CN103265693A - 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 polyether sulphone polymer materials and preparation method thereof.
Background technology
Fragrance main chain polyether sulphone with its good mechanical property, dimensional stability is good, electrical property is excellent and excellent properties such as easy-formation processing, is widely used in fields such as machinery, electronics, automobile, medicine equipment, foodstuffs industry and space flight and aviation.But unformed polyether sulphone is responsive to solvent, the corrosion of anti-intensive polar solvent and the vitriol oil, concentrated nitric acid hardly, and these have limited its application.Functional groups is incorporated into the aromatic polymer main chain can obtain anti-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 scientific worker's concern.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 group.
Pure boron is considered as a kind of important strategic goods and materials by western countries always, and is main because it militarily has important purposes.At first, the pure boron powder has the characteristic of high-energy-density and clean fuel, is a kind of good solid rocket propellant; Secondly,
10The B isotropic substance has the very high slow-neutron cross-section (3.99 * 10 of capturing
-25m
2), it and neutron effect generation nuclear reaction:
Generate stable lithium and alpha-particle
, alpha-particle is easy to absorb, can be as control and the shielding material of reactor.
The boron atom is incorporated in the macromolecular material, can improve characteristics such as the thermotolerance of macromolecular material, instantaneous ablation resistance, wear-resisting wiping, mechanical property and anti-neutron radiation to a certain extent, simultaneously, the aliphatics macromolecular material can reduce the speed of neutron effectively, be conducive to the absorption of boron atom pairs neutron, the boracic aliphatic polymer has purposes widely in fields such as Nuclear power plants.
Fatty boric acid ester side chain polymer can be used as reaction intermediate.For example: 2002, the people such as J.Y.Dong of Bin Nifaniya state university (Macromolecules2002,35,3439-3447) prepared fatty side chain boric acid ester polystyrene, adopt the method for hydrogen peroxide oxidation that boric acid ester is taken off then, obtain fatty pure side chain polystyrene; Adopt the method for oxygen catalysis to come acid anhydrides to be incorporated into polymer lateral chain span, also can cause methyl methacrylate polymerization and obtain the crosslinked polystyrene material of polymethylmethacrylate.
The present invention has selected the method for boron hydrogen addition for use, successfully the aliphatic chain boric acid ester is incorporated on the polyether sulphone main chain, has prepared a kind of polyether sulphone that contains phenoxy group boric acid ester side chain boric acid ester.The present invention synthesizes, and to contain phenoxy group aliphatic chain boric acid ester side chain polyether sulphone be a kind of novel macromolecular material, is again a kind of important reaction intermediate.
Summary of the invention
The technical problem to be solved in the present invention is that hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 prepared in reaction contain allyl benzene base side chain polyether sulphone material and contain phenoxy group allyl side chain polyether sulphone and pinacol ester borine prepared in reaction contains phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material; Contain the performance that phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material has fragrant main chain and aliphatics boric acid ester side chain concurrently, have good thermostability.
Its preparation method is first by 2-(3`-p-methoxy-phenyl)-1, and 4-Resorcinol and 4,4`-, two fluoro-sulfobenzides obtain containing p-methoxy-phenyl polyether sulphone (PES-OCH according to the feed ratio reaction of 1: 1 (mol ratio)
3), in pyridine hydrochloride, go the ether reaction again, obtain hydroxyl phenyl polyether sulphone, hydroxyl phenyl polyether sulphone and allyl bromide 98 obtain containing allyl benzene base side chain polyether sulphone according to the feed ratio reaction of 1: 5 (mol ratio), at last, at (1,5-cyclooctadiene) iridochloride (I) dimer [Ir (COD) Cl]
2With 1, under the catalysis of two (diphenylphosphine) ethane (dppe) of 2-, contain allyl benzene base side chain polyether sulphone and pinacol ester borine and go out the novel phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone material that contains according to the feed ratio prepared in reaction of 1:5 (mol ratio).The valency of (I) expression iridium in (1,5-cyclooctadiene) iridochloride (I) dimer is 1 valency.
The phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material that contains of the present invention, formed by polyether sulphone main chain and phenoxy group aliphatic chain boric acid pinacol ester side chain, wherein the molar content according to design boric acid pinacol ester is 100%(100%, and namely all side chains all contain the boric acid pinacol ester).The aliphatic chain phenylo boric acid pinacol ester of side chain can be positioned at ortho position, a position and the contraposition of side-chain benzene ring.
