CN100503595C - Second-order non-linear optical polymer containing azo and thiophene ring, and its synthesizing method and use - Google Patents
Second-order non-linear optical polymer containing azo and thiophene ring, and its synthesizing method and use Download PDFInfo
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- CN100503595C CN100503595C CNB2005100113072A CN200510011307A CN100503595C CN 100503595 C CN100503595 C CN 100503595C CN B2005100113072 A CNB2005100113072 A CN B2005100113072A CN 200510011307 A CN200510011307 A CN 200510011307A CN 100503595 C CN100503595 C CN 100503595C
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Abstract
The present invention relates to a second-order non-linear optical polymer containing azo and thiophene rings and a synthetic method thereof, the polymer has the following structure, and the present iThe invention relates second nonlinear optics polymer and its synthetic method, and cross linking polyurethanes polymer or polarizing polymer film. It belongs to nonlinear optical material field. Becanvention belongs to the field of non-linear optical materials. The present invention also relates to crosslinking polyurethane polymers or polarization polymer films which are prepared by the second-ouse it replaces C=C bond by N=N bond, the photochemistry stability is greatly improved. This material has two or more OH, and can further react to make cross linking polymer film or polarizing polymerrder non-linear optical polymer containing azo and thiophene rings. In the second-order non-linear optical polymer containing azo and thiophene rings of the present invention, an N=N bond replaces a C film. It also can be used as color, dye, and coating. =C bond, so photochemical stability is greatly increased. The material comprises two ore more than two-OH and can prepare the crosslinking polymer films or polarization polymer films via further reaction. Compared with non-crosslinking polymers, the polymers have higher thermal stability, higher light stability and higher orientation stability. In addition, the azo compounds or azo intermediates thereof are blue to red compounds and can be used as pigments, dyes, coatings, etc.
Description
Technical field
The present invention relates to the nonlinear optical material field, be particularly related to second-order non-linear optical polymer and synthetic method thereof that a class novel high-performance contains azo and thiphene ring, and prepare cross-linked type polyurethane base polymer or polarized polymer thin film with the second-order non-linear optical polymer that contains azo and thiphene ring.
Background technology
Second-order non-linear optical materials is mainly used in Electro-optical Modulation, frequency inverted and photoswitch (modulation) etc., and they have a wide range of applications at optical communication and optical signal process fields such as (photometry calculations).At present, Shi Yong second-order non-linear optical materials mainly is an inorganic materials.Organic materials is compared with inorganic materials to have that nonlinear optical coefficients are big, response speed is fast, optical damage threshold is high, can carry out molecular designing as requested, is easy to advantages such as processing and cheapness.As the present electrooptical material Lithium niobium trioxide that uses, its nonlinear second-order optical susceptibility is 30pm/V, and bandwidth is 10GHz, and the highest electro-optic coefficient of the organic materials of bibliographical information has reached 128pm/V, and high bandwidth surpasses 200GHz, and the expection bandwidth is 350GHz.
Though some single indexs such as the nonlinear optical coefficients of organic materials, bandwidth are considerably beyond inorganic materials, and have commodity selling with the device that electro-optical organic material is made, but particularly also there is certain defective in they aspect the optical stability aspect stable.Seeking all more superior organic second-order non-linear optical material of every performance index and replace existing inorganic materials, thereby realize high transmission speed, is a heat subject in present nonlinear optical material field.
Existing patent about the organic second-order non-linear optical material has many, but wherein most of nonlinear optical coefficients are not high.The higher patent of report nonlinear optical coefficients has: US6067186, WO02/08215 etc.But this class material all adopts the C=C key as the conjugated pi electron bridge, and the carbon-carbon double bond system exists creating singlet oxygen by using to make the problem of its stability decreases.
Summary of the invention
A purpose of the present invention provides the good novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring of a class optical stability.
A further object of the present invention provides a kind of preparation method who contains the novel high-performance second-order non-linear optical polymer of azo and thiphene ring.
Another object of the present invention provides cross-linked type polyurethane base polymer or the cross-linking type polarized polymer thin film of preparing with the second-order non-linear optical polymer that contains azo and thiphene ring.
An also purpose of the present invention provides the method for preparing cross-linked type polyurethane base polymer or cross-linking type polarized polymer thin film with the second-order non-linear optical polymer that contains azo and thiphene ring.
The novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring of the present invention has following structure:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following; The electron acceptor moiety of structure below the A representative:
Or
Wherein, R in the A formula
3=H or-(CH
2)
nR ', n=1～10, R '=H or OH; R
4=H or-(CH
2)
nR ', n=1～10, R '=H or OH; Work as R
3During for the substituting group on the phenyl ring, the position of its replacement is arbitrarily.
