CN102633923A - Water-soluble triple response intelligent polymer and preparation method thereof - Google Patents
Water-soluble triple response intelligent polymer and preparation method thereof Download PDFInfo
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- CN102633923A CN102633923A CN2012101067743A CN201210106774A CN102633923A CN 102633923 A CN102633923 A CN 102633923A CN 2012101067743 A CN2012101067743 A CN 2012101067743A CN 201210106774 A CN201210106774 A CN 201210106774A CN 102633923 A CN102633923 A CN 102633923A
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Abstract
The invention discloses a water-soluble triple response intelligent polymer and a preparation method of the water-soluble triple response intelligent polymer. The preparation method takes an azobenzene derivative containing a 2-bromoisobutyryl radical as an initiator and prepares a poly (methacrylic acid N, N-dimethylamino ethyl ester) (PDMAEMA) through an atom transfer radical polymerization reaction. The novel water-soluble triple response intelligent polymer can generate responses to stimulation of external environments, including light, heat, pH (Potential of Hydrogen) and the like, and has potential application in the fields of drug controlled release and intelligent materials.
Description
Technical field
The present invention relates to a kind of water-soluble triple response intelligent polymers and preparation method thereof, especially relate to a kind of water-soluble triple response intelligent polymers that contain nitrogen benzide and preparation method thereof.
Background technology
Stimulating responsive polymer can stimulate the generation response to many environment sensitive sexual factors such as temperature, pH, light, electric field, magnetic field or ionic strength etc., thereby has important use value in fields such as medicine transmission, bio-sensing, protein separation.In recent years, the research to this base polymer is progressively developed to multiple stimulation responsiveness direction by single stimulating responsive.
Polymethyl acrylic acid N, N-dimethylaminoethyl (PDMAEMA) is a kind of water-soluble polymers.When reaching, solution temperature occurs being separated when a certain threshold value is minimum critical solution temperature (LCST).Under condition of different pH, cause its LCST to change owing to the protonated degree of amido is different, so PDMAEMA can be simultaneously to temperature and pH generation stimulating responsive with pH.Polymkeric substance with light/hot dual responsiveness has good accessibility because of it and Long-distance Control property has caused people's attention, this base polymer that wherein contains nitrogen benzide owing to the ultraviolet irradiation down nitrogen benzide generation cis-trans isomerization turn into to change and make it in application, have more potentiality with the LCST that causes polymkeric substance.At present less based on the polymkeric substance report of triple and multiple stimulation response, and the homopolymer that has triple responses does not simultaneously appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide that a kind of reaction conditions is gentle, simple to operate, product has predetermined molecular weight and structure is clear and definite, product has intelligent polymer of triple responsivenesss and preparation method thereof
Water-soluble triple response intelligent polymers of the present invention, its structural formula is:
Wherein: n is for gathering the polymerization degree of (methylacrylic acid N, N-dimethylaminoethyl), n=1～200.
Further preferred mode is: the n in the said structure formula is for gathering the polymerization degree of (methylacrylic acid N, N-dimethylaminoethyl), n=50～150.
The preparation method of water-soluble triple response intelligent polymers according to the invention, step is:
1) preparation contains the initiator of nitrogen benzide:
Under nitrogen atmosphere protection, meter in molar ratio, with 4-hydroxy ethoxy-4 '-the oxyethyl group nitrogen benzide: 2-bromine isobutyl acylbromide: triethylamine: THF is 1: 5.0～15.0: 7.5～22.5: 30～90 to place jointly under the ice-water bath and react; Reaction finishes after-filtration; The methylene dichloride that in filtrating, adds equal volume amounts is used sodium hydrogen carbonate solution, deionized water, Hydrogen chloride and deionized water wash at least 1 time, separatory successively; Organic layer is dry with siccative; Filter, methylene dichloride is removed in the filtrate decompression distillation, obtain containing the initiator of nitrogen benzide;
2) preparation contains triple responsive polymers of nitrogen benzide:
Under protection of inert gas, be catalyzer with the cuprous chloride, with three (2-(dimethylamino) ethyl) amine (Me
6TREN) being catalyst ligand, is initiator according to mol ratio: catalyzer: catalyst ligand: methylacrylic acid N, N-dimethylaminoethyl=1: 1: 1: 10～500 mixed; Reaction mixture through 3 times freezing-vacuumize-thaw cycles after; Under 25～120 ℃ of temperature, carry out atom transition free radical polymerization reaction 4～20h, institute's synthetic polymkeric substance is dissolved with THF or methylene dichloride, and remove catalyzer through the neutral alumina post; Again it is deposited in precipitation agent ether or the alkane; After repeated precipitation-dissolving-deposition at least 3 times, product is dried 24～30h in vacuum drying oven, must contain triple responsive polymers of nitrogen benzide.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: the purity of the said nitrogen of step 1) preferably surpasses 99.99% by quality ratio.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: the said sodium hydrogen carbonate solution of step 1) is preferably saturated solution; The concentration of said Hydrogen chloride is preferably 0.1mol/L; Said siccative is preferably anhydrous magnesium sulfate or SODIUM SULPHATE ANHYDROUS 99PCT.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: step 2) the preferred purity of said rare gas element surpasses 99.99% nitrogen by quality ratio.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: step 2) said polymeric reaction temperature is preferably 55～100 ℃, and the reaction times is preferably 8～15h.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: step 2) said freezing be to adopt liquid nitrogen, be preferably under the temperature condition below-80 ℃ and carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is preferably 0.08～0.1MPa.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: step 2) said precipitation agent preferably selects sherwood oil or normal hexane.
