CN105694041B - The polyarylether sulfone copolymer of a kind of side chain containing porphyrin and preparation method thereof - Google Patents
The polyarylether sulfone copolymer of a kind of side chain containing porphyrin and preparation method thereof Download PDFInfo
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- IISBACLAFKSPIT-UHFFFAOYSA-N CC(C)(c(cc1)ccc1O)c(cc1)ccc1O Chemical compound CC(C)(c(cc1)ccc1O)c(cc1)ccc1O IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- OJYIBEYSBXIQOP-UHFFFAOYSA-N CC(C)(c(cc1)ccc1OC)c(cc1)ccc1OC Chemical compound CC(C)(c(cc1)ccc1OC)c(cc1)ccc1OC OJYIBEYSBXIQOP-UHFFFAOYSA-N 0.000 description 1
- QRUIPTPYZSVQME-KGEYYWKASA-N CNc(cc1)ccc1/C(/c1ccc(/C(/c2ccccc2)=C2\N=C3C=C2)[nH]1)=C(\C=C1)/N=C1/C(/c1ccccc1)=C(/C=C1)\N/C1=C3/c1ccccc1 Chemical compound CNc(cc1)ccc1/C(/c1ccc(/C(/c2ccccc2)=C2\N=C3C=C2)[nH]1)=C(\C=C1)/N=C1/C(/c1ccccc1)=C(/C=C1)\N/C1=C3/c1ccccc1 QRUIPTPYZSVQME-KGEYYWKASA-N 0.000 description 1
- 0 Cc1cc(-c(cc2C)cc(C)c2O)cc(C)c1* Chemical compound Cc1cc(-c(cc2C)cc(C)c2O)cc(C)c1* 0.000 description 1
- LZRFEVSDBKMZJX-UHFFFAOYSA-N Cc1cc(-c(cc2C)cc(C)c2OC)cc(C)c1OC Chemical compound Cc1cc(-c(cc2C)cc(C)c2OC)cc(C)c1OC LZRFEVSDBKMZJX-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N Oc1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2O)cc1 Chemical compound Oc1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2O)cc1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N Oc1ccc(C2(c(cccc3)c3-c3c2cccc3)c(cc2)ccc2O)cc1 Chemical compound Oc1ccc(C2(c(cccc3)c3-c3c2cccc3)c(cc2)ccc2O)cc1 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
A kind of side chain contains polyarylether sulfone copolymer of porphyrin and preparation method thereof, belongs to field of polymer material preparing technology.Because porphyrin is the special Conjugate macrocycle compound of a class, with armaticity, the delocalization degree of pi-electron is very big so that Porphyrin Molecule shows significant third-order nonlinear optical effect.The present invention is acted on by chemical bonding, and mono amino porphyrin is introduced into the polyether sulphone side chain with carboxyl, and successfully invention is prepared for the polyarylether sulfone copolymer that side chain contains Amino Porphyrins.Both the excellent heat of polyether sulphone, mechanical property had been remained, its novel optical property is imparted again.The polyarylethersulfone polymer that side chain prepared by the present invention contains porphyrin integrates the feature of the structural and porphyrin of high-performance polymer, is expected to the laser protective material as protection human eye and precision optics sensor.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of side chain contains the polyarylether sulfone copolymer of porphyrin
And preparation method thereof.
Background technology
In recent years, with the development of science and technology, people start to propose the performance of material new requirement.Macromolecule material
The features such as material has big molecular weight, light weight, small density, also excellent mechanical property, insulating properties and heat-proof quality are met
The different needs of people.Speciality polymer and functional polymer are the Disciplinary Frontiers of high polymer material development.Polyether sulphone
(PAES) it is one of important kind of special engineering plastics, the aromatic ring structure and rigid chain segment enriched in its main chain is imparted
The excellent temperature classification of polymer, creep resistance and outstanding anti-flammability.The excellent combination property of poly (ether ketone ketone) material makes
It is widely used in mechanical industry, electronic apparatus, communications and transportation, medicine equipment and energy industry.
