CN103626994A - Polyaryletherketone containing boric acid ester, azo polyaryletherketone and preparation method thereof - Google Patents
Polyaryletherketone containing boric acid ester, azo polyaryletherketone and preparation method thereof Download PDFInfo
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 boric acid ester Chemical class 0.000 title claims description 55
- 239000004327 boric acid Substances 0.000 title description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract 10
- 150000002148 esters Chemical class 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002523 gelfiltration Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims 1
- 230000037396 body weight Effects 0.000 claims 1
- 239000000539 dimer Substances 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 238000004809 thin layer chromatography Methods 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 4
- 239000004305 biphenyl Substances 0.000 abstract description 3
- 235000010290 biphenyl Nutrition 0.000 abstract description 3
- COQOYMRZIFLJII-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].CC(C)(O)C(C)(C)O COQOYMRZIFLJII-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical class [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 28
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 24
- 239000000126 substance Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229960001701 chloroform Drugs 0.000 description 7
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 5
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- 229960002645 boric acid Drugs 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229920000090 poly(aryl ether) Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- FCJNITIJYWQFCM-UHFFFAOYSA-N 3-fluoro-5-iodobenzonitrile Chemical compound FC1=CC(I)=CC(C#N)=C1 FCJNITIJYWQFCM-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000124209 Crocus sativus Species 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
含硼酸酯聚芳醚酮、偶氮聚芳醚酮及其制备方法，属于高分子材料制备技术领域。首先，合成了双酚A型聚芳醚酮，利用该聚芳醚酮与联硼频哪醇酯在1,5-环辛二烯氯化铱二聚体催化硼化反应制备含硼酸酯聚芳醚酮材料；其次，合成4-碘-4’-(N,N-二甲基胺)偶氮苯单体，最后利用含硼酸酯聚芳醚酮材料与4-碘-4’-(N,N-二甲基胺)偶氮苯单体在四三苯基膦化钯催化下反应制备含偶氮聚芳醚酮；利用这种方法可以成功地将偶氮单体引入到聚芳醚酮中。不但不会影响聚芳醚酮本身的性能，也能够生成性能稳定的联苯结构偶氮聚芳醚酮，可以改善偶氮材料的存储稳定性，该方法有望在制备新型的偶氮高分子材料方面获得应用。
Borate-containing polyaryletherketones, azopolyaryletherketones and preparation methods thereof belong to the technical field of polymer material preparation. First, bisphenol A type polyarylether ketone was synthesized, and the polyarylether ketone and boron pinacol ester were used to catalyze the boronation reaction of 1,5-cyclooctadiene iridium chloride dimer to prepare boron-containing ester Polyaryletherketone material; secondly, synthesize 4-iodo-4'-(N,N-dimethylamine) azobenzene monomer, and finally use borate-containing polyaryletherketone material and 4-iodo-4' -(N,N-dimethylamine) azobenzene monomer reacts under the catalysis of tetrakistriphenylphosphine palladium to prepare azo-containing polyaryletherketone; using this method can successfully introduce azo monomer into polyaryletherketone. Not only will it not affect the performance of polyaryletherketone itself, but it can also generate azopolyaryletherketone with stable biphenyl structure, which can improve the storage stability of azo materials. This method is expected to be used in the preparation of new azo polymer materials get applied.
Description
Technical field
The invention belongs to field of polymer material preparing technology, be specifically related to boracic acid esters polyaryletherketone material, the azo polyaryletherketone material being prepared by it and the preparation method of this bi-material.