Among the preparation method of above-mentioned water-soluble triple response intelligent polymers: step 2) said vacuum-drying temperature is preferably 20～40 ℃; Vacuum tightness is preferably 0.08～-0.1MPa.
The preparation feedback formula of above-mentioned water-soluble triple response intelligent polymers is following:
Wherein: polymerization single polymerization monomer is methylacrylic acid N, and N-dimethylaminoethyl (DMAEMA), solvent are dioxane, and n is polymethyl acrylic acid N, the polymerization degree of N-dimethylaminoethyl (PDMAEMA).
The present invention is an initiator with the end capped azobenzene derivatives of bromine, through the synthetic polymethyl acrylic acid N of atom transition free radical polymerization reaction, and N-dimethylaminoethyl (PDMAEMA) polymkeric substance, beneficial effect of the present invention is:
1. employing ATRP, reaction conditions is gentle, and product yield is high, and being compared to general radical polymerization, to have the structure of temperature of reaction and reaction product of milder distincter, and MWD is narrower.
2. the final product among the present invention is a kind of homopolymer, is water-soluble, and has the triple responsivenesss of light, heat and pH.
Embodiment
For being easy to further understand the present invention, the following example will be done further elaboration to the present invention.
Embodiment 1
1) under the protection of nitrogen (purity by quality ratio surpass 99.99%) atmosphere, umber meter in molar ratio, with 1 part of 4-hydroxy ethoxy-4 '-oxyethyl group nitrogen benzide, 5 parts of 2-bromine isobutyl acylbromides, 7.5 parts of triethylamines, 30 parts of THFs react under ice-water bath.Behind reinforced the finishing, continue reaction 4h under the room temperature, reaction finishes after-filtration; In filtrating, add the methylene dichloride of equal volume amounts, use saturated sodium bicarbonate solution, deionized water, concentration to be 0.1mol/L hydrochloric acid and deionized water wash, repeated washing 3 times successively; Separatory; Organic layer is used anhydrous magnesium sulfate drying, refilters, and dichloromethane solvent is removed in the filtrate decompression distillation obtained the end capped nitrogen benzide initiator of lurid bromine;
2) under nitrogen (purity surpasses 99.99% by quality ratio) atmosphere protection (the necessary strict deoxygenation of reaction system); The umber meter is catalyzer, 2 part of three (2-(dimethylamino) ethyl) amine (Me with 1 part of end capped nitrogen benzide initiator of active bromine, 1 part of cuprous chloride in molar ratio
6TREN) be the methylacrylic acid N of catalyst ligand and 100 parts; N-dimethylaminoethyl (DMAEMA) mixes for monomer; Reaction mixture through 3 times freezing-vacuumize-thaw cycles after, behind 60 ℃ of following reacting by heating 10h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran solvent; Solution after will diluting is removed catalyzer through the neutral alumina post; It is deposited in the precipitation agent normal hexane, with product (vacuum tightness is 0.08Mpa) oven dry 24h in 30 ℃ of vacuum drying ovens, obtains end product after repeated precipitation-dissolving-deposition at least 3 times.