A kind of structural formula (position) that contains phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material is
Wherein, n=10～12.
The phenoxy group aliphatic chain boric acid ester side chain polyether sulphone preparation methods that contains of the present invention has to prepare to contain allyl benzene lateral group polyarylether sulfone and prepare the process that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone;
Described preparation contains phenoxy group allyl group lateral group polyarylether sulfone material, be with the hydroxyl benzene lateral group polyether sulphone band thermometer of packing into, the nitrogen through hole, mechanical stirring, in the there-necked flask of water-taker, 1.05 times the Anhydrous potassium carbonate that adds hydroxyl molar weight in the hydroxyl benzene lateral group polyether sulphone then, 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, being warmed up to azeotropy dehydrant refluxes, reacted 1～3 hour, get rid of azeotropy dehydrant, be cooled to 30～50 ℃, add 5 times allyl bromide 98 of hydroxyl molar weight in the hydroxyl benzene lateral group polyether sulphone, spherical condensation tube is installed, be warmed up to 100～120 ℃ and continue reaction 6～10 hours; Then, the polymers soln that obtains is separated out in deionized water, through pulverizing, washing, drying obtains containing the polyether sulphone polymkeric substance of phenoxy group allyl group side group.
Described preparation contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone, be to contain the polyether sulphone of phenoxy group allyl group side group and pack into to be placed with in the container of stirrer, add an amount of (1,5-cyclooctadiene) iridochloride (I) dimer [Ir (COD) Cl] again
2(contain in the polyether sulphone of allyl benzene side group allylic molar weight 0.015 times) and 1, two (diphenylphosphine) ethane (dppe) of 2-(contain in the phenoxy group allyl group lateral group polyarylether sulfone allylic molar weight 0.03 times), vacuumize then and put high pure nitrogen and (can vacuumize again and put high pure nitrogen, 3～5 times repeatedly), inject organic solvent, dissolving, inject an amount of pinacol ester borine (contain the allylic molar weight of phenoxy group allyl group lateral group polyarylether sulfone 1.5 times), sealing then, open and stir room temperature reaction 60～78 hours; Adopt diatomite filtration, removal of solvent under reduced pressure, acetone is washed 3～5 times, filters, and vacuumizes 80 ℃ of oven dry, namely obtains containing phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone material; Used organic solvent can be trichloromethane, tetrahydrofuran (THF) or dioxane.
The building-up reactions formula that contains m-phenoxy allyl group lateral group polyarylether sulfone polymer of the present invention is as follows:
The building-up reactions formula that contains m-phenoxy aliphatic chain boric acid pinacol ester side chain polyether sulphone of the present invention is as follows:
Contain in synthesizing of phenoxy group allyl group lateral group polyarylether sulfone at hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 prepared in reaction, used organic solvent can be N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), used azeotropy dehydrant can be toluene or dimethylbenzene.
Contain in the reaction that phenoxy group allyl group lateral group polyarylether sulfone and pinacol ester borine prepared in reaction contain phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material, used pinacol ester borine, have another name called: pineapple alcohol borine, the product that can select for use the chemical company limited of A Faaisha (Tianjin) to produce.
