CN103242530B - Amido bond phenylboronic acid ester-containing polyether sulphone polymer and preparation method thereof - Google Patents
Amido bond phenylboronic acid ester-containing polyether sulphone polymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an amido bond phenylboronic acid ester-containing polyether sulphone polymer and a preparation method thereof, belonging to the technical field of macromolecular materials. The amido bond-containing phenylboronic acid ester polyether sulphone polymer is of a polymer with a polyether sulphone main chain and an amido bond phenylboronic acid ester-containing side chain. The preparation method comprises the steps of: firstly, synthesizing amino-benzene side group-containing polyether sulphone, then performing an amidation reaction on the amino-benzene side group-containing polyether sulphone and carboxyl phenylboronic acid pinacol ester, and carrying out acetone treatment to obtain the amido bond phenylboronic acid ester-containing polyether sulphone material. The phenylboronic acid ester can be quantitatively introduced into the polyether sulphone main chain by adopting an amidation method, thus having potential applications to aspects of catalysis, inorganic material blend polymer composites, flame retardance and the like; in addition, the phenylboronic acid ester is an important reaction intermediate in organic synthesis, and therefore, the amido bond phenylboronic acid ester-containing polyether sulphone is an important reaction intermediate in functionalized polymer synthesis, thus having potential applications on the aspects of preparing luminescent materials, sensing materials and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of amide bond borate ester polyarylethersulfone polymer and preparation method thereof.
Background technology
Owing to having excellent heat and chemical stability, fragrant main chain polyether sulphone remains a kind of important special engineering plastics.Functional groups is incorporated into aromatic polymer backbones can obtain specific function, strengthen the property and potential application more widely.In recent years, the polyether sulphone of functionalization had been made into multiple film material, such as, and ion permeable membrane, gas separation membrane and fuel battery proton exchange film etc.
Suzuki chapter, Richard He Ke, root bank English obtain Nobel chemistry Prize in 2010 jointly because of the major contribution of reacting Suzuki-Miyaura, Suzuki-Miyaura reaction has very strong substrate adaptability and functional group tolerance, be usually used in synthesizing polyene hydrocarbon, vinylbenzene and connection benzene derivate, be widely used in the synthesis of organic materials.Thus, boron-containing compound becomes a kind of important reaction intermediate in organic synthesis.
Usually, functional group is incorporated in polyether sulphone there is two kinds of methods: (1) is by the direct copolymerization of functionalization monomer; (2) method of Post functionalization.But the activity of boron itself adds the difficulty of boron compound synthesis, especially the hydrolysis of boron-containing compound and oxidation sensitive significantly limit the development of boracic macromolecular material, carrying out in affine polycondensation mode being difficult under the condition of reacting adopt the method for direct copolymerization to be incorporated in polymkeric substance by boron, recent years, because compounds forming apparatus and technology reach its maturity, synthesis for boron-containing polymer provides thinking widely, obtains broad-spectrum boron-containing polymer material.
The people such as Tae Soo Jo have delivered one section in J.AM.CHEM.SOC. in 2009 and have adopted Ir catalyst connection pinacol borate and polyether ethersulfone to react, obtain the polyether sulphone material of main chain boracic acid esters, but the boron of boron-containing polymer that this method the obtains position of introducing and content cannot be incorporated in polyarylethersulfone polymer according to the method for molecular designing.
Summary of the invention
The present invention has selected the method for amidation grafting, and boron is successfully incorporated in polyether sulphone by profit in this way.Borate ester positioning and quantitative can be incorporated on polyether sulphone main chain by present method, and the amide bond borate ester polyether sulphone of the present invention's synthesis is a kind of novel macromolecular material, is again a kind of important reaction intermediate.
The object of this invention is to provide a kind of by Carboxybenzeneboronic acid pinacol ester with containing amino polyether sulphone (PES-NH
2) the amide bond borate ester polyether sulphone material prepared of amidation; This material is made up of the phenylo boric acid pinacol ester side chain of polyether sulphone main chain and amide bond, and its structural formula is as follows:
Wherein, 0.1≤y≤1, and x+y=1, m are the integer of 10 ~ 15;
The preparation method of amide bond borate ester polyether sulphone material of the present invention, comprise the polyether sulphone containing amino-benzene lateral group synthesis and containing amino-benzene lateral group polyether sulphone with amidate action carried out to Carboxybenzeneboronic acid pinacol ester prepare amide bond borate ester polyether sulphone material two steps.
