CN106883434A - One class is containing side base structure combed polyether sulphone membrane material long and preparation method thereof - Google Patents

One class is containing side base structure combed polyether sulphone membrane material long and preparation method thereof Download PDF

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Publication number
CN106883434A
CN106883434A CN201710075189.4A CN201710075189A CN106883434A CN 106883434 A CN106883434 A CN 106883434A CN 201710075189 A CN201710075189 A CN 201710075189A CN 106883434 A CN106883434 A CN 106883434A
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side base
base structure
long
containing side
combed
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汪称意
徐常
赵晓燕
李坚
任强
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Changzhou University
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Changzhou University
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    • 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
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention provides a class containing side base structure combed polyether sulphone membrane material long and preparation method thereof, its preparation method is：Under nitrogen protection; respectively by a certain amount of containing side base structure-activity bis-phenol long, '-biphenyl diphenol and 4; 4 ' three kinds of difluorodiphenyl sulfone monomers are added in reaction bulb; add appropriate solvent and dehydrating agent; under base catalyst effect; by nucleophilic aromatic substitution polycondensation reaction, you can obtain the side base structure combed polyaryl ether sulphone resin long containing 3,5 dimethyl phenoxy benzene.Such has good dissolving film forming containing side base structure combed polyaryl ether sulphone resin long, and institute's made membrane has important application value in gas separation membrane field；Additionally, such can also further by functionalized reaction, for preparing high performance anion-exchange membrane material containing side base structure combed polyaryl ether sulphone resin long.