Background technology
Azobenzene polymer because of its photic two-phase look, photopolymerizable liquid crystal change mutually,, the aspect such as photomechanical effect, nonlinear optical material, information storage, optical drive molecular switch and photonic material shows excellent photoresponse behavior, and shows huge application potential in reversible optical storage, all-optical switch, integrated optoelectronics and photon technology field.For the research and development of azo material, particularly synthetic, the structure of novel, high-performance optical responsive polymer material and the research of property relationship are the emphasis of scientific research personnel's concern all the time.Applied research using azo material as storage medium is at present still in basic stage, and the storage stability of azo material is still a problem demanding prompt solution.Temperature classification is high owing to having for polyarylether polymer, the over-all properties of chemical-resistant resistance, shock-resistant, good excellences such as dimensional stability has a wide range of applications in high-tech sectors such as aerospace, information, telecommunications.Method by azo group by rear grafting is incorporated in the polyarylether polymer of high glass-transition temperature, can improve significantly the storage stability of material.But currently used grafting method is generally the method for esterification, amidation and Liv Ullmann coupling, and these methods all exist some shortcomings.Ester bond, amido linkage as easy as rolling off a log hydrolysis under the effect of acid or alkali or even water, and the copper catalytic condition that Liv Ullmann coupling is used tends to cause the degraded of polyarylether main chain, thus cause the second-order transition temperature of polymkeric substance to decline.Thereby, select a kind of new research direction that method that the performance of polymkeric substance own can generate again stable product becomes this field that neither affects.
Summary of the invention
The object of the invention is to prepare boracic acid esters polyaryletherketone material by the boronation reaction of connection boron pinacol ester (Bis (pinacolato) diboron) and polyaryletherketone, and boracic acid esters polyaryletherketone material and iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer reaction preparation of 4-are contained to azo polyaryletherketone.
The present invention has selected the method for the reaction of 1,5-cyclooctadiene iridium chloride dimer catalysis boronation and four triphenylphosphine palladium catalysis borate esters and iodobenzene coupling, and profit is successfully incorporated into azo monomer in polyaryletherketone in this way.Not only can not affect the performance of polyaryletherketone itself, also can generate the biphenyl structural azo polyaryletherketone of stable performance, what the present invention synthesized is a kind of novel macromolecular material containing azo polyaryletherketone.
It is before this by dihydroxyphenyl propane and 4,4 '-bis-fluoro-benzophenone obtain respectively bisphenol A type polyaromatic ether ketone (PAEK) according to the molar ratio reaction of 1:1, again 1,5-cyclooctadiene iridium chloride dimer and 4,4 '-di-t-butyl-2, under the acting in conjunction of 2 '-dipyridyl, react with connection boron pinacol ester generation boronation, prepare the polyaryletherketone material of novel boracic acid esters; The polyaryletherketone of boracic acid esters generates novel containing azo polyaryletherketone material with iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer reaction of 4-under the acting in conjunction of four triphenylphosphine palladiums and salt of wormwood.
Boracic acid esters polyaryletherketone of the present invention is comprised of polyaryletherketone main chain and pinacol borate side chain, and wherein the content of pinacol borate is 15%～150%.
Boracic acid esters poly aryl ether ketone polymer of the present invention, is the bisphenol A type polyaromatic ether ketone of boracic acid esters, and its structural formula is
N is 15～25 integer, represents the polymerization degree;
2a+b+c=0.075～0.5, d=1-(2a+b+c); Or 2a+b+c=0.5～0.75, d=0;
The azo polyaryletherketone that contains of the present invention is comprised of polyaryletherketone main chain and azo side chain, according to the content of design azo, is wherein 15%～30%.
Of the present invention containing azo poly aryl ether ketone polymer, be the bisphenol A type polyaromatic ether ketone containing azo; Its structural formula is
The integer that wherein p is 12～20; 2e+f+g=0.075～0.15, k=1-(2e+f+g).
The preparation method of boracic acid esters polyaryletherketone material of the present invention, comprises that the synthetic and polyaryletherketone of polyaryletherketone reacts and prepares two steps of boracic acid esters polyaryletherketone process with connection pinacol borate boronation.
The preparation of described boracic acid esters polyaryletherketone, by dihydroxyphenyl propane and equimolar 4,4 '-difluoro benzophenone monomer, the Anhydrous potassium carbonate of 1.05～1.10 times of molar weights of dihydroxyphenyl propane monomer, 3～6 times to the organic solvent of reaction monomers (not comprising salt of wormwood) quality, the azeotropy dehydrant of organic solvent volume 20% is put into the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed, logical nitrogen, start stirring, being warmed up to azeotropy dehydrant refluxes, react 1～3 hour, get rid of azeotropy dehydrant, be warmed up to 170～200 ℃ and continue reaction 7～10 hours; Then, the polymers soln obtaining is separated out in deionized water, through pulverizing, wash, being dried, obtain bisphenol A type polyaromatic ether ketone polymkeric substance.