The preparation method who contains the novel high-performance second-order non-linear optical polymer of azo and thiphene ring of the present invention may further comprise the steps:
(1) with 3,5-nitro-the 2 thiophene carboxaldehyde of 4 replacements or non-replacement mixes with tindichloride and concentrated hydrochloric acid, wherein 3, the mol ratio of 5-nitro-2 thiophene carboxaldehyde, tindichloride and the concentrated hydrochloric acid of 4 replacements or non-replacement is 1: 2～5:1～5, stirred 0.5～5 hour down at 20～100 ℃, replaced or the complex compound aaerosol solution of the tin tetrachloride of non-replacement 5-amino-2 thiophene carboxaldehyde;
(2) the tin tetrachloride complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde of replacement that step (1) is obtained or non-replacement joins in the NaOH aqueous solution that concentration is 5～40wt%, regulate the pH value to alkalescence, use extracted with diethyl ether then, boil off that ether is replaced or the 5-amino-2 thiophene carboxaldehyde of non-replacement;
(3) replacement that obtains of the complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde tin tetrachloride of replacement that step (1) is obtained or non-replacement or step (2) or the 5-amino-2 thiophene carboxaldehyde of non-replacement mix 1:1～1.5 in molar ratio with Sodium Nitrite, under-5～5 ℃ and acidic conditions, carry out diazotization reaction and obtain diazonium salt, again with N, N-disubstituted benzenes aminated compounds carries out coupling and obtains azothiazole aldehyde in solvent, the coupled reaction temperature is-5～5 ℃; In the reaction process of carrying out step (3), regulate the pH value between 3～6 with sodium hydroxide or sodium-acetate;
(4) (mol ratio of electron acceptor(EA) and aldehyde radical is 1～5:1) to react in the solvent of catalyzer is arranged to the azothiazole aldehyde that step (3) is obtained with the electron acceptor compound that contains labile methyl group or methylene radical after purifying, generate the azothiazole functional group of carbon-carbon double bonds, temperature of reaction is 10～150 ℃.
Described 3,4 replace or the substituting group of the 5-nitro-2 thiophene carboxaldehyde of non-replacement is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl.
Described step (3) acidic conditions is that (mol ratio of hydrochloric acid and Sodium Nitrite is 2～4:1) to 1～4M hydrochloric acid soln, (mol ratio of hydrochloric acid and Sodium Nitrite is 2～20:1 to concentrated hydrochloric acid/acetic acid solution, the volume ratio of concentrated hydrochloric acid and acetate is 1:0.5～5), (mol ratio of sulfuric acid and Sodium Nitrite is 5～20:1 to the vitriol oil/acetic acid solution, the volume ratio of the vitriol oil and acetate is 1:0.5～5) or the vitriol oil/acetate/propionic acid solution (mol ratio of the vitriol oil and Sodium Nitrite is 5～20:1, the volume ratio of the vitriol oil and acetate is 1:0.5～5, and the volume ratio of acetate and propionic acid is 3～5:1).
Described step (3) N, N-disubstituted benzenes aminated compounds carry out the solvent that coupling adopts and are selected from water, acetone, N, N-dimethylformamide, N, N-dimethyl acetyl ammonia, tetrahydrofuran (THF), formic acid, acetate or their any mixture in solvent; The N that coupled reaction is used, the mol ratio of N-disubstituted benzenes aminated compounds and Sodium Nitrite is 1～1.5:1, N, the concentration of N-disubstituted benzenes aminated compounds is 1～60wt%.
The method of purification of described step (4) azothiazole aldehyde is column chromatography or thin-layer chromatography method, and wherein, stationary phase is a silica gel, and elutriant is sherwood oil/acetone (volume ratio 0.5～3/1).
The solvent of described step (4) is selected from ethanol, tetrahydrofuran (THF), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, 1,4-dioxane, pimelinketone, chloroform or their any mixture; Catalyzer is selected from piperidines, piperidines-acetate, acetate-ammonium acetate or ammonium acetate.
Described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde are:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl.
The complex compound of the tin tetrachloride of described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde is:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; X=1～10.
Described azothiazole aldehyde is:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following.
The described electron acceptor compound that contains labile methyl group or methylene radical is:
Wherein, R in the A formula
3=H or-(CH
2)
nR ', n=1～10, R '=H or OH; R
4=H or-(CH
2)
nR ', n=1～10, R '=H or OH; Work as R
3During for the substituting group on the phenyl ring, the position of its replacement is arbitrarily.