Description

One class is containing side base structure combed polyether sulphone membrane material long and preparation method thereof
Technical field
The invention belongs to polyether sulphone membrane material and its preparation field, a more particularly to class contains side base structure combed polyarylether long Sulfone membrane material and preparation method thereof.
Background technology
Polyether sulphone is the important functional high molecule material of a class, can respectively be applied as Flat Membrane and hollow-fibre membrane In many high-tech areas such as gas separation, desalinization, haemodialysis, fuel cell ion exchange membrane.But as gas During seperation film application, due to the rigidity and regularity of polymer molecule chain structure, it is low generally to there is infiltration coefficient in polyether sulphone film, Separating rate waits not enough slowly, it is difficult to meet the development need of modern efficient separation equipment.Molecule is carried out to polyether sulphone membrane material Structurally-modified, further improving its performance has important researching value and application value.Research finds, in rigid polymer point Big substitution side base is introduced in minor structure, can preferably improve the separating property of rigid polymer membrane material.Current polyether sulphone Molecular structure is modified mainly to carry out rear modification by its polymer macromolecule structure, and the method is difficult to control accurate and changes Polymer molecular structure and performance after property, and easily cause the degraded of strand.And rationally set from monomer structure Meter is modified, then can control accurate polymer macromolecule structure and performance, have no effect on subsequent polymer strand.Patent of the present invention It is further intended to improve the separating property of polyether sulphone membrane material, uses a kind of active biphenol monomer containing side base structure long to rise Beginning raw material, a class is prepared for containing side base structure combed polyether sulphone membrane material long by aromatic nucleophilic copolycondensation, such comb Side base content long in type polyether sulphone molecular structure can Effective Regulation, such that it is able to the property of convenient control polymeric film material Energy.Additionally, patent of the present invention provided containing side base structure combed polyether sulphone membrane material long, due to containing two in molecular structure Methyl benzene lateral group, can be further used for the preparation of polymer anion-exchange membrane material, be applied to alkaline solid-state fuel cell Field.
The content of the invention
Patent of the present invention is intended to improve the separating property of polyether sulphone membrane material, further improves its infiltration coefficient and separation Speed a, there is provided class is containing side base structure combed polyether sulphone membrane material long and preparation method thereof：Due in polyether sulphone molecule 3,5- dimethyl phenoxy benzene side base structure long is introduced in structure, the free volume of polymer molecular structure can be significantly increased, Such that it is able to effectively improve the separation permeability and separating rate of polyether sulphone membrane material.Additionally, provided containing side base knot long Structure combed polyether sulphone membrane material, due to containing dimethyl benzene side base in molecular structure, can be further used for polymer it is cloudy from The preparation of proton exchange membrane material, is applied to alkaline solid-state fuel cell field.
Contain side base structure combed polyether sulphone membrane material long the invention provides a class, its structural formula is：
Its polymer molecule knot Side base long in structure is 3,5- dimethyl phenoxy benzene structures, its content x=0.30~0.60, constitutional repeating unit n=80~ 150。
Present invention also offers preparation method of the class containing side base structure combed polyether sulphone membrane material long, specific steps For：
(1) under nitrogen protection, be separately added into there-necked flask x parts (x=0.30~0.60) containing side base structure long Active bis-phenol, 1-x part of '-biphenyl diphenol and 1 part 4,4 '-difluorodiphenyl sulfone, three kinds of monomers add appropriate solvent and dehydrating agent, After base catalyst acts on lower 110~140 DEG C of 2~4h of azeotropic dehydration, dehydrating agent is steamed, further heated up to 150~170 DEG C of contractings Terminate reaction after 5~10h of poly- reaction, by reactant pour into sedimentation in ethanol can obtain it is fibrous containing side base structure combed long Polyaryl ether sulphone resin；
(2) will be dissolved in organic solvent that to be made into concentration be 10~20wt%'s containing side base structure combed polyaryl ether sulphone resin long Polymer solution, the film on plate glass, in an oven in dry 24 hours under uniform temperature, you can obtain containing side base knot long Structure combed polyether sulphone film.
The described active biphenol monomer containing side base structure long is double (4- hydroxy phenyls) -1- (4- (the 3,5- diformazans of 1,1- Base) phenoxy group) phenyl -2,2,2- HFC-143as, its structural formula is：
The solvent for polymerization, dehydrating agent and catalyst are respectively 1-METHYLPYRROLIDONE, toluene and potassium carbonate, in system The consumption of 1-METHYLPYRROLIDONE is three kinds the 2~4 of reaction monomers gross mass times, and the consumption of toluene is 1-METHYLPYRROLIDONE body Long-pending 20%~50%, the consumption of potassium carbonate is 4,1.0~1.3 times of 4 '-difluorodiphenyl sulfone monomer molar number.
Described casting solution is the one kind in chloroform, DMA, 1-METHYLPYRROLIDONE, wherein using chlorine It is 30 DEG C to imitate drying temperature when making solvent, when making solvent with DMA or 1-METHYLPYRROLIDONE, drying temperature It is 70 DEG C.
Specific synthetic route containing side base structure combed polyether sulphone long of the invention is as follows：
The beneficial effects of the invention are as follows：
(1) side base structure combed polyether sulphone membrane material long, such polyether sulphone membrane material are contained the invention provides a class Preparation process is simple, the content of 3, the 5- dimethyl phenoxy benzene side base structure long in molecular structure can conveniently regulating and controlling；
(2) present invention provide containing side base structure combed polyether sulphone membrane material long, with good dissolving film forming, can It is dissolved in chloroform, DMA, 1-METHYLPYRROLIDONE equal solvent, it is convenient to gathered using its solution coating Aryl ether sulfone gas separation membrane, and with good gas separating property；
(3) present invention provide containing side base structure combed polyether sulphone membrane material long, due to containing diformazan in molecular structure Base benzene lateral group, can be further used for the preparation of polymer anion-exchange membrane material, be applied to alkaline solid-state fuel cell neck Domain.
Brief description of the drawings
Fig. 1 is containing side base structure combed polyarylethersulfone polymer long in embodiment 11H NMR spectras (wherein 3,5- diformazans Phenoxyl benzene side base structural content x=0.4 long).
Specific embodiment
Embodiment 1
(1) in the 100ml equipped with mechanical agitation, nitrogen protection and water knockout drum dries there-necked flask, it is separately added into Double (4- hydroxy phenyls) -1- (4- (3,5- dimethyl) phenoxy group) phenyl -2,2,2- trifluoro second of the 1,1- of 1.8579g (4mmol) Alkane (as a example by dredging the big substitution side base structural unit content x=0.4 of shape), '-biphenyl diphenol, the 2.5425g of 1.1173g (6mmol) 4,4 '-difluorodiphenyl sulfone monomer of (10mmol), the potassium carbonate of 1.3821g (10mmol), the 1-METHYLPYRROLIDONE of 11ml and The toluene of 5ml, after 110 DEG C of azeotropic dehydration 4h, further heats up to 150 DEG C of copolycondensation 10h, terminates reaction, will react Solution is poured into ethanol, obtains fibrous containing side base structure combed polyaryl ether sulphone resin long, and yield is 99%；1H NMR (CDCl3, 400MHz) as shown in Figure 1.
(2) will further contain side base structure combed polyaryl ether sulphone resin long to be dissolved in chloroformic solution, be made into the poly- of 20wt% Polymer solution, by polymer solution film on plate glass, 24h is dried in baking oven at 30 DEG C, you can obtained containing side base long Structure combed polyether sulphone film.
Embodiment 2
(1) in the 100ml equipped with mechanical agitation, nitrogen protection and water knockout drum dries there-necked flask, it is separately added into Double (4- hydroxy phenyls) -1- (4- (3,5- dimethyl) phenoxy group) phenyl -2,2,2- trifluoro second of the 1,1- of 2.7869g (6mmol) Alkane (as a example by dredging the big substitution side base structural unit content x=0.6 of shape), '-biphenyl diphenol, the 2.5425g of 0.7448g (4mmol) 4,4 '-difluorodiphenyl sulfone monomer of (10mmol), the potassium carbonate of 1.7967g (13mmol), the 1-METHYLPYRROLIDONE of 23ml and The toluene of 6ml, after 140 DEG C of azeotropic dehydration 2h, further heats up to 170 DEG C of copolycondensation 5h, terminates reaction, will react molten Liquid is poured into ethanol, obtains fibrous containing side base structure combed polyaryl ether sulphone resin long, and yield is 99%.
(2) will further contain side base structure combed polyaryl ether sulphone resin long to be dissolved in 1-METHYLPYRROLIDONE solution, be made into The polymer solution of 10wt%, by polymer solution film on plate glass, 24h is dried in baking oven at 70 DEG C, you can To containing side base structure combed polyether sulphone film long.