Contain in synthesizing of phenoxy group allyl group lateral group polyarylether sulfone at hydroxyl benzene lateral group polyether sulphone and allyl bromide 98 prepared in reaction, raw materials used hydroxyl benzene lateral group polyether sulphone can obtain according to the method for embodiment 1 among the Chinese patent application publication number CN102174199A and 2, also can prepare according to process as described below: the polyether sulphone of first synthesizing methoxy benzene lateral group, go etherificate to prepare hydroxyl benzene lateral group polyether sulphone again
The described synthetic polyether sulphone that contains the anisole side group, be with Resorcinol monomer and equimolar 4,4`-difluorodiphenyl sulfone monomer or 4, the 4`-dichloro diphenyl sulfone is reactant, with 4,4`-difluorodiphenyl sulfone monomer or 4,1.05 times Anhydrous potassium carbonate of 4`-dichloro diphenyl sulfone, 4 times to the organic solvent of reactant quality, and the azeotropy dehydrant of organic solvent volume 20% is put into together the 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 and reflux, reacted 1～3 hour, get rid of azeotropy dehydrant, be warmed up to 160～190 ℃ and continue reaction 6～10 hours; Then, the polymers soln that obtains is separated out in deionized water, through pulverizing, washing, drying obtains the polyether sulphone polymkeric substance of anisole side group; Described Resorcinol monomer, be the 2-(3`-p-methoxy-phenyl)-1,4-Resorcinol, 2-(2`-p-methoxy-phenyl)-1,4-Resorcinol or 2-(4`-p-methoxy-phenyl)-1, the 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;
The described etherificate of going prepares hydroxyl benzene lateral group polyether sulphone, be earlier a certain amount of pyridine to be joined the band thermometer, the nitrogen through hole, mechanical stirring, in the there-necked flask of constant pressure funnel, in dropping funnel, add the concentrated hydrochloric acid of (HCl in the concentrated hydrochloric acid and pyridine equimolar amount) in right amount, while stirring concentrated hydrochloric acid is added drop-wise in the pyridine, remove constant pressure funnel after dripping off, still head is installed, the vacuum tail is taken over, the single port flask, rubber hose, logical nitrogen is also opened heating, lentamente water is steamed, be warming up to 200～215 ℃ and namely stop heating, remove still head after being down to room temperature, the vacuum tail is taken over, the single port flask, the polyether sulphone polymkeric substance that will contain the anisole side group joins in the there-necked flask, and containing the polyether sulphone polymkeric substance add-on of anisole side group and the mass volume ratio of pyridine is 12～19g/L; Spherical condensation tube is installed, is opened heating, be warming up to 160～180 ℃, reacted 10～16 hours, be cooled to 80～100 ℃, discharging is washed in frozen water, and drying obtains hydroxyl benzene lateral group polyether sulphone material.
The above-mentioned anisole lateral group polyarylether sulfone polymer that contains, main chain is common aromatic ring; The anisole that contains anisole lateral group polyarylether sulfone can be in benzene lateral group ortho position, a position and contraposition.Preferably contain anisole lateral group polyarylether sulfone polymer and be in the side chain anisole methoxyl group at the polymkeric substance of a position.
The phenoxy group aliphatic chain boric acid ester side chain polyether sulphone polymkeric substance of containing of the present invention successfully is incorporated into boric acid ester by a kind of boron addition reaction of hydrogen and obtains on the polyether sulphone main chain, this polymkeric substance has the performance of fragrant main chain and aliphatics boric acid ester side chain concurrently, has good thermostability.Simultaneously, this preparation method is simple and easy to do, the reaction efficiency height, be applicable to the polyarylether system, in addition, because to contain boron material be important neutron absorbing material and reaction intermediate, make it at the nuclear industry shielding material and prepare to have potential application aspect the crosslinked polyaryl ether sulphone resin.
Description of drawings
Fig. 1 is the DSC curve that contains the polyether sulphone of phenoxy group allyl group side group of the present invention
Fig. 2 is the DSC curve that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of the present invention
Fig. 3 is the NMR spectrogram that contains 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 that contains phenoxy group allyl group lateral group polyarylether sulfone of the present invention
Fig. 6 is the NMR spectrogram that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of the present invention
Fig. 7 is the FT-IR spectrogram that contains phenoxy group allyl group lateral group polyarylether sulfone of the present invention
Fig. 8 is the FT-IR spectrogram that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of the present invention
Fig. 9 is the TGA curve under air conditions that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of the present invention
Embodiment
Embodiment 1: contain the preparation (1) of anisole lateral group polyarylether sulfone
With 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, the 75ml tetramethylene sulfone, 25mL dewatering agent (toluene or dimethylbenzene) is put into the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant and reflux, reacted 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 that obtains is separated out in deionized water, through pulverizing, wash, drying obtains containing meta-methoxy benzene lateral group polyether sulphone polymkeric substance.
Molecular formula is as follows:
Fig. 3 provides the proton magnetic spectrum figure that contains anisole lateral group polyarylether sulfone of present embodiment, and each hydrogen in the polymer architecture has correct ownership as we can see from the figure.
