CN104844782B - A kind of polyurethane of carbazolyl-containing and preparation method thereof - Google Patents
A kind of polyurethane of carbazolyl-containing and preparation method thereof Download PDFInfo
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- CN104844782B CN104844782B CN201510263253.2A CN201510263253A CN104844782B CN 104844782 B CN104844782 B CN 104844782B CN 201510263253 A CN201510263253 A CN 201510263253A CN 104844782 B CN104844782 B CN 104844782B
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- 0 Cc1ccc([C@](C2C=CC(*3c4ccccc4-c4c3cccc4)=CC2)C=Cc2ccc(C)cc2)cc1 Chemical compound Cc1ccc([C@](C2C=CC(*3c4ccccc4-c4c3cccc4)=CC2)C=Cc2ccc(C)cc2)cc1 0.000 description 5
- CCXNODMPTZUQQP-UHFFFAOYSA-N Cc(cc1)ccc1[N](c1c2cccc1)(c1ccc(C)cc1)O[NH+]2[O-] Chemical compound Cc(cc1)ccc1[N](c1c2cccc1)(c1ccc(C)cc1)O[NH+]2[O-] CCXNODMPTZUQQP-UHFFFAOYSA-N 0.000 description 1
- CCWXJPWQTAITST-UHFFFAOYSA-N O=C=Nc(cc1)ccc1N(c(cc1)ccc1-[n]1c(C=CCC2)c2c2ccccc12)c(cc1)ccc1N=C=O Chemical compound O=C=Nc(cc1)ccc1N(c(cc1)ccc1-[n]1c(C=CCC2)c2c2ccccc12)c(cc1)ccc1N=C=O CCWXJPWQTAITST-UHFFFAOYSA-N 0.000 description 1
- FSMCNDPPMHQABZ-UHFFFAOYSA-N OC1=CCC(C(C2C3C=CC(O)=CC3)C22C3C=CCCC3C3C=CCCC23)C=C1 Chemical compound OC1=CCC(C(C2C3C=CC(O)=CC3)C22C3C=CCCC3C3C=CCCC23)C=C1 FSMCNDPPMHQABZ-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N Oc(cc1)ccc1C(c(cc1)ccc1O)=O Chemical compound Oc(cc1)ccc1C(c(cc1)ccc1O)=O RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- TVQSDJIKDZDBDU-UHFFFAOYSA-N Oc1ccc(C(C=C2)C#CC=C2O)cc1 Chemical compound Oc1ccc(C(C=C2)C#CC=C2O)cc1 TVQSDJIKDZDBDU-UHFFFAOYSA-N 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N Oc1ccc(C(c2c3cccc2)(c(cc2)ccc2O)OC3=O)cc1 Chemical compound Oc1ccc(C(c2c3cccc2)(c(cc2)ccc2O)OC3=O)cc1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/7881—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
Abstract
A kind of polyurethane of carbazolyl-containing and preparation method thereof, it is related to a kind of polyurethane and preparation method thereof.The invention aims to solve existing polyurethane, solubility is low in organic solvent, machinability difference and the low problem of light-spot positioning response sensitivity.A kind of structural formula of the polyurethane of carbazolyl-containing is：Wherein, described Ar is：Described R is： The span of described n is 1≤n≤100, and n is integer.Preparation method：First, monoamine monomer is synthesized；2nd, triaryl amine monomer is synthesized；3rd, synthesizing isocyanate monomer；4th, the polyurethane of carbazolyl-containing is synthesized.The present invention can obtain a kind of polyurethane of carbazolyl-containing.
Description
Technical field
The present invention relates to a kind of polyurethane and preparation method thereof.
Background technology
Carbazole is a famous hole transport and electroluminescence cell.Due to their excellent photoelectric properties such as photoelectricity
Lead, electroluminescent, photochromic material, therefore polymer main chain or side chain introduce carbazole group receive very big pass
Note.In electrochromism, carbazole derivates are conventional material hole mobile material and luminescent layers.Additionally, from structure click
Azoles has the planar structure of different diphenylamines, while many alkyl groups in 9 substitutions position can also increase its dissolubility, therefore it can be with
Further improve the conjugation performance and electronic transmission performance of triphenylamine.
The unique micro phase separation structure of polyurethane makes it have good elasticity and mechanical strength, and because it has absolutely
The characteristic such as heat, sound insulation, wear-resisting, oil resistant, sun-proof, is widely used in artificial synthesized leather, soft or hard foamed plastics, fiber (especially
Elastomer), bonding agent, coating, waterproof material, pavement material, the field such as elastomer.But existing polyurethane is still present
Dissolubility is low, it is difficult to which film forming is processed, the problem that light-spot positioning response sensitivity is low, heat endurance is poor, needs further research and carries
It is high.
The content of the invention
The invention aims to solve existing polyurethane, solubility is low in organic solvent, and machinability difference and photoelectricity become
The low problem of colour response sensitivity, and a kind of polyurethane of carbazolyl-containing and preparation method thereof is provided.
A kind of structural formula of the polyurethane of carbazolyl-containing is：Wherein, it is described
Ar is：Described R is： The span of described n
It is 1≤n≤100, and n is integer.
