CN110423223A - A kind of preparation method and its epoxidation application of Phthalazinone biphenol monomer - Google Patents
A kind of preparation method and its epoxidation application of Phthalazinone biphenol monomer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
- C07D237/32—Phthalazines with oxygen atoms directly attached to carbon atoms of the nitrogen-containing ring
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/26—Di-epoxy compounds heterocyclic
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Abstract
The invention belongs to new material technology fields, disclose the preparation method and its epoxidation application of a kind of Phthalazinone biphenol monomer.Steps are as follows: (1) Friedel-Crafts reaction prepares MHPZ；(2) with MHPZ, BPM, PNTM and CuI, MMPZ monomer has been synthesized using " one pot of two-step method "；(3) MMPZ is restored to obtain subject monomers HHPZ through lewis acid.Synthetic reaction condition of the invention has reaction condition mild, the advantage that product postprocessing is easy and product purity is high.Purity through LC-MS test target monomer is 99%, 90% or more yield.It is explored based on above-mentioned synthesis, by the further functionalization in both ends of the active biphenol monomer of synthesis.The activity hydroxy at the both ends HHPZ carries out epoxidation with epoxychloropropane, has obtained low melting point, novel intrinsic fire retarding epoxide resin resistant to high temperature, flame retardant rating is up to V-0 grades.
Description
Technical field
The invention belongs to new material technology field, a kind of preparation method of Phthalazinone biphenol monomer (HHPZ).
Background technique
Bisphenol compound is the primary raw material for synthesizing polyarylate, polyarylether, epoxy resin and polysulfones resinoid, will be special
Different functional group introduces main polymer chain, and then improves service performance (temperature tolerance, anti-flammability, the optical property, thoroughly of polymer
Wave or absorbing property etc.).This patent preparation synthesis biphenol monomer in ehter bond can both increase main polymer chain ductility and
Flexibility, and the fusing point of polymer can be reduced；Meanwhile the special distortion non-co-planar structure of Phthalazinone can improve polymerization
Arrangement between object segment can assign polymer heat resistance outstanding and dissolubility.Such as the poly(aryl ether ketone) in traditional polyarylether
Class material, belongs to semi-crystalline polymer, has excellent chemical stability and mechanical performance, but dissolubility is poor, under room temperature
It is only soluble in the concentrated sulfuric acid.However, in polyarylether system introduce Phthalazinone after prepare a series of polymer (PPESK,
PPENK, PPES etc.) show excellent temperature tolerance and dissolubility.To have full aromatic ring, distortion, non-co-planar benzodiazine
The biphenol monomer function of ring structure turns to epoxy resin, balances the relationship between processability and service performance.
Summary of the invention
The purpose of the present invention is a kind of preparation method of Phthalazinone biphenol monomer and its epoxidation applications.
