CN103319707B - Polyaryletherketone copolymer containing porphyrin structure at main chain, and preparation method thereof - Google Patents
Polyaryletherketone copolymer containing porphyrin structure at main chain, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyaryletherketone copolymer containing a porphyrin structure at a main chain and a preparation method of the polyaryletherketone copolymer and belongs to the field of high polymer material preparation technology. Nucleophilic polycondensation is carried out on dyhydroxyl tetraphenyl porphyrin, aromatic organic bisphenol and 4,4'-difluoro diphenyl ketone to prepare the dissolvable polyaryletherketone copolymer. As the porphyrin has significant nonlinear optical effect, excellent thermal stability and chemical stability and is the representative of optical limiting organic dye molecules to be intensively researched by people, by introducing the porphyrin into the main chain structure of the polyaryletherketone, the three-stage nonlinear optical effect and the optical limiting property are provided to the polymer, and the heat resistance of the polymer is improved to a greater degree. A porphyrin-containing polyaryletherketone film prepared by the tape casting maintains better mechanical property and fluorescence characteristic. The polyaryletherketone copolymer containing the porphyrin structure at the main chain prepared by the invention possibly can be used for the fields of laser protection, nonlinear optics, fluorescence response detection and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of main chain poly (aryl ether ketone) copolymer containing porphyrin structure and preparation method thereof.
Background technology
From the later stage 1980s, laser technology is militarily developed rapidly.For the low energy laser weapon of laser blinding, target attacks various opticinstrument and human eye, and its medium wavelength is that the damage of green glow to eye ground of 532nm is maximum.Along with the development of laser technology and the continuous expansion of Application Areas, short pulse, high-power laser apparatus are also increasing, and therefore lasing safety is more and more subject to the attention of domestic and international scientific research personnel.Optical limitation refers to that medium has higher linear transmittance under lower input light intensity, and output intensity linearly increases with the increase of incident intensity; And under height input light intensity, because the non-linear optical effect (non-linear absorption, refraction or scattering) of medium causes transmissivity to decline, after input light intensity reaches certain threshold value, output intensity is limited the optical phenomena changed within the specific limits and not.
Porphyrins is the organic molecule that a class has large ring conjugated structure, be widespread in nature and have special physiologically active, in fields such as mimic photosynthesis effect, solar cell, Journal of Molecular Catalysis, cancer cells detection and photoelectric conversions, all tool is of great significance and wide application prospect.Owing to having larger delocalizedπelectron conjugated system, porphyrin excited state (singlet state or triplet state) absorbs the reverse saturated absorption that causes clearly, shows the Third-order nonlinearity of macroscopic view, and fast response time, lifetime of excited state is long.Effectively can be changed its absorption spectrum and excited state properties by the metal complex to Porphyrin Molecule, the design of peripheric substitution base and axial coordination, this makes porphyrin become one of representational optical limiting materials of most.But small molecules Porphyrin and its derivative is difficult to processing, fusing point and hardness is low, can only play a role with solution state, and intermolecular being easy to piles up gathering, thus porphyrin is introduced polymeric system, in conjunction with respective advantage, the nonlinear optical material that can be used for lasing safety of preparation mechanical property and thermal characteristics excellence is the research topic with academic significance and actual application value.
Poly aryl ether ketone material belongs to high-temperature-resistant thermoplastic polymkeric substance, the many merits such as have resistance to chemical attack, radiation hardness, fire-retardant, resistance to fatigue good, shock strength is high.Since succeeding in developing also commercialization from early 1980s at first by ICI company of Britain, polyaryletherketone is widely used in fields such as petrochemical complex, machinery, nuclear power, aerospace, military equipment, electronic information.Domestic still not open in the technology of polyarylether class material introducing porphyrin at present, the document about polyaryletherketone and porphyrin matrix material also rarely has report.
Summary of the invention
The technical problem to be solved in the present invention designs and synthesizes the poly (aryl ether ketone) copolymer that main chain contains porphyrin, by 4,4 '-difluoro benzophenone, aromatic organic bisphenol and 5,10-bis-(4-hydroxy phenyl)-15, the nucleophilic condensation polymerization of 20-phenylbenzene porphyrin or 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin, synthesize the multipolymer that a series of porphyrin content is different, prepare the high temperature resistant nonlinear optics of a class and optical limiting materials.
