CN1488660A - Second-order non-linear optical polymer of isocyanate crosslinked epoxy resin - Google Patents
Second-order non-linear optical polymer of isocyanate crosslinked epoxy resin Download PDFInfo
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Abstract
本发明公开了属于集成光学器件材料制备技术范围的一种异氰酸酯交联环氧树脂类二阶非线性光学聚合物。先通过环氧类单体和苯胺、甲基取代苯胺或萘胺的开环聚合反应，得到聚合物链段上含羟基的各种环氧树脂类先驱聚合物，再通过先驱聚合物的重氮偶合反应，制备含有生色团的环氧树脂类非线性光学聚合物，将制备的环氧树脂类非线性光学聚合物和异氰酸酯交联剂共混，得到了异氰酸酯改性的双组分聚合物体系；该双组分聚合物膜在外加强电场下极化，得到异氰酸酯交联的非线性光学聚合物膜；体系中的非线性光学生色团的取向有序度较环氧树脂类非线性光学聚合物本身有大幅度的提高，二阶非线性光学系数可提高100－300％。同时，上述异氰酸酯交联改性后的非线性光学聚合物的极化偶极取向的稳定性达到200℃以上。The invention discloses an isocyanate cross-linked epoxy resin-based second-order nonlinear optical polymer belonging to the technical scope of integrated optical device material preparation. First, through the ring-opening polymerization reaction of epoxy monomers and aniline, methyl-substituted aniline or naphthylamine, various epoxy resin precursor polymers containing hydroxyl groups on the polymer chain segment are obtained, and then through the diazonium of the precursor polymer Coupling reaction to prepare epoxy resin-based nonlinear optical polymers containing chromophores, and blend the prepared epoxy resin-based nonlinear optical polymers with isocyanate crosslinking agents to obtain isocyanate-modified two-component polymers system; the two-component polymer film is polarized under an externally enhanced electric field to obtain an isocyanate-crosslinked nonlinear optical polymer film; the orientation order of the nonlinear optical chromophore in the system is higher than that of epoxy resin nonlinear optical The polymer itself is greatly improved, and the second-order nonlinear optical coefficient can be increased by 100-300%. At the same time, the stability of the polarized dipole orientation of the nonlinear optical polymer after cross-linking modification by isocyanate reaches above 200°C.
Description
Technical field
The invention belongs to integrated optical device material preparation technology scope, particularly isocyanate-crosslinked epoxy resin second-order non-linear optical polymer.
Background technology
Along with fast development of information technology, utilize light will be widely used as the integrated optical device (as electrooptic modulator, photoswitch, frequency multiplier etc.) of information transmission, storage, processing tool, second nonlinear optic (NLO) material is one of key material of realizing this goal.Compare with the inorganic second-order non-linear optical materials (as LiNbO3, KH2PO4 crystal etc.) of present use, the polymkeric substance nonlinear optical material has that nonlinear optical coefficients are big, response speed is fast, dielectric is often imitated low, good processability and advantage such as low price.Therefore, the second-order non-linear optical polymer with practical value is the focus and the forward position of Recent study, is subjected to extensive concern.
It is the prerequisite that material demonstrates macroscopical second-order nonlinear optical property that the non-centrosymmetry of the non-linear optical chromophore that polymkeric substance is contained is arranged.Making chromophore in the polymkeric substance along direction of an electric field orientation-electropolarization by strong electrostatic field, is the most popular method of preparation nonlinear optics polyalcohol material
The non-centrosymmetry of chromophore arrangement is a thermodynamic instability in the non-linear optical polymer, and the chromophore that polarized electric field is removed the back orientation usually can be returned to unordered state gradually, causes optically nonlinearity progressively to be lost.Therefore, there is the second nonlinear optic polar polymer of actual application prospect not only will have bigger nonlinear optical coefficients, also should has chromophore's dipole orientation stability preferably.
Since reported first electric field polarization nonlinear optics polyalcohol materials such as Meredith and Garito, people after deliberation the different non-linear optical polymer systems of various structures, and obtained the breakthrough of nonlinear optical coefficients and dipole orientation stability respectively.At present, polar polymer is at the highest 70pm/v that reached of electro-optic coefficient of 1.3 μ m, polar polymer the upper limit temperature of heat tolerance has reached 350 ℃, simultaneously IBM, chemistry institute of the Chinese Academy of Sciences and University of Southern California reported respectively can long-term stability 225 ℃, 195 ℃ and 175 ℃ of dipole orientations polar polymer.But up to the present, it is still rare with the report of the high-performance second-order non-linear optical polymer system of better dipole orientation stability than big nonlinear optical coefficients to have simultaneously, and the over-all properties of polar polymer still remains to be improved.
