CN1137044A - Process for preparing polyimide having side chain with azo-functional group - Google Patents

Process for preparing polyimide having side chain with azo-functional group Download PDF

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CN1137044A
CN1137044A CN 96104966 CN96104966A CN1137044A CN 1137044 A CN1137044 A CN 1137044A CN 96104966 CN96104966 CN 96104966 CN 96104966 A CN96104966 A CN 96104966A CN 1137044 A CN1137044 A CN 1137044A
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aromatic ring
alkyl
aryl
thick
replacement
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CN1057782C (en
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沈玉全
麻洪
段晓芳
邱玲
张家新
翟剑锋
孟继本
陈萍
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沈玉全
麻洪
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Abstract

A process for preparing polyimide with high content of azo functional groups includes the reaction of polyaniline containing pendant group of phenylamine with micromolecular diazonium salt, or the reaction of polydiazonium salt containing pendant group of diazonium salt with micromolecular substituted phenylamine, or the reaction of polyaniline containing pendant group of phenylamine with polydiazonium-salt containing pendant group of diazonium salt, and imidization to obtain said polyimide with azo functional groups on side chain, used as excellent optical material, and features high polymerization degree and 100% content of azo pendant group.

Description

A kind of preparation method of polyimide of side chain with azo-functional group
The present invention relates to the preparation method of a kind of preparation method's of polyimide, particularly a kind of side chain with azo-functional group polyimide.
The polyimide that has the azo side group with response characteristics to light, second-order transition temperature height, chemical stability and Heat stability is good, thereby on electro-optic waveguide devices, optical information recording, photochromic and other optically functional device, important use is arranged.For example, coat the film that obtains with this material, functional group dipole wherein is behind electric field polarization, can in 300～2000nm hertzian wave scope, produce second harmonic and Electro-optical Modulation, thereby be the necessary raw material that is produced on the electrooptic modulator that extensive use is arranged in telecommunications, telecommunication and the jeep.
At present, synthesize the polyimide material that on side chain, has functional group two kinds of approach arranged:
(1)
Figure A9610496600091
As mentioned above, synthetic earlier the light functionally active small molecules (DAFG) that has two hydroxyls with push-and-pull electron substituent group group, with 4-acid chloride group phthalic anhydride, obtain containing the dianhydride of photoresponse active function group, then further with the diamine reactant synthesis of polyimides.
As mentioned above, the characteristics of this method are that the DAFG group is received two amine moieties.
The route of synthesis of described two kinds of synthesis of polyimides, all be earlier with substituted aniline and corresponding diazonium salt after diazo coupling reaction, the small molecules dianhydride of the resulting DAFG of containing or diamines obtain polyimide again with diamines or two anhydride reactants.The shortcoming of this synthetic route is: have the dianhydride of DAFG functional group or diamines influences final formed polymkeric substance in polymerization process the polymerization degree, and the polymerization degree is vital for film forming properties.In addition, in other polymkeric substance (as polymethylmethacrylate, polystyrene) and the diazonium salt coupling resulting polymers the highest of the content of azo side group about 50～60%.
The purpose of this invention is to provide that a kind of polymerization degree that can make polymkeric substance obviously improves and the content that makes the azo side group up to the preparation method of 100% polyimide.
The preparation method of polyimide of the present invention be make the aniline side group be bonded in dianhydride or (with) polyaniline and the small molecules diazonium salt of the band aniline side group of two amine moieties carry out coupling, and then carry out imidization and handle.Chemical equation is as follows:
Figure A9610496600102
Or
Figure A9610496600112
Or
Figure A9610496600113
Figure A9610496600114
Or
Figure A9610496600115
Wherein Ar is: aromatic ring, thick aromatic ring, hetero-aromatic ring, assorted thick aromatic ring, replace aromatic ring, replace thick aromatic ring, replace hetero-aromatic ring or replace assorted thick aromatic ring;
Ar ' is: same Ar; Ar " be:
Figure A9610496600121
Or
R 1, R 2Represent H, F, alkyl or fluoro-alkyl; R 3Represent alkyl, fluoro-alkyl, aryl, heteroaryl, thick aryl or assorted thick aryl; A is :-NO 2,-CN,
Figure A9610496600123
-COOR, -PO (R) 3,-PO (OR) 3Or-CX 1=CX 2X 3X 1, X 2, X 3Represent H ,-NO 2,-CN,
Figure A9610496600125
-COOR,
Figure A9610496600126
-PO (R) 3, or-PO (OR) 3R represents H, alkyl or aryl;
X -For: BF 4 -, PF 6 -Or Cl -
Solvent is: N, and the binary mixed solvent system of dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, acetonitrile, acetone, methyl alcohol or they and formic acid or acetate, the content of acetate and formic acid can change 0～100%.
The preparation method of another kind of polyimide of the present invention is: make the diazonium salt side group be bonded in dianhydride or (with) the poly-diazonium salt that contains the diazonium salt side group and the small molecules substituted aniline of two amine moieties carry out diazo coupling, and then carry out imidization and handle.Chemical equation is as follows:
Figure A9610496600131
Or
Figure A9610496600133
Or
Figure A9610496600135
Or Wherein Ar, Ar ', Ar ", A, X -The same with solvent.A ' is:
Figure A9610496600142
Or
Figure A9610496600143
R ', R " are: H, alkyl or aryl.
The preparation method of another kind of polyimide of the present invention makes the aniline side group be bonded in the polyaniline that contains the aniline side group of dianhydride or two amine moieties and the poly-diazonium salt that contains the diazonium salt side group that the diazonium salt side group is bonded in dianhydride or two amine moieties carries out coupling, and then carries out imidization and handle.
Chemical equation is as follows:
Figure A9610496600151
Wherein Ar, Ar ', Ar ", A, X -, " and solvent is the same for A ', R ', R.
In the preparation method of polyimide of the present invention, the imidization of polyamic acid is handled and can also be carried out like this, the solution of polyamic acid and solvent is reacted with acetic anhydride and triethylamine under stirring condition, at room temperature stirred 2 hours, and then in methyl alcohol, precipitate, obtain red precipitate, in vacuum drying oven under 80 ℃ of conditions dry 5 hours, obtain the polyimide of good filming performance.
The preparation method of polyimide of the present invention has changed synthetic route in the past, impels that diazo coupling reaction is very easy carries out, thereby has not only improved the polymerization degree of polyimide, but also makes the content of its azo side group be up to 100%.
This synthetic method has changed common diazonium coupling and has been reflected at the restriction of carrying out in the aqueous solution, has realized carrying out the diazonium coupling reaction of above-mentioned polyaniline or poly-diazonium salt in non-aqueous system, and has obtained good result.
The preparation method of polyimide of the present invention is fit to the synthetic of various functional group content other series of polymers material high, band azo side group equally.
Below by embodiment the present invention is described further.
Embodiment 1
Synthetic at the polyimide of two amine moiety band azo side groups
At room temperature, to containing glycol, triphenyl phosphorus (Ph 3P) and drip the tetrahydrofuran solution of ethyl azodicaboxylate (DEAD) in the tetrahydrofuran solution of phthalic imidine, stirring is spent the night, and adds a small amount of tetrahydrofuran (THF) again, suction filtration, and the gained solid matter is recrystallization in chloroform, ethane mixed solvent; Get crystal and be dissolved in the tetrahydrofuran (THF), and add hydrazine hydrate, after nitrogen atmosphere flows through night next time, be chilled to room temperature; Tell the tetrahydrofuran (THF) layer and concentrate gained diamines crude product recrystallization in the chloroform/methanol mixed solvent.Again under room temperature, logical nitrogen and agitation condition, in N-Methyl pyrrolidone (NMP) solution of the above-mentioned diamines that makes, add pyromellitic dianhydride (PMDA) in two batches, and remaining PMDA is flushed in the reaction mixture with small amount of N-crassitude ketone solvent, at room temperature stirred 5 hours, and obtained polyaniline polyamic acid performed polymer.Then under-10 ℃ of temperature and vigorous stirring, in the solution of Glacial acetic acid (the HAc)/dimethyl formamide (DMF) of the polyamic acid performed polymer of the two amine moiety band aniline side groups that make, add p-nitrophenyl diazonium a tetrafluoro borate and sodium-acetate simultaneously, stirred 5 hours under the room temperature, again under vigorous stirring, the above-mentioned red solution that makes dripped in the water precipitate, suction filtration, and wash precipitation with water for several times, after the room temperature vacuum-drying, get red solid, be the polyamic acid of band azo side group functional group, its azo side group content is 100%.Under the condition of logical nitrogen, heating was carried out imidization in 30 minutes in 200 ℃ of temperature, made purpose product polyimide with red solid in continuation.Chemical equation is as follows;
Figure A9610496600171
Embodiment two
Synthetic at the polyimide of two anhydride component band azo side groups
Preparation is in the process similar embodiment 1 of the polyamic acid of two anhydride component band azo side groups, and its imidization process is as follows: will contain the azo side group polyamic acid N-Methyl pyrrolidone solution under agitation with acetic anhydride (A C2O) and triethylamine (E T3N) reaction was at room temperature stirred 2 hours, precipitated in methyl alcohol, got red precipitate, filtered, and solid is in loft drier, and drying is 5 hours under 80 ℃ of temperature, the polyimide that obtains having the good filming performance.Chemical equation is as follows:
Figure A9610496600181
Embodiment three
Synthetic at the polyimide of two amine moiety band diazonium salt side groups
Under 25 ℃ of temperature, in the tetrahydrofuran solution of acetamido benzene sulfonyl chloride, drip the tetrahydrofuran solution of trolamine and pyridine, stir suction filtration after 24 hours, tell solid recrystallization in ethanol.Change the glycol of gained into diamines with the method for embodiment 1, carry out polymerization with two anhydride reactants again, and then handle through diazotization and imidization and to obtain the purpose product.
Chemical equation is as follows:
Figure A9610496600191

Claims (10)

1, a kind of preparation method of polyimide of side chain with azo-functional group after polyaniline that contains the aniline side group that it is characterized in that making the aniline side group be bonded in dianhydride and/or two amine moieties and small molecules diazonium salt carry out coupling, carries out imidization and handles.
2, method as claimed in claim 1 is characterized in that described reaction undertaken by following formula:
Figure A9610496600021
Or
Figure A9610496600022
Figure A9610496600023
Or
Figure A9610496600024
Figure A9610496600031
Or
Wherein Ar is: aromatic ring, thick aromatic ring, hetero-aromatic ring, assorted thick aromatic ring, the aromatic ring of replacement, the thick aromatic ring of replacement, the hetero-aromatic ring of replacement or the assorted thick aromatic ring of replacement;
Ar ' is: same Ar; Ar " be:
Figure A9610496600033
Or
Figure A9610496600034
R 1, R 2Represent H, F, alkyl or fluoro-alkyl; R 3Represent alkyl, fluoro-alkyl, aryl, heteroaryl, thick aryl or assorted thick aryl; A is :-NO 2,-CN, -COOR,
Figure A9610496600036
-PO (R) 3,-PO (OR) 3, or-CX 1=CX 2X 3X 1, X 2, X 3Represent H ,-NO 2,-CN, -COOR,
Figure A9610496600042
-PO (R) 3, or-PO (OR) 3R represents H, alkyl or aryl;
X -For: BF 4 -, PF 6 -Or Cl -A ' is:
Figure A9610496600043
Or
R ', R " are: H, alkyl or aryl.
3,, it is characterized in that diazo coupling reaction carries out in the presence of-10 ℃ to 50 ℃ temperature and sodium-acetate and solvent as the method for claim 1 or 2.
4, a kind of preparation method of polyimide of side chain with azo-functional group, it is characterized in that making the diazonium salt side group be bonded in dianhydride or/and the poly-diazonium salt that contains the diazonium salt side group and the small molecules substituted aniline of two amine moieties carry out diazo coupling, and then carry out imidization and handle.
5, method as claimed in claim 4 is characterized in that described reaction undertaken by following formula: Or
Figure A9610496600046
Figure A9610496600051
Or Or
A wherein rFor: aromatic ring, thick aromatic ring, hetero-aromatic ring, assorted thick aromatic ring, the aromatic ring of replacement, the thick aromatic ring of replacement, the hetero-aromatic ring of replacement or the assorted thick aromatic ring of replacement;
Ar ' is: same Ar; Ar " be: Or
R 1, R 2Represent H, F, alkyl or fluoro-alkyl; R 3Represent alkyl, fluoro-alkyl, aryl, heteroaryl, thick aryl or assorted thick aryl; A is :-NO 2,-CN, -COOR, -PO (R) 3,-PO (OR) 3, or-CX 1=CX 2X 3X 1, X 2, X 3Represent H ,-NO 2,-CN, -COOR,
Figure A9610496600066
-PO (R) 3, or-PO (OR) 3R represents H, alkyl or aryl; X -For: BF 4 -, PF 6 -Or Cl -A ' is:
Figure A9610496600067
Or
Figure A9610496600068
R ', R " are: H, alkyl or aryl.
6,, it is characterized in that diazo coupling reaction carries out in the presence of-10 ℃ to 50 ℃ temperature and sodium-acetate and solvent as the method for claim 4 or 5.
7, a kind of preparation method of polyimide of side chain with azo-functional group, the poly-diazonium salt that contains the diazonium salt side group that polyaniline that contains the aniline side group that it is characterized in that making the aniline side group be bonded in dianhydride or two amine moieties and diazonium salt side group are bonded in dianhydride or two amine moieties carries out coupling, and then carries out imidization and handle.
8, method as claimed in claim 7 is characterized in that reacting and is undertaken by following formula:
A wherein rFor: aromatic ring, thick aromatic ring, hetero-aromatic ring, assorted thick aromatic ring, the aromatic ring of replacement, the thick aromatic ring of replacement, the hetero-aromatic ring of replacement or the assorted thick aromatic ring of replacement;
Ar ' is: same Ar; Ar " be:
Figure A9610496600081
Or
R 1, R 2Represent H, F, alkyl or fluoro-alkyl; R 3Represent alkyl, fluoro-alkyl, aryl, heteroaryl, thick aryl or assorted thick aryl; A is :-NO 2,-CN,
Figure A9610496600083
-COOR, -PO (R) 3,-PO (OR) 3, or-CX 1=CX 2X 3X 1, X 2, X 3Represent H ,-NO 2,-CN, -COOR,
Figure A9610496600086
-PO (R) 3, or-PO (OR) 3R represents H, alkyl or aryl; X -For: BF 4 -, PF 6 -Or Cl -A ' is:
Figure A9610496600087
Or
Figure A9610496600088
R ', R " are: H, alkyl or aryl.
9,, it is characterized in that coupled reaction carries out in the presence of-10 ℃ to 50 ℃ temperature and sodium-acetate and solvent as the method for claim 7 or 8.
10, as claim 3,6 or 9 method, it is characterized in that described solvent is N, the binary mixed solvent system of dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, acetonitrile, acetone, methyl alcohol or they and formic acid or acetate.
CN96104966A 1996-05-10 1996-05-10 Process for preparing polyimide having side chain with azo-functional group Expired - Fee Related CN1057782C (en)

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CN106939081A (en) * 2017-05-04 2017-07-11 长沙新材料产业研究院有限公司 A kind of side-chain polyimide material and its preparation method and application

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US4022927A (en) * 1975-06-30 1977-05-10 International Business Machines Corporation Methods for forming thick self-supporting masks
JPS5560526A (en) * 1978-10-31 1980-05-07 Res Inst For Prod Dev Viscosity control of high polymer solution with light irradiation
JPH0813886B2 (en) * 1988-03-01 1996-02-14 三菱化学株式会社 Process for producing azo group-containing polymer
JPH0720514A (en) * 1993-06-30 1995-01-24 Osaka Gas Co Ltd Nonlinear optical material
JP3050028B2 (en) * 1993-12-28 2000-06-05 日本電気株式会社 Encryption key generation circuit for multiple remainder encryption
JP3529533B2 (en) * 1995-07-07 2004-05-24 株式会社ショーワ Work gripping mechanism of plating equipment

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CN106939081A (en) * 2017-05-04 2017-07-11 长沙新材料产业研究院有限公司 A kind of side-chain polyimide material and its preparation method and application
CN106939081B (en) * 2017-05-04 2019-03-15 长沙新材料产业研究院有限公司 A kind of side-chain polyimide material and its preparation method and application

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