Porphyrin is introduced in the backbone structure of polyaryletherketone in the mode of chemical bonding by the present invention, has prepared the soluble poly aromatic ether ketone material that main chain contains porphyrin structure.The introducing of porphyrin structure imparts the excellent Third-order nonlinearity of polyaryletherketone and optical limiting properties, and improve thermostability and the physical strength of material to a certain extent, improve porphyrin degree of scatter in the polymer simultaneously, avoid small molecules porphyrin and assemble the fluorescent quenching caused.
Main chain of the present invention is as follows containing porphyrin poly (aryl ether ketone) copolymer structure:
Wherein Por is:
Ar is:
Wherein 0 < m≤0.50, n represents the polymerization degree, is the integer of 10 ~ 80.
Described main chain contains the preparation method of the poly (aryl ether ketone) copolymer of porphyrin structure, comprises the steps:
Under nitrogen protection, by dihydroxyl tetraphenylporphyrin, aromatic organic bisphenol, 4,4 '-difluoro benzophenone and Anhydrous potassium carbonate join in the there-necked flask with mechanical stirring device, with N-Methyl pyrrolidone (NMP) or tetramethylene sulfone (TMS) for solvent, add water entrainer toluene, through stirring and dissolving post-heating to 120 ° C ~ 140, ° C's mixture refluxes 2 ~ 4 hours, removes the water of toluene and reaction generation completely, then temperature is risen to 150 ° of C ~ 190 ° C and reacts 2 ~ 6 hours; Again the solution of thickness is poured in dehydrated alcohol, obtain pliable and tough polymer strands, broken into powder with tissue pulverizer, boil 5 ~ 10 times respectively with deionized water and ethanol, to remove desolventizing and small-molecule substance; After suction filtration, product is placed in vacuum drying oven dry 24 ~ 48 hours, thus obtains the poly (aryl ether ketone) copolymer that main chain contains porphyrin structure.
Described dihydroxyl tetraphenylporphyrin monomer is 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin or 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin, and two kinds of porphyrins all have higher reactive behavior.Its structural formula is as follows:
The crude product standby with mixing aromatic aldehyde Adler legal system by pyrroles is purified through chromatographic column, collect third and fourth colour band, 5 are obtained respectively after evaporate to dryness eluent, 15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin and 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin, reference literature (synthesis of serial hydroxy phenyl porphyrin and fluorescence spectrum research ［ J ］ thereof. organic chemistry, 2006,26(2): the preparation method recorded 247-251) synthesizes above-mentioned two kinds of porphyrins.
Good solvability and thermotolerance is taken into account in order to make polymkeric substance, described fragrant organic bisphenol selects 2 of flexible structure, 2-bis-(4-hydroxy phenyl) propane, fluorine-containing 2,2-bis-(4-hydroxy phenyl) HFC-236fa, 3-trifluoromethyl Resorcinol or 3,5,3 ', 5 '-tetramethyl biphenyl diphenol, structure is as follows respectively:
Described dihydroxyl tetraphenylporphyrin and the mole number total amount of aromatic organic bisphenol equal 4, the mole number of 4 '-difluoro benzophenone, wherein the mol ratio of dihydroxy phenyl porphyrin and aromatic organic bisphenol is 1:19 ~ 1:1, the consumption of Anhydrous potassium carbonate is 4,1.1 ~ 1.2 times of 4 '-difluoro benzophenone mole number.
Experimental result shows: along with the increase of porphyrin molar content, and the polymer color of preparation is deepened to atropurpureus gradually by pink, and its molecular weight rises, and second-order transition temperature and 5% heat decomposition temperature all show ascendant trend, and elongation at break declines to some extent.
Described main chain measures containing the nonlinear optical property Z scan method of porphyrin polyaryletherketone, light source used is the q-multiplier Nd:YAG laser apparatus of 21ps pulsewidth, 532nm wavelength, single pulse energy is 0.37 μ J, repetition rate is 10Hz, cuvette thickness is 2mm, take trichloromethane as solvent, polymer residual is 5mg/mL.
Described main chain is containing the characterizing method of the optical Limiting character of porphyrin polyaryletherketone, the light source adopted is the q-multiplier Nd:YAG laser apparatus of 4ns pulsewidth, 532nm wavelength, and single pulse energy is 0.21 μ J, and repetition rate is 10Hz, cuvette thickness is 5mm, is regulated the power of light by losser.Take trichloromethane as solvent, polymer residual is 0.5mg/mL.