The synthesis of the described polyether sulphone containing amino-benzene lateral group, by 2-(4`-aminophenyl)-1, 4-Resorcinol (or 2-(2`-aminophenyl)-1, 4-Resorcinol, or 2-(3`-aminophenyl)-1, 4-Resorcinol), 4, 4`-dihydroxy diphenyl ether, 4, 4`-difluorodiphenyl sulfone (or 4, 4`-dichloro diphenyl sulfone), 4, 4`-difluorodiphenyl sulfone (or 4, 4`-dichloro diphenyl sulfone) Anhydrous potassium carbonate of 1.0 ~ 1.2 times of molar weights, the organic solvent of 4 ~ 6 times of solid reaction amounts, the azeotropic dehydration machine of organic solvent volume 20 ~ 30% is put in the lump and nitrogen through hole is housed, in the reaction unit of mechanical stirring and water-taker, logical nitrogen is also under agitation warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be warmed up to 160 ~ 190 ° of C and continue reaction 6 ~ 10 hours, then, the polymers soln obtained is separated out in deionized water, through pulverizing, washing, drying, obtain the polyarylethersulfone polymer containing amino-benzene lateral group, wherein, 4,4`-dihydroxy diphenyl ether, 2-(4`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol (or 2-(2`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol, or 2-(3`-aminophenyl)-1,4-Resorcinol), the mol ratio of 4,4`-difluorodiphenyl sulfones (4,4`-dichloro diphenyl sulfone) is xn:yn:n(0.1≤y≤1, and x+y=1, n are the integer of 10 ~ 15),
Containing amino-benzene lateral group polyether sulphone and amidate action carried out to carboxyl pinacol borate prepare amide bond borate ester polyether sulphone material, to contain the polyether sulphone of amino-benzene lateral group and to be its 1.05 ~ 1.2 times of molar weights Carboxybenzeneboronic acid pinacol ester is loaded be placed with in the container of stirrer, adding is the N of amino molar weight 1.5 ~ 2.0 times in polyether sulphone containing amino-benzene lateral group again, N-dicyclohexyl diimine (DCC), it is the DMAP (DMAP) of amino molar weight 0.15 ~ 0.20 times in the polyether sulphone containing amino-benzene lateral group, then vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 3 ~ 5 times repeatedly, inject organic solvent dissolution, then seal, open and stir, react 60 ~ 78 hours under room temperature, finally adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 3 ~ 5 times, vacuumizes 80 ~ 90 ° of C and dries, namely obtain amide bond borate ester polyether sulphone material.
Wherein to Carboxybenzeneboronic acid pinacol ester, the product of peace resistance to Jilin Chemical-Sa En chemical technology (Shanghai) Co., Ltd. production can be selected.
In the synthesis of the polyether sulphone containing amino-benzene lateral group, organic solvent used can be tetramethylene sulfone or N-Methyl pyrrolidone, and azeotropy dehydrant used can be toluene or dimethylbenzene.
Containing amino-benzene lateral group polyether sulphone and to Carboxybenzeneboronic acid pinacol ester reaction prepare in the reaction of amide bond borate ester polyether sulphone, organic solvent used can be trichloromethane, tetrahydrofuran (THF) or dioxane.
Of the present invention containing amino-benzene lateral group (for 2-(4`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol) the building-up reactions formula of polyarylethersulfone polymer as follows:
Wherein, 0.1≤y≤1, and x+y=1, n are the integer of 10 ~ 15.
Polyether sulphone containing amino-benzene lateral group of the present invention and to carry out the reaction formula of amidate action to Carboxybenzeneboronic acid pinacol ester as follows:
Boric acid ester to be successfully incorporated into by a kind of amidate action and polyether sulphone main chain obtains by amide bond borate ester polyarylethersulfone polymer of the present invention, it is this that method is simple, percentage of grafting is very high, be applicable to polyarylether system, this series polymer has excellent high temperature ablation resistance, can see from the TGA test result of Figure 12, along with the raising of boric acid ester content after 600 ° of C, the thermolysis speed of polymkeric substance reduces gradually.In addition, because boron-containing compound is important luminescence, catalytic material and reaction intermediate, it is made in boron-containing polymer materials and in organic synthesis, to have potential application.
