CN101775138A - Novel polytriazoles imide resin and preparation method thereof - Google Patents
Novel polytriazoles imide resin and preparation method thereof Download PDFInfo
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- CN101775138A CN101775138A CN200910045230A CN200910045230A CN101775138A CN 101775138 A CN101775138 A CN 101775138A CN 200910045230 A CN200910045230 A CN 200910045230A CN 200910045230 A CN200910045230 A CN 200910045230A CN 101775138 A CN101775138 A CN 101775138A
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- Prior art keywords
- imide
- polytriazole
- reaction
- compound
- alkynyl
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- 150000003949 imides Chemical class 0.000 title claims abstract description 63
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- -1 alkynyl imide compounds Chemical group 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 8
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 69
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 66
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 33
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000967 suction filtration Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 11
- 229960005055 sodium ascorbate Drugs 0.000 claims description 11
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 11
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 9
- 150000008282 halocarbons Chemical class 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000006352 cycloaddition reaction Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical class CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 31
- 229920001721 polyimide Polymers 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 10
- 150000001540 azides Chemical class 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 125000001425 triazolyl group Chemical group 0.000 abstract 1
- 150000002466 imines Chemical class 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- 150000003852 triazoles Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- MWYDOXLDDPKKCP-UHFFFAOYSA-N 1,4-bis(azidomethyl)benzene Chemical compound [N-]=[N+]=NCC1=CC=C(CN=[N+]=[N-])C=C1 MWYDOXLDDPKKCP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FZTDWZQGFQIIDA-UHFFFAOYSA-N ethoxyethane;isoindole-1,3-dione Chemical compound CCOCC.C1=CC=C2C(=O)NC(=O)C2=C1 FZTDWZQGFQIIDA-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- ZEEHTZPHMVRWHO-UHFFFAOYSA-N 2-ethynyl-4-phenylisoindole-1,3-dione Chemical compound C(#C)N1C(C=2C(C1=O)=C(C=CC=2)C1=CC=CC=C1)=O ZEEHTZPHMVRWHO-UHFFFAOYSA-N 0.000 description 4
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical compound COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 3
- XCJNTCCFVMAYRG-UHFFFAOYSA-N CC1=C(C=CC(=C1)N=[N+]=[N-])C2=CC=C(C=C2)N=[N+]=[N-] Chemical group CC1=C(C=CC(=C1)N=[N+]=[N-])C2=CC=C(C=C2)N=[N+]=[N-] XCJNTCCFVMAYRG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 238000012650 click reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WDBDEYYNGRPAJQ-UHFFFAOYSA-N [(4-diazonioimino-3-methylcyclohexa-2,5-dien-1-ylidene)hydrazinylidene]azanide Chemical compound CC1=CC(=NN=[N-])C=CC1=N[N+]#N WDBDEYYNGRPAJQ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 238000010462 azide-alkyne Huisgen cycloaddition reaction Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses polyimide with triazole rings in a main chain structure, i.e. polytriazoles imide resin and a preparation method thereof. The method comprises the following steps: firstly, designing and synthesizing binary azides; then, using binary anhydride and m-phenylacetylene as raw materials for designing and synthesizing terminal alkynyl imide compounds; and thirdly, using the terminal alkynyl imide compounds and azides with equimolar amounts to take 1, 3-Dipolar cycloaddition polymerization reaction in a solvent or adopting thermal polymerization reaction, or adopting redox catalysed polymerization for synthesizing novel polytriazoles imide. The polytriazoles imide resin prepared by the method of the invention has good processing performance, has high thermal stability, simultaneously has good mechanical property and electric performance, and embodies the characteristics of high corrosion resistance performance, high binding power and the like of the polytriazoles imide resin. The invention has wide application prospects in the fields of aviation, astronavigation, micro-electronics, automobiles, shipping industries and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of chemistry and chemical engineering and materials, relates to a novel polytriazole imide resin and a preparation method thereof, and particularly relates to a novel polytriazole imide resin prepared by a1, 3-dipolar cycloaddition polymerization reaction of a dialkynyl imide compound and a diazide compound.
[ background of the invention ]
Baldwin et al found in their studies in the late 60 s of the 20 th century that the molecular structures were the sameWhen the compound with azide group and alkynyl can generate 1, 3-dipolar cycloaddition polymerization reaction to generate 1, 4-substituted and 1, 5-substituted linear triazole resin, and the formed polymer has high thermal stability. In the 80's of the 20 th century, Mock et al found that 1, 3-dipolar cycloaddition of azido-alkynyl groups catalyzed by some amino-bearing reagents resulted in the formation of only 1, 4-substituted triazole ring structures. The novel energy-containing adhesive is prepared by using azide and alkyne reactions in the former Soviet Union and the national Beijing university of science and technology and the like. In 2002, Huangfa Rong laboratory, university of east China's university, started studying the reaction of alkyne and azide and utilized the thermal reaction of alkyne and azide to prepare polytriazole resins. In the same year, Sharpless et al reported that 1, 3-dipolar addition of azido-alkynes catalyzed by monovalent copper salts (Cu (I)) and found that the rate of the catalyzed addition reaction was increased by 106And stereoselectivity, yielding only 1, 4-disubstituted 1, 2, 3-triazole compounds, the Click chemistry concept proposed by Sharpless.