Porphyrin is the special Conjugate macrocycle compound of a class, with armaticity, universally present in organism and energy
In the related-organelles of transfer.Due to the special construction of Porphyrin Molecule, the delocalization degree of pi-electron is very big, shows significant sharp
Send out the third-order nonlinear optical effect of the macroscopic views such as state absorption or anti-saturated absorption；By the MOLECULE DESIGN to porphyrin, such as substituent,
Axial ligand and metal complex can be with the ground state and excitation state photophysical property of Effective Regulation its molecule, therefore porphyrins
It is widely used in terms of photoelectric conversion, photocatalysis, nonlinear optical material.
However, this kind of compound molecule easily accumulates aggregation, fusing point and hardness are relatively low, and it can only be typically played in the solution
Excellent optical property.Polyether sulphone has good combination property, therefore porphyrin is introduced into polyether sulphone by being chemically bonded
In the strand of resin, the accumulation rendezvous problem of porphyrin is solved.Meanwhile, with reference to the two unique excellent properties, prepare one
Plant the novel polymer material for having mechanical strength, heat endurance and unique optical properties concurrently.
The content of the invention
The technical problem to be solved in the present invention is, designs and synthesizes the polyarylether sulfone copolymer that side chain contains porphyrin.It is first
4,4'- difluorodiphenyls sulfone, aromatic organic bisphenol and phenolphthalin are first subjected to copolymerization, a series of different carboxyl-contents have been synthesized
Polyarylether sulfone copolymer；Then 5- (4- aminophenyls) -10,15,20- triphenyl porphins are introduced in polyarylether sulfone copolymer side chain
Quinoline, is prepared for a series of polyarylether sulfone copolymer that side bases are different porphyrin contents.Side chain prepared by the present invention contains porphyrin
Polyarylethersulfone polymer integrate high-performance polymer structural and porphyrin feature, be expected to as protection human eye and
The laser protective material of precision optics sensor.
The present invention is by 5- (4- aminophenyls) -10, and 15,20- Triphenylporphyrins graft on the side chain of polyarylether sulfone copolymer,
The polyarylether sulfone copolymer that side chain contains porphyrin structure is prepared for, the excellent heat of polyarylether sulfone copolymer, mechanical property is being remained
While energy, the novel optical property of copolymer is imparted.Copolymer has stronger fluorescence response, can inherit small molecule porphyrin
Excellent nonlinear optical properties and optical limiting properties,.
The structural formula of side chain polyether sulphone containing porphyrin copolymerization of the present invention is as follows：
Wherein Ar is：
0.01≤m≤0.50, n represents the degree of polymerization, the integer for being 10~80.
A kind of side chain of the present invention contains the preparation method of the polyarylether sulfone copolymer of porphyrin, comprises the following steps：
(1) under nitrogen protection, by aromatic organic bisphenol, phenolphthalin, 4,4 '-difluorodiphenyl sulfone and Anhydrous potassium carbonate,
Reaction dissolvent, water entrainer are added to be passed through in the reaction vessel of mouth with mechanical stirring device and nitrogen, is added after agitated dissolving
Heat is to 120 DEG C~130 DEG C, and flow back 2~4h, and after the water and toluene that react generation are all removed, reaction system is warming up into 150
DEG C~190 DEG C, react 2~6h；After the completion of reaction, in the aqueous hydrochloric acid solution that solution is poured into mass fraction 5~10%, obtain
Flexible polymer strands, are broken into after powder, and boiling washing is distinguished 5~10 times with deionized water and ethanol, molten to remove
Agent and small-molecule substance；Then product is dried after 24~48h under vacuum, you can obtain the polyether sulphone containing carboxyl
Copolymer；
(2) polyarylether sulfone copolymer containing carboxyl for taking 1g steps (1) to prepare, is dissolved in 10~20mL nothing at room temperature
In water tetrahydrofuran, the oxalyl chloride of 2~5 times of carboxyl mole in polyarylether sulfone copolymer, 1~3h of stirring at normal temperature are added；By nothing
After water tetrahydrofuran and unreacted oxalyl chloride are removed by the method for vacuum distillation, 10~20mL anhydrous tetrahydrochysene is added again
Furans, until completely dissolved, the mono amino porphyrin of 2~5 times of carboxyl mole in addition polyarylether sulfone copolymer, reaction 24~
After 72h, product is poured into absolute ethyl alcohol, then with ethanol boiling washing 3~5 times, to remove solvent and unreacted monoamine
Base porphyrin, then dries product after 24~48h, you can obtain the polyether sulphone copolymerization that side chain contains porphyrin under vacuum
Thing.
