CN102675580B - Electrochromatic epoxy resin polymer and preparation method thereof - Google Patents
Electrochromatic epoxy resin polymer and preparation method thereof Download PDFInfo
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- CN102675580B CN102675580B CN 201210164096 CN201210164096A CN102675580B CN 102675580 B CN102675580 B CN 102675580B CN 201210164096 CN201210164096 CN 201210164096 CN 201210164096 A CN201210164096 A CN 201210164096A CN 102675580 B CN102675580 B CN 102675580B
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Abstract
The invention relates to an epoxy resin polymer and a preparation method thereof, particularly relates to an electrochromatic epoxy resin polymer and a preparation method thereof, and aims to solve the problem that existing polymer films are prone to shed in organic solution and difficult in detection of electrochromatic performance. The chemical formula of the epoxy resin polymer is shown as follows. The method includes: adding hydroxyl-contained monomer material A into epichlorohydrin, stirring at 60-80 DEG C while dripping aqueous sodium hydroxide solution into epichlorohydrin solution of the material A, and reacting for two to eight hours to obtain the electrochromatic epoxy resin polymer. The epoxy resin polymer is highly adhesive, highly resistant to acid, alkali and heat and high in mechanical performance, and has the electrochromatic performance of triphenylamine, the shear strength of the epoxy resin polymer is about 30MPa, and the maximum service temperature of the epoxy resin polymer is up to 120 DEG C. The electrochromatic epoxy resin polymer and the preparation method thereof are applicable to the field of electrochromism.
Description
Technical field
The present invention relates to a kind of epoxy-based polymer and preparation method thereof.
Background technology
1, epoxyn
As a kind of emerging chemical materials, it is good that epoxy glue has chemical stability, and cure shrinkage is little, and adhesive property is superior, increasing in the effect of every field.
Epoxy glue has following features, (1) bonding is in extensive range, solved performance difference large (such as steel and concrete), size difference is large (as thin as a wafer, extremely thick) adhesion problem, (2) interconnecting piece is in the rational situation of joint, it connects the stressed of connecting portion is uniform, (3) compare with traditional tackiness agent that to have a processing quality of connection light, very important to aircraft and aerospace aspect.Deficiency is also arranged certainly, and such as shock strength, stripping strength is not high, and bonding quality is affected by several factors.Epoxy resin glue demonstrates excellent performance gradually in continuous modification, 21 century, its Bright Prospect was open.
But epoxy glue easily comes off in organic solvent at present, and preparation is difficulty.
2, electrochromism
Electrochromism refers to that the phenomenon of stable, reversible colour-change occurs the optical properties (reflectivity, transmitance, specific absorption etc.) of material, shows as the reversible change of color and transparency in appearance under the effect of extra electric field.Material with electrochromic property is called electrochromic material, and the device made from electrochromic material is called electrochromic device.
Electrochromic material is divided into inorganic electrochromic material and organic electrochromic material.Inorganic materials research comparatively early and moulding, organic in electrochromic material take purple sieve essence class as functional materials obtained practical application.
Electrochromic intelligent glass is applied in the office building residential building, cool in summer and warm in winter, solve the light pollution problem, electrochromic display device has without the ablepsia angle with traditional comparing, the characteristics that contrast gradient is high, some equipment such as automatic anti-glare rear vision mirror of electrochromism preparation have been shown up prominently, and intellectuality is more and more stronger.
But the epoxy resin glue electrochromic property is poor at present, is difficult to measure.
Summary of the invention
The objective of the invention is easily to come off in organic solution in order to solve existing polymeric film, be difficult to measure the problem of its electrochromic property, and a kind of electrochromic property epoxy-based polymer and preparation method thereof that has is provided.
