CN103265693B - Polyether sulphone material containing phenoxy aliphatic chain boric acid ester side chain and preparation method of material - Google Patents
Polyether sulphone material containing phenoxy aliphatic chain boric acid ester side chain and preparation method of material Download PDFInfo
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Abstract
The invention relates to a polyether sulphone material containing a phenoxy aliphatic chain boric acid ester side chain and a preparation method of the material, belonging to the technical filed of high polymer materials. The polyether sulphone material containing the phenoxy aliphatic chain boric acid ester side chain is a polymer containing a polyether sulphone main chain and a phenoxy aliphatic chain boric acid pinacol ester side chain, polyether sulphone containing a phenoxy allyl side chain is obtained through a reaction between polyether sulphone containing a phenol lateral group and allyl bromide, and under the catalysis of [Ir(COD)Cl]2 and dppe (dipalmitoylphosphatidylcholine), the polyether sulphone containing the phenoxy allyl side chain and pinacol ester borane react so as to prepare the polyether sulphone material containing the phenoxy aliphatic chain boric acid ester side chain. The preparation method is simple to operate, high in reaction efficiency and suitable for polyarylether systems; the prepared polymer has the properties of an aroma main chain and an aliphatic series boric acid ester side chain and heat stability; and a boracic material is an important neutron absorbing material and a reaction intermediate, and has potential application in an atomic energy industry shielding material and preparation of crosslinking polyether sulphone resin.
Description
Technical field
The invention belongs to the technical field of macromolecular material, be specifically related to fatty chain boric acid ester phenyl side chain polyarylethersulfone polymer material and preparation method thereof.
Background technology
Fragrance main chain polyether sulphone, with excellent properties such as its good mechanical property, good stability of the dimension, excellent electrical property and easy-formation processing, is widely used in the fields such as machinery, electronics, automobile, medicine equipment, foodstuffs industry and space flight and aviation.But unformed polyether sulphone is more responsive to solvent, the corrosion of resistance to intensive polar solvent and the vitriol oil, concentrated nitric acid hardly, these limit its application.Functional groups is incorporated into aromatic polymer backbones and can obtains resistance to intensive polar solvent and corrosion resistant polyether sulphone is an extremely important job.Therefore, the study on the modification of polyether sulphone is enjoyed always to the concern of scientific worker.In recent years, developed with cyanate radical, amino, ethynyl, vinyl, propenyl, allyl group, epoxy group(ing), dimaleoyl imino, and cyano group isoreactivity group is as the polyether sulphone of END CAPPED GROUP or side base.
Pure boron is considered as a kind of important strategic materials by western countries always, main because it militarily has important purposes.First, pure boron powder has the characteristic of high-energy-density and clean fuel, is a kind of excellent solid rocket propellant; Secondly,
10b isotropic substance has very high captures slow-neutron cross-section (3.99 × 10
-25m
2), it and neutron effect generation nuclear reaction:
Generate stable lithium and alpha-particle
, alpha-particle is easy to absorb, and can be used as control and the shielding material of reactor.
Boron atom is incorporated in macromolecular material, the characteristics such as the thermotolerance of macromolecular material, instantaneous ablation resistance, rub, mechanical property and anti-neutron radiation can be improved to a certain extent, simultaneously, aliphatics macromolecular material can reduce the speed of neutron effectively, be conducive to the absorption of boron atom pairs neutron, boracic aliphatic polymer has been widely used at field tools such as Nuclear power plants.
Fatty boric acid ester side chain polymer can as reaction intermediate.Such as: 2002, people (the Macromolecules2002 such as the J.Y.Dong of Bin Nifaniya state university, 35,3439-3447) prepare fatty side chain boric acid ester polystyrene, then adopt the method for hydrogen peroxide oxidation to be taken off by boric acid ester, obtain fatty alcohol side chain polystyrene; Adopt the method for oxygen catalytic that two maleic anhydride is incorporated into polymer lateral chain, also Methyl Methacrylate polymerization can obtain the crosslinked polystyrene material of polymethylmethacrylate.
