CN104974151B - Organic second-order nonlinear optical chromophore containing azide group and synthetic method and application thereof - Google Patents
Organic second-order nonlinear optical chromophore containing azide group and synthetic method and application thereof Download PDFInfo
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- 230000003287 optical effect Effects 0.000 title claims abstract description 106
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 title abstract 5
- 229920000642 polymer Polymers 0.000 claims abstract description 77
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 31
- 229920006254 polymer film Polymers 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 100
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 23
- -1 alkyl azide Chemical class 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 16
- 239000000370 acceptor Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 13
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 9
- 239000012675 alcoholic extract Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- JMQGGPRJQOQKRT-UHFFFAOYSA-N diphenyl hydrogen phosphate;azide Chemical compound [N-]=[N+]=[N-].C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 JMQGGPRJQOQKRT-UHFFFAOYSA-N 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
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- 239000003999 initiator Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000001649 bromium compounds Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000010287 polarization Effects 0.000 abstract description 8
- 239000000382 optic material Substances 0.000 abstract 2
- 238000005873 Huisgen reaction Methods 0.000 abstract 1
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 239000011368 organic material Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- SORGEQQSQGNZFI-UHFFFAOYSA-N [azido(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(N=[N+]=[N-])OC1=CC=CC=C1 SORGEQQSQGNZFI-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical class CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 0 C[C@](CC*)CCCOc1c(CCC(C(C)(C)O*2=C(*)C#N)=C2C#N)cc2c3c1C(C)(C)CCN3CCC2(C)C Chemical compound C[C@](CC*)CCCOc1c(CCC(C(C)(C)O*2=C(*)C#N)=C2C#N)cc2c3c1C(C)(C)CCN3CCC2(C)C 0.000 description 1
- 101100001675 Emericella variicolor andJ gene Proteins 0.000 description 1
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 description 1
- HKFHBWOEJFFQMY-UHFFFAOYSA-N O=C(C=C1)N(C2C=CC=CC2)C1=O Chemical compound O=C(C=C1)N(C2C=CC=CC2)C1=O HKFHBWOEJFFQMY-UHFFFAOYSA-N 0.000 description 1
- PESOTAWRBXZLFY-UHFFFAOYSA-N OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.N Chemical compound OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.N PESOTAWRBXZLFY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 238000012650 click reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- 150000002466 imines Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an organic second-order nonlinear optical chromophore containing azide groups, a synthetic method and application thereof. The invention introduces azide groups into organic second-order nonlinear optical chromophoreIn the raw material of the donor, an organic second-order nonlinear optical chromophore containing an azide group and having the following structure is prepared. The organic second-order nonlinear optical chromophore containing azide groups and the polymer containing end group alkyne are subjected to post functionalization through a Huisgen reaction to prepare a hanging type polymer electro-optic material containing the organic second-order nonlinear optical chromophore, and the hanging type polymer electro-optic material is subjected to film coating and polarization after being dissolved by an organic solvent to prepare an electro-optic polymer film.
Description
Technical field
The present invention relates to organic/polymer as electro-optical material, the more particularly to organic second-order non-linear optical containing azido group
Chromophore and its synthetic method and application.
Background technology
More and more apply to the field such as signal transacting and communication along with electro-optical organic material, electro-optical organic material
Research is also of increased attention.Compared to traditional inorganic/semi-conductor electricity luminescent material, electro-optical organic material has more
Excellent electro-optical properties.Certainly, want to allow electro-optical organic material to put among actual application, also many problems need to solve
Certainly, such as the stability of reinforcing material, electro-optical properties of material etc. are further improved.
Polymer and organic second order non-linear optical chromophore are often subjected to physical doping at present, so as to prepare host and guest's type
（guest-host）Electro-optical organic material, although this material prepare it is simple, in place of also having embodied some shortcomings.Example
Such as：Stronger dipole-idol between organic second order non-linear optical chromophore molecule in the electro-optical organic material of host and guest's type be present
Pole interaction force so that organic second order non-linear optical chromophore molecule is easily assembled, reduce polymer with
The compatibility of organic second order non-linear optical chromophore, when the concentration of organic second order non-linear optical chromophore increases, easily
There is macroscopic view to be separated, while the enhancing of aggtegation can also reduce host and guest's type between organic second order non-linear optical chromophore
Macroscopical electro-optic coefficient of electro-optical organic material；Secondly, in the electro-optical organic material of doping type, due to organic second-order non-linear light
Learn between chromophore molecule and polymer segment without chemical key connection, so that organic second order non-linear optical chromophore molecule
Easy movement in the polymer, so as to cause material to possess comparatively ideal stability, particularly when the temperature increases, host and guest
The electro-optical properties decay of the electro-optical organic material of type becomes more serious.
Therefore, the connection for organic second order non-linear optical chromophore being carried out into chemical bond with polymer is that a kind of raising is organic
The effective means of electrooptical material performance.Some using by after organic second order non-linear optical chromophore elder generation functionalization again with other lists
Body is polymerized polymer, so as to mount or be embedded in the form of chemical bond by organic second order non-linear optical chromophore molecule
In polymer segment, it can effectively suppress the aggregation of organic second order non-linear optical chromophore molecule, when organic second is non-thread
Property optical chromophore concentration increase when, macroscopic view be separated can be effectively suppressed.Simultaneously as organic second-order non-linear optical
Chromophore molecule is accessed in polymer segment in the form of chemical bond, the motion of organic second order non-linear optical chromophore molecule by
Certain influence is arrived, so that the electro-optical organic material of mounting type possesses more preferable stability.But some organic two
Rank non-linear optical chromophore can not bear slightly to show harsh polymerizing condition, therefore limit first functionalization polymerization again
Using.
Can be by different organic second order non-linear optical chromophores with the shape of chemical bond by the Post functionalization of polymer
Formula is articulated in similar polymers, but also due to organic second order non-linear optical chromophore molecule is quicker to reaction condition
Sense, therefore, suitable Post functionalization condition are extremely important for preparing mounting type electro-optical organic material.Nitrine-alkynyl
Huisgen coupling reactions are a kind of effective click-reactions, can be carried out by the catalysis of mantoquita under the temperate condition of normal temperature
Reaction.Therefore, azido group can be incorporated into organic second order non-linear optical chromophore, alkynyl is incorporated into polymer
Post functionalization reaction is carried out again, so as to realize the preparation of the polymer containing organic second order non-linear optical chromophore.
But it is to first have to asking for solution how azido group to be incorporated into organic second order non-linear optical chromophore
Inscribe, be all that azido group is introduced by the stronger sodium azide of toxicity in most of document, the present invention is less folded using toxicity
Azido group is effectively incorporated into organic second order non-linear optical chromophore by nitrogen diphenyl phosphate.The present invention's contains azido
The organic second order non-linear optical chromophore and phenyl maleimide of group-（4- propynyloxy base phenyl maleimides）- methyl
Methyl acrylate copolymer carries out Huisgen coupling reactions, and that has prepared excellent performance contains organic second-order non-linear optical
The mounting type electrooptical material of chromophore molecule.
The content of the invention
An object of the present invention is to provide the organic second order non-linear optical chromophore containing azido group.
The second object of the present invention is to provide a kind of conjunction of the organic second order non-linear optical chromophore containing azido group
Into method.
The third object of the present invention is the application for providing the organic second order non-linear optical chromophore containing azido group, with
Organic second order non-linear optical chromophore containing azido group and the polymer containing end-group alkyne, prepare non-thread containing organic second
The mounting type polymer as electro-optical material of property optical chromophore molecule.
The fourth object of the present invention be to provide a kind of phenyl maleimide-（4- propynyloxy base benzyl maleimides
Amine）Polymer containing end-group alkyne of-methylmethacrylate copolymer and preparation method thereof.
The organic second order non-linear optical chromophore containing azido group of the present invention has following structure：
Wherein, R1、R2It is independently alkyl, or R1、R2It is all 3,3- dimethyl propyls, and R1、R2The carbon atom of upper 3 with
The carbon atom bonding at phenyl ring amino ortho position（Its structure is as shown in Formula II）；R3For alkyl azide；R4And R5It is simultaneously methyl or R4For
Trifluoromethyl, R5For phenyl.
Described R1、R2In the carbon number of alkyl be preferably 1~10.
The carbon number of alkyl in described alkyl azide is preferably 1~20, and carbon number is more preferably 3~6.
The synthetic method of the organic second order non-linear optical chromophore containing azido group of the present invention comprises the following steps：
（1）Organic second order non-linear optical chromophore electron donor raw material and haloalkyl alcohol are dissolved in anhydrous solvent,
Phase transfer catalyst 18- crown ether -6 of dry potassium carbonate and catalytic amount are added, wherein, described organic second-order non-linear optical
The mol ratio of chromophoric Electrons donor raw material and haloalkyl alcohol is 1：1~2, described potassium carbonate and described organic second are non-
The mol ratio of linear optics chromophoric Electrons donor raw material is 1.2~3:1；In inert gas（Such as nitrogen）It is in temperature under protection
Reacted at 55~150 DEG C（The time of General reactions is 12~36 hours）, it is filtered to remove consolidating in resulting solution after reacting
Anhydrous solvent decompression is steamed after body, by obtained residue through pillar layer separation, it is non-to obtain the organic second containing alcoholic extract hydroxyl group
Linear optics chromophoric Electrons donor；
（2）By step（1）The obtained organic second order non-linear optical chromophore electron donor and nitrine containing alcoholic extract hydroxyl group
Diphenyl phosphate is dissolved in dry anhydrous solvent, in inert gas（Such as nitrogen）- 10~0 DEG C is cooled under protection, adds 1,
Carbon -7- the alkene of 8- diazabicylos 11, is kept for 0.5~2 hour at -10~0 DEG C, is returned after then heating to reflux temperature
Stream（General return time is 12 hours or so）, anhydrous solvent is removed under reduced pressure after the completion of backflow, by obtained residue through post color
Spectrum separation, obtains the electron donor containing azido group；Wherein, the organic second order non-linear optical chromophore electronics containing alcoholic extract hydroxyl group
Donor and the mol ratio of diphenyl phosphate azide are 1：1.2~3；Organic second order non-linear optical chromophore electricity containing alcoholic extract hydroxyl group
Sub- donor and the mol ratio of the carbon -7- alkene of 1,8- diazabicylos 11 are 1：1.2~3；
（3）By step（2）Obtained electron donor containing azido group and electron acceptor is dissolved in organic solvent, wherein,
The mol ratio of electron donor and electron acceptor containing azido group is 1：0.9~1, back flow reaction is carried out at a reflux temperature（One
As return time be 5 hours or so）, or in the presence of the pyridine of catalytic amount（Electron acceptor reactivity is not required to add when stronger
Pyridine）, back flow reaction is carried out at a reflux temperature（General return time is 5 hours or so）；Depressurize and steam after the completion of back flow reaction
Except organic solvent, obtained crude product is recrystallized in methyl alcohol, it is non-thread to obtain the pure organic second containing azido group
Property optical chromophore.
Described organic second order non-linear optical chromophore electron donor raw material has the structure shown in formula III：
R1、R2It is independently alkyl（The carbon number of alkyl is preferably 1~10）, or R1、R2It is all 3,3- dimethyl propylenes
Base, and R1、R2The carbon atom of upper 3 and the carbon atom bonding at phenyl ring amino ortho position（Organic second-order non-linear optical color development now
Group's electron donor raw material is 8- hydroxyl -1,1,7,7- tetramethyl julolidine -9- formaldehyde）.
The carbon number of alkyl in described haloalkyl alcohol is 1~20, and carbon number is preferably 3~6, it is preferred that
6- Mecorals or 3- bromopropyl alcohols.
Described electron acceptor is 2- dicyano methene -3- cyano group -4,5,5- trimethyl -2,5- dihydrofuran（TCF）Electricity
The 2- dicyano methene -3- cyano group -4,5,5- trimethyl -2,5- dihydrofuran of sub- acceptor or trifluoro substitution（CF3-TCF）Electronics
Acceptor.
Step（1）Described in anhydrous solvent be acetone or N,N-dimethylformamide.
Step（2）Described in anhydrous solvent be tetrahydrofuran or toluene.
Step（3）Described in organic solvent be methanol, ethanol or chloroform.
The organic second order non-linear optical chromophore containing azido group of the present invention can be with the polymer containing end-group alkyne（Such as
Phenyl maleimide-（4- propynyloxy base phenyl maleimides）- methylmethacrylate copolymer）It is even by Huisgen
Connection reaction carries out Post functionalization, prepares the mounting type electrostrictive polymer finish containing organic second order non-linear optical chromophore molecule
Material；Gained mounting type polymer as electro-optical material can be prepared into electro-optic polymer film and as in integrated optics or photoelectronics
Materials'use.
The organic second order non-linear optical chromophore containing azido group of the present invention passes through with the polymer containing end-group alkyne
Huisgen coupling reactions carry out Post functionalization, and successfully organic second order non-linear optical chromophore molecule has been incorporated into containing end
In the segment of the polymer of base alkynes, while it can be adjusted by adjusting the content of end-group alkyne in the polymer containing end-group alkyne in segment
Organic second order non-linear optical chromophore molecule number, so as to be effectively prepared containing organic second-order non-linear optical send out
The mounting type polymer as electro-optical material of color group's molecule.The organic second order non-linear optical chromophore system containing azido group of the present invention
Film after-polarization is dissolved through organic solvent for the mounting type polymer as electro-optical material gone out, for preparing electro-optic polymer film.
The described polymer containing end-group alkyne be phenyl maleimide-（4- propynyloxy base phenyl maleimides）- first
Base methyl acrylate copolymer, it has following structure：
Wherein, x, y be respectively phenyl maleimide-（4- propynyloxy base phenyl maleimides）- methyl methacrylate
The mol ratio of phenyl maleimide and methyl methacrylate and 4- propynyloxy base phenyl maleimides in ester copolymer,
X ＞ 0, y ＞ 0, preferably 10 >=x >=0.2,20 >=y >=2.
The organic second order non-linear optical chromophore containing azido group of the present invention can lead to the polymer containing end-group alkyne
Cross Huisgen coupling reactions and carry out Post functionalization, prepare the mounting type containing organic second order non-linear optical chromophore molecule
Polymer as electro-optical material, its preparation method are：
Organic second order non-linear optical chromophore containing azido group, the polymer containing end-group alkyne are dissolved in N, N- dimethyl
In formamide, (triphenyl phosphorus) cuprous bromide of catalyst three and diisopropylethylamine are added, in inert gas（Such as nitrogen）Protection
Under be stirred reaction at room temperature（The time of general stirring reaction is 12~60 hours）；Wherein, containing the organic of azido group
The mol ratio of second-order nonlinear optical chromophore and contained end-group alkyne in the polymer containing end-group alkyne is 1.5~2：1；Three (triphens
Base phosphorus) mol ratio of contained end-group alkyne is 0.1~0.3 in cuprous bromide and the polymer containing end-group alkyne：1；Diisopropylethylamine
Mol ratio with contained end-group alkyne in the polymer containing end-group alkyne is 0.5~1:1；
The solution that reaction is completed to obtain afterwards is added in methanol, ether or water, obtains the solution containing precipitation；Filter
Solution containing precipitation obtains the crude product of the mounting type polymer containing organic second order non-linear optical chromophore molecule, will take out
The crude product for filtering obtained described mounting type polymer uses methanol or extracted by ether to apparatus,Soxhlet's in apparatus,Soxhlet's
In solution fade to colourless, that is, obtain the mounting type electrostrictive polymer finish containing organic second order non-linear optical chromophore molecule
Material.
Described phenyl maleimide-（4- propynyloxy base phenyl maleimides）- methylmethacrylate copolymer
Preparation method be：
By phenyl maleimide, 4- propynyloxy bases phenyl maleimide, methyl methacrylate, initiator azo two
Isobutyronitrile is dissolved in anhydrous DMF, in inert gas（Such as nitrogen）Sealed after protection；It is 65~70 in temperature
Polymerisation is carried out at DEG C；Wherein：The dosage of azodiisobutyronitrile is phenyl maleimide, 4- propynyloxy base phenyl Malaysia acyl
5th/3000 to thousand/1000ths of imines and methyl methacrylate gross mass, phenyl maleimide：4- propynyloxy base phenyl
Maleimide：The mol ratio of methyl methacrylate is x：1：Y, and x ＞ 0（It is preferred that 10 >=x >=0.2）, y ＞ 0（It is preferred that 20 >=
y≥2）；After reaction to be polymerized terminates, resulting polymers solution is added in methanol, ether or water, obtained containing the molten of precipitation
Liquid；Filter containing precipitation solution obtain phenyl maleimide-（4- propynyloxy base phenyl maleimides）- methacrylic acid
Methyl terpolymer.
The organic second order non-linear optical chromophore containing azido group of the present invention is prepared non-thread containing organic second
The mounting type polymer as electro-optical material of property optical chromophore molecule well by organic second order non-linear optical chromophore molecule with
The form of chemical bond is connected in polymer segment, is effectively improved the stability of electro-optical organic material, is the device of material
Change is laid a good foundation.
The organic second order non-linear optical chromophore containing azido group of the present invention is prepared non-thread containing organic second
The mounting type polymer as electro-optical material of property optical chromophore molecule is through organic solvent（Such as cyclopentanone, methylene bromide）Dissolving, rotation
Transfer film after-polarization, prepares electro-optic polymer film, and prepared electro-optic polymer film can be used as integrated optics or photoelectron
Materials'use in.
The advantage of the invention is that：
1）For the present invention using the less diphenyl phosphate azide of toxicity as raw material, can be easy be incorporated into azido group is organic
In second-order nonlinear optical chromophore, reaction efficiency is high.
2）The organic second order non-linear optical chromophore containing azido group of the present invention can be with the polymer containing end-group alkyne
Prepare the mounting type containing organic second order non-linear optical chromophore molecule under mild conditions by Huisgen coupling reactions
Polymer as electro-optical material；Mounting type polymer as electro-optical material of the gained containing organic second order non-linear optical chromophore molecule can be made
For into electro-optic polymer film and as the materials'use in integrated optics or photoelectronics.
3）The present invention can adjust containing of preparing by adjusting the content of end-group alkyne in the polymer containing end-group alkyne
Chromophore content in the mounting type polymer as electro-optical material of organic second order non-linear optical chromophore molecule.
4）The organic second order non-linear optical chromophore containing azido group of the present invention is prepared non-containing organic second
The mounting type polymer as electro-optical material of linear optics chromophore molecule is by organic second order non-linear optical chromophore molecule with chemistry
The form of key is connected in polymer segment, and processing the electro-optical organic material prepared has good stability.
5）The synthetic method of the present invention is fairly simple, easy to operate, is adapted to a large amount of productions.
Brief description of the drawings
Phenyl maleimide in Fig. 1 embodiment of the present invention 3-（4- propynyloxy base phenyl maleimides）- methyl-prop
E pioic acid methyl ester copolymer p 11HNMR spectrograms.
The mounting type polymer P 1-C3's containing organic second order non-linear optical chromophore in Fig. 2 embodiment of the present invention 31HNMR spectrograms.
The mounting type polymer P 1-C2's containing organic second order non-linear optical chromophore in Fig. 3 embodiment of the present invention 41HNMR spectrograms.
Phenyl maleimide in Fig. 4 embodiment of the present invention 5-（4- propynyloxy base phenyl maleimides）- methyl-prop
E pioic acid methyl ester copolymer p 21HNMR spectrograms.
The stability curve figure of electro-optic polymer film electro-optical properties in Fig. 5 embodiment of the present invention 7.
Embodiment
Raw material in synthetic method as described below is commercially available prod unless otherwise instructed；2- dicyano methene -3- cyanogen
Base -4,5,5- trimethyl -2,5- dihydrofuran（TCF）And the 2- dicyano methene -3- cyano group -4,5,5- front threes of trifluoro substitution
Base -2,5- dihydrofuran（CF3-TCF）Can be according to document（M.Q.He,T.M.Leslie andJ.A.Sinicropi,
Chem.Mater.,2002,14,2393-2400.）Disclosed method is synthesized to obtain；4- propynyloxy base phenyl Malaysia acyl
Imines can be according to document（F.Liu,J.Liu and T.Zhao,Journalof Applied Polymer Science,2010,
115,3103-3109）Disclosed method is synthesized to obtain.
Embodiment 1
Chromophore molecule C2 of the synthesis with following structure:
Synthetic route is as follows：
Wherein, DPPA is diphenyl phosphate azide, DBU 1, the carbon -7- alkene of 8- diazabicylos 11；TCF is 2- dicyan
Base methene -3- cyano group -4,5,5- trimethyls-DHF, its structure are as follows：
Synthetic method is：
(1) in formula compound 2 synthesis
In 100mL three-necked flasks, by 2.73g（0.01mol）Compound 1 is dissolved in 50mL dry acetones, adds 2.09g
（0.015mol）3- bromopropyl alcohols, 3g（0.022mol）Phase transfer catalyst 18- crown ether -6 of Anhydrous potassium carbonate and catalytic amount, nitrogen
Back flow reaction is carried out at temperature is 65 DEG C 12 hours, be then filtered to remove the solid in resulting solution after reacting under gas shielded,
Vacuum rotary steam removes acetone, by obtained residue through pillar layer separation（Using the silica gel of 200~300 mesh as stationary phase, with oil
The mixed liquor of ether and ethyl acetate is mobile phase, wherein：The volume ratio of petroleum ether and ethyl acetate is 7：1）Obtain 2.56g chemical combination
Thing 2（Pale yellowish oil liquid, yield 77%）；
(2) in formula compound 3 synthesis
Take 1.66g（0.005mol）Step（1）Obtained compound 1 is placed in 50mL there-necked flasks, accesses condenser pipe, nitrogen
Protection, sealing, is injected into 25mL tetrahydrofurans and 1.72mL（0.008mol）It is placed in after diphenyl phosphate azide cold in ice salt bath
But to -5 DEG C, slowly it is injected into 1.20mL（0.008mol）Carbon -7- the alkene of 1,8- diazabicylo 11, low temperature keeps 1 at -5 DEG C
Hour, ice salt bath is then removed, carries out stopping back flow reaction after flowing back 12 hours after being to slowly warm up to reflux temperature；Backflow is completed
After vacuum rotary steam removes tetrahydrofuran afterwards, by obtained residue through pillar layer separation（Using the silica gel of 200~300 mesh as fixation
Phase, using the mixed liquor of petroleum ether and ethyl acetate as mobile phase, wherein：The volume ratio of petroleum ether and ethyl acetate is 10：1）, obtain
To 1.50g compounds 3（Slightly yellow oily liquids, yield 84%）；
MS,m/z:(356M+)1H NMR(400MHz,CDCl3)δ9.87(s,1H),7.55(s,1H),4.04(t,J=
6.2Hz,2H),3.60(t,J=6.8Hz,2H),3.34–3.19(m,4H),2.19–2.08(m,2H),1.71(m,4H),1.43
(s,6H),1.27(s,6H)。
（3) in formula target chromophore molecule C2 synthesis
1.07g is added in 50mL single port bottles（30mmol）Step（2）Obtained compound 3,0.56g（28.1mmol）
TCF acceptors, 30mL methanol is added, instill 2 drop pyridines as catalyst, be heated to reflux temperature, carry out at a reflux temperature
Backflow stops heating after 5 hours, methanol is removed under reduced pressure after the completion of back flow reaction, after obtained crude product is recrystallized in methyl alcohol
Obtain 1.19g target chromophore molecules C2（Darker yellow green solid, yield 79%）.
MS,m/z:(537M+)1H NMR(400MHz,CDCl3)δ7.90(d,J=15.7Hz,1H),7.41(s,1H),6.61
(d,J=15.7Hz,1H),3.92(t,J=6.8Hz,2H),3.58(t,J=6.3Hz,2H),3.46–3.30(m,4H),2.26–
2.14(m,2H),1.81–1.70(m,10H),1.43(s,6H),1.31(s,6H)。
Embodiment 2
Chromophore molecule C3 and C4 of the synthesis with following structure：
Synthetic route is as follows：
Wherein, DPPA is diphenyl phosphate azide, DBU 1, the carbon -7- alkene of 8- diazabicylos 11；TCF is 2- dicyan
Base methene -3- cyano group -4,5,5- trimethyls-DHF, CF3- TCF is the 2- dicyano methene -3- cyanogen of trifluoro substitution
Base -4,5,5- trimethyls-DHF, its structure are as follows：
TCFCF3-TCF
Synthetic method is：
（1) in formula compound 2 synthesis
In 100mL three-necked flasks, by 2.73g（0.01mol）Compound 1 is dissolved in 50mL and dried in DMF, adds 2.09g
（0.015mol）6- Mecorals, 3g（0.022mol）Phase transfer catalyst 18- crown ether -6 of Anhydrous potassium carbonate and catalytic amount, nitrogen
Reacted 12 hours at temperature is 100 DEG C under protection；Afterwards, the solid in resulting solution after reacting is filtered to remove, is evaporated under reduced pressure
DMF is removed, by obtained residue through pillar layer separation（Using the silica gel of 200~300 mesh as stationary phase, with petroleum ether and acetic acid
The mixed liquor of ethyl ester is mobile phase, wherein：The volume ratio of petroleum ether and ethyl acetate is 5：1）Obtain 2.76g compounds 2（It is pale yellow
Color solid, yield 74%）；
MS,m/z:(373M+)1H NMR(400MHz,CDCl3)δ9.92(s,1H),7.57(s,1H),3.96(t,2H),
3.66(t,2H),3.29(t,J=5.9Hz,2H),3.25–3.20(m,2H),2.02(s,1H),1.89(m,2H),1.76–1.66
(t,4H),1.61(d,J=6.6Hz,2H),1.55–1.44(m,4H),1.42(s,6H),1.26(s,6H).
(2) in formula compound 3 synthesis
Take 1.87g（0.005mol）Step（1）Obtained compound 1 is placed in 50mL there-necked flasks, accesses condenser pipe, nitrogen
Protection, sealing, is injected into 25mL tetrahydrofurans and 1.72mL（0.008mol）It is placed in after diphenyl phosphate azide cold in ice salt bath
But to -5 DEG C, slowly it is injected into 1.20mL（0.008mol）Carbon -7- the alkene of 1,8- diazabicylo 11, kept for 1 hour at -5 DEG C,
Then ice salt bath is removed, backflow 12 hours is carried out after being to slowly warm up to reflux temperature, stops back flow reaction；Depressurized after the completion of backflow
After revolving removes tetrahydrofuran, by obtained residue through pillar layer separation（Using the silica gel of 200~300 mesh as stationary phase, with stone
The mixed liquor of oily ether and ethyl acetate is mobile phase, wherein：The volume ratio of petroleum ether and ethyl acetate is 8：1）, obtain 1.73g
Compound 3（Slightly yellow oily liquids, yield 87%）；
MS,m/z:(398M+)1H NMR(400MHz,CDCl3)δ9.93(s,1H),7.58(s,1H),3.96(t,J=
6.8Hz,2H),3.29(dd,J=9.3,6.6Hz,4H),3.26–3.20(m,2H),1.96–1.82(m,2H),1.76–1.37
(m,16H),1.27(s,6H).
(3) in formula target chromophore molecule C3 synthesis
1.00g is added in 50mL single port bottles（25mmol）Step（2）Obtained compound 3,0.48g（24.1mmol）
TCF acceptors, 30mL methanol is added, instill 2 drop pyridines as catalyst, be heated to reflux temperature, carry out at a reflux temperature
Backflow stops heating after 5 hours, methanol is removed under reduced pressure after the completion of back flow reaction, after obtained crude product is recrystallized in methyl alcohol
Obtain 1.09g target chromophore molecules C3（Darker yellow green solid, yield 78%）.
MS,m/z:(579M+)1H NMR(400MHz,CDCl3)δ7.83(d,J=15.7Hz,1H),7.43(s,1H),6.70
(d,J=15.7Hz,1H),3.83(t,J=7.2Hz,2H),3.49–3.41(m,2H),3.40–3.35(m,2H),3.33(t,J=
6.7Hz,2H),2.03–1.90(m,2H),1.82–1.73(m,10H),1.71–1.62(m,2H),1.55–1.47(m,4H),
1.45(s,6H),1.33(s,6H).
(4) in formula target chromophore molecule C4 synthesis
1.00g is added in 50mL single port bottles（25mmol）Step（2）Obtained compound 3,0.76g（24.1mmol）
CF3- TCF acceptors, 30mL methanol is added, be heated to reflux temperature, stop adding after carrying out backflow at a reflux temperature 5 hours
Heat, methanol is removed under reduced pressure after the completion of back flow reaction, 1.21g target color developments are obtained after obtained crude product is recrystallized in methyl alcohol
Group molecule C4（Blue-green solid, yield 72%）.
1H NMR(400MHz,CDCl3)δ7.90(d,J=15.1Hz,1H),7.60–7.45(m,5H),7.34(s,1H),
6.72(d,J=15.1Hz,1H),3.71-3.53(m,2H),3.51–3.42(m,2H),3.42–3.33(m,2H),3.29(t,J=
6.8Hz,2H),1.79–1.50(m,8H),1.45–1.17(m,16H).
Embodiment 3
The following mounting type polymer P 1-C3 containing organic second order non-linear optical chromophore of composite structure：
Synthetic route is as follows：
Synthesis step is as follows：
(1) by 0.454g4- propynyloxy base phenyl maleimides（2mmol）, 0.346g phenyl maleimides
（2mmol）, 1.000g methyl methacrylates（10mmol）And 0.0072g azodiisobutyronitrile is dissolved in the anhydrous N of 8mL, N-
In dimethylformamide, seal, after carrying out polymerisation 48 hours at being 68 DEG C in temperature, gained is gathered afterwards under nitrogen protection
Polymer solution is added dropwise in 500mL methanol and settled, and obtains the methanol solution containing precipitation；It is molten to filter the methanol containing precipitation
Cleaned for several times with methanol after liquid, obtain white fluffy solid, as phenyl maleimide-（4- propynyloxy base phenyl Malaysia acyl
Imines）- methylmethacrylate copolymer P1.Tg=159 DEG C, Td=358 DEG C.Phenyl maleimide-（4- propynyloxy base phenyl
Maleimide）- methylmethacrylate copolymer P1's1HNMR spectrograms are shown in Fig. 1.
(2) by 0.27g steps（1）Obtained phenyl maleimide-（4- propynyloxy base phenyl maleimides）- methyl
Methyl acrylate copolymer P1（2.5mmol containing alkynyl）, 0.29g chromophore molecules C3（The chromophore molecule that embodiment 2 obtains
C3,5mmol）, 0.047g Cu (PPh3)3Br (0.5mmol) is dissolved in 10mLN, in dinethylformamide, adds 0.044mL
Diisopropylethylamine（2.5mmol）, seal, be stirred at room temperature after 60 hours after nitrogen protection, reaction completion is obtained
Solution be added dropwise in 400mL methanol and settled, obtain the methanol solution containing precipitation；It is molten to filter the methanol containing precipitation
Liquid, obtain the phenyl maleimide containing organic second order non-linear optical chromophore molecule-（4- propynyloxy base phenyl Malaysia acyl
Imines）The crude product of-methylmethacrylate copolymer, the described crude product that suction filtration obtains is inserted in apparatus,Soxhlet's,
The solution extracted with methanol into apparatus,Soxhlet's fade to it is colourless, gained blue solid be contain organic second-order non-linear optical
The phenyl maleimide of chromophore-（4- propynyloxy base phenyl maleimides）- methylmethacrylate copolymer, i.e. target
Mounting type polymer P 1-C3 containing organic second order non-linear optical chromophore, the extension containing organic second order non-linear optical chromophore
The reactivity of end-group alkyne and chromophore molecule C3 in direct type polymer P 1 is 87.5%.Tg=170 DEG C, Td=303 DEG C.Containing organic
The mounting type polymer P 1-C3's of second-order nonlinear optical chromophore1HNMR spectrograms are shown in Fig. 2.
Embodiment 4
The following mounting type polymer P 1-C2 containing organic second order non-linear optical chromophore of composite structure：
Synthetic route is as follows：
Synthetic schemes is as follows：
By 0.27g phenyl maleimides-（4- propynyloxy base phenyl maleimides）- methylmethacrylate copolymer
P1（The phenyl maleimide that embodiment 3 obtains-（4- propynyloxy base phenyl maleimides）- methyl methacrylate copolymer
Thing P1,2.5mmol containing alkynyl）, 0.27g chromophore molecules C2（The chromophore molecule C2,5mmol that embodiment 1 obtains）, 0.047g
Cu(PPh3)3Br (0.5mmol) is dissolved in 10mL DMFs, adds 0.044mL diisopropylethylamine
（2.5mmol）, seal, be stirred at room temperature after 48 hours after nitrogen protection, the solution that reaction is completed to obtain is added dropwise to
Settled in 400mL methanol, obtain the methanol solution containing precipitation；The methanol solution containing precipitation is filtered, is obtained containing having
The phenyl maleimide of machine second-order nonlinear optical chromophore molecule-（4- propynyloxy base phenyl maleimides）- methyl-prop
The crude product of e pioic acid methyl ester copolymer, obtained described crude product will be filtered and inserted in apparatus,Soxhlet's, with methanol extract to
Solution in apparatus,Soxhlet's fades to colourless, the gained blue solid as phenyl containing organic second order non-linear optical chromophore
Maleimide-（4- propynyloxy base phenyl maleimides）- methylmethacrylate copolymer, i.e. target are non-containing organic second
The mounting type polymer P 1-C2 of linear optics chromophore, the mounting type polymer P 1 containing organic second order non-linear optical chromophore
In end-group alkyne and chromophore molecule C2 reactivity be 78%.P1-C2's1HNMR spectrograms are shown in Fig. 3.
Embodiment 5
The following phenyl maleimide of composite structure-（4- propynyloxy base phenyl maleimides）- methyl methacrylate
Ester copolymer P2：
Synthetic route is as follows：
Synthetic schemes is as follows：
By 0.85g4- propynyloxy base phenyl maleimides（3.7mmol）, 0.65g phenyl maleimides
（3.7mmol）, 0.75g methyl methacrylates（7.5mmol）And 0.0092g azodiisobutyronitrile is dissolved in the anhydrous N of 10mL,
In dinethylformamide, seal afterwards under nitrogen protection, after carrying out polymerisation 48 hours at being 68 DEG C in temperature, by gained
Polymer solution is added dropwise in 500mL methanol and settled, and obtains the methanol solution containing precipitation；Filter the methanol containing precipitation
Cleaned for several times with methanol after solution, obtain white fluffy solid, as phenyl maleimide-（4- propynyloxy base phenyl Malaysia
Acid imide）- methylmethacrylate copolymer P2.Tg=183℃.Phenyl maleimide-（4- propynyloxy base phenyl Malaysia acyl
Imines）- methylmethacrylate copolymer P2's1HNMR spectrograms are shown in Fig. 4.
Embodiment 6
The mounting type polymer P 1-C3 containing organic second order non-linear optical chromophore of the gained of 0.08g embodiments 3 is added
Into 0.8mL methylene bromides, it is stirred overnight at room temperature, obtains the mounting type polymer containing organic second order non-linear optical chromophore
P1-C3 methylene bromide solution, filtering, spin-coating method film use on ito glass substrate, control spin coating rotating speed be 600~
1200 revs/min, obtained thin polymer film is dried 24 hours in vacuum drying chamber, and it is poly- between 2~3 μm to obtain thickness
Compound film.
The polarization of prepared thin polymer film and electro-optic coefficient measure：
Thin polymer film uses corona polarizing, and poling temperature is 180~185 DEG C, and the polarization time is 10~20 minutes, polarization
Voltage is controlled in 10000~11500V or so；Electro-optic coefficient（r33）Pass through simple reflex method（Simple Reflection
Method, also known as Teng-Man methods, referring to Teng C.C., Man H.T., Simple reflection technique
for measuring the electro-optic coefficient of poled polymers,Applied Physics
Letters,1990,56(18),1734-1736.）Measure the maximum electricity of the preparation-obtained electro-optic polymer film after polarization
Backscatter extinction logarithmic ratio is 50pm/V.
Embodiment 7
The stability test of the electro-optical properties of electro-optic polymer film after the polarization of embodiment 6：
By the electro-optic polymer film heating after polarization to 85 DEG C of insulations, an electro-optic coefficient is tested at regular intervals,
Length of testing speech is 200 hours.Electro-optic polymer film after polarization, its electro-optical properties have preferable stability, are heated to 85
After DEG C, in more than 10 individual hours for most starting, slightly decaying occur in electro-optical properties, and electro-optic coefficient is held essentially constant thereafter, 85 DEG C
After placing 200 hours, the electro-optical properties of material remain to be maintained at 92% of initial value or so.Thus, prepared electro-optic polymer
Film can be as the materials'use of photoelectronics, and can be as the materials'use of integrated optics.
The stability curve of electro-optical properties is shown in Fig. 5.
Claims (11)
1. a kind of organic second order non-linear optical chromophore containing azido group, it is characterized in that, the having containing azido group
Machine second-order nonlinear optical chromophore has following structure：
Wherein, R1、R2It is independently the alkyl that carbon number is 1~10, or R1、R2It is all 3,3- dimethyl propyls, and R1、R2On
The carbon atom of 3 and the carbon atom bonding at phenyl ring amino ortho position；R3For alkyl azide；R4And R5It is simultaneously methyl or R4For trifluoro
Methyl, R5For phenyl；
The carbon number of alkyl in described alkyl azide is 1~20.
2. the organic second order non-linear optical chromophore according to claim 1 containing azido group, it is characterized in that：Described
The carbon number of alkyl in alkyl azide is 3~6.
3. a kind of synthetic method of the organic second order non-linear optical chromophore containing azido group described in claim 1 or 2, its
It is characterized in, described synthetic method comprises the following steps：
(1) organic second order non-linear optical chromophore electron donor raw material and haloalkyl alcohol are dissolved in anhydrous solvent, added
Dry potassium carbonate and phase transfer catalyst 18- crown ether -6 of catalytic amount, wherein, described organic second-order non-linear optical color development
The mol ratio of group's electron donor raw material and haloalkyl alcohol is 1：1~2, described potassium carbonate and described organic second-order non-linear
The mol ratio of optical chromophore electron donor raw material is 1.2~3:1；Under inert gas shielding at temperature is 55~150 DEG C
Reacted, anhydrous solvent decompression is steamed after being filtered to remove the solid after reacting in resulting solution, obtained residue is passed through
Pillar layer separation, obtain the organic second order non-linear optical chromophore electron donor containing alcoholic extract hydroxyl group；
(2) the organic second order non-linear optical chromophore electron donor containing alcoholic extract hydroxyl group for obtaining step (1) and nitrine phosphoric acid
Diphenyl ester is dissolved in dry anhydrous solvent, and -10~0 DEG C is cooled under inert gas shielding, adds 1,8- diazabicylos
11 carbon -7- alkene, are kept for 0.5~2 hour at -10~0 DEG C, are flowed back after then heating to reflux temperature, and backflow is completed
After remove anhydrous solvent under reduced pressure, by obtained residue through pillar layer separation, obtain the electron donor containing azido group；Wherein,
The mol ratio of organic second order non-linear optical chromophore electron donor and diphenyl phosphate azide containing alcoholic extract hydroxyl group is 1：1.2~
3；Organic second order non-linear optical chromophore electron donor containing alcoholic extract hydroxyl group rubs with the carbon -7- alkene of 1,8- diazabicylos 11
You are than being 1：1.2~3；
(3) electron donor containing azido group and electron acceptor obtained step (2) is dissolved in organic solvent, wherein, containing folded
The electron donor of nitrogen groups and the mol ratio of electron acceptor are 1：0.9~1, back flow reaction is carried out at a reflux temperature, or is being urged
In the presence of the pyridine of change amount, back flow reaction is carried out at a reflux temperature；Remove organic solvent after the completion of back flow reaction under reduced pressure, will
To crude product recrystallized in methyl alcohol, obtain the pure organic second order non-linear optical chromophore containing azido group；
Described organic second order non-linear optical chromophore electron donor raw material has the structure shown in formula III：
R1、R2It is independently the alkyl that carbon number is 1~10, or R1、R2It is all 3,3- dimethyl propyls, and R1、R2Upper 3
Carbon atom and the carbon atom bonding at phenyl ring amino ortho position；
Described electron acceptor is 2- dicyano methene -3- cyano group -4,5,5- trimethyls -2,5- dihydrofuran electron acceptors or three
The 2- dicyano methene -3- cyano group -4,5,5- trimethyl -2,5- dihydrofuran electron acceptors of fluorine substitution；
The carbon number of alkyl in described haloalkyl alcohol is 1~20.
4. synthetic method according to claim 3, it is characterized in that：The carbon number of alkyl in described haloalkyl alcohol
For 3~6.
5. synthetic method according to claim 4, it is characterized in that：Described haloalkyl alcohol is 6- Mecorals or 3- bromines third
Alcohol.
6. synthetic method according to claim 3, it is characterized in that：Anhydrous solvent described in step (1) is acetone or N,
Dinethylformamide；Anhydrous solvent described in step (2) is tetrahydrofuran or toluene；It is organic molten described in step (3)
Agent is methanol, ethanol or chloroform.
7. a kind of application of the organic second order non-linear optical chromophore containing azido group described in claim 1 or 2, its feature
It is：The described organic second order non-linear optical chromophore containing azido group and the polymer containing end-group alkyne is even by Huisgen
Connection reaction carries out Post functionalization, prepares the mounting type electrostrictive polymer finish containing organic second order non-linear optical chromophore molecule
Material；Gained mounting type polymer as electro-optical material is prepared into electro-optic polymer film and as the material in integrated optics or photoelectronics
Material uses；
The described polymer containing end-group alkyne is phenyl maleimide-(4- propynyloxy bases phenyl maleimide)-methyl-prop
E pioic acid methyl ester copolymer, it has following structure：
Wherein, x, y are respectively that phenyl maleimide-(4- propynyloxy bases phenyl maleimide)-methyl methacrylate is common
The mol ratio of phenyl maleimide and methyl methacrylate and 4- propynyloxy base phenyl maleimides in polymers, x ＞
0, y ＞ 0.
8. application according to claim 7, it is characterized in that：Described contains organic second order non-linear optical chromophore molecule
The preparation method of mounting type polymer as electro-optical material be：
Organic second order non-linear optical chromophore containing azido group, the polymer containing end-group alkyne are dissolved in N, N- dimethyl formyls
In amine, (triphenyl phosphorus) cuprous bromide of catalyst three and diisopropylethylamine are added, is entered at room temperature under inert gas shielding
Row stirring reaction；Wherein, it is contained in the organic second order non-linear optical chromophore containing azido group and the polymer containing end-group alkyne
The mol ratio of end-group alkyne is 1.5~2：1；Three (triphenyl phosphorus) cuprous bromides and contained end-group alkyne in the polymer containing end-group alkyne
Mol ratio is 0.1~0.3：1；In diisopropylethylamine and the polymer containing end-group alkyne the mol ratio of contained end-group alkyne for 0.5~
1:1；
The solution that reaction is completed to obtain afterwards is added in methanol, ether or water, obtains the solution containing precipitation；Suction filtration contains
The solution of precipitation obtains the crude product of the mounting type polymer containing organic second order non-linear optical chromophore molecule, will filter
To described mounting type polymer crude product in apparatus,Soxhlet's with methanol or extracted by ether into apparatus,Soxhlet's
Solution fades to colourless, obtains the mounting type polymer as electro-optical material containing organic second order non-linear optical chromophore molecule.
9. application according to claim 7, it is characterized in that：Described x is 10 >=x >=0.2, and described y is 20 >=y >=2.
10. the application according to claim 7 or 9, it is characterized in that, described phenyl maleimide-(4- propynyloxy base benzene
Base maleimide)-methylmethacrylate copolymer is prepared by following methods：
By phenyl maleimide, 4- propynyloxy bases phenyl maleimide, methyl methacrylate, the isobutyl of initiator azo two
Nitrile is dissolved in anhydrous DMF, is sealed after inert gas shielding；It is polymerize at being 65~70 DEG C in temperature
Reaction；Wherein：The dosage of azodiisobutyronitrile is phenyl maleimide, 4- propynyloxy base phenyl maleimides and methyl-prop
5th/3000 to thousand/1000ths of e pioic acid methyl ester gross mass, phenyl maleimide：4- propynyloxy base phenyl maleimides：First
The mol ratio of base methyl acrylate is x：1：Y, and x ＞ 0, y ＞ 0；After reaction to be polymerized terminates, resulting polymers solution is added
Into methanol, ether or water, the solution containing precipitation is obtained；Filter the solution containing precipitation and obtain phenyl maleimide-(4-
Propynyloxy base phenyl maleimide)-methylmethacrylate copolymer.
11. application according to claim 10, it is characterized in that：Described x is 10 >=x >=0.2, described y be 20 >=y >=
2。
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| CN109293643A (en) * | 2017-07-24 | 2019-02-01 | 中国科学院理化技术研究所 | Flexible spacer group modified organic second-order nonlinear optical chromophore, and preparation method and application thereof |
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| CN109438459B (en) * | 2018-11-26 | 2021-03-19 | 成都师范学院 | Organic second-order nonlinear optical chromophore and synthetic method and application thereof |
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