A kind of chemical structural formula with electrochromic property epoxy-based polymer of the present invention is as follows:
Wherein, n is that 10 ~ 20, R is
A kind of preparation method with electrochromic property epoxy-based polymer of the present invention carries out according to the following steps:
One, monomer is synthetic
A, with diamino triphenylamine derivative and p-Hydroxybenzaldehyde in molar ratio for the ratio of 1:2 ~ 3 mixes, get mixture; B, the mixture that step a is obtained and solvent are that the ratio of 0.8 ~ 2.1g:100mL mixes and obtains mixed solution in mass volume ratio, then under the condition of nitrogen protection, temperature is risen to 120 ℃ ~ 140 ℃, speed with 20 ~ 50rpm stirs 12h, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected remaining 1/4 volume of liquid put into distilled water, leave standstill 6 ~ 12h, then under being the condition of 0.09MPa, vacuum tightness carries out suction filtration, collect solid formation, the solid formation of collecting is put into vacuum drying oven, be 0.09MPa in vacuum tightness, temperature is dry 6 ~ 12h under 50 ℃ the condition, namely gets monomer; Wherein, solvent be toluene and DMF by volume for the ratio of 3:1 mixes, the volume ratio that step b collects remaining 1/4 volume of liquid and distilled water is 1:30;
Two, epoxy-based polymer is synthetic
The epoxy chloropropane liquid of a, the monomer that step 1 is obtained and reduced pressure treatment is that the ratio of 0.01 ~ 0.10g:20mL mixes in mass volume ratio, puts into there-necked flask, gets mixing solutions; B, under the condition of nitrogen protection, temperature is risen to 60 ℃, then use mixed solution and dripping concentration that constant pressure funnel obtains take from the speed of 0.1 ~ 0.3mL/s to step a as 6 * 10
-3~ 10 * 10
-3The sodium hydroxide solution of g/mL after dripping, is heated to 61 ℃ ~ 100 ℃, and the speed stirring 6 ~ 8h with 20 ~ 50rpm gets just mixed liquid; C, the first mixed liquid that step b is obtained are poured in methyl alcohol or the distilled water, leave standstill 6 ~ 12h, then remove the water layer on upper strata with separating funnel after, collect the solution of lower floor; After the ratio that the solution collected and solidifying agent are 5 ~ 10:1 by volume mixes, be heated to 100 ~ 200 ℃, curing reaction 2 ~ 12h, room temperature namely gets epoxy-based polymer after cooling off; Wherein, the synthetic monomer mole ratio of sodium hydroxide solution and step 1 is 1:1, and just the volume ratio of mixed liquid and methyl alcohol or distilled water is 1:30, and solidifying agent is tolylene diisocyanate or isophorone diisocyanate.
Monomer building-up process of the present invention is as follows:
The building-up process of epoxy-based polymer of the present invention is as follows:
Beneficial effect of the present invention is:
Epoxy-based polymer adhesive property of the present invention is good, and shearing resistance is about 30MPa, and the acid and alkali-resistance resistance toheat is good, and maximum operation (service) temperature can reach 120 ℃, has good mechanical property, has again the electrochromic property of anilino simultaneously.Epoxy-based polymer luminous response speed of the present invention is 1000 times of liquid crystal, in the exploitation of molecular designing device potential value is arranged.The epoxy-based polymer oxirane value that the present invention synthesized has performance gluing and coating at 0.12 ~ 0.30 equivalent/100g.
Description of drawings
Fig. 1 is the test 1 epoxy-based polymer cyclic voltammogram that obtains;
Fig. 2 is the test 1 epoxy-based polymer ultraviolet figure that obtains;
Fig. 3 is the test 1 epoxy-based polymer infrared spectrogram that obtains;
Fig. 4 is the test 2 epoxy-based polymer infrared spectrograms that obtain;
Fig. 5 is the test 3 epoxy-based polymer infrared spectrograms that obtain;
Fig. 6 is the test 4 epoxy-based polymer infrared spectrograms that obtain;
Fig. 7 is the test 5 epoxy-based polymer infrared spectrograms that obtain.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: it is as follows that present embodiment a kind of has the chemical structural formula of electrochromic property epoxy-based polymer:
Wherein, n is that 10 ~ 20, R is
The epoxy-based polymer adhesive property of present embodiment is good, and shearing resistance is about 30MPa, and the acid and alkali-resistance resistance toheat is good, and maximum operation (service) temperature can reach 120 ℃, has good mechanical property, has again the electrochromic property of anilino simultaneously.The epoxy-based polymer luminous response speed of present embodiment is 1000 times of liquid crystal, in the exploitation of molecular designing device potential value is arranged.The epoxy-based polymer oxirane value that present embodiment is synthesized has performance gluing and coating at 0.12 ~ 0.30 equivalent/100g.