Summary of the invention
The purpose of this invention is to provide a kind of isocyanate-crosslinked epoxy resin second-order non-linear optical polymer, it is characterized in that: earlier by epoxies monomer and aniline, the ring-opening polymerization of methyl substituted aniline or naphthylamines, obtain the various epoxy resin pioneer polymkeric substance of hydroxyl on the polymer segment, pass through the diazo coupling reaction of pioneer's polymkeric substance again, preparation contains the epoxy resin non-linear optical polymer of chromophore, epoxy resin non-linear optical polymer and isocyanate crosslinking blend with preparation have obtained isocyanate-modified bi-component polymeric system; This bi-component polymeric film adds polarization under the highfield outside, obtains isocyanate-crosslinked non-linear optical polymer film; Mainly may further comprise the steps:
(1) preparation of epoxy resin primary polymer
Primary polymer is the Resins, epoxy family macromolecule that has hydroxyl, for shortening later reaction formula length, represents with alphabetical F; Its general structural formula can be expressed as follows:
Wherein, X is:
The epoxy resin primary polymer is reacted under melting condition by epoxy monomer and aniline or naphthylamines and obtains, and general reaction formula is as follows:
Wherein, the following formula preceding paragraph is commercial epoxy monomer, as bisphenol-A diglycidylether, 1,4 cyclohexane dimethanol diglycidylether and Resorcinol diglycidylether; R in the following formula is:
Following formula is consequent to be aromatic amine aniline, methyl substituted aniline or naphthylamines;
The preparation method is as follows for the epoxy resin primary polymer: under nitrogen protection, with etc. a kind of uniform mixing in a kind of and aromatic amine in the epoxy monomer of amount, and when being heated to 110 ℃, keep homo(io)thermism, under this temperature, polyreaction 24-48 hour, obtain primary polymer white transparent solid;
(2) primary polymer diazo coupling
1) diazonium salt solution preparation
Aromatic amino compound is prepared into diazonium salt, and general reaction formula is as follows
Y=Cl.HSO
4.
Abc.Be used for carrying out diazotizing aromatic amine Ar-NH
2Have: a. aniline or substituted aniline, b. naphthylamines or napthylamine sulfonic acid, c. amino-heterocyclic compounds;
Diazonium salt solution preparation method 1: with above-mentioned aromatic amine uniform mixing in the mixing solutions of the vitriol oil and Glacial acetic acid, Ar-NH
2: H
2SO
4=1: 2-3 (amount ratio), the volume ratio of the vitriol oil and Glacial acetic acid is 1: 12.5-20.Under 5 ℃, slowly add 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio) obtains transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 2: with above-mentioned aromatic amine uniform mixing in the 10M concentrated hydrochloric acid solution, Ar-NH
2: HCl=1: 2.5-3 (amount ratio) under 5 ℃, slowly adds 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 3: under 70 ℃, solid sodium nitrite is progressively joined in the vitriol oil NaNO
2: H
2SO
4=1: 2 (weight/volume), in adition process, control adding speed makes temperature be no more than 75 ℃, to obtain nitrosyl-sulfuric acid solution cools off in ice-water bath, adding simultaneously is 10-12.5 Glacial acetic acid dilution doubly with vitriol oil volume ratio, amino-heterocyclic compounds is added in the above-mentioned nitrosyl-sulfuric acid solution Ar-NH
2: NaNO
2=1: 1-1,2 (amounts than) obtain the diazonium salt solution of homogeneous transparent;
2) the heavy ammonia coupled reaction of primary polymer
Above-mentioned primary polymer is dissolved in the polar organic solvent of 5-500 times of weight ratio, in ice-water bath, solution temperature is dropped to 0 ℃, and remain on this temperature; Above-mentioned diazonium salt solution is slowly added above-mentioned polymers soln; Its diazonium salt: but the reaction member=0.2-1.25 in the primary polymer: 1 (amount ratio); Diazonium salt and primary polymer reacted 8-12 hour under the situation of vigorous stirring; General reaction formula is as follows
Wherein, P is the above-mentioned various group that carries out diazo coupling reaction, Ar is above-mentioned aromatic group, after reaction is finished, the 5-100 water doubly that in above-mentioned reaction system, adds the reaction system cumulative volume, obtain polymer precipitation, after filtration, after washing and the drying, promptly obtain elementary non-linear optical polymer product;
(3) the epoxy resin non-linear optical polymer of isocyanate-crosslinked modification
The above-mentioned elementary non-linear optical polymer that contains chromophore is dissolved in the polar organic solvent of 2-50 times of weight ratio, in solution, add isocyanate crosslinking, stir, spin-coating on ito glass, polymeric film polarizes under the impressed voltage of 5-30kV, the polarization temperature is 60-160 ℃, obtains the epoxy resin non-linear optical polymer of isocyanate crosslinking modification.
The substituting group of described substituted aniline can be methyl, chlorine, nitro, methoxyl group, oxyethyl group, phenoxy group, carboxyl, hydroxyl, ester group, amide group and sulfonic group.
The amount of described isocyanic ester and elementary non-linear optical polymer than for isocyanic ester-NCO unit: the hydroxyl=0.5-4 in the polymkeric substance: 1.
Described polar organic solvent such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), N-Methyl pyrrolidone.
