CN110437362A - A kind of preparation method and application of the photochromic polymer of Photocrosslinkable - Google Patents
A kind of preparation method and application of the photochromic polymer of Photocrosslinkable Download PDFInfo
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- CN110437362A CN110437362A CN201910727990.1A CN201910727990A CN110437362A CN 110437362 A CN110437362 A CN 110437362A CN 201910727990 A CN201910727990 A CN 201910727990A CN 110437362 A CN110437362 A CN 110437362A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
The present invention provides a kind of photochromic polymer of Photocrosslinkable, shown in the chemical formula of the polymer such as formula (I):
Description
Technical field
The present invention relates to Macroscopic single crystal fields, more particularly to the light of the Photocrosslinkable containing spiro-pyrans and cumarin system
Cause the preparation method and application of electrochromic polymer.
Background technique
Photochromic polymer has wide in the fields such as photoswitch, data record and storage, nonlinear optics, display
Application prospect.And spiro-pyrans analog derivative then has excellent photochromic performance, spiro-pyrans (Spiropyran, SP) is one
Class research is most extensive, the most in-depth organic electrochromic compound, and colourless closed loop body spiro-pyrans (SP) and coloured open loop body can occur
Spend structural isomerism reversible between cyanines (MC) in portion.It is by chromene and indoline two in common Indoline spiropyran structure
Part aromatic ring is formed by connecting by the spiral shell C atom of a sp3 hydridization.Two parts aromatic ring is mutually orthogonal, on spiro-pyrans molecular structure
It is not conjugated, forms colourless closed loop body；Under the action of ultraviolet light, heat or power, the C-O key of spiro-pyrans closed loop body occurs different
Split, isomerization or rearrangement occur for electron configuration, become coplanar coloured of two parts aromatic ring and open ring body portion flower cyanines
(Merocyanine, MC) state, entire molecule form a big conjugate planes；Under visible light illumination, open loop system is returned again
To the SP state of closed loop；
Cumarin is a kind of important phenolic compound, it both can be by extracting in nature, can also be by manually being closed
At.It is in medicine, photoelectricity, food, has a wide range of applications in the industries such as cosmetics.In the photochemistry and optical physics of cumarin
In matter, reversible dimerization can occur for the photon for absorbing different wave length, and which results in the extensive concerns of people.And it can will gather
It closes object and carries out reversible photo-crosslinking and photodestruciton.Such as can by polymer of the invention under 365nm ultraviolet light photo-crosslinking, In
Photodestruciton under 254nm ultraviolet light.
Summary of the invention
The present invention is intended to provide a kind of preparation method and application of the photochromic polymer of Photocrosslinkable.
A kind of molecular formula of the photochromic polymer of Photocrosslinkable provided by the present invention is as shown below:
Wherein R1 and R2 is ester group, hydroxyl, bromine isobutyl group, methyl methacrylate and alkoxy etc..
Above-mentioned ester group can be expressed as-COOR ', wherein R ' representative-CnH2n+1, and n is natural number, preferably 1≤n≤24, more excellent
Select 1≤n≤18.
Above-mentioned alkoxy can be expressed as-OCxH2x+1, and x is natural number, preferably 1≤x≤24, more preferable 1≤x≤18.
The present invention also provides the preparation methods of above compound, comprising the following steps:
(1) from umbelliferone, by the way that with 1,6 Bromofumes are reacted in nitrogen protection to reflux can obtain for 12 hours
Acetone, DMF, ethyl alcohol etc. specifically can be using solvent to 7- (6- bromine hexyloxy)-cumarin (compound A)；
(2) product of step (1) is put into three-necked flask, vinyl terephthalic acid (TPA) and potassium carbonate is added, is made with DMF
For solvent, reacts 24 hours, be spin-dried for column and obtain compound monomer B；
(3) 2,3,3- trimethyl -3H- indoles are put into flask, if literature method is by series reaction, are finally obtained
Monomer C.
(4) monomer (B) and spiro-pyrans monomer (C) are put into tube sealing, tetrahydrofuran are added as solvent, use AIBN as
Initiator polymerize about 12 hours, obtains subject polymer, initiator can also be BPO etc..
The present invention devises photochromic polymer of a kind of Photocrosslinkable containing cumarin and spiro-pyrans, and cumarin can
So that copolymer carries out photo-crosslinking, and spiro-pyrans can make copolymer have photochromic effect.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of subject copolymers in the embodiment of the present invention 1, and Cong Tuzhong is it is understood that successfully synthesize
Subject polymer.
Fig. 2 is the ultraviolet spectrogram of subject copolymers in the embodiment of the present invention 1, in the ultraviolet light irradiation different time of 365nm
Afterwards, the absorption peak of cumarin reduces at 310nm, illustrates that the phenomenon that apparent photo-crosslinking occurs in subject polymer.
Fig. 3 be in the embodiment of the present invention 1 subject copolymers the ultraviolet light irradiation 0-60min of 365nm photo, in photo altogether
Polymers color is significantly deepened, and illustrates there is photochromism.