Embodiment two: a kind of preparation method with electrochromic property epoxy-based polymer of present embodiment carries out according to the following steps:
One, monomer is synthetic
A, with diamino triphenylamine derivative and p-Hydroxybenzaldehyde in molar ratio for the ratio of 1:2 ~ 3 mixes, get mixture; B, the mixture that step a is obtained and solvent are that the ratio of 0.8 ~ 2.1g:100mL mixes and obtains mixed solution in mass volume ratio, then under the condition of nitrogen protection, temperature is risen to 120 ℃ ~ 140 ℃, speed with 20 ~ 50rpm stirs 12h, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected remaining 1/4 volume of liquid put into distilled water, leave standstill 6 ~ 12h, then under being the condition of 0.09MPa, vacuum tightness carries out suction filtration, collect solid formation, the solid formation of collecting is put into vacuum drying oven, be 0.09MPa in vacuum tightness, temperature is dry 6 ~ 12h under 50 ℃ the condition, namely gets monomer; Wherein, solvent be toluene and DMF by volume for the ratio of 3:1 mixes, the volume ratio that step b collects remaining 1/4 volume of liquid and distilled water is 1:30;
Two, epoxy-based polymer is synthetic
The epoxy chloropropane liquid of a, the monomer that step 1 is obtained and reduced pressure treatment is that the ratio of 0.01 ~ 0.10g:20mL mixes in mass volume ratio, puts into there-necked flask, gets mixing solutions; B, under the condition of nitrogen protection, temperature is risen to 60 ℃, then use mixed solution and dripping concentration that constant pressure funnel obtains take from the speed of 0.1 ~ 0.3mL/s to step a as 5 * 10
-3~ 13 * 10
-3The sodium hydroxide solution of g/mL after dripping, is heated to 61 ℃ ~ 100 ℃, and the speed stirring 6 ~ 8h with 20 ~ 50rpm gets just mixed liquid; C, the first mixed liquid that step b is obtained are poured in methyl alcohol or the distilled water, leave standstill 6 ~ 12h, then remove the water layer on upper strata with separating funnel after, collect the solution of lower floor; After the ratio that the solution collected and solidifying agent are 5 ~ 10:1 by volume mixes, be heated to 100 ~ 200 ℃, curing reaction 2 ~ 12h, room temperature namely gets epoxy-based polymer after cooling off; Wherein, the synthetic monomer mole ratio of sodium hydroxide solution and step 1 is 1:1, and just the volume ratio of mixed liquid and methyl alcohol or distilled water is 1:30, and solidifying agent is tolylene diisocyanate or isophorone diisocyanate.
The epoxy-based polymer adhesive property of present embodiment is good, and shearing resistance is about 30MPa, and the acid and alkali-resistance resistance toheat is good, and maximum operation (service) temperature can reach 120 ℃, has good mechanical property, has again the electrochromic property of anilino simultaneously.The epoxy-based polymer luminous response speed of present embodiment is 1000 times of liquid crystal, in the exploitation of molecular designing device potential value is arranged.The epoxy-based polymer oxirane value that present embodiment is synthesized has performance gluing and coating at 0.12 ~ 0.30 equivalent/100g.
Embodiment three: what present embodiment and embodiment two were different is: the described diamino triphenylamine derivative of step 1 is 4,4 '-diamino-4 " N-carbazyl triphenylamine; N; N-two (4-aminophenyl)-N '; N '-phenylbenzene-1; 4-phenylenediamine; N '-(4-aminophenyl)-N '-(4-oxyethyl group) phenyl-1, the 4-phenylenediamine, N, N '-two (betanaphthyl)-N, N '-two (4-aniline) Ursol D or N '-(4-aminophenyl)-N '-phenyl-1, the 4-phenylenediamine, N ', N '-phenylbenzene-N, N '-two (4-aniline) Ursol D, N ', N '-phenylbenzene-N, N '-two (4-aniline) benzidine or N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine.Other is identical with step 2.
Embodiment four: what present embodiment and embodiment two to three were different is: the described diamino triphenylamine derivative of step 1 and p-Hydroxybenzaldehyde are 1:2 in molar ratio.Other is identical with step 2 to three.
Embodiment five: what present embodiment was different from one of embodiment two to four is: the mixture that the described step a of step 1 obtains and solvent are 1.3 ~ 1.6g:100mL by mass volume ratio.Other is identical with one of step 2 to four.
Embodiment six: what present embodiment was different from one of embodiment two to five is: the monomer that the described step 1 of step 2 obtains and epoxy chloropropane liquid are 0.04 ~ 0.06g:20mL by mass volume ratio.Other is identical with one of step 2 to five.
Embodiment seven: what present embodiment was different from one of embodiment two to six is: the epoxy chloropropane liquid of the described reduced pressure treatment of step 2: epoxy chloropropane liquid is carried out underpressure distillation under the condition of vacuum tightness 0.009MPa ~ 0.010MPa, collect that 60 ℃ ~ 65 ℃ cut obtains.Other is identical with one of step 2 to six.