The Cli ck reaction is a simple and efficient synthesis reaction in chemistry, is a nearly perfect chemical reaction, and is characterized by simple reaction conditions, insensitivity to water and oxygen in general conditions, easy obtainment of starting materials and reagents, high yield and easy separation of products. The azide-alkynyl 1.3-dipolar cycloaddition reaction is a typical Click reaction and becomes a hotspot in material science research. Hawker, Sharpless et al, has first applied Huisgen1, 3-dipolar cycloaddition to the synthesis of dendrimers. Then, polymers having novel molecular structures such as linear, crosslinked, star-shaped, and hyperbranched polymers have been successively synthesized by the Click reaction. The Click reaction is taken as an important synthesis method, is also combined with other polymerization methods, such as living polymerization and atom transfer radical polymerization, in material synthesis, and is widely applied to design and preparation of novel high polymer materials.
The 1, 3-dipolar cycloaddition reaction of azide group and alkyne group at lower temperature is applied to the synthesis of the polymer containing triazole ring in Huangfa Rong laboratory of Huadong Rich chemical university, and linear, crosslinking curing type low-temperature curable polytriazole resin containing 1, 4-disubstituted and 1, 5-disubstituted-1, 2, 3-triazole ring is successfully developed. The research result shows that the polytriazole resin cured by thermal crosslinking has excellent processing performance, thermal performance and mechanical performance. Recently, Tang Benzhou et al also utilize non-catalytic cycloaddition reaction of azide and alkyne to prepare a benzene ring-containing linear polytriazole functional material with the weight-average molecular weight of 2-3 ten thousand.
The triazole ring is used as a rigid aromatic ring, has good heat resistance, thermal oxidation resistance and chemical resistance, has good adhesion to metal, and can be widely used as an anti-corrosion coating of metal materials.
Polyimide materials are high molecular materials containing five-membered imide rings on a molecular main chain, not only have good heat resistance, but also have excellent dimensional stability, oxidation stability, chemical corrosion resistance, irradiation resistance, and good mechanical property and dielectric property, so the polyimide materials have outstanding application value and are widely applied to the fields of aerospace, electrical and electronic, transportation and the like.
Currently, the application forms of polyimide are:
manufacturing a thin film. Kapton film developed by dupont in the 60 s was one of the earliest commodities of polyimide; subsequently, Upliex-R and Upliex-S films, which had low shrinkage, low coefficient of thermal expansion, low water absorption, as well as hydrolysis resistance and excellent mechanical properties, were developed by Unitika, Japan.
② preparing the coating. The paint is used as insulating paint or high-temperature resistant paint.
And making advanced composite material. The high-temperature-resistant resin-based composite material is widely applied to structural parts and engine parts in the aerospace industry.
And fourthly, manufacturing fibers. The elastic modulus of the manufactured fiber is only second to that of carbon fiber and is a reinforcing agent of the advanced composite material.
Fifthly, manufacturing foam and engineering plastics. The former is used as heat-insulating and sound-insulating material with high-temp. resistance and low-temp. resistance, and the latter is mainly used for self-lubricating, sealing, insulating and structural material.
In addition, the polyimide is used as a functional material and is widely applied to the fields of microelectronic devices, liquid crystal displays, nonlinear photoelectric materials and the like.
However, a great deal of research shows that the polyimide has high molecular chain rigidity, strong acting force among molecular chains and close stacking of molecular chains, so that the polyimide is difficult to dissolve. In response to this disadvantage, many studies have been made to improve the properties of polyimide by various methods. In recent years, by molecular design of monomers, special structural units (such as flexible structural units, large side groups or solvent-philic groups, twisted and non-coplanar structures), aromatic heterocycles, fluorine and silicon and other elements are introduced into a molecular structure, or polyimide is modified by copolymerization and other modes. Currently, polyimides have been studied and developed:
firstly, flexible structural units are introduced into dianhydride or diamine monomers to improve the fluidity of polyimide molecular chains or improve the solubility and the meltability of polyimide;
introducing a twisted and non-coplanar structure into the polyimide to twist the molecular chain segment of the formed polyimide, reducing or destroying the conjugated system of the main chain of the polyimide molecules, and reducing the acting force among the molecules, thereby improving the solubility of the polyimide;
and thirdly, large side groups or solvent-philic groups are introduced into the main molecular chain to reduce the stacking density of polymer molecular chains, so that solvent molecules can easily permeate into the polymer molecular chains, thereby having good solubility.
In recent years, the introduction of aromatic heterocyclic structures into the molecular backbone of polymers has been a focus of research. The introduction of aromatic heterocyclic structural units into the molecular main chain of polyimide not only can remarkably improve the processing performance of polyimide while maintaining the excellent mechanical property and heat resistance, but also can improve the performances of polyimide in the aspects of electricity, magnetism and the like. At present, pyridine rings are more introduced into aromatic heterocyclic structures. The pyridine ring is a rigid aromatic heterocyclic molecule with aromaticity, symmetry, basicity and polarity. Research results show that the polyimide with the main chain containing pyridine rings not only has excellent thermal stability and chemical stability, but also has good solubility and film forming property. The preparation of polyimide with a main chain containing a pyridine ring is mainly realized by designing and synthesizing dianhydride or diamine monomers containing the pyridine ring. John et al obtained a dinitro compound containing a pyridine ring by the Claisen-Schmidt reaction, and then obtained pyridine-containing diamine by Pd/C catalytic hydrogenation reduction. The Lianfeng standard of Lanzhou university synthesizes series polyimide containing pyridine ring. However, the pyridine ring-containing monomer has the disadvantages of difficult synthesis, low yield and high cost, which greatly hinders the development of polyimide with a main chain containing a pyridine ring.