The present invention has selected the method for boron hydrogen addition, is successfully incorporated on polyether sulphone main chain by aliphatic chain boric acid ester, has prepared a kind of polyether sulphone containing phenoxy group boric acid ester side chain boric acid ester.What the present invention synthesized is a kind of novel macromolecular material containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone, is again a kind of important reaction intermediate.
Summary of the invention
The technical problem to be solved in the present invention is hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 reaction preparation containing allyl benzene base side chain polyether sulphone material and reacts to prepare containing phenoxy group allyl side chain polyether sulphone and pinacol ester borine and contain phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material; Have the performance of fragrant main chain and aliphatics boric acid ester side chain containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material concurrently, there is good thermostability.
Its preparation method is first obtained by reacting containing p-methoxy-phenyl polyether sulphone (PES-OCH according to the feed ratio of 1: 1 (mol ratio) by 2-(3`-p-methoxy-phenyl)-Isosorbide-5-Nitrae-Resorcinol and the fluoro-sulfobenzide of 4,4`-bis-
3), ether reaction is carried out again in pyridine hydrochloride, obtain hydroxyl phenyl polyether sulphone, hydroxyl phenyl polyether sulphone and allyl bromide 98 are obtained by reacting containing allyl benzene base side chain polyether sulphone according to the feed ratio of 1: 5 (mol ratio), finally, at (1,5-cyclooctadiene) iridochloride (I) dimer [Ir (COD) Cl]
2with 1, under the catalysis of two (diphenylphosphine) ethane (dppe) of 2-, react to prepare according to the feed ratio of 1:5 (mol ratio) containing allyl benzene base side chain polyether sulphone and pinacol ester borine and novel contain phenoxy group aliphatic chain pinacol borate side chain polyether sulphone material.(I) in (1,5-cyclooctadiene) iridochloride (I) dimer represents that the valency of iridium is 1 valency.
Of the present invention containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material, be made up of polyether sulphone main chain and phenoxy group aliphatic chain pinacol borate side chain, wherein according to design pinacol borate molar content be 100%(100%, namely all side chains all contain pinacol borate).The aliphatic chain phenylo boric acid pinacol ester of side chain can be positioned at the ortho position of side-chain benzene ring, a position and contraposition.
A kind of structural formula (position) containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material is
Wherein, n=10 ~ 12.
Preparation method containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material of the present invention, has preparation containing allyl benzene lateral group polyarylether sulfone and the process of preparation containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone;
Described preparation is containing phenoxy group allyl group lateral group polyarylether sulfone material, by hydroxyl benzene lateral group polyether sulphone tape loaded thermometer, nitrogen through hole, mechanical stirring, in the there-necked flask of water-taker, then the Anhydrous potassium carbonate of 1.05 times of hydroxyl molar weight in hydroxyl benzene lateral group polyether sulphone is added, 4 times to the organic solvent of reactant (hydroxybenzene lateral group polyarylether sulfone and allyl bromide 98) quality, the azeotropy dehydrant of organic solvent volume 20%, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be cooled to 30 ~ 50 DEG C, add the allyl bromide 98 of 5 times of hydroxyl molar weight in hydroxyl benzene lateral group polyether sulphone, spherical condensation tube is installed, be warmed up to 100 ~ 120 DEG C and continue reaction 6 ~ 10 hours, then, the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the polyarylethersulfone polymer containing phenoxy group allyl group side base.
Described preparation is containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone, that the polyether sulphone containing phenoxy group allyl group side base is placed with in the container of stirrer with loading, add appropriate (1,5-cyclooctadiene) iridochloride (I) dimer [Ir (COD) Cl] again
2(in the polyether sulphone containing allyl group benzene lateral group allylic molar weight 0.015 times) and 1, two (diphenylphosphine) ethane (dppe) (0.03 times containing allylic molar weight in phenoxy group allyl group lateral group polyarylether sulfone) of 2-, then vacuumize and put high pure nitrogen and (can vacuumize again and put high pure nitrogen, 3 ~ 5 times repeatedly), inject organic solvent, dissolve, inject appropriate pinacol ester borine (1.5 times containing the allylic molar weight of phenoxy group allyl group lateral group polyarylether sulfone), then seal, open and stir, room temperature reaction 60 ~ 78 hours; Adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 3 ~ 5 times, filters, vacuumizes 80 DEG C of oven dry, namely obtains containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone material; Organic solvent used can be trichloromethane, tetrahydrofuran (THF) or dioxane.