By following verification experimental verification effect of the present invention
A kind of preparation method with electrochromic property epoxy-based polymer of this test:
One, monomer M 1 is synthetic
A, take by weighing 4 of 0.5000g with electronic balance, 4 '-diamino-4 " p-Hydroxybenzaldehyde of N-carbazyl triphenylamine and 0.3466g is put into there-necked flask; measure the toluene of 75mL and the DMF of 25mL (DMF) is poured in the there-necked flask again, mixes; B, under the condition of nitrogen protection, temperature is risen to 140 ℃, and keeps temperature, stir 12h with the speed of 30rpm, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected the distilled water that remaining 25mL liquid is put into 750mL, after leaving standstill 12h, it is suction filtration under the condition of 0.09MPa in vacuum tightness, collect solid formation, the solid formation of collecting is put into vacuum drying oven, is 0.09MPa in vacuum tightness, is under 60 ℃ of conditions in temperature, dry 12h namely gets monomer M 1;
Two, epoxy-based polymer P1's is synthetic
A, take by weighing the monomer M 1 that the step 1 of 0.068g obtains with electronic balance, measure the epoxy chloropropane liquid of the reduced pressure treatment of 20mL, put into there-necked flask, after stirring with the speed of 50rpm, be warming up to again 60 ℃, then with constant pressure funnel take the speed of 0.3mL/s with 15mL concentration as 5.8 * 10
-3The sodium hydroxide solution of g/mL all splashes in the there-necked flask; After b, dropping finish, be warming up to 85 ℃, then the speed stirring 8h with 50rpm leaves standstill 12h, removes water layer with separating funnel, gets epoxide resin polymer; C, get the 0.036g epoxy-based polymer, add the 0.006g solidifying agent, be heated to 200 ℃ and solidify 12h, for subsequent use after the room temperature cooling; Wherein, solidifying agent is tolylene diisocyanate (TDI); It is to collect the epoxy chloropropane that 60 ℃ ~ 65 ℃ cut obtains under 0.009MPa ~ 0.010MPa that the epoxy chloropropane liquid of reduced pressure treatment refers in vacuum tightness.
Hence one can see that, and the epoxy-based polymer structure that this test obtains is:
4,4 of this test '-diamino-4 " N-carbazyl fluorine-triphenylamine structure formula is as follows:
The reaction process of this test is as follows:
One. the synthetic reaction process of monomer M 1 is as follows:
Two. epoxy-based polymer P1 is synthetic
Three. the curing of epoxy-based polymer
A kind of preparation method with epoxy-based polymer of electrochromic property of this test:
One, monomer M 2 is synthetic
A, take by weighing the N of 0.5000g with electronic balance, N-two (4-aminophenyl)-N ', N '-phenylbenzene-1, the p-Hydroxybenzaldehyde of 4-phenylenediamine and 0.3450g is put into there-necked flask, measure 75mL toluene and 25mLN, dinethylformamide (DMF) is poured in the there-necked flask, mixes again; B, under the condition of nitrogen protection, temperature is risen to 140 ℃, and keeps temperature, stir 12h with the speed of 30rpm, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected the distilled water that remaining 25mL liquid is put into 750mL, after leaving standstill 12h, it is suction filtration under the condition of 0.09MPa in vacuum tightness, collect solid formation, the solid formation of collecting is put into vacuum drying oven, is 0.09MPa in vacuum tightness, is under 60 ℃ of conditions in temperature, dry 12h namely gets monomer M 2;
Two, epoxy-based polymer P2's is synthetic
A, take by weighing the monomer that the step 1 of 0.068g obtains with electronic balance, measure the epoxy chloropropane liquid of the reduced pressure treatment of 20mL, put into there-necked flask, stir with the speed of 50rpm, be warming up to again 60 ℃, then with constant pressure funnel take the speed of 0.3mL/s with 15mL concentration as 8.6 * 10
-3The sodium hydroxide solution of g/mL all splashes in the there-necked flask; After b, dropping finish, be warming up to 85 ℃, then the speed stirring 8h with 50rpm leaves standstill 12h, removes water layer with separating funnel, gets epoxy-based polymer; C, get the 0.036g epoxy-based polymer, add the 0.006g solidifying agent, be heated to 200 ℃ and solidify 12h, for subsequent use after the room temperature cooling; Wherein, solidifying agent is tolylene diisocyanate (TDI); It is to collect the epoxy chloropropane that 60 ℃ ~ 65 ℃ cut obtains under 0.009MPa ~ 0.010MPa that the epoxy chloropropane liquid of reduced pressure treatment refers in vacuum tightness.