The second-order non-linear optical polymer that contains azo and thiphene ring of the present invention can be used for preparing the cross-linked type polyurethane base polymer or the cross-linking type polarized polymer thin film of the second-order non-linear optical polymer that contains azo and thiphene ring.
Cross-linked type polyurethane base polymer or the cross-linking type polarized polymer thin film that contains the second-order non-linear optical polymer of azo and thiphene ring of the present invention prepares by the following method:
(1) the novel high-performance second-order non-linear optical polymer that will contain azo and thiphene ring reacted 0.5～20 hour in 20～120 ℃ with the compound that contains two-NCO in dry solvent, wherein, the novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring is 1:2～20 with the compound mol ratio that contains two-NCO; Then, add and to contain more than three-polymkeric substance of the compound of OH or contain-OH, in 20～120 ℃ of reactions 1 minute～10 hours, obtain prepolymer, wherein ,-OH is 0.8～1:1 with the ratio of residue-NCO; Prepolymer is filmed through spin-coating method, and spin speed is 1000～3000 rev/mins, and the spin coating time is 5 seconds～10 minutes, obtains the thick film of 0.1～5 μ m in 20～30 ℃ of vacuum-dryings 6～48 hours;
(2) pre-polymer film that step (1) is obtained heated 0.5～10 hour under 50～140 ℃ of dry atmosphere, can obtain the cross-linked type polyurethane quasi-copolymer film; Or
The pre-polymer film that step (1) is obtained heats under 50～140 ℃ of dry atmosphere, adopts the method for corona polarizing to apply the electric field of 3000～5000V simultaneously on pre-polymer film, can obtain the cross-linking type polarized polymer thin film.
The dry solvent of described step (1) is selected from chloroform, acetone, tetrahydrofuran (THF), chlorobenzene, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethyl acetyl ammonia, pimelinketone or their any mixture.
The compound that described step (1) contains two-NCO is selected from:
L=O or CH
2M=H or CH
3Or OCH
3Y=H or CH
3N=2-10
Described step (1) contains more than three-and the compound of OH is selected from TriMethylolPropane(TMP), glycerine, 1,2,6-hexanetriol, tetramethylolmethane, trolamine; Contain-polymkeric substance of OH is selected from poly-hexanodioic acid Viscotrol C ester polyol, polyoxytrimethylene polyvalent alcohol, polyether glycol, phenol polyvalent alcohol, Viscotrol C, bisphenol type tetraglycidel ether epoxy resin or bisphenol type tetraglycidel ether epoxy resin-aniline etc.
The preparation method's of the second-order non-linear optical polymer that contains azo and thiphene ring of the present invention reaction equation is as follows:
The novel high-performance second-order non-linear optical polymer that contains azo and thiphene ring of the present invention, owing to the C=C key that has replaced the higher nonlinear optical material of report in the existing patent (as US6067186) with the N=N key, photochemical stability improves greatly.This class material contains two or more-OH, can pass through crosslinked polymeric film or the polarized polymer thin film of further prepared in reaction, and they are compared with non-cross-linked polymer has higher thermostability, light stability and orientation stability.In addition, because this type of azo-compound or its azo intermediate are blue to red compound, they also can be used as pigment, dyestuff and coating etc.
The organic second-order non-linear optical polymkeric substance that the present invention prepares is at electro-optical device and utilize in the various opto-electronic devices of its frequency-doubled effect and photorefractive effect etc. the important application prospect is arranged.
Embodiment
Embodiment 1
3,4-dibutyl-5-amino-2 thiophene carboxaldehyde tin tetrachloride complex compound synthetic
Under ice bath and vigorous stirring, restrain (0.2mol) SnCl with 45
22H
2O is dissolved in the 60ml concentrated hydrochloric acid, when system temperature is reduced to 5 ℃, once adds 3,4-dibutyl-5-nitro-2 thiophene carboxaldehyde 17.8 grams (0.066mol), and 40 ℃ were stirred 1 hour, got the pale solid suspension liquid.
Embodiment 2
3,4-dibutyl-5-amino-2 thiophene carboxaldehyde synthetic
The pale solid suspension liquid that embodiment 1 is obtained arrives alkalescence with 40wt% NaOH aqueous solution adjust pH, uses extracted with diethyl ether then, ether layer MgSO
4The evaporation of dry back, the thick product that obtains can be directly used in next step reaction.