Contain anisole lateral group polyarylether sulfone (with the 2-(3`-p-methoxy-phenyl)-1, the 4-Resorcinol is example) the building-up reactions formula of polymkeric substance is as follows:
Embodiment 2: the preparation (1) of hydroxyl benzene lateral group polyether sulphone
Earlier the 322ml pyridine is joined the band thermometer, the nitrogen through hole, mechanical stirring, in the there-necked flask of constant pressure funnel, the concentrated hydrochloric acid that adds 336ml in the dropping funnel, while stirring concentrated hydrochloric acid is added drop-wise in the pyridine, remove constant pressure funnel after dripping off, still head is installed, the vacuum tail is taken over, the single port flask, rubber hose, logical nitrogen is also opened heating, lentamente water is steamed, be warming up to 200～215 ° of C and namely stop heating, remove still head after being down to room temperature, the vacuum tail is taken over, the single port flask, the polyether sulphone polymkeric substance that contains the meta-methoxy benzene lateral group of 5g is joined in the there-necked flask, spherical condensation tube is installed, is opened heating, be warming up to 160～180 ° of C, reacted 10～16 hours, be cooled to 80～100 ° of C, discharging is washed in frozen water, drying obtains containing a hydroxybenzene lateral group polyarylether sulfone material.
Molecular formula is as follows:
Fig. 4 provides the proton magnetic spectrum figure of the hydroxyl benzene lateral group polyether sulphone of present embodiment, and each hydrogen in the polymer architecture has correct ownership as we can see from the figure.
It is as follows to contain a building-up reactions formula of hydroxybenzene lateral group polyarylether sulfone polymer:
Embodiment 3: contain the preparation (1) of allyl group oxygen benzene lateral group polyether sulphone
2.0823g is contained a hydroxyl polyether sulphone pack in the there-necked flask of band thermometer, nitrogen through hole, mechanical stirring, water-taker, add the 0.4491g Anhydrous potassium carbonate then, 10mlN, the N-N,N-DIMETHYLACETAMIDE, 5ml toluene, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant and reflux, reacted 1～3 hour, get rid of azeotropy dehydrant, be cooled to 30～50 ° of C, add the 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 that obtains is separated out in deionized water, through pulverizing, wash, drying obtains containing m-phenoxy allyl group lateral group polyarylether sulfone polymer.
Molecular formula is as follows:
Fig. 1 has provided the DSC curve of the polyether sulphone that contains phenoxy group allyl group side group, and the Tg that contains the polyether sulphone of phenoxy group allyl group side group as we can see from the figure is 137 ℃, and tangible crosslinked exothermic peak occurred at 230～300 degrees centigrade.Fig. 5 provides the proton magnetic spectrum figure that contains phenoxy group allyl group lateral group polyarylether sulfone of present embodiment, and each hydrogen in the polymer architecture has correct ownership as we can see from the figure.Fig. 7 provides the infrared spectrum that contains phenoxy group allyl group lateral group polyarylether sulfone of present embodiment, and the characteristic group in the polymkeric substance has the obvious characteristics absorption peak as we can see from the figure; Especially at 3075cm
-1～3090cm
-1The charateristic avsorption band of the c h bond stretching vibration on the olefinic double bonds has appearred in the place.
Embodiment 4: contain the preparation (1) of phenoxy group aliphatic chain boric acid ester side chain polyether sulphone
Contain m-phenoxy aliphatic side chains boric acid pinacol ester side chain polyether sulphone material by containing m-phenoxy allyl group lateral group polyarylether sulfone and pinacol ester borine prepared in reaction, be 1.3726g to be contained allyl group oxygen phenyl polyether sulphone and packs into be placed with in the container of stirrer, add 0.0303g (1,5-cyclooctadiene) iridochloride (I) dimer [Ir (COD) Cl] again
2And 0.0359g1, two (diphenylphosphine) ethane (dppe) of 2-, vacuumize then and put high pure nitrogen and vacuumize again and put high pure nitrogen, 3～5 times repeatedly, inject the 20ml tetrahydrofuran (THF), dissolving, inject 0.5ml pinacol ester borine (contain the allylic molar weight of phenoxy group allyl group lateral group polyarylether sulfone 1.1 times), sealing is then opened and is stirred, room temperature reaction 60～78 hours; Adopt diatomite filtration, removal of solvent under reduced pressure, acetone is washed 3～5 times, filters, and vacuumizes 80 ° of C oven dry, namely obtains 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 that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone, and the Tg that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone as we can see from the figure is 161 degrees centigrade.Fig. 6 provides the proton magnetic spectrum figure that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of present embodiment, and each hydrogen in the polymer architecture has correct ownership as we can see from the figure.Fig. 8 provides the infrared spectrum that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of present embodiment, and the characteristic group in the polymkeric substance has the obvious characteristics absorption peak as we can see from the figure; Especially at 2930cm
-1The methyl charateristic avsorption band of phenylo boric acid pinacol ester has appearred in the place, at 1080cm
-1The boron oxygen stretching vibration absorption peak of borate ester has appearred in the place.Fig. 9 gives the TGA curve that contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone of present embodiment.Polymkeric substance has shown good thermostability as we can see from the figure.