Further, the reaction dissolvent in step (1) is 1-METHYLPYRROLIDONE or sulfolane, in reaction system, solid
The mass content scope of material is 20%~30%.
Further, the water entrainer in step (1) be toluene, its volumetric usage for reaction dissolvent volumetric usage 40%~
60%.
Further, in step (1) phenolphthalin and the mole dosage sum and 4 of aromatic organic bisphenol, 4 '-difluoro two
The mole dosage of benzene sulfone is identical, and the mole dosage ratio of phenolphthalin and aromatic organic bisphenol is 1：99~1：1.
Further, the aromatic organic bisphenol in step (1) is 2,2- bis- (4- hydroxy phenyls) HFC-236fa, 2,2- bis-
(4- hydroxy phenyls) propane, 3,5,3 ', 5 '-tetramethyl biphenyl diphenol or 9,9- bis- (4- hydroxy phenyls) fluorenes, structure difference are as follows：
Further, the mono amino porphyrin in step (2) be 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins, its
Synthetic method reference literature (high yield synthesis 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins [A] Yunnan Institute for nationalities
Journal (natural science edition), 2007,16 (2)：Preparation method described in 178-184).
Here is the reaction equation for the polyarylether sulfone copolymer that synthesis side chain of the invention contains porphyrin：
M=0.01~0.50, n is the degree of polymerization, the integer for being 10~80.
Side chain of the present invention contains the polyarylether sulfone copolymer of mono amino porphyrin, by introducing mono amino porphyrin, makes
Polymer has preferable dissolubility, heat resistance and optical property；Preparation method of the present invention is easy to operate, repeatability
Height, the series polymer integrates the feature of the structural and porphyrin compound of high-performance polymer, is expected to as protection
The laser protective material of human eye and some optical sensors.
Brief description of the drawings
Fig. 1：Polyarylether sulfone copolymer 6FBPA-PAES-Por-1% of the side chain containing porphyrin prepared by embodiment 1 nuclear-magnetism is total to
Shake spectrogram；
It can be seen that it is porphyrin ring hydrogen at 8 and 9 respectively that 8.90~8.88ppm of chemical shift is corresponding,
It is hydrogen at hydrogen at 1,2,3,14,16, chemical shift 7.9ppm corresponding 15 that 7.13ppm~6.90ppm is corresponding respectively, because
The structure of polymer prepared by this explainable present invention is consistent with expection.
Fig. 2：Polyarylether sulfone copolymer 6FBPA-PAES-Por-20% of the side chain containing porphyrin prepared by embodiment 2 is infrared
Spectrogram；
It can be seen that the structure of the 6FBPA-PAES-Por-1% prepared by the present invention:3317cm-1、798cm-1
Corresponding to the hydrogen bound to nitrogen and carbonnitrogen bond of pyrrole ring in side chain porphyrin；1684cm-1Locate the characteristic absorption peak for acid amides；1584cm-1、
1489cm-1Corresponding to the characteristic absorption peak of phenyl ring；1281cm-1Corresponding to the ehter bond in main chain；1170cm-1、1240cm-1Correspondence
Sulfuryl absworption peak in polyether sulphone main chain.