A kind of preparation method of the polyurethane of carbazolyl-containing, is specifically realized by the following steps：
First, monoamine monomer is synthesized：
1., in a nitrogen atmosphere, carbazole is dissolved in anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and sodium hydride,
36h~48h is heated to reflux at being again 150 DEG C~160 DEG C in temperature, the distilled water that temperature is 0 DEG C~5 DEG C is reused and is settled out generation
Thing A, reuses and product A is recrystallized with acetonitrile again, then dries 10h~12h in the case where temperature is for 40 DEG C~50 DEG C, obtains
Triphenylamine nitro compound；
Step one 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of carbazole be (0.1g~0.5g):
10mL；
Step one 1. described in the mol ratio of carbazole and p-fluoronitrobenzene be 1:1；
Step one 1. described in the mass ratio of carbazole and sodium hydride be (8~12):1；
2. triphenylamine nitro compound, is dissolved in N, in N '-solvent dimethylformamide, Pb/C catalyst is added, then
It is that 8MPa~10MPa, temperature are 60 DEG C~80 DEG C and mixing speed is 100r/min~300r/min in hydrogen atmosphere and pressure
Under conditions of 30~40h of stirring reaction, add the distilled water that temperature is 0 DEG C~5 DEG C and settle out product B；Reuse toluene pair
Product B is recrystallized, then dries 10h~12h in the case where temperature is for 40 DEG C~50 DEG C, obtains monoamine monomer；
Step one 2. described in triphenylamine nitro compound quality and the volume ratio of N, N '-solvent dimethylformamide
It is (0.1g~0.5g):10mL；
Step one 2. described in the mass ratio of triphenylamine nitro compound and Pb/C catalyst be (8~10):1；
2nd, triaryl amine monomer is synthesized：
1., under nitrogen atmosphere, monoamine monomer is dissolved into anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and hydrogenation
Sodium, then 36h~48h is heated to reflux in the case where temperature is for 150 DEG C~160 DEG C, reuse the distilled water that temperature is 0 DEG C~5 DEG C and settle out
Product C, then product C is recrystallized with acetonitrile, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain three
Arylamine nitro compound；
Step 2 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of monoamine monomer be (0.1g~0.5g):
10mL；
Step 2 1. described in the mol ratio of monoamine monomer and p-fluoronitrobenzene be 1:1；
Step 2 1. described in the mass ratio of monoamine monomer and sodium hydride be (8~12):1；
2., by N, N '-dimethylformamide is added in reactor, then triaryl amine nitro compound is dissolved into N, and N '-
In dimethylformamide, add Pb/C catalyst, then hydrogen atmosphere and pressure be 8MPa~10MPa, temperature be 60 DEG C~
80 DEG C is 30~40h of stirring reaction under conditions of 100r/min~300r/min with mixing speed, and it is 0 DEG C~5 to add temperature
DEG C distilled water settle out product D；Reuse toluene to recrystallize product D, then done in the case where temperature is for 40 DEG C~50 DEG C
Dry 10h~12h, obtains triaryl amine monomer；
Step 2 2. described in the quality of triaryl amine nitro compound and the volume ratio of N, N '-dimethylformamide be
(0.1g~0.5g):10mL；
Step 2 2. described in the mass ratio of triaryl amine nitro compound and Pb/C catalyst be (8~10):1；
3rd, synthesizing isocyanate monomer：
Under nitrogen atmosphere, triaryl amine monomer and triphosgene are dissolved in anhydrous dichloroethanes, then are 80 DEG C~85 in temperature
8h~10h is heated to reflux at DEG C, Rotary Evaporators is reused and is steamed anhydrous dichloroethanes, obtain isocyanate-monomer；
The quality of the triaryl amine monomer described in step 3 is (0.1g~0.5g) with the volume ratio of anhydrous dichloroethanes:
10mL；
Triaryl amine monomer and the mol ratio of triphosgene described in step 3 are 3:(1~2)；
4th, the polyurethane of carbazolyl-containing is synthesized：
1., under nitrogen atmosphere, dihydroxy compounds is dissolved in anhydrous dichloroethanes, obtains dihydroxy compounds solution；
Step 4 1. described in dihydroxy compounds quality and anhydrous dichloroethanes volume ratio for (0.1g~
0.5g):10mL；
2., under nitrogen atmosphere, isocyanate-monomer is dissolved in anhydrous dichloroethanes, obtains isocyanate solution；
Step 4 2. described in isocyanate-monomer quality and anhydrous dichloroethanes volume ratio for (0.1g~
0.5g):10mL；
3., under nitrogen atmosphere, isocyanate solution is mixed with dihydroxy compounds solution, then is 80 DEG C~85 in temperature
DEG C and nitrogen atmosphere under react 24h~36h, reuse the distilled water that temperature is 0 DEG C~5 DEG C and settle out product E, reuse methyl alcohol
60h~72h is extracted to product E, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain the poly- ammonia of carbazolyl-containing
Ester；
Step 4 3. described in isocyanate solution in dihydroxy in isocyanate-monomer and dihydroxy compounds solution
The mol ratio of based compound is 1:1；
The structural formula of the polyurethane of the 3. described carbazolyl-containing of step 4 is：Its
In, described Ar is：Described R is： The span of described n is 1≤n≤100, and n is integer.
A kind of polyurethane of carbazolyl-containing is used for electrochromism, photochromic, hole mobile material, three as photoelectric material
Rank is non-linear, false proof, in camouflage material and display material.
Advantages of the present invention：
First, the polyurethane of carbazolyl-containing prepared by the present invention overcomes conventional polyurethane and is poorly soluble in common organic solvents
Shortcoming, the polyurethane of carbazolyl-containing improves the solubility property of whole polymer using carbazolyl-containing macoradical is introduced, makes containing click
The polyurethane of oxazolyl is dissolved in most organic solvent；The CO-NH structures that the polyurethane of carbazolyl-containing is formed simultaneously are connected to benzene
Ring, causes color to change after oxidation, and reversible change can occur and along with reversible color change；
2nd, in a nitrogen atmosphere, temperature is weightless at 206 DEG C~218 DEG C to the polyurethane of carbazolyl-containing prepared by the present invention
It is 10%, in 500 DEG C of surpluses up to 40%~56%, therefore, the polyurethane of carbazolyl-containing prepared by the present invention has very well
Resistance to elevated temperatures, be adapted to use in the devices；
3rd, the polyurethane of carbazolyl-containing prepared by the present invention has good electrochromic property.
The present invention can obtain a kind of polyurethane of carbazolyl-containing.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one；
Fig. 2 is the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one；
Fig. 3 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment one；
Fig. 4 is the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one；
Fig. 5 be embodiment one prepare carbazolyl-containing polyurethane electrochromism spectrogram, in Fig. 51 be voltage be 0V when
Ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；
Fig. 6 is the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two；
Fig. 7 is the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two；
Fig. 8 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment two；
Fig. 9 is the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two；
Figure 10 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two, and 1 is that voltage is 0V in Figure 10
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；
Figure 11 is the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three；
Figure 12 is the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three；
Figure 13 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment three；
Figure 14 is the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three；
Figure 15 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three, and 1 is that voltage is 0V in Figure 15
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；
Figure 16 is the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by example IV；
Figure 17 is the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by example IV；
Figure 18 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by example IV；
Figure 19 is the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by example IV；
Figure 20 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by example IV, and 1 is that voltage is 0V in Figure 20
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；
Figure 21 is the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five；
Figure 22 is the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five；
Figure 23 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment five；
Figure 24 is the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five；
Figure 25 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five, and 1 is that voltage is 0V in Figure 25
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve.
Specific embodiment
Specific embodiment one：Present embodiment is that a kind of structural formula of the polyurethane of carbazolyl-containing is：Wherein, described Ar is：Described R is： The span of described n is 1≤n≤100, and n is whole
Number.
The advantage of present embodiment：
First, the polyurethane of carbazolyl-containing prepared by present embodiment overcomes conventional polyurethane and is poorly soluble in general organic
The shortcoming of solvent, the polyurethane of carbazolyl-containing is made using the solubility property for introducing the carbazolyl-containing macoradical whole polymer of raising
The polyurethane of carbazolyl-containing is dissolved in most organic solvent；The CO-NH structures connection that the polyurethane of carbazolyl-containing is formed simultaneously
Phenyl ring, causes color to change after oxidation, and reversible change can occur and along with reversible color change；
2nd, in a nitrogen atmosphere, temperature is at 206 DEG C~218 DEG C for the polyurethane of carbazolyl-containing prepared by present embodiment
Weightlessness is 10%, in 500 DEG C of surpluses up to 40%~56%, therefore, the polyurethane of carbazolyl-containing prepared by present embodiment
With good resistance to elevated temperatures, it is adapted to use in the devices；
3rd, the polyurethane of carbazolyl-containing prepared by present embodiment has good electrochromic property.
