CN100509869C - Multiple environment-responsive di-block copolymer and preparation method thereof - Google Patents
Multiple environment-responsive di-block copolymer and preparation method thereof Download PDFInfo
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- CN100509869C CN100509869C CNB2007101712380A CN200710171238A CN100509869C CN 100509869 C CN100509869 C CN 100509869C CN B2007101712380 A CNB2007101712380 A CN B2007101712380A CN 200710171238 A CN200710171238 A CN 200710171238A CN 100509869 C CN100509869 C CN 100509869C
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Abstract
The invention relates to a two-block copolymer with multiple environmental responsibilities and a preparation method thereof. The temperature-sensitive monomer is first initiated to be polymerized using the initiators and the chain transfer agents so as to form the macromolecular transfer reagents by adopting the reversible addition-fragmentation chain transfer living radical polymerization RAFT method and then the photosensitive monomer and the pH value sensitive monomer are initiated to be copolymerized with each other using the initiators and macromolecular transfer reagents so as to prepare the two-block copolymer, thus preparing a novel two-block copolymer with multiple environmental responsibilities by introducing three monomers having the temperature, pH and photo responsibilities in the same polymer chain. The aqueous solution of the two-block copolymers has response characteristics over the temperature, pH value and light, and simultaneously the introduced photo-sensitive monomer can be optically dimerized and also can be photolyzed under different wavelengths, so the two-block copolymer can form a plurality of aggregation morphologies, and the reversible transformation between the dissolution and insolubilization of the two-block copolymer can be realized, thus ensuring that the two-block copolymer has a wider application value.
Description
Technical field
The present invention relates to di-block copolymer of a kind of multiple environment-responsive and preparation method thereof, be specifically related to a kind of multiple environment-responsive di-block copolymer to temperature, pH value and response characteristics to light and preparation method thereof that has simultaneously.Belong to chemical field of polymer material preparing technology.
Background technology
The environment-responsive polymkeric substance be self to external world the slight change of environment (stimulation) make response, produce a family macromolecule of the variation even the sudden change of corresponding physical structure and chemical property, external stimulus can be temperature, pH, ionic strength (ionogen), electric field, light etc.Environment-responsive polymer application wide range is general, as be applied to fields such as transmitter, power element, intelligent switch, driving mechanism, indicating meter, optical communication, pharmaceutical carrier, biocatalysis, immobilized enzyme, materials abstraction, cell cultures, intelligent catalysis agent, smart fabric, intelligent dimming material, intelligent tamanori, artificial-muscle, material with memory, cause the numerous investigators' in countries in the world interest.
At present, the research of environment-responsive polymkeric substance focuses mostly in the research of single or double stimuli responsive polymkeric substance, can satisfy certain needs, as use the PNIPAM immobilized enzyme, can prepare thermally sensitive dissolving-non-and dissolve immobilized enzyme, be easy to separate, can reuse again, the stability of enzyme also increases; And for example with the monomer and the N-isopropylacrylamide copolymerization of suitable-reflective isomerized azobenzene, when the monomeric content of azobenzene is 2.6mol% in this multipolymer, after UV-irradiation, trans nitrogen benzide isomer is converted into polarity and becomes big cis-structure, the lower critical solution temperature LCST of solution rises to 27 ℃ by 20 ℃, can be made into the precipitation that " photoswitch " device is controlled PNIPAM like this.But for complex environment more, these polymkeric substance just can not well embody the characteristic of this base polymer.Therefore researching and developing the multiple response polymkeric substance has become new focus.
Summary of the invention
The objective of the invention is to provides di-block copolymer of a kind of multiple environment-responsive and preparation method thereof at the deficiencies in the prior art, and this analog copolymer that makes has the response characteristic to temperature, pH value and light simultaneously, has more wide in range range of application.
For realizing this purpose, the present invention adopts the method for reversible addition-fracture chain transfer activity radical polymerization RAFT, at first cause temperature sensitive monomer polymerization with initiator and chain-transfer agent, form the macromolecular chain transfer agent, cause photosensitive monomer and the copolymerization of pH value sensitive monomer with initiator and macromolecular chain transfer agent then, make di-block copolymer, thereby will have temperature, three kinds of monomers of pH and optical Response are introduced in the same macromolecular chain, prepare a kind of novel multiple environment-responsive di-block copolymer, this analog copolymer is had simultaneously to temperature, the response characteristic of pH value and light.