Described isocyanate crosslinking comprises:
1) aliphatic diisocyanate:
OCN-R
1-NCO
R
1Be 2～12 carbon atoms straight chained alkyl, have the straight chained alkyl of 2～12 carbon atoms of at least one alkyl, halogen atom, cycloalkyl or alkoxyl group;
OCN-(CH
2)
x-S-(CH
2)
y-NCO
OCN-(CH
2)
x-O-(CH
2)
y-NCO
OCN-(CH
2)
x-C
6H
4·C
6H
4-(CH
2)
x-NCO
OCN-(CH
2)
x-O-(CH
2)
y-O-(CH
2)
x-NCO
OCN-(CH
2)
x-S-(CH
2)
y-S-(CH
2)
x-NCO
X＝1～6；Y＝1～6
C
5H
10(CH
2NCO)
21,2,1,3 or 1,4-dimethyl cyclohexane vulcabond
OCN-C
6H
10-NCO cyclohexyl diisocyanate (THDI)
CH
2(C
6H
10NCO)
2Dicyclohexyl methane diisocyanate (H
12MDI)
C
6H
4(CH
2NCO)
21,2,1,3 or 1,4-dimethyl penylene vulcabond
2) aromatic diisocyanate:
OCN-C
6H
4-NCO PPDI (PPDI)
CH
3(C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-tolylene diisocyanate (TDI)
CH
3CH
2(C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-ethylbenzene vulcabond (EDI)
(CH
3)
2CH (C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-isopropyl benzene vulcabond (IPDI)
(CH
3)
2(C
6H
3) (NCO)
2, dimethyl benzene vulcabond (DMDI)
[OCN (CH
3) C
6H
3]
2, dimethyl diphenyl vulcabond (DMBDI)
[OCN (CH
3O) C
6H
3]
2Dimethoxy-biphenyl vulcabond (DMOBDI)
(CH
3CH
2)
2(C
6H
3) (NCO)
2Diethylbenzene vulcabond (DEDI)
((CH
3)
2CH)
2(C
6H
3) (NCO)
2Di-isopropyl phenylene diisocyanate (DIPDI)
C
10H
6(NCO)
21,4-, 1,5,2,6 or 2,7-naphthalene diisocyanate (NDI)
OCN C
10H
6C
10H
6NCO biphenyl-4,4 ', 2,4 ', 2,2 '-vulcabond (BDI)
OCN C
10H
6-O-C
10H
6NCO biphenyl ether vulcabond (BODI)
OCN-C
6H
4-CH-C
6H
4-NCO '-diphenylmethane diisocyanate (MDI)
(CH
3)
2: C:(C
6H
4NCO)
2Phenylbenzene dimethylmethane vulcabond
3) modified isocyanate:
The polymeric acceptor of above-mentioned isocyanic ester and with the mixture of M20S, M20R or M20W.
The invention has the beneficial effects as follows the epoxy resin non-linear optical polymer with isocyanate crosslinking modification in addition, do not changing chromophore's kind and do not increasing under the condition of chromophore's number density, epoxy resin non-linear optical polymer after isocyanate-crosslinked is under the extra electric field polarization, the ordered orientation degree of the non-linear optical chromophore in the system itself is greatly improved than the epoxy resin non-linear optical polymer, and nonlinear second-order optical susceptibility can improve 100-300%.Simultaneously, the stability of the polarized dipole and electrical of the non-linear optical polymer after above-mentioned isocyanate-crosslinked modification orientation reaches more than 200 ℃.
Embodiment
The present invention is a kind of isocyanate-crosslinked epoxy resin second-order non-linear optical polymer, the concrete preparation method who takes is: earlier by epoxies monomer and aniline, the ring-opening polymerization of methyl substituted aniline or naphthylamines, obtain the various epoxy resin pioneer polymkeric substance of hydroxyl on the polymer segment, pass through the diazo coupling reaction of pioneer's polymkeric substance again, preparation contains the epoxy resin non-linear optical polymer of chromophore, epoxy resin non-linear optical polymer and isocyanate crosslinking blend with preparation have obtained isocyanate-modified bi-component polymeric system; This bi-component polymeric film adds polarization under the highfield outside, obtains isocyanate-crosslinked non-linear optical polymer film; Mainly may further comprise the steps:
(1) preparation of epoxy resin primary polymer
Primary polymer is the Resins, epoxy family macromolecule that has hydroxyl, for shortening later reaction formula length, represents with alphabetical F; Its general structural formula can be expressed as follows:
Wherein, X is:
The epoxy resin primary polymer is reacted under melting condition by epoxy monomer and aniline or naphthylamines and obtains, and general reaction formula is as follows:
Wherein, the following formula preceding paragraph is commercial epoxy monomer, as bisphenol-A diglycidylether, 1,4 cyclohexane dimethanol diglycidylether and Resorcinol diglycidylether; R in the following formula is:
Following formula is consequent to be aromatic amine aniline, methyl substituted aniline or naphthylamines.
The preparation method is as follows for the epoxy resin primary polymer: under nitrogen protection; with etc. a kind of uniform mixing in a kind of and aromatic amine in the epoxy monomer of amount; and slowly heating; when temperature reaches 110 ℃; keep homo(io)thermism; under this temperature, polyreaction 24-48 hour, obtain primary polymer white transparent solid.
(2) primary polymer diazo coupling
1) diazonium salt solution preparation
Aromatic amino compound is prepared into diazonium salt, and general reaction formula is as follows
Y＝Cl.HSO
4.
abc.
