的浓度为5~800mM;反应性单体b的非极性溶液中,反应性单体b的浓度为0.05~2mM。
优选的,反应性单体a的离子液体溶液涂层的厚度为50~1000μm。
优选的,将涂有反应性单体a的离子液体溶液涂层的传输机构浸入溶有反应性单体b的非极性溶液中的时间为30~3600s;
或将溶有反应性单体b的非极性溶液喷涂至反应性单体a的离子液体溶液涂层表面的喷涂速率为0.5~2mL min-1。
传送机构的运动速率为0.02~3cm min-1。
所制得的聚合物自支撑纳米薄膜的种类为聚酰胺、聚酯、聚甲亚胺、聚脲、聚氨酯、聚吡咯、聚噻吩或聚苯胺。
本发明还提供了一种上述制备方法制得的聚合物自支撑纳米薄膜在海水淡化、废水处理、贵金属提取、浓差发电、有机溶剂回收、药物分离纯化、材料表面保护、导电薄膜中的应用。
若所合成的聚合物自支撑纳米薄膜为聚酰胺或聚酯或聚甲亚胺,则可将其与聚合物或陶瓷的微滤或超滤基底复合,构成薄层复合膜,用于正渗透海水淡化、反渗透海水淡化、水系纳滤、有机纳滤、压力延迟渗透发电等领域。
若所合成的聚合物自支撑纳米薄膜为聚氨酯或聚脲,则可将其包覆在船体、墙面以及其他需要保护的材料表面上,充当保护涂层。
若所合成的聚合物自支撑纳米薄膜为聚吡咯或聚噻吩或聚苯胺,则可将其用作电极修饰层等电化学材料。
与现有技术相比,本发明的有益效果为:
(1)本发明的聚合物自支撑纳米薄膜的连续和宏量制备方法极大拓展了反应物的可选种类,使非水溶性的具有特殊结构的反应物能够应用于聚合物薄膜的界面合成,并在传统的薄膜应用领域中引入新的聚合物薄膜材料,从而实现了特定的性能。
(2)由于离子液体的高粘度,界面聚合反应通过减缓反应物扩散速率得到控制,可以得到超薄聚合物自支撑膜,其厚度可低至3nm。
(3)本发明的聚合物自支撑纳米薄膜的连续和宏量制备方法避免了常规水/油界面聚合体系副反应导致薄膜缺陷较多的问题,使用该方法制备的聚合物纳米薄膜均匀致密,交联度高达96%。
(4)由于离子液体内部复杂的相互作用和其可调节的黏度,该方法能够在各种材料的输送带表面涂覆均匀稳定的反应物离子液体溶液,并可以灵活通过浸入或喷涂另一反应物的非极性溶液引发界面聚合,可实现聚合物自支撑纳米薄膜的连续化宏量制备。
(5)所得聚合物自支撑纳米薄膜能够附载在聚合物、陶瓷、金属、石墨等基材表面,并用于分离纯化、能源再生、材料保护以及电子器件等领域,拥有巨大的应用前景。
附图说明
图1为一种优选的聚合物自支撑纳米薄膜的连续和宏量制备装置的结构示意图;
图2为实施例20制备的聚合物自支撑纳米薄膜的表面电镜图(a)、截面电镜图(b)、原子力显微镜图(c)和相应的高度图(d)。
具体实施方式
下面结合附图和实施例对本发明作进一步详细描述,需要指出的是,以下所述实施例旨在便于对本发明的理解,而对其不起任何限定作用。
在以下具体实施例中,所选用的制备装置如图1所示,包括输送带、出口带有刮刀的料液缸a、出口带有雾化器的料液缸b、水槽、热处理装置和卷绕装置;
料液缸a和料液缸b设置在输送带上方,料液缸b位于料液缸a的下游、水槽的上游,输送带的一部分进入水槽的液面下。刮刀与输送带的间距可调。
制备方法包括:首先配制反应物a的离子液体溶液和反应物b的非极性溶液,并分别加料至料液缸a和料液缸b。反应物a的离子液体溶液从料液缸a下方的喷嘴挤出,通过可调高度的刮刀刮涂在向前运动的传送带上。反应物b的非极性溶液通过料液缸b下方的雾化器喷涂在涂覆有离子液体溶液的向前运动的传送带上,反应物a与反应物b的界面聚合反应由此开始。传送带继续向前移动至水槽内,离子液体溶液即溶解在水中,界面聚合反应停止,所合成的聚合物自支撑纳米薄膜因水的表面张力而自支撑在水表面。水槽内的水循环泵送,不断更新,使得聚合物自支撑纳米薄膜在水槽中被漂洗。薄膜运动到水槽末端后被输送带捞出水面,在空气中干燥,并被送至热处理装置中处理,完毕后通过辊卷绕成卷以待使用。
若所合成聚合物自支撑纳米薄膜为聚酰胺或聚酯或聚甲亚胺,则可将其与聚合物或陶瓷的微滤或超滤基底复合,构成薄层复合膜,用于正渗透海水淡化、反渗透海水淡化、水系纳滤、有机纳滤、压力延迟渗透发电等领域。
若所合成的聚合物自支撑纳米薄膜为聚氨酯或聚脲,则可将其包覆在船体、墙面以及其他需要保护的材料表面上,充当保护涂层。若所合成的聚合物自支撑纳米薄膜为聚吡咯或聚噻吩或聚苯胺,则可将其用作电极修饰层等电化学材料。
当本发明制备的聚合物自支撑纳米薄膜以分离纯化应用为具体实施例时,渗透通量、截留或分离比为评估薄膜性能的重要参数。对于液相分离纯化,溶剂通量F定义为:
其中V表示一定时间内透过膜的液体体积,A表示分离过程中所用薄膜的有效面积,t表示分离过程持续时间,p为测试压力。
截留率R定义为:
其中cf表示分离前溶液待截留物质的浓度,cp表示处理后溶液中待截留物质的浓度。