Preparation method of the present invention is easy and simple to handle, and repeatability is high, containing higher porphyrin content in multipolymer, inherits nonlinear optical properties and the optical limiting properties of small molecules porphyrin excellence.This prepared series material had both had good thermal characteristics, and (second-order transition temperature is at 170 ° of more than C, 5% thermal weight loss temperature is at 540 ° of more than C), there is again good film-forming properties, adopt the method for solvent plastic film mulch can obtain pliable and tough polymeric film, and polymers soln and film all have very strong fluorescence response.This series material integrates high-performance polymer and functional polymer, is expected to the laser protective material as protection human eye and some optical pickocffs.
Accompanying drawing explanation
Fig. 1: main chain prepared by embodiment 1 contains the nmr spectrum of the poly (aryl ether ketone) copolymer PAEK-6FBPA-cisDHTPP-25% of porphyrin, and this figure can illustrate the structure of the multipolymer of preparation.
Fig. 2: main chain prepared by embodiment 1 contains the infrared spectrum of the poly (aryl ether ketone) copolymer PAEK-6FBPA-cisDHTPP-25% of porphyrin.This figure can illustrate the copolymer structure of preparation: 3315cm
-1place is the stretching vibration peak of pyrrole ring imino-; 1657cm
-1place is the charateristic avsorption band of polymer carboxyl; 1596cm
-1place is the charateristic avsorption band of phenyl ring; 1243cm
-1for the charateristic avsorption band of main chain ether-oxygen bond; 800cm
-1place is the charateristic avsorption band of pyrrole ring carbonnitrogen bond.
Fig. 3: main chain prepared by embodiment 2 contains the infrared spectrum of porphyrin poly (aryl ether ketone) copolymer PAEK-BPA-cisDHTPP-5%.This figure can illustrate the copolymer structure of preparation: 3309cm
-1place is the stretching vibration peak of pyrrole ring imino-; 2964cm-1 place is the stretching vibration peak of methyl; 1654cm
-1place is the charateristic avsorption band of polymer carboxyl; 1593cm
-1place is the charateristic avsorption band of phenyl ring; 1237cm
-1for the charateristic avsorption band of main chain ether-oxygen bond.
Fig. 4: main chain prepared by embodiment 3 contains the uv-visible absorption spectra of the poly (aryl ether ketone) copolymer PAEK-6FBPA-transDHTPP-15% of porphyrin.It is the absorption of polymer backbone between 250nm to 330nm; The absorption that 419nm place is with for porphyrin S; 516nm, 551nm, 589nm, 646nm place is the absorption of four Q bands of porphyrin.
Fig. 5: the fluorescence emission spectrum of embodiment 2, polymer solution concentration is 2mg/L, and when 419nm wavelength place excites, multipolymer occurs emission peak at 650nm and 713nm place.
Fig. 6: main chain prepared by embodiment 1,3,5 contains the thermogravimetric curve of porphyrin poly (aryl ether ketone) copolymer.
Fig. 7: in embodiment 1,5mg/ml main chain is containing the perforate Z scanning curve of porphyrin poly (aryl ether ketone) copolymer PAEK-6FBPA-cisDHTPP-25% solution.The linear transmittance of sample is 52%.Sample is scanned twice from left to right, and the perforate obtained and closed pore Z scanning curve are through the Fitting Calculation non-linear absorption coefficient β=3.75 × 10
-11m/W, third-order nonlinear susceptibility | χ
(3)|=1.63 × 10
-12esu.
Fig. 8: in embodiment 3,0.5mg/ml main chain is containing the optical Limiting test curve of porphyrin poly (aryl ether ketone) copolymer PAEK-6FBPA-transDHTPP-15%.The linear transmittance recording sample is 32%, and limiting threshold is 0.64J/cm
2.
Embodiment
Be described method of the present invention below by specific embodiment, the specific descriptions of described embodiment just to claim of the present invention, claim includes but not limited to described embodiment content.
Reagent described in following embodiment and material if no special instructions, all can obtain from commercial channels; Described experimental technique, if no special instructions, is ordinary method.