Present embodiment can obtain a kind of polyurethane of carbazolyl-containing.
Specific embodiment two：Present embodiment is that a kind of preparation method of the polyurethane of carbazolyl-containing is specifically by following
What step was completed：
First, monoamine monomer is synthesized：
1., in a nitrogen atmosphere, carbazole is dissolved in anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and sodium hydride,
36h~48h is heated to reflux at being again 150 DEG C~160 DEG C in temperature, the distilled water that temperature is 0 DEG C~5 DEG C is reused and is settled out generation
Thing A, reuses and product A is recrystallized with acetonitrile again, then dries 10h~12h in the case where temperature is for 40 DEG C~50 DEG C, obtains
Triphenylamine nitro compound；
Step one 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of carbazole be (0.1g~0.5g):
10mL；
Step one 1. described in the mol ratio of carbazole and p-fluoronitrobenzene be 1:1；
Step one 1. described in the mass ratio of carbazole and sodium hydride be (8~12):1；
2. triphenylamine nitro compound, is dissolved in N, in N '-solvent dimethylformamide, Pb/C catalyst is added, then
It is that 8MPa~10MPa, temperature are 60 DEG C~80 DEG C and mixing speed is 100r/min~300r/min in hydrogen atmosphere and pressure
Under conditions of 30~40h of stirring reaction, add the distilled water that temperature is 0 DEG C~5 DEG C and settle out product B；Reuse toluene pair
Product B is recrystallized, then dries 10h~12h in the case where temperature is for 40 DEG C~50 DEG C, obtains monoamine monomer；
Step one 2. described in triphenylamine nitro compound quality and the volume ratio of N, N '-solvent dimethylformamide
It is (0.1g~0.5g):10mL；
Step one 2. described in the mass ratio of triphenylamine nitro compound and Pb/C catalyst be (8~10):1；
2nd, triaryl amine monomer is synthesized：
1., under nitrogen atmosphere, monoamine monomer is dissolved into anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and hydrogenation
Sodium, then 36h~48h is heated to reflux in the case where temperature is for 150 DEG C~160 DEG C, reuse the distilled water that temperature is 0 DEG C~5 DEG C and settle out
Product C, then product C is recrystallized with acetonitrile, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain three
Arylamine nitro compound；
Step 2 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of monoamine monomer be (0.1g~0.5g):
10mL；
Step 2 1. described in the mol ratio of monoamine monomer and p-fluoronitrobenzene be 1:1；
Step 2 1. described in the mass ratio of monoamine monomer and sodium hydride be (8~12):1；
2., by N, N '-dimethylformamide is added in reactor, then triaryl amine nitro compound is dissolved into N, and N '-
In dimethylformamide, add Pb/C catalyst, then hydrogen atmosphere and pressure be 8MPa~10MPa, temperature be 60 DEG C~
80 DEG C is 30~40h of stirring reaction under conditions of 100r/min~300r/min with mixing speed, and it is 0 DEG C~5 to add temperature
DEG C distilled water settle out product D；Reuse toluene to recrystallize product D, then done in the case where temperature is for 40 DEG C~50 DEG C
Dry 10h~12h, obtains triaryl amine monomer；
Step 2 2. described in the quality of triaryl amine nitro compound and the volume ratio of N, N '-dimethylformamide be
(0.1g~0.5g):10mL；
Step 2 2. described in the mass ratio of triaryl amine nitro compound and Pb/C catalyst be (8~10):1；
3rd, synthesizing isocyanate monomer：
Under nitrogen atmosphere, triaryl amine monomer and triphosgene are dissolved in anhydrous dichloroethanes, then are 80 DEG C~85 in temperature
8h~10h is heated to reflux at DEG C, Rotary Evaporators is reused and is steamed anhydrous dichloroethanes, obtain isocyanate-monomer；
The quality of the triaryl amine monomer described in step 3 is (0.1g~0.5g) with the volume ratio of anhydrous dichloroethanes:
10mL；
Triaryl amine monomer and the mol ratio of triphosgene described in step 3 are 3:(1~2)；
4th, the polyurethane of carbazolyl-containing is synthesized：
1., under nitrogen atmosphere, dihydroxy compounds is dissolved in anhydrous dichloroethanes, obtains dihydroxy compounds solution；
Step 4 1. described in dihydroxy compounds quality and anhydrous dichloroethanes volume ratio for (0.1g~
0.5g):10mL；
2., under nitrogen atmosphere, isocyanate-monomer is dissolved in anhydrous dichloroethanes, obtains isocyanate solution；
Step 4 2. described in isocyanate-monomer quality and anhydrous dichloroethanes volume ratio for (0.1g~
0.5g):10mL；
3., under nitrogen atmosphere, isocyanate solution is mixed with dihydroxy compounds solution, then is 80 DEG C~85 in temperature
DEG C and nitrogen atmosphere under react 24h~36h, reuse the distilled water that temperature is 0 DEG C~5 DEG C and settle out product E, reuse methyl alcohol
60h~72h is extracted to product E, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain the poly- ammonia of carbazolyl-containing
Ester；
Step 4 3. described in isocyanate solution in dihydroxy in isocyanate-monomer and dihydroxy compounds solution
The mol ratio of based compound is 1:1；
The structural formula of the polyurethane of the 3. described carbazolyl-containing of step 4 is：Its
In, described Ar is：Described R is： The span of described n is 1≤n≤100, and n is integer.
The advantage of present embodiment：
First, the polyurethane of carbazolyl-containing prepared by present embodiment overcomes conventional polyurethane and is poorly soluble in general organic
The shortcoming of solvent, the polyurethane of carbazolyl-containing is made using the solubility property for introducing the carbazolyl-containing macoradical whole polymer of raising
The polyurethane of carbazolyl-containing is dissolved in most organic solvent；The CO-NH structures connection that the polyurethane of carbazolyl-containing is formed simultaneously
Phenyl ring, causes color to change after oxidation, and reversible change can occur and along with reversible color change；
2nd, in a nitrogen atmosphere, temperature is at 206 DEG C~218 DEG C for the polyurethane of carbazolyl-containing prepared by present embodiment
Weightlessness is 10%, in 500 DEG C of surpluses up to 40%~56%, therefore, the polyurethane of carbazolyl-containing prepared by present embodiment
With good resistance to elevated temperatures, it is adapted to use in the devices；
3rd, the polyurethane of carbazolyl-containing prepared by present embodiment has good electrochromic property.
Present embodiment can obtain a kind of polyurethane of carbazolyl-containing.
Specific embodiment three：Present embodiment is with the difference of specific embodiment two：The isocyanide that step 3 is obtained
The structure of acid ester monomer isOther are identical with specific embodiment two.