Epoxy-based polymer after this test solidified carries out infrared spectra and detects, the result as shown in Figure 4, as shown in Figure 4, at 3344cm
-1The place is the O-H stretching vibration peak on the phenolic group.3036cm
-1The C-H stretching vibration peak of phenyl ring has appearred in the place.2924cm
-1And 2870cm
-1The peak at place is respectively the stretching vibration peak of methyl and methylene radical.1599cm
-1And 1503cm
-1The place is the skeleton stretching vibration peak of phenyl ring.912cm
-1The place is the charateristic avsorption band of epoxy group(ing), illustrates and has introduced epoxide group on the polymkeric substance.
The N of this test, N-two (4-aminophenyl)-N ', the structural formula of N '-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine is as follows:
The epoxy-based polymer structure that this test obtains is as follows:
The reaction process of this experiment is as follows:
One. monomer M 2 is synthetic
Two. epoxy-based polymer P2 is synthetic
Three. the curing of epoxy-based polymer
A kind of preparation method with epoxy-based polymer of electrochromic property of this test:
One, monomer M 3 is synthetic
A, take by weighing the N ' of 0.7422g-(4-aminophenyl)-N '-(4-oxyethyl group) phenyl-1 with electronic balance, the p-Hydroxybenzaldehyde of 4-phenylenediamine and 0.7095g is put into there-necked flask, measure again 75mL toluene and 25mL N, dinethylformamide (DMF) is poured in the there-necked flask, mixes; B, under the condition of nitrogen protection, temperature is risen to 140 ℃, and keeps temperature, stir 12h with the speed of 30rpm, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected the distilled water that remaining 25mL liquid is put into 750mL, after leaving standstill 12h, it is suction filtration under the condition of 0.09MPa in vacuum tightness, collect solid formation, the solid formation of collecting is put into vacuum drying oven, is 0.09MPa in vacuum tightness, is under 60 ℃ of conditions in temperature, dry 12h namely gets monomer M 3;
Two, epoxy-based polymer P3's is synthetic
A, take by weighing the monomer that the step 1 of 0.068g obtains with electronic balance, measure the epoxy chloropropane liquid of the reduced pressure treatment of 20mL, put into there-necked flask, stir with the speed of 50rpm, be warming up to again 60 ℃, then with constant pressure funnel take the speed of 0.3mL/s with 15mL concentration as 12.5 * 10
-3The sodium hydroxide solution of g/mL all splashes in the there-necked flask; After b, dropping finish, be warming up to 85 ℃, then the speed stirring 8h with 50rpm leaves standstill 12h, removes water layer with separating funnel, gets epoxy-based polymer; C, get the 0.036g epoxy-based polymer, add the 0.006g solidifying agent, be heated to 200 ℃ and solidify 12h, for subsequent use after the room temperature cooling; Wherein, solidifying agent is tolylene diisocyanate (TDI); It is to collect the epoxy chloropropane that 60 ℃ ~ 65 ℃ cut obtains under 0.009MPa ~ 0.010MPa that the epoxy chloropropane liquid of reduced pressure treatment refers in vacuum tightness.
Epoxy-based polymer after this test solidified carries out infrared spectra and detects, the result as shown in Figure 5, as shown in Figure 5, at 3366cm
-1The place is the O-H stretching vibration peak on the phenolic group.3041cm
-1The C-H stretching vibration peak of phenyl ring has appearred in the place.2923cm
-1And 2874cm
-1The peak at place is respectively the stretching vibration peak of methyl and methylene radical.1601cm
-1And 1504cm
-1The place is the skeleton stretching vibration peak of phenyl ring.921cm
-1The place is the charateristic avsorption band of epoxy group(ing), illustrates and has introduced epoxide group on the polymkeric substance.
