CN1315909C - Temperature sensitive saper branched polyether and its preparation method - Google Patents
Temperature sensitive saper branched polyether and its preparation method Download PDFInfo
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- CN1315909C CN1315909C CNB2005100284536A CN200510028453A CN1315909C CN 1315909 C CN1315909 C CN 1315909C CN B2005100284536 A CNB2005100284536 A CN B2005100284536A CN 200510028453 A CN200510028453 A CN 200510028453A CN 1315909 C CN1315909 C CN 1315909C
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Abstract
The present invention relates to temperature sensitive super-branched polyether and a preparation method thereof. The preparation method comprises: polyhydric alcohol and an initiator react under the protection of argon or nitrogen to form an anionic initiation center; then, two diepoxy monomer are initiated to be polymerized, and the temperature sensitive super-branched polyether is obtained. The lowest critical dissolution temperature of the temperature sensitive super-branched polyether of the present invention can be adjusted by changing the hydrophilic/hydrophobic proportion of the two diepoxy monomers and the polyhydric alcohol. The temperature sensitive super-branched polyether of the present invention simultaneously has the characteristics of a super-branched polymer and a temperature sensitive polymer. The temperature sensitive super-branched polyether has wide application in the fields of medicine controlled release, memory element switches, sensors, etc.
Description
Technical field: the present invention relates to a kind of functional high molecule material and preparation method thereof, particularly a kind of temperature sensitive saper branched polyether and preparation method thereof.
Background technology: highly-branched polymers is paid close attention to because of its particular structure and performance have caused widely.Highly-branched polymers comprises branch-shape polymer, hyperbranched polymer two classes.Compare with traditional linear polymer, branch-shape polymer, hyperbranched polymer have characteristics such as lower solution and melt viscosity, good solubility, a large amount of functional end-groups.
Temperature sensitive polymer be a class self to external world the slight change of envrionment temperature make response, produce a family macromolecule of the variation even the sudden change of corresponding physical structure and chemical property.Temperature sensing polymer shows unusual temperature-responsive in the aqueous solution: when the aqueous solutions of polymers temperature is elevated to certain temperature when above, aqueous solutions of polymers occurs muddy; And being lower than this temperature when following when temperature, solution recovers water white transparency again.Make the temperature that aqueous solutions of polymers takes place to change mutually be called lowest critical solution temperature (LCST).
Current research to temperature sensing polymer mainly concentrates on (Chinese invention patent, the patent No.: 01129696.8 on linear polymer and the hydrogel; Application number: 200410052649.4).Research to temperature sensing polymer with highly branched structure is less.Temperature sensitive property branched polymer is generally by two kinds of synthetic method preparations.First method be with the temperature-responsive polymer graft on hyperbranched polymer or dendritic macromole.(Ni Peihong, Cao Xinpei, Yan Deyue such as Ni Peihong, wait and be good for, the mansion longevity is wide, Science Bulletin 2001,46,1174.) prepared the temperature sensitive property of the star multipolymer of hyperbranched poly (3-ethyl-3-methylol epoxy fourth ring) grafting polymethyl acrylic acid-2-(N, N-dimethylamino) ethyl ester.Pan Caiyuan (You Y.Z.; Hong C.Y.; Pan C.Y.; Wang P.H.AdvancedMaterials, 2004,16,1953.), Kimura (Kimura M.; Kato M.; Muto T.; Hanabusa K.; Shirai H.Macromolecules, 2000,33,1117.) respectively PNIPAM is grafted on the dendritic macromole, obtain the temperature sensitive property of star multipolymer.Another kind of mode is that the functional end-group to dendritic macromole carries out modification, makes it to have temperature sensitive property.Haba (Haba Y.; Harada A.; Takagishi T.; Kono K.Journal ofthe American Chemical Society, 2004,126,12760.) the sec.-propyl amide group is received the end of polyamide-amide (PAMAM) type dendritic macromole, polypropylene imines (PPI) dendritic macromole, obtained temperature sensitive property dendritic macromole.
Summary of the invention: the objective of the invention is highly branched structure is incorporated in the temperature sensing polymer, make it to have simultaneously the physicochemical property of highly-branched polymers uniqueness and the temperature-responsive of temperature sensing polymer.Commercial diepoxy monomer of this hair and polyvalent alcohol are raw material, by anionic polymerisation, prepare a series of temperature sensitive saper branched polyethers with different lowest critical solution temperatures.
Temperature sensitive saper branched polyether molecular weight of the present invention is 2,000～7730, and lowest critical solution temperature is 0～100 ℃.