Embodiment 5: contain the preparation (2) of anisole lateral group polyarylether sulfone
With the 2-(3`-p-methoxy-phenyl among the embodiment 1)-1, the 4-Resorcinol changes into the 2-(2`-p-methoxy-phenyl)-1,4-Resorcinol or 2-(4`-p-methoxy-phenyl)-1, the 4-Resorcinol, also can access contain the neighbour, to the polyether sulphone polymkeric substance of anisole side group.
Embodiment 6: the preparation (2 of hydroxyl benzene lateral group polyether sulphone
Polyether sulphone of methoxy benzene lateral group that contains among the embodiment 2 is changed into and contains the O-methoxy benzene lateral group and to anisole lateral group polyarylether sulfone, carry out pyridine hydrochloride then and go etherificate, can access respectively and contain neighbour, para hydroxybenzene lateral group polyarylether sulfone.
Embodiment 7: contain the preparation (2) of the polyether sulphone of phenoxy group allyl group side group
Polyether sulphone of hydroxybenzene side group that contains among the embodiment 3 is changed into and contains o-hydroxy lateral group polyarylether sulfone and contain para hydroxybenzene lateral group polyarylether sulfone, can access respectively contain the neighbour, to the polyether sulphone of phenoxy group allyl group side group.
Embodiment 8: contain the preparation (2) of phenoxy group aliphatic chain boric acid ester side chain polyether sulphone
The m-phenoxy allyl group lateral group polyarylether sulfone that contains among the embodiment 4 is changed into and contains adjacent phenoxy group allyl group lateral group polyarylether sulfone or contain phenoxy group allyl group lateral group polyarylether sulfone, also can access contain the neighbour, to phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material.
Claims (6)
1. one kind contains phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material, is made up of polyether sulphone main chain and phenoxy group aliphatic chain boric acid pinacol ester side chain, and the molar content of boric acid pinacol ester is 100%; The aliphatic chain phenylo boric acid pinacol ester of side chain is positioned at ortho position, a position and the contraposition of side-chain benzene ring.
2. the phenoxy group aliphatic chain boric acid ester side chain polyether sulphone material that contains according to claim 1 is characterized in that the structural formula that contains phenoxy group aliphatic chain boric acid ester side chain polyether sulphone is
Wherein, n=10～12.
A claim 1 contain phenoxy group aliphatic chain boric acid ester side chain polyether sulphone preparation methods, have preparation to contain the process that phenoxy group allyl group lateral group polyarylether sulfone, preparation contain phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone;
Described preparation contains phenoxy group allyl group lateral group polyarylether sulfone, is to be reactant with hydroxyl benzene lateral group polyether sulphone and allyl bromide 98, and the allyl bromide 98 consumption is 5 times of hydroxyl molar weight in the hydroxyl benzene lateral group polyether sulphone; Hydroxyl benzene lateral group polyether sulphone is packed in the container, the Anhydrous potassium carbonate that adds 1.05 times of hydroxyl molar weights in the 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, being warmed up to azeotropy dehydrant refluxes, reacted 1～3 hour, and got rid of azeotropy dehydrant, be cooled to 30～50 ℃; Add allyl bromide 98, be warmed up to 100～120 ℃ and continue reaction 6～10 hours; The polymers soln that obtains is separated out in deionized water, through pulverizing, washing, drying obtains containing the polyether sulphone polymkeric substance of phenoxy group allyl group side group;
Described preparation contains phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone, be that the polyether sulphone that will contain phenoxy group allyl group side group is packed into and is placed with in the container of stirrer, add (1 of 0.015 times of being respectively allylic molar weight in the polyether sulphone that contains phenoxy group allyl group side group and 0.03 times again, the 5-cyclooctadiene) iridochloride dimer and 1, two (diphenylphosphine) ethane of 2-, vacuumize then and put high pure nitrogen, inject the organic solvent trichloromethane, tetrahydrofuran (THF) or dioxane dissolving, 1.5 times pinacol ester borine of the allylic molar weight in the polyether sulphone that contains phenoxy group allyl group side group of reinjecting, sealing stirring reaction 60～78 hours; Adopt diatomite filtration, removal of solvent under reduced pressure, acetone is washed 3～5 times, filters, and vacuumizes 80 ℃ of oven dry, namely obtains containing phenoxy group aliphatic chain boric acid pinacol ester side chain polyether sulphone material.