Building-up reactions formula containing m-phenoxy allyl group lateral group polyarylether sulfone polymer of the present invention is as follows:
Building-up reactions formula containing m-phenoxy aliphatic chain pinacol borate side chain polyether sulphone of the present invention is as follows:
React at hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 in the synthesis prepared containing phenoxy group allyl group lateral group polyarylether sulfone, organic solvent used can be N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), azeotropy dehydrant used can be toluene or dimethylbenzene.
React containing phenoxy group allyl group lateral group polyarylether sulfone and pinacol ester borine in the reaction prepared containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material, pinacol ester borine used, have another name called: pineapple alcohol borine, the product that A Faaisha (Tianjin) Chemical Co., Ltd. produces can be selected.
React at hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 in the synthesis prepared containing phenoxy group allyl group lateral group polyarylether sulfone, raw materials used hydroxyl benzene lateral group polyether sulphone can obtain according to the method for embodiment 1 and 2 in Chinese patent application publication number CN102174199A, also can prepare according to process as described below: the polyether sulphone of first synthesizing methoxy benzene lateral group, etherificate is gone to prepare hydroxyl benzene lateral group polyether sulphone again
Described synthesis is containing the polyether sulphone of methoxyl group benzene lateral group, with Resorcinol monomer and equimolar 4, 4`-difluorodiphenyl sulfone monomer or 4, 4`-dichloro diphenyl sulfone is reactant, with 4, 4`-difluorodiphenyl sulfone monomer or 4, the Anhydrous potassium carbonate of 1.05 times of 4`-dichloro diphenyl sulfone, 4 times to the organic solvent of reactant quality, the azeotropy dehydrant of organic solvent volume 20% is put into together and nitrogen through hole is housed, in the there-necked flask of mechanical stirring and water-taker, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be warmed up to 160 ~ 190 DEG C and continue reaction 6 ~ 10 hours, then, the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the polyarylethersulfone polymer of methoxyl group benzene lateral group, described Resorcinol monomer, 2-(3`-p-methoxy-phenyl)-1,4-Resorcinol, 2-(2`-p-methoxy-phenyl)-1,4-Resorcinol or 2-(4`-p-methoxy-phenyl)-1,4-Resorcinol, described organic solvent can be N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or N-Methyl pyrrolidone, and described azeotropy dehydrant can be toluene or dimethylbenzene,
Described etherificate of going prepares hydroxyl benzene lateral group polyether sulphone, first a certain amount of pyridine is joined band thermometer, nitrogen through hole, mechanical stirring, in the there-necked flask of constant pressure funnel, the concentrated hydrochloric acid of appropriate (HCl in concentrated hydrochloric acid and pyridine equimolar amount) is added in dropping funnel, while stirring concentrated hydrochloric acid is added drop-wise in pyridine, constant pressure funnel is removed after dripping off, still head is installed, vacuum tail is taken over, single port flask, rubber hose, logical nitrogen also opens heating, lentamente water is steamed, be warming up to 200 ~ 215 DEG C and namely stop heating, still head is removed after being down to room temperature, vacuum tail is taken over, single port flask, polyarylethersulfone polymer containing methoxyl group benzene lateral group is joined in there-necked flask, be 12 ~ 19g/L containing the polyarylethersulfone polymer add-on of methoxyl group benzene lateral group and the mass volume ratio of pyridine, install spherical condensation tube, open heating, be warming up to 160 ~ 180 DEG C, react 10 ~ 16 hours, be cooled to 80 ~ 100 DEG C, discharging is in frozen water, and washing, drying, obtains hydroxyl benzene lateral group polyether sulphone material.
Above-mentioned contains anisole lateral group polyarylether sulfone polymer, and main chain is common aromatic ring; Containing anisole lateral group polyarylether sulfone anisole can at benzene lateral group ortho position, a position and contraposition.Preferred containing anisole lateral group polyarylether sulfone polymer be in side chain anisole methoxyl group at the polymkeric substance of a position.