Be used for carrying out diazotizing aromatic amine Ar-NH
2Have: a. aniline or substituted aniline (substituting group can be methyl, chlorine, nitro, methoxyl group, oxyethyl group, phenoxy group, carboxyl, hydroxyl, ester group, amide group and sulfonic group etc.), b. naphthylamines or napthylamine sulfonic acid, c. amino-heterocyclic compounds;
Diazonium salt solution preparation method 1: with above-mentioned aromatic amine uniform mixing in the mixing solutions of the vitriol oil and Glacial acetic acid, Ar-NH
2: H
2SO
4=1: 2-3 (amount ratio), the volume ratio of the vitriol oil and Glacial acetic acid is 1: 12.5-20.Under 5 ℃, slowly add 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 2: with above-mentioned aromatic amine uniform mixing in the 10M concentrated hydrochloric acid solution, Ar-NH
2: HCl=1: 2.5-3 (amount ratio) under 5 ℃, slowly adds 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 3: under 70 ℃, solid sodium nitrite is progressively joined in the vitriol oil NaNO
2: H
2SO
4=1: 2 (weight/volume), in adition process, control adding speed makes temperature be no more than 75 ℃, will obtain nitrosyl-sulfuric acid solution and cool off in ice-water bath, and adding simultaneously is 10-12.5 Glacial acetic acid dilution doubly with vitriol oil volume ratio.Amino-heterocyclic compounds is added in the above-mentioned nitrosyl-sulfuric acid solution Ar-NH
2: NaNO
2=1: 1-1.2 (amount than) obtains the diazonium salt solution of homogeneous transparent;
2) primary polymer diazo coupling reaction
Above-mentioned primary polymer is dissolved in the polar organic solvent, in ice-water bath, solution temperature is dropped to 0 ℃, and remain on this temperature; Above-mentioned diazonium salt solution is slowly added above-mentioned polymers soln.The ratio of diazonium salt and primary polymer is determined according to the requirement of using, diazonium salt: but the reaction member=0.2-1.25 in the primary polymer: 1 (amount ratio); Diazonium salt and primary polymer reacted 8-12 hour under the situation of vigorous stirring; General reaction formula is as follows
Wherein, P is the above-mentioned various group that carries out diazo coupling reaction, Ar is above-mentioned aromatic group, after reaction is finished, the 5-100 water doubly that in above-mentioned reaction system, adds the reaction system cumulative volume, obtain polymer precipitation, after filtration, after washing and the drying, promptly obtain elementary non-linear optical polymer product.
(3) the epoxy resin non-linear optical polymer of isocyanate-crosslinked modification
The above-mentioned elementary non-linear optical polymer that contains chromophore is dissolved in the polar organic solvent of 2-50 times of weight ratio, the admixture mass ratio is isocyanic ester-NCO unit in the solution: the hydroxyl=0.5-4 in the polymkeric substance: 1 isocyanate crosslinking, stir spin-coating on ito glass.Polymeric film polarizes under the impressed voltage of 5-30kV, and the polarization temperature is 60-160 ℃, obtains the epoxy resin non-linear optical polymer of isocyanate crosslinking modification.
Described polar organic solvent such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), N-Methyl pyrrolidone.
Described isocyanate crosslinking comprises:
1) aliphatic diisocyanate:
OCN-R
1-NCO
R
1Be 2～12 carbon atoms straight chained alkyl, have the straight chained alkyl of 2～12 carbon atoms of at least one alkyl, halogen atom, cycloalkyl or alkoxyl group;
OCN-(CH
2)
x-S-(CH
2)
y-NCO
OCN-(CH
2)
x-O-(CH
2)
y-NCO
OCN-(CH
2)
x-C
6H
4·C
6H
4-(CH
2)
x-NCO
OCN-(CH
2)
x-O-(CH
2)
y-O-(CH
2)
x-NCO
OCN-(CH
2)
x-S-(CH
2)
y-S-(CH
2)
x-NCO
X＝1～6；Y＝1～6
C
6H
10(CH
2NCO)
21,2,1,3 or 1,4-dimethyl cyclohexane vulcabond
OCN-C
6H
10-NCO cyclohexyl diisocyanate (THDI)
CH
2(C
6H
10NCO)
2Dicyclohexyl methane diisocyanate (H
12MDI)
C
6H
4(CH
2NCO)
21,2,1,3 or 1,4-dimethyl penylene vulcabond
2) aromatic diisocyanate:
OCN-C
6H
4-NCO PPDI (PPDI)
CH
3(C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-tolylene diisocyanate (TDI)
CH
3CH
2(C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-ethylbenzene vulcabond (EDI)
(CH
3)
2CH (C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-isopropyl benzene vulcabond (IPDI)
(CH
3)
2(C
6H
3) (NCO)
2, dimethyl benzene vulcabond (DMDI)
[OCN (CH
3) C
6H
3]
2, dimethyl diphenyl vulcabond (DMBDI)
[OCN (CH
3O) C
6H
3]
2Dimethoxy-biphenyl vulcabond (DMOBDI)
(CH
3CH
2)
2(C
6H
3) (NCO)
2Diethylbenzene vulcabond (DEDI)
((CH
3)
2CH)
2(C
6H
3) (NCO)
2Di-isopropyl phenylene diisocyanate (DIPDI)
C
10H
6(NCO)
21,4-, 1,5,2,6 or 2,7-naphthalene diisocyanate (NDI)
OCN C
10H
6C
10H
6NCO biphenyl-4,4 ', 2,4 ', 2,2 '-vulcabond (BDI)
OCN C
10H
6-O-C
10H
6NCO biphenyl ether vulcabond (BODI)
OCN-C
6H
4-CH
2-C
6H
4-NCO '-diphenylmethane diisocyanate (MDI)
(CH
3)
2: C:(C
6H
4NCO)
2Phenylbenzene dimethylmethane vulcabond
3) modified isocyanate:
The polymeric acceptor of above-mentioned isocyanic ester and mixture thereof (as commercially produced product M20S, M20R and M20W etc.)