Accompanying drawing explanation
Fig. 1: the DSC curve of the polyether sulphone (embodiment 1,3,5) containing p-aminophenyl side base of the present invention;
Fig. 2: the DSC curve of the polyether sulphone (embodiment 2,4,6) of amide bond borate ester of the present invention;
Fig. 3: polyether sulphone (embodiment 1) the NMR spectrogram containing 10% p-aminophenyl side base of the present invention;
Fig. 4: polyether sulphone (embodiment 3) the NMR spectrogram containing 30% p-aminophenyl side base of the present invention;
Fig. 5: polyether sulphone (embodiment 5) the NMR spectrogram containing 50% p-aminophenyl side base of the present invention;
Fig. 6: the polyether sulphone NMR spectrogram containing 100% p-aminophenyl side base of the present invention;
Fig. 7: boric acid ester molar content of the present invention is amide bond borate ester polyether sulphone (embodiment 2) the NMR spectrogram of 10%;
Fig. 8: boric acid ester molar content of the present invention is amide bond borate ester polyether sulphone (embodiment 4) the NMR spectrogram of 30%;
Fig. 9: boric acid ester molar content of the present invention is amide bond borate ester polyether sulphone (embodiment 6) the NMR spectrogram of 50%;
Figure 10: the present invention is containing the FT-IR spectrogram of the polyether sulphone (embodiment 1,3,5) of p-aminophenyl side base;
Figure 11: the FT-IR spectrogram of amide bond borate ester polyether sulphone of the present invention (embodiment 2,4,6).
Figure 12: the TGA curve of amide bond borate ester polyether sulphone of the present invention (embodiment 2,4,6).
What Fig. 1 provided is amino molar content be respectively 10%, 30%, 50% and 100% the DSC curve of polyether sulphone containing amino-benzene lateral group, amino content is 10%, 30%, 50% and 100% be respectively 184 degrees Celsius, 189 degrees Celsius, 197 degrees Celsius and 213 degrees Celsius containing the Tg of the polyether sulphone of amino-benzene lateral group as we can see from the figure.
What Fig. 2 provided is amido linkage borate ester molar content is respectively the DSC curve of the amide bond borate ester polyether sulphone of 10%, 30%, 50%, and amido linkage borate ester content is that the Tg of 10%, 30% and 50% amide bond borate ester polyether sulphone is respectively 145 degrees Celsius, 151 degrees Celsius and 168 degrees Celsius as we can see from the figure.
What Fig. 3 provided is the hydrogen nuclear magnetic spectrogram containing the polyether sulphone (embodiment 1) of 10% amino-benzene lateral group of the present invention, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 4 provided is the hydrogen nuclear magnetic spectrogram containing the polyether sulphone (embodiment 3) of 30% amino-benzene lateral group of the present invention, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 5 provided is the hydrogen nuclear magnetic spectrogram containing the polyether sulphone (embodiment 5) of 50% amino-benzene lateral group of the present invention, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 6 provided is the hydrogen nuclear magnetic spectrogram containing the polyether sulphone (embodiment 7) of 100% amino-benzene lateral group of the present invention, and each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 7 provided is boric acid ester molar content of the present invention be 10% amide bond borate ester polyether sulphone (embodiment 2) hydrogen nuclear magnetic spectrogram, each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 8 provided is boric acid ester molar content of the present invention be 30% amide bond borate ester polyether sulphone (embodiment 4) hydrogen nuclear magnetic spectrogram, each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 9 provided is boric acid ester molar content of the present invention be 50% amide bond borate ester polyether sulphone (embodiment 6) hydrogen nuclear magnetic spectrogram, each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Figure 10 provided is amino content of the present invention be 10%, 30%, 50% and 100% the infrared spectrum of polyether sulphone (embodiment 1,3,5) containing amino-benzene lateral group, the characteristic group as we can see from the figure in polymkeric substance has obvious charateristic avsorption band; Especially at 3300cm
-1~ 3400cm
-1there is amino charateristic avsorption band in place.