In aforesaid method, organic solvent used can be dimethyl sulfoxide (DMSO), tetramethylene sulfone or N-Methyl pyrrolidone, and azeotropy dehydrant used can be toluene or dimethylbenzene.
Described polyaryletherketone and connection pinacol borate carry out boronation reaction and prepare boracic acid esters polyaryletherketone material, that bisphenol A type polyaromatic ether ketone and the connection pinacol borate that is 1.5～2 times of molar weights of its repeating unit are together encased in the container that is placed with stirrer, adding is 1 of 0.01～0.03 times of molar weight of connection pinacol borate again, 5-cyclooctadiene iridium chloride dimer ([IrCl (COD)]
2), be 4,4 '-di-t-butyl-2 of connection pinacol borate 0.02～0.04 times of molar weight, 2 '-dipyridyl, is filled with high pure nitrogen after vacuumizing, 3～5 times repeatedly, seal after adding organic solvent, at room temperature stirring reaction is 12～48 hours; Then organic solvent is removed in decompression, the polymkeric substance crude product acetone obtaining is washed 3～5 times, filter, dry, by the polymkeric substance obtaining, with after organic solvent dissolution, tlc silica gel filters 1～3 time, again polymkeric substance is washed 3～5 times with acetone, filter, vacuumize post-drying, obtain boracic acid esters polyaryletherketone material.
In above-mentioned reaction, organic solvent used is trichloromethane, tetrahydrofuran (THF) or dioxane etc.Adopting the solvent using in tlc silica gel filtration is trichloromethane, tetrahydrofuran (THF) or N,N-dimethylacetamide etc.
Preparation method containing azo polyaryletherketone material of the present invention, comprise the iodo-4 '-(N of 4-, N-dimethyl amine) the synthetic and boracic acid esters polyaryletherketone of nitrogen benzide monomer and iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer of 4-carry out the preparation of Suzuki-Miyaura linked reaction containing two steps such as azo polyaryletherketone materials.
Iodo-4 '-(the N of described 4-, N-dimethyl amine) nitrogen benzide monomer is synthetic, that 4-Iodoaniline is put into beaker, after adding water, stir into pasty state, dropwise splashing into is concentrated hydrochloric acid (10～15mol/L) solution of 3～5 times of molar weights of 4-Iodoaniline again, is cooled to-5～10 ℃ after reacting 1～2h; Then the Sodium Nitrite that is 2～3 times of molar weights of 4-Iodoaniline is dissolved in water, at-5～10 ℃, this solution is splashed in the hydrochloric acid soln of above-mentioned 4-Iodoaniline, after filtration, at-5～10 ℃, filtrate is dropwise added drop-wise to be again 2～5 times of molar weights of 4-Iodoaniline sodium acetate and be the N of 1～3 times of molar weight of 4-Iodoaniline, in the mixed aqueous solution of accelerine, after dripping off, at room temperature react 3～5h; In the solution of backward gained, drip is that the aqueous sodium hydroxide solution of 5～8 times of molar weights of 4-Iodoaniline neutralizes, reaction product is washed to vacuum-drying at 60～80 ℃ after neutrality, use again organic solvent recrystallization, obtain iodo-4 '-(N, the N-dimethyl amine) nitrogen benzide of 4-.
The organic solvent using in recrystallization process can be methyl alcohol, ethanol or toluene.