The vulcabond that adopts among the embodiment has:
'-diphenylmethane diisocyanate (MDI)
Normal hexane 1,6-vulcabond (HDI)
Ethylbenzene vulcabond (EDI)
Dimethyl cyclohexane vulcabond (DMCDI)
Dicyclohexyl methane diisocyanate (H
12MDI)
Dimethyl penylene vulcabond (DMPDI)
Phenylbenzene dimethylmethane vulcabond (DPDMDI)
Cyclohexyl diisocyanate (THDI)
PPDI (PPDI)
Biphenyl diisocyanate (BDI)
The isocyanic ester M20S of modification
Specific embodiment is:
Embodiment 1: under nitrogen protection, and with 76 gram (0.2mol) bisphenol-A diglycidylethers (molecular weight=381) and 18.6 gram (0.2mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 24 hours obtains primary polymer white transparent solid.With vinylbenzene is standard specimen, is 57000 with the molecular weight of this polymkeric substance of gel permeation chromatography.
1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6906 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.5 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains wine-colored elementary non-linear optical polymer.
Above-mentioned elementary NLO polymkeric substance 0.623 gram (2mmol-OH) is dissolved in 5 milliliters of N, and dinethylformamide (DMF) adds 0.250 gram (2mmol-NCO) MDI, stirs spin-coating on ito glass.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy NLO polymkeric substance of isocyanate crosslinking modification.
Embodiment 2: adopt elementary NLO polymkeric substance and the isocyanate crosslinking identical with embodiment 1.0.623 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution is in 5 milliliters of N, dinethylformamide (DMF) adds 0.375 gram (3mmol-NCO) '-diphenylmethane diisocyanate (MDI), stirs spin-coating on ito glass.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy NLO polymkeric substance of isocyanate crosslinking modification.
Embodiment 3: synthesis step is similar to embodiment 1, just changes MDI into normal hexane 1,6-vulcabond (HDI) 0.336 gram (2mmol-NCO).
Embodiment 4: synthesis step is similar to embodiment 1, just MDI is changed into ethylbenzene vulcabond (EDI) 0.377 gram (2mmol-NCO).
Embodiment 5: synthesis step is similar to embodiment 1, just changes MDI into dimethyl cyclohexane vulcabond (DMCDI) 0.331g (2mmol-NCO).
Embodiment 6: synthesis step is similar to embodiment 1, just changes MDI into dicyclohexyl methane diisocyanate (H
12MDI) 0.4706 gram (2mmol-NCO).
Embodiment 7: synthesis step is similar to embodiment 1, just MDI is changed into dimethyl penylene vulcabond (DMPDI) 0.3774 gram (2mmol-NCO).
Embodiment 8: synthesis step is similar to embodiment 1, just MDI is changed into phenylbenzene dimethylmethane vulcabond (DPDMDI) 0.4101 gram (2mmol-NCO).
Embodiment 9: synthesis step is similar to embodiment 1, just MDI is changed into cyclohexyl diisocyanate (THDI) 0.3308 gram (2mmol-NCO).
Embodiment 10: synthesis step is similar to embodiment 1, just MDI is changed into PPDI (PPDI) 0.3215 gram (2mmol-NCO).
Embodiment 11: synthesis step is similar to embodiment 1, just MDI is changed into biphenyl diisocyanate (BDI) 0.4706 gram (2mmol-NCO).
Embodiment 12: synthesis step is similar to embodiment 1, just MDI is changed into modified isocyanate M20S0.284 gram (2mmol-NCO).
Embodiment 13: under nitrogen protection, and with 51.27 gram (0.2mol) 1,4 cyclohexane dimethanol diglycidylethers and 18.63 gram (0.2mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 36 hours obtains primary polymer white transparent solid.Molecular weight with this polymkeric substance of gel permeation chromatography is 3500.
1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6906 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.5 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1 milliliter of 40% (w/y) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains wine-colored elementary non-linear optical polymer.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.250 gram (2mmol-NCO) MDI, stirs spin-coating on ito glass with 0.35 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 14: synthesis step is similar to embodiment 13, just changes MDI into normal hexane 1,6-vulcabond (HDI) 0.336 gram (2mmol-NCO).
Embodiment 15: synthesis step is similar to embodiment 13, just MDI is changed into ethylbenzene vulcabond (EDI) 0.377 gram (2mmol-NCO).
Embodiment 16: synthesis step is similar to embodiment 13, just changes MDI into dimethyl cyclohexane vulcabond (DMCDI) 0.331g (2mmol-NCO).
Embodiment 17: synthesis step is similar to embodiment 13, just changes MDI into dicyclohexyl methane diisocyanate (H
12MDI) 0.4706 gram (2mmol-NCO).
Embodiment 18: synthesis step is similar to embodiment 13, just MDI is changed into dimethyl penylene vulcabond (DMPDI) 0.3774 gram (2mmol-NCO).
Embodiment 19: synthesis step is similar to embodiment 13, just MDI is changed into phenylbenzene dimethylmethane vulcabond (DPDMDI) 0.4101 gram (2mmol-NCO).
Embodiment 20: synthesis step is similar to embodiment 13, just MDI is changed into cyclohexyl diisocyanate (THDI) 0.3308 gram (2mmol-NCO).
Embodiment 21: synthesis step is similar to embodiment 13, just MDI is changed into PPDI (PPDI) 0.3215 gram (2mmol-NCO).