Fig. 3：Polyarylether sulfone copolymer BPA-PAES-Por-30% of the side chain containing porphyrin prepared by embodiment 3 INFRARED SPECTRUM
Figure；
It can be seen that BPA-PAES-Por-40% structures prepared by the present invention：3319cm-1、798cm-1Correspondence
The hydrogen bound to nitrogen and carbonnitrogen bond of pyrrole ring in side chain porphyrin；1680cm-1Locate the characteristic absorption peak for acid amides；1584cm-1、
1492cm-1Corresponding to the characteristic absorption peak of phenyl ring；1293cm-1Corresponding to the ehter bond in main chain；1152cm-1、1242cm-1Correspondence
Sulfuryl absworption peak in polyether sulphone main chain.
Fig. 4：Embodiment 3 prepare polyarylether sulfone copolymer BPA-PAES-Por-30% of the side chain containing porphyrin it is ultraviolet-can
See optical absorption spectra；
It can be seen that being the absorption of polymer backbone between 250nm to 330nm；It is porphyrin S bands at 419nm
Absorb；It is the absorption of four Q bands of porphyrin at 516nm, 551nm, 589nm, 646nm.The figure can be explained the presence of porphyrin and be total to
The absorption characteristic of polymers.
Fig. 5：BPA-PAES-Por-30% prepared by embodiment 3 fluorescence emission spectrum；
It can be seen that BPA-PAES-Por-30% solution concentrations are 2mg/L, it is total to when being excited at 418nm wavelength
There is emission peak at 650nm and 715nm in copolymer solution.The figure can be explained the polyether sulphone for introducing mono amino porphyrin in side chain and be total to
Polymers has very strong fluorescent characteristic.
Fig. 6：The thermogravimetric curve of polyarylether sulfone copolymer of the side chain containing porphyrin prepared by embodiment 2,3,4,5.The figure can
Illustrate the copolymer prepared, 5% thermal weight loss temperature is above more than 450 DEG C, all with excellent heat endurance；
Embodiment
The method of the present invention is illustrated below by specific embodiment, described embodiment is the power to the present invention
The specific descriptions that profit is required, claim includes but is not limited to described embodiment content.
Reagent and material described in following embodiments are commercially obtained unless otherwise specified；The experiment
Method, is conventional method unless otherwise specified.
Embodiment 1：
(1) preparation and purification of 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins：In 500mL three neck round bottom
In, the tetraphenylporphyrins of 2g 5,10,15,20- are added, 200mL chloroforms, electric stirring, ice salt bath is cooled to 0 DEG C or so, will
1.10mL (27mmol) fuming nitric aicd is dissolved in 30mL chloroform, 1.5h completion of dropping, continues to react 2h, detects anti-with TLC
It should be wholly absent up to tetraphenylporphyrin, stop reaction.Then pH=8 is neutralized to 0.5mol/L sodium hydroxide, washed
(150mL × 6) collect organic phase, the anhydrous MgSO of organic phase4Dry 8h, concentration.Separated by silica gel column chromatography, obtain purple
The Triphenylporphyrin 1.24g of color crystal 5- (4- nitrobenzophenones) -10,15,20-, then add 1g in 250mL three neck round bottom
5- (4- nitrobenzophenones) -10,15,20- Triphenylporphyrins add 80mL concentrated hydrochloric acids, lead to after nitrogen 10min, electric stirring, add
2g stannous chlorides, heating water bath is warming up to 70 DEG C of backflows, reacts 2h.Solution is cooled to addition 50mL frozen water after room temperature, filtering
Go out precipitation, sediment is dispersed in water, pH=8 is adjusted with ammoniacal liquor, extracted with chloroform (100mL × 6) and merge organic phase, plus
Enter anhydrous MgSO4Dry after 12h, concentration, using silica gel as stationary phase, using dichloromethane as eluent, collect the second pure color band, obtain
Product 0.8318g.