The building-up reactions formula of iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer of 4-of the present invention is as follows:
Iodo-4 '-(the N of described boracic acid esters polyaryletherketone and 4-, N-dimethyl amine) nitrogen benzide monomer carries out palladium catalysed cross coupling reaction preparation containing azo polyaryletherketone material, by boric acid ester polyaryletherketone and be the iodo-4 '-(N of 4-of its 1～2 times of molar weight, N-dimethyl amine) nitrogen benzide is put into reaction vessel, adding is four triphenylphosphine palladiums of boric acid ester polyaryletherketone molar weight 1%～3% again, the salt of wormwood of 1～5 times of molar weight of boric acid ester polyaryletherketone, then vacuumize and be filled with high pure nitrogen, 3～5 times repeatedly, inject organic solvent dissolution, finally, slowly inject the distilled water of organic solvent volume 3%～10%, sealing, in oil bath, 60～80 ℃ are reacted 10～20 hours, revolve to steam and remove organic solvent, with acetone extracting 20～30h, with organic solvent dissolution, adopt tlc silica gel to filter, revolve to steam and remove organic solvent, acetone is washed 4～6 times, filters, and dries, and obtains containing azo polyaryletherketone material.
Boracic acid esters polyaryletherketone and 4-be iodo-4 ' and-organic solvent that (N, N-dimethyl amine) nitrogen benzide monomer is used while carrying out linked reaction can be chloroform, tetrahydrofuran (THF) or dioxane.
It can be trichloromethane, tetrahydrofuran (THF) or dioxane that tlc silica gel filters the solvent using.
It is as follows containing the reaction formula of azo polyaryletherketone material that iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer of described boracic acid esters bisphenol A type polyaromatic ether ketone and 4-carries out palladium catalysed cross coupling reaction preparation:
P=12～20 wherein.
First the azo poly aryl ether ketone polymer that contains of the present invention is successfully incorporated into boric acid ester on polyaryletherketone main chain and obtains by a kind of boronation reaction, then utilize the iodo-4 '-(N of this boracic acid esters polyaryletherketone and 4-, N-dimethyl amine) nitrogen benzide obtains by palladium catalysed cross coupling reaction, this method can not affect the molecular weight of polymkeric substance, the biphenyl type azo polyaryletherketone obtaining has stability preferably, has potential application improving aspect the storage stability of material.
Accompanying drawing explanation
Fig. 1: bisphenol A type polyaromatic ether ketone 1H-NMR spectrogram of the present invention;
Fig. 2: boracic acid esters bisphenol A type polyaromatic ether ketone 1H-NMR spectrogram of the present invention;
Fig. 3: iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer 1H-NMR spectrogram of 4-of the present invention;
Fig. 4: of the present invention containing azo bisphenol A type polyaromatic ether ketone 1H-NMR spectrogram;
Fig. 5: the DSC curve of bisphenol A type polyaromatic ether ketone of the present invention;
Fig. 6: the DSC curve of boracic acid esters bisphenol A type polyaromatic ether ketone of the present invention;
Fig. 7: the DSC curve containing azo bisphenol A type polyaromatic ether ketone of the present invention;
Fig. 8: the UV-Vis curve containing azo bisphenol A type polyaromatic ether ketone of the present invention;
Fig. 9: the TGA curve containing azo bisphenol A type polyaromatic ether ketone of the present invention.
What Fig. 1 provided is the hydrogen nuclear magnetic spectrogram of bisphenol A type polyaromatic ether ketone of the present invention (embodiment 1), and each hydrogen in polymer architecture has correct ownership as we can see from the figure.
What Fig. 2 provided is the hydrogen nuclear magnetic spectrogram of boracic acid esters bisphenol A type polyaromatic ether ketone of the present invention (embodiment 2), and each hydrogen in polymer architecture has correct ownership as we can see from the figure.
What Fig. 3 provided is the hydrogen nuclear magnetic spectrogram of iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer (embodiment 3) of 4-of the present invention, and each hydrogen in polymer architecture has correct ownership as we can see from the figure.
What Fig. 4 provided is the hydrogen nuclear magnetic spectrogram containing azo bisphenol A type polyaromatic ether ketone (embodiment 4) of the present invention, and each hydrogen in polymer architecture has correct ownership as we can see from the figure.