Technical solution of the present invention:
A kind of preparation method of Phthalazinone biphenol monomer, steps are as follows:
(1) Friedel-Crafts reaction prepares unilateral methoxy monomer (MHPZ)；
(2) with MHPZ, BPM (para-bromoanisole), PNTM (1,10- Phen) and CuI (cuprous iodide), using " one
Pot two-step method " has synthesized bilateral methoxy monomer (MMPZ)；
(3) MMPZ is restored to obtain double hydroxyl subject monomers (HHPZ) through lewis acid；
The synthetic route of MHPZ, MMPZ and HHPZ are as follows:
(1) Friedel-Crafts reaction prepares MHPZ the specific method is as follows: under ice bath environment, using methylene chloride as reaction dissolvent,
Alchlor (AlCl3) it is catalyst, reactant PA:AS:AlCl3Between molar ratio be 1:1.5:1.5, reactant feeds intake completion
Afterwards, continue to stir 1h under ice bath environment；Above-mentioned mixed system is reacted into 3h at 25 DEG C, sinks to ice acid bath after reaction
In, obtain white solid powder；The mixing that above-mentioned white solid powder is dissolved in sulfolane and chlorobenzene that volume ratio is 3:1 is molten
In liquid, 30min is mixed at 110 DEG C, corresponding reactant intermediate sour (product of PA and AS) mole point is then added dropwise
Several hydrazine hydrates maintains 2h at such a temperature, will finally filter after reaction solution cooling and obtains needle-like white solid, as MHPZ；
(2) the specific method is as follows by a kind of bi-methoxy MMPZ prepared containing naphthyridine ketone structure: stirring to equipped with machinery
It mixes, MHPZ and K is added in the three-necked flask of reflux condensate device2CO3, K2CO3Dosage be 2.5 times of MHPZ mole, In
Salt-forming reaction 5-6 hours at 140-150 DEG C, after salt-forming reaction, reaction solution is down to room temperature, it is even that Liv Ullmann is then added
Join ligand PNTM, catalyst CuI and reactant B PM, is protected from light 12-24h, reaction temperature is gradually heated to 160- by room temperature
It 180 DEG C, after reaction, will be sunk in hot water after reaction solution cooling, it is overnight to drain, brown solid is dissolved in chloroform, filters institute
It obtains filtrate and excessive anhydrous sodium sulfate water removal is added, obtain light yellow powder solid after revolving, ethyl alcohol is rinsed 1-2 times, obtained
White solid is placed in 10~12h of vacuum drying in 100 DEG C of vacuum ovens；Wherein, mole of MHPZ, BPM, PNTM and CuI
Than for 1:1.5-2:0.01-0.02:0.05-0.15；
(3) the specific method is as follows by a kind of biphenol monomer HHPZ containing naphthyridine ketone structure: to equipped with mechanical stirring and return
It flows and MMPZ, CH is added in the three-necked flask of condensing unit3CN and KI, solvent C H3CN dosage is every 5g MMPZ addition
100mLCH3CN, feed ratio MMPZ:KI:AlCl3AlCl is added at 0 DEG C in=1:12-16:12-16 in batches3In ice bath ring
AlCl is added under border in batches3, and after continuously stirring 1h, by reaction solution as being reacted for 24 hours at 60-90 DEG C；Reaction solution is cooling
After sink in ice sour water, be collected into pale yellow powder, white solid can be obtained with the mixed liquor repeated flushing of second alcohol and water.
A kind of bifunctionality epoxy containing Phthalazinone EEPZ's the preparation method is as follows: to magnetic agitation is equipped with
HHPZ, benzyltriethylammoinium chloride and epoxy is added according to molar ratio (1:0.15:50) in the there-necked flask of reflux condensate device
Chloropropane reacts 3h at 85 DEG C, is that the NaOH that 1:2.5 dropwise addition mass fraction is 40% is water-soluble by HHPZ:NaOH molar ratio
Liquid, and 1h is reacted at the same temperature, it repeatedly washes, and vacuum rotary steam removes extra water and epoxychloropropane, obtains transparent
Sticky mass.
Beneficial effects of the present invention: synthetic reaction condition of the invention has reaction condition mild, and product postprocessing is easy
And the advantage that product purity is high.Purity through LC-MS test target monomer is 99%, 90% or more yield.Based on above-mentioned
Synthesis is explored, by the further functionalization in both ends of the active biphenol monomer of synthesis.The same epoxy chloropropionate of the activity hydroxy at the both ends HHPZ
Alkane carries out epoxidation, has obtained low melting point, novel intrinsic fire retarding epoxide resin resistant to high temperature, flame retardant rating is up to V-0 grades.
Detailed description of the invention
Fig. 1 is MHPZ nuclear magnetic spectrogram.
Fig. 2 is MMPZ nuclear magnetic spectrogram.
Fig. 3 is HHPZ nuclear magnetic spectrogram.
Fig. 4 is EEPZ nuclear magnetic spectrogram.
Fig. 5 is the LC-MS spectrogram of HHPZ.
Fig. 6 is the alternating temperature rheological curve of EEPZ.