Embodiment 22: synthesis step is similar to embodiment 13, just MDI is changed into biphenyl diisocyanate (BDI) 0.4706 gram (2mmol-NCO).
Embodiment 23: synthesis step is similar to embodiment 13, just MDI is changed into modified isocyanate M20S0.284 gram (2mmol-NCO)
Embodiment 24: under nitrogen protection, and with 44.5 gram (0.2mol) Resorcinol diglycidylethers (molecular weight=222.24) and 18.6 gram (0.2mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 24 hours obtains primary polymer white transparent solid.
1.261 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6906 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.6 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.2 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains wine-colored elementary non-linear optical polymer.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.250 gram (2mmol-NCO) MDI, stirs spin-coating on ito glass with 0.315 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 25: synthesis step is similar to embodiment 24, just changes MDI into normal hexane 1,6-vulcabond (HDI) 0.336 gram (2mmol-NCO).
Embodiment 26: synthesis step is similar to embodiment 24, just MDI is changed into ethylbenzene vulcabond (EDI) 0.377 gram (2mmol-NCO).
Embodiment 27: synthesis step is similar to embodiment 24, just changes MDI into dimethyl cyclohexane vulcabond (DMCDI) 0.331g (2mmol-NCO).
Embodiment 28: synthesis step is similar to embodiment 24, just changes MDI into dicyclohexyl methane diisocyanate (H
12MDI) 0.4706 gram (2mmol-NCO).
Embodiment 29: synthesis step is similar to embodiment 24, just MDI is changed into dimethyl penylene vulcabond (DMPDI) 0.3774 gram (2mmol-NCO).
Embodiment 30: synthesis step is similar to embodiment 24, just MDI is changed into phenylbenzene dimethylmethane vulcabond (DPDMDI) 0.4101 gram (2mmol-NCO).
Embodiment 31: synthesis step is similar to embodiment 24, just MDI is changed into cyclohexyl diisocyanate (THDI) 0.3308 gram (2mmol-NCO).
Embodiment 32: synthesis step is similar to embodiment 24, just MDI is changed into PPDI (PPDI) 0.3215 gram (2mmol-NCO).
Embodiment 33: synthesis step is similar to embodiment 24, just MDI is changed into biphenyl diisocyanate (BDI) 0.4706 gram (2mmol-NCO).
Embodiment 34: synthesis step is similar to embodiment 24, just MDI is changed into modified isocyanate M20S0.284 gram (2mmol-NCO)
Embodiment 35: under nitrogen protection, and with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.143 gram (0.02mol) 2-aminotoluene uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
1.953 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.15 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 8 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains wine-colored elementary non-linear optical polymer.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.250 gram (2mmol-NCO) MDI, stirs spin-coating on ito glass with 0.488 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 36: under nitrogen protection, and with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.143 gram (0.02mol) 3-monomethylaniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
1.953 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.15 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 8 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains wine-colored elementary non-linear optical polymer.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.336 gram (2mmol-NCO) 1 with 0.488 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution, and 6-vulcabond (HDI) stirs, spin-coating on ito glass.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy NLO polymkeric substance of isocyanate crosslinking modification.
Embodiment 37: under nitrogen protection, with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.424 gram (0.02mol) 2,5-xylidine uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
2.009 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 0.9 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 10 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the elementary NLO polymkeric substance of scarlet.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.377 gram (2mmol-NCO) ethylbenzene vulcabond (EDI), stirs spin-coating on ito glass with 0.502 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 38: under nitrogen protection, with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.424 gram (0.02mol) 2,6-xylidine uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
2.009 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 0.9 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 10 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the elementary non-linear optical polymer of scarlet.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.331g (2mmol-NCO) dimethyl cyclohexane vulcabond (DMCDI), stirs spin-coating on ito glass with 0.502 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 39: under nitrogen protection, and with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.8636 gram (0.02mol) naphthalidine uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
2.097 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.1 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the elementary non-linear optical polymer of scarlet.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.4706 gram (2mmol-NCO) dicyclohexyl methane diisocyanate (H with 0.524 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution
12MDI), stir spin-coating on ito glass.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, gets the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 40: adopt the identical primary polymer of embodiment 1.18.92 gram (40mmol) above-mentioned primary polymers are dissolved in 2 liters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
6.580 gram (48mmol) para-amino benzoic acid are mixed in 64 milliliter of 3% (w/v) aqueous sodium hydroxide solution, add 13.4 milliliters of concentrated hydrochloric acids (37%).Under 5 ℃, slowly add 12 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent para-amino benzoic acid diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the elementary non-linear optical polymer of yellowish red color.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.3774 gram (2mmol-NCO) dimethyl penylene vulcabond (DMPDI), stirs spin-coating on ito glass with 0.622 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 41: adopt the identical primary polymer of embodiment 1.18.92 gram (40mmol) above-mentioned primary polymers are dissolved in 2 liters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
Under 70 ℃, 3.5 gram Sodium Nitrites are progressively joined in 8 milliliters the vitriol oil, in adition process, controlled temperature is no more than 75 ℃.To obtain nitrosyl-sulfuric acid solution and in ice-water bath, cool off, simultaneously with 100 milliliters of Glacial acetic acid dilutions.7.26 gram (50mmol) 2-amino-5-nitrothiazoles are added above-mentioned nitrosyl-sulfuric acid solution.Obtain the diazonium salt solution of homogeneous transparent.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the elementary non-linear optical polymer of avy blue.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.284 gram (2mmol-NCO) modified isocyanate M20S, stirs spin-coating on ito glass with 0.630 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Embodiment 42: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 0.9409 gram (5mmol) to 4-nitro-naphthalidine uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.2 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent 4-nitro-naphthalidine diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains wine-colored elementary non-linear optical polymer.