What Fig. 5 provided is the DSC curve of bisphenol A type polyaromatic ether ketone of the present invention (embodiment 1), and the Tg of bisphenol A type polyaromatic ether ketone is respectively 159 degrees Celsius as we can see from the figure.
What Fig. 6 provided is the DSC curve of boracic acid esters bisphenol A type polyaromatic ether ketone of the present invention (embodiment 2), and Tg of the present invention is respectively 167 degrees Celsius as we can see from the figure.
What Fig. 7 provided is the DSC curve containing azo bisphenol A type polyaromatic ether ketone (embodiment 4) of the present invention, and Tg of the present invention is respectively 171 degrees Celsius as we can see from the figure.
What Fig. 8 provided is the UV-Vis curve containing azo bisphenol A type polyaromatic ether ketone (embodiment 4) of the present invention; Containing azo bisphenol A type polyaromatic ether ketone, in 426 nanometers, there is obvious uv-absorbing as we can see from the figure.
Fig. 9: the TGA curve containing azo bisphenol A type polyaromatic ether ketone (embodiment 4) of the present invention.As can be seen from the figure polymkeric substance has good thermostability.
Embodiment
By 13.6974g dihydroxyphenyl propane monomer, 13.0920g4,4 '-difluoro benzophenone monomer and 9.1205g Anhydrous potassium carbonate, 107mL tetramethylene sulfone, 36mL toluene, puts into the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed, logical nitrogen, start stirring, be warming up to 130 ℃ and reflux to azeotropy dehydrant, react 2 hours, get rid of azeotropy dehydrant, be warmed up to 175 ℃ and continue reaction 8 hours; The polymers soln obtaining is separated out in deionized water, through pulverizing, washing, dry, obtain bisphenol A type polyaromatic ether ketone polymkeric substance.
Molecular formula is as follows:
M=15～25 wherein.
First there-necked flask is burned with gaslight under the condition vacuumizing, after cooling, pour nitrogen, put into magnetic stirring, add 4.0748g(10mmol) bisphenol A type polyaromatic ether ketone and 2.0316g(8mmol) connection pinacol borate, then add 0.0806g[IrCl (COD)]
2and 0.0644g4,4'-di-t-butyl-2,2'-dipyridyl, vacuumizes and is filled with high pure nitrogen, and 3 times repeatedly, inject 50mL tetrahydrofuran (THF) and dissolve, sealing, in oil bath, 80 ℃ are reacted 12 hours; Cooling rear with chloroform dissolving, use chloroform give solvent to adopt tlc silica gel (200～400 order) to filter, revolve to steam and remove tetrahydrofuran (THF), acetone is washed 5 times, and oven dry, obtains faint yellow block boracic acid esters bisphenol A type polyaromatic ether ketone polymkeric substance.
Molecular formula is as follows:
N=15～25 wherein.
Take 21.9g (0.1mol) 4-Iodoaniline and put into 250 ml beakers, add 50mL water, mechanical stirring becomes pasty state, dropwise splashes into 33.6mL concentrated hydrochloric acid (12mol/L).Drip off rear continuation reaction 1.5h, be cooled to-5 ℃.6.9g Sodium Nitrite is dissolved in 50mL water, in the time of-5 ℃, this solution is splashed in the above-mentioned 4-Iodoaniline hydrochloride aqueous solution.After filtration, be dropwise added drop-wise to and contain 16.4g sodium acetate, in the 200mL aqueous solution of 12.1g DMA, solution temperature is controlled at-5 ℃.After dripping off, at room temperature react 3～5h.To dripping 24g aqueous sodium hydroxide solution in the solution of gained, neutralize.Be washed to 60 ℃ of vacuum-dryings in vacuum drying oven after neutrality.With ethanol, carry out recrystallization, obtain iodo-4 '-(N, N-dimethyl amine) the nitrogen benzide monomer of the pulverous 4-of safran.