Polyimide has various ways in synthesis, and the polycondensation reaction of aromatic dianhydride and diamine is a general method for preparing polyimide, which usually needs high-temperature heat treatment to ensure that the imidization is complete, and is mostly limited to the application in the aspects of films and coatings. In addition, the synthesis of melt-processable or soluble polyimides has been the focus of research because the polyamic acid solution is sensitive to temperature during storage and the polycondensation process is very limited.
[ summary of the invention ]
The invention aims to provide a novel polytriazole imide resin which has excellent mechanical property and heat resistance, can be dissolved and melted, has greatly improved processability, has special properties in the aspects of electricity and magnetism and is easy to process through molecular design and synthesis; still another object of the present invention is to provide a method for preparing the polytriazole imide resin, thereby ensuring broader application of polyimide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a polytriazole imide resin, which has the chemical structural formula:
n＝20～100，
in the formula,
in the polytriazole imide resin, the structure of the terminal alkynyl imide compound is as follows:
in the polytriazole imide resin, the structure of the azide compound is as follows:
in order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of polytriazole imide resin is characterized in that terminal alkynyl imide compounds and azide compounds are used for preparing polytriazole imide through Click chemical cycloaddition polymerization reaction of alkyne-azide, catalytic polymerization reaction or thermal polymerization reaction is adopted, and the preparation method comprises the following steps:
(1) preparation of Azide Compounds
Sodium azide and halogenated hydrocarbon are used as raw materials, and the azide compound is prepared through nucleophilic substitution reaction, wherein the preparation process comprises the following steps: synthesizing an azide compound in a solution, wherein a solvent is N, N' -Dimethylformamide (DMF), benzene, toluene, dimethyl sulfoxide (DMSO) or Tetrahydrofuran (THF); adding a mixed solvent of toluene and DMF (dimethyl formamide) into a reaction kettle, wherein the volume ratio of the toluene to the DMF is 1: 1-2, and the addition amount of the mixed solvent is 800-1500 mL per mole of halogenated hydrocarbon; adding halogenated hydrocarbon, wherein the halogenated hydrocarbon is chloride, bromide or iodide; the feeding equivalent ratio of the reaction raw material sodium azide to the halohydrocarbon is 1.0-3.0: 1.0, the reaction temperature is 20-80 ℃, the reaction time is 2-10 h, and the structural formula is as follows:
wherein,
(2) preparation of terminal alkynyl imide Compounds
The preparation method comprises the following steps of reacting acid anhydride with an amine compound with alkynyl, dehydrating and cyclizing with acetic anhydride to synthesize an alkynyl-terminated imide compound, wherein the preparation process comprises the following two steps:
firstly, reacting aromatic acid anhydride and aromatic amine with alkynyl in an organic solvent (acetone and the like) to generate amic acid;
secondly, acetic anhydride is used as a dehydrating agent and triethylamine is used as a catalyst to carry out dehydration cyclization, so as to generate an alkynyl-terminated imide compound;
these operations should be performed under the protection of inert gas such as nitrogen, helium or argon, and finally, the terminal alkynyl imide compound obtained by washing with acetone and purification treatment has the structural formula:
wherein:
(3) preparation of Polytriazoleimides
Carrying out 1, 3-dipolar cycloaddition polymerization reaction on the prepared dialkynyl imide compound and diazide compound in an equimolar amount in a solvent, wherein the polymerization reaction is thermal polymerization reaction or catalytic polymerization reaction;
the solvent is one or more of N, N '-Dimethylformamide (DMF), N' -dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP);
the thermal polymerization reaction comprises the following steps: adding equimolar dikynylimide compound and diazide compound into a three-neck flask, adding a solvent to prepare a mixed solution (preferably 15-30%) with the mass concentration of 5-50%, stirring fully, heating to 70-120 ℃ (preferably 80-100 ℃), and stirring for reaction for 12-48 hours (preferably 24-36 hours) to obtain a polymer solution; cooling to room temperature, and then pouring the reaction solution into ethanol for precipitation to obtain a white product; carrying out suction filtration, washing with hot ethanol, and drying in a vacuum drying oven at 100 ℃ overnight to obtain polytriazole imide resin;
the catalytic polymerization reaction comprises the following steps: adding equimolar terminal alkynyl imide compound and diazide compound into a three-neck flask, adding DMF, DMAc, DMSO or N-methylpyrrolidone as solvents to ensure that the mass concentration of the reaction reaches 5-50% (preferably 15-30%), and stirringAfter fully stirring, heating to 20-80 ℃ (preferably 40-60 ℃); adding CuSO45H2Adding O and sodium ascorbate catalysts, wherein the adding amount of the O and the sodium ascorbate catalysts is 5% and 10% of the mole number of the alkynyl compound respectively, simultaneously adding triethylamine complexing agent with the same amount as the mole number of the terminal alkynyl imide compound, and stirring and reacting for 2-8 hours (preferably 3-4 hours) at constant temperature to obtain viscous polymer solution; cooling to room temperature, pouring the reaction mixture into deionized water to obtain fibrous polytriazole imide resin, repeatedly soaking and washing with deionized water to remove catalyst and triethylamine, filtering, washing with hot ethanol, drying in a vacuum drying oven at 100 ℃ overnight to obtain polytriazole imide with high molecular weight, dissolving in dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone, precipitating and purifying, and drying to obtain polytriazole imide resin, wherein the chemical reaction equation is as follows:
n＝20～100，
in the formula:
the novel polytriazole imide resin has the following advantages:
(1) the triazole ring is introduced into the main chain structure of the polyimide, so that the polytriazole imide resin is easy to dissolve and melt and has good processing performance;
(2) has high thermal stability and thermal decomposition temperature Td5Up to 360 ℃ glass transition temperature (T)g) Can be above 200 ℃;
(3) the material has good mechanical properties and good electrical properties;
(4) has the functional characteristics of corrosion resistance, high bonding force and the like, and has wide application prospect in the fields of aviation, aerospace, microelectronics, automobiles, ship industry and the like.
