CN1814595A - Second-order nonlinear optical polymer containing azo and thiophene ring and synthetic method and application thereof - Google Patents
Second-order nonlinear optical polymer containing azo and thiophene ring and synthetic method and application thereof Download PDFInfo
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- CN1814595A CN1814595A CN 200510011307 CN200510011307A CN1814595A CN 1814595 A CN1814595 A CN 1814595A CN 200510011307 CN200510011307 CN 200510011307 CN 200510011307 A CN200510011307 A CN 200510011307A CN 1814595 A CN1814595 A CN 1814595A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 230000003287 optical effect Effects 0.000 title claims abstract description 44
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title abstract 4
- 229960005222 phenazone Drugs 0.000 title abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 44
- 239000010408 film Substances 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000004132 cross linking Methods 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000004185 ester group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 16
- 238000004528 spin coating Methods 0.000 claims description 15
- 125000003368 amide group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 13
- QFBSIUIFNVITOR-UHFFFAOYSA-N 5-aminothiophene-2-carbaldehyde Chemical compound NC1=CC=C(C=O)S1 QFBSIUIFNVITOR-UHFFFAOYSA-N 0.000 claims description 12
- 235000010288 sodium nitrite Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 229920005601 base polymer Polymers 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 5
- 150000001989 diazonium salts Chemical class 0.000 claims description 5
- CHTSWZNXEKOLPM-UHFFFAOYSA-N 5-nitrothiophene-2-carbaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)S1 CHTSWZNXEKOLPM-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- -1 Viscotrol C ester polyol Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 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 description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- JORBYSXQJCFTAR-UHFFFAOYSA-J [Sn](Cl)(Cl)(Cl)Cl.NC1=CC=C(S1)C=O Chemical compound [Sn](Cl)(Cl)(Cl)Cl.NC1=CC=C(S1)C=O JORBYSXQJCFTAR-UHFFFAOYSA-J 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000006193 diazotization reaction Methods 0.000 claims description 2
- 230000005684 electric field Effects 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 229920006254 polymer film Polymers 0.000 abstract description 8
- 229920006037 cross link polymer Polymers 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920006112 polar polymer Polymers 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NJXCHSZRMBDKDP-UHFFFAOYSA-N 3,4-dibutylthiophene-2-carbaldehyde Chemical compound CCCCC1=CSC(C=O)=C1CCCC NJXCHSZRMBDKDP-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IQVCFLQILLKEFW-UHFFFAOYSA-J [Sn](Cl)(Cl)(Cl)Cl.C(CCC)C1=C(SC(=C1CCCC)N)C=O Chemical compound [Sn](Cl)(Cl)(Cl)Cl.C(CCC)C1=C(SC(=C1CCCC)N)C=O IQVCFLQILLKEFW-UHFFFAOYSA-J 0.000 description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NHNUFAASKXPOQA-UHFFFAOYSA-N (3-acetamido-2-hydroxyphenyl)arsonic acid Chemical compound C(C)(=O)NC=1C(=C(C=CC1)[As](O)(=O)O)O NHNUFAASKXPOQA-UHFFFAOYSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- XRPYNQBYUKDMFE-UHFFFAOYSA-N 3,4-dibutyl-5-nitrothiophene-2-carbaldehyde Chemical compound CCCCC1=C(C=O)SC([N+]([O-])=O)=C1CCCC XRPYNQBYUKDMFE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GDIQHHVUOCKMQF-UHFFFAOYSA-N 5-amino-3,4-dibutylthiophene-2-carbaldehyde Chemical compound CCCCC1=C(N)SC(C=O)=C1CCCC GDIQHHVUOCKMQF-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- OZZOVSQSDIWNIP-UHFFFAOYSA-N acetic acid;azane Chemical compound [NH4+].[NH4+].CC([O-])=O.CC([O-])=O OZZOVSQSDIWNIP-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 150000003053 piperidines Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of nonlinear optical materials, in particular to a second-order nonlinear optical polymer containing azo and thiophene rings and a synthetic method thereof, and a cross-linked polyurethane polymer or a poled polymer film prepared from the second-order nonlinear optical polymer containing the azo and thiophene rings. The novel high-performance second-order nonlinear optical polymer containing azo and thiophene rings has greatly improved photochemical stability because N-N bond is used for replacing C-C bond. The material contains two or more-OH groups, can be subjected to further reaction to prepare a cross-linked polymer film or a polarized polymer film, and has higher thermal stability, light stability and orientation stability compared with a non-cross-linked polymer. Further, since such azo compounds or azo intermediates thereof are blue to red compounds, they can also be used as pigments, dyes, paints and the like.