The N ' of this test-(4-aminophenyl)-N '-(4-oxyethyl group) phenyl-Isosorbide-5-Nitrae-the phenylenediamine structural formula is as follows:
The structural formula of the epoxy-based polymer that this experiment obtains is as follows:
The reaction process of this experiment is as follows:
One. monomer M 3 is synthetic
Two. epoxy-based polymer P3 is synthetic
Three. the curing of epoxy-based polymer
Test 4
A kind of preparation method with electrochromic property epoxy-based polymer of this test:
One, monomer M 4 is synthetic
A, take by weighing the N of 1.0000g with electronic balance, N '-two (betanaphthyl)-N, the p-Hydroxybenzaldehyde of N '-two (4-aniline) Ursol D and 0.5626g is put into there-necked flask, measures 75mL toluene and 25mLN again, dinethylformamide (DMF) is poured in the there-necked flask, mixes; B, under the condition of nitrogen protection, temperature is risen to 140 ℃, and keeps temperature, stir 12h with the speed of 30rpm, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected the distilled water that remaining 25mL liquid is put into 750mL, after leaving standstill 12h, it is suction filtration under the condition of 0.09MPa in vacuum tightness, collect solid formation, the solid formation of collecting is put into vacuum drying oven, is 0.09MPa in vacuum tightness, is under 60 ℃ of conditions in temperature, dry 12h namely gets monomer M 4;
Two, epoxy-based polymer P4's is synthetic
A, take by weighing the monomer that the step 1 of 0.068g obtains with electronic balance, with the epoxy chloropropane liquid of the reduced pressure treatment of 20mL, put into there-necked flask, stir with the speed of 50rpm, be warming up to again 60 ℃, then with constant pressure funnel take the speed of 0.3mL/s with 15mL concentration as 9.6 * 10
-3The sodium hydroxide solution of g/mL all splashes in the there-necked flask; After b, dropping finish, be warming up to 85 ℃, and keep temperature, then the speed stirring 8h with 50rpm leaves standstill 12h, removes water layer with separating funnel, gets epoxy-based polymer; C, get the 0.036g epoxy-based polymer, add the 0.006g solidifying agent, be heated to 200 ℃ and solidify 12h, for subsequent use after the room temperature cooling; Wherein, solidifying agent is tolylene diisocyanate (TDI), and it is to collect the epoxy chloropropane that 60 ℃ ~ 65 ℃ cut obtains under 0.009MPa ~ 0.010MPa that the epoxy chloropropane liquid of reduced pressure treatment refers in vacuum tightness.
Epoxy-based polymer after this test solidified carries out infrared spectra and detects, the result as shown in Figure 6, as shown in Figure 6, at 3373cm
-1The place is the O-H stretching vibration peak on the phenolic group.3046cm
-1The C-H stretching vibration peak of phenyl ring has appearred in the place.2951cm
-1And 2878cm
-1The peak at place is respectively the stretching vibration peak of methyl and methylene radical.1597cm
-1And 1499cm
-1The place is the skeleton stretching vibration peak of phenyl ring.973cm
-1The place is the charateristic avsorption band of epoxy group(ing), illustrates and has introduced epoxide group on the polymkeric substance.
The N of this test, N '-two (betanaphthyl)-N, N '-two (4-aniline) Ursol D structural formula is as follows:
It is as follows that this experiment obtains the structural formula of epoxy-based polymer:
The reaction process of this test is as follows:
One, monomer M 4 is synthetic
Two. epoxy-based polymer P4's is synthetic
Three. the curing of epoxy-based polymer
Experiment 5
A kind of preparation method with electrochromic property epoxy-based polymer of this test:
One, monomer M 5 is synthetic
A, take by weighing the N ' of 1.0000g-(4-aminophenyl)-N '-phenyl-1 with electronic balance, the p-Hydroxybenzaldehyde of 4-phenylenediamine and 0.5626g is put into there-necked flask, measure again 75mL toluene and 25mL DMF (DMF) is poured in the there-necked flask, mix; B, under the condition of nitrogen protection, temperature is risen to 140 ℃, and keeps temperature, stir 12h with the speed of 30rpm, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected the distilled water that remaining 25mL liquid is put into 750mL, after leaving standstill 12h, it is suction filtration under the condition of 0.09MPa in vacuum tightness, collect solid formation, the solid formation of collecting is put into vacuum drying oven, is 0.09MPa in vacuum tightness, is under 60 ℃ of conditions in temperature, dry 12h namely gets monomer M 5;
Two, epoxy-based polymer P5's is synthetic
A, take by weighing the monomer that the step 1 of 0.068g obtains with electronic balance, measure the epoxy chloropropane liquid of the reduced pressure treatment of 20mL, put into there-necked flask, stir with the speed of 50rpm, be warming up to again 60 ℃, then with constant pressure funnel take the speed of 0.3mL/s with 15mL concentration as 12.3 * 10
-3The sodium hydroxide solution of g/mL all splashes in the there-necked flask; After b, dropping finish, be warming up to 85 ℃, then the speed stirring 8h with 50rpm leaves standstill 12h, removes water layer with separating funnel, gets epoxy-based polymer; C, get the 0.036g epoxy-based polymer, add the 0.006g solidifying agent, be heated to 200 ℃ and solidify 12h, for subsequent use after the room temperature cooling; Wherein, solidifying agent is tolylene diisocyanate (TDI), and it is to collect the epoxy chloropropane that 60 ℃ ~ 65 ℃ cut obtains under 0.009MPa ~ 0.010MPa that the epoxy chloropropane liquid of reduced pressure treatment refers in vacuum tightness.