The repeated structural unit of the di-block copolymer of multiple environment-responsive of the present invention is as follows:
Wherein, R
1Be N-sec.-propyl, N, N-dimethyl, N, N-diethyl; R
2Be carboxyl, pyridyl, pyrryl, N, N-dimethyl ethyl, N, N-diethyl ethyl; R
3Be H or CH
3R
4Be H or CH
3
The preparation method of the di-block copolymer of multiple environment-responsive of the present invention is as follows:
1, the preparation of photosensitive monomer methacrylic acid tonka bean camphor base ester (CMA)
In having the there-necked flask of stirring, umbelliferone, triethylamine are dissolved in organic solvent, wherein the two mol ratio is umbelliferone: triethylamine=1:1.2-4.Under 0 ℃, logical N
2Protection dropwise adds the methacrylic isoxazolecarboxylic acid with the triethylamine equimolar amount.After dropwising, continue 0 ℃ of reaction 1-2 hour down, system is warming up to 20-30 ℃ and reacted 3-5 hour again then.After reaction finished, filtering reacting liquid was removed the triethylamine hydrochloride that generates in the reaction process, then with the filtrate precipitating in ether, filter also and use the ether washing and precipitating, vacuum-drying makes photosensitive monomer methacrylic acid tonka bean camphor base ester CMA.Its structural formula is shown below:
Wherein, R is H or CH
3
2, with azo-bis-isobutyl cyanide (AIBN), chain-transfer agent (CTA), temperature sensitive monomer N-isopropylacrylamide (PNIPAAm) is dissolved in the organic solvent, be mixed with the solution that solid content is 10-30%, three's molar ratio is [AIBN]: [CTA]: [PNIPAAm]=1:3-10:400-1000, reacted 40-80 hour down at 60 ℃-90 ℃.After reaction finishes, solution poured in the ether precipitates, filter, 40 ℃ of vacuum-drying 48 hours, the poly-sec.-propyl third rare acid amides (PNIPAAm-CTA) of target product macromolecular chain transfer agent.
3, with AIBN, PNIPAAm-CTA, photosensitive monomer methacrylic acid coumarin ester CMA and pH value sensitive monomer vinylformic acid (AA) are dissolved in the organic solvent, be mixed with the solution that solid content is 10-30%, wherein get molar ratio and be [AIBN]: [PNIPAAm-CTA]: [AA+CMA]=1:3-8:400-1000 (wherein [AA]: [CMA]=3-6:1), reacted 10-40 hour down at 60 ℃-90 ℃.After reaction finishes, solution poured in the ether precipitate, filter, the filter cake dissolve with ethanol is removed insolubles, evaporate to dryness solution, 60 ℃ of vacuum-drying 48 hours, di-block copolymer that must the target product multiple environment-responsive.
The aqueous solution of the multiple environment-responsive di-block copolymer that the present invention relates to has the response characteristic to temperature, pH value and light simultaneously, but photodimerization also can photodissociation under different wavelength for the photosensitive monomer of Yin Ruing simultaneously, therefore such di-block copolymer can form multiple accumulation shape, but can under multiple condition, realize dissolving and undissolved inverse conversion, make such di-block copolymer have using value more widely.
Description of drawings
Fig. 1 is the infrared spectra of the di-block copolymer of embodiment 1 multiple environment-responsive.
Fig. 2 is the nucleus magnetic hydrogen spectrum of the di-block copolymer of embodiment 1 multiple environment-responsive.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
(a) in having the there-necked flask of stirring, add 20ml DMF, 75mmol (7.67g) triethylamine and 30mmol (4.86g) umbelliferone, under 0 ℃, logical N
2Protect, dropwise add the 20mlDMF solution of 75mmol (7.84g) methacrylic chloride, the control rate of addition dripped off in 1 hour.Continuation is 0 ℃ of down reaction 1 hour, and system is warming up to room temperature and reacted 3 hours again then.After reaction finished, filtering reacting liquid was removed triethylamine hydrochloride, and then precipitating at room temperature stirred 5 hours in the 400ml ether, and filtration is also used the ether washing and precipitating, in 40 ℃ of following vacuum-dryings 48 hours, obtains methacrylic acid coumarin ester (CMA).
(b) with AIBN0.02g, dithiobenzoic acid styroyl ester 0.13g, sec.-propyl third rare acid amides (NIPAAm) 7.00g is dissolved in 25ml 1, in the 4-dioxane, reacts 80 hours down at 60 ℃.After reaction finishes, solution poured in the ether precipitates, filter, 40 ℃ of vacuum-dryings 48 hours target product PNIPAAm macromolecular chain transfer agent.