Specific embodiment four：Present embodiment is with the difference of specific embodiment two or three：Step 4 1. middle institute
The dihydroxy compounds stated is Other with it is specific
Implementation method two or three is identical.
Specific embodiment five：Present embodiment is with the difference of specific embodiment two to four：Step one 2. middle institute
The mass fraction of Pb is 10% in the Pb/C catalyst stated.Other are identical with specific embodiment two to four.
Specific embodiment six：Present embodiment is with the difference of specific embodiment two to five：Step 2 2. middle institute
The mass fraction of Pb is 10% in the Pb/C catalyst stated.Other are identical with specific embodiment two to five.
Specific embodiment seven：Present embodiment is with the difference of specific embodiment two to six：Step one 1. middle institute
The quality of the carbazole stated is 10 with the mass ratio of sodium hydride:1.Other are identical with specific embodiment two to six.
Specific embodiment eight：Present embodiment is with the difference of specific embodiment two to seven：Step 2 1. middle institute
The monoamine monomer stated is 10 with the mass ratio of sodium hydride:1.Other are identical with specific embodiment two to seven.
Specific embodiment nine：Present embodiment is with the difference of specific embodiment two to eight：Described in step 3
The mol ratio of triaryl amine monomer and triphosgene be 3:2.Other are identical with specific embodiment two to eight.
Specific embodiment ten：Present embodiment is that a kind of polyurethane of carbazolyl-containing is used for electroluminescent change as photoelectric material
In color, photochromic, hole mobile material, third-order non-linear, false proof, camouflage material and display material.
The advantage of present embodiment：
First, the polyurethane of carbazolyl-containing prepared by present embodiment overcomes conventional polyurethane and is poorly soluble in general organic
The shortcoming of solvent, the polyurethane of carbazolyl-containing is made using the solubility property for introducing the carbazolyl-containing macoradical whole polymer of raising
The polyurethane of carbazolyl-containing is dissolved in most organic solvent；The CO-NH structures connection that the polyurethane of carbazolyl-containing is formed simultaneously
Phenyl ring, causes color to change after oxidation, and reversible change can occur and along with reversible color change；
2nd, in a nitrogen atmosphere, temperature is at 206 DEG C~218 DEG C for the polyurethane of carbazolyl-containing prepared by present embodiment
Weightlessness is 10%, in 500 DEG C of surpluses up to 40%~56%, therefore, the polyurethane of carbazolyl-containing prepared by present embodiment
With good resistance to elevated temperatures, it is adapted to use in the devices；
3rd, the polyurethane of carbazolyl-containing prepared by present embodiment has good electrochromic property.
Present embodiment can obtain a kind of polyurethane of carbazolyl-containing.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of the polyurethane of carbazolyl-containing, is specifically realized by the following steps：
First, monoamine monomer is synthesized：
1., in a nitrogen atmosphere, carbazole is dissolved in anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and sodium hydride,
42h is heated to reflux at being again 155 DEG C in temperature, the distilled water that temperature is 3 DEG C is reused and is settled out product A, reused and use second again
Nitrile is recrystallized to product A, then dries 12h in the case where temperature is for 50 DEG C, obtains triphenylamine nitro compound；
Step one 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of carbazole be 0.3g:10mL；
Step one 1. described in the mol ratio of carbazole and p-fluoronitrobenzene be 1:1；
Step one 1. described in the mass ratio of carbazole and sodium hydride be 10:1；
2. triphenylamine nitro compound, is dissolved in N, in N '-solvent dimethylformamide, Pb/C catalyst is added, then
It is stirring reaction 40h under conditions of 8MPa, temperature are 70 DEG C and mixing speed is 120r/min in hydrogen atmosphere and pressure, then adds
Enter the distilled water that temperature is 3 DEG C to settle out product B；Toluene is reused to recrystallize product B, then in the case where temperature is for 50 DEG C
12h is dried, monoamine monomer is obtained；
Step one 2. described in triphenylamine nitro compound quality and the volume ratio of N, N '-solvent dimethylformamide
It is 0.3g:10mL；
Step one 2. described in the mass ratio of triphenylamine nitro compound and Pb/C catalyst be 10:1；
Step one 2. described in Pb/C catalyst in Pb mass fraction be 10%；
2nd, triaryl amine monomer is synthesized：
1., under nitrogen atmosphere, monoamine monomer is dissolved into anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and hydrogenation
Sodium, then be heated to reflux 40h at being 160 DEG C in temperature, reuses the distilled water that temperature is 3 DEG C and settles out product C, then with acetonitrile pair
Product C is recrystallized, then dries 12h in the case where temperature is for 50 DEG C, obtains triaryl amine nitro compound；
Step 2 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of monoamine monomer be 0.5g:10mL；
Step 2 1. described in the mol ratio of monoamine monomer and p-fluoronitrobenzene be 1:1；
Step 2 1. described in the mass ratio of monoamine monomer and sodium hydride be 10:1；
2., by N, N '-dimethylformamide is added in reactor, then triaryl amine nitro compound is dissolved into N, and N '-
In dimethylformamide, Pb/C catalyst is added, then be that 8MPa, temperature are 70 DEG C and mixing speed in hydrogen atmosphere and pressure
It is stirring reaction 40h under conditions of 120r/min, adds the distilled water that temperature is 3 DEG C and settle out product D；Reuse toluene pair
Product D is recrystallized, then dries 12h in the case where temperature is for 50 DEG C, obtains triaryl amine monomer；
Step 2 2. described in the quality of triaryl amine nitro compound and the volume ratio of N, N '-dimethylformamide be
0.5g:10mL；
Step 2 2. described in the mass ratio of triaryl amine nitro compound and Pb/C catalyst be 10:1；
Step 2 2. described in Pb/C catalyst in Pb mass fraction be 10%；
3rd, synthesizing isocyanate monomer：
Under nitrogen atmosphere, triaryl amine monomer and triphosgene are dissolved in anhydrous dichloroethanes, then added in the case where temperature is for 80 DEG C
Heat backflow 10h, reuses Rotary Evaporators and steams anhydrous dichloroethanes, obtains isocyanate-monomer；
The quality of the triaryl amine monomer described in step 3 is 0.3g with the volume ratio of anhydrous dichloroethanes:10mL；
Triaryl amine monomer and the mol ratio of triphosgene described in step 3 are 3:2；
4th, the polyurethane of carbazolyl-containing is synthesized：
1., under nitrogen atmosphere, dihydroxy compounds is dissolved in anhydrous dichloroethanes, obtains dihydroxy compounds solution；
Step 4 1. described in dihydroxy compounds quality and anhydrous dichloroethanes volume ratio be 0.3g:10mL；
2., under nitrogen atmosphere, isocyanate-monomer is dissolved in anhydrous dichloroethanes, obtains isocyanate solution；
Step 4 2. described in isocyanate-monomer quality and anhydrous dichloroethanes volume ratio be 0.3g:10mL；
3., under nitrogen atmosphere, isocyanate solution is mixed with dihydroxy compounds solution, then is 85 DEG C and nitrogen in temperature
30h is reacted under gas atmosphere, the distilled water that temperature is 3 DEG C is reused and is settled out product E, reused methyl alcohol and product E is extracted
65h, then 12h is dried in the case where temperature is for 45 DEG C, obtain the polyurethane of carbazolyl-containing；
Step 4 3. described in isocyanate solution in dihydroxy in isocyanate-monomer and dihydroxy compounds solution
The mol ratio of based compound is 1:1.