Epoxy-based polymer after this test solidified carries out infrared spectra and detects, the result as shown in Figure 7, as shown in Figure 7, at 3405cm
-1The place is the O-H stretching vibration peak on the phenolic group.3038cm
-1The C-H stretching vibration peak of phenyl ring has appearred in the place.2927cm
-1And 2874cm
-1The peak at place is respectively the stretching vibration peak of methyl and methylene radical.1599cm
-1And 1511cm
-1The place is the skeleton stretching vibration peak of phenyl ring.914cm
-1The place is the charateristic avsorption band of epoxy group(ing), illustrates and has introduced epoxide group on the polymkeric substance.
The N ' of this experiment-(4-aminophenyl)-N '-phenyl-Isosorbide-5-Nitrae-phenylenediamine structural formula is as follows:
The structural formula of the epoxy-based polymer that this test obtains is as follows:
The reaction process of this experiment is as follows:
One. monomer M 5 is synthetic
Two. epoxy-based polymer P5's is synthetic
Three. the curing of epoxy-based polymer
Carry out following test to testing 1 epoxy-based polymer after solidifying:
1, with the electrochromic property of epoxy-based polymer in the acetonitrile solution of lithium perchlorate after ultraviolet-cyclic voltammetric online testing curing, the result as shown in Figure 1, an oxidation peak occurs at 1.4V as shown in Figure 1, reduction peak about 0.7V, occurs, illustrate that the reaction formula that occurs is reversible.In the cyclic voltammetry scan process color of polymeric film become emerald green by yellow and along with the color restoration of the loading film of reverse voltage to original state.So epoxy-based polymer P1 of the present invention
Can be used as electrochromic material.
2, the epoxy-based polymer after the curing that this test is obtained carries out UV spectrum and detects under different voltages, the result as shown in Figure 2, as shown in Figure 2, be coated in the original UV spectrum curve of the formed film of epoxy-based polymer on the conductive glass, be the UV spectrum curve of on load voltage when being 0V, and the UV spectrum curve (being spaced apart 0.1V) when film loads 0.1 ~ 2.0V.As can be seen from the figure along with the loading of different voltages, obvious variation has occured in the UV spectrum curve, illustrates that the color of epoxy-based polymer film under the loading of voltage variation has occured, and this polymkeric substance can be used as electrochromic material.
3, the epoxy-based polymer after the curing that this test is obtained carries out infrared spectra and detects, the result as shown in Figure 3, as shown in Figure 3, at 3352cm
-1The place is the O-H stretching vibration peak on the phenolic group; At 3042cm
-1The C-H stretching vibration peak of phenyl ring has appearred in the place; At 2925cm
-1And 2875cm
-1The peak at place is respectively the stretching vibration peak of methyl and methylene radical; At 1596cm
-1And 1508cm
-1The place is the skeleton stretching vibration peak of phenyl ring; At 910cm
-1The place is the charateristic avsorption band of epoxy group(ing), illustrates and has introduced epoxide group on the polymkeric substance.
In sum, epoxy chloropropane and the above-mentioned prepared monomer that contains terminal hydroxy group react as can be known, and the material of gained has electrochromic property after solidifying, and can use at photoelectric field as type material.