4. the phenoxy group aliphatic chain boric acid ester side chain polyether sulphone preparation methods that contains according to claim 3 is characterized in that, contains in the phenoxy group allyl group lateral group polyarylether sulfone in preparation, described organic solvent, be N, dinethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO); Described azeotropy dehydrant is toluene or dimethylbenzene.
5. according to claim 3 or the 4 described phenoxy group aliphatic chain boric acid ester side chain polyether sulphone preparation methods that contain, 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, go etherificate to prepare hydroxyl benzene lateral group polyether sulphone again
The described synthetic polyether sulphone that contains the anisole side group, be with Resorcinol monomer and equimolar 4,4`-difluorodiphenyl sulfone monomer or 4, the 4`-dichloro diphenyl sulfone is reactant, with 4,4`-difluorodiphenyl sulfone monomer or 4,1.05 times Anhydrous potassium carbonate of 4`-dichloro diphenyl sulfone, 4 times to the organic solvent of reactant quality, and the azeotropy dehydrant of organic solvent volume 20% is put into together the 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 and reflux, reacted 1～3 hour, get rid of azeotropy dehydrant, be warmed up to 160～190 ℃ and continue reaction 6～10 hours; Then, the polymers soln that obtains is separated out in deionized water, through pulverizing, washing, drying obtains the polyether sulphone polymkeric substance of anisole side group; Described Resorcinol monomer, be the 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, be N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), tetramethylene sulfone or N-Methyl pyrrolidone, described azeotropy dehydrant is toluene or dimethylbenzene;
The described etherificate of going prepares hydroxyl benzene lateral group polyether sulphone, be earlier pyridine to be 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 the pyridine HCl and pyridine equimolar amount in the concentrated hydrochloric acid of adding again; Remove constant pressure funnel after dripping off, still head, the adapter of vacuum tail, single port flask, rubber hose are installed, logical nitrogen is also opened heating, lentamente water is steamed, be warming up to 200～215 ℃ and namely stop heating, remove still head, the adapter of vacuum tail, single port flask after being down to room temperature, the polyether sulphone polymkeric substance that will contain the anisole side group joins in the there-necked flask, and containing the polyether sulphone polymkeric substance add-on of anisole side group and the mass volume ratio of pyridine is 12～19g/L; Spherical condensation tube is installed, is opened heating, be warming up to 160～180 ℃, reacted 10～16 hours, be cooled to 80～100 ℃, discharging is washed in frozen water, and drying obtains hydroxyl benzene lateral group polyether sulphone material.
6. the phenoxy group aliphatic chain boric acid ester side chain polyether sulphone preparation methods that contains according to claim 5 is characterized in that, the described anisole lateral group polyarylether sulfone polymer that contains, and main chain is common aromatic ring; Contain anisole lateral group polyarylether sulfone polymer and be in the side chain anisole methoxyl group at the polymkeric substance of a position.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923311A (en) * | 2014-04-22 | 2014-07-16 | 吉林大学 | Carbazole-containing side chain type polyether sulfone, and preparation method and applications |
| CN112011052A (en) * | 2020-09-11 | 2020-12-01 | 四川大学 | Functional boron-containing polyarylene sulfide copolymer and preparation method thereof |
| CN112159422A (en) * | 2020-10-21 | 2021-01-01 | 上海应用技术大学 | Method for catalytic synthesis of phenylboronic acid ester derivative by using iridium catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923311A (en) * | 2014-04-22 | 2014-07-16 | 吉林大学 | Carbazole-containing side chain type polyether sulfone, and preparation method and applications |
| CN103923311B (en) * | 2014-04-22 | 2016-02-03 | 吉林大学 | Side chain type polyether sulphone containing carbazole, preparation method and application |
| CN112011052A (en) * | 2020-09-11 | 2020-12-01 | 四川大学 | Functional boron-containing polyarylene sulfide copolymer and preparation method thereof |
| CN112011052B (en) * | 2020-09-11 | 2022-02-08 | 四川大学 | Functional boron-containing polyarylene sulfide copolymer and preparation method thereof |
| CN112159422A (en) * | 2020-10-21 | 2021-01-01 | 上海应用技术大学 | Method for catalytic synthesis of phenylboronic acid ester derivative by using iridium catalyst |
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