Above-mentioned freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.1MPa.
Embodiment 2
1) under the protection of nitrogen (purity by quality ratio surpass 99.99%) atmosphere, umber meter in molar ratio, with 1 part of 4-hydroxy ethoxy-4 '-oxyethyl group nitrogen benzide, 7.5 parts of 2-bromine isobutyl acylbromides, 10 parts of triethylamines, 45 parts of THFs react under ice-water bath.Behind reinforced the finishing, continue reaction 4h under the room temperature, reaction finishes after-filtration; In filtrating, add the methylene dichloride of equal volume amounts, use saturated sodium bicarbonate solution, deionized water, concentration to be 0.1mol/L hydrochloric acid and deionized water wash, repeated washing 3 times successively; Separatory; Organic layer is used anhydrous magnesium sulfate drying, refilters, and dichloromethane solvent is removed in the filtrate decompression distillation obtained the end capped nitrogen benzide initiator of lurid bromine;
2) under nitrogen (purity surpasses 99.99% by quality ratio) atmosphere protection (the necessary strict deoxygenation of reaction system); The umber meter is catalyzer, 2 part of three (2-(dimethylamino) ethyl) amine (Me with 1 part of end capped nitrogen benzide initiator of active bromine, 1 part of cuprous chloride in molar ratio
6TREN) be the methylacrylic acid N of catalyst ligand and 100 parts; N-dimethylaminoethyl (DMAEMA) mixes for monomer; Reaction mixture through 3 times freezing-vacuumize-thaw cycles after, behind 70 ℃ of following reacting by heating 8h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran solvent; Solution after will diluting is removed catalyzer through the neutral alumina post; It is deposited in the precipitation agent normal hexane, with product (vacuum tightness is 0.08Mpa) oven dry 24h in 30 ℃ of vacuum drying ovens, obtains end product after repeated precipitation-dissolving-deposition at least 3 times.
Above-mentioned freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.1MPa.
Embodiment 3
1) under the protection of nitrogen (purity by quality ratio surpass 99.99%) atmosphere, umber meter in molar ratio, with 1 part of 4-hydroxy ethoxy-4 '-oxyethyl group nitrogen benzide, 10 parts of 2-bromine isobutyl acylbromides, 15 parts of triethylamines, 60 parts of THFs react under ice-water bath.Behind reinforced the finishing, continue reaction 4h under the room temperature, reaction finishes after-filtration; In filtrating, add methylene dichloride, use saturated sodium bicarbonate solution, deionized water, concentration to be 0.1mol/L hydrochloric acid and deionized water wash, repeated washing 3 times successively; Separatory; Organic layer is used anhydrous magnesium sulfate drying, refilters, and dichloromethane solvent is removed in the filtrate decompression distillation obtained the end capped nitrogen benzide initiator of lurid bromine;
2) under nitrogen (purity surpasses 99.99% by quality ratio) atmosphere protection (the necessary strict deoxygenation of reaction system); The umber meter is catalyzer, 2 part of three (2-(dimethylamino) ethyl) amine (Me with 1 part of end capped nitrogen benzide initiator of active bromine, 1 part of cuprous chloride in molar ratio
6TREN) be the methylacrylic acid N of catalyst ligand and 100 parts; N-dimethylaminoethyl (DMAEMA) mixes for monomer; Reaction mixture through 3 times freezing-vacuumize-thaw cycles after, behind 80 ℃ of following reacting by heating 6h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran solvent; Solution after will diluting is removed catalyzer through the neutral alumina post; It is deposited in the precipitation agent normal hexane, with product (vacuum tightness is 0.08Mpa) oven dry 24h in 30 ℃ of vacuum drying ovens, obtains end product after repeated precipitation-dissolving-deposition at least 3 times.
Above-mentioned freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.1MPa.
Claims (10)
1. water-soluble triple response intelligent polymers, its structural formula is:
Wherein: n is for gathering the polymerization degree of (methylacrylic acid N, N-dimethylaminoethyl), n=1～200.
2. water-soluble triple response intelligent polymers as claimed in claim 1 is characterized in that: the n in the said structural formula is for gathering the polymerization degree of (methylacrylic acid N, N-dimethylaminoethyl), n=50～150.