Embodiment 1:
(1) 5,15-bis-(4-hydroxy phenyl)-10, the preparation of 20-phenylbenzene porphyrin and 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin: add 5.306g(50mmol in 1000ml there-necked flask) phenyl aldehyde, 6.106g(50mmol) 4-hydroxy benzaldehyde, add 350ml propionic acid to dissolve, be heated to backflow, dropwise add 6.94ml(100mmol) newly steam pyrroles, within about 20 minutes, dropwise, continue backflow and add equal-volume distilled water after 40 minutes, be cooled to room temperature.With the propionic acid in saturated sodium carbonate solution and in system, decompress filter, filter cake respectively through saturated sodium carbonate solution, distilled water wash for several times after, dissolve with the mixed solvent of chloroform and ethanol and admix silica gel and be spin-dried for upper prop.Take chloroform as wash-out machine washing first and second colour band lower; Then with chloroform than the ethanol solvent that is 100:2 for lower third and fourth colour band of wash-out machine washing, be spin-dried for solvent and obtain 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin and 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin respectively.
(2) at one, mechanical stirring is housed, nitrogen port, thermometer, in the 50ml there-necked flask of water-taker and prolong, add 5, 10-bis-(4-hydroxy phenyl)-15, 20-phenylbenzene porphyrin 1.615g(2.5mmol), 2, 2-bis-(4-hydroxy phenyl) HFC-236fa 2.522g(7.5mmol), 4, 4 '-difluoro benzophenone 2.182g(10mmol) and Anhydrous potassium carbonate 1.656g(12mmol) be dissolved in N-Methyl pyrrolidone (25ml), add water entrainer toluene (12ml), pass into nitrogen 15 minutes after monomer all dissolves, be warming up to 135 ° of C to reflux 2.5 hours, then water and the water entrainer toluene of reaction generation is released, reaction system is warming up to 183 ° of C, copolyreaction is completed after 5 hours.The solution of thickness is slowly poured in dehydrated alcohol, obtains pliable and tough polymer strands, smash it to pieces powdered with tissue pulverizer, respectively boil 5 times to remove desolventizing and small-molecule substance with distilled water and ethanol.Finally dry after product suction filtration in vacuum drying oven, obtain product P AEK-6FBPA-cisDHTPP-25%, productive rate is 94%.The structural formula of this multipolymer is as follows:
Embodiment 2:
The preparation of (1) 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin is with described in embodiment 1.
(2) at one, mechanical stirring is housed, nitrogen port, thermometer, in the 50ml there-necked flask of water-taker and prolong, add 5, 10-bis-(4-hydroxy phenyl)-15, 20-phenylbenzene porphyrin 0.323g(0.5mmol), 2, 2-bis-(4-hydroxyphenyl) propane 2.169g(9.5mmol), 4, 4 '-difluoro benzophenone 2.182g(10mmol) and Anhydrous potassium carbonate 1.656g(12mmol) be dissolved in N-Methyl pyrrolidone (20ml), add water entrainer toluene (11ml), pass into nitrogen 15 minutes after monomer all dissolves, be warming up to 135 ° of C to reflux 3 hours, then the water of water entrainer toluene and reaction generation is released, reaction system is warming up to 170 ° of C, copolyreaction is completed after 2.5 hours.The solution of thickness is slowly poured in dehydrated alcohol, obtains pliable and tough polymer strands, smash it to pieces powdered with tissue pulverizer, respectively boil 5 times to remove desolventizing and small-molecule substance with distilled water and ethanol.Finally dry after product suction filtration in vacuum drying oven, obtain product P AEK-BPA-cisDHTPP-5%, productive rate is 95%.The structural formula of this multipolymer is as follows:
Embodiment 3:
The preparation of (1) 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin as described in Example 1.
(2) at one, mechanical stirring is housed, nitrogen port, thermometer, in the 50ml there-necked flask of water-taker and prolong, add 5, 15-bis-(4-hydroxy phenyl)-10, 20-phenylbenzene porphyrin 0.972g(1.5mmol), 2, 2-bis-(4-hydroxy phenyl) HFC-236fa 2.858g(8.5mmol), 4, 4 '-difluoro benzophenone 2.182g(10mmol) and Anhydrous potassium carbonate 1.656g(12mmol) be dissolved in N-Methyl pyrrolidone (24ml), add water entrainer toluene (12ml), pass into nitrogen 15 minutes after monomer dissolves, be warming up to 138 ° of C to reflux 3 hours, then the water of water entrainer toluene and reaction generation is released, reaction system is warming up to 176 ° of C, copolyreaction is completed after 2 hours.The solution of thickness is slowly poured in dehydrated alcohol, obtains pliable and tough polymer strands, smash it to pieces powdered with tissue pulverizer, respectively boil 5 times to remove desolventizing and small-molecule substance with distilled water and ethanol.Finally dry after product suction filtration in vacuum drying oven, obtain product P AEK-6FBPA-transDHTPP-15%, productive rate is 93%.The structural formula of this multipolymer is as follows:
Embodiment 4:
The preparation of (1) 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin as described in Example 1.