Embodiment 3
2-[4-(N, N-dihydroxy ethyl amino) azobenzene] 3,4-dibutyl-5-thiophenecarboxaldehyde synthetic
With embodiment 1 obtain 3,4-dibutyl-5-amino-2 thiophene carboxaldehyde tin tetrachloride complex compound canescence solution; Or with embodiment 2 obtain 3, the hydrochloric acid soln of 4-dibutyl-5-amino-2 thiophene carboxaldehyde is cooled to 2 ℃; With 0.067 mole of NaNO
2Be dissolved in the 15ml water, and, in the hydrochloric acid soln of 4-dibutyl-5-amino-2 thiophene carboxaldehyde, continue to stir 1 hour, get diazonium salt solution in slowly being added drop-wise to above-mentioned canescence solution or 3 below 5 ℃.
N with 0.080mol, N-dihydroxy ethyl aniline is dissolved among the 10ml36%HOAC, cryosel is bathed and is cooled to 3 ℃, above-mentioned diazonium salt solution slowly is added drop-wise to N, in the HOAC solution of N-dihydroxy ethyl aniline, temperature of reaction is controlled at below 5 ℃,, between 3～6, continue to stir 1.5 hours with the pH value of NaOH regulation system, filter, the pink solid that obtains is dissolved in the 100ml acetone, remove insoluble pink salt, column chromatography is separated (sherwood oil/acetone=2/1), gets pink azothiazole aldehyde, IR:3420 (OH), 2859-2956 (CH
2, CH
3), 1650 (CHO), 1596 (phenyl ring); Uv-vis:537nm (DMF).
Embodiment 4
With compound and 0.1g (0.50mmol) the 2-dicyan methene-3-cyano group-4,5 that 0.1g (0.31mmol) embodiment 3 obtains, 5 trimethylammoniums-2, the 5-dihydrofuran is dissolved in the 5mL ethanol.The NH that adds catalytic amount
4AcO and acetic acid, reflux 4 hours is chilled to room temperature.Suction filtration, and be blue-greenish colour until filtrate with washing with alcohol precipitation.The dry black solid 0.20g that gets.The column chromatography separation obtains the pure product ZCN of second nonlinear compound (53%).IR(KBr)：3448(OH)；2870-2960(CH)；2226(CN)cm
-1；UV-vis(CHCl
3)：668nm；
1HNMR(CDCl
3)：68.41(d，1H)，8.08(d，2H)，7.37(d，2H)，6.77(d，1H)，4.14(br，4H)，3.95(br，4H)，2.78(m，4H)，1.87(s，6H)，1.71(m，8H)，1.13(m，6H)；MS：612(M
+)。
Embodiment 5
Prepolymer I preparation
Under the nitrogen atmosphere, the product (ZCN) of 34.8mg embodiment 4 is dissolved in the 0.8ml pimelinketone, adds 64 microlitre TDI, reactant stirred 1.5 hours in 80 ℃, the dioxane solution that adds 150 microlitre trolamines (0.779mmol/ml) then, 80 ℃ are continued to stir 15 minutes.Standby after the solution concentration.
Embodiment 6
The preparation of crosslinking polymer I film
The pre-polymer solution that obtains among the embodiment 5 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 100 ℃ were heated 2 hours then, can obtain the crosslinking polymer film.
UV-vis：690nm。
Embodiment 7
The preparation of cross-linking type polar polymer I film
The pre-polymer solution that obtains among the embodiment 5 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, the control heat-up rate also increases voltage synchronously, temperature rises to 50 ℃ in 20 minutes, voltage is increased to 3000 volts, keep after 20 minutes, temperature and voltage are risen to 60 ℃, 3200 volts, kept again 20 minutes, and then temperature and voltage were risen to 80 ℃, 3400 volts, kept 10 minutes, at last, temperature and voltage are risen to 120 ℃, 3800 volts kept 20 minutes, stop heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 8
The preparation of prepolymer II
Under the nitrogen atmosphere, the product (ZCN) that 11.7mg embodiment 4 is obtained is dissolved in the 0.5ml pimelinketone, add 10 times of equivalents to the TDI of ZCN, reactant stirred 12 hours in 75 ℃, the dioxane solution that adds 338 microlitres polyaniline-dihydroxyphenyl propane glycidyl ether (0.508mmol/ml) then stirred 15 minutes.It is standby that solution filters the back.
Embodiment 9
The preparation of crosslinking polymer II film
The pre-polymer solution that obtains among the embodiment 8 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 140 ℃ were heated 5 hours then, can obtain the crosslinking polymer film.