(c) with AIBN 12.3mg, PNIPAAm 4.5g, CMA 0.65g, vinylformic acid (AA) 1.02g is dissolved in 30ml 1, in the 4-dioxane, reacts 20 hours down at 60 ℃.After reaction finishes, solution poured in the ether precipitate, filter, the filter cake dissolve with ethanol is removed insolubles, evaporate to dryness solution, the di-block copolymer that 40 ℃ of vacuum-dryings 48 hours must the target product multiple environment-responsive.
Fig. 1 is the infrared spectrum of the di-block copolymer of multiple environment-responsive, records 3342cm among the figure with KBr salt sheet method
-1The place is N-H vibration absorption peak, 2976cm
-1The place is C-H vibration absorption peak, 1718cm
-1The place is ester bond C=O vibration absorption peak, 1636cm
-1The place is amido linkage C=O vibration absorption peak.
Fig. 2 is the di-block copolymer of multiple environment-responsive
1H nuclear magnetic spectrogram (solvent is DMSO, and vibrational frequency is 400MHz): δ=12.45-12.26 is the chemical shift of COOH hydrogen, and δ=7.95-6.15 is the chemical shift of phenyl ring hydrogen, and δ=3.92-1.12 is on the main chain-CH-CH
2The chemical shift of hydrogen, δ=1.12-0.83 be on N-isopropyl group on-CH
3The chemical shift of hydrogen.
(a) in having the there-necked flask of stirring, add 20ml DMF, 75mmol (7.67g) triethylamine and 30mmol (4.86g) umbelliferone, under 0 ℃, logical N
2Protect, dropwise add the 20ml DMF solution of 75mmol (7.84g) methacrylic chloride, the control rate of addition dripped off in 1 hour.Continuation is 0 ℃ of down reaction 1 hour, and system is warming up to room temperature and reacted 3 hours again then.After reaction finished, filtering reacting liquid was removed triethylamine hydrochloride, and then precipitating at room temperature stirred 5 hours in the 400ml ether, and filtration is also used the ether washing and precipitating, in 40 ℃ of following vacuum-dryings 48 hours, obtains methacrylic acid coumarin ester (CMA).
(b) with AIBN 0.02g, dithiobenzoic acid styroyl ester 0.18g, sec.-propyl third rare acid amides (NIPAAm) 8.00g is dissolved in 30ml 1, in the 4-dioxane, reacts 50 hours down at 80 ℃.After reaction finishes, solution poured in the ether precipitates, filter, 40 ℃ of vacuum-dryings 48 hours target product PNIPAAm macromolecular chain transfer agent.
(c) with AIBN 12.3mg, PNIPAAm 6.0g, CMA 0.65g, vinylformic acid (AA) 1.33g is dissolved in 40ml 1, in the 4-dioxane, reacts 12 hours down at 80 ℃.After reaction finishes, solution poured in the ether precipitate, filter, the filter cake dissolve with ethanol is removed insolubles, evaporate to dryness solution, the di-block copolymer that 40 ℃ of vacuum-dryings 48 hours must the target product multiple environment-responsive.
Embodiment 3
(a) in having the there-necked flask of stirring, add 20ml DMF, 75mmol (7.67g) triethylamine and 30mmol (4.86g) umbelliferone, under 0 ℃, logical N
2Protect, dropwise add the 20ml DMF solution of 75mmol (7.84g) methacrylic chloride, the control rate of addition dripped off in 1 hour.Continuation is 0 ℃ of down reaction 1 hour, and system is warming up to room temperature and reacted 3 hours again then.After reaction finished, filtering reacting liquid was removed triethylamine hydrochloride, and then precipitating at room temperature stirred 5 hours in the 400ml ether, and filtration is also used the ether washing and precipitating, in 40 ℃ of following vacuum-dryings 48 hours, obtains methacrylic acid coumarin ester (CMA).
(b) with AIBN 0.02g, dithiobenzoic acid styroyl ester 0.26g, sec.-propyl third rare acid amides (NIPAAm) 7.00g is dissolved in 30ml 1, in the 4-dioxane, reacts 40 hours down at 90 ℃.After reaction finishes, solution poured in the ether precipitates, filter, 40 ℃ of vacuum-dryings 48 hours target product PNIPAAm macromolecular chain transfer agent.