What Figure 11 provided is amido linkage borate ester content of the present invention is the infrared spectrum of the amide bond borate ester polyether sulphone (embodiment 2,4,6) of 10%, 30%, 50%, 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 borate ester in place, at 1640cm
-1there is the carbonyl absorption peak of amido linkage in place.
The TGA curve of amide bond borate ester polyether sulphone (embodiment 2,4,6) that what Figure 12 provided is.As we can see from the figure along with the rising of boric acid ester content, the high temperature ablation resistance of polymkeric substance improves gradually.Wherein, curve a: the amide bond borate ester polyether sulphone in embodiment 6; Curve b: the amide bond borate ester polyether sulphone in embodiment 4; Curve c: the amide bond borate ester polyether sulphone in embodiment 2.
Embodiment
Embodiment 1: containing the preparation (1) of the polyether sulphone of p-aminophenyl side base
By 5.4597g (0.027mol) 4,4`-dihydroxy diphenyl ether, 0.6037g(0.003mol) 2-(4`-aminophenyl)-1,4-Resorcinol monomer, 7.6275g(0.03mol) 4, the Anhydrous potassium carbonate of 4`-difluorodiphenyl sulfone monomer and 4.5603g, 57mL tetramethylene sulfone, 20mL toluene, put into the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed, logical nitrogen, starts stirring, be warmed up to azeotropy dehydrant backflow, react 2 hours, get rid of azeotropy dehydrant, be warmed up to 170 ° of C and continue reaction 8 hours; Then the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the linen polyarylethersulfone polymer powder containing p-aminophenyl side base of 12g.
Molecular formula is as follows,
Wherein n is 14.
Embodiment 2: containing p-aminophenyl side base polyether sulphone and amidate action carried out to Carboxybenzeneboronic acid pinacol ester prepare amide bond borate ester polyether sulphone material (1)
The polyether sulphone and the 0.27g that 4.16g are contained p-aminophenyl side base are placed with in the container of stirrer to Carboxybenzeneboronic acid pinacol ester (1.1 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group) loading, add 0.31g N again, N-dicyclohexyl diimine (DCC) (1.5 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), 0.18g4-Dimethylamino pyridine (DMAP) (0.15 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), then vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 4 times repeatedly, finally inject 100mL tetrahydrofuran (THF) to dissolve, then seal, open and stir, room temperature reaction 72 hours, adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 4 times, filters, and vacuumizes 80 ° of C and dries, namely obtain the amide bond borate ester polyether sulphone material that 3.8g boric acid ester molar content is 30%.
Embodiment 3: containing the preparation (2) of the polyether sulphone of p-aminophenyl side base
By 4.2464g (0.009mol) 4,4`-dihydroxy diphenyl ether, 1.8110g(0.021mol) 2-(4`-aminophenyl)-1,4-Resorcinol monomer, 7.6275g(0.03mol) 4, the Anhydrous potassium carbonate of 4`-difluorodiphenyl sulfone monomer and 4.5603g, 55ml tetramethylene sulfone, the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed put into by 12mL toluene, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 2 hours, get rid of azeotropy dehydrant, be warmed up to 170 ° of C and continue reaction 8 hours; Then the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the polyarylethersulfone polymer powder of 13g linen p-aminophenyl side base.
Molecular formula is as follows:
Wherein n=13.
Embodiment 4: containing p-aminophenyl side base polyether sulphone and amidate action carried out to Carboxybenzeneboronic acid pinacol ester prepare amide bond borate ester polyether sulphone material (2)
The polyether sulphone and the 0.82g that 4.16g are contained p-aminophenyl side base are placed with in the container of stirrer to Carboxybenzeneboronic acid pinacol ester (1.1 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group) loading, add 0.93gN again, N-dicyclohexyl diimine (DCC) (1.5 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), 0.55g4-Dimethylamino pyridine (DMAP) (0.15 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), then vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 4 times repeatedly, finally inject 100mL tetrahydrofuran (THF) to dissolve, then seal, open and stir, room temperature reaction 72 hours, adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 4 times, filters, and vacuumizes 80 ° of C and dries, namely obtain the amide bond borate ester polyether sulphone material that 4.0g boric acid ester molar content is 30%.