Embodiment 10
The preparation of cross-linking type polar polymer II film
The pre-polymer solution that obtains among the embodiment 8 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, and in 95 ℃, 5500V polarizes half an hour, is warming up to 110 ℃ then and keeps half an hour, stops heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 11
2-[4-(N, N-dihydroxy ethyl amino-2-kharophen) azobenzene] 3,4-dibutyl-5-thiophenecarboxaldehyde (5) synthetic
With 0.725g (10.5mmol) NaNO
2Be added to the dense H of 8mL in batches
2SO
4In (＜10 ℃), slowly be heated to about 65 ℃.Treat NaNO
2After molten entirely, be chilled to below 5 ℃, with 5mL propionic acid/acetate (V/V:1/4) dilution.Mixture is chilled to 0 ℃, adds embodiment 2 gained 3 in batches, 4-dibutyl-5-amino-2 thiophene carboxaldehyde (10.4mmol), and 0 ℃ was stirred 1 hour then, got diazonium salt solution (tawny viscous solution).About 0 ℃ of temperature control splashes into 3-acetylaminohydroxyphenylarsonic acid N with it then, in the solution of N-two (2-hydroxyethyl) aniline (11mmol) DMF.Drip and finish, stir after 0.5 hour about 0 ℃, transfer pH=5～6, continue to stir 0.5 hour with NaAcO.Under the vigorous stirring, in a large amount of frozen water of impouring, and use NaHCO
3Transfer pH=7～8.Extracted with diethyl ether three times, organic phase saturated common salt water washing, anhydrous MgSO
4Dry.Filter, filtrate is revolved and is steamed to doing, and gets the red-purple sticky solid.Cross post with petrol ether/ethyl acetate (1/5), get the red-purple solid product.IR (KBr, cm
-1): 3420 (OH), 2859-2956 (CH
2, CH
3), 1650 (CHO), 1596 (phenyl ring).Uv-vis：548/CHCl
3。
Embodiment 12
With 0.1g (0.23mmol) embodiment 11 gained compounds and 0.1g (0.50mmol) 2-dicyan methene-3-cyano group-4,5,5 trimethylammoniums-2,5-dihydrofuran acceptor is dissolved in the 5mL ethanol.Piperidines-the acetate (piperidines-acetate volume ratio is 1:3) that adds catalytic amount, reflux got blue-green solution after 1 hour, and rotary evaporation is removed ethanol, and the residuum acetone solution removes and desolvates, and column chromatography is separated, eluent acetone/sherwood oil (1/4).Get green solid 0.09g, productive rate 64%.MS(MALDI-TOF，m/z)：669.6(M
+)，692(M
++Na)，708(M
++K)。
1H-NMR (chloroform-d
1) 8.32 (s, 1H), 8.12 (d, 1H), 7.75 (d, 1H), 6.97 (s, 1H), 6.62 (d, 1H), 3.99 (S, 4H), 3.80 (S, 4H), 2.96 (t, 2H) 2.75 (t, 2H), 2.61 (m, 3H), 2.32 (S, 3H), 1.82 (S, 2H), 1.74 (s, 6H), 1.46 (2H, m), 1.26 (s, and 4H) 1.05 (q, 6H).
Embodiment 13
The preparation of prepolymer III
Under the nitrogen atmosphere, 24.6mg embodiment 12 gained chromophoric grouies are dissolved in the 0.4ml pimelinketone, add 42 microlitre TDI, reactant stirred 3 hours in 80 ℃, the dioxane solution that adds 176 microlitre trolamines (0.779mmol/ml) then, 80 ℃ are continued to stir 15 minutes.Standby after the solution concentration.
Embodiment 14
The preparation of crosslinking polymer III film
The pre-polymer solution that obtains among the embodiment 13 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500-3000r/min, and thickness is 1～2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 100 ℃ were heated 2 hours then, can obtain the crosslinking polymer film.
Embodiment 15
The preparation of cross-linking type polar polymer III film
The pre-polymer solution that obtains among the embodiment 13 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～3 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.
Above-mentioned film is placed the corona polarizing device, corona needle point and film surface are apart from 1.5cm, the control heat-up rate also increases voltage synchronously, temperature rises to 50 ℃ in 20 minutes, voltage is increased to 3000 volts, keep after 20 minutes temperature and voltage being risen to 60 ℃, 3200 volts, kept again 20 minutes, then temperature and voltage are risen to 80 ℃, 3400 volts, kept 10 minutes, last, temperature and voltage are risen to 120 ℃, 3800 volts maintenances 20 minutes, stop heating, naturally after being cooled to room temperature, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 16
The preparation of prepolymer IV
Under the nitrogen atmosphere, 12.7mg embodiment 12 gained chromophoric grouies are dissolved in the 0.5ml pimelinketone, add the TDI of 27 microlitres, reactant stirred 12 hours in 75 ℃, the dioxane solution that adds 338 microlitres polyaniline-dihydroxyphenyl propane glycidyl ether (0.508mmol/ml) then, stirring at room 15 minutes.It is standby that solution filters the back.