The preparation method of the polytriazole imide resin has the positive effects that:
(1) the Click chemical cycloaddition polymerization reaction has mild and controllable conditions, can be carried out under simple conditions, is not sensitive to water and oxygen, and does not need protection of nitrogen, helium, argon and the like;
(2) the terminal alkynyl imide compound is easy to prepare, can be fully imidized at a lower temperature, and avoids high-temperature imidization and side reaction in polyimide synthesis;
(3) the Click chemical cycloaddition reaction has completeness and specificity, does not influence other functional groups, has good compatibility, and can conveniently introduce reactive active groups such as carboxyl, hydroxyl and the like into polytriazole imide through reasonable molecular design;
(4) no small molecular substance is discharged in the polymerization process, no side reaction or by-product is generated, and the polyimide with high molecular weight is easy to synthesize.
[ detailed description ] embodiments
The preparation method of the present invention is specifically described below by 9 examples, which are intended to better understand the contents of the present invention, but the scope of the present invention is not limited to the following examples.
The following experiments and verifications were carried out according to the preparation procedure of the above-described preparation method of polytriazoloimide resin.
Example 1
(1) Synthesis of 1, 4-diazidomethylbenzene (A1)
Adding 1 into a three-neck flask50mmol, NaN of 4-dichloromethylbenzene3150mmol, 20ml of toluene and 20ml of DMF, heating to 70-75 ℃ under stirring, reacting for 3h at constant temperature, cooling a reaction product to room temperature after the reaction is finished, pouring into 200ml of deionized water, standing overnight under a freezing condition to separate out white flaky crystals, filtering, washing a filter cake with the deionized water, and drying to obtain a white powdery solid, wherein the yield is 90.0% and the mp.26.0-27.5 ℃.
(2) Synthesis of bis (N-ethynylphenyl) -bisphenol A Ether phthalimide (B1)
Adding 20mmol of bisphenol A dianhydride (BPADA) and 40mmol of m-aminophenylacetylene into a 250ml four-neck flask provided with a stirring constant-pressure funnel and a spherical condenser, adding 50ml of acetone as a solvent, heating and refluxing for 6 hours, then adding 50ml of acetic anhydride, adding 75ml of triethylamine as a catalyst, refluxing for 6 hours at 80 ℃, cooling and precipitating after the reaction is finished, washing with acetone, performing suction filtration and drying to obtain a product, wherein the yield is 92%; FTIR (cm)-1): 3254(≡ C-H), 1776(C ═ O antisymmetric stretching), 1714(C ═ O symmetric stretching, imine I), 1384(C-N-C, imine II), 748(C ═ O);1H-NMR(DMSO)：7.2～8.0(Ar-H)，4.31(≡CH)，1.67(-CH3) The structural formula is as follows:
(3) preparation of polytriazoloimide PTAI-A1-B1
Adding 10mmol of 1, 4-diazidomethylbenzene, 10mmol of bis (N-ethynylphenyl) -bisphenol A ether phthalimide and 30ml of DMAc into a reactor, fully stirring and dissolving to form a transparent solution, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1mmol of sodium ascorbate and 10mmol of complexing agent triethylamine, and stirring and reacting for 2 hours at 60 ℃ to obtain viscous polymer solution; cooling to room temperature, slowly pouring the reaction mixture into deionized water to obtain filamentous polytriazole imide, and simultaneouslySoaking and washing the mixture for three times by using deionized water, removing a catalyst and triethylamine, performing suction filtration, washing the mixture by using hot ethanol, and drying the mixture overnight in a vacuum drying oven at 100 ℃ to obtain white polytriazole imide; then dissolving in DMAc to carry out reprecipitation purification and drying to obtain polytriazole imide, FTIR (cm)-1): 1777(C ═ O antisymmetric telescopic), 1722(C ═ O symmetric telescopic, imine I), 1372(C-N-C, imine II), 744(C ═ O);1H-NMR (DMSO): 8.52 (H on the triazole ring), 7.2-8.0 (Ar-H), 5.62 (CH)2)，1.68(-CH3) (ii) a The structural formula is as follows:
number average molecular weight Mn of the obtained polymer: 35500(GPC), Mw/Mn ═ 2.78; intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) of 0.42 and water absorption of 1.71 percent; polytriazolimide PTAI-A2-B1 has good solubility, and is easily dissolved in solvents such as DMF, DMAc, DMSO and NMP at room temperature.