The preparation method of temperature sensitive saper branched polyether of the present invention is as follows:
Under argon gas or nitrogen protection; according to mol ratio is 1～100; polyvalent alcohol and initiator for reaction are formed the anionic initiation center; add diepoxy monomer again with the mol ratio 0.4～50 of polyvalent alcohol; in 20 ℃～150 ℃ reactions 4～240 hours, wherein the monomeric volume ratio of non-proton organic solvent and diepoxy was 0.2～50 in non-proton organic solvent, stopped the back with methyl alcohol and handled with hydrogen type cation exchange resin; precipitation, vacuum-drying obtain temperature sensitive saper branched polyether.
The used polyvalent alcohol of the present invention is selected from ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, five ethylene glycol, six ethylene glycol, polyoxyethylene glycol, 1, ammediol, 1,2-propylene glycol, polypropylene glycol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,2-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, TriMethylolPropane(TMP), trimethylolethane, 1,2,4-trihydroxybutane, 1,2, a kind of in 3-glycerol, trolamine or the tetramethylolmethane.
The used diepoxy monomer of the present invention is selected from 1,2,3,4-diepoxy butane, 1,2,5,6-diepoxy hexane, 1,2,7,8-diepoxy octane, 1,2,9,10-diepoxy decane, ethylene glycol diglycidylether, the Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, 1, the ammediol diglycidylether, polypropylene glycol diglycidyl ether, the glycerol diglycidylether, the glycerol triglycidyl ether, the 1,3 butylene glycol diglycidylether, 1, the 4-butanediol diglycidyl ether, a kind of in trihydroxymethylpropanyltri diglycidyl ether or the hot pentanediol diglycidylether.
The used initiator of the present invention is selected from a kind of in potassium metal, sodium Metal 99.5, potassium hydride KH, sodium hydride, naphthalene potassium or the naphthalene sodium.
The used non-proton organic solvent of the present invention is selected from benzene, toluene, tetrahydrofuran (THF), dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, N, dinethylformamide, N, a kind of in N-diethylformamide, dimethyl sulfoxide (DMSO) or the N-methyl-pyrrolidone.
Temperature sensitive saper branched polyether of the present invention has the characteristic of hyperbranched polymer and temperature sensing polymer simultaneously.Raw material sources are extensive, and used dibasic alcohol and diepoxy monomer are commercial prod.The lowest critical solution temperature of temperature sensitive saper branched polyether of the present invention can recently be regulated by the hydrophilic/hydrophobic that changes diepoxy monomer and polyvalent alcohol.Temperature sensitive saper branched polyether of the present invention has in fields such as medicine sustained release, memory cell switch, transmitters widely to be used.
Description of drawings:
The temperature sensitive saper branched polyether of Fig. 1: embodiment 1 preparation
13C DEPT135 NMR (a) and
13CNMR (b) collection of illustrative plates.
Fig. 2: the transmittance of the temperature sensing superbranching polymer aqueous solution varies with temperature curve.The temperature sensing superbranching polymer of curve 1～5 respectively corresponding embodiment 1～5 preparation among the figure.
Embodiment: following examples are to further specify of the present invention, rather than limit the scope of the invention.
The molecular weight of this temperature sensing superbranching polymer is measured with gel permeation chromatography (GPC), is eluent with the tetrahydrofuran (THF).Lowest critical solution temperature (LCST) is measured with intensification uv-visible absorption spectra (UV-Vis), the temperature of correspondence when LCST is defined as 90% transmittance.
Embodiment 1: under argon shield, potassium hydride KH KH (be suspended in 35% mineral oil in) is joined in two mouthfuls of bottles of 100mL of weighing in advance; The tetrahydrofuran (THF) 5mL that crosses with drying treatment washs three times, to remove mineral oil; Weigh after the drying, the add-on that calculates KH in the flask is 0.18g (4.49mmol); In reaction flask, add 20mL dimethyl sulfoxide (DMSO), 1.15g (18.5mmol) ethylene glycol; Add 2.49g (17.5mmol) 1,2,7,8-diepoxy octane after stirring 30min; Under 40 ℃, react after 48 hours, add the methyl alcohol termination reaction; Reaction soln is used dissolve with methanol again with acetone/anhydrous diethyl ether (volume ratio is 1/4) post precipitation, and solution is handled to remove potassium ion with Hydrogen type Zeo-karb; Carry dense after, with anhydrous diethyl ether precipitation, vacuum-drying obtains light yellow heavy-gravity temperature sensitive saper branched polyether; After the terminal hydroxy group of product was used the Benzoyl chloride end-blocking, recording molecular weight was 6,050.