Embodiment 17
The preparation of crosslinking polymer IV film
The pre-polymer solution that obtains among the embodiment 16 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 140 ℃ were heated 5 hours then, can obtain the crosslinking polymer film.
UV-vis：708nm。
Embodiment 18
The preparation of cross-linking type polar polymer IV film
The pre-polymer solution that obtains among the embodiment 16 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～3 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.
Above-mentioned film is placed the corona polarizing device, and corona needle point and film surface are apart from 1.5cm, in 95 ℃, 5500V polarizes half an hour, is warming up to 105 ℃ then and keeps half an hour, stops heating, naturally after being cooled to room temperature, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 19
With compound and 0.1g (0.53mmol) 3 that 0.1g (0.23mmol) embodiment 3 obtains, 5-dinitrobenzene-2-thiotolene acceptor is dissolved in the 5mL ethanol.The NH that adds catalytic amount
4AcO and acetic acid, reflux 5h adds proper catalyst and acceptor, continues to reflux 3 hours.Reaction finishes, and is chilled to room temperature, adds 30mL water, separates out a large amount of solids.Suction filtration, solid washes with water earlier, uses ethanol/sherwood oil (V/V:1/3) washed twice again, drying.Cross post with petrol ether/ethyl acetate (1/5), get green solid 0.07g, productive rate 51%.IR (KBr, cm
-1): 3391 (OH), 3122 (thiphene ring C-H), 2956-2869 (CH), 1598 (phenyl ring C=C), 1541,1321 (NO
2).Uv-vis(λ
max，nm)：431，630/CHCl
3；434，635/THF。
1H-NMR (acetone-d
6): 8.37 (s, 1H), 7.96 (d, J
H-H=15.6,1H), 7.85 (d, J
H-H=15.6,1H), 7.73 (d, J
H-H9.2,2H), 6.90 (d, J
H-H=9.3,2H), 3.80 (t, J
H-H=11.5,4H), 3.70 (t, J
H-H=11.5,4H), 300 (t, J
H-H=15.5,2H), 2.88 (t, J
H-H=15.6,2H), 1.65 (m, 2H), 1.59 (m, 2H), 1.46 (m, 4H), 0.96 (m, 6H).
Embodiment 20
Prepolymer V preparation
Under the nitrogen atmosphere, the product that 34.1mg embodiment 19 is obtained is dissolved in the 0.8ml pimelinketone, adds 64 microlitre TDI, and reactant stirred 1.5 hours in 80 ℃, the dioxane solution that adds 150 microlitre trolamines (0.779mmol/ml) then, 80 ℃ are continued to stir 15 minutes.Standby after the solution concentration.
Embodiment 21
The preparation of crosslinking polymer V film
The pre-polymer solution that obtains among the embodiment 20 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 100 ℃ were heated 2 hours then, can obtain the crosslinking polymer film.
Embodiment 22
The preparation of cross-linking type polar polymer V film
The pre-polymer solution that obtains among the embodiment 20 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, the control heat-up rate also increases voltage synchronously, temperature rises to 50 ℃ in 20 minutes, voltage is increased to 3000 volts, keep after 20 minutes, temperature and voltage are risen to 60 ℃, 3200 volts, kept again 20 minutes, and then temperature and voltage were risen to 80 ℃, 3400 volts, kept 10 minutes, at last, temperature and voltage are risen to 120 ℃, 3800 volts kept 20 minutes, stop heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Embodiment 23
The preparation of prepolymer VI
Under the nitrogen atmosphere, the product that 11.4mg embodiment 19 is obtained is dissolved in the 0.5ml pimelinketone, the TDI that adds the product that 10 times of equivalents obtain to embodiment 19, reactant stirred 12 hours in 75 ℃, the dioxane solution that adds 338 microlitres polyaniline-dihydroxyphenyl propane glycidyl ether (0.508mmol/ml) then stirred 15 minutes.It is standby that solution filters the back.
Embodiment 24
The preparation of crosslinking polymer VI film
The pre-polymer solution that obtains among the embodiment 23 is filmed with spin-coating method on glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in room temperature vacuum-drying 24 hours, and 140 ℃ were heated 5 hours then, can obtain the crosslinking polymer film.