The structural formula of the monoamine monomer that 2. step one of embodiment one obtains is：
The structure of the isocyanate-monomer that the step 3 of embodiment one is obtained is
The step 4 of embodiment one 1. described in dihydroxy compounds be phenolphthalein；The structure of described phenolphthalein is
The reaction equation of the step one of embodiment one is：
The reaction equation of the step 2 of embodiment one is：
The reaction equation of the step 3 of embodiment one is：
Embodiment one
The reaction equation of step 4 is：
The structure of the polyurethane of the carbazolyl-containing that 3. step 4 of embodiment one obtains is
Wherein the span of n is 1≤n≤100, and
N is integer；
The infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one is as shown in Figure 1；Fig. 1 is prepared for embodiment one
Carbazolyl-containing polyurethane infrared spectrogram；From fig. 1, it can be seen that 1669cm-1Represent carbonylic stretching vibration；1219cm-1Represent
Hydrocarbon nitrogen combination vibration absworption peak；1593cm-1Represent the stretching vibration of carbon nitrogen and nitrogen hydrogen flexural vibrations absworption peak；1659cm-1、
1507cm-1And 754cm-1Represent the hydrocarbon flexural vibrations absworption peak of phenyl ring.
The nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one is as shown in Figure 2；Fig. 2 is prepared by embodiment one
The nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing；With DMSO-d6It is solvent, in Fig. 2,7.95ppm represents the feature of NH-COO groups
Absworption peak；6.67ppm~7.51ppm represents the absworption peak of hydrogen on phenyl ring.
The structural characterization of the polyurethane of the carbazolyl-containing that comprehensive infrared and nuclear-magnetism is prepared to embodiment one, may certify that implementation
Example one has synthesized the polyurethane of target carbazolyl-containing.
The thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment one is as shown in figure 3, test condition is nitrogen gas
Under atmosphere, programming rate is 10 DEG C/min；Fig. 3 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment one；From Fig. 3
In as can be seen that in a nitrogen atmosphere, under conditions of programming rate is 10 DEG C/min, carbazolyl-containing prepared by embodiment one it is poly-
Urethane is that weightlessness is 10% at 218 DEG C in temperature, and surplus is 45% at 500 DEG C.
The cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one is as shown in figure 4, Fig. 4 makes for embodiment one
The cyclic voltammetric spectrogram of the polyurethane of standby carbazolyl-containing；The polyurethane dissolving of carbazolyl-containing prepared by 0.001g embodiments one
In 2mL dichloroethanes, then the polyurethane for applying the carbazolyl-containing of the preparation of embodiment one of 80nm on electro-conductive glass with spin-coating method
Film, will scribble the electro-conductive glass of polyurethane film of carbazolyl-containing prepared by embodiment one as working electrode, platinum filament be to electrode,
Saturation calomel is reference electrode, with solution of the 0.1M lithium perchlorates in acetonitrile as electrolyte, test voltage scope 0V~1.6V；
As can be seen from Figure 4, cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one under applied voltage, there is two pairs of peaks,
It is oxidation peak at the peak of 0.89V and 1.24V, simultaneous color is changed into blue again from the colourless green that is changed into；In 0.60V and
Have two corresponding reduction peaks at 0.96V, now color from blueness be changed into green become colorless again, multiple circulating phenomenon is identical,
The polyurethane electrochemical properties stabilization of carbazolyl-containing prepared by embodiment one is illustrated, and has preferable invertibity.
The electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment one is as shown in figure 5, test condition is with circulation
Volt-ampere test；Fig. 5 be embodiment one prepare carbazolyl-containing polyurethane electrochromism spectrogram, in Fig. 51 be voltage be 0V when
Ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；From fig. 5, it can be seen that embodiment one is made
The polyurethane of standby carbazolyl-containing has an obvious absorption in the case where pressure (when voltage is 0V) is not powered at 314nm
Peak, and polymer now is presented colourless；When applied voltage is 0.9V, the absworption peak at 314nm is gradually increasing, while
Occurs absworption peak new at two at 400nm and 808nm respectively, the color of polymer is now changed into blue, says from the colourless green that is changed into
The polyurethane of carbazolyl-containing prepared by bright embodiment one has good electrochromic property.
Embodiment two：The present embodiment is with the difference for implementing：Step 4 1. described in dihydroxy compounds be
Bisphenol-A, the structure of described bisphenol-A isOther and the phase of embodiment one
Together.
The reaction equation of the step 4 of embodiment two is：
Implement
The structure of the polyurethane of the carbazolyl-containing that 3. step 4 of example two obtains is
Wherein the span of n is 1≤n≤100, and n is integer；
The infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two is as shown in Figure 6；Fig. 6 is prepared for embodiment two
Carbazolyl-containing polyurethane infrared spectrogram；In 6 figures, 1702cm-1Represent carbonylic stretching vibration；1225cm-1Represent carbon
Hydrogen nitrogen combination vibration absworption peak；1593cm-1Represent the stretching vibration of carbon nitrogen and nitrogen hydrogen flexural vibrations absworption peak；1655cm-1、
1507cm-1And 748cm-1Represent the hydrocarbon flexural vibrations absworption peak of phenyl ring.
The nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two is as shown in Figure 7；Fig. 7 is prepared by embodiment two
The nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing；With DMSO-d6It is solvent, in Fig. 7,7.95ppm represents the feature of NH-COO groups
Absworption peak；6.58ppm~7.53ppm represents the absworption peak of hydrogen on phenyl ring.
The structural characterization of the polyurethane of the carbazolyl-containing that comprehensive infrared and nuclear-magnetism is prepared to embodiment two, may certify that implementation
Example two has synthesized the polyurethane of target carbazolyl-containing.
The thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment two is as shown in figure 8, test condition：Nitrogen gas
Atmosphere, programming rate is 10 DEG C/min；Fig. 8 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment two；Can from Fig. 8
Know, in a nitrogen atmosphere, programming rate is under conditions of 10 DEG C/min, the polyurethane of carbazolyl-containing prepared by embodiment two is in temperature
Spend for weightlessness is 10% at 206 DEG C, surplus is 50% at 500 DEG C.
The cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two is as shown in Figure 9；Fig. 9 makes for embodiment two
The cyclic voltammetric spectrogram of the polyurethane of standby carbazolyl-containing；The polyurethane dissolving of carbazolyl-containing prepared by 0.001g embodiments two
In 2mL dichloroethanes, then the polyurethane for applying the carbazolyl-containing of the preparation of embodiment two of 80nm on electro-conductive glass with spin-coating method
Film, will scribble the electro-conductive glass of polyurethane film of carbazolyl-containing prepared by embodiment two as working electrode, platinum filament be to electrode,
Saturation calomel is reference electrode, with solution of the 0.1M lithium perchlorates in acetonitrile as electrolyte, 0~1.6V of test voltage scope；
As can be seen from Figure 9, cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two under applied voltage, there is two pairs of peaks,
It is oxidation peak at the peak of 0.88V and 1.19V, simultaneous color is changed into blue again from the colourless green that is changed into；In 0.67V and
Have two corresponding reduction peaks at 0.93V, now color from blueness be changed into green become colorless again, multiple circulating phenomenon is identical,
The polyurethane electrochemical properties stabilization of carbazolyl-containing prepared by embodiment two is illustrated, and has preferable invertibity.
As shown in Figure 10, test condition is with circulation for the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two
Volt-ampere test；Figure 10 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment two；1 is that voltage is 0V in Figure 10
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；From fig. 10 it can be seen that embodiment
The polyurethane of two carbazolyl-containings for preparing has one significantly in the case where pressure (when voltage is 0V) is not powered at 316nm
Absworption peak, and polymer now is presented colourless；When applied voltage is 0.9V, the absworption peak at 316nm is gradually increasing, while
Occur absworption peak new at two respectively at 400nm and 800nm, the color of polymer is now changed into blue from the colourless green that is changed into,
Illustrating the polyurethane of carbazolyl-containing prepared by embodiment two has good electrochromic property.
Embodiment three：The present embodiment is with the difference of embodiment one：Step 4 1. described in dihydroxy compounds be
4,4- dihydroxybiphenyls；The structure of described 4,4- dihydroxybiphenyls isOther
It is identical with embodiment one.
The reaction equation of the step 4 of embodiment three is：
Embodiment
The structure of the polyurethane of the carbazolyl-containing that 3. three step 4 obtain is
Wherein the span of n is 1≤n≤100, and n is integer；
As shown in figure 11, Figure 11 makes the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three for embodiment three
The infrared spectrogram of the polyurethane of standby carbazolyl-containing；In fig. 11,1699cm-1Represent carbonylic stretching vibration；1225cm-1Generation
The hydrocarbon nitrogen combination vibration absworption peak of table；1605cm-1Represent the stretching vibration of carbon nitrogen and nitrogen hydrogen flexural vibrations absworption peak；1662cm-1、
1503cm-1And 748cm-1Represent the hydrocarbon flexural vibrations absworption peak of phenyl ring.
As shown in figure 12, Figure 12 is prepared the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three for embodiment three
Carbazolyl-containing polyurethane nuclear magnetic spectrogram；With DMSO-d6It is solvent, Tu12Zhong, 7.95ppm represents the spy of NH-COO groups
Levy absworption peak；6.73ppm~7.52ppm represents the absworption peak of hydrogen on phenyl ring.
The structural characterization of the polyurethane of the carbazolyl-containing that comprehensive infrared and nuclear-magnetism is prepared to embodiment three, may certify that implementation
Example three has synthesized polyurethane of the target containing triaryl amine.
The thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment three is as shown in figure 13, test condition, nitrogen gas
Atmosphere, programming rate is 10 DEG C/min；Figure 13 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment three；From Figure 13
In as can be seen that in a nitrogen atmosphere, under conditions of programming rate is 10 DEG C/min, carbazolyl-containing prepared by embodiment three it is poly-
Urethane is that weightlessness is 10% at 216 DEG C in temperature, and surplus is 42% at 500 DEG C.
As shown in figure 14, Figure 14 is embodiment three to the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three
The cyclic voltammetric spectrogram of the polyurethane of the carbazolyl-containing of preparation；The polyurethane of carbazolyl-containing prepared by 0.001g embodiments three is molten
Solution is in 2mL dichloroethanes, then the poly- ammonia for applying the carbazolyl-containing of the preparation of embodiment three of 80nm on electro-conductive glass with spin-coating method
Ester film, will scribble the electro-conductive glass of polyurethane film of carbazolyl-containing prepared by embodiment three as working electrode, and platinum filament is to electricity
Pole, saturation calomel is reference electrode, with solution of the 0.1M lithium perchlorates in acetonitrile as electrolyte, test voltage scope 0~
1.6V；As can be seen from Figure 14, cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three under applied voltage, there is two
It is oxidation peak at the peak of 1.03V and 1.34V to peak, simultaneous color is changed into blue again from the colourless green that is changed into；
There are two corresponding reduction peaks at 0.72V and 0.96V, now color is changed into green and becomes colorless again from blueness, and repeatedly circulation is existing
As identical, the polyurethane electrochemical properties stabilization of carbazolyl-containing prepared by embodiment three is illustrated, and have preferable invertibity.
As shown in figure 15, test condition is with circulation for the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three
Volt-ampere test；Figure 15 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment three；1 is that voltage is 0V in Figure 15
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；It can be seen from fig. 15 that embodiment
The polyurethane of three carbazolyl-containings for preparing has one significantly in the case where pressure (when voltage is 0V) is not powered at 324nm
Absworption peak, and polymer now is presented colourless；When applied voltage is 0.9V, the absworption peak at 324nm is gradually reduced, while
Occur absworption peak new at two respectively at 400nm and 828nm, the color of polymer is now changed into blue from the colourless green that is changed into,
Illustrating the polyurethane of carbazolyl-containing prepared by embodiment three has good electrochromic property.
Example IV：The present embodiment is with the difference of embodiment one：Step 4 1. described in dihydroxy compounds be 4,
4'- dihydroxy benaophenonels；The structure of described 4,4'- dihydroxy benaophenonels is
Other are identical with embodiment one.
The reaction equation of example IV step 4 is：
The structure of the polyurethane of the carbazolyl-containing that 3. example IV step 4 obtains isWherein the span of n is 1≤n≤100, and n is integer；
As shown in figure 16, Figure 16 is example IV system to the infrared spectrogram of the polyurethane of carbazolyl-containing prepared by example IV
The infrared spectrogram of the polyurethane of standby carbazolyl-containing；In figure 16,1669cm-1Represent carbonylic stretching vibration；1219cm-1Generation
The hydrocarbon nitrogen combination vibration absworption peak of table；1597cm-1Represent the stretching vibration of carbon nitrogen and nitrogen hydrogen flexural vibrations absworption peak；1659cm-1、
1503cm-1And 748cm-1Represent the hydrocarbon flexural vibrations absworption peak of phenyl ring.
The nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by example IV is as shown in figure 17；Figure 17 is prepared for example IV
Carbazolyl-containing polyurethane nuclear magnetic spectrogram；With DMSO-d6It is solvent, Tu17Zhong, 7.95ppm represents the spy of NH-COO groups
Levy absworption peak；6.82ppm~7.63ppm represents the absworption peak of hydrogen on phenyl ring.