Description
Technical field
The present invention relates to the nonlinear optical material field, be particularly related to second-order non-linear optical polymer and synthetic method thereof that a class novel high-performance contains azo and thiphene ring, and prepare cross-linked type polyurethane base polymer or polarized polymer thin film with the second-order non-linear optical polymer that contains azo and thiphene ring.
Background technology
Second-order non-linear optical materials is mainly used in Electro-optical Modulation, frequency inverted and photoswitch (modulation) etc., and they have a wide range of applications at optical communication and optical signal process fields such as (photometry calculations).At present, Shi Yong second-order non-linear optical materials mainly is an inorganic materials.Organic materials is compared with inorganic materials to have that nonlinear optical coefficients are big, response speed is fast, optical damage threshold is high, can carry out molecular designing as requested, is easy to advantages such as processing and cheapness.As the present electrooptical material Lithium niobium trioxide that uses, its nonlinear second-order optical susceptibility is 30pm/V, and bandwidth is 10GHz, and the highest electro-optic coefficient of the organic materials of bibliographical information has reached 128pm/V, and high bandwidth surpasses 200GHz, and the expection bandwidth is 350GHz.
Though some single indexs such as the nonlinear optical coefficients of organic materials, bandwidth are considerably beyond inorganic materials, and have commodity selling with the device that electro-optical organic material is made, but particularly also there is certain defective in they aspect the optical stability aspect stable.Seeking all more superior organic second-order non-linear optical material of every performance index and replace existing inorganic materials, thereby realize high transmission speed, is a heat subject in present nonlinear optical material field.
Existing patent about the organic second-order non-linear optical material has many, but wherein most of nonlinear optical coefficients are not high.The higher patent of report nonlinear optical coefficients has: US6067186, WO02/08215 etc.But this class material all adopts the C=C key as the conjugated pi electron bridge, and the carbon-carbon double bond system exists creating singlet oxygen by using to make the problem of its stability decreases.
Summary of the invention
A purpose of the present invention provides the good novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring of a class optical stability.
A further object of the present invention provides a kind of preparation method who contains the novel high-performance second-order non-linear optical polymer of azo and thiphene ring.
Another object of the present invention provides cross-linked type polyurethane base polymer or the cross-linking type polarized polymer thin film of preparing with the second-order non-linear optical polymer that contains azo and thiphene ring.
An also purpose of the present invention provides the method for preparing cross-linked type polyurethane base polymer or cross-linking type polarized polymer thin film with the second-order non-linear optical polymer that contains azo and thiphene ring.
The novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring of the present invention has following structure:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following; The electron acceptor moiety of structure below the A representative:
Or
Wherein, R in the A formula
3=H or-(CH
2)
nR ', n=1~10, R '=H or OH; R
4=H or-(CH
2)
nR ', n=1~10, R '=H or OH; Work as R
3During for the substituting group on the phenyl ring, the position of its replacement is arbitrarily.
The preparation method who contains the novel high-performance second-order non-linear optical polymer of azo and thiphene ring of the present invention may further comprise the steps:
(1) with 3,5-nitro-the 2 thiophene carboxaldehyde of 4 replacements or non-replacement mixes with tindichloride and concentrated hydrochloric acid, wherein 3, the mol ratio of 5-nitro-2 thiophene carboxaldehyde, tindichloride and the concentrated hydrochloric acid of 4 replacements or non-replacement is 1: 2~5: 1~5, stirred 0.5~5 hour down at 20~100 ℃, replaced or the complex compound aaerosol solution of the tin tetrachloride of non-replacement 5-amino-2 thiophene carboxaldehyde;
(2) the tin tetrachloride complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde of replacement that step (1) is obtained or non-replacement joins in the NaOH aqueous solution that concentration is 5~40wt%, regulate the pH value to alkalescence, use extracted with diethyl ether then, boil off that ether is replaced or the 5-amino-2 thiophene carboxaldehyde of non-replacement;
(3) replacement that obtains of the complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde tin tetrachloride of replacement that step (1) is obtained or non-replacement or step (2) or the 5-amino-2 thiophene carboxaldehyde of non-replacement mix with Sodium Nitrite 1: 1 in molar ratio~1.5, under-5~5 ℃ and acidic conditions, carry out diazotization reaction and obtain diazonium salt, again with N, N-disubstituted benzenes aminated compounds carries out coupling and obtains azothiazole aldehyde in solvent, the coupled reaction temperature is-5~5 ℃; In the reaction process of carrying out step (3), regulate the pH value between 3~6 with sodium hydroxide or sodium-acetate;
(4) (mol ratio of electron acceptor(EA) and aldehyde radical is 1~5 to the azothiazole aldehyde that step (3) is obtained: 1) react in the solvent of catalyzer is arranged with the electron acceptor compound that contains labile methyl group or methylene radical after purifying, generate the azothiazole functional group of carbon-carbon double bonds, temperature of reaction is 10~150 ℃.