Specific embodiment
The content of patent for a better understanding of the present invention illustrates below by way of specific embodiment containing cumarin and spiral shell pyrrole
Mutter Photocrosslinkable photochromic copolymer synthetic method.Specifically include the preparation of intermediate and target product, but these realities
It applies example and is not intended to limit the present invention.
Embodiment 1
A kind of photochromic polymer compound of Photocrosslinkable, concrete structure formula are as follows:
The preparation method is as follows:
(1) synthesis of 7- (6- bromine hexyloxy)-cumarin (compound A)
Umbelliferone (1.62g, 10mmol) and 1 are weighed, 6- dibromo-hexane (12.19g, 50mmol) is added to
In the three-necked flask of 100mL, solvent acetone (60mL) is added, installs reflux unit, takes out applying argon gas 3 times, is eventually adding carbonic acid
Potassium solid (13.8g, 100mmol), then take out applying argon gas 3 times, under nitrogen protection, it is heated to reflux 14 hours (60 degree of oil bath), is spin-dried for
Solvent is extracted with ethyl acetate three times, is then dried under reduced pressure, and obtains white solid 1.6g, yield 50%.
(2) synthesis of monomer B
Weigh Compound A (1.6g, 5mmol) and vinyl terephthalic acid (TPA) (0.32g, 1.67mmol) are added to 100mL
Three-necked flask in, add solvent DMF (60mL), install reflux unit, take out applying argon gas 3 times, be eventually adding potash solid
(1.38g, 10mmol) takes out applying argon gas 3 times again, under nitrogen protection, is heated to reflux 14 hours (100 degree of oil bath), is spin-dried for solvent,
It is extracted with ethyl acetate three times, is then dried under reduced pressure, obtain white monomer 10.4g, yield 35%.
(3) polymerization of target product
White monomer B and spiro-pyrans monomer C is added in tube sealing, initiator A IBN is added, adds tetrahydrofuran solution,
Tube sealing is taken out inflated with nitrogen 3 times, then carries out tube sealing with gas stove.80 DEG C are reacted 12 hours, and subject copolymers are obtained.
Embodiment 2
A kind of photochromic polymer compound of Photocrosslinkable, concrete structure formula are as follows:
The preparation method is as follows:
(1) synthesis of 7- (6- bromine butoxy)-cumarin (compound A)
It weighs umbelliferone (1.62g, 10mmol) and Isosorbide-5-Nitrae-dibromobutane (11.59g, 50mmol) is added to
In the three-necked flask of 100mL, solvent acetone (60mL) is added, installs reflux unit, takes out applying argon gas 3 times, is eventually adding carbonic acid
Potassium solid (13.8g, 100mmol), then take out applying argon gas 3 times, it under nitrogen protection, is heated to reflux 14 hours (60 degree of oil bath), revolves
Dry solvent is extracted with ethyl acetate three times, is then dried under reduced pressure, and obtains white solid 1.6g, yield 50%.
(2) synthesis of monomer 1
Weigh Compound A (1.6g, 5mmol) and vinyl terephthalic acid (TPA) (0.32g, 1.67mmol) are added to 100mL
Three-necked flask in, add solvent DMF (60mL), install reflux unit, take out applying argon gas 3 times, be eventually adding potash solid
(1.38g, 10mmol), then take out applying argon gas 3 times, under nitrogen protection, it is heated to reflux 14 hours (100 degree of oil bath), is spin-dried for solvent,
It is extracted with ethyl acetate three times, is then dried under reduced pressure, obtain white monomer 10.4g, yield 35%.
(3) polymerization of target product
In in white monomer 1 and spiro-pyrans monomer addition tube sealing, initiator A IBN is added, it is molten to add tetrahydrofuran
Tube sealing is taken out inflated with nitrogen 3 times, then carries out tube sealing with gas stove by liquid.80 DEG C are reacted 12 hours, and subject copolymers are obtained.
Embodiment 3
A kind of photochromic polymer compound of Photocrosslinkable, concrete structure formula are as follows:
The preparation method is as follows:
(1) 7- (6- bromine oxethyl)-cumarin (compound A) synthesis
Umbelliferone (1.62g, 10mmol) and 1 are weighed, 2- Bromofume (10.48g, 50mmol) is added to
In the three-necked flask of 100mL, solvent acetone (60mL) is added, installs reflux unit, takes out applying argon gas 3 times, is eventually adding carbonic acid
Potassium solid (13.8g, 100mmol), then take out applying argon gas 3 times, it under nitrogen protection, is heated to reflux 14 hours (60 degree of oil bath), revolves
Dry solvent is extracted with ethyl acetate three times, is then dried under reduced pressure, and obtains white solid 1.6g, yield 50%.
(2) synthesis of monomer 2
Weigh Compound A (1.6g, 5mmol) and vinyl terephthalic acid (TPA) (0.32g, 1.67mmol) are added to 100mL
Three-necked flask in, add solvent DMF (60mL), install reflux unit, take out applying argon gas 3 times, be eventually adding potash solid
(1.38g, 10mmol), then take out applying argon gas 3 times, under nitrogen protection, it is heated to reflux 14 hours (100 degree of oil bath), is spin-dried for solvent,
It is extracted with ethyl acetate three times, is then dried under reduced pressure, obtain white monomer 10.4g, yield 35%.
(3) polymerization of target product
In in white monomer 2 and spiro-pyrans monomer addition tube sealing, initiator A IBN is added, it is molten to add tetrahydrofuran
Tube sealing is taken out inflated with nitrogen 3 times, then carries out tube sealing with gas stove by liquid.80 DEG C are reacted 12 hours, and subject copolymers are obtained.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (11)
1. a kind of photochromic polymer of the Photocrosslinkable containing spiro-pyrans and cumarin, which is characterized in that the polymer
Shown in chemical formula such as formula (I):
Wherein R1 and R2 is ester group, hydroxyl, bromine isobutyl group, methyl methacrylate and alkoxy etc.；
Above-mentioned ester group can be expressed as-COOR ', wherein R ' representative-CnH2n+1, n is natural number, preferably 1≤n≤24, more preferable 1≤n
≤18；Above-mentioned alkoxy can be expressed as-OCxH2x+1, and x is natural number, preferably 1≤x≤24, more preferable 1≤x≤18.
2. the preparation method of above-mentioned crosslinkable photochromic polymer molecule, which comprises the steps of:
(1) from umbelliferone, by the way that with 1,6 dibromo-hexanes react to obtain 7- (6 bromine hexyloxy) cumarin (compound
A)；
(2) monomer B is obtained from compound A by reacting with vinyl terephthalic acid (TPA).
It sets out from 2,3,3- trimethyl -3H- indoles, by such as literature method, reacts, finally obtain with vinyl terephthalic acid (TPA)
Monomer C.[Greg O'Bryan,*Bryan M.Wong,and James R.McElhano.Stress Sensing in
Polycaprolactone Films via an Embedded Photochromic Compound.APPLIED
MATERIALS&INTERFACES,VOL.2·NO.6·1594–1600·2010】
(3) monomer B and spiropyran compounds (C) are copolymerized, obtain copolymer D.
Wherein R base is ester group, hydroxyl, bromine isobutyl group, methyl methacrylate and alkoxy etc., and m is natural number 2≤m≤20.
3. preparation method as claimed in claim 2, which is characterized in that reaction dissolvent in the preparation method of the compound A
It can be acetone, can also be ethyl alcohol or DMF etc..
4. preparation method as claimed in claim 2, which is characterized in that reaction temperature can in the preparation method of the monomer B
Between 90-110 DEG C.
5. preparation method as claimed in claim 2, which is characterized in that the initiation polymerizeing in the preparation method of the monomer B
Agent can also be DMT or DMA etc..
6. preparation method as claimed in claim 2, which is characterized in that alkali can be in the preparation method of the compound A
Potassium carbonate or saleratus etc..
7. preparation method as claimed in claim 2, which is characterized in that can be added in the preparation method of the monomer B few
Point potassium iodide is as the catalyst to improve yield.
8. preparation method as claimed in claim 2, which is characterized in that can also be used in the preparation method of the copolymer C
Toluene and N-Methyl pyrrolidone.
9. above-mentioned copolymer can both realize in the solution it is photochromic, can also solid-state realize it is photochromic.
10. above-mentioned copolymer can be irradiated under the ultraviolet lamp of 365nm occur it is photochromic, irradiation time can from 0min to
60min etc..
11. above-mentioned copolymer can issue third contact of a total solar or lunar eclipse crosslinking in the ultraviolet light irradiation of 365nm, irradiation time can be from 0min to 60min
Differ.
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| CN201910727990.1A CN110437362A (en) | 2019-08-08 | 2019-08-08 | A kind of preparation method and application of the photochromic polymer of Photocrosslinkable |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499885A (en) * | 2020-04-24 | 2020-08-07 | 广东工业大学 | Photo-stimulus response reversible color-changing hydrogel and preparation method thereof and optical device |
| CN111501124A (en) * | 2020-03-13 | 2020-08-07 | 广东工业大学 | Color-variable microwire, light-emitting heterojunction and optical component |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
-
2019
- 2019-08-08 CN CN201910727990.1A patent/CN110437362A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
Non-Patent Citations (2)
| Title |
|---|
| GREG O’BRYAN ET AL.: ""Stress Sensing in Polycaprolactone Films via an Embedded Photochromic Compound"", 《APPLIED MATERIALS & INTERFACES》 * |
| 李业飞: ""点击化学方法制备可逆光响应聚酯胶束"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111501124A (en) * | 2020-03-13 | 2020-08-07 | 广东工业大学 | Color-variable microwire, light-emitting heterojunction and optical component |
| CN111501124B (en) * | 2020-03-13 | 2022-10-21 | 广东工业大学 | Color-variable microwire, light-emitting heterojunction and optical component |
| CN111499885A (en) * | 2020-04-24 | 2020-08-07 | 广东工业大学 | Photo-stimulus response reversible color-changing hydrogel and preparation method thereof and optical device |
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