Example 2
(1) Synthesis of 4, 4' -diazido-methylbiphenyl (A2)
50mmol of 4, 4' -dichloromethyl biphenyl and NaN are added into a three-neck flask3150mmol, 20ml of benzene and 20ml of DMF, heating to 75 ℃ under stirring, reacting at constant temperature for 3h, cooling a reaction product to room temperature after the reaction is finished, pouring the reaction product into 200ml of deionized water, standing overnight, separating out a white solid, filtering, washing a filter cake with the deionized water, and drying to obtain a white powdery solid, wherein the yield is 89.0%, and the melting point is 67-71 ℃.
(2) Preparation of polytriazoloimide PTAI-A2-B1
Adding 10mmol of 4, 4' -diazido methyl biphenyl, 10mmol of bis (N-ethynylphenyl) -bisphenol A ether phthalimide and 40ml of DMAc into a reactor to form a transparent solution, fully stirring and dissolving, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1.0mmol of sodium ascorbate and 10.0mmol of triethylamine serving as a complexing agent are stirred and reacted for 4 hours at the temperature of 60 ℃ to obtain viscous polymer solution; cooling to room temperature, slowly pouring the reaction mixture into deionized water to obtain filamentous polytriazole imide, soaking and washing with deionized water for three times, removing the catalyst and triethylamine, performing suction filtration, washing with hot ethanol, and drying in a vacuum drying oven at 100 ℃ overnight to obtain white biphenyl polytriazole imide; then dissolving the triazole imide in DMAc for re-precipitation purification, and drying to obtain polytriazole imide; FTIR (cm)-1): 1777(C ═ O antisymmetric stretching), 1722(C ═ O symmetric stretching, imine I), 1372(C-N-C, imine II), 744(C ═ O);1H-NMR (DMSO): 8.52 (H on the triazole ring), 7.2-8.0 (Ar-H), 5.62 (CH)2)，1.67(-CH3) The structural formula is as follows:
number average molecular weight Mn of the obtained polymer: 13000(GPC), Mw/Mn ═ 1.73; intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃)0.36, water absorption of which is 1.62%; polytriazoleimide PTAI-A2-B1 is readily soluble in solvents such as DMF, DMAc, DMSO, and NMP at room temperature.
Example 3
(1) Synthesis of 4, 4' -diazido methyl diphenyl ether (A3)
50mmol of 4, 4' -dichloromethyl diphenyl ether and NaN are added into a three-neck flask3150mmol, 20ml of toluene and 20ml of DMF, heating to 75 ℃ under stirring, reacting for 4h at constant temperature, cooling the reaction product to room temperature after the reaction is finished, pouring the reaction product into 200ml of deionized water, standing overnight, separating out white solid, filtering, washing a filter cake with the deionized water, and drying to obtain white powdery solid with the yield of 85.0%.
(2) Preparation of polytriazoloimide PTAI-A3-B1
Adding 10mmol of 4, 4' -diazido methyl diphenyl ether, 10mmol of bis (N-ethynylphenyl) -bisphenol A ether phthalimide and 40ml of DMAc into a reactor to form a transparent solution, fully stirring and dissolving, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1.0mmol of sodium ascorbate and 10.0mmol of triethylamine serving as a complexing agent are stirred and reacted for 8 hours at the temperature of 60 ℃ to obtain viscous polymer solution; cooling to room temperature, and slowly pouring the reaction mixture into deionized water to obtain filamentous polytriazole imide; the work-up was carried out as in example 2 and drying gave polytriazoloimides; FTIR (cm)-1) As in example 2, the structural formula is:
the prepared polytriazoloimide PTAI-A3-B1 is dissolved in solvents such as DMF, DMAc, DMSO and NMP, and has intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃): 0.30, a glass transition temperature of 200 ℃ and a 5% thermal weight loss temperature of 350 ℃ (N)2)。
Example 4
(1) Synthesis of bis (N-ethynylphenylphthalimide) ether (B2)
Adding 12.4g (0.04mol) of 4, 4' -oxydiphthalic anhydride and 11.23g (0.096mol) of m-aminophenylacetylene into a 250ml four-neck flask provided with a stirring constant-pressure funnel and a spherical condenser tube, adding 100ml of acetone as a solvent, heating and refluxing for 4 hours, then adding 50ml of acetic anhydride, adding 75ml of triethylamine as a catalyst, refluxing for 4 hours at 80 ℃, cooling after the reaction is finished, adding the mixture into 200ml of ethanol for precipitation, performing suction filtration, washing with acetone, performing suction filtration, drying again to obtain a product, stirring for 30 minutes at low temperature (in an ice water bath), performing suction filtration to obtain a white product, washing with ethanol, performing vacuum drying, and obtaining the yield of 96%; FTIR (cm)-1): 3254(≡ C-H), 1776(C ═ O antisymmetric stretching), 1714(C ═ O symmetric stretching, imine I), 1384(C-N-C, imino-N-C, oh-O-y, oh-OAmine II), 1230(-O-), 748(C ═ O);1H-NMR (DMSO): 7.1-8.0 (Ar-H), 4.32(≡ CH), having the formula:
(2) preparation of polytriazoloimide PTAI-A1-B2
Adding 10mmol of 1, 4-diazidomethylbenzene, 10mmol of bis (N-ethynyl phenyl phthalimide) ether and 30ml of DMSO (dimethyl sulfoxide) into a reactor to form turbid mixed solution, fully stirring, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1.0mmol of sodium ascorbate and 10.0mmol of triethylamine serving as a complexing agent are stirred and reacted for 4 hours at the temperature of 60 ℃ to obtain viscous polymer solution; cooling to room temperature, slowly pouring the reaction mixture into 500mL of deionized water to obtain filamentous polytriazole imide, soaking and washing with deionized water for three times to remove the catalyst and triethylamine, performing suction filtration, washing with hot ethanol, and drying in a vacuum drying oven at 100 ℃ overnight to obtain light yellow polytriazole imide; then dissolving the triazole imide in DMAc to carry out reprecipitation, purification and drying to obtain polytriazole imide; FTIR (cm)-1): 1777(C ═ O antisymmetric stretching), 1722(C ═ O symmetric stretching, imine I), 1372(C-N-C, imine II), 1230(-O-), 744(C ═ O);1H-NMR (DMSO): 8.52 (H on the triazole ring), 7.2-8.0 (Ar-H), 5.61 (-CH)2) (ii) a The structural formula is as follows:
the prepared polytriazole imide is dissolved in solvents such as DMF, DMAc, DMSO, NMP and the like at room temperature, the intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) is 0.46, the glass transition temperature is 230 ℃, and the 5% thermal weight loss temperature is 360 ℃ (N & ltC & gt2)。
Example 5
Preparation of polytriazoloimide PTAI-A2-B2
Adding 10mmol of 4, 4' -diazido methyl biphenyl, 10mmol of bis (N-ethynyl phenyl phthalimide) ether and 50ml of NMP into a reactor to form turbid mixed solution, fully stirring, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1mmol of sodium ascorbate and 10mmol of complexing agent triethylamine, and stirring and reacting for 4 hours at 60 ℃ to obtain viscous polymer solution; cooling to room temperature, slowly pouring the reaction mixture into 500ml of deionized water to obtain filamentous polytriazole imide, soaking and washing with deionized water for three times to remove the catalyst and triethylamine, performing suction filtration, washing with hot ethanol, and drying in a vacuum drying oven at 100 ℃ overnight to obtain light yellow polytriazole imide; then dissolving NMP for re-precipitation purification, and drying to obtain polytriazole imide; FTIR (cm)-1): 1777(C ═ O antisymmetric stretching), 1724(C ═ O symmetric stretching, imine I), 1378(C-N-C, imine II), 1232(-O-), 754(C ═ O);1H-NMR (DMSO): 8.5 (H on the triazole ring), 7.2-8.0 (Ar-H), 5.6 (-CH)2) (ii) a The structural formula is as follows:
the prepared polytriazole imide is dissolved in solvents such as DMF, DMAc, DMSO, NMP and the like at room temperature, the intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) is 0.35, the glass transition temperature is 210 ℃, and the 5% thermal weight loss temperature is 358 ℃ (N2)。
Example 6
(1) Synthesis of bis (N-ethynylphenylphthalimide) methanone (B3)
In a 250ml four-necked flask equipped with a stirring, constant pressure funnel and a spherical condenser were charged 12.4g (0.0 g) of 3, 3 ', 4, 4' benzophenonetetracarboxylic dianhydride4mol), 11.23g (0.096mol) of m-aminophenylacetylene, adding 100ml of acetone as a solvent, heating and refluxing for 4 hours, then adding 50ml of acetic anhydride, adding 75ml of triethylamine as a catalyst, refluxing for 4 hours at 80 ℃, cooling after the reaction is finished, adding into 200ml of ethanol for precipitation, performing suction filtration, washing with acetone, performing suction filtration, and drying to obtain a product, wherein the yield is 96%; FTIR (cm)-1): 3267(≡ C-H), 1778(C ═ O antisymmetric stretch), 1720(C ═ O, symmetric stretch I), 1640 (keto C ═ O), 1384(C-N-C, II), 748(C ═ O);1H-NMR: 7.2-8.0 (Ar-H), 4.3(≡ CH), having the formula:
(2) preparation of polytriazoloimide PTAI-A1-B3
Adding 10mmol of 1, 4-diazido-methylbenzene, 10mmol of bis (N-ethynyl phenyl phthalimide) ketone and 30ml of DMAc into a reactor to form turbid mixed solution, fully stirring, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1mmol of sodium ascorbate and 10mmol of complexing agent triethylamine, and stirring and reacting for 3 hours at 60 ℃ to obtain viscous polymer solution; the post-treatment method was the same as in example 4, whereby a pale yellow polytriazole imide was obtained; FTIR (cm)-1): 1779(C ═ O antisymmetric stretch), 1725(C ═ O symmetric stretch, imine I), 1640 (keto group C ═ O), 1374(C-N-C, imine II), 752(C ═ O);1H-NMR (DMSO): 8.5 (H on the triazole ring), 7.2-8.0 (Ar-H), 5.6 (-CH)2) (ii) a The structural formula is as follows:
the prepared polytriazole imide is dissolved in solvents such as DMF, DMAc, DMSO, NMP and the like, has an intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) of 0.40, and is vitrifiedThe transition temperature is 230 ℃ and the 5% thermal weight loss temperature is 355 ℃ (N)2)。
Example 7
Preparation of polytriazoloimide PTAI-A2-B3
The procedure was as for the preparation of polytriazoloimide PTAI-A1-B3 of example 6, but the reaction was carried out at 60 ℃ with stirring for 4 hours to give the pale yellow polytriazoloimide; FTIR (cm)-1) The same as in example 6; the structural formula is as follows:
the prepared polytriazole imide is dissolved in solvents such as DMF, DMAc, DMSO, NMP and the like, the intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) is 0.30, the glass transition temperature is 235 ℃, and the 5% thermal weight loss temperature is 360 ℃ (N & ltn & gt)2)。
Example 8
(1) Synthesis of bis (N-ethynylphenylphthalimide) hexafluoroisopropylpropane (B4)
Adding 40mmol of 4, 4' -hexafluoroisopropylidene phthalic anhydride and 96mmol of m-aminophenylacetylene into a 250ml four-neck flask provided with a stirring constant-pressure funnel and a spherical condenser, adding 100ml of acetone as a solvent, heating and refluxing for 4 hours, then adding 50ml of acetic anhydride, adding 75ml of triethylamine as a catalyst, refluxing for 4 hours at 80 ℃, adding into 500ml of deionized water after the reaction is finished, stirring and precipitating, carrying out suction filtration to obtain a white product, washing with ethanol, and carrying out vacuum drying to obtain a product, wherein the yield is 90%; FTIR (cm)-1): 1782(C ═ O antisymmetric stretching), 1724(C ═ O symmetric stretching, imine I), 1384(C-N-C, II imine), 1136 (-CF)3)，753(C＝O)；1H-NMR (DMSO): 7.2-8.0 (Ar-H), 4.30(≡ CH), having the formula:
(2) preparation of polytriazoloimide PTAI-A1-B4
Adding 10mmol of 1, 4-diazidomethylbenzene, 10mmol of bis (N-ethynyl phenyl phthalimide) hexafluoro-isopropyl propane and 30ml of DMF into a reactor to form a transparent solution, fully stirring and dissolving, heating to 60 ℃, and adding a catalyst CuSO4·5H20.5mmol of O, 1mmol of sodium ascorbate and 10mmol of complexing agent triethylamine, stirring and reacting for 4 hours at 60 ℃ to obtain a viscous polymer solution, cooling to room temperature, slowly pouring a reaction mixture into 500mL of deionized water to obtain filamentous polytriazole imide, soaking and washing with deionized water for three times, removing a catalyst and triethylamine, performing suction filtration, washing with hot ethanol, drying overnight in a vacuum drying oven at 100 ℃ to obtain white polytriazole imide, dissolving in DMF, performing reprecipitation and purification, and drying to obtain polytriazole imide; FTIR (cm)-1): 1782(C ═ O antisymmetric stretching), 1724(C ═ O symmetric stretching, imine I), 1375(C-N-C, imine II), 1136 (-CF)3)，752(C＝O)；1H-NMR (DMSO): 8.53 (H on the triazole ring), 7.2-8.0 (Ar-H), 5.61 (-CH)2) The structural formula is as follows:
the prepared polytriazole imide is dissolved in solvents such as DMF, DMAc, DMSO, NMP and the like, the intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) is 0.30, the glass transition temperature is 235 ℃, and the 5% thermal weight loss temperature is 360 ℃ (N & ltn & gt)2)。
Example 9
Preparation of polytriazoloimide PTAI' -A1-B1 by thermal polymerization
10mmol of 1, 4-diazidomethylbenzene and bis (N-ethynylphenyl) -Adding 10mmol of bisphenol A ether phthalimide and 30ml of DMAc into a reactor, fully stirring and dissolving to form a transparent solution, heating to 100 ℃, and stirring at 100 ℃ for reacting for 24 hours to obtain a polymer solution; cooling to room temperature, pouring the reaction mixture into 200ml of ethanol for precipitation to obtain a white product, performing suction filtration, washing with hot ethanol, and drying in a vacuum drying oven at 100 ℃ overnight to obtain polytriazole imide; FTIR (cm)-1): 1777(C ═ O antisymmetric telescopic), 1722(C ═ O symmetric telescopic, imine I), 1372(C-N-C, imine II), 1150 (-CH)3)，744(C＝O)；1H-NMR (DMSO): 8.4 to 8.5 (H on the triazole ring), 7.2 to 8.0(Ar-H), 5.62 (CH)2)，1.68(-CH3) The structural formula is as follows:
the prepared polytriazoloimide PTAI' -A1-B1 has good solubility and is easily soluble in solvents such as DMF, DMAc, DMSO and NMP at room temperature; intrinsic viscosity (0.5 g/dl DMAc solution at 30 ℃) 0.28; the glass transition temperature is 180 ℃, and the 5 percent thermal weight loss temperature is 360 ℃ (N)2)。
Claims (7)
1. A polytriazole imide resin is characterized by being represented by the chemical structural formula:
n＝20～100，
in the formula,
one of (1);
2. The polytriazole imide resin of claim 1 wherein the terminal alkynyl imide compound has the chemical structure:
one kind of (1).