对于气相分离纯化,气体渗透率Q由下式计算:
其中Pu为进气端压强,Pd为出气端压强,Patm为大气压,T为测试温度,A为有效薄膜面积,dV/dt为测试时皂泡流量计的体积增速。
气体分离比α定义为:
其中Q1和Q2分别为两种气体的渗透率。
对于压力延迟发电,发电功率W由下式计算:
W=A(Δp-P)P
其中,A为有效薄膜面积,Δπ为渗透压差,P为外加压力。
实施例1—3
(1)选用哌嗪为反应物a。将哌嗪溶解于离子液体1-丁基-3-甲基咪唑四氟硼酸盐中,得到浓度为120mM的离子液体溶液,黏度为165cP。选用均苯三甲酰氯为反应物b,将均苯三甲酰氯溶于正己烷中,得到浓度为5.6mM的非极性溶液。分别将两溶液加入料液缸a和料液缸b。
(2)装置开启后,哌嗪的离子液体溶液经刮刀均匀涂覆在尼龙输送带表面,得到厚度为1000μm的稳定液膜。待液膜移动到雾化器处,均苯三甲酰氯正己烷溶液被喷涂至输送带上液膜表面,喷涂速率为1mL min-1,喷涂时间为30s。
(3)输送带继续向前移动至水槽中,合成的聚酰胺自支撑纳米薄膜漂浮于水面上漂洗。
(4)薄膜被输送带持续向前推进至水槽末端输送带,并被牵伸出水面,薄膜在空气中干燥,然后被送入热处理装置,处理完毕后卷绕得到成品哌嗪聚酰胺自支撑纳米薄膜。
(5)实施例1—3的区别在于输送带的移动速度。实施例1—3中,传送带向前运动的速率分别为3cm s-1、1.5cm s-1、0.3cm s-1。
(6)将所制备的薄膜与聚醚砜超滤基底复合,就得到用于水系纳滤的1薄层复合膜。该膜使用平板错流装置评估其性能,待分离溶液为1000ppm的MgSO4水溶液,测试温度为30℃,错流流速为30L min-1,测试压力为6bar。测试性能如表1所示:
表1
实施例4—8
将刮刀涂布液膜厚度分别替换为50μm、200μm、400μm、600μm、800μm,其余条件同实施例2。测试性能如表2所示:
表2
实施例9—13
将哌嗪浓度分别替换为100mM、90mM、80mM、70mM、60mM,其余条件同实施例2。测试性能如表3所示:
表3
实施例14—18
将离子液体1-丁基-3-甲基咪唑四氟硼酸盐分别替换为1-乙基-3-甲基咪唑四氟硼酸盐(C2)、1-己基-3-甲基咪唑四氟硼酸盐(C6)、1-辛基-3-甲基咪唑四氟硼酸盐(C8)、1-癸基-3-甲基咪唑四氟硼酸盐(C10)、1-十二烷基-3-甲基咪唑四氟硼酸盐(C12),其余条件同实施例2。测试性能如表4所示:
表4
实施例19—23
将反应物a替换为1,3-苯二胺,浓度分别为600mM、500mM、400mM、300mM、200mM,并将所得全芳族聚酰胺自支撑纳米薄膜与聚醚砜超滤基底复合,构成反渗透膜用于海水淡化。此类实施例性能评估所用待分离溶液为2000ppm NaCl水溶液,所用压力为10bar,其余条件同实施例2。测试性能如表5所示:
表5
实施例24—30
分别将非极性溶剂分别换为庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、异构烷烃H,其余条件同实施例20。测试性能如表6所示:
表6
实施例31—37
分别将反应物a替换为2,2'-双(4-氨基苯基)丙烷(BAP)、2,2'-双(4-氨基苯基)六氟丙烷(BAHFP)、四(4-氨苯基)甲烷(TAM)、9,9'-双(4-氨基苯基)芴(BAF)、四(4-氨基苯基)乙烯(TAPE)、4,4'-二氨基二苯砜(BAS)、4,4'-双(4-氨基苯氧基)二苯砜(BAPS),并将制备得到的纳米薄膜与阳极氧化铝陶瓷基底(孔径20nm)复合,构成用于有机纳滤的薄层复合膜。此类实施例性能评估所用待分离溶液为50ppm罗丹明B的甲醇溶液,过滤类型为死端过滤,所用压力为3bar,其余条件同实施例15。测试性能如表7所示:
表7
实施例38—42
将待分离溶液替换为分子量分别为200Da、400Da、600Da、800Da、1000Da的聚乙二醇水溶液,浓度为2g L-1,其余条件同实施例34。测试性能如表8所示:
表8
实施例43—47
将反应物a替换为1,3,5-三(4-氨苯基)苯,分别将反应物b替换为对苯二甲醛(PMD)、1,3,5-苯三醛(TMD)、2,4,6-三羟基-1,3,5-苯三甲醛(THMD)、4,4'-联苯二甲醛(DMD)、3,5,3',5'-联苯四甲醛(TDD),非极性溶剂替换为1,3,5-三甲基苯。输送带运动速度为0.02cm s-1。将制备的聚甲亚胺共价有机框架自支撑纳米薄膜与XP84交联聚酰亚胺基底复合,用于气体分离的薄层复合膜。此类实施例性能评估所用待分离气体对为H2/CH4,进气端压力为0.1bar,出气端压力为1atm,其余条件同实施例42。测试性能如表9所示:
表9