Embodiment 25
The preparation of cross-linking type polar polymer VI film
The pre-polymer solution that obtains among the embodiment 23 is filmed with spin-coating method on the ito glass substrate.Rotating speed is controlled at 1500～3000r/min, and thickness is 1～2 μ m.The film that coats was in 30 ℃ of vacuum-dryings 24 hours.Above-mentioned film is placed the corona polarizing device, and in 95 ℃, 5500V polarizes half an hour, is warming up to 110 ℃ then and keeps half an hour, stops heating, be cooled to room temperature naturally after, close voltage, promptly obtain the cross-linking type polarized polymer thin film.
Claims (9)
1. second-order non-linear optical polymer that contains azo and thiphene ring, it is characterized in that: this polymkeric substance has following structure:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following; R
7=H or-(CH
2)
nR ', n=1～10, R '=H or OH; R
8=H or-(CH
2)
nR ', n=1～10, R '=H or OH.
2. preparation method who contains the second-order non-linear optical polymer of azo and thiphene ring according to claim 1 is characterized in that this method may further comprise the steps:
(1) with 3,5-nitro-the 2 thiophene carboxaldehyde of 4 replacements or non-replacement mixes with tindichloride and concentrated hydrochloric acid, wherein 3, the mol ratio of 5-nitro-2 thiophene carboxaldehyde, tindichloride and the concentrated hydrochloric acid of 4 replacements or non-replacement is 1: 2～5: 1～5, stir down at 20～100 ℃, replaced or the complex compound aaerosol solution of the tin tetrachloride of non-replacement 5-amino-2 thiophene carboxaldehyde;
(2) the tin tetrachloride complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde of replacement that step (1) is obtained or non-replacement joins in the NaOH aqueous solution, regulate the pH value to alkalescence, use extracted with diethyl ether then, boil off that ether is replaced or the 5-amino-2 thiophene carboxaldehyde of non-replacement;
(3) replacement that obtains of the complex compound aaerosol solution of the 5-amino-2 thiophene carboxaldehyde tin tetrachloride of replacement that step (1) is obtained or non-replacement or step (2) or the 5-amino-2 thiophene carboxaldehyde of non-replacement mix 1:1～1.5 in molar ratio with Sodium Nitrite, under-5～5 ℃ and acidic conditions, carry out diazotization reaction and obtain diazonium salt, again with N, N-disubstituted benzenes aminated compounds carries out coupling and obtains azothiazole aldehyde in solvent, the coupled reaction temperature is-5～5 ℃; In the reaction process of carrying out step (3), regulate the pH value between 3～6 with sodium hydroxide or sodium-acetate;
(4) the azothiazole aldehyde that step (3) is obtained reacts in the solvent of catalyzer is arranged with the electron acceptor compound that contains labile methyl group or methylene radical after purifying, generate the azothiazole functional group of carbon-carbon double bonds, temperature of reaction is 10～150 ℃, wherein, the mol ratio of electron acceptor(EA) and aldehyde radical is 1～5:1;
The described electron acceptor compound that contains labile methyl group or methylene radical is:
R wherein
7=H or-(CH
2)
nR ', n=1～10, R '=H or OH; R
8=H or-(CH
2)
nR ', n=1～10, R '=H or OH.
3. method according to claim 2, it is characterized in that: described 3,4 replace or the substituting group of the 5-nitro-2 thiophene carboxaldehyde of non-replacement is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl.
4. method according to claim 2, it is characterized in that: described step (3) acidic conditions is 1～4M hydrochloric acid soln, the mol ratio of hydrochloric acid and Sodium Nitrite is 2～4:1, concentrated hydrochloric acid/acetic acid solution, the mol ratio of hydrochloric acid and Sodium Nitrite is 2～20:1, the volume ratio of concentrated hydrochloric acid and acetate is 1:0.5～5, the vitriol oil/acetic acid solution, the mol ratio of sulfuric acid and Sodium Nitrite is 5～20:1, the volume ratio of the vitriol oil and acetate is 1:0.5～5, or the vitriol oil/acetate/propionic acid solution, the mol ratio of the vitriol oil and Sodium Nitrite is 5～20:1, the volume ratio of the vitriol oil and acetate is 1:0.5～5, and the volume ratio of acetate and propionic acid is 3～5:1.
5. method according to claim 2 is characterized in that: the N that described step (3) coupled reaction is used, the mol ratio of N-disubstituted benzenes aminated compounds and Sodium Nitrite is 1～1.5:1.