Fig. 1 is the polymkeric substance that embodiment 1 obtains
13C DEPT135 NMR and
13C NMR spectrogram.Peak a, b are tetramethylene (CH
2CH
2CH
2CH
2-) go up the absorption peak of carbon atom; Peak c, d are the resonance absorbing peak of epoxide group; Peak e, h are-OCH
2CH
2The absorption peak of-OH Central Asia methine carbon atom; Peak f is R
2The absorption peak of methine carbon atom among the CH-OH; Peak g is-OCH
2CH
2The absorption peak of O-Central Asia methine carbon atom; Peak i is ROCH
2The absorption peak of R Central Asia methine carbon atom; Peak j is R
2The absorption peak of methine carbon atom among the CH-OR.From
13C DEPT135 NMR and
13C NMR spectrogram can prove that the polymkeric substance of generation has dissaving structure.
Fig. 2 is that the transmittance of the temperature sensing superbranching polymer aqueous solution varies with temperature curve.Curve 1 is the temperature sensing superbranching polymer of embodiment 1 preparation among the figure.As can be seen from the figure, the lowest critical solution temperature of the temperature sensing superbranching polymer of embodiment 1 preparation is 38.1 ℃.
Embodiment 2: under argon shield, potassium hydride KH KH (be suspended in 35% mineral oil in) is joined in two mouthfuls of bottles of 100mL of weighing in advance; The tetrahydrofuran (THF) 5mL that crosses with drying treatment washs three times, to remove mineral oil; Weigh after the drying, the add-on that calculates KH in the flask is 0.30g (7.5mmol); In reaction flask, add 20mL dimethyl sulfoxide (DMSO), 2.30g (7.6mmol) 1,2-propylene glycol; Add 1.51g (7.6mmol) 1,2,7,8-diepoxy octane after stirring 30min; Under 40 ℃, react after 48 hours, add the methyl alcohol termination reaction; Reaction soln is used dissolve with methanol again with acetone/anhydrous diethyl ether (volume ratio is 1/4) post precipitation, and solution is handled to remove potassium ion with Hydrogen type Zeo-karb; Carry dense after, with anhydrous diethyl ether precipitation, vacuum-drying obtains light yellow heavy-gravity temperature sensitive saper branched polyether; After the terminal hydroxy group of product was used the Benzoyl chloride end-blocking, recording molecular weight was 7,730.
Fig. 2 is that the transmittance of the temperature sensing superbranching polymer aqueous solution varies with temperature curve.Curve 2 is temperature sensing superbranching polymers of embodiment 2 preparations among the figure.As can be seen from the figure, the lowest critical solution temperature of the temperature sensing superbranching polymer of embodiment 2 preparations is 23.6 ℃.
Embodiment 3: under argon shield, potassium hydride KH KH (be suspended in 35% mineral oil in) is joined in two mouthfuls of bottles of 100mL of weighing in advance; The tetrahydrofuran (THF) 5mL that crosses with drying treatment washs three times, to remove mineral oil; Weigh after the drying, the add-on that calculates KH in the flask is 0.095g (2.37mmol); In reaction flask, add 20mL dimethyl sulfoxide (DMSO), 1.43g (9.52mmol) triethylene glycol; Add 1.37g (9.63mmol) 1,2,7,8-diepoxy octane after stirring 30min; Under 40 ℃, react after 48 hours, add the methyl alcohol termination reaction; Reaction soln is used dissolve with methanol again with acetone/anhydrous diethyl ether (volume ratio is 1/4) post precipitation, and solution is handled to remove potassium ion with Hydrogen type Zeo-karb; Carry dense after, with anhydrous diethyl ether precipitation, vacuum-drying obtains light yellow heavy-gravity temperature sensitive saper branched polyether; After the terminal hydroxy group of product was used the Benzoyl chloride end-blocking, recording molecular weight was 7,260.
Fig. 2 is that the transmittance of the temperature sensing superbranching polymer aqueous solution varies with temperature curve.Curve 3 is temperature sensing superbranching polymers of embodiment 3 preparations among the figure.As can be seen from the figure, the lowest critical solution temperature of the temperature sensing superbranching polymer of embodiment 3 preparations is 67.2 ℃.
Embodiment 4: under argon shield, potassium hydride KH KH (be suspended in 35% mineral oil in) is joined in two mouthfuls of bottles of 100mL of weighing in advance; The tetrahydrofuran (THF) 5mL that crosses with drying treatment washs three times, to remove mineral oil; Weigh after the drying, the add-on that calculates KH in the flask is 0.083g (2.07mmol); In reaction flask, add 20mL dimethyl sulfoxide (DMSO), 0.69g (9.07mmol) 1, ammediol; Add 1.81g (8.94mmol) 1, the 4-butanediol diglycidyl ether after stirring 30min; Under 40 ℃, react after 24 hours, add the methyl alcohol termination reaction; Reaction soln is used dissolve with methanol again with acetone/anhydrous diethyl ether (volume ratio is 1/4) post precipitation, and solution is handled to remove potassium ion with Hydrogen type Zeo-karb; Carry dense after, with anhydrous diethyl ether precipitation, vacuum-drying obtains light yellow heavy-gravity temperature sensitive saper branched polyether; After the terminal hydroxy group of product was used the Benzoyl chloride end-blocking, recording molecular weight was 6,250.