(2) in a 100mL there-necked flask that mouth, thermometer, water-taker and condenser pipe are passed through equipped with mechanical agitation, nitrogen
In, add 4,4 '-difluorodiphenyl sulfone 5.085g (20mmol), 2,2- bis- (4- hydroxy phenyls) HFC-236fa 6.388g
(19mmol), phenolphthalin 0.32g (1mmol) and Anhydrous potassium carbonate 3.40g (24.6mmol) are dissolved in sulfolane (34mL), add
Water entrainer toluene (17mL), is passed through nitrogen, after after monomer all dissolving, being warming up to 120 DEG C of backflow 3h, then except dereaction is generated
Water and water entrainer toluene, continuation reaction system is warming up to 175 DEG C, polymerisation is completed after 5h.Sticky solution is slow
Pour into the aqueous hydrochloric acid solution of mass fraction 5%, obtain flexible polymer strands, it is ground into powder with tissue pulverizer,
After distilled water and each boiling washing of ethanol 5 times, to remove solvent and small-molecule substance.Copolymer 6FBPA- is obtained after drying
PAES-COOH-1%9.88g.
(3) polymer prepared in 1g steps (2) is taken, its carboxyl mole is 0.0182mmol, and 15mL is dissolved at room temperature
In tetrahydrofuran, oxalyl chloride 3uL (0.0364mmol) is added, 3h is stirred.Then solvent and oxalyl chloride are removed by vacuum distillation,
Again by molten time 15mL tetrahydrofuran of solid, 0.023g (0.0364mmol) 5- (4- aminophenyls) -10,15,20- triphenyls are added
After porphyrin, stirring 24h, polymer solution is poured into absolute ethyl alcohol, reaction is had neither part nor lot in remove with ethanol boiling washing 5 times
Porphyrin.The dry 12h of lower 60 DEG C of vacuum condition obtains aubergine subject polymer 6FBPA-PAES-Por-1%1.25g.
Copolymer 6FBPA-PAES-Por-1% structural formula is as follows：
Wherein Por is：
Embodiment 2：
(1) preparation of 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins is as described in the step (1) in embodiment 1.
(2) in a 100mL there-necked flask that mouth, thermometer, water-taker and condenser pipe are passed through equipped with mechanical agitation, nitrogen
In, add 4,4 '-difluorodiphenyl sulfone 5.085g (20mmol), 2,2- bis- (4- hydroxy phenyls) HFC-236fa 5.3797g
(16mmol), phenolphthalin 1.2814g (4mmol) and Anhydrous potassium carbonate 3.649g (26.4mmol) are dissolved in sulfolane (34mL),
Water entrainer toluene (17mL) is added, nitrogen is passed through, after after monomer all dissolving, being warming up to 120 DEG C of backflow 3h, then except dereaction
Reaction system is warming up to 175 DEG C by the water and water entrainer toluene of generation, continuation, and polymerisation is completed after 5h.By sticky solution
It is poured slowly into the aqueous hydrochloric acid solution of mass fraction 5%, obtains flexible polymer strands, it is ground into powder with tissue pulverizer
End, after distilled water and each boiling washing of ethanol 5 times, to remove solvent and small-molecule substance.The dry 12h of lower 60 DEG C of vacuum condition
Polyether sulphone carboxyl copolymer 10.85g is obtained, 6FBPA-PAES-COOH-20%10.85g is named as.
(3) polymer prepared in 1g steps (2) is taken, its carboxyl mole is 0.365mmol, and 15mL tetra- is dissolved at room temperature
In hydrogen furans, oxalyl chloride 0.06mL (0.73mmol) is added, 3h is stirred.Then solvent and oxalyl chloride are removed by vacuum distillation,
Again by molten time 15mL tetrahydrofuran of solid, 0.46g (0.73mmol) 5- (4- aminophenyls) -10,15,20- triphenyl porphin is added
After quinoline, stirring 24h, polymer solution is poured into absolute ethyl alcohol, the porphin of reaction is had neither part nor lot in remove with ethanol boiling washing 5 times
Quinoline.The dry 12h of lower 60 DEG C of vacuum condition obtains aubergine subject polymer 1.05g, is named as 6FBPA-PAES-Por-20%.