Claims (7)
1. one kind has the electrochromic property epoxy-based polymer, and the chemical structural formula that it is characterized in that having the electrochromic property epoxy-based polymer is as follows:
Wherein, n is that 10～20, R is
2. a kind of preparation method with electrochromic property epoxy-based polymer as claimed in claim 1 is characterized in that having the electrochromic property epoxy-based polymer and carries out according to the following steps:
One, monomer is synthetic
A, the diamino triphenylamine derivative that will have the R structure and p-Hydroxybenzaldehyde are that 1: 2～3 ratio mixes in molar ratio, get mixture; B, the mixture that step a is obtained and solvent are that the ratio of 0.8～2.1g: 100mL mixes and obtains mixed solution in mass volume ratio, then under the condition of nitrogen protection, temperature is risen to 120 ℃～140 ℃, speed with 20～50rpm stirs 12h, when solvent evaporation in the mixed solution to mixeding liquid volume is original volume 1/4, stop to stir, collect remaining 1/4 volume of liquid; C, step b is collected remaining 1/4 volume of liquid put into distilled water, leave standstill 6～12h, then under being the condition of 0.09MPa, vacuum tightness carries out suction filtration, collect solid formation, the solid formation of collecting is put into vacuum drying oven, be 0.09MPa in vacuum tightness, temperature is dry 6～12h under 50 ℃ the condition, namely gets monomer; Wherein, solvent is that toluene and DMF are that 3: 1 ratio mixes by volume, and the volume ratio that step b collects remaining 1/4 volume of liquid and distilled water is 1: 30;
Two, epoxy-based polymer is synthetic
The epoxy chloropropane liquid of a, the monomer that step 1 is obtained and reduced pressure treatment is that the ratio of 0.01～0.10g: 20mL mixes in mass volume ratio, puts into there-necked flask, gets mixing solutions; B, under the condition of nitrogen protection, temperature is risen to 60 ℃, the mixed solution and dripping concentration that then obtains take the speed of 0.1～0.3mL/s to step a with constant pressure funnel is as 6 * 10
-3～10 * 10
-3The sodium hydroxide solution of g/mL after dripping, is heated to 61 ℃～100 ℃, and the speed stirring 6～8h with 20～50rpm gets just mixed liquid; C, the first mixed liquid that step b is obtained are poured in methyl alcohol or the distilled water, leave standstill 6～12h, then remove the water layer on upper strata with separating funnel after, collect the solution of lower floor; Be after 5～10: 1 ratio mixes, to be heated to 100～200 ℃ by volume with the solution collected and solidifying agent, curing reaction 2～12h, room temperature namely gets epoxy-based polymer after cooling off; Wherein, the synthetic monomer mole ratio of sodium hydroxide solution and step 1 is 1: 1, and just the volume ratio of mixed liquid and methyl alcohol or distilled water is 1: 30, and solidifying agent is 2,4 toluene diisocyanate.
3. a kind of preparation method with electrochromic property epoxy-based polymer according to claim 2, the diamino triphenylamine derivative that it is characterized in that the described R of the having structure of step 1 is 4,4 '-diamino-4 " N-carbazyl triphenylamine; N; N-two (4-aminophenyl)-N '; N '-phenylbenzene-1; 4-phenylenediamine; N '-(4-aminophenyl)-N '-(4-oxyethyl group) phenyl-1, the 4-phenylenediamine, N, N '-two (betanaphthyl)-N, N '-two (4-aniline) Ursol D or N '-(4-aminophenyl)-N '-phenyl-1, the 4-phenylenediamine, N ', N '-phenylbenzene-N, N '-two (4-aniline) Ursol D, N ', N '-phenylbenzene-N, N '-two (4-aniline) benzidine or N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine.
4. a kind of preparation method with electrochromic property epoxy-based polymer according to claim 2 is characterized in that the diamino triphenylamine derivative of the described R of the having structure of step 1 and p-Hydroxybenzaldehyde are 1: 2 in molar ratio.
5. a kind of preparation method with electrochromic property epoxy-based polymer according to claim 2 is characterized in that mixture and solvent that the described step a of step 1 obtains are 1.3～1.6g: 100mL by mass volume ratio.
6. a kind of preparation method with electrochromic property epoxy-based polymer according to claim 2 is characterized in that monomer and epoxy chloropropane liquid that the described step 1 of step 2 obtains are 0.04～0.06g: 20mL by mass volume ratio.
7. a kind of preparation method with electrochromic property epoxy-based polymer according to claim 2, the epoxy chloropropane liquid that it is characterized in that the described reduced pressure treatment of step 2: epoxy chloropropane liquid is carried out underpressure distillation under the condition of vacuum tightness 0.009MPa～0.010MPa, collect that 60 ℃～65 ℃ cut obtains.
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| CN101775115A (en) * | 2010-01-06 | 2010-07-14 | 上海应用技术学院 | Polyurethane elastomer with lateral chain containing fluoroalkyl and preparation method thereof |
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| CN101775115A (en) * | 2010-01-06 | 2010-07-14 | 上海应用技术学院 | Polyurethane elastomer with lateral chain containing fluoroalkyl and preparation method thereof |
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