Fig. 7 is the constant temperature rheological curve of EEPZ.
Specific embodiment
Only the present invention is further illustrated for the case study on implementation being provided below, but does not limit the scope of the invention.
Case 1 is the preparation case of the monomer of mono methoxy containing Phthalazinone (MHPZ).
Case study on implementation 1
Using methylene chloride as reaction dissolvent, alchlor (AlCl3) is catalyst, and ice bath feeds intake, reactant (PA:AS:
AlCl3) between molar ratio be 1:1.5:1.5, after the completion of feeding intake, continue under ice bath environment stir 1h.By above-mentioned mixed system
3h is reacted at 25 DEG C, is sunk in ice acid bath after reaction, is obtained white solid powder.Above-mentioned white solid powder is molten
In the mixed solution of sulfolane and chlorobenzene (volume ratio 3:1), 30min is mixed at 110 DEG C, is then added dropwise and corresponds to
The hydrazine hydrate of reactant molar fraction maintains 2h at such a temperature, finally will reaction solution it is cooling after filter and obtain needle-like white and consolidate
Body.
As shown in Fig. 2 nuclear magnetic spectrogram, chemical shift 8.4ppm or so is the absorption peak of the peri-position hydrogen on diaza naphthalene nucleus,
It on the basis of H herein, can be accurately positioned in compound MHPZ, generate the chemical shift at the peak functional group N-H about in 12.7ppm
Near, while nearby also there is the characteristic peak of methoxyl group in chemical shift 3-4ppm.
Case 2 is the preparation case of the monomer of dimethoxy containing naphthyridine ketone structure (MMPZ).
Case study on implementation 2: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light for 24 hours, and reaction temperature is gradually heated to 160 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
Case study on implementation 3: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light 18h, and reaction temperature is gradually heated to 170 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
Case study on implementation 4: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light 12h, and reaction temperature is gradually heated to 180 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
Case study on implementation 5: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light 18h, and reaction temperature is gradually heated to 180 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
As shown in Fig. 3 nuclear magnetic spectrogram, by chemical shift 8.4ppm or so be diaza naphthalene nucleus on peri-position hydrogen on the basis of,
Its near 3-4ppm the ratio between peak area be 1:6, in addition, also occurring phenyl ring hydrogen characteristic peak at 6.7ppm, it was demonstrated that MHPZ
C-N coupling reaction success between BPM.
Case 3 is the preparation case of biphenol monomer containing naphthyridine ketone structure (HHPZ)
Case study on implementation 6: being added MMPZ into the three-necked flask equipped with mechanical stirring, reflux condensate device, and in molar ratio 1:
12 are added AlCl3, in 0 DEG C of CH3After continuously stirring 1h in CN and KI system, by reaction solution as being reacted for 24 hours at 90 DEG C.It will reaction
Liquid cooling is but sunk in ice sour water afterwards, is collected into pale yellow powder, and white can be obtained with the mixed liquor repeated flushing of second alcohol and water
Solid.
Case study on implementation 7: being added MMPZ into the three-necked flask equipped with magnetic agitation, reflux condensate device, and in molar ratio 1:
16 are added AlCl3, in 0 DEG C of CH3After continuously stirring 1h in CN and KI system, by reaction solution as being reacted for 24 hours at 90 DEG C.It will reaction
Liquid cooling is but sunk in ice sour water afterwards, is collected into pale yellow powder, and white can be obtained with the mixed liquor repeated flushing of second alcohol and water
Solid.
Case study on implementation 8: being added MMPZ into the three-necked flask equipped with magnetic agitation, reflux condensate device, and in molar ratio 1:
16 are added AlCl3, in 0 DEG C of CH3After continuously stirring 1h in CN and KI system, by reaction solution as being reacted for 24 hours at 90 DEG C.It will reaction
Liquid cooling is but sunk in ice sour water afterwards, is collected into pale yellow powder, and white can be obtained with the mixed liquor repeated flushing of second alcohol and water
Solid.
