CN1470548A - Oligomerized thiophene derivatives, and their preparing method and use - Google Patents
Oligomerized thiophene derivatives, and their preparing method and use Download PDFInfo
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- CN1470548A CN1470548A CNA03126963XA CN03126963A CN1470548A CN 1470548 A CN1470548 A CN 1470548A CN A03126963X A CNA03126963X A CN A03126963XA CN 03126963 A CN03126963 A CN 03126963A CN 1470548 A CN1470548 A CN 1470548A
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Abstract
The present invention relates to a new-type oligopolymer thiophene derivative, its preparation method and application. Said invention provides the molecular formula of said derivative. According to the characteristics of that the oligopolymer thiophene self-body has excellent optical and electric properties said invention utilizes the rotary coating process to make said derivative into film on the ITO conductive glass surface, then the derivative film can be made into electrochromism device, and under the action of electric field said device can change its colour.
Description
Technical field
The present invention relates to organic polymer photoelectric material technical field, specifically be meant novel Uniformpoly thiophene derivative and preparation method thereof and as the application of electrochromic film.
Background technology
The high purity Uniformpoly thiophene that the polymerization degree and polymerization position can be controlled, have definite molecular weight is not only " model " compound of research Polythiophene, self also is that a kind of πDian Zi with excellent light, electrical property is a conjugated compound.Because its excellent light, electrical property in recent years, are used as functional organic material and research and develop.Up to the present, according to the research and development target of Uniformpoly thiophene, design, synthesized various Uniformpoly thiophene derivatives as the photoelectric information functional organic materials.These Uniformpoly thiophene derivatives mainly are used to the research of following several respects: (1) studies the relation of the electric conductivity of resulting ion free radical salt with conjugate length by electrochemical doping.Result of study shows, improves the conjugate length of Uniformpoly thiophene, and electric conductivity also will improve thereupon.For example, the electric conductivity of 6 aggressiveness (6T) of thiophene is 10
0～10
-1Scm
-1, and the electric conductivity of 12 aggressiveness (4Oc12T) of thiophene reaches 10Scm
-1(2) the research and development Uniformpoly thiophene is as the photoelectric characteristic of photoelectric conversion material.Result of study demonstrates, and Uniformpoly thiophene is a kind of very excellent p N-type semiconductorN material.(3) the research Uniformpoly thiophene is as the characteristics of luminescence of luminous organic material.
Summary of the invention
At present, being used for electrochromic material almost is inorganic materials entirely, and inorganic materials has the cost height, is difficult for film forming, and the shortcoming of unsuitable flexible processing also has nondegradable toxicity in addition.Purpose of the present invention is exactly the weak point that exists in this technology in order to solve, a kind of Uniformpoly thiophene derivative is provided, and this derivative is easy to film forming, is easy to flexible processing, have excellent light, electrical property, utilize this derivatives membrane group can assemble the novel electrochromic device.
Uniformpoly thiophene derivative of the present invention is made of following molecular formula:
DNC
18DOc4T
The structural parameter of this Uniformpoly thiophene derivative are as follows:
Molecular weight: 1145,
Proton nmr spectra: δ (ppm)=7.45 (t, 2H, NH), 7.40 (s, 2H, ArH), 7.24 (d, 2H, ArH) 7.15 (d, 2H, ArH), 3.31 (t, 4H, stearyl α-CH
2), 2.79 (t, 4H, octyl α-CH
2), 1.68 (tt, 4H, stearyl β-CH
2), 1.56 (tt, 4H, octyl β-CH
2), 1.49-1.11 (m, 80H), 0.88 (t, 12H),
Infrared spectra: (KBr method, cm
-1): 3288 (ν
N-H), 2955,2921,2849 (ν
C-H), 1615 (ν
C-O).
The preparation method of Uniformpoly thiophene derivative of the present invention comprises the steps and processing condition:
The first step is at-78 ℃, N
2Under the protection, with tetrahydrofuran (THF) (THF) the solution adding diisopropylamine lithium of DOc4T
(LDA) in tetrahydrofuran (THF) (THF) solution, stirring reaction 1-3 hour;
Second step added dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 3-5 hour down,
Be warmed up to room temperature then, continue reaction 3-5 hour;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 5-8 hour, removed by filter THF and water, washing,
Dry;
The 4th step joined sulfur oxychloride (SOCl with product
2) 1, in the 2-dichloroethane solution, back flow reaction 5-8 is little
The time, remove and desolvate;
The 5th step with product and octadecylamine at 0 ℃, N
2Protection was reacted 6-10 hour in dichloromethane solution down,
Remove and desolvate, obtain crude product, separate with silicagel column then, promptly get pure products DNC
18DOc4T.
Said process can be expressed as follows:
In order to realize the present invention better, can add triethylamine earlier in the dichloromethane solution in the 5th step; Can be chloroform with the isolating washing fluid of silicagel column.
Uniformpoly thiophene derivative of the present invention is with the method for spin coated (spin coating) chloroformic solution of described Uniformpoly thiophene derivative to be made film as the application of electrochromic material, can variable color under electric field action with the device of this film assembling; Method comprises the steps: more specifically
The first step utilizes the method for spin coated (spin coating) with DNC
18The chloroformic solution of DOc4T is coated in the ITO conductive glass surface and makes film.The thickness of film is the 1-10 micron.
It is that the propylene carbonate solution of 20% polymethylmethacrylate is coated in the ITO conductive glass surface and makes film with concentration that second step was utilized the method for spin coated.The thickness of film is 10 microns.The LiClO that also contains 0.1M in the propylene carbonate solution of polymethylmethacrylate
4
The 3rd step is overlapping with above-mentioned two ITO conductive glass, respectively as electrode, is assembled into the electrochromic device with sandwich structure.
When applying voltage during for+5V, the color of device becomes blueness, and when applying voltage be-during 5V, the color of device becomes redness from blueness, thereby the realization electrochromism.
The present invention compared with prior art has following advantage and beneficial effect:
The present invention is based on Uniformpoly thiophene self and have excellent light, these characteristics of electrical property, the method by spin coated (spin coating) is with DNC
18DOc4T makes film on the ITO conductive glass.Device with this film assembling can variable color under electric field action.The present invention has overcome inorganic electrochromic material and has had the cost height, is difficult for film forming, should not flexiblely process and have nondegradable toxic shortcoming.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The preparation Uniformpoly thiophene derivative
The first step is at-78 ℃, N
2Protection down adds in tetrahydrofuran (THF) (THF) solution of diisopropylamine lithium (LDA) stirring reaction 1 hour with tetrahydrofuran (THF) (THF) solution of DOc4T;
Second step added dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 3 hours down, is warmed up to room temperature then, continues reaction 3 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 5 hours, removed by filter THF and water, washing, drying;
The 4th step joined sulfur oxychloride (SOCl with product
2) 1, in the 2-dichloroethane solution, back flow reaction 5 hours is removed and to be desolvated;
The 5th step with product and octadecylamine at 0 ℃, N
2Protection was reacted 6 hours in dichloromethane solution down, removed and desolvated, and obtained crude product, separated with silicagel column then, promptly got pure products DNC
18DOc4T.
The making of electrochromic film
The first step utilizes the method for spin coated (spin coating) with DNC
18The chloroformic solution of DOc4T is coated in the ITO conductive glass surface and makes film.The thickness of film is 1 micron.
It is that the propylene carbonate solution of 20% polymethylmethacrylate is coated in the ITO conductive glass surface and makes film with concentration that second step was utilized the method for spin coated.The thickness of film is 10 microns.The LiClO that also contains 0.1M in the propylene carbonate solution of polymethylmethacrylate
4
The 3rd step is overlapping with above-mentioned two ITO conductive glass, respectively as electrode, is assembled into the electrochromic device with sandwich structure.
When applying voltage during for+5V, the color of device becomes blueness, and when applying voltage be-during 5V, the color of device becomes redness from blueness.
Embodiment 2
The preparation Uniformpoly thiophene derivative
The first step is at-78 ℃, N
2Protection down adds in tetrahydrofuran (THF) (THF) solution of diisopropylamine lithium (LDA) stirring reaction 2 hours with tetrahydrofuran (THF) (THF) solution of DOc4T;
Second step added dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 4 hours down, is warmed up to room temperature then, continues reaction 4 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 6 hours, removed by filter THF and water, washing, drying;
The 4th step joined sulfur oxychloride (SOCl with product
2) 1, in the 2-dichloroethane solution, back flow reaction 6 hours is removed and to be desolvated;
The 5th step with product and octadecylamine at 0 ℃, N
2Protection was reacted 7 hours in dichloromethane solution down, removed and desolvated, and obtained crude product, separated with silicagel column then, promptly got pure products DNC
18DOc4T.
The making of electrochromic film
The first step utilizes the method for spin coated (spin coating) with DNC
18The chloroformic solution of DOc4T is coated in the ITO conductive glass surface and makes film.The thickness of film is 3 microns.
It is that the propylene carbonate solution of 20% polymethylmethacrylate is coated in the ITO conductive glass surface and makes film with concentration that second step was utilized the method for spin coated.The thickness of film is 10 microns.The LiClO that also contains 0.1M in the propylene carbonate solution of polymethylmethacrylate
4
The 3rd step is overlapping with above-mentioned two ITO conductive glass, respectively as electrode, is assembled into the electrochromic device with sandwich structure.
When applying voltage during for+5V, the color of device becomes blueness, and when applying voltage be-during 5V, the color of device becomes redness from blueness.
Embodiment 3
The preparation Uniformpoly thiophene derivative
The first step is at-78 ℃, N
2Protection down adds in tetrahydrofuran (THF) (THF) solution of diisopropylamine lithium (LDA) stirring reaction 3 hours with tetrahydrofuran (THF) (THF) solution of DOc4T;
Second step added dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 5 hours down, is warmed up to room temperature then, continues reaction 5 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 8 hours, removed by filter THF and water, washing, drying;
The 4th step joined sulfur oxychloride (SOCl with product
2) 1, in the 2-dichloroethane solution, back flow reaction 8 hours is removed and to be desolvated;
The 5th step with product and octadecylamine at 0 ℃, N
2Protection was reacted 10 hours in dichloromethane solution down, removed and desolvated, and obtained crude product, separated with silicagel column then, promptly got pure products DNC
18DOc4T.