实施例48—52
使用实施例20中的聚酰胺自支撑纳米薄膜的制备条件,将所得薄膜与具有垂直通孔结构的聚偏氟乙烯微滤膜复合,构成用于压力延迟渗透发电的薄层复合膜。进料液为去离子水,汲取剂为MgCl2水溶液,浓度分别为2M、3M、4M、5M、6M。测试温度为30℃,错流流速为15L min-1。测试性能如表10所示:
表10
实施例53—55
将反应物a替换为过硫酸铵,浓度为0.5M,分别将反应物b替换为吡咯、噻吩、苯胺,浓度为5mM,非极性溶剂替换为苯。输送带运动速度为0.3cm s-1。将制备的导电聚合物自支撑纳米薄膜石英基片复合,构成改性电极。测试性能如表11所示:
表11
实施例56—60
将反应物a替换为1,6-己二胺,浓度为300M,分别将反应物b替换为甲苯-2,4-二异氰酸酯(24TDI)、甲苯-2,6-二异氰酸酯(26TDI)、4,4-二苯基甲烷二异氰酸酯(MDI)、1,5-萘二异氰酸酯(NDI)、3,3'-二甲基-4,4'-联苯二异氰酸酯(TODI),浓度为5mM,非极性溶剂替换为异构烷烃G。输送带运动速度为0.17cm s-1。聚脲自支撑纳米薄膜作为保护层与混凝土片材复合。通过浸入模拟海水测定保护性能,使用TABERCS-17轮测试耐磨性,载荷1000g,往复100次。测试性能如表12所示:
表12
以上所述的实施例对本发明的技术方案和有益效果进行了详细说明,应理解的是以上所述仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充和等同替换等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种聚合物自支撑纳米薄膜的连续和宏量制备方法,其特征在于,包括以下步骤:
(1)将反应性单体a的离子液体溶液均匀涂布在连续向前运动的平整的传输机构上,形成稳定均匀的反应性单体a的离子液体溶液涂层;
(2)将步骤(1)中的反应性单体a的离子液体溶液涂层与溶有反应性单体b的非极性溶液接触,发生界面聚合反应,合成聚合物自支撑纳米薄膜;
反应性单体a的离子液体溶液涂层的厚度为50~1000 μm;
反应性单体a的离子液体溶液涂层与溶有反应性单体b的非极性溶液接触的方式为:将溶有反应性单体b的非极性溶液喷涂至反应性单体a的离子液体溶液涂层表面,喷涂速率为0.5~2 mL min-1;
所述反应性单体a的离子液体溶液中,反应性单体a的浓度为5~800 mM;反应性单体b的非极性溶液中,反应性单体b的浓度为0.05~2 mM;
(3)将步骤(2)中的聚合物自支撑纳米薄膜用水洗涤,其自动从传输机构上脱落,经干燥热处理后,即获得所述的聚合物自支撑纳米薄膜。
2.根据权利要求1所述的聚合物自支撑纳米薄膜的连续和宏量制备方法,其特征在于,所述的离子液体的熔点为-100℃~100℃;所述的离子液体的黏度为10 cP~1000 cP。
3.根据权利要求1所述的聚合物自支撑纳米薄膜的连续和宏量制备方法,其特征在于,所述非极性溶液的溶剂为正烷烃、异构烷烃、环烷烃和芳烃中的至少一种。
4.根据权利要求1所述的聚合物自支撑纳米薄膜的连续和宏量制备方法,其特征在于,所述反应性单体a为胺类化合物、醇类化合物、酚类化合物、过氧化氢、过硫酸盐和偶氮二异丁腈中的至少一种。
5.根据权利要求1或4所述的聚合物自支撑纳米薄膜的连续和宏量制备方法,其特征在于,所述反应性单体b为酰氯化合物、醛类化合物、异氰酸酯、吡咯、噻吩和苯胺中的至少一种。
6.一种聚合物自支撑纳米薄膜,其特征在于,根据权利要求1—5任一项所述的连续和宏量制备方法制备得到。
7.一种根据权利要求6所述的聚合物自支撑纳米薄膜在海水淡化、废水处理、贵金属提取、浓差发电、有机溶剂回收、药物分离纯化、材料表面保护、导电薄膜中的应用。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110609091.9A CN113461933B (zh) | 2021-06-01 | 2021-06-01 | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 |
PCT/CN2021/126889 WO2022252484A1 (zh) | 2021-06-01 | 2021-10-28 | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110609091.9A CN113461933B (zh) | 2021-06-01 | 2021-06-01 | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113461933A CN113461933A (zh) | 2021-10-01 |