In 5 milliliters of N, dinethylformamide (DMF) adds 0.3308 gram (2mmol-NCO) cyclohexyl diisocyanate (THDI), stirs spin-coating on ito glass with 0.628 gram (2mmol-OH) above-mentioned elementary NLO polymer dissolution.Polymeric film polarizes under the impressed voltage of 5-10kV, and the polarization temperature is 60-160 ℃, obtains the Resins, epoxy non-linear optical polymer of isocyanate crosslinking modification.
Claims (5)
1. isocyanate-crosslinked epoxy resin second-order non-linear optical polymer, it is characterized in that: the ring-opening polymerization that passes through epoxies monomer and aniline, methyl substituted aniline or naphthylamines earlier, obtain the various epoxy resin pioneer polymkeric substance of hydroxyl on the polymer segment, pass through the diazo coupling reaction of pioneer's polymkeric substance again, preparation contains the epoxy resin non-linear optical polymer of chromophore, epoxy resin non-linear optical polymer and isocyanate crosslinking blend with preparation have obtained isocyanate-modified bi-component polymeric system; This bi-component polymeric film adds polarization under the highfield outside, obtains isocyanate-crosslinked non-linear optical polymer film; Mainly may further comprise the steps:
(1) preparation of epoxy resin primary polymer
Primary polymer is the Resins, epoxy family macromolecule that has hydroxyl, for shortening later reaction formula length, represents with alphabetical F; Its general structural formula can be expressed as follows:
Wherein, X is:
The epoxy resin primary polymer is reacted under melting condition by epoxy monomer and aniline or naphthylamines and obtains, and general reaction formula is as follows:
Wherein, the following formula preceding paragraph is commercial epoxy monomer, as bisphenol-A diglycidylether, 1,4 cyclohexane dimethanol diglycidylether and Resorcinol diglycidylether; R in the following formula is:
Following formula is consequent to be aromatic amine aniline, methyl substituted aniline or naphthylamines;
The preparation method is as follows for the epoxy resin primary polymer: under nitrogen protection, with etc. a kind of uniform mixing in a kind of and aromatic amine in the epoxy monomer of amount, and be heated to 110 ℃, keep homo(io)thermism, under this temperature, polyreaction 24-48 hour, obtain primary polymer white transparent solid;
(2) primary polymer diazo coupling
1) diazonium salt solution preparation
Aromatic amino compound is prepared into diazonium salt, and general reaction formula is as follows
Y＝Cl.HSO
4.
abc.
Be used for carrying out diazotizing aromatic amine Ar-NH
2Have: a. aniline or substituted aniline, b. naphthylamines or napthylamine sulfonic acid, c. amino-heterocyclic compounds;
Diazonium salt solution preparation method 1: with above-mentioned aromatic amine uniform mixing in the mixing solutions of the vitriol oil and Glacial acetic acid, Ar-NH
2: H
2SO
4=1: 2-3 (amount ratio), the volume ratio of the vitriol oil and Glacial acetic acid is 1: 12.5-20.Under 5 ℃, slowly add 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio) obtains the heavy ammonia salts solution of transparent aromatic amine behind the stirring reaction;
Diazonium salt solution preparation method 2: with above-mentioned aromatic amine uniform mixing in the 10M concentrated hydrochloric acid solution, Ar-NH
2: HCl=1: 2.5-3 (amount ratio) under 5 ℃, slowly adds 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 3: under 70 ℃, solid sodium nitrite is progressively joined in the vitriol oil NaNO
2: H
2SO
4=1: 2 (weight/volume), in adition process, control adding speed makes temperature be no more than 75 ℃, to obtain nitrosyl-sulfuric acid solution cools off in ice-water bath, adding simultaneously is 10-12.5 Glacial acetic acid dilution doubly with vitriol oil volume ratio, amino-heterocyclic compounds is added in the above-mentioned nitrosyl-sulfuric acid solution Ar-NH
2: NaNO
2=1: 1-1.2 (amount than) obtains the diazonium salt solution of homogeneous transparent;
2) primary polymer diazo coupling reaction
Above-mentioned primary polymer is dissolved in the polar organic solvent of 5-500 times of weight ratio, in ice-water bath, solution temperature is dropped to 0 ℃, and remain on this temperature; Above-mentioned diazonium salt solution is slowly added above-mentioned polymers soln.The ratio of diazonium salt and primary polymer is determined according to the requirement of using, diazonium salt: but the reaction member=0.2-1.25 in the primary polymer: 1 (amount ratio); Diazonium salt and primary polymer reacted 8-12 hour under the situation of vigorous stirring; General reaction formula is as follows
Wherein, P is the above-mentioned various group that carries out diazo coupling reaction, Ar is above-mentioned aromatic group, after reaction is finished, the 5-100 water doubly that in above-mentioned reaction system, adds the reaction system cumulative volume, obtain polymer precipitation, after filtration, after washing and the drying, promptly obtain elementary non-linear optical polymer product;
(3) the epoxy resin non-linear optical polymer of isocyanate-crosslinked modification
The above-mentioned elementary non-linear optical polymer that contains chromophore is dissolved in the polar organic solvent of 2-50 times of weight ratio, in solution, adds isocyanate crosslinking, stir spin-coating on ito glass.Polymeric film polarizes under the impressed voltage of 5-30kV, and the polarization temperature is 60-160 ℃, obtains the epoxy resin non-linear optical polymer of isocyanate crosslinking modification.