6. method according to claim 2 is characterized in that: described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde are:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl;
The complex compound of the tin tetrachloride of described replacement or non-replacement 5-amino-2 thiophene carboxaldehyde is:
Wherein, R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; X=1～10;
Described azothiazole aldehyde is:
Wherein, R
1, R
2It is the substituting group that contains following alkyl, alkoxyl group or ester group of 10 carbon atoms of hydroxyl; R
3, R
4It is the substituting group of following alkyl, aryl, alkoxyl group or ester group of H, 20 carbon atoms following alkyl, aryl, alkoxyl group, ester group, amido or 10 carbon atoms that contain hydroxyl; R
5, R
6Be H, 10 alkyl, alkoxyl group, ester group or amidos that carbon atom is following.
7. purposes that contains the second-order non-linear optical polymer of azo and thiphene ring according to claim 1, it is characterized in that: this polymkeric substance is used to prepare cross-linked type polyurethane base polymer or cross-linking type polarized polymer thin film.
8. purposes according to claim 7 is characterized in that, described cross-linked type polyurethane base polymer or cross-linking type polarized polymer thin film prepare by the following method:
(1) second-order non-linear optical polymer that will contain azo and thiphene ring in dry solvent with contain the compound of two-NCO in 20～120 ℃ of reactions, wherein, the second-order non-linear optical polymer that contains azo and thiphene ring is 1:2～20 with the compound mol ratio that contains two-NCO; Then, add and to contain more than three-polymkeric substance of the compound of OH or contain-OH, in 20～120 ℃ of reactions, obtain prepolymer, wherein ,-OH is 0.8～1:1 with the ratio of residue-NCO; Prepolymer is filmed through spin-coating method, obtains the thick film of 0.1～5 μ m in 20～30 ℃ of vacuum-dryings;
(2) pre-polymer film that step (1) is obtained heats under 50～140 ℃ of dry atmosphere, can obtain the cross-linked type polyurethane quasi-copolymer film; Or
The pre-polymer film that step (1) is obtained heats under 50～140 ℃ of dry atmosphere, adopts the method for corona polarizing to apply the electric field of 3000～5000V simultaneously on pre-polymer film, can obtain the cross-linking type polarized polymer thin film.
9. purposes according to claim 8 is characterized in that: the compound that described step (1) contains two-NCO is selected from:
L=O or CH
2M=H or CH
3Or OCH
3Y=H or CH
3N=2-10
Described step (1) contains more than three-and the compound of OH is selected from TriMethylolPropane(TMP), glycerine, 1,2,6-hexanetriol, tetramethylolmethane or trolamine;
Described step (1) contains-and the polymkeric substance of OH is selected from poly-hexanodioic acid Viscotrol C ester polyol, polyoxytrimethylene polyvalent alcohol, polyether glycol, phenol polyvalent alcohol, Viscotrol C, bisphenol type tetraglycidel ether epoxy resin or bisphenol type tetraglycidel ether epoxy resin-aniline.
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| US10196343B2 (en) | 2013-01-30 | 2019-02-05 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10308886B2 (en) | 2015-04-22 | 2019-06-04 | Ecolab Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
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| CN101497785B (en) * | 2008-01-28 | 2012-07-04 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore group containing dendritic structured tricyano pyrroline receptor, synthesizing method and use thereof |
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| US6067186A (en) * | 1998-07-27 | 2000-05-23 | Pacific Wave Industries, Inc. | Class of high hyperpolarizability organic chromophores and process for synthesizing the same |
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| US6067186A (en) * | 1998-07-27 | 2000-05-23 | Pacific Wave Industries, Inc. | Class of high hyperpolarizability organic chromophores and process for synthesizing the same |
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| US10703710B2 (en) | 2013-01-30 | 2020-07-07 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11339118B2 (en) | 2013-01-30 | 2022-05-24 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10308886B2 (en) | 2015-04-22 | 2019-06-04 | Ecolab Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US11085002B2 (en) | 2015-04-22 | 2021-08-10 | Championx Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US10407626B2 (en) | 2015-09-08 | 2019-09-10 | Ecolab Usa Inc. | Hydrocarbon soluble/dispersible hemiformals as hydrogen sulfide scavengers |
| US10584286B2 (en) | 2015-09-08 | 2020-03-10 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10336950B2 (en) | 2016-07-29 | 2019-07-02 | Ecolab Usa Inc. | Antifouling and hydrogen sulfide scavenging compositions and methods |
| US10538710B2 (en) | 2017-07-13 | 2020-01-21 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11499108B2 (en) | 2019-01-23 | 2022-11-15 | Championx Usa Inc. | Complete removal of solids during hydrogen sulfide scavenging operations using a scavenger and a Michael acceptor |
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