The structural characterization of the polyurethane of the carbazolyl-containing that comprehensive infrared and nuclear-magnetism is prepared to example IV, may certify that implementation
Example four has synthesized polyurethane of the target containing triaryl amine.
The thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by example IV is as shown in figure 18, test condition：Nitrogen gas
Atmosphere, programming rate is 10 DEG C/min；Figure 18 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by example IV；From Figure 18
In as can be seen that in nitrogen atmosphere, under conditions of programming rate is 10 DEG C/min, the poly- ammonia of carbazolyl-containing prepared by example IV
Ester is that weightlessness is 10% at 214 DEG C in temperature, and surplus is 40% at 500 DEG C.
As shown in figure 19, Figure 19 is example IV to the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by example IV
The cyclic voltammetric spectrogram of the polyurethane of the carbazolyl-containing of preparation.The polyurethane of carbazolyl-containing prepared by 0.001g example IVs is molten
Solution is in 2mL dichloroethanes, then the poly- ammonia for applying the carbazolyl-containing of the example IV preparation of 80nm on electro-conductive glass with spin-coating method
Ester film, will scribble the electro-conductive glass of polyurethane film of the carbazolyl-containing of example IV preparation as working electrode, and platinum filament is to electricity
Pole, saturation calomel is reference electrode, with solution of the 0.1M lithium perchlorates in acetonitrile as electrolyte, test voltage scope 0~
1.6V；As can be seen from Figure 19, cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by example IV under applied voltage, there is two
It is oxidation peak at the peak of 0.95V and 1.21V to peak, simultaneous color is changed into blue again from the colourless green that is changed into；
There are two corresponding reduction peaks at 0.76V and 0.98V, now color is changed into green and becomes colorless again from blueness, and repeatedly circulation is existing
As identical, the polyurethane electrochemical properties stabilization of carbazolyl-containing prepared by example IV is illustrated, and have preferable invertibity.
As shown in figure 20, test condition is with circulation for the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by example IV
Volt-ampere test；Figure 20 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by example IV；1 is that voltage is 0V in Figure 20
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；It can be observed from fig. 20 that embodiment
The polyurethane of four carbazolyl-containings for preparing has one significantly in the case where pressure (when voltage is 0V) is not powered at 314nm
Absworption peak, and polymer now is presented colourless；When applied voltage is 0.9V, the absworption peak at 314nm is gradually reduced, while
Occur absworption peak new at two respectively at 400nm and 808nm, the color of polymer is now changed into blue from the colourless green that is changed into,
Illustrating the polyurethane of carbazolyl-containing prepared by example IV has good electrochromic property.
Embodiment five：The present embodiment is with the difference of embodiment one：Step 4 1. described in dihydroxy compounds be
Bisphenol fluorene, the structure of described bisphenol fluorene isOther are identical with embodiment one.
The reaction equation of the step 4 of embodiment five is：
The structure of the polyurethane of the carbazolyl-containing that 3. step 4 of embodiment five obtains isWherein the span of n is 1≤n≤100, and n is integer；
The infrared spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five is as shown in figure 21；Figure 21 makes for embodiment five
The infrared spectrogram of the polyurethane of standby carbazolyl-containing；In figure 21,1705cm-1Represent carbonylic stretching vibration；1220cm-1Generation
The hydrocarbon nitrogen combination vibration absworption peak of table；1593cm-1Represent the stretching vibration of carbon nitrogen and nitrogen hydrogen flexural vibrations absworption peak；1659cm-1、
1503cm-1And 745cm-1Represent the hydrocarbon flexural vibrations absworption peak of phenyl ring.
As shown in figure 22, Figure 22 is prepared the nuclear magnetic spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five for embodiment five
Carbazolyl-containing polyurethane nuclear magnetic spectrogram；With DMSO-d6It is solvent, Tu22Zhong, 7.95ppm represents the spy of NH-COO groups
Levy absworption peak；6.57ppm~7.53ppm represents the absworption peak of hydrogen on phenyl ring.
The structural characterization of the polyurethane of the carbazolyl-containing that comprehensive infrared and nuclear-magnetism is prepared to embodiment 5, may certify that implementation
Example five has synthesized the polyurethane of target carbazolyl-containing.
As shown in figure 23, test condition is nitrogen gas to the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment five
Atmosphere, programming rate is 10 DEG C/min；Figure 23 is the thermogravimetric curve figure of the polyurethane of carbazolyl-containing prepared by embodiment five；From Figure 23
In as can be seen that in a nitrogen atmosphere, under conditions of programming rate is 10 DEG C/min, carbazolyl-containing prepared by embodiment five it is poly-
Urethane is that weightlessness is 10% at 215 DEG C in temperature, and surplus is 56% at 500 DEG C.
As shown in figure 24, Figure 24 is embodiment five to the cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five
The cyclic voltammetric spectrogram of the polyurethane of the carbazolyl-containing of preparation；The polyurethane of carbazolyl-containing prepared by 0.001g embodiments five is molten
Solution is in 2mL dichloroethanes, then the poly- ammonia for applying the carbazolyl-containing of the preparation of embodiment five of 80nm on electro-conductive glass with spin-coating method
Ester film, will scribble the electro-conductive glass of polyurethane film of carbazolyl-containing prepared by embodiment five as working electrode, and platinum filament is to electricity
Pole, saturation calomel is reference electrode, with solution of the 0.1M lithium perchlorates in acetonitrile as electrolyte, test voltage scope 0~
1.8V；As shown in figure 24, cyclic voltammetric spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five under applied voltage, there is two
It is oxidation peak at the peak of 0.94V and 1.56V to peak, simultaneous color is changed into blue again from the colourless green that is changed into；
There are two corresponding reduction peaks at 0.54V and 0.89V, now color is changed into green and becomes colorless again from blueness, and repeatedly circulation is existing
As identical, the polyurethane electrochemical properties stabilization of carbazolyl-containing prepared by embodiment five is illustrated, and have preferable invertibity.
As shown in figure 25, test condition is with circulation for the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five
Volt-ampere test；Figure 25 is the electrochromism spectrogram of the polyurethane of carbazolyl-containing prepared by embodiment five.1 is that voltage is 0V in Figure 25
When ultravioletvisible absorption curve, 2 be voltage be 0.9V when ultravioletvisible absorption curve；As can be seen from Figure 25, embodiment
The polyurethane of five carbazolyl-containings for preparing has one significantly in the case where pressure (when voltage is 0V) is not powered at 310nm
Absworption peak, and polymer now is presented colourless；When applied voltage is 0.9V, the absworption peak at 310nm is gradually increasing, while
Occur absworption peak new at two respectively at 400nm and 816nm, the color of polymer is now changed into blue from the colourless green that is changed into,
Illustrating the polyurethane of carbazolyl-containing prepared by embodiment five has good electrochromic property.