3. The polytriazole imide resin of claim 1 wherein the azide compound has the chemical structure:
one kind of (1).
4. A process for preparing polytriazole imide resins as claimed in claim 1, wherein said polytriazole imides are prepared from alkynyl-terminated imide compounds and azide compounds by the Click chemical cycloaddition polymerization of alkyne-azide compounds, which comprises the steps of:
(1) preparation of Azide Compounds
Sodium azide and halogenated hydrocarbon are used as raw materials, and the azide compound is prepared through nucleophilic substitution reaction, wherein the preparation process comprises the following steps: synthesizing an azide compound in a solution, wherein a solvent is N, N' -Dimethylformamide (DMF), benzene, toluene, dimethyl sulfoxide (DMSO) or Tetrahydrofuran (THF); adding a mixed solvent of toluene and DMF (dimethyl formamide) into a reaction kettle, wherein the volume ratio of the toluene to the DMF is 1: 1-2, and the addition amount of the mixed solvent is 800-1500 mL per mole of halogenated hydrocarbon; adding halogenated hydrocarbon, wherein the halogenated hydrocarbon is chloride, bromide or iodide; the feeding ratio (equivalent ratio) of the reaction raw material sodium azide to the halogenated hydrocarbon is 1.0-3.0: 1.0, the reaction temperature is 20-80 ℃, the reaction time is 2-10 h, and the structural formula is as follows:
wherein,
(2) preparation of terminal alkynyl imide Compounds
The preparation method comprises the following steps of reacting acid anhydride with an amine compound with alkynyl, dehydrating and cyclizing with acetic anhydride to synthesize an alkynyl-terminated imide compound, wherein the preparation process comprises the following two steps:
firstly, reacting aromatic acid anhydride and aromatic amine with alkynyl in an organic solvent (acetone and the like) to generate amic acid;
secondly, acetic anhydride is used as a dehydrating agent and triethylamine is used as a catalyst to carry out dehydration cyclization, so as to generate an alkynyl-terminated imide compound;
finally, washing with acetone, and purifying to obtain the terminal alkynyl imide compound, wherein the structural formula is as follows:
wherein:
(3) preparation of Polytriazoleimides
Carrying out 1, 3-dipolar cycloaddition polymerization reaction or thermal polymerization reaction on the prepared dialkynyl imide compound and diazide compound in an equimolar amount in a solvent; the solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone; the thermal polymerization reaction comprises the following steps: adding equimolar double-end alkynyl imide compounds and diazide compounds into a three-neck flask, adding a polar solvent to prepare a mixed solution with the mass concentration of 5-50%, fully stirring, heating to 70-120 ℃, and stirring for reaction for 12-48 hours to obtain a polymer solution; cooling to room temperature, and then pouring the reaction solution into ethanol for precipitation to obtain a white product; and (3) carrying out suction filtration, washing with hot ethanol, and drying in a vacuum drying oven at 100 ℃ overnight to obtain the polytriazole imide resin, wherein the structural formula of the polytriazole imide resin is as follows:
in the formula:
one of (1);
5. The method for producing polytriazole imide resin according to claim 4, wherein the solution is prepared by a thermal polymerization reaction of polytriazole imide, wherein the solution is stirred sufficiently and then heated to 80-100 ℃ for 24-36 hours to obtain a polymer solution.
6. The process for preparing polytriazole imide resins of claim 4 wherein said polymerization for preparing polytriazole imides is a catalytic polymerization comprising: adding equimolar terminal alkynyl imide compound and diazide compound into a three-neck flask, adding solvents DMF, DMAc, DMSO or N-methylpyrrolidone to enable the mass concentration of the reaction to reach 5-50%, stirring fully,heating to 20-80 ℃, and adding CuSO45H2Adding O and sodium ascorbate catalysts, wherein the adding amount of the O and the sodium ascorbate catalysts is 5% and 10% of the mole number of the alkynyl compound respectively, simultaneously adding triethylamine complexing agent with the same mole number as that of the terminal alkynyl imide compound, and stirring and reacting for 2-8 hours at constant temperature to obtain viscous polymer solution; cooling to room temperature, pouring the reaction mixture into deionized water to obtain fibrous polytriazole imide resin, repeatedly soaking and washing with deionized water to remove catalyst and triethylamine, filtering, washing with hot ethanol, drying in a vacuum drying oven at 100 ℃ overnight to obtain polytriazole imide with high molecular weight, dissolving in dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone, precipitating and purifying, and drying to obtain polytriazole imide resin.
7. The method for producing polytriazole imide resin according to claim 6, wherein in the catalytic polymerization reaction for producing polytriazole imide, the mass concentration of the reactants is 15-30%, the temperature is raised to 40-60 ℃ after sufficient stirring; stirring and reacting for 3-4 hours at constant temperature to obtain a viscous polymer solution.
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| DE4436355A1 (en) * | 1993-10-21 | 1995-06-01 | Chemie Linz Deutschland | New oligomeric and polymeric maleimide cpds. |
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