Copolymer 6FBPA-PAES-Por-20% structural formula is as follows：
Wherein Por is：
Embodiment 3：
(1) preparation of 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins is as described in the step (1) in embodiment 1.
(2) in a 100mL there-necked flask equipped with mechanical agitation, nitrogen port, thermometer, water-taker and condenser pipe,
Add 4,4 '-difluorodiphenyl sulfone 5.085g (20mmol), 2,2- bis- (4- hydroxy phenyls) propane 2.740g (14mmol), phenolphthalin
2.563g (6mmol) and Anhydrous potassium carbonate 3.18g (23mmol) are dissolved in sulfolane (30mL), add water entrainer toluene
(15mL), is passed through nitrogen, after after monomer all dissolving, being warming up to 130 DEG C of backflow 3h, then except the water of dereaction generation and with water
Reaction system is warming up to 175 DEG C by agent toluene, continuation, and polymerisation is completed after 5h.Sticky solution is poured slowly into containing 5%
In aqueous hydrochloric acid solution, flexible polymer strands are obtained, it is ground into powder with tissue pulverizer, it is each with distilled water and ethanol
Boiling washing 5 times is to remove solvent and small-molecule substance.The dry 12h of lower 60 DEG C of vacuum condition obtains polyether sulphone carboxyl copolymer
9.68g, is named as BPA-PAES-COOH-30%.
(3) polymer described in 1g steps (2) is taken, its carboxyl mole is 0.638mmol.15mL tetra- is dissolved at room temperature
In hydrogen furans, oxalyl chloride 0.108mL (1.276mmol) is added, 3h is stirred.Then solvent and oxalyl are removed by vacuum distillation
Chlorine, then by molten time 15mL tetrahydrofuran of solid, add 0.804g (1.276mmol) 5- (4- aminophenyls) -10,15,20- triphens
After base porphyrin, stirring 24h, mixed liquor is poured into absolute ethyl alcohol, 5 times are washed with hot ethanol and removes the porphyrin for having neither part nor lot in reaction,
The dry 12h of lower 60 DEG C of vacuum condition obtains aubergine subject polymer 1.22g, is named as BPA-PAES-Por-30%.
Copolymer BPA-PAES-Por-30% structural formula is as follows：
Wherein Por is：
Embodiment 4：
(1) preparation of 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins is as described in the step (1) in embodiment 1.
(2) in a 100mL there-necked flask equipped with mechanical agitation, nitrogen port, thermometer, water-taker and condenser pipe,
Add 4,4 '-difluorodiphenyl sulfone 5.085g (20mmol), 3,5,3 ', 5 '-tetramethyl biphenyl diphenol 2.907g (12mmol), phenolphthalein
Quinoline 2.562g (8mmol) and Anhydrous potassium carbonate 3.98g (28.8mmol) are dissolved in sulfolane (30mL), add water entrainer toluene
(15mL), is passed through nitrogen, after after monomer all dissolving, being warming up to 126 DEG C of backflow 3h, then except the water of dereaction generation and with water
Reaction system is warming up to 170 DEG C by agent toluene, continuation, and polymerisation is completed after 3h.Sticky solution is poured slowly into 5% hydrochloric acid
In the aqueous solution, flexible polymer strands are obtained, it is ground into powder with tissue pulverizer, are respectively boiled with distilled water and ethanol
5 times are washed to remove solvent and small-molecule substance.Copolymer 4Me-PAES-COOH-40%9.85g is obtained after drying.
(3) polymer described in 1g steps (2) is taken, its carboxyl mole is 0.758mmol.15mL tetra- is dissolved at room temperature
In hydrogen furans, oxalyl chloride 0.13mL (1.516mmol) is added, 3h is stirred.Then solvent and oxalyl chloride are removed by vacuum distillation,
Again by molten time 15mL tetrahydrofuran of solid, 0.956g (1.516mmol) 5- (4- aminophenyls) -10,15,20- triphenyls are added
After porphyrin, stirring 24h, mixed liquor is poured into absolute ethyl alcohol, 5 times are washed with hot ethanol and removes the porphyrin for having neither part nor lot in reaction, very
The dry 12h of lower 60 DEG C of empty condition obtains aubergine subject polymer 1.32g, is named as 4Me-PAES-Por-40%.