Polyether sulphone main chain is obtained of the present invention being successfully incorporated into by boric acid ester by a kind of boron addition reaction of hydrogen containing phenoxy group aliphatic chain boric acid ester side chain polyarylethersulfone polymer, this polymkeric substance has the performance of fragrant main chain and aliphatics boric acid ester side chain concurrently, has good thermostability.Meanwhile, this preparation method is simple and easy to do, and reaction efficiency is high, be applicable to polyarylether system, in addition, owing to being important neutron absorber material and reaction intermediate containing boron material, make it in nuclear industry shielding material and the crosslinked polyaryl ether sulphone resin of preparation, have potential application.
Accompanying drawing explanation
Fig. 1 is the DSC curve of the polyether sulphone containing phenoxy group allyl group side base of the present invention
Fig. 2 is the DSC curve containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present invention
Fig. 3 is the NMR spectrogram containing anisole lateral group polyarylether sulfone of the present invention
Fig. 4 is the NMR spectrogram of hydroxyl benzene lateral group polyether sulphone of the present invention
Fig. 5 is the NMR spectrogram containing phenoxy group allyl group lateral group polyarylether sulfone of the present invention
Fig. 6 is the NMR spectrogram containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present invention
Fig. 7 is the FT-IR spectrogram containing phenoxy group allyl group lateral group polyarylether sulfone of the present invention
Fig. 8 is the FT-IR spectrogram containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present invention
Fig. 9 is the TGA curve under air conditions containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present invention
Embodiment
Embodiment 1: containing the preparation (1) of anisole lateral group polyarylether sulfone
By 10.0812g (0.05mol) 2-(3`-p-methoxy-phenyl)-1,4-Resorcinol monomer, 12.7125g (0.05mol) 4,4`-difluorodiphenyl sulfone and 7.6005g Anhydrous potassium carbonate, 75ml tetramethylene sulfone, the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed put into by 25mL dewatering agent (toluene or dimethylbenzene), logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be warmed up to 140 ~ 180 ° of C and continue reaction 7 ~ 10 hours; Then the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain containing meta-methoxy benzene lateral group polyarylethersulfone polymer.
Molecular formula is as follows:
Fig. 3 provides the hydrogen nuclear magnetic spectrogram containing anisole lateral group polyarylether sulfone of the present embodiment, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.
Containing anisole lateral group polyarylether sulfone (for 2-(3`-p-methoxy-phenyl)-Isosorbide-5-Nitrae-Resorcinol) the building-up reactions formula of polymkeric substance is as follows:
Embodiment 2: the preparation (1) of hydroxyl benzene lateral group polyether sulphone
First 322ml pyridine is joined band thermometer, nitrogen through hole, mechanical stirring, in the there-necked flask of constant pressure funnel, the concentrated hydrochloric acid of 336ml is added in dropping funnel, while stirring concentrated hydrochloric acid is added drop-wise in pyridine, constant pressure funnel is removed after dripping off, still head is installed, vacuum tail is taken over, single port flask, rubber hose, logical nitrogen also opens heating, lentamente water is steamed, be warming up to 200 ~ 215 ° of C and namely stop heating, still head is removed after being down to room temperature, vacuum tail is taken over, single port flask, the polyarylethersulfone polymer containing meta-methoxy benzene lateral group of 5g is joined in there-necked flask, spherical condensation tube is installed, open heating, be warming up to 160 ~ 180 ° of C, react 10 ~ 16 hours, be cooled to 80 ~ 100 ° of C, discharging is in frozen water, washing, dry, hydroxybenzene lateral group polyarylether sulfone material between obtaining containing.
Molecular formula is as follows:
Fig. 4 provides the hydrogen nuclear magnetic spectrogram of the hydroxyl benzene lateral group polyether sulphone of the present embodiment, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.