(2) at one, mechanical stirring is housed, nitrogen port, thermometer, in the 50ml there-necked flask of water-taker and prolong, add 5, 15-bis-(4-hydroxy phenyl)-10, 20-phenylbenzene porphyrin 1.361g(2.1mmol), 3-trifluoromethyl Resorcinol 1.937g(7.9mmol), 4, 4 '-difluoro benzophenone 2.182g(10mmol) and Anhydrous potassium carbonate 1.656g(12mmol) be dissolved in (18ml) in tetramethylene sulfone, add water entrainer toluene (10ml), pass into nitrogen 15 minutes after monomer all dissolves, be warming up to 138 ° of C to reflux 2.5 hours, then the water of water entrainer toluene and reaction generation is released, reaction system is warming up to 189 ° of C, copolyreaction is completed after 3.5 hours.The solution of thickness is slowly poured in dehydrated alcohol, obtains pliable and tough polymer strands, smash it to pieces powdered with tissue pulverizer, respectively boil 5 times to remove desolventizing and small-molecule substance with distilled water and ethanol.Finally dry after product suction filtration in vacuum drying oven, obtain product P AEK-3FHQ-transDHTPP-21%, productive rate is 96%.The structural formula of this multipolymer is as follows:
Embodiment 5:
The preparation of (1) 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin is with described in embodiment 1.
(2) at one, mechanical stirring is housed, nitrogen port, thermometer, in the 50ml there-necked flask of water-taker and prolong, add 5, 10-bis-(4-hydroxy phenyl)-15, 20-phenylbenzene porphyrin 0.323g(0.5mmol), 2, 2-bis-(4-hydroxy phenyl) HFC-236fa 3.194g(9.5mmol), 4, 4 '-difluoro benzophenone 2.182g(10mmol) and Anhydrous potassium carbonate 1.656g(12mmol) be dissolved in N-Methyl pyrrolidone (22ml), add water entrainer toluene (12ml), pass into nitrogen 15 minutes after monomer all dissolves, be warming up to 135 ° of C to reflux 2 hours, then the water of water entrainer toluene and reaction generation is released, reaction system is warming up to 180 ° of C, copolyreaction is completed after 4 hours.The solution of thickness is slowly poured in dehydrated alcohol, obtains pliable and tough polymer strands, smash it to pieces powdered with tissue pulverizer, respectively boil 5 times to remove desolventizing and small-molecule substance with distilled water and ethanol.Finally dry after product suction filtration in vacuum drying oven, obtain product P AEK-6FBPA-cisDHTPP-5%, productive rate is 92%.The structural formula of this multipolymer is as follows:
Embodiment 6:
The preparation of (1) 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin as described in Example 1.