Claims (9)
1. a kind of polyurethane of carbazolyl-containing, it is characterised in that a kind of structural formula of the polyurethane of carbazolyl-containing is：Wherein, described Ar is：Described R is： The span of described n is 1≤n≤100, and n is whole
Number.
2. a kind of a kind of preparation method of the polyurethane of carbazolyl-containing, it is characterised in that preparation method of the polyurethane of carbazolyl-containing
It is specifically realized by the following steps：
First, monoamine monomer is synthesized：
1., in a nitrogen atmosphere, carbazole is dissolved in anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and sodium hydride, then
Temperature is to be heated to reflux 36h~48h at 150 DEG C~160 DEG C, reuses the distilled water that temperature is 0 DEG C~5 DEG C and settles out product A,
Reuse acetonitrile to recrystallize product A, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain triphenylamine nitre
Based compound；
Step one 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of carbazole be (0.1g~0.5g):10mL；
Step one 1. described in the mol ratio of carbazole and p-fluoronitrobenzene be 1:1；
Step one 1. described in the mass ratio of carbazole and sodium hydride be (8~12):1；
2. triphenylamine nitro compound, is dissolved in N, in N '-solvent dimethylformamide, Pb/C catalyst is added, then in hydrogen
Gas atmosphere and pressure are that 8MPa~10MPa, temperature are 60 DEG C~80 DEG C and mixing speed is the bar of 100r/min~300r/min
30~40h of stirring reaction under part, adds the distilled water that temperature is 0 DEG C~5 DEG C and settles out product B；Toluene is reused to generation
Thing B is recrystallized, then dries 10h~12h in the case where temperature is for 40 DEG C~50 DEG C, obtains monoamine monomer；
Step one 2. described in the quality of triphenylamine nitro compound and the volume ratio of N, N '-solvent dimethylformamide be
(0.1g~0.5g):10mL；
Step one 2. described in the mass ratio of triphenylamine nitro compound and Pb/C catalyst be (8~10):1；
2nd, triaryl amine monomer is synthesized：
1., under nitrogen atmosphere, monoamine monomer is dissolved into anhydrous dimethyl sulphoxide, adds p-fluoronitrobenzene and sodium hydride,
36h~48h is heated to reflux at being again 150 DEG C~160 DEG C in temperature, the distilled water that temperature is 0 DEG C~5 DEG C is reused and is settled out generation
Thing C, then product C is recrystallized with acetonitrile, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain triaryl amine
Nitro compound；
Step 2 1. described in the volume ratio of quality and anhydrous dimethyl sulphoxide of monoamine monomer be (0.1g~0.5g):
10mL；
Step 2 1. described in the mol ratio of monoamine monomer and p-fluoronitrobenzene be 1:1；
Step 2 1. described in the mass ratio of monoamine monomer and sodium hydride be (8~12):1；
2., by N, N '-dimethylformamide is added in reactor, then triaryl amine nitro compound is dissolved into N, N '-diformazan
In base formamide, Pb/C catalyst is added, then be that 8MPa~10MPa, temperature are 60 DEG C~80 DEG C in hydrogen atmosphere and pressure
It is 30~40h of stirring reaction under conditions of 100r/min~300r/min with mixing speed, it is 0 DEG C~5 DEG C to add temperature
Distilled water settles out product D；Reuse toluene to recrystallize product D, then 10h is dried in the case where temperature is for 40 DEG C~50 DEG C
~12h, obtains triaryl amine monomer；
Step 2 2. described in triaryl amine nitro compound quality and N, N '-dimethylformamide volume ratio be (0.1g
~0.5g):10mL；
Step 2 2. described in the mass ratio of triaryl amine nitro compound and Pb/C catalyst be (8~10):1；
3rd, synthesizing isocyanate monomer：
Under nitrogen atmosphere, triaryl amine monomer and triphosgene are dissolved in anhydrous dichloroethanes, then in the case where temperature is for 80 DEG C~85 DEG C
8h~10h is heated to reflux, Rotary Evaporators is reused and is steamed anhydrous dichloroethanes, obtain isocyanate-monomer；
The quality of the triaryl amine monomer described in step 3 is (0.1g~0.5g) with the volume ratio of anhydrous dichloroethanes:10mL；
Triaryl amine monomer and the mol ratio of triphosgene described in step 3 are 3:(1~2)；
4th, the polyurethane of carbazolyl-containing is synthesized：
1., under nitrogen atmosphere, dihydroxy compounds is dissolved in anhydrous dichloroethanes, obtains dihydroxy compounds solution；
Step 4 1. described in dihydroxy compounds quality and anhydrous dichloroethanes volume ratio be (0.1g~0.5g):
10mL；
2., under nitrogen atmosphere, isocyanate-monomer is dissolved in anhydrous dichloroethanes, obtains isocyanate solution；
Step 4 2. described in isocyanate-monomer quality and anhydrous dichloroethanes volume ratio be (0.1g~0.5g):
10mL；
3., under nitrogen atmosphere, isocyanate solution is mixed with dihydroxy compounds solution, then temperature be 80 DEG C~85 DEG C and
24h~36h is reacted under nitrogen atmosphere, the distilled water that temperature is 0 DEG C~5 DEG C is reused and is settled out product E, reuse methyl alcohol opposite
60h~72h is extracted into thing E, then 10h~12h is dried in the case where temperature is for 40 DEG C~50 DEG C, obtain the polyurethane of carbazolyl-containing；
Step 4 3. described in isocyanate solution in dihydroxy in isocyanate-monomer and dihydroxy compounds solution
The mol ratio of compound is 1:1；
The structural formula of the polyurethane of the 3. described carbazolyl-containing of step 4 is：Wherein,
Described Ar is：Described R is： The span of described n is 1≤n≤100, and n is integer.
3. the preparation method of the polyurethane of a kind of carbazolyl-containing according to claim 2, it is characterised in that step 3 is obtained
The structure of isocyanate-monomer be
4. the preparation method of the polyurethane of a kind of carbazolyl-containing according to claim 2, it is characterised in that step 4 1. in
Described dihydroxy compounds is
5. the preparation method of the polyurethane of a kind of carbazolyl-containing according to claim 2, it is characterised in that step one 2. in
The mass fraction of Pb is 10% in described Pb/C catalyst.
6. the preparation method of the polyurethane of a kind of carbazolyl-containing according to claim 2, it is characterised in that step 2 2. in
The mass fraction of Pb is 10% in described Pb/C catalyst.
7. the preparation method of the polyurethane of a kind of carbazolyl-containing according to claim 2, it is characterised in that step one 1. in
The quality of described carbazole is 10 with the mass ratio of sodium hydride:1.
8. the preparation method of the polyurethane of a kind of carbazolyl-containing according to claim 2, it is characterised in that step 2 1. in
Described monoamine monomer is 10 with the mass ratio of sodium hydride:1.
9. a kind of preparation method of the polyurethane of carbazolyl-containing according to claim 2, it is characterised in that institute in step 3
The triaryl amine monomer stated is 3 with the mol ratio of triphosgene:2.
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