CN113461933B true CN113461933B (zh) | 2022-09-06 |
Family
ID=77872104
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110609091.9A Active CN113461933B (zh) | 2021-06-01 | 2021-06-01 | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN113461933B (zh) |
WO (1) | WO2022252484A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019534786A (ja) * | 2016-10-01 | 2019-12-05 | オキシメム リミテッド | セルフコイリング中空糸膜 |
CN113461933B (zh) * | 2021-06-01 | 2022-09-06 | 浙江大学 | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 |
CN113736097B (zh) * | 2021-10-15 | 2022-04-26 | 四川大学 | 图灵结构共价有机框架膜材料及其用途 |
CN114957591B (zh) * | 2022-03-24 | 2024-04-09 | 万华化学集团股份有限公司 | 一种用于药物缓释的cof基聚氨酯多孔膜的制备方法 |
CN116272897B (zh) * | 2023-02-27 | 2024-08-27 | 中国检验检疫科学研究院 | 富集香豆素类化合物的磁性纳米粒及其制备方法和应用 |
CN116023282B (zh) * | 2023-03-30 | 2023-08-01 | 吉林省卓材新研科技有限公司 | 一种共价有机框架材料及其配体和它在药物传递中的应用 |
CN117946355B (zh) * | 2024-03-27 | 2024-06-18 | 中国科学技术大学 | 一种不对称自支撑共价有机框架薄膜的制备方法及其应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04346864A (ja) * | 1991-05-23 | 1992-12-02 | Japan Vilene Co Ltd | 多層膜の製造方法及びその製造装置 |
JPH0938474A (ja) * | 1995-07-27 | 1997-02-10 | Toyobo Co Ltd | 複合膜の製造方法及び製造装置 |
JP2002086476A (ja) * | 2000-09-20 | 2002-03-26 | Ube Ind Ltd | 多孔質膜の連続製造方法および連続製造装置 |
CN105879700A (zh) * | 2016-04-07 | 2016-08-24 | 天津珑源新材料科技有限公司 | 一种晶须掺混复合反渗透膜的制备方法 |
CN108187512A (zh) * | 2018-01-11 | 2018-06-22 | 中国石油大学(华东) | 一种高通量聚酰胺纳滤复合膜及其制备方法 |
CN108727615A (zh) * | 2018-06-27 | 2018-11-02 | 河南科技大学 | 一种离子液体-水界面制备Ag-聚合物纳米复合膜的方法 |
CN110026091A (zh) * | 2019-03-15 | 2019-07-19 | 清华大学 | 一种离子液体改性的荷正电复合纳滤膜及其制备方法 |
CN110064312A (zh) * | 2019-04-29 | 2019-07-30 | 袁书珊 | 一种高通量耐溶剂界面聚合复合膜及其制备方法 |
CN112755817A (zh) * | 2021-02-22 | 2021-05-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | 一种具有高性能的复合纳滤膜、其制备方法及应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104474926B (zh) * | 2014-12-12 | 2016-05-04 | 杭州水处理技术研究开发中心有限公司 | 一种聚酰胺反渗透膜的制备方法 |
CN106739363A (zh) * | 2016-05-05 | 2017-05-31 | 林小锋 | 一种多层复合结构的薄膜复合膜及其制备方法 |