Described 3,4 replace or the substituting group of the 5-nitro-2 thiophene carboxaldehyde of non-replacement is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl.
Described step (3) acidic conditions is that (mol ratio of hydrochloric acid and Sodium Nitrite is 2~4 to 1~4M hydrochloric acid soln: 1), (mol ratio of hydrochloric acid and Sodium Nitrite is 2~20: 1 to concentrated hydrochloric acid/acetic acid solution, the volume ratio of concentrated hydrochloric acid and acetate is 1: 0.5~5), (mol ratio of sulfuric acid and Sodium Nitrite is 5~20: 1 to the vitriol oil/acetic acid solution, the volume ratio of the vitriol oil and acetate is 1: 0.5~5) or the vitriol oil/acetate/propionic acid solution (mol ratio of the vitriol oil and Sodium Nitrite is 5~20: 1, the volume ratio of the vitriol oil and acetate is 1: 0.5~5, and the volume ratio of acetate and propionic acid is 3~5: 1).
Described step (3) N, N-disubstituted benzenes aminated compounds carry out the solvent that coupling adopts and are selected from water, acetone, N, N-dimethylformamide, N, N-dimethyl acetyl ammonia, tetrahydrofuran (THF), formic acid, acetate or their any mixture in solvent; The N that coupled reaction is used, the mol ratio of N-disubstituted benzenes aminated compounds and Sodium Nitrite is 1~1.5: 1, N, the concentration of N-disubstituted benzenes aminated compounds is 1~60wt%.
The method of purification of described step (4) azothiazole aldehyde is column chromatography or thin-layer chromatography method, and wherein, stationary phase is a silica gel, and elutriant is sherwood oil/acetone (volume ratio 0.5~3/1).
The solvent of described step (4) is selected from ethanol, tetrahydrofuran (THF), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, 1,4-dioxane, pimelinketone, chloroform or their any mixture; Catalyzer is selected from piperidines, piperidines-acetate, acetate-ammonium acetate or ammonium acetate.
Described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde are:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl.
The complex compound of the tin tetrachloride of described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde is:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; X=1~10.
Described azothiazole aldehyde is:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following.
The described electron acceptor compound that contains labile methyl group or methylene radical is:
Wherein, R in the A formula
3=H or-(CH
2)
nR ', n=1~10, R '=
HOr OH; R
4=H or-(CH
2)
nR ', n=1~10, R '=H or OH; Work as R
3During for the substituting group on the phenyl ring, the position of its replacement is arbitrarily.
The second-order non-linear optical polymer that contains azo and thiphene ring of the present invention can be used for preparing the cross-linked type polyurethane base polymer or the cross-linking type polarized polymer thin film of the second-order non-linear optical polymer that contains azo and thiphene ring.
Cross-linked type polyurethane base polymer or the cross-linking type polarized polymer thin film that contains the second-order non-linear optical polymer of azo and thiphene ring of the present invention prepares by the following method:
(1) the novel high-performance second-order non-linear optical polymer that will contain azo and thiphene ring reacted 0.5~20 hour in 20~120 ℃ with the compound that contains two-NCO in dry solvent, wherein, the novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring is 1: 2~20 with the compound mol ratio that contains two-NCO; Then, add and to contain more than three-polymkeric substance of the compound of OH or contain-OH, in 20~120 ℃ of reactions 1 minute~10 hours, obtain prepolymer, wherein ,-OH is 0.8~1: 1 with the ratio of residue-NCO; Prepolymer is filmed through spin-coating method, and spin speed is 1000~3000 rev/mins, and the spin coating time is 5 seconds~10 minutes, obtains the thick film of 0.1~5 μ m in 20~30 ℃ of vacuum-dryings 6~48 hours;
(2) pre-polymer film that step (1) is obtained heated 0.5~10 hour under 50~140 ℃ of dry atmosphere, both can obtain the cross-linked type polyurethane quasi-copolymer film; Or
The pre-polymer film that step (1) is obtained heats under 50~140 ℃ of dry atmosphere, adopts the method for corona polarizing to apply the electric field of 3000~5000V simultaneously on pre-polymer film, both can obtain the cross-linking type polarized polymer thin film.
The dry solvent of described step (1) is selected from chloroform, acetone, tetrahydrofuran (THF), chlorobenzene, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethyl acetyl ammonia, pimelinketone or their any mixture.
The compound that described step (1) contains two-NCO is selected from:
Or OCN-(CH
2) n-NCO
L=O or CH
2M=H or CH
3Or OCH
3Y=H or CH
3N=2-10
Described step (1) contains more than three-and the compound of OH is selected from TriMethylolPropane(TMP), glycerine, 1,2,6-hexanetriol, tetramethylolmethane, trolamine; Contain-polymkeric substance of OH is selected from poly-hexanodioic acid Viscotrol C ester polyol, polyoxytrimethylene polyvalent alcohol, polyether glycol, phenol polyvalent alcohol, Viscotrol C, bisphenol type tetraglycidel ether epoxy resin or bisphenol type tetraglycidel ether epoxy resin-aniline etc.
The preparation method's of the second-order non-linear optical polymer that contains azo and thiphene ring of the present invention reaction equation is as follows:
The novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring of the present invention, owing to the C=C key that has replaced the higher nonlinear optical material of report in the existing patent (as US6067186) with the N=N key, photochemical stability improves greatly.This class material contains two or more-OH, can pass through crosslinked polymeric film or the polarized polymer thin film of further prepared in reaction, and they are compared with non-cross-linked polymer has higher thermostability, light stability and orientation stability.In addition, because this type of azo-compound or its azo intermediate are blue to red compound, they also can be used as pigment, dyestuff and coating etc.
The organic second-order non-linear optical polymkeric substance that the present invention prepares is at electro-optical device and utilize in the various opto-electronic devices of its frequency-doubled effect and photorefractive effect etc. the important application prospect is arranged.
Embodiment
Embodiment 1
3,4-dibutyl-5-amino-2 thiophene carboxaldehyde tin tetrachloride complex compound synthetic
Under ice bath and vigorous stirring, restrain (0.2mol) SnCl with 45
22H
2O is dissolved in the 60ml concentrated hydrochloric acid, when system temperature is reduced to 5 ℃, once adds 3,4-dibutyl-5-nitro-2 thiophene carboxaldehyde 17.8 grams (0.066mol), and 40 ℃ were stirred 1 hour, got the pale solid suspension liquid.
Embodiment 2
3,4-dibutyl-5-amino-2 thiophene carboxaldehyde synthetic
The pale solid suspension liquid that embodiment 1 is obtained arrives alkalescence with 40wt%NaOH aqueous solution adjust pH, uses extracted with diethyl ether then, ether layer MgSO
4The evaporation of dry back, the thick product that obtains can be directly used in next step reaction.
Embodiment 3
2-[4-(N, N-dihydroxy ethyl amino) azobenzene] 3,4-dibutyl-5-thiophenecarboxaldehyde synthetic
With embodiment 1 obtain 3,4-dibutyl-5-amino-2 thiophene carboxaldehyde tin tetrachloride complex compound canescence solution; Or with embodiment 2 obtain 3, the hydrochloric acid soln of 4-dibutyl-5-amino-2 thiophene carboxaldehyde is cooled to 2 ℃; With 0.067 mole of NaNO
2Be dissolved in the 15ml water, and, in the hydrochloric acid soln of 4-dibutyl-5-amino-2 thiophene carboxaldehyde, continue to stir 1 hour, get diazonium salt solution in slowly being added drop-wise to above-mentioned canescence solution or 3 below 5 ℃.
N with 0.080mol, N-dihydroxy ethyl aniline is dissolved among the 10ml 36%HOAC, cryosel is bathed and is cooled to 3 ℃, above-mentioned diazonium salt solution slowly is added drop-wise to N, in the HOAC solution of N-dihydroxy ethyl aniline, temperature of reaction is controlled at below 5 ℃,, between 3~6, continue to stir 1.5 hours with the pH value of NaOH regulation system, filter, the pink solid that obtains is dissolved in the 100ml acetone, remove insoluble pink salt, column chromatography is separated (sherwood oil/acetone=2/1), gets pink azothiazole aldehyde, IR:3420 (OH), 2859-2956 (CH
2, CH
3), 1650 (CHO), 1596 (phenyl ring); Uv-vis:537nm (DMF).
Embodiment 4
With compound and 0.1g (0.50mmol) the 2-dicyan methene-3-cyano group-4,5 that 0.1g (0.31mmol) embodiment 3 obtains, 5 trimethylammoniums-2, the 5-dihydrofuran is dissolved in the 5mL ethanol.The NH that adds catalytic amount
4AcO and acetic acid, reflux 4 hours is chilled to room temperature.Suction filtration, and be blue-greenish colour until filtrate with washing with alcohol precipitation.The dry black solid 0.20g that gets.The column chromatography separation obtains the pure product ZCN of second nonlinear compound (53%).IR(KBr):3448(OH);2870-2960(CH);2226(CN)cm
-1;UV-vis(CHCl
3):668nm;
1HNMR(CDCl
3):δ8.41(d,1H),8.08(d,2H),7.37(d,2H),6.77(d,1H),4.14(br,4H),3.95(br,4H),2.78(m,4H),1.87(s,6H),1.71(m,8H),1.13(m,6H);MS:612(M
+)。
Embodiment 5
Prepolymer I preparation
Under the nitrogen atmosphere, the product (ZCN) of 34.8mg embodiment 4 is dissolved in the 0.8ml pimelinketone, adds 64 microlitre TDI, reactant stirred 1.5 hours in 80 ℃, the dioxane solution that adds 150 microlitre trolamines (0.779mmol/ml) then, 80 ℃ are continued to stir 15 minutes.Standby after the solution concentration.
Embodiment 6
The preparation of crosslinking polymer I film
The pre-polymer solution that obtains among the embodiment 5 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 100 ℃ were heated 2 hours then, can obtain the crosslinking polymer film.
UV-vis:690nm。
Embodiment 7
The preparation of cross-linking type polar polymer I film
The pre-polymer solution that obtains among the embodiment 5 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, the control heat-up rate also increases voltage synchronously, temperature rises to 50 ℃ in 20 minutes, voltage is increased to 3000 volts, keep after 20 minutes, temperature and voltage are risen to 60 ℃, 3200 volts, kept again 20 minutes, and then temperature and voltage were risen to 80 ℃, 3400 volts, kept 10 minutes, at last, temperature and voltage are risen to 120 ℃, 3800 volts kept 20 minutes, stop heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 8
The preparation of prepolymer II
Under the nitrogen atmosphere, the product (ZCN) that 11.7mg embodiment 4 is obtained is dissolved in the 0.5ml pimelinketone, add 10 times of equivalents to the TDI of ZCN, reactant stirred 12 hours in 75 ℃, the dioxane solution that adds 338 microlitres polyaniline-dihydroxyphenyl propane glycidyl ether (0.508mmol/ml) then stirred 15 minutes.It is standby that solution filters the back.
Embodiment 9
The preparation of crosslinking polymer II film
The pre-polymer solution that obtains among the embodiment 8 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 140 ℃ were heated 5 hours then, can obtain the crosslinking polymer film.
Embodiment 10
The preparation of cross-linking type polar polymer II film
The pre-polymer solution that obtains among the embodiment 8 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, and in 95 ℃, 5500V polarizes half an hour, is warming up to 110 ℃ then and keeps half an hour, stops heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 11
2-[4-(N, N-dihydroxy ethyl amino-2-kharophen) azobenzene] 3,4-dibutyl-5-thiophenecarboxaldehyde (5) synthetic
With 0.725g (10.5mmol) NaNO
2Be added to the dense H of 8mL in batches
2SO
4In (<10 ℃), slowly be heated to about 65 ℃.Treat NaNO
2After molten entirely, be chilled to below 5 ℃, with 5mL propionic acid/acetate (V/V: 1/4) dilution.Mixture is chilled to 0 ℃, adds embodiment 2 gained 3 in batches, 4-dibutyl-5-amino-2 thiophene carboxaldehyde (10.4mmol), and 0 ℃ was stirred 1 hour then, got diazonium salt solution (tawny viscous solution).About 0 ℃ of temperature control splashes into 3-acetylaminohydroxyphenylarsonic acid N with it then, in the solution of N-two (2-hydroxyethyl) aniline (11mmol) DMF.Drip and finish, stir after 0.5 hour about 0 ℃, transfer pH=5~6, continue to stir 0.5 hour with NaAcO.Under the vigorous stirring, in a large amount of frozen water of impouring, and use NaHCO
3Transfer pH=7~8.Extracted with diethyl ether three times, organic phase saturated common salt water washing, anhydrous MgSO
4Dry.Filter, filtrate is revolved and is steamed to doing, and gets the red-purple sticky solid.Cross post with petrol ether/ethyl acetate (1/5), get the red-purple solid product.IR (KBr, cm
-1): 3420 (OH), 2859-2956 (CH
2, CH
3), 1650 (CHO), 1596 (phenyl ring).Uv-vis:548/CHCl
3。
Embodiment 12
With 0.1g (0.23mmol) embodiment 11 gained compounds and 0.1g (0.50mmol) 2-dicyan methene-3-cyano group-4,5,5 trimethylammoniums-2,5-dihydrofuran acceptor is dissolved in the 5mL ethanol.Piperidines-the acetate (piperidines-acetate volume ratio is 1: 3) that adds catalytic amount, reflux got blue-green solution after 1 hour, and rotary evaporation is removed ethanol, and the residuum acetone solution removes and desolvates, and column chromatography is separated, eluent acetone/sherwood oil (1/4).Get green solid 0.09g, productive rate 64%.MS(MALDI-TOF,m/z):669.6(M
+),692(M
++Na),708(M
++K)。
1H-NMR (chloroform-d
1) 8.32 (s, 1H), 8.12 (d, 1H), 7.75 (d, 1H), 6.97 (s, 1H), 6.62 (d, 1H), 3.99 (S, 4H), 3.80 (S, 4H), 2.96 (t, 2H) 2.75 (t, 2H), 2.61 (m, 3H), 2.32 (S, 3H), 1.82 (S, 2H), 1.74 (s, 6H), 1.46 (2H, m), 1.26 (s, and 4H) 1.05 (q, 6H).
Embodiment 13
The preparation of prepolymer III
Under the nitrogen atmosphere, 24.6mg embodiment 12 gained chromophoric grouies are dissolved in the 0.4ml pimelinketone, add 42 microlitre TDI, reactant stirred 3 hours in 80 ℃, the dioxane solution that adds 176 microlitre trolamines (0.779mmol/ml) then, 80 ℃ are continued to stir 15 minutes.Standby after the solution concentration.
Embodiment 14
The preparation of crosslinking polymer III film
The pre-polymer solution that obtains among the embodiment 13 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500-3000r/min, and thickness is 1~2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 100 ℃ were heated 2 hours then, can obtain the crosslinking polymer film.
Embodiment 15
The preparation of cross-linking type polar polymer III film
The pre-polymer solution that obtains among the embodiment 13 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~3 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.
Above-mentioned film is placed the corona polarizing device, corona needle point and film surface are apart from 1.5cm, the control heat-up rate also increases voltage synchronously, temperature rises to 50 ℃ in 20 minutes, voltage is increased to 3000 volts, keep after 20 minutes temperature and voltage being risen to 60 ℃, 3200 volts, kept again 20 minutes, then temperature and voltage are risen to 80 ℃, 3400 volts, kept 10 minutes, last, temperature and voltage are risen to 120 ℃, 3800 volts maintenances 20 minutes, stop heating, naturally after being cooled to room temperature, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 16
The preparation of prepolymer IV
Under the nitrogen atmosphere, 12.7mg embodiment 12 gained chromophoric grouies are dissolved in the 0.5ml pimelinketone, add the TDI of 27 microlitres, reactant stirred 12 hours in 75 ℃, the dioxane solution that adds 338 microlitres polyaniline-dihydroxyphenyl propane glycidyl ether (0.508mmol/ml) then, stirring at room 15 minutes.It is standby that solution filters the back.
Embodiment 17
The preparation of crosslinking polymer IV film
The pre-polymer solution that obtains among the embodiment 16 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 140 ℃ were heated 5 hours then, can obtain the crosslinking polymer film.
UV-vis:708nm。
Embodiment 18
The preparation of cross-linking type polar polymer IV film
The pre-polymer solution that obtains among the embodiment 16 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~3 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.
Above-mentioned film is placed the corona polarizing device, and corona needle point and film surface are apart from 1.5cm, in 95 ℃, 5500V polarizes half an hour, is warming up to 105 ℃ then and keeps half an hour, stops heating, naturally after being cooled to room temperature, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 19
With compound and 0.1g (0.53mmol) 3 that 0.1g (0.23mmol) embodiment 3 obtains, 5-dinitrobenzene-2-thiotolene acceptor is dissolved in the 5mL ethanol.The NH that adds catalytic amount
4AcO and acetic acid, reflux 5h adds proper catalyst and acceptor, continues to reflux 3 hours.Reaction finishes, and is chilled to room temperature, adds 30mL water, separates out a large amount of solids.Suction filtration, solid washes with water earlier, uses ethanol/sherwood oil (V/V: 1/3) washed twice, drying again.Cross post with petrol ether/ethyl acetate (1/5), get green solid 0.07g, productive rate 51%.IR (KBr, cm
-1): 3391 (OH), 3122 (thiphene ring C-H), 2956-2869 (CH), 1598 (phenyl ring C=C), 1541,1321 (NO
2).Uv-vis(λ
max,nm):431,630/CHCl
3;434,635/THF。
1H-NMR (acetone-d
6): 8.37 (s, 1H), 7.96 (d, J
H-H=15.6,1H), 7.85 (d, J
H-H=5.6,1H), 7.73 (d, J
H-H=9.2,2H), 6.90 (d, J
H-H=9.3,2H), 3.80 (t, J
H-H=11.5,4H), 3.70 (t, J
H-H=11.5,4H), 300 (t, J
H-H=15.5,2H), 2.88 (t, J
H-H=15.6,2H), 1.65 (m, 2H), 1.59 (m, 2H), 1.46 (m, 4H), 0.96 (m, 6H).
Embodiment 20
Prepolymer V preparation
Under the nitrogen atmosphere, the product that 34.1mg embodiment 19 is obtained is dissolved in the 0.8ml pimelinketone, adds 64 microlitre TDI, and reactant stirred 1.5 hours in 80 ℃, the dioxane solution that adds 150 microlitre trolamines (0.779mmol/ml) then, 80 ℃ are continued to stir 15 minutes.Standby after the solution concentration.
Embodiment 21
The preparation of crosslinking polymer V film
The pre-polymer solution that obtains among the embodiment 20 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 100 ℃ were heated 2 hours then, can obtain the crosslinking polymer film.
Embodiment 22
The preparation of cross-linking type polar polymer V film
The pre-polymer solution that obtains among the embodiment 20 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, the control heat-up rate also increases voltage synchronously, temperature rises to 50 ℃ in 20 minutes, voltage is increased to 3000 volts, keep after 20 minutes, temperature and voltage are risen to 60 ℃, 3200 volts, kept again 20 minutes, and then temperature and voltage were risen to 80 ℃, 3400 volts, kept 10 minutes, at last, temperature and voltage are risen to 120 ℃, 3800 volts kept 20 minutes, stop heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 23
The preparation of prepolymer VI
Under the nitrogen atmosphere, the product that 11.4mg embodiment 19 is obtained is dissolved in the 0.5ml pimelinketone, the TDI that adds the product that 10 times of equivalents obtain to embodiment 19, reactant stirred 12 hours in 75 ℃, the dioxane solution that adds 338 microlitres polyaniline-dihydroxyphenyl propane glycidyl ether (0.508mmol/ml) then stirred 15 minutes.It is standby that solution filters the back.
Embodiment 24
The preparation of crosslinking polymer VI film
The pre-polymer solution that obtains among the embodiment 23 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 140 ℃ were heated 5 hours then, can obtain the crosslinking polymer film.
Embodiment 25
The preparation of cross-linking type polar polymer VI film
The pre-polymer solution that obtains among the embodiment 23 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500~3000r/min, and thickness is 1~2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, and in 95 ℃, 5500V polarizes half an hour, is warming up to 110 ℃ then and keeps half an hour, stops heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Claims (10)
1. second-order non-linear optical polymer that contains azo and thiphene ring, it is characterized in that: this polymkeric substance has following structure:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following; The electron acceptor moiety of structure below the A representative:
Wherein, R in the A formula
3=H or-(CH
2)
nR ', n=1~10, R '=H or OH; R
4=H or-(CH
2)
nR ', n=1~10, R '=H or OH; Work as R
3During for the substituting group on the phenyl ring, the position of its replacement is arbitrarily.
2. preparation method who contains the second-order non-linear optical polymer of azo and thiphene ring according to claim 1 is characterized in that this method may further comprise the steps:
(1) with 3,5-nitro-the 2 thiophene carboxaldehyde of 4 replacements or non-replacement mixes with tindichloride and concentrated hydrochloric acid, wherein 3, the mol ratio of 5-nitro-2 thiophene carboxaldehyde, tindichloride and the concentrated hydrochloric acid of 4 replacements or non-replacement is 1: 2~5: 1~5, stir down at 20~100 ℃, replaced or the complex compound aaerosol solution of the tin tetrachloride of non-replacement 5-amino-2 thiophene carboxaldehyde;
(2) the tin tetrachloride complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde of replacement that step (1) is obtained or non-replacement joins in the NaOH aqueous solution, regulate the pH value to alkalescence, use extracted with diethyl ether then, boil off that ether is replaced or the 5-amino-2 thiophene carboxaldehyde of non-replacement;
(3) replacement that obtains of the complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde tin tetrachloride of replacement that step (1) is obtained or non-replacement or step (2) or the 5-amino-2 thiophene carboxaldehyde of non-replacement mix with Sodium Nitrite 1: 1 in molar ratio~1.5, under-5~5 ℃ and acidic conditions, carry out diazotization reaction and obtain diazonium salt, again with N, N-disubstituted benzenes aminated compounds carries out coupling and obtains azothiazole aldehyde in solvent, the coupled reaction temperature is-5~5 ℃; In the reaction process of carrying out step (3), regulate the pH value between 3~6 with sodium hydroxide or sodium-acetate;
(4) the azothiazole aldehyde that step (3) is obtained reacts in the solvent of catalyzer is arranged with the electron acceptor compound that contains labile methyl group or methylene radical after purifying, generate the azothiazole functional group of carbon-carbon double bonds, temperature of reaction is 10~150 ℃, wherein, the mol ratio of electron acceptor(EA) and aldehyde radical is 1~5: 1.
3. method according to claim 2, it is characterized in that: described 3,4 replace or the substituting group of the 5-nitro-2 thiophene carboxaldehyde of non-replacement is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl.
4. method according to claim 2, it is characterized in that: described step (3) acidic conditions is 1~4M hydrochloric acid soln, the mol ratio of hydrochloric acid and Sodium Nitrite is 2~4: 1, concentrated hydrochloric acid/acetic acid solution, the mol ratio of hydrochloric acid and Sodium Nitrite is 2~20: 1, the volume ratio of concentrated hydrochloric acid and acetate is 1: 0.5~5, the vitriol oil/acetic acid solution, the mol ratio of sulfuric acid and Sodium Nitrite is 5~20: 1, the volume ratio of the vitriol oil and acetate is 1: 0.5~5, or the vitriol oil/acetate/propionic acid solution, the mol ratio of the vitriol oil and Sodium Nitrite is 5~20: 1, the volume ratio of the vitriol oil and acetate is 1: 0.5~5, and the volume ratio of acetate and propionic acid is 3~5: 1.
5. method according to claim 2 is characterized in that: the N that described step (3) coupled reaction is used, the mol ratio of N-disubstituted benzenes aminated compounds and Sodium Nitrite is 1~1.5: 1.
6. method according to claim 2 is characterized in that: described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde are:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl;
The complex compound of the tin tetrachloride of described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde is:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; X=1~10;
Described azothiazole aldehyde is:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following.
7. method according to claim 2 is characterized in that: the described electron acceptor compound that contains labile methyl group or methylene radical is:
Wherein, R in the A formula
3=H or-(CH
2)
nR ', n=1~10, R '=H or OH; R
4=H or-(CH
2)
nR ', n=1~10, R '=H or OH; Work as R
3During for the substituting group on the phenyl ring, the position of its replacement is arbitrarily.
8. purposes that contains the second-order non-linear optical polymer of azo and thiphene ring according to claim 1, it is characterized in that: this polymkeric substance is used to prepare cross-linked type polyurethane base polymer or cross-linking type polarized polymer thin film.
9. purposes according to claim 8 is characterized in that, described cross-linked type polyurethane base polymer or cross-linking type polarized polymer thin film prepare by the following method:
(1) second-order non-linear optical polymer that will contain azo and thiphene ring in dry solvent with contain the compound of two-NCO in 20~120 ℃ of reactions, wherein, the second-order non-linear optical polymer that contains azo and thiphene ring is 1: 2~20 with the compound mol ratio that contains two-NCO; Then, add and to contain more than three-polymkeric substance of the compound of OH or contain-OH, in 20~120 ℃ of reactions, obtain prepolymer, wherein ,-OH is 0.8~1: 1 with the ratio of residue-NCO; Prepolymer is filmed through spin-coating method, obtains the thick film of 0.1~5 μ m in 20~30 ℃ of vacuum-dryings;
(2) pre-polymer film that step (1) is obtained heats under 50~140 ℃ of dry atmosphere, both can obtain the cross-linked type polyurethane quasi-copolymer film; Or
The pre-polymer film that step (1) is obtained heats under 50~140 ℃ of dry atmosphere, adopts the method for corona polarizing to apply the electric field of 3000~5000V simultaneously on pre-polymer film, both can obtain the cross-linking type polarized polymer thin film.
10. purposes according to claim 9 is characterized in that: the compound that described step (1) contains two-NCO is selected from:
L=O or CH
2M=H or CH
3Or OCH
3Y=H or CH
3N=2-10
Described step (1) contains more than three-and the compound of OH is selected from TriMethylolPropane(TMP), glycerine, 1,2,6-hexanetriol, tetramethylolmethane or trolamine;
Described step (1) contains-and the polymkeric substance of OH is selected from poly-hexanodioic acid Viscotrol C ester polyol, polyoxytrimethylene polyvalent alcohol, polyether glycol, phenol polyvalent alcohol, Viscotrol C, bisphenol type tetraglycidel ether epoxy resin or bisphenol type tetraglycidel ether epoxy resin-aniline.
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