The making of electrochromic film
The first step utilizes the method for spin coated (spin coating) with DNC
18The chloroformic solution of DOc4T is coated in the ITO conductive glass surface and makes film.The thickness of film is 10 microns.
It is that the propylene carbonate solution of 20% polymethylmethacrylate is coated in the ITO conductive glass surface and makes film with concentration that second step was utilized the method for spin coated.The thickness of film is 10 microns.The LiClO that also contains 0.1M in the propylene carbonate solution of polymethylmethacrylate
4
The 3rd step is overlapping with above-mentioned two ITO conductive glass, respectively as electrode, is assembled into the electrochromic device with sandwich structure.
When applying voltage during for+5V, the color of device becomes blueness, and when applying voltage be-during 5V, the color of device becomes redness from blueness.
Claims (5)
1, a kind of Uniformpoly thiophene derivative is characterized in that, it is made of following molecular formula:
DNC
18DOc4T
The structural parameter of described Uniformpoly thiophene derivative are as follows:
Molecular weight: 1145,
Proton nmr spectra: δ (ppm)=7.45 (t, 2H, NH), 7.40 (s, 2H, ArH), 7.24 (d, 2H, ArH) 7.15 (d, 2H, ArH), 3.31 (t, 4H, stearyl α-CH
2), 2.79 (t, 4H, octyl α-CH
2), 1.68 (tt, 4H, stearyl β-CH
2), 1.56 (tt, 4H, octyl β-CH
2), 1.49-1.11 (m, 80H), 0.88 (t, 12H),
Infrared spectra: (KBr method, cm
-1): 3288 (ν
N-H), 2955,2921,2849 (ν
C-H), 1615 (ν
C-O).
2, the preparation method of the described Uniformpoly thiophene derivative of claim 1 is characterized in that comprising the steps:
The first step is at-78 ℃, N
2Protection down adds in the tetrahydrofuran solution of diisopropylamine lithium stirring reaction 1-3 hour with the tetrahydrofuran solution of DOc4T;
Second step added dry ice in reaction soln, at-78 ℃, N
2Protection continues reaction 3-5 hour down, is warmed up to room temperature then, continues reaction 3-5 hour;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 5-8 hour, removed by filter THF and water, washing, drying;
The 4th step joined 1 of sulfur oxychloride with product, in the 2-dichloroethane solution, back flow reaction 5-8 hour, removed and desolvated;
The 5th step with product and octadecylamine at 0 ℃, N
2Protect down, reaction is 6-10 hour in dichloromethane solution, removes and desolvates, and obtains crude product, separates with silicagel column then, gets pure products DNC
18DOc4T.
3, the preparation method of Uniformpoly thiophene derivative according to claim 2 is characterized in that, adds triethylamine in the dichloromethane solution in the 5th step earlier; With the isolating washing fluid of silicagel column is chloroform.
4, the described Uniformpoly thiophene derivative of claim 1 is as the application of electrochromic film.
5, Uniformpoly thiophene derivative according to claim 4 is characterized in that as the application of electrochromic film described electrochromic film is prepared by following method:
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126963 CN1247665C (en) | 2003-06-25 | 2003-06-25 | Oligomerized thiophene derivatives, and their preparing method and use |
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|---|---|---|---|
| CN 03126963 CN1247665C (en) | 2003-06-25 | 2003-06-25 | Oligomerized thiophene derivatives, and their preparing method and use |
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| Publication Number | Publication Date |
|---|---|
| CN1470548A true CN1470548A (en) | 2004-01-28 |
| CN1247665C CN1247665C (en) | 2006-03-29 |
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ID=34153155
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100489007C (en) * | 2006-08-18 | 2009-05-20 | 中国科学院长春应用化学研究所 | Preparation method of crosslinking kind net conductive polythiofuran meterial |
| CN101405347B (en) * | 2006-03-31 | 2012-09-12 | 独立行政法人产业技术综合研究所 | Organic compound, semiconductor thin film electrode using the same, photoelectric transducer, and photoelectrochemical solar cell |
-
2003
- 2003-06-25 CN CN 03126963 patent/CN1247665C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405347B (en) * | 2006-03-31 | 2012-09-12 | 独立行政法人产业技术综合研究所 | Organic compound, semiconductor thin film electrode using the same, photoelectric transducer, and photoelectrochemical solar cell |
| CN100489007C (en) * | 2006-08-18 | 2009-05-20 | 中国科学院长春应用化学研究所 | Preparation method of crosslinking kind net conductive polythiofuran meterial |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1247665C (en) | 2006-03-29 |
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Assignee: Shenzhen Fuxing Technology Co., Ltd. Assignor: South China University of Technology Contract record no.: 2010440020037 Denomination of invention: Oligomerized thiophene derivatives, and their preparing method and use Granted publication date: 20060329 License type: Exclusive License Open date: 20040128 Record date: 20100507 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060329 Termination date: 20120625 |