CN108452691B (zh) * | 2018-03-01 | 2020-01-14 | 广州中国科学院先进技术研究所 | 界面聚合反应装置、中空纤维复合纳滤膜制备装置及方法 |
CN108889139B (zh) * | 2018-07-31 | 2020-11-03 | 南京工业大学 | 一种基于界面聚合制备高通量共价有机骨架纳滤膜的方法 |
CN112516810B (zh) * | 2020-11-11 | 2022-08-16 | 南京工业大学 | 一种纳滤膜的制造方法及装置 |
CN113527729B (zh) * | 2021-05-28 | 2022-08-30 | 浙江大学 | 一种聚集诱导发光聚合物薄膜及其宏量制备方法 |
CN113457459B (zh) * | 2021-05-28 | 2022-11-11 | 浙江大学 | 一种聚酰胺功能复合膜的连续制备方法及装置 |
CN113461933B (zh) * | 2021-06-01 | 2022-09-06 | 浙江大学 | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 |
-
2021
- 2021-06-01 CN CN202110609091.9A patent/CN113461933B/zh active Active
- 2021-10-28 WO PCT/CN2021/126889 patent/WO2022252484A1/zh active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04346864A (ja) * | 1991-05-23 | 1992-12-02 | Japan Vilene Co Ltd | 多層膜の製造方法及びその製造装置 |
JPH0938474A (ja) * | 1995-07-27 | 1997-02-10 | Toyobo Co Ltd | 複合膜の製造方法及び製造装置 |
JP2002086476A (ja) * | 2000-09-20 | 2002-03-26 | Ube Ind Ltd | 多孔質膜の連続製造方法および連続製造装置 |
CN105879700A (zh) * | 2016-04-07 | 2016-08-24 | 天津珑源新材料科技有限公司 | 一种晶须掺混复合反渗透膜的制备方法 |
CN108187512A (zh) * | 2018-01-11 | 2018-06-22 | 中国石油大学(华东) | 一种高通量聚酰胺纳滤复合膜及其制备方法 |
CN108727615A (zh) * | 2018-06-27 | 2018-11-02 | 河南科技大学 | 一种离子液体-水界面制备Ag-聚合物纳米复合膜的方法 |
CN110026091A (zh) * | 2019-03-15 | 2019-07-19 | 清华大学 | 一种离子液体改性的荷正电复合纳滤膜及其制备方法 |
CN110064312A (zh) * | 2019-04-29 | 2019-07-30 | 袁书珊 | 一种高通量耐溶剂界面聚合复合膜及其制备方法 |
CN112755817A (zh) * | 2021-02-22 | 2021-05-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | 一种具有高性能的复合纳滤膜、其制备方法及应用 |
Non-Patent Citations (1)
Title |
---|
Interfacial Polymerizationatthe Alkane/Ionic Liquid Interface;Chang Liu;《Angewandte Chemie International Edition》;20210519;第60卷(第26期);introduction,conclusion部分,Supporting Information部分第2.2.10节 * |
Also Published As
Publication number | Publication date |
---|---|
WO2022252484A1 (zh) | 2022-12-08 |
CN113461933A (zh) | 2021-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113461933B (zh) | 聚合物自支撑纳米薄膜及其连续和宏量制备方法和应用 | |
JP7256152B2 (ja) | 選択透過性酸化グラフェン膜 | |
