CN107099006A - A kind of preparation method with liquid crystal and light memory storage type Comblike polymers material - Google Patents
A kind of preparation method with liquid crystal and light memory storage type Comblike polymers material Download PDFInfo
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- CN107099006A CN107099006A CN201710351965.9A CN201710351965A CN107099006A CN 107099006 A CN107099006 A CN 107099006A CN 201710351965 A CN201710351965 A CN 201710351965A CN 107099006 A CN107099006 A CN 107099006A
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- liquid crystal
- azobenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
- C09K19/3852—Poly(meth)acrylate derivatives
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
- G11C13/04—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using optical elements ; using other beam accessed elements, e.g. electron or ion beam
Abstract
A kind of preparation method with liquid crystal and light memory storage type Comblike polymers material, belong to Polymer Synthesizing, functionalized polymer to prepare and application field, be prepared for a series of novel liquid crystal memory storage Comblike polymers material of different molecular weights and azo benzene content.First brominated monomer (methacrylic acid (α bromines Isobutanovloxyethvl) ester is prepared with hydroxyethyl methacrylate and 2 bromo isobutyl acylbromides, BiBEM), secondly, brominated monomer carries out reversible addition chain transfer polymerization with methyl methacrylate, prepare methacrylate copolymers compound P0 of the controllable side chain of molecular weight containing brominated esters, finally, P0 is used as macromole evocating agent, ATRP is carried out to azobenzene monomer, prepare Comblike polymers, show that azobenzene polymer has excellent liquid crystal behavior and photoresponse activity by petrographic microscope (POM) and AFM (AFM), it is expected to be applied to photoactive liquid crystal material and light memory storage material.
Description
Technical field
The present invention relates to the Comblike polymers material of side chain functional structure containing azobenzene, belong to Polymer Synthesizing, functionalization
Polymer is prepared and application field.
Background technology
The active functional group of azobenzene compound, can occur cis-trans isomerization in the presence of light or heat.Will be even
Pyridine functional group is linked in polymer, not only with the optical activity with small molecule azobenzene compound, with high score
The excellent mechanics of sub- material and processing characteristics, therefore, in liquid crystal material, optical storage material, nonlinear optical material, stimulation
There is huge application potential in terms of response material, surface relief grating.Wherein, side chain contains optically active azobenzene knot
The functional polymer of structure has designability strong, wide variety, superior performance, before have become functional polymer research one
Along field, wide application prospect is shown.Azo monomer and mesogenic monomers are carried out copolymerization by such as Finkelmann et al., are obtained
Liquid crystal polymer containing azo group and mesomorphic group simultaneously on side chain, has a high polymer material due to them, small simultaneously
The combination property of molecular liquid crystal compound and azo chromophore, therefore arouse great concern immediately.1984,
Ringsdorf et al. proposes the structural model of liquid crystal polymer of the side chain containing azo group, so as to contain azo group for side chain
Liquid crystal polymer synthesis provide theoretical foundation.In addition, Coles et al. have studied the liquid crystal high score containing azo group at first
The optical information storage performance of sub- material, hereafter, the research of the side chain liquid crystalline polymer information storage material containing azo group are rapid
Exploitation focus as area information storage.In recent years, liquid crystal polymer non-linear optical material of the side chain containing azo group
Exploitation also becomes increasingly active, and (Fu Zhengsheng, Wang Changqing, Xue Huali wait optical activities containing azobenzene side group polymers progress
[J] macromolecules are circulated a notice of：2004,10-20；Zhang Huiqi, Huang Wenqiang, Li Chenxi, wait side chain liquid crystalline polymers of the containing azo group
Progress [J] Journal of Functional Polymers, 1998：416-422.)
Radical polymerization is the most common process side one for preparing side chain type azobenzene polymer.Earliest Natansohn et al.