3. the preparation method of the described water-soluble triple response intelligent polymers of claim 1, step is:
1) preparation contains the initiator of nitrogen benzide:
Under nitrogen atmosphere protection, meter in molar ratio, with 4-hydroxy ethoxy-4 '-the oxyethyl group nitrogen benzide: 2-bromine isobutyl acylbromide: triethylamine: THF is 1: 5.0～15.0: 7.5～22.5: 30～90 to place jointly under the ice-water bath and react; Reaction finishes after-filtration; The methylene dichloride that in filtrating, adds equal volume amounts is used sodium hydrogen carbonate solution, deionized water, Hydrogen chloride and deionized water wash at least 1 time, separatory successively; Organic layer is dry with siccative; Filter, methylene dichloride is removed in the filtrate decompression distillation, obtain containing the initiator of nitrogen benzide;
2) preparation contains triple responsive polymers of nitrogen benzide:
Under protection of inert gas, be catalyzer with the cuprous chloride, with three (2-(dimethylamino) ethyl) amine (Me
6TREN) being catalyst ligand, is initiator according to mol ratio: catalyzer: catalyst ligand: methylacrylic acid N, N-dimethylaminoethyl=1: 1: 1: 10～500 mixed; Reaction mixture through 3 times freezing-vacuumize-thaw cycles after; Under 25～120 ℃ of temperature, carry out atom transition free radical polymerization reaction 4～20h, institute's synthetic polymkeric substance is dissolved with THF or methylene dichloride, and remove catalyzer through the neutral alumina post; Again it is deposited in precipitation agent ether or the alkane; After repeated precipitation-dissolving-deposition at least 3 times, product is dried 24～30h in vacuum drying oven, must contain triple responsive polymers of nitrogen benzide.
4. like the preparation method of the said triple responsive polymers of claim 3, it is characterized in that: the purity of the said nitrogen of step 1) surpasses 99.99% by quality ratio.
5. like the preparing method's of the said triple responsive polymers of claim 3 preparation method, it is characterized in that: the said sodium hydrogen carbonate solution of step 1) is a saturated solution; The concentration of said Hydrogen chloride is 0.1mol/L; Said siccative is anhydrous magnesium sulfate or SODIUM SULPHATE ANHYDROUS 99PCT.
6. like the preparation method of the said triple responsive polymers of claim 3, it is characterized in that: step 2) said rare gas element is that purity surpasses 99.99% nitrogen by quality ratio.
7. like the preparation method of the said triple responsive polymers of claim 3, it is characterized in that: step 2) said polymeric reaction temperature is 55～100 ℃, the reaction times is 8～15h.
8. like the preparation method of the said triple responsive polymers of claim 3, it is characterized in that: step 2) said freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.08～0.1MPa.
9. like the preparation method of the said triple responsive polymers of claim 3, it is characterized in that: step 2) said precipitation agent selects sherwood oil or normal hexane.
10. like the preparation method of the said triple responsive polymers of claim 3, it is characterized in that: step 2) temperature of said vacuum drying is 20～40 ℃; Vacuum tightness is 0.08～-0.1MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601841A (en) * | 2016-02-18 | 2016-05-25 | 厦门大学 | Photo-responsive random copolymer and preparation method thereof |
| CN110507633A (en) * | 2019-08-25 | 2019-11-29 | 南京理工大学 | Respond pH and the drug gene carrier of ultraviolet light and preparation method thereof |
| CN117964824B (en) * | 2024-03-29 | 2024-05-28 | 天津师范大学 | Multiple stimulus responsive homopolymer and preparation method and application thereof |
-
2012
- 2012-04-12 CN CN2012101067743A patent/CN102633923A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 唐新德等: "水溶性三重响应智能聚合物的合成与性能", 《高分子材料科学与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601841A (en) * | 2016-02-18 | 2016-05-25 | 厦门大学 | Photo-responsive random copolymer and preparation method thereof |
| CN110507633A (en) * | 2019-08-25 | 2019-11-29 | 南京理工大学 | Respond pH and the drug gene carrier of ultraviolet light and preparation method thereof |
| CN110507633B (en) * | 2019-08-25 | 2022-03-18 | 南京理工大学 | Drug gene vector responding to pH and ultraviolet light and preparation method thereof |
| CN117964824B (en) * | 2024-03-29 | 2024-05-28 | 天津师范大学 | Multiple stimulus responsive homopolymer and preparation method and application thereof |
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Application publication date: 20120815 |