Copolymer 4Me-PAES-Por-40% structural formula is as follows：
Wherein Por is：
Embodiment 5：
(1) preparation of 5- (4- aminophenyls) -10,15,20- Triphenylporphyrins is as described in the step (1) in embodiment 1.
(2) in a 100mL there-necked flask equipped with mechanical agitation, nitrogen port, thermometer, water-taker and condenser pipe,
Add 4,4 '-difluorodiphenyl sulfone 5.085g (20mmol), 9,9- bis- (4- hydroxy phenyls) fluorenes 3.504g (10mmol), phenolphthalin
3.203g (10mmol) and Anhydrous potassium carbonate 4.15g (30mmol) are dissolved in sulfolane (34mL), add water entrainer toluene
(17mL), is passed through nitrogen, after after monomer all dissolving, being warming up to 120 DEG C of backflow 3h, then except the water of dereaction generation and with water
Reaction system is warming up to 175 DEG C by agent toluene, continuation, and copolyreaction is completed after 3.5h.By sticky solution be poured slowly into containing
In 5% aqueous hydrochloric acid solution, flexible polymer strands are obtained, it is ground into powder with tissue pulverizer, with distilled water and second
Each boiling washing of alcohol 5 times is to remove solvent and small-molecule substance.BHPF-PAES-COOH-50%9.53g is obtained after drying.
(3) polymer described in 1g steps (2) is taken, its carboxyl mole is 0.91mmol.15mL tetra- is dissolved at room temperature
In hydrogen furans, oxalyl chloride 0.154mL (1.82mmol) is added, 3h is stirred.Then solvent and oxalyl chloride are removed by vacuum distillation,
Again by molten time 15mL tetrahydrofuran of solid, 1.15g (1.82mmol) 5- (4- aminophenyls) -10,15,20- triphenyl porphin is added
After quinoline, stirring 24h, mixed liquor is poured into absolute ethyl alcohol, 5 times are washed with hot ethanol and removes the porphyrin for having neither part nor lot in reaction, vacuum
Aubergine subject polymer BHPF-PAES-Por-50%1.24g is obtained after drying.
Copolymer BHPF-PAES-Por-50% structural formula is as follows：
Wherein Por is：
Side chain of the present invention, which contains mono amino porphyrin polyarylether sulfone copolymer, has (the vitrifying turn of preferable thermostability
Temperature is more than 200 DEG C, and 5% thermal weight loss temperature has very strong fluorescence response more than 450 DEG C.In protection human eye and one
A little optical sensors in terms of laser damage from having potential application.
Claims (6)
1. a kind of side chain contains the polyarylether sulfone copolymer of porphyrin, it is characterised in that：Its structural formula is as follows,
Wherein Ar is
0.01≤m≤0.50, n represents the degree of polymerization, the integer for being 10~80.