The azo benzene monomer containing vinyl structure unit has been synthesized, corresponding azobenzene polymer has been prepared with this.Then,
Natasohn (Azo Polymers for Reversible Optical Storage.Macromolecules [J] .1992,
25：Side chain 2268-2273) et al. has been obtained by radical polymerization with azo benzene monomer of the end with naphthalene nucleus and carbazole structure
Type azobenzene polymer.Barrett et al. is prepared with azo benzene monomer, MMA as comonomer by free radical polymerisation process
Random copolymer.
Polymer with topological structure has highly branched three-dimensional globular structure and numerous end groups due to it, therefore
The property completely different with corresponding linear macromolecule, such as low viscosity, good solubility, no chain entanglement etc. are shown, in high score
The directions such as muonic catalysis complexing agent, rheology control agent, have broad application prospects.Star polymer is passed through by a plurality of linear chain
The polymer of Node connectedness.Regular star polymer has single branch point, the even molecular weight distribution of all arms.
Angiolini triggers polymerization azo benzene monomer using three arm star ATRP initiators, obtains all arm even molecular weight distributions
Three arm star azobenzene homopolymers, the type polymer has very different chiral optical property compared with linear polymer.
The content of the invention
This patent discloses a kind of preparation method of pectination azobenzene high polymer material, i.e., gathered using reversible addition chain tra nsfer
It is legal, methacrylate copolymers compound of the controllable side chain of molecular weight containing brominated esters is prepared, atom transferred free radical is utilized
Polymerization, using the brominated structural polymer of side chain as macromole evocating agent, polymerize to azobenzene monomer, prepares side chain containing azobenzene
Liquid crystal polymer, with excellent liquid crystal behavior and photoresponse activity, applied to photoactive liquid crystal material and light memory storage
Material.
Brief description of the drawings
Fig. 1：Pectination azobenzene synthesis of polymer material route map；
Fig. 2：Pectination azobenzene high polymer material nucleus magnetic hydrogen spectrum (1H-NMR) figure, the hydrogen of pectination azobenzene macromolecular structure
Proton is corresponded with nuclear magnetic signal, and azo benzene content is higher, and azobenzene signal is stronger, shows successfully to prepare different azobenzenes
The pectination azobenzene macromolecule of content；
Fig. 3：The petrographic microscope figure of pectination azobenzene high polymer material：A：120 DEG C, B：90 DEG C, show that polymer has
Thermotropic liquid crystal behavior.
Fig. 4：AFM (AFM) figure of pectination azobenzene high polymer material, shows to live with typical photoresponse
Property, surface relief grating is formed, with excellent light memory storage performance.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to further reason of going together
The solution present invention, but the invention is not limited in any way.It should be pointed out that for colleague, not departing from present inventive concept
On the premise of, various modifications and improvements can be made.These belong to protection scope of the present invention.
Embodiment 1, the preparation of methacrylic acid (α-bromine Isobutanovloxyethvl) ester (BiBEM)
In a kettle. add hydroxyethyl methacrylate (58.228g, 0.49mol), triethylamine (50.68g,
0.49mol) with 500mL tetrahydrofuran, it is well mixed, 36.5mL 2- bromo isobutyl acylbromides are dissolved in 200mLTHF to be added dropwise
Enter in round-bottomed flask, stirring reaction at 0-5 DEG C.3-5h is reacted after dripping off again, is filtered after the completion of reaction, filtrate is washed 3 times, acetic acid
Ethyl ester is extracted, and takes organic layer to rotate to solvent-free, product is purified with chromatographic column, obtains 83.16g, and yield is 89%, kept dry
It is stand-by in refrigerator-freezer.
Embodiment 2, macromole evocating agent P0 preparation
Brominated monomer BiBEM (14g, 0.05mol), methyl methacrylate are added in the polymerization reaction kettle with stirring
Ester (MMA, 10g, 0.1mol), chain-transferring agent CPDN (0.41g, 0.0015mol) and azo-bis-isobutyl cyanide AIBN (0.082g,
0.0005mol), 100mL methyl phenyl ethers anisoles lead to after argon gas deoxygenation 20min and sealed, under 60 DEG C of oil baths after magnetic agitation 12h, open anti-
Kettle, plus a small amount of THF dissolvings polymer are answered, then solution is poured into 2000mL industrial alcohol and precipitated, collected by suction precipitation, normal temperature
Vacuum drying oven drying is to constant weight, and polymer P 0 is made, and (23g, yield is 95%), to be used as the macromole evocating agent of lower step.