(2) at one, mechanical stirring is housed, nitrogen port, thermometer, in the 50ml there-necked flask of water-taker and prolong, add 5, 15-bis-(4-hydroxy phenyl)-10, 20-phenylbenzene porphyrin 0.775g(1.2mmol), 3, 5, 3 ', 5 '-tetramethyl biphenyl diphenol 2.132g(8.8mmol), 4, 4 '-difluoro benzophenone 2.182g(10mmol) and Anhydrous potassium carbonate 1.656g(12mmol) be dissolved in (19ml) in tetramethylene sulfone, add water entrainer toluene (11ml), pass into nitrogen 15 minutes after monomer all dissolves, be warming up to 138 ° of C to reflux 2.5 hours, then the water of water entrainer toluene and reaction generation is released, reaction system is warming up to 173 ° of C, copolyreaction is completed after 3.5 hours.The solution of thickness is slowly poured in dehydrated alcohol, obtains pliable and tough polymer strands, smash it to pieces powdered with tissue pulverizer, respectively boil 5 times to remove desolventizing and small-molecule substance with distilled water and ethanol.Finally dry after product suction filtration in vacuum drying oven, obtain product P AEK-4Me-transDHTPP-12%, productive rate is 92%.The structural formula of this multipolymer is as follows:
Main chain is containing the poly (aryl ether ketone) copolymer of porphyrin, both (second-order transition temperature is at 170 ° of more than C to have had good thermal characteristics, 5% thermal weight loss temperature is at 540 ° of more than C), there is again good film-forming properties and (be equipped with the polymers soln of 100mg/ml, adopt after dissolving completely and prolong stream method casting film, use the omnipotent mechanics machine of Shimadzu AG-1 type to test, film useful area is 15mm × 4mm, rate of extension 2mm/min, gets the mean value of 5 groups of panel datas as test data.The Young's modulus of polymkeric substance is 1.42GPa-1.85GPa, and tensile strength is 75.8MPa-80.7Mpa, and elongation at break is 8.2%-36.7%), polymers soln and film all have very strong fluorescence response (accompanying drawing 5).This series material integrates high-performance polymer and functional polymer, is expected to the laser protective material as protection human eye and some optical pickocffs.
Claims (4)
1. main chain is containing a poly (aryl ether ketone) copolymer for porphyrin structure, and its structural formula is as follows:
Wherein Por is:
Ar is:
0 < m≤0.50, n represents the polymerization degree, is the integer of 10 ~ 80.
2. main chain according to claim 1 is containing a preparation method for the poly (aryl ether ketone) copolymer of porphyrin structure, and its step is as follows:
1) under nitrogen protection, by dihydroxyl tetraphenylporphyrin, aromatic organic bisphenol, 4,4 '-difluoro benzophenone, Anhydrous potassium carbonate and reaction solvent join in reaction vessel, then water entrainer toluene is added, mixture was through stirring and dissolving post-heating to 120 DEG C ~ 140 DEG C backflow 2 ~ 4 hours, remove the water of toluene and reaction generation completely, then temperature is risen to 150 DEG C ~ 190 DEG C reactions 2 ~ 6 hours;
2) above-mentioned viscous solution is poured in dehydrated alcohol, obtain pliable and tough polymer strands, broken into powder with tissue pulverizer, boil 5 ~ 10 times respectively with deionized water and ethanol, to remove desolventizing and small-molecule substance; After suction filtration, product is placed in vacuum drying oven dry 24 ~ 48 hours, thus obtains the poly (aryl ether ketone) copolymer that main chain contains porphyrin structure;
Described dihydroxyl tetraphenylporphyrin is 5,10-bis-(4-hydroxy phenyl)-15,20-phenylbenzene porphyrin or 5,15-bis-(4-hydroxy phenyl)-10,20-phenylbenzene porphyrin; Described aromatic organic bisphenol is 2,2-bis-(4-hydroxy phenyl) propane, 2,2-bis-(4-hydroxy phenyl) HFC-236fa, 3-trifluoromethyl Resorcinol or 3,5,3 ', 5 '-tetramethyl biphenyl diphenol.
3. main chain as claimed in claim 2 is containing the preparation method of the poly (aryl ether ketone) copolymer of porphyrin structure, it is characterized in that: reaction solvent is N-Methyl pyrrolidone or tetramethylene sulfone.
4. main chain as claimed in claim 2 is containing the preparation method of the poly (aryl ether ketone) copolymer of porphyrin structure, it is characterized in that: described dihydroxy phenyl porphyrin and the mol ratio of aromatic organic bisphenol are 1:19 ~ 1:1, the mole number total amount of dihydroxyl tetraphenylporphyrin and aromatic organic bisphenol equals 4, the mole number of 4 '-difluoro benzophenone, the consumption of Anhydrous potassium carbonate is 4,1.1 ~ 1.2 times of 4 '-difluoro benzophenone mole number.
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| CN102020781A (en) * | 2010-10-30 | 2011-04-20 | 华南理工大学 | Modified sulfonated poly ether ether ketone (SPEEK) membrane applied to direct methanol fuel cell (DMFC) and preparation method of SPEEK membrane |
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| CN102020781A (en) * | 2010-10-30 | 2011-04-20 | 华南理工大学 | Modified sulfonated poly ether ether ketone (SPEEK) membrane applied to direct methanol fuel cell (DMFC) and preparation method of SPEEK membrane |
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