Between containing, the building-up reactions formula of hydroxybenzene lateral group polyarylether sulfone polymer is as follows:
Embodiment 3: containing the preparation (1) of allyl group oxygen benzene lateral group polyether sulphone
Between 2.0823g is contained hydroxyl polyether sulphone tape loaded thermometer, nitrogen through hole, mechanical stirring, water-taker there-necked flask in, then add 0.4491g Anhydrous potassium carbonate, 10mlN, N-N,N-DIMETHYLACETAMIDE, 5ml toluene, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be cooled to 30 ~ 50 ° of C, add 2.2ml allyl bromide 98, spherical condensation tube is installed, be warmed up to 100 ~ 120 ° of C and continue reaction 6 ~ 10 hours; Then, the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain containing m-phenoxy allyl group lateral group polyarylether sulfone polymer.
Molecular formula is as follows:
Fig. 1 gives the DSC curve of the polyether sulphone containing phenoxy group allyl group side base, and the Tg as we can see from the figure containing the polyether sulphone of phenoxy group allyl group side base is 137 DEG C, and has occurred significantly crosslinked exothermic peak at 230 ~ 300 degrees Celsius.Fig. 5 provides the hydrogen nuclear magnetic spectrogram containing phenoxy group allyl group lateral group polyarylether sulfone of the present embodiment, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.Fig. 7 provides the infrared spectrum containing phenoxy group allyl group lateral group polyarylether sulfone of the present embodiment, and the characteristic group as we can see from the figure in polymkeric substance has obvious charateristic avsorption band; Especially at 3075cm
-1~ 3090cm
-1there is the charateristic avsorption band of the c h bond stretching vibration on olefinic double bonds in place.
Embodiment 4: containing the preparation (1) of phenoxy group aliphatic chain boric acid ester side chain polyether sulphone
Prepare containing m-phenoxy aliphatic side chains pinacol borate side chain polyether sulphone material by reacting containing m-phenoxy allyl group lateral group polyarylether sulfone and pinacol ester borine, that 1.3726g is placed with in the container of stirrer containing allyl group oxygen phenyl polyether sulphone and loading, add 0.0303g (1,5-cyclooctadiene) iridochloride (I) dimer [Ir (COD) Cl] again
2and 0.0359g1, two (diphenylphosphine) ethane (dppe) of 2-, then vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 3 ~ 5 times repeatedly, inject 20ml tetrahydrofuran (THF), dissolve, inject 0.5ml pinacol ester borine (1.1 times containing the allylic molar weight of phenoxy group allyl group lateral group polyarylether sulfone), then seal, open and stir, room temperature reaction 60 ~ 78 hours; Adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 3 ~ 5 times, filters, and vacuumizes 80 ° of C and dries, namely obtain containing m-phenoxy aliphatic chain boric acid ester side chain polyether sulphone material.
Molecular formula is as follows:
What Fig. 2 provided is the DSC curve containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone, and the Tg as we can see from the figure containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone is 161 degrees Celsius.Fig. 6 provides the hydrogen nuclear magnetic spectrogram containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present embodiment, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.Fig. 8 provides the infrared spectrum containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present embodiment, and the characteristic group as we can see from the figure in polymkeric substance has obvious charateristic avsorption band; Especially at 2930cm
-1there is the methyl charateristic avsorption band of phenylo boric acid pinacol ester in place, at 1080cm
-1there is the boron oxygen stretching vibration absorption peak of borate ester in place.Fig. 9 is to the TGA curve containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone of the present embodiment.Polymers exhibit has gone out good thermostability as we can see from the figure.
Embodiment 5: containing the preparation (2) of anisole lateral group polyarylether sulfone
2-(3`-p-methoxy-phenyl by embodiment 1)-1,4-Resorcinol changes into 2-(2`-p-methoxy-phenyl)-1,4-Resorcinol or 2-(4`-p-methoxy-phenyl)-Isosorbide-5-Nitrae-Resorcinol, also can obtain containing adjacent, to methoxyl group benzene lateral group polyarylethersulfone polymer.