EP2632575B1 (en) | Method for making a composite polyamide membrane | |
Ba et al. | Chemical modification of P84 copolyimide membranes by polyethylenimine for nanofiltration | |
AU2001284640B2 (en) | Acid stable membranes for nanofiltration | |
Setiawan et al. | Fabrication and characterization of forward osmosis hollow fiber membranes with antifouling NF-like selective layer | |
CN104470627A (zh) | 复合聚酰胺膜 | |
KR102155533B1 (ko) | 복합 반투막 및 그 제조 방법 | |
KR101733264B1 (ko) | 염제거율 및 투과유량 특성이 우수한 폴리아미드계 수처리 분리막 및 그 제조 방법 | |
EP3322514B1 (en) | A process for preparing a thin film composite membrane, thin film composite membrane prepared according to the process and method of purifying tap water or seawater or brackish water using the membrane | |
WO2021134060A1 (en) | High-flux water permeable membranes | |
KR101961344B1 (ko) | 폴리아미드 계면중합용 조성물 및 이를 이용한 역삼투막의 제조방법 | |
CN114534524B (zh) | 一种基于离子液体界面聚合制备共价有机骨架膜的方法 | |
CA1249111A (en) | Method for producing a very thin, dense membrane and (supported) membrane so produced | |
Zhang et al. | Dynamic pressure‐driven covalent assembly of inner skin hollow fiber multilayer membrane | |
AU2011345304C1 (en) | Polysulfonamide membrane by interfacial polymerisation | |
CN113842783B (zh) | 一种耐酸型高通量聚芳醚复合纳滤膜、制备方法及应用 | |
Choi et al. | High-performance nanofiltration of outer-selective thin-film composite hollow-fiber membranes via continuous interfacial polymerization | |
JP3250644B2 (ja) | 複合中空糸膜およびその製造方法 | |
KR101440969B1 (ko) | 폴리설폰아미드계 역삼투 분리막의 제조방법 및 이에 의해 제조된 역삼투 분리막 | |
WO2007084921A2 (en) | Water permeable membranes and methods of making water permeable membranes | |
CN114130220B (zh) | 一种聚三嗪类耐碱复合纳滤膜的制备方法 | |
Duan et al. | High selective organic solvent nanofiltration composite membranes constructed from hydroxyl binaphthol and diacyl chloride by interfacial polymerization | |
AU2019343597A1 (en) | Forward osmosis membrane and membrane module including same | |
KR102157929B1 (ko) | 수처리 모듈의 제조방법 및 이에 의하여 제조된 수처리 모듈 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |