CN100540529C - Azo monomer and polymkeric substance with third order non-linear optical property - Google Patents
Azo monomer and polymkeric substance with third order non-linear optical property Download PDFInfo
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- CN100540529C CN100540529C CNB2006101559719A CN200610155971A CN100540529C CN 100540529 C CN100540529 C CN 100540529C CN B2006101559719 A CNB2006101559719 A CN B2006101559719A CN 200610155971 A CN200610155971 A CN 200610155971A CN 100540529 C CN100540529 C CN 100540529C
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Abstract
The invention discloses a kind of azo monomer and polymkeric substance thereof with third order non-linear optical property, it is by substituting group aniline and phenol are obtained azo intermediate by diazonium-coupled reaction, obtain containing the acrylic ester monomer of functional azo group again with the reaction of (methyl) acrylate chloride, and adopt atom transfer radical polymerization (ATRP) method to obtain azo side chain type polymkeric substance.This polymkeric substance has good third order non-linear optical property, and film-forming properties is better.
Description
Technical field
The present invention relates to a kind of azo-compound and polymkeric substance thereof, be specifically related to a kind of azo-compound and polymkeric substance thereof with third-order nonlinear optical characteristic, and the method for preparing this polymkeric substance with atom transfer radical polymerization method.
Background technology
In recent years, the research of polymkeric substance nonlinear optical material more and more is subjected to people's attention.Because compare with organic non linear optical material with inorganic, polymkeric substance has its advantageous advantage, the advantages such as it is big except the nonlinear optical coefficients of having inherited the organic molecule nonlinear optical material, response speed fast, the direct current specific inductivity is low, because its molecular chain connects with covalent linkage, therefore physical strength height, the chemical stability of material are good, processing characteristics is good, can make different shape according to service requirements, as film, sheet, fiber etc.
The method of synthetic polymer nonlinear optical material has a lot, as Appl.Phys.Lett.1986, and 49, reported p.248 that Singer etc. mixes the Red-1 200 dyestuff to obtain the higher host and guest's three-dimensional polymer of nonlinear factor among the PMMA; Polymer, 2000,41 (16), p.6049 reported that chromophore's stilbene dye that Samyn etc. will have high second harmonic (SHG) characteristic is connected on the poly-bismaleimides, obtain second-order transition temperature and be 178 ℃～228 ℃ side chain type non-linear polymer Macromolecules, 1997,30, p.4584-4589 reported that Tsutsumi etc. is connected on the polyurethane backbone T-type polymkeric substance that synthesising stability is good with the chromophore that contains nitrogen benzide.Domestic research about this respect is relative less with report.This is wherein the most representative to be by diazonium-coupled reaction the azo chromophore to be introduced in the polymer lateral chain.Because azo-compound particularly aromatic azo compound itself has bigger conjugated system, the electronics good fluidity helps producing non-linear optical effect, aspect light conversion and the optical storage good prospects for application is being arranged all.Yet, in the present report, normally azo-compound is got on by the side chain that back diazonium-coupled reaction is grafted to polymkeric substance, and since the restriction of percentage of grafting in the reaction process, the polymer properties of acquisition, and particularly its non-linear optical property is affected.
Thereby, seek a kind of new method and prepare azo polymer, to such an extent as to, be the focus that those skilled in the art pay close attention to solve in the prior art because of the affected problem of the not high polymer performance of functional group content in the polymer chain that percentage of grafting was caused.
Summary of the invention
The object of the invention provides the good azo-compound of a kind of third order non-linear optical property, and to provide with it be polymer of monomers, to such an extent as to solve because of the affected problem of the not high polymer performance of functional group content in the polymer chain that percentage of grafting was caused.
For achieving the above object, the technical solution used in the present invention is: a kind of azo monomer with third order non-linear optical property, represent by following general formula (I):
In the formula, R represents nitro, cyano group, chlorine, bromine, methoxyl group, carboxyl or sulfonic group, R ' expression hydrogen or methyl.
A kind of azo polymer with third order non-linear optical property, represent by following general formula (II):
In the formula, R represents nitro, cyano group, chlorine, bromine, methoxyl group, carboxyl or sulfonic group, R ' expression hydrogen or methyl, and n is 10～50 integer.
Wherein, the monomeric preparation method of general formula (I) expression may further comprise the steps, with molar ratio computing:
A. prepare diazonium salt solution to substituting group aniline, described to substituting group aniline be selected from p-Nitroaniline, to cyano-aniline, p-Chlorobenzoic acid amide, para-bromoaniline, P-nethoxyaniline, to carboxyl aniline or p-sulfonic acid base aniline;
B. with phenol coupling reagent, under weakly alkaline, carry out diazo coupling reaction, the weakly alkaline solution of phenol places ice bath to cool off, stirring the diazonium salt solution that down step a is obtained splashes into, keep temperature of reaction to be lower than 10 ℃, dropwise and continue to stir 1～2 hour, be incubated 2～4 hours again, obtain azo intermediate with the reaction solution suction filtration and with deionized water wash;
C. getting a dried azo intermediate dissolves in the tetrahydrofuran (THF), add 1～2 part triethylamine, drip (methyl) acrylate chloride of 2～3 parts, under ice bath, reacted 1～3 hour, reacted at normal temperatures again 4～6 hours, and extracted from reaction solution with chloroform and obtain required monomer.
In the technique scheme, among the step a, the preparation of diazonium salt solution is a prior art, for example, portion can be made hydrochloride solution to substituting group aniline cools off in ice bath, stir 15～20% the sodium nitrite in aqueous solution that drips 1.1～1.2 parts down, drip off the back and continue to stir and promptly obtain diazonium salt solution half an hour.Diazo coupling reaction among the step b is carried out under weakly alkaline, generally makes reaction solution be weakly alkaline by adding NaOH solution.Among the step c, triethylamine is attached sour agent.
The preparation method of the polymkeric substance of general formula (II) expression, the compound that adopts general formula (I) expression is as monomer, adding is with 0.5～5% initiator of molar ratio computing monomer consumption, 0.5～5% catalyzer and 0.5～10% part, after stirring, solubilizing agent eliminates oxygen in the polymerizing pipe, tube sealing, put and carry out atom transition free radical polymerization reaction in the oil bath, oil bath temperature is 80-120 ℃, reaction times 1-5 days, do the precipitating agent with methyl alcohol and separate out polymkeric substance, remove residual monomer with methanol wash again, promptly get required polymkeric substance.
In the technique scheme, described initiator is selected from alpha-brominated ethyl isobutyrate, benzyl chlorine, to chloromethyl benzoic acid or 5-chloromethyl-2-methoxybenzaldehyde; Described catalyzer is selected from cuprous chloride or cuprous bromide; Described part is selected from pentamethyl--diethylenetriamine or 2,2 '-dipyridyl.
Described solvent is selected from pimelinketone, N, N '-dimethyl formamide, methyl-phenoxide, toluene or acetone.
Above-mentioned preparation method can be expressed as follows:
R＝-NO
2，-CN，-Cl，-Br，-OCH
3，COOH，SO
3H R′＝-H，-CH
3
Preferred manufacturing procedure can be: portion is made hydrochloride solution to substituting group aniline, cool off the 15-20% sodium nitrite in aqueous solution of 1.1～1.2 parts of back agitation and dropping in ice bath, continuation is stirred and is promptly obtained diazonium salt solution half an hour after dripping off.Equimolar phenol is dissolved in 10～20% the aqueous sodium hydroxide solution, puts in the ice bath and cool off, stir down above-mentioned diazonium salt is slowly splashed into, keep temperature of reaction＜10 ℃.Dropwise and continue to stir 1～2 hour, be incubated 2-4 hour, the reaction solution suction filtration is also obtained azo intermediate with a large amount of deionized water wash; Dried azo intermediate is dissolved in the tetrahydrofuran (THF), add 1～2 part triethylamine, drip (methyl) acrylate chloride of 2～3 parts, under ice bath, reacted 1～3 hour, reacted at normal temperatures again 4～6 hours.Extract from reaction solution with chloroform and to obtain monomer.Take by weighing monomer, initiator, catalyzer and part by above-mentioned setting proportioning, eliminate oxygen in the polymerizing pipe after solubilizing agent stirs, tube sealing is put and is reacted 1～5 day in the oil bath, and oil bath temperature is 80～120 ℃.Do the precipitating agent with methyl alcohol and separate out polymkeric substance, remove residual monomer with a large amount of methanol wash again.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention has obtained a kind of polymer monomer that can be used for preparing homopolymer, thereby, obtain polymkeric substance by the functional monomer homopolymerization, each link units all contains the azo side chain in the resulting polymers chain, and polymkeric substance shows higher macroscopic third-order nonlinear susceptibility coefficient;
2. the main polymer chain that obtains of the present invention is an acrylate, and polymkeric substance performance good solubility and film-forming properties show higher third-order nonlinear susceptibility coefficient after making film, also provide the basis for its application on optics;
3. substituting group can produce different electronic effects on the azobenzene group by changing, thus the third order non-linear optical property of energy telomerized polymer;
4. realize polymerization by atom transfer radical polymerization method, the resulting polymers molecular weight is controlled, narrow molecular weight distribution, and can be used as macromole evocating agent and carry out the polymkeric substance of polyreaction such as further block with synthetic more excellent performance.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
Get the 2-3g p-Nitroaniline and make hydrochloride solution, put ice bath cooling back and drip 15-20% sodium nitrite in aqueous solution 10g, under ice bath, react half an hour, obtain the p-Nitroaniline diazonium salt solution.Get phenol 2g, sodium hydroxide 2g, add 100g water stirring and dissolving, put in the ice bath and cool off, drip above-mentioned diazonium salt solution, reaction is 4 hours under ice bath.Filter and wash and obtain the nitro-azo intermediate with massive laundering.The third-order nonlinear susceptibility coefficient that records a sample of this intermediate with the four-wave mixing method is 4.87 * 10
-12Esu.
Get nitro-azo intermediate 2-3g, be dissolved in the 40ml tetrahydrofuran (THF), add the 2ml triethylamine, under ice bath, stir.Get the 1-2g acrylate chloride and slowly be added drop-wise in the above-mentioned solution, reaction continued to stir at normal temperatures 4 hours after 1 hour under ice bath.Reaction solution obtains the nitro-azo monomer with chloroform extraction and recrystallization.The third-order nonlinear susceptibility coefficient that records this monomeric sample with the four-wave mixing method is 5.59 * 10
-12Esu.
In polymerizing pipe, add nitro-azo monomer 150-180mg; take by weighing other batching according to proportioning to nitro-azo monomer/alpha-brominated ethyl isobutyrate/cuprous bromide/pentamethyl--diethylenetriamine=40-60/1/1/1; add pimelinketone 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is two days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 3896, and molecular weight distribution is 1.28; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 6.86 * 10
-12Esu.
In polymerizing pipe, add nitro-azo monomer 300-360mg; take by weighing other batching according to proportioning to nitro-azo monomer/alpha-brominated ethyl isobutyrate/cuprous bromide/pentamethyl--diethylenetriamine=80-120/1/1/1; add pimelinketone 2-4ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is two days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 5012, and molecular weight distribution is 1.30; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 7.43 * 10
-12Esu.
Embodiment two:
Get the 2-3g P-nethoxyaniline and make hydrochloride solution, put ice bath cooling back and drip 15-20% sodium nitrite in aqueous solution 10g, under ice bath, react half an hour, obtain the P-nethoxyaniline diazonium salt solution.Get phenol 2g, sodium hydroxide 2g, add 80-100g water stirring and dissolving, put in the ice bath and cool off, drip above-mentioned diazonium salt solution, reaction is 4 hours under ice bath.Filter and obtain the methoxyl group azo intermediate with a large amount of deionized water wash.The third-order nonlinear susceptibility coefficient that records a sample of this intermediate with the four-wave mixing method is 4.16 * 10
-12Esu.
Get methoxyl group azo intermediate 2-3g, be dissolved in the 20-30ml tetrahydrofuran (THF), add the 2-3ml triethylamine, under ice bath, stir.Get the 1-2g acrylate chloride and slowly be added drop-wise in the above-mentioned solution, reaction continued to stir at normal temperatures 4 hours after 1 hour under ice bath.Reaction solution obtains the methoxyl group azo monomer with chloroform extraction and recrystallization.The third-order nonlinear susceptibility coefficient that records this monomeric sample with the four-wave mixing method is 5.76 * 10
-12Esu.
In polymerizing pipe, add methoxyl group azo monomer 130-160mg; proportioning according to monomer/alpha-brominated ethyl isobutyrate/cuprous bromide/pentamethyl--diethylenetriamine=40-60/1/1/1 takes by weighing other batching; add pimelinketone 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is 2 days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 4348, and molecular weight distribution is 1.29; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 7.04 * 10
-12Esu.
In polymerizing pipe, add methoxyl group azo monomer 130-160mg; by the monomer/proportioning of chloromethyl benzoic acid/cuprous chloride/pentamethyl--diethylenetriamine=40-60/1/1/1 is taken by weighing other batching; add pimelinketone 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is two days in the rearmounted 108-112 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 4564, and molecular weight distribution is 1.26; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 7.18 * 10
-12Esu.
Embodiment three:
Get the 3-4g para-bromoaniline and make hydrochloride solution, put ice bath cooling back and drip 15-20% sodium nitrite in aqueous solution 10g, reaction obtains the para-bromoaniline diazonium salt solution half an hour under ice bath.Get phenol 2g, sodium hydroxide 2g, add the 80-100g water dissolution, put in the ice bath and cool off, drip above-mentioned diazonium salt solution, reaction is 4 hours under ice bath.Filter and obtain the bromine azo intermediate with a large amount of deionized water wash.The third-order nonlinear susceptibility coefficient that records a sample of this intermediate with the four-wave mixing method is 4.36 * 10
-12Esu.
Get bromine azo intermediate 3-4g, be dissolved in the 30-40ml tetrahydrofuran (THF), add the 2-3ml triethylamine, under ice bath, stir evenly.Get the 1-2g acrylate chloride and slowly be added drop-wise in the above-mentioned solution, reaction was stirred 4 hours after 1 hour at normal temperatures under ice bath.Reaction solution obtains the bromine azo monomer with chloroform extraction and recrystallization.The third-order nonlinear susceptibility coefficient that records this monomeric sample with the four-wave mixing method is 5.67 * 10
-12Esu.
In polymerizing pipe, add bromine azo monomer 170-200mg; proportioning according to monomer/alpha-brominated ethyl isobutyrate/cuprous bromide/pentamethyl--diethylenetriamine=40-60/1/1/1 takes by weighing other batching; add pimelinketone 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is two days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 4502, and molecular weight distribution is 1.32; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 6.92 * 10
-12Esu.
In polymerizing pipe, add bromine azo monomer 170-200mg; proportioning according to monomer/alpha-brominated ethyl isobutyrate/cuprous bromide/dipyridyl=40-60/1/1/1 takes by weighing other batching; add pimelinketone 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is 4 days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 4103, and molecular weight distribution is 1.23; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 6.92 * 10
-12Esu.
Embodiment four:
Get the 2-3g p-Nitroaniline and make the rearmounted ice bath cooling of diazonium salt solution, drip 15-20% sodium nitrite in aqueous solution 10g, reaction obtains the p-Nitroaniline diazonium salt solution half an hour under ice bath.Get phenol 2g, sodium hydroxide 2g, add the 80-100g water dissolution, put in the ice bath and cool off, drip above-mentioned diazonium salt solution, reaction is 4 hours under ice bath.Filter and wash and obtain the nitro-azo intermediate with massive laundering.The third-order nonlinear susceptibility coefficient that records a sample of this intermediate with the four-wave mixing method is 4.87 * 10
-12Esu.
Get nitro-azo intermediate 2-3g, be dissolved in the 30-40ml tetrahydrofuran (THF), add the 2-3ml triethylamine, under ice bath, stir evenly.Get the 1-2g methacrylic chloride and slowly be added drop-wise in the above-mentioned solution, reaction continued to stir at normal temperatures 4 hours after 1 hour under ice bath.Reaction solution obtains the nitro-azo monomer with chloroform extraction and recrystallization.Recording this monomeric third-order nonlinear susceptibility coefficient with the four-wave mixing method is 5.64 * 10
-12Esu.
In polymerizing pipe, add nitro-azo monomer 160-190mg; proportioning according to monomer/benzyl chlorine/cuprous chloride/pentamethyl--diethylenetriamine=40-60/1/1/1 takes by weighing other batching; add pimelinketone 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is two days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 4231, and molecular weight distribution is 1.30; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 6.98 * 10
-12Esu.
In polymerizing pipe, add nitro-azo monomer 160-190mg; proportioning according to monomer/benzyl chlorine/cuprous chloride/dipyridyl=40-60/1/1/1 takes by weighing other batching; add N; N '-dimethyl formamide 1-2ml; remove middle oxygen and inflated with nitrogen protection although stir evenly the back, reaction is four days in the rearmounted 98-102 ℃ of oil bath of tube sealing.Polymer fluid obtains polymerisate with methyl alcohol precipitating and washing, suction filtration oven dry.The molecular weight that is recorded a sample of this polymkeric substance by gel permeation chromatography is 3865, and molecular weight distribution is 1.32; Recording its third-order nonlinear susceptibility coefficient by the four-wave mixing method is 6.74 * 10
-12Esu.
Claims (5)
1. azo monomer with third order non-linear optical property, represent by following general formula (I):
In the formula, R represents nitro, cyano group, chlorine, bromine, methoxyl group, carboxyl or sulfonic group, R ' expression hydrogen or methyl.
2. azo polymer with third order non-linear optical property, represent by following general formula (II):
In the formula, R represents nitro, cyano group, chlorine, bromine, methoxyl group, carboxyl or sulfonic group, R ' expression hydrogen or methyl, and n is 10～50 integer.
3. the described monomeric preparation method of claim 1, this method may further comprise the steps, with molar ratio computing:
A. prepare diazonium salt solution to substituting group aniline, described to substituting group aniline be selected from p-Nitroaniline, to cyano-aniline, p-Chlorobenzoic acid amide, para-bromoaniline, P-nethoxyaniline, to carboxyl aniline or p-sulfonic acid base aniline;
B. with phenol coupling reagent, under weakly alkaline, carry out diazo coupling reaction, the weakly alkaline solution of phenol places ice bath to cool off, stirring the diazonium salt solution that down step a is obtained splashes into, keep temperature of reaction to be lower than 10 ℃, dropwise and continue to stir 1～2 hour, be incubated 2～4 hours again, obtain azo intermediate with the reaction solution suction filtration and with deionized water wash;
C. getting a dried azo intermediate dissolves in the tetrahydrofuran (THF), add 1～2 part triethylamine, drip (methyl) acrylate chloride of 2～3 parts, under ice bath, reacted 1～3 hour, reacted at normal temperatures again 4～6 hours, and extracted from reaction solution with chloroform and obtain required monomer.
4. the preparation method of the described polymkeric substance of claim 2, it is characterized in that: adopt the described monomer of claim 1, adding is with 0.5～5% initiator of molar ratio computing monomer consumption, 0.5～5% catalyzer and 0.5～10% part, after stirring, solubilizing agent eliminates oxygen in the polymerizing pipe, tube sealing, put and carry out atom transition free radical polymerization reaction in the oil bath, oil bath temperature is 80-120 ℃, reaction times 1-5 days, do the precipitating agent with methyl alcohol and separate out polymkeric substance, remove residual monomer with methanol wash again, promptly get required polymkeric substance; Described initiator is selected from alpha-brominated ethyl isobutyrate, benzyl chlorine, to chloromethyl benzoic acid or 5-chloromethyl-2-methoxybenzaldehyde; Described catalyzer is selected from cuprous chloride or cuprous bromide; Described part is selected from pentamethyl--diethylenetriamine or 2,2 '-dipyridyl.
5. the preparation method of polymkeric substance according to claim 4, it is characterized in that: described solvent is selected from pimelinketone, N, N '-dimethyl formamide, methyl-phenoxide, toluene or acetone.
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| CN101805421B (en) * | 2010-03-12 | 2011-12-21 | 江苏大学 | Preparation method of azobenzene optical rotation polymer polyacrylate |
| JP5566160B2 (en) * | 2010-03-31 | 2014-08-06 | 富士フイルム株式会社 | Liquid crystal compound, liquid crystal composition, light absorption anisotropic film, and liquid crystal display device |
| CN102432497A (en) * | 2011-09-23 | 2012-05-02 | 北京化工大学 | Synthesis and application of bis-o-substituted acrylate azobenzene containing intramolecular hydrogen bonds |
| CN104262191B (en) * | 2014-08-21 | 2016-06-15 | 上海东升新材料有限公司 | Azo amides, its preparation method and the application as polymerization starter |
| CN108864332B (en) * | 2017-05-09 | 2020-09-04 | 天津大学 | Linear double-branched azobenzene polymer and preparation method and application thereof |
| CN110305038B (en) * | 2019-07-18 | 2022-06-24 | 郑州大学 | 4-aminomethyl isophthalate-2, 3-dimethyl azobenzene and preparation method and application thereof |
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