As shown in Fig. 4 nuclear magnetic spectrogram, occur phenolic hydroxyl group absorption peak between chemical shift 9.5-10ppm, meanwhile, 3-4 it
Between methoxyl group characteristic peak peak disappear, show that MMPZ is successfully reduced to HHPZ.And by LC-MS as shown in fig. 6, into one
Step characterizes product purity.
Case 4 is the preparation case of epoxy containing naphthyridine ketone structure (EEPZ)
Case study on implementation 9: into the there-necked flask equipped with magnetic agitation and reflux condensate device according to molar ratio (1:0.15:
50) HHPZ, benzyltriethylammoinium chloride and epoxychloropropane is added, reacts 3h at 85 DEG C, is by HHPZ:NaOH molar ratio
1:2.5 is added dropwise mass fraction and is 40% NaOH aqueous solution, and reacts 1h at the same temperature, repeatedly washes, and vacuum rotary steam
Extra water and epoxychloropropane are removed, transparent sticky mass is obtained.
As shown in figure 5, occurring the proton peak on epoxy alkyl chain at 2.5-4.5ppm, show the both ends HHPZ epoxy
Change is completed.Simultaneously rheometer test characterization has been carried out to the processing performance of EEPZ epoxy, by Fig. 6 it is found that EEPZ epoxy have compared with
Low fusing point is about 65 DEG C, and process window is about 85-225 DEG C wider.The gel time of EEPZ resin is about known to Fig. 7
45min.In addition, vertical burn test the results show that for the first time light flame, extinguish in 4s, after lighting for the second time
Extinguish in 10s, no molten drop is low, and flame retardant rating is up to V-0 grades.
Claims (2)
1. a kind of preparation method of Phthalazinone biphenol monomer, which is characterized in that steps are as follows:
The synthetic route of MHPZ, MMPZ and HHPZ are as follows:
(1) Friedel-Crafts reaction prepares MHPZ the specific method is as follows:
Under ice bath environment, using methylene chloride as reaction dissolvent, AlCl3For catalyst, reactant PA:AS:AlCl3Between mole
Than after the completion of reactant feeds intake, continuing to stir 1h under ice bath environment for 1:1.5:1.5；By above-mentioned mixed system at 25 DEG C
3h is reacted, is sunk in ice acid bath after reaction, obtains white solid powder；Above-mentioned white solid powder, which is dissolved in volume ratio, is
In the sulfolane of 3:1 and the mixed solution of chlorobenzene, 30min is mixed at 110 DEG C, corresponding reactant intermediate is then added dropwise
The hydrazine hydrate of sour molar fraction maintains 2h at such a temperature, will finally filter after reaction solution cooling and obtains needle-like white solid, i.e.,
For MHPZ；
(2) the specific method is as follows by a kind of bi-methoxy MMPZ prepared containing naphthyridine ketone structure:
MHPZ and K is added into the three-necked flask equipped with mechanical stirring, reflux condensate device2CO3, K2CO3Dosage be that MHPZ rubs
2.5 times of that amount, salt-forming reaction 5-6 hours at 140-150 DEG C, after salt-forming reaction, are down to room temperature for reaction solution, then
Liv Ullmann coupling ligand PNTM, catalyst CuI and reactant B PM is added, is protected from light 12-24h, reaction temperature by room temperature gradually
It is warming up to 160-180 DEG C, after reaction, will be sunk in hot water after reaction solution cooling, it is overnight to drain, brown solid is dissolved in chlorine
It is imitative, it filters gained filtrate and excessive anhydrous sodium sulfate water removal is added, obtain light yellow powder solid after revolving, ethyl alcohol rinses 1-2
Time, white solid is obtained, is placed in 100 DEG C of vacuum ovens and is dried in vacuo 10~12h to get MMPZ；Wherein, MHPZ, BPM,
The molar ratio of PNTM and CuI is 1:1.5-2:0.01-0.02:0.05-0.15；
(3) the specific method is as follows by a kind of biphenol monomer HHPZ containing naphthyridine ketone structure:
MMPZ, CH are added into the three-necked flask equipped with mechanical stirring and reflux condensate device3CN and KI is added in batches at 0 DEG C
AlCl3AlCl is added in batches under ice bath environment3, and after continuously stirring 1h, by reaction solution as being reacted for 24 hours at 60-90 DEG C；
Solvent C H3CN dosage is that 100mLCH is added in every 5g MMPZ3CN, feed ratio MMPZ:KI:AlCl3=1:12-16:12-16；It will
It is sunk in ice sour water after reaction solution is cooling, is collected into pale yellow powder, with the mixed liquor repeated flushing of second alcohol and water up to white
Solid is HHPZ.