2. according to the isocyanate-crosslinked epoxy resin second-order non-linear optical polymer of claim 1, it is characterized in that: the substituting group of described substituted aniline can be methyl, chlorine, nitro, methoxyl group, oxyethyl group, phenoxy group, carboxyl, hydroxyl, ester group, amide group and sulfonic group.
3. according to the isocyanate-crosslinked epoxy resin second-order non-linear optical polymer of claim 1, it is characterized in that: the amount of described isocyanic ester and elementary non-linear optical polymer than for isocyanic ester-NCO unit: the hydroxyl=0.5-4 in the polymkeric substance: 1.
4. according to the isocyanate-crosslinked epoxy resin second-order non-linear optical polymer of claim 1, it is characterized in that: described polar organic solvent such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), N-Methyl pyrrolidone.
5. according to the isocyanate-crosslinked epoxy resin second-order non-linear optical polymer of claim 1, it is characterized in that: described isocyanate crosslinking comprises:
1) aliphatic diisocyanate:
OCN-R
1-NCO
R
1Be 2～12 carbon atoms straight chained alkyl, have the straight chained alkyl of 2～12 carbon atoms of at least one alkyl, halogen atom, cycloalkyl or alkoxyl group;
OCN-(CH
2)
x-S-(CH
2)
y-NCO
OCN-(CH
2)
x-O-(CH
2)
y-NCO
OCN-(CH
2)
x-C
6H
4·C
6H
4-(CH
2)
x-NCO
OCN-(CH
2)
x-O-(CH
2)
y-O-(CH
2)
x-NCO
OCN-(CH
2)
x-S-(CH
2)
y-S-(CH
2)
x-NCO
X＝1～6；Y＝1～6
C
6H
10(CH
2NCO)
21,2,1,3 or 1,4-dimethyl cyclohexane vulcabond
OCN-C
6H
10-NCO cyclohexyl diisocyanate (THDI)
CH
2(C
6H
10NCO)
2Dicyclohexyl methane diisocyanate (H
12MDI)
C
6H
4(CH
2NCO)
21,2,1,3 or 1,4-dimethyl penylene vulcabond;
2) aromatic diisocyanate:
OCN-C
6H
4-NCO PPDI (PPDI)
CH
3(C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-tolylene diisocyanate (TDI)
CH
3CH
2(C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-ethylbenzene vulcabond (EDI)
(CH
3)
2CH (C
6H
3) (NCO)
2, 2,4,2,5,2,6,3,5-isopropyl benzene vulcabond (IPDI)
(CH
3)
2(C
6H
3) (NCO)
2, dimethyl benzene vulcabond (DMDI)
[OCN (CH
3) C
6H
3]
2, dimethyl diphenyl vulcabond (DMBDI)
[OCN (CH
3O) C
6H
3]
2Dimethoxy-biphenyl vulcabond (DMOBDI)
(CH
3CH
2)
2(C
6H
3) (NCO)
2Diethylbenzene vulcabond (DEDI)
((CH
3)
2CH)
2(C
6H
3) (NCO)
2Di-isopropyl phenylene diisocyanate (DIPDI)
C
10H
6(NCO)
21,4-, 1,5,2,6 or 2,7-naphthalene diisocyanate (NDI)
OCN C
10H
8C
10H
6NCO biphenyl-4,4 ', 2,4 ', 2,2 '-vulcabond (BDI)
OCNC
10H
6-O-C
10H
6NCO biphenyl ether vulcabond (BODI)
OCN-C
6H
4-CH
2-C
6H
4-NCO '-diphenylmethane diisocyanate (MDI)
(CH
3)
2: C:(C
6H
4NCO)
2Phenylbenzene dimethylmethane vulcabond
3) modified isocyanate:
The polymeric acceptor of above-mentioned isocyanic ester and with the mixture of M20S, M20R or M20W.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492360A (en) * | 2011-12-01 | 2012-06-13 | 常州光辉化工有限公司 | Solvent-free polyurethane wear-resistant terrace paint and preparation method thereof |
| CN107022168A (en) * | 2016-02-02 | 2017-08-08 | 上纬企业股份有限公司 | Thermoplastic epoxy resin-based formula, prepreg, composite material and manufacturing method thereof |
-
2003
- 2003-09-05 CN CN 03156221 patent/CN1252118C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492360A (en) * | 2011-12-01 | 2012-06-13 | 常州光辉化工有限公司 | Solvent-free polyurethane wear-resistant terrace paint and preparation method thereof |
| CN102492360B (en) * | 2011-12-01 | 2014-01-29 | 常州光辉化工有限公司 | Solvent-free polyurethane wear-resistant terrace paint and preparation method thereof |
| CN107022168A (en) * | 2016-02-02 | 2017-08-08 | 上纬企业股份有限公司 | Thermoplastic epoxy resin-based formula, prepreg, composite material and manufacturing method thereof |
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|---|---|
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