Embodiment 5: containing the preparation (3) of the polyether sulphone of p-aminophenyl side base
By 5.0553g (0.025mol) 4,4`-dihydroxy diphenyl ether, 5.0305g(0.025mol) 2-(4`-aminophenyl)-1,4-Resorcinol monomer, 12.7125g(0.05mol) 4, the Anhydrous potassium carbonate of 4`-difluorodiphenyl sulfone monomer and 7.6005g, 70mL tetramethylene sulfone, the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed put into by 20mL toluene, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 2 hours, get rid of azeotropy dehydrant, be warmed up to 170 ° of C and continue reaction 8 hours; Then the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the polyarylethersulfone polymer powder of 20g linen p-aminophenyl side base.
Molecular formula is as follows:
Wherein n=14.
Embodiment 6: containing p-aminophenyl side base polyether sulphone and amidate action carried out to Carboxybenzeneboronic acid pinacol ester prepare amide bond borate ester polyether sulphone material (3)
The polyether sulphone and the 1.37g that 4.16g are contained p-aminophenyl side base are placed with in the container of stirrer to Carboxybenzeneboronic acid pinacol ester (1.1 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group) loading, add 1.55 grams of N again, N-dicyclohexyl diimine (DCC) (1.5 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), 0.92g4-Dimethylamino pyridine (DMAP) (0.15 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), then vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 4 times repeatedly, finally inject 100mL tetrahydrofuran (THF) to dissolve, then seal, open and stir, room temperature reaction 72 hours, adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 4 times, filters, and vacuumizes 80 ° of C and dries, namely obtain the amide bond borate ester polyether sulphone material that 4.0g boric acid ester molar content is 50%.
Embodiment 7: containing the preparation (4) of the polyether sulphone of amino-benzene lateral group
By 6.0366g(0.03mol) 2-(4`-aminophenyl)-1,4-Resorcinol monomer, 7.6275g(0.03mol) Anhydrous potassium carbonate of 4,4`-difluorodiphenyl sulfone monomers and 4.5603g, 57mL tetramethylene sulfone, the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed put into by 20mL toluene, and logical nitrogen, starts stirring, be warmed up to azeotropy dehydrant backflow, react 2 hours, get rid of azeotropy dehydrant, be warmed up to 170 ° of C and continue reaction 8 hours; Then the polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain the linen polyarylethersulfone polymer powder containing p-aminophenyl side base of 12g.
Molecular formula is as follows:
Wherein n=10.
Embodiment 8: containing p-aminophenyl side base polyether sulphone and amidate action carried out to Carboxybenzeneboronic acid pinacol ester prepare amide bond borate ester polyether sulphone material (4)
The polyether sulphone and the 2.73g that 4.17g are contained p-aminophenyl side base are placed with in the container of stirrer to Carboxybenzeneboronic acid pinacol ester (1.1 times containing molar weight amino in the poly aryl ether sulfone of amino-benzene lateral group) loading, add 3.10g N again, N-dicyclohexyl diimine (DCC) (1.5 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), 1.83g4-Dimethylamino pyridine (DMAP) (0.15 times containing molar weight amino in the polyether sulphone of amino-benzene lateral group), then vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 3 ~ 5 times repeatedly, finally inject 100mL tetrahydrofuran (THF) to dissolve, then seal, open and stir, gel is there is in the room temperature reaction post-consumer polymer of 24 hours, the polymkeric substance obtained is insoluble to any organic solvent.
Embodiment 9: the preparation (5) containing the polyether sulphone of neighbour or m-aminophenyl side base
2-(4`-aminophenyl by embodiment 1)-Isosorbide-5-Nitrae-Resorcinol changes into 2-(2`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol or 2-(3`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol, also can obtain the polyarylethersulfone polymer containing adjacent or m-aminophenyl side base.
Embodiment 10: contain the polyether sulphone of neighbour or m-aminophenyl side base and prepared by amide bond borate ester polyether sulphone material (5) to the reaction of Carboxybenzeneboronic acid pinacol ester
The polyether sulphone containing p-aminophenyl side base in embodiment 2 is changed into the polyether sulphone containing adjacent amino-benzene lateral group or m-aminophenyl side base, also can obtain the polyether sulphone material of amide bond borate ester.