2. a kind of preparation method of the bifunctionality epoxy EEPZ containing Phthalazinone, which is characterized in that steps are as follows: to
HHPZ, benzyl triethyl ammonium chlorine is added according to molar ratio 1:0.15:50 in there-necked flask equipped with magnetic agitation and reflux condensate device
Change ammonium and epoxychloropropane, react 3h at 85 DEG C, is that mass fraction is added dropwise is 40% to 1:2.5 by HHPZ:NaOH molar ratio
NaOH aqueous solution, and 1h is reacted at the same temperature, it repeatedly washes, and vacuum rotary steam removes extra water and epoxychloropropane,
Obtain transparent sticky mass.
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| CN201910680796.2A CN110423223A (en) | 2019-07-26 | 2019-07-26 | A kind of preparation method and its epoxidation application of Phthalazinone biphenol monomer |
| CN202010728062.XA CN111704581B (en) | 2019-07-26 | 2020-07-24 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
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| CN202010728062.XA Active CN111704581B (en) | 2019-07-26 | 2020-07-24 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
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| CN111530298A (en) * | 2020-05-12 | 2020-08-14 | 福建师范大学 | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group |
| CN111704581A (en) * | 2019-07-26 | 2020-09-25 | 大连理工大学 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
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| CN113956458B (en) * | 2021-10-09 | 2023-03-28 | 万华化学集团股份有限公司 | Copolycarbonate with high refractive index, high heat resistance and high weather resistance, preparation method and application thereof |
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| CN101619131B (en) * | 2009-07-25 | 2012-07-25 | 大连理工大学 | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof |
| CN102585225B (en) * | 2011-05-20 | 2014-10-22 | 大连理工大学 | Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer |
| CN106905136A (en) * | 2017-02-08 | 2017-06-30 | 泰力特医药（湖北）有限公司 | A kind of preparation method of 2 (4 (2-hydroxybenzoyl)) benzoic acid |
| CN117586108A (en) * | 2017-10-30 | 2024-02-23 | 科罗拉多州立大学董事会法人团体 | TOLL-like receptor 8 (TLR 8) specific antagonists, methods of making and uses thereof |
| CN109456435B (en) * | 2018-10-09 | 2021-05-11 | 大连理工大学 | Synthetic method of perfluorocyclobutyl polyarylether containing heteronaphthalene biphenyl structure |
| CN109851563B (en) * | 2019-03-04 | 2022-06-14 | 大连理工大学 | Preparation method of bisphenol monomer containing phthalazinone structure |
| CN110423223A (en) * | 2019-07-26 | 2019-11-08 | 大连理工大学 | A kind of preparation method and its epoxidation application of Phthalazinone biphenol monomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111704581A (en) * | 2019-07-26 | 2020-09-25 | 大连理工大学 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
| CN111704581B (en) * | 2019-07-26 | 2021-08-24 | 大连理工大学 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
| CN111530298A (en) * | 2020-05-12 | 2020-08-14 | 福建师范大学 | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group |
| CN111530298B (en) * | 2020-05-12 | 2021-11-23 | 福建师范大学 | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group |
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Application publication date: 20191108 |