Molecular formula is as follows:
First there-necked flask is burned with gaslight under the condition vacuumizing, poured nitrogen after cooling, put into magnetic stirring, the bisphenol A type polyaromatic ether ketone and the iodo-4 '-(N of 0.2897g4-that add 1.1140g boracic acid esters, N-dimethyl amine) nitrogen benzide, then add 0.0806g tetra-triphenylphosphine palladiums and 0.3420g salt of wormwood, then vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 50mL tetrahydrofuran (THF) and dissolve, last, slowly inject 5mL distilled water, sealing, 80 ℃ of reaction 12h in oil bath; Revolve and steam except desolventizing, with acetone extracting 24h, with chloroform, dissolve, adopt tlc silica gel to filter, revolve and steam except desolventizing, acetone is washed 5 times, filters, and dries, and obtains red blocks of solid.
Molecular formula is as follows:
P=12～20 wherein.
The molecular weight test of polymer with bis phenol A aryl ether ketone, boracic acid esters polymer with bis phenol A aryl ether ketone and azo polymer with bis phenol A aryl ether ketone.
Test condition:
Use instrument Shimadzu Prominence gpc analysis system;
40 ℃ of column temperatures, tetrahydrofuran (THF) is moving phase, polystyrene is standard specimen.
Bisphenol A type polyaromatic ether ketone, boracic acid esters bisphenol A type polyaromatic ether ketone, containing the molecular weight of azo bisphenol A type polyaromatic ether ketone, list in table 1.
Table 1: the molecular weight of bisphenol A-type polymkeric substance
| Polymkeric substance | Number-average molecular weight | Specific dispersivity |
| Polymer with bis phenol A aryl ether ketone | 7.9×10 4 | 1.44 |
| Boracic acid esters bisphenol A type polyaromatic ether ketone | 8.4×10 4 | 1.35 |
| Containing azo bisphenol A type polyaromatic ether ketone | 8.1×10 4 | 1.45 |
Claims (7)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725630A (en) * | 2015-02-03 | 2015-06-24 | 吉林大学 | Pyrene-containing polyaryletherketone and preparation method thereof as well as application of pyrene-containing polyaryletherketone in single-wall carbon nanometer tube/polyether-ether-ketone composite material |
| CN106046282A (en) * | 2016-07-13 | 2016-10-26 | 吉林大学 | Diatomite modified by polyaryletherketone containing boric m-benzene and reinforced polyether-ether-ketone composite material 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 |
|---|---|---|---|---|
| US20100041834A1 (en) * | 2007-04-02 | 2010-02-18 | The Board of Regents of the Nevada System of Higher Education on Behalf of the UNLV | Incorporation of functional groups into polymers using C-H activation |
| CN102924720A (en) * | 2012-12-03 | 2013-02-13 | 吉林大学 | Boric acid ester-containing polyarylether sulphone material and preparation method thereof |
-
2013
- 2013-11-16 CN CN201310571617.4A patent/CN103626994A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100041834A1 (en) * | 2007-04-02 | 2010-02-18 | The Board of Regents of the Nevada System of Higher Education on Behalf of the UNLV | Incorporation of functional groups into polymers using C-H activation |
| CN102924720A (en) * | 2012-12-03 | 2013-02-13 | 吉林大学 | Boric acid ester-containing polyarylether sulphone material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JINGJING ZHANG ET AL: "Synthesis and photoresponsive behaviors of novel poly(arylene ether)s", 《REACTIVE & FUNCTIONAL POLYMERS》 * |
| 赵晓刚等: "双酚A型聚芳醚酮的合成与表征", 《高分子材料科学与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725630A (en) * | 2015-02-03 | 2015-06-24 | 吉林大学 | Pyrene-containing polyaryletherketone and preparation method thereof as well as application of pyrene-containing polyaryletherketone in single-wall carbon nanometer tube/polyether-ether-ketone composite material |
| CN104725630B (en) * | 2015-02-03 | 2016-09-21 | 吉林大学 | Containing pyrene PAEK, preparation method and the application in SWCN/polyether-ether-ketone composite material |
| CN106046282A (en) * | 2016-07-13 | 2016-10-26 | 吉林大学 | Diatomite modified by polyaryletherketone containing boric m-benzene and reinforced polyether-ether-ketone composite material 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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