2. the side chain described in claim 1 contains the preparation method of the polyarylether sulfone copolymer of porphyrin, its step is as follows：
(1) under nitrogen protection, by aromatic organic bisphenol, phenolphthalin, 4,4 '-difluorodiphenyl sulfone and Anhydrous potassium carbonate, reaction
Solvent, water entrainer are added to be passed through in the reaction vessel of mouth with mechanical stirring device and nitrogen, is heated to after agitated dissolving
120 DEG C~130 DEG C, flow back 2~4h, will react generation water and toluene all remove after, by reaction system be warming up to 150 DEG C~
190 DEG C, react 2~6h；After the completion of reaction, in the aqueous hydrochloric acid solution that solution is poured into mass fraction 5~10%, obtain flexible
Polymer strands, broken into after powder, boiling washing distinguished 5~10 times with deionized water and ethanol, with remove solvent and
Small-molecule substance；Then product is dried after 24~48h under vacuum, you can obtain the polyether sulphone copolymerization containing carboxyl
Thing；
(2) polyarylether sulfone copolymer containing carboxyl for taking 1g steps (1) to prepare, is dissolved in anhydrous the four of 10~20mL at room temperature
In hydrogen furans, the oxalyl chloride of 2~5 times of carboxyl mole in polyarylether sulfone copolymer, 1~3h of stirring at normal temperature are added；By anhydrous four
After hydrogen furans and unreacted oxalyl chloride are removed by the method for vacuum distillation, 10~20mL anhydrous tetrahydrochysene furan is added again
Mutter, until completely dissolved, add the mono amino porphyrin of 2~5 times of carboxyl mole in polyarylether sulfone copolymer, react 24~72h
Afterwards, product is poured into absolute ethyl alcohol, then with ethanol boiling washing 3~5 times, to remove solvent and unreacted mono amino porphin
Quinoline, then dries product after 24~48h, you can obtain the polyarylether sulfone copolymer that side chain contains porphyrin under vacuum.
3. side chain as claimed in claim 2 contains the preparation method of the polyarylether sulfone copolymer of porphyrin, it is characterised in that：Step
(1) during reaction dissolvent in is 1-METHYLPYRROLIDONE or sulfolane, reaction system, the mass content scope of solid matter is
20%~30%.
4. side chain as claimed in claim 2 contains the preparation method of the polyarylether sulfone copolymer of porphyrin, it is characterised in that：Step
(1) water entrainer in is toluene, and its volumetric usage is the 40%~60% of reaction dissolvent volumetric usage.
5. side chain as claimed in claim 2 contains the preparation method of the polyarylether sulfone copolymer of porphyrin, it is characterised in that：Step
(1) the mole dosage sum and 4 of phenolphthalin and aromatic organic bisphenol in, the mole dosage of 4 '-difluorodiphenyl sulfone is identical, phenol
The mole dosage ratio of phthalein quinoline and aromatic organic bisphenol is 1：99~1.
6. side chain as claimed in claim 2 contains the preparation method of the polyarylether sulfone copolymer of porphyrin, it is characterised in that：Step
(1) aromatic organic bisphenol in is 2,2- bis- (4- hydroxy phenyls) HFC-236fa, 2,2- bis- (4- hydroxy phenyls) propane, 3,5,
3 ', 5 '-tetramethyl biphenyl diphenol or 9,9- bis- (4- hydroxy phenyls) fluorenes.
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| CN108641083B (en) * | 2018-04-26 | 2021-08-10 | 吉林大学 | High-temperature-resistant ultraviolet fluorescent polyether sulfone copolymer, preparation method and copolymer film |
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| CN111617644B (en) * | 2020-05-12 | 2022-03-15 | 福建师范大学 | Preparation method of monolithic polyaryletherketone bipolar membrane with side chain containing porphyrin water dissociation catalytic group |
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| CN1397030A (en) * | 2000-01-10 | 2003-02-12 | 莱克斯马克国际公司 | Electrophotographic photoconductors comprising polyaryl ethers |
| WO2008005647A2 (en) * | 2006-07-03 | 2008-01-10 | General Electric Company | Sulfonated polyaryletherketone-block-polyethersulfone copolymers |
| CN103319707A (en) * | 2013-07-09 | 2013-09-25 | 吉林大学 | Polyaryletherketone copolymer containing porphyrin structure at main chain, and preparation method thereof |
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| CN1397030A (en) * | 2000-01-10 | 2003-02-12 | 莱克斯马克国际公司 | Electrophotographic photoconductors comprising polyaryl ethers |
| WO2008005647A2 (en) * | 2006-07-03 | 2008-01-10 | General Electric Company | Sulfonated polyaryletherketone-block-polyethersulfone copolymers |
| CN103319707A (en) * | 2013-07-09 | 2013-09-25 | 吉林大学 | Polyaryletherketone copolymer containing porphyrin structure at main chain, and preparation method thereof |
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