Under the same terms, BiBEM, MMA, CPDN and AIBN mol ratio are 50:50：1：0.2,60:40：1：0.2,
80:20：1：0.2,20:80：1：0.2,40:60：1：0.2, a series of macromolecular for preparing different molecular weights and bromine content triggers
Agent.
Embodiment 3, the preparation of pectination azobenzene high polymer material
Macromole evocating agent P0 (13.75g, 1mmol), benzene monomer containing azo are added in the polymerization reaction kettle with stirring
(5.68g, 76mmol), CuBr (0.34g, 3.4mmol), pentamethyl-diethylenetriamine PMDETA (0.12mg, 7mmol) and 50mL
Methyl phenyl ethers anisole, leads to after argon gas deoxygenation 20min and seals, at normal temperatures after magnetic agitation 20min, is placed in reaction in 70 DEG C of oil baths and extremely sets
Time.Reactor, plus a small amount of THF dissolvings polymer are opened, then solution is poured into 1000mL industrial alcohol and precipitated, suction filtration is received
Collection precipitation, normal-temperature vacuum oven drying is to constant weight, and weigh to obtain 18g,.
Under the same terms, the mol ratio of the monomer and macromole evocating agent P0 that change azobenzene group is 10:1,20:1,
40:1,100:1, prepare a series of new pectination azobenzene high polymer material of different molecular weights.
Claims (4)
1. a kind of preparation method with liquid crystal and light memory storage type Comblike polymers material, uses hydroxyethyl methacrylate second first
Ester and 2- bromo isobutyl acylbromides prepare brominated monomer (methacrylic acid (α-bromine Isobutanovloxyethvl) ester, BiBEM), secondly,
Brominated monomer carries out reversible addition chain transfer polymerization with methyl methacrylate, prepares the controllable side chain of molecular weight containing brominated esters
Methacrylate copolymers compound P0, finally, it is free that P0 carries out atom transfer as macromole evocating agent, to azobenzene monomer
Base polymerize, and prepares side chain liquid crystal polymer containing azobenzene, with excellent liquid crystal behavior and photoresponse activity, is lived applied to light
The liquid crystal material and light memory storage material of property；Its preparation method is：
(1) preparation of methacrylic acid (α-bromine Isobutanovloxyethvl) ester (BiBEM), adds successively in 250mL round-bottomed flasks
Enter the tetrahydrofuran (THF) of hydroxyethyl methacrylate, triethylamine and 50mL, be well mixed, bromo isobutyl acylbromide is dissolved in
It is added dropwise in round-bottomed flask, stirring reaction at 0-5 DEG C reacts 3-5h again after dripping off, is filtered after the completion of reaction in 20mLTHF,
Washing 3 times, ethyl acetate extraction, concentration obtains product；
(2) brominated monomer BiBEM, methyl methacrylate (MMA), chain-transferring agent CPDN and azo two are added in polymerization reaction kettle
Isobutyl cyanogen AIBN, mol ratio may be designed as 50:50：1：0.2,60:40：1：0.2,80:20：1：0.2,33:67：1：0.2,
20:80：1：0.2,40:60：1：0.2, lead to argon gas deoxygenation, under 60 DEG C of oil baths after magnetic agitation 12h, stop reaction, plus on a small quantity
THF dissolves polymer, then pours into 250mL industrial alcohol solution and precipitates, and collected by suction precipitation obtains macromole evocating agent
P0；
(3) benzene monomer containing azo is added in reactor, macromole evocating agent P0, CuBr, pentamethyl-diethylenetriamine PMDETA are even
Pyridine monomer and macromole evocating agent P0 mol ratios may be designed as：10:1,20:Isosorbide-5-Nitrae 0:1,76：1,100:1, methyl phenyl ethers anisole conduct
Solvent, leads to after argon gas deoxygenation 20min and seals, at normal temperatures after magnetic agitation 20min, when being placed in reaction to setting in 70 DEG C of oil baths
Between, stop reaction, plus a small amount of THF dissolvings polymer, then solution is poured into 250mL industrial alcohol and precipitated, collected by suction sinks
Shallow lake obtains comb-shaped polymer.
2. azobenzene comb-shaped polymer according to claim 1 and preparation method thereof, it is characterized in that azobenzene dressing polymerize
The molecular weight of thing is 1 × 104~2 × 105, molecular weight distribution is less than 1.3.
3. azobenzene comb-shaped polymer according to claim 1 and preparation method thereof, it is characterized in that glass transition temperature is 60
~80 DEG C, as azo benzene content is improved, fusing point (TS-N) temperature rises to 125 DEG C from 80 DEG C, with typical thermotropic liquid crystal
Energy.
4. azobenzene comb-shaped polymer according to claim 1 and preparation method thereof, it is characterized in that after polymer film forming
Under diffraction light irradiation, surface relief grating is formed, diffraction efficiency is up to 3%, groove depth 130nm, with excellent photo absorption property, should
For light memory storage.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317293A (en) * | 2019-07-22 | 2019-10-11 | 常州大学 | A kind of preparation method of recyclable reprocessing thermosetting property azobenzene polymer |
| CN110343079A (en) * | 2019-07-22 | 2019-10-18 | 常州大学 | It is a kind of can Diels-Alder addition reaction azo benzene monomer preparation method and application |
| CN110364205A (en) * | 2018-03-26 | 2019-10-22 | Imec 非营利协会 | The method for storing data |
| CN110937999A (en) * | 2019-11-19 | 2020-03-31 | 苏州斐然医药科技有限公司 | Synthetic method of artificial cell membrane raw material 2, 3-dibromo-2-methyl hydroxyethyl propionate |
| CN111718724A (en) * | 2020-05-27 | 2020-09-29 | 国科广化(南雄)新材料研究院有限公司 | Reactive azobenzene main side chain liquid crystal compound and preparation method and application thereof |
| CN114605281A (en) * | 2022-03-22 | 2022-06-10 | 苏州经贸职业技术学院 | Photoresponse polymer and monomer based on azobenzene side group, and synthesis method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364205A (en) * | 2018-03-26 | 2019-10-22 | Imec 非营利协会 | The method for storing data |
| CN110364205B (en) * | 2018-03-26 | 2022-03-29 | Imec 非营利协会 | Method for storing data |
| CN110317293A (en) * | 2019-07-22 | 2019-10-11 | 常州大学 | A kind of preparation method of recyclable reprocessing thermosetting property azobenzene polymer |
| CN110343079A (en) * | 2019-07-22 | 2019-10-18 | 常州大学 | It is a kind of can Diels-Alder addition reaction azo benzene monomer preparation method and application |
| CN110317293B (en) * | 2019-07-22 | 2021-03-23 | 常州大学 | Preparation method of recyclable reprocessed thermosetting azobenzene polymer |
| CN110937999A (en) * | 2019-11-19 | 2020-03-31 | 苏州斐然医药科技有限公司 | Synthetic method of artificial cell membrane raw material 2, 3-dibromo-2-methyl hydroxyethyl propionate |
| CN110937999B (en) * | 2019-11-19 | 2022-08-02 | 苏州斐然医药科技有限公司 | Synthetic method of artificial cell membrane raw material 2, 3-dibromo-2-methyl hydroxyethyl propionate |
| CN111718724A (en) * | 2020-05-27 | 2020-09-29 | 国科广化(南雄)新材料研究院有限公司 | Reactive azobenzene main side chain liquid crystal compound and preparation method and application thereof |
| CN114605281A (en) * | 2022-03-22 | 2022-06-10 | 苏州经贸职业技术学院 | Photoresponse polymer and monomer based on azobenzene side group, and synthesis method and application thereof |
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