Embodiment 6: the preparation (2 of hydroxyl benzene lateral group polyether sulphone
The polyether sulphone of methoxy benzene lateral group between containing in embodiment 2 is changed into containing O-methoxy benzene lateral group with to anisole lateral group polyarylether sulfone, then carries out pyridine hydrochloride and go etherificate, can obtain respectively containing adjacent, para hydroxybenzene lateral group polyarylether sulfone.
Embodiment 7: containing the preparation (2) of the polyether sulphone of phenoxy group allyl group side base
The polyether sulphone of hydroxyl benzene lateral group between containing in embodiment 3 is changed into containing o-hydroxy lateral group polyarylether sulfone with containing para hydroxybenzene lateral group polyarylether sulfone, can obtain respectively containing adjacent, to phenoxy group allyl group side base polyether sulphone.
Embodiment 8: containing the preparation (2) of phenoxy group aliphatic chain boric acid ester side chain polyether sulphone
By changing into containing adjacent phenoxy group allyl group lateral group polyarylether sulfone or containing to phenoxy group allyl group lateral group polyarylether sulfone containing m-phenoxy allyl group lateral group polyarylether sulfone in embodiment 4, also can obtain containing neighbour, to phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material.
Claims (6)
1., containing a phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material, be made up of polyether sulphone main chain and phenoxy group aliphatic chain pinacol borate side chain, all side chains all contain pinacol borate; The aliphatic chain phenylo boric acid pinacol ester of side chain is positioned at the ortho position of side-chain benzene ring, a position and contraposition.
2. according to claim 1 containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material, it is characterized in that, the structural formula containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone is
Wherein, n=10 ~ 12.
3. the preparation method containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material of claim 1, has preparation containing phenoxy group allyl group lateral group polyarylether sulfone, prepares the process containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone;
Described preparation containing phenoxy group allyl group lateral group polyarylether sulfone, is that allyl bromide 98 consumption is 5 times of hydroxyl molar weight in hydroxyl benzene lateral group polyether sulphone with hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 for reactant; Hydroxyl benzene lateral group polyether sulphone is loaded in container, add the Anhydrous potassium carbonate of hydroxyl molar weight 1.05 times in hydroxyl benzene lateral group polyether sulphone, 4 times to the organic solvent of reactant quality, the azeotropy dehydrant of organic solvent volume 20%, logical nitrogen, stirs, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be cooled to 30 ~ 50 DEG C; Add allyl bromide 98, be warmed up to 100 ~ 120 DEG C and continue reaction 6 ~ 10 hours; The polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the polyarylethersulfone polymer containing phenoxy group allyl group side base;
Described preparation is containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone, the polyether sulphone containing phenoxy group allyl group side base is loaded be placed with in the container of stirrer, add 0.015 times of allylic molar weight and 0.03 times (1 in the polyether sulphone be respectively containing phenoxy group allyl group side base again, 5-cyclooctadiene) iridochloride dimer and 1, two (diphenylphosphine) ethane of 2-, then vacuumize and put high pure nitrogen, inject organic solvent trichloromethane, tetrahydrofuran (THF) or dioxane dissolve, reinject containing the pinacol ester borine of 1.5 times of allylic molar weight in the polyether sulphone of phenoxy group allyl group side base, sealing stirring reaction 60 ~ 78 hours, adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 3 ~ 5 times, filters, vacuumizes 80 DEG C of oven dry, namely obtains containing phenoxy group aliphatic chain pinacol borate side chain polyether sulphone material.
4. the preparation method containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material according to claim 3, is characterized in that, in preparation containing in phenoxy group allyl group lateral group polyarylether sulfone, described organic solvent, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO); Described azeotropy dehydrant is toluene or dimethylbenzene.