Claims (5)

1. a class contains side base structure combed polyether sulphone membrane material long, it is characterised in that：The combed polyether sulphone structural formula is：Side long in polymer molecular structure Base is 3,5- dimethyl phenoxy benzene structures, its content x=0.30~0.60, constitutional repeating unit n=80~150.
2. a class as claimed in claim 1 contains the preparation method of side base structure combed polyether sulphone membrane material long, and its feature exists In：The step of preparation method is
(1) under nitrogen protection, x parts (x=0.30~0.60) is separately added into there-necked flask contains side base structure-activity long Bis-phenol, 1-x part of '-biphenyl diphenol and 1 part 4,4 '-difluorodiphenyl sulfone, three kinds of monomers add appropriate solvent and dehydrating agent, in alkalescence Under catalyst action after 110~140 DEG C of 2~4h of azeotropic dehydration, dehydrating agent is steamed, further heated up anti-to 150~170 DEG C of polycondensations Answer and terminate reaction after 5~10h, by reactant pour into sedimentation in ethanol can obtain it is fibrous poly- fragrant containing side base structure combed long Ether sulfone resin；
(2) will be dissolved in organic solvent that to be made into the polymer that concentration is 10~20wt% molten containing side base combed polyaryl ether sulphone resin long Liquid, the film on plate glass, in an oven in dry 24 hours under uniform temperature, you can obtain poly- containing side base structure combed long Aryl ether sulfone film.
It is 3. according to claim 2 to prepare the method containing side base structure combed polyether sulphone membrane material long, it is characterised in that： Described in step (1) is double (4- hydroxy phenyls) -1- (4- (3,5- dimethyl) benzene of 1,1- containing side base structure-activity biphenol monomer long Epoxide) phenyl -2,2,2- HFC-143as, its structural formula is：
It is 4. according to claim 2 to prepare the method containing side base structure combed polyether sulphone membrane material long, it is characterised in that： Solvent, dehydrating agent and catalyst described in step (1) are respectively 1-METHYLPYRROLIDONE (NMP), toluene and potassium carbonate, in system The consumption of 1-METHYLPYRROLIDONE is three kinds the 2~4 of reaction monomers gross mass times, and the consumption of toluene is 1-METHYLPYRROLIDONE body Long-pending 20%~50%, the consumption of potassium carbonate is 4,1.0~1.3 times of 4 '-difluorodiphenyl sulfone monomer molar number.
It is 5. as claimed in claim 2 to prepare the method containing side base structure combed polyether sulphone membrane material long, it is characterised in that：Step Suddenly the casting solution described in (2) is the one kind in chloroform, DMA, 1-METHYLPYRROLIDONE, wherein using chloroform Drying temperature is 30 DEG C when making solvent, and when making solvent with DMA or 1-METHYLPYRROLIDONE, drying temperature is 70℃。
CN201710075189.4A 2017-02-13 2017-02-13 One class is containing side base structure combed polyether sulphone membrane material long and preparation method thereof Pending CN106883434A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432436A (en) * 2010-09-29 2012-05-02 中国科学院化学研究所 Poly-fluorophenyl-substituted aromatic diphenol and synthesis method and application thereof
CN104370712A (en) * 2014-10-17 2015-02-25 常州大学 Bisphenol monomer containing trimethoxy benzene structure and preparation method thereof
CN104861167A (en) * 2015-05-29 2015-08-26 常州大学 Polyether sulphone containing plurality of quaternary ammonium salt phenyl side group structures and preparation method for polyether sulphone
CN105504284A (en) * 2016-01-04 2016-04-20 中国科学院长春应用化学研究所 Polymer containing quaternary ammonium group, anion exchange membrane and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432436A (en) * 2010-09-29 2012-05-02 中国科学院化学研究所 Poly-fluorophenyl-substituted aromatic diphenol and synthesis method and application thereof
CN104370712A (en) * 2014-10-17 2015-02-25 常州大学 Bisphenol monomer containing trimethoxy benzene structure and preparation method thereof
CN104861167A (en) * 2015-05-29 2015-08-26 常州大学 Polyether sulphone containing plurality of quaternary ammonium salt phenyl side group structures and preparation method for polyether sulphone
CN105504284A (en) * 2016-01-04 2016-04-20 中国科学院长春应用化学研究所 Polymer containing quaternary ammonium group, anion exchange membrane and preparation method thereof

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