(c) with AIBN 12.3mg, PNIPAAm 7.8g, CMA 0.65g, vinylformic acid (AA) 1.60g is dissolved in 50ml 1, in the 4-dioxane, reacts 10 hours down at 90 ℃.After reaction finishes, solution poured in the ether precipitate, filter, the filter cake dissolve with ethanol is removed insolubles, evaporate to dryness solution, the di-block copolymer that 40 ℃ of vacuum-dryings 48 hours must the target product multiple environment-responsive.
Claims (4)
1, a kind of preparation method of di-block copolymer of multiple environment-responsive is characterized in that comprising the steps:
(a) in having the there-necked flask of stirring, umbelliferone, triethylamine are dissolved in organic solvent, wherein get mol ratio umbelliferone: triethylamine=1:1.2-4; Under 0 ℃, logical N
2Protection dropwise adds the methacrylic isoxazolecarboxylic acid with the triethylamine equimolar amount; After dropwising, continue 0 ℃ of reaction 1-2 hour down, system is warming up to 20-30 ℃ and reacted 3-5 hour again then; After reaction finished, filtering reacting liquid was removed the triethylamine hydrochloride that generates in the reaction process, then with the filtrate precipitating in ether, filter also and use the ether washing and precipitating, vacuum-drying makes photosensitive monomer methacrylic acid tonka bean camphor base ester CMA, its structural formula is:
In the formula, R is CH
3
(b) with azo-bis-isobutyl cyanide AIBN, chain-transfer agent CTA, temperature sensitive monomer N-isopropylacrylamide PNIPAAm is dissolved in the organic solvent, is mixed with the solution that solid content is 10-30%, wherein get mol ratio AIBN:CTA:NIPAAm=1:3-10:400-1000, reacted 40-80 hour down at 60 ℃-90 ℃; After reaction finishes, solution poured in the ether precipitates, filter, 40 ℃ of vacuum-drying 48 hours, the poly-sec.-propyl third rare acid amides PNIPAAm-CTA of target product macromolecular chain transfer agent;
(c) with AIBN, PNIPAAm-CTA, photosensitive monomer methacrylic acid coumarin ester CMA and pH value sensitive monomer vinylformic acid AA are dissolved in the organic solvent, be mixed with the solution that solid content is 10-30%, wherein get mol ratio AIBN:PNIPAAm-CTA:AA+CMA=1:3-8:400-1000, wherein AA:CMA=3-6:1; Reacted 10-40 hour down at 60 ℃-90 ℃; After reaction finishes, solution poured in the ether precipitate, filter, the filter cake dissolve with ethanol is removed insolubles, evaporate to dryness solution, the di-block copolymer that 60 ℃ of vacuum-dryings 48 hours must the target product multiple environment-responsive.
2, according to the preparation method of the di-block copolymer of the multiple environment-responsive of claim 1, it is characterized in that described chain-transfer agent is dithiobenzoic acid styroyl ester, dithiobenzoic acid sec.-propyl phenyl ester or dithiobenzoic acid isobutyl hydrocyanic ester.
3, according to the preparation method of the di-block copolymer of the multiple environment-responsive of claim 1, it is characterized in that described solvent is 1,4-dioxane, N, dinethylformamide, methyl-sulphoxide or N-pyrrolidone.
4, the di-block copolymer of the multiple environment-responsive of a kind of method of claim 1 preparation is characterized in that its structure is shown below:
Wherein, R
1Be the N-sec.-propyl; R
2Be carboxyl; R
3Be H; R
4Be CH
3
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| CN101481439B (en) * | 2009-01-15 | 2011-03-16 | 同济大学 | Preparation of thermosensitive degradable graft copolymer |
| CN101935373B (en) * | 2010-08-05 | 2011-12-07 | 江南大学 | Preparation method of multi-sensitivity photosensitive polyamphoteric electrolyte micelle |
| CN102604007B (en) * | 2012-03-13 | 2014-01-08 | 中国科学院长春应用化学研究所 | Preparation method for photoresponse hybrid nano-particle |
| CN105732556A (en) * | 2016-03-24 | 2016-07-06 | 中国科学技术大学 | Acrylate derivative, preparation method thereof and fluorescent coating |
| CN110359279A (en) * | 2019-06-20 | 2019-10-22 | 浙江理工大学 | A method of textile spatter property and snugness of fit are improved using temperature sensitive-photosensitive copolymers are crosslinked |
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| pH/温度响应的两亲性嵌段共聚物的研究. 赵群，倪沛红.化学进展，第18卷第6期. 2006 |
| pH/温度响应的两亲性嵌段共聚物的研究. 赵群，倪沛红.化学进展，第18卷第6期. 2006 * |
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