5. the preparation method containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material according to claim 3 or 4, it is characterized in that, described hydroxyl benzene lateral group polyether sulphone, preparation process is the polyether sulphone of first synthesizing methoxy benzene lateral group, etherificate is gone to prepare hydroxyl benzene lateral group polyether sulphone again
Described synthesis is containing the polyether sulphone of methoxyl group benzene lateral group, with Resorcinol monomer and equimolar 4, 4`-difluorodiphenyl sulfone monomer or 4, 4`-dichloro diphenyl sulfone is reactant, with 4, 4`-difluorodiphenyl sulfone monomer or 4, the Anhydrous potassium carbonate of 1.05 times of 4`-dichloro diphenyl sulfone, 4 times to the organic solvent of reactant quality, the azeotropy dehydrant of organic solvent volume 20% is put into together and nitrogen through hole is housed, in the there-necked flask of mechanical stirring and water-taker, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be warmed up to 160 ~ 190 DEG C and continue reaction 6 ~ 10 hours, then, the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the polyarylethersulfone polymer of methoxyl group benzene lateral group, described Resorcinol monomer, 2-(3`-p-methoxy-phenyl)-1,4-Resorcinol, 2-(2`-p-methoxy-phenyl)-1,4-Resorcinol or 2-(4`-p-methoxy-phenyl)-Isosorbide-5-Nitrae-Resorcinol, described organic solvent, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), tetramethylene sulfone or N-Methyl pyrrolidone, described azeotropy dehydrant is toluene or dimethylbenzene,
Described etherificate of going prepares hydroxyl benzene lateral group polyether sulphone, first pyridine is joined in the there-necked flask of band thermometer, nitrogen through hole, mechanical stirring, constant pressure funnel, while stirring concentrated hydrochloric acid is added drop-wise in pyridine again, HCl and pyridine equimolar amount in the concentrated hydrochloric acid added; Constant pressure funnel is removed after dripping off, still head, the adapter of vacuum tail, single port flask, rubber hose are installed, logical nitrogen also opens heating, lentamente water is steamed, be warming up to 200 ~ 215 DEG C and namely stop heating, remove still head, the adapter of vacuum tail, single port flask after being down to room temperature, joining in there-necked flask by the polyarylethersulfone polymer containing methoxyl group benzene lateral group, is 12 ~ 19g/L containing the polyarylethersulfone polymer add-on of methoxyl group benzene lateral group and the mass volume ratio of pyridine; Install spherical condensation tube, open heating, be warming up to 160 ~ 180 DEG C, react 10 ~ 16 hours, be cooled to 80 ~ 100 DEG C, discharging is in frozen water, and washing, drying, obtains hydroxyl benzene lateral group polyether sulphone material.
6. the preparation method containing phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material according to claim 5, is characterized in that, described contains anisole lateral group polyarylether sulfone polymer, and main chain is common aromatic ring; Containing anisole lateral group polyarylether sulfone polymer be in side chain anisole methoxyl group at the polymkeric substance of a position.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310181782.9A CN103265693B (en) | 2013-05-16 | 2013-05-16 | Polyether sulphone material containing phenoxy aliphatic chain boric acid ester side chain and preparation method of material |
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| CN201310181782.9A CN103265693B (en) | 2013-05-16 | 2013-05-16 | Polyether sulphone material containing phenoxy aliphatic chain boric acid ester side chain and preparation method of material |
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| Publication Number | Publication Date |
|---|---|
| CN103265693A CN103265693A (en) | 2013-08-28 |
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| CN112011052B (en) * | 2020-09-11 | 2022-02-08 | 四川大学 | Functional boron-containing polyarylene sulfide copolymer and preparation method thereof |
| CN112159422B (en) * | 2020-10-21 | 2022-11-15 | 上海应用技术大学 | Method for synthesizing phenylboronic acid ester derivative under catalysis of iridium catalyst |
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| CN101550234A (en) * | 2009-05-13 | 2009-10-07 | 中国科学院上海微系统与信息技术研究所 | Fluorescent sensing material with sensing function to phenyl amine compounds, method and application thereof |
| CN102924720A (en) * | 2012-12-03 | 2013-02-13 | 吉林大学 | Boric acid ester-containing polyarylether sulphone material and preparation method thereof |
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| CN101550234A (en) * | 2009-05-13 | 2009-10-07 | 中国科学院上海微系统与信息技术研究所 | Fluorescent sensing material with sensing function to phenyl amine compounds, method and application thereof |
| CN102924720A (en) * | 2012-12-03 | 2013-02-13 | 吉林大学 | Boric acid ester-containing polyarylether sulphone material and preparation method thereof |
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