Embodiment 11: the preparation (6) containing the polyether sulphone of neighbour or m-aminophenyl side base
2-(4`-aminophenyl by embodiment 3)-Isosorbide-5-Nitrae-Resorcinol changes into 2-(2`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol or 2-(3`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol, also can obtain the polyarylethersulfone polymer containing adjacent or m-aminophenyl side base.
Embodiment 12: contain the polyether sulphone of neighbour or m-aminophenyl side base and prepared by amide bond borate ester polyether sulphone material (6) to the reaction of Carboxybenzeneboronic acid pinacol ester
The polyether sulphone containing p-aminophenyl side base in embodiment 4 is changed into the polyether sulphone containing adjacent amino-benzene lateral group or m-aminophenyl side base, also can obtain the polyether sulphone material of amide bond borate ester.
Embodiment 13: the preparation (7) containing the polyether sulphone of neighbour or m-aminophenyl side base
2-(4`-aminophenyl by embodiment 5)-Isosorbide-5-Nitrae-Resorcinol changes into 2-(2`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol or 2-(3`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol, also can obtain the polyarylethersulfone polymer containing adjacent or m-aminophenyl side base.
Embodiment 14: contain the polyether sulphone of neighbour or m-aminophenyl side base and prepared by amide bond borate ester polyether sulphone material (7) to the reaction of Carboxybenzeneboronic acid pinacol ester
The poly aryl ether sulfone containing p-aminophenyl side base in embodiment 6 is changed into the polyether sulphone containing adjacent amino-benzene lateral group or m-aminophenyl side base, also can obtain the polyether sulphone material of amide bond borate ester.
Embodiment 15: the preparation (7) containing the polyether sulphone of neighbour or m-aminophenyl side base
2-(4`-aminophenyl by embodiment 6)-1,4-Resorcinol changes into 2-(2`-aminophenyl)-1,4-Resorcinol or 2-(3`-aminophenyl)-Isosorbide-5-Nitrae-Resorcinol, also can obtain the poly aryl ether sulfone polymer containing adjacent or m-aminophenyl side base.
Embodiment 16: contain the polyether sulphone of neighbour or m-aminophenyl side base and prepared by amide bond borate ester polyether sulphone material (7) to the reaction of Carboxybenzeneboronic acid pinacol ester
The polyether sulphone containing p-aminophenyl side base in embodiment 7 is changed into the polyether sulphone containing adjacent amino-benzene lateral group or m-aminophenyl side base, also can obtain the polyether sulphone material of amide bond borate ester.
Claims (3)
1. amide bond borate ester polyarylethersulfone polymer, its structural formula is as follows:
Wherein, 0.1≤y≤1, and x+y=1, m are the integer of 10 ~ 15.
2. the preparation method of amide bond borate ester polyarylethersulfone polymer according to claim 1, it is characterized in that: will the polyether sulphone of amino-benzene lateral group be contained and be its 1.05 ~ 1.2 times of molar weights Carboxybenzeneboronic acid pinacol ester is loaded be placed with in the container of stirrer, adding is the N of amino molar weight 1.5 ~ 2.0 times in polyether sulphone containing amino-benzene lateral group again, N-dicyclohexyl diimine, it is the DMAP of amino molar weight 0.15 ~ 0.20 times in the polyether sulphone containing amino-benzene lateral group, vacuumize and put high pure nitrogen and vacuumize again and put high pure nitrogen, 3 ~ 5 times repeatedly, inject organic solvent dissolution, then seal, open and stir, react 60 ~ 78 hours under room temperature, finally adopt diatomite filtration, removal of solvent under reduced pressure, acetone washes 3 ~ 5 times, vacuumizes 80 ~ 90 DEG C of oven dry, namely obtains amide bond borate ester polyether sulphone material.
3. the preparation method of amide bond borate ester polyarylethersulfone polymer as claimed in claim 2, is characterized in that: organic solvent is trichloromethane, tetrahydrofuran (THF) or dioxane.
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| CN109880098B (en) * | 2019-02-22 | 2021-06-08 | 江西金海新能源科技有限公司 | Polyarylethersulfone resin with amino as crosslinking group and crosslinked product thereof |
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| CN101463128A (en) * | 2008-12-30 | 2009-06-24 | 吉林大学 | Polyarylether polymer containing amino-benzene lateral group and method for synthesizing the same |
| 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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