Fig. 2 is that the transmittance of the temperature sensing superbranching polymer aqueous solution varies with temperature curve.Curve 4 is temperature sensing superbranching polymers of embodiment 4 preparations among the figure.As can be seen from the figure, the lowest critical solution temperature of the temperature sensing superbranching polymer of embodiment 4 preparations is 56.4 ℃.
Embodiment 5: under argon shield, potassium hydride KH KH (be suspended in 35% mineral oil in) is joined in two mouthfuls of bottles of 100mL of weighing in advance; The tetrahydrofuran (THF) 5mL that crosses with drying treatment washs three times, to remove mineral oil; Weigh after the drying, the add-on that calculates KH in the flask is 0.097g (2.42mmol); In reaction flask, add 20mL dimethyl sulfoxide (DMSO), 1.11g (12.3mmol) butyleneglycol; Add 1.91g (9.44mmol) 1, the 4-butanediol diglycidyl ether after stirring 30min; Under 40 ℃, react after 24 hours, add the methyl alcohol termination reaction; Reaction soln is used dissolve with methanol again with acetone/anhydrous diethyl ether (volume ratio is 1/4) post precipitation, and solution is handled to remove potassium ion with Hydrogen type Zeo-karb; Carry dense after, with anhydrous diethyl ether precipitation, vacuum-drying obtains light yellow heavy-gravity temperature sensitive saper branched polyether; After the terminal hydroxy group of product was used the Benzoyl chloride end-blocking, recording molecular weight was 5,480.
Fig. 2 is that the transmittance of the temperature sensing superbranching polymer aqueous solution varies with temperature curve.Curve 5 is temperature sensing superbranching polymers of embodiment 5 preparations among the figure.As can be seen from the figure, the lowest critical solution temperature of the temperature sensing superbranching polymer of embodiment 5 preparations is 51.8 ℃.
Claims (6)
1. the preparation method of a temperature sensitive saper branched polyether is characterized in that the preparation method is as follows:
Under argon gas or nitrogen protection; according to mol ratio is 1～100; polyvalent alcohol and initiator for reaction are formed the anionic initiation center; add diepoxy monomer again with the mol ratio 0.4～50 of polyvalent alcohol; in 20 ℃～150 ℃ reactions 4～240 hours, wherein the monomeric volume ratio of non-proton organic solvent and diepoxy was 0.2～50 in non-proton organic solvent, stopped the back with methyl alcohol and handled with hydrogen type cation exchange resin; precipitation, vacuum-drying obtain temperature sensitive saper branched polyether.
2. the preparation method of temperature sensitive saper branched polyether according to claim 1, it is characterized in that polyvalent alcohol is selected from ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, five ethylene glycol, six ethylene glycol, polyoxyethylene glycol, 1, ammediol, 1,2-propylene glycol, polypropylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,2-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,10-decanediol, TriMethylolPropane(TMP), trimethylolethane, 1,2,4-trihydroxybutane, 1,2, a kind of in 3-glycerol, trolamine or the tetramethylolmethane.
3. the preparation method of temperature sensitive saper branched polyether according to claim 1, it is characterized in that the diepoxy monomer is selected from 1,2,3,4-diepoxy butane, 1,2,5,6-diepoxy hexane, 1,2,7,8-diepoxy octane, 1,2,9,10-diepoxy decane, ethylene glycol diglycidylether, the Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, 1, the ammediol diglycidylether, polypropylene glycol diglycidyl ether, the glycerol diglycidylether, the glycerol triglycidyl ether, 1, the 3-butanediol diglycidyl ether, 1, the 4-butanediol diglycidyl ether, a kind of in trihydroxymethylpropanyltri diglycidyl ether or the hot pentanediol diglycidylether.
4. the preparation method of temperature sensitive saper branched polyether according to claim 1 is characterized in that initiator is selected from a kind of in potassium metal, sodium Metal 99.5, potassium hydride KH, sodium hydride, naphthalene potassium or the naphthalene sodium.
5. the preparation method of temperature sensitive saper branched polyether according to claim 1, it is characterized in that non-proton organic solvent is selected from benzene, toluene, tetrahydrofuran (THF), dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, N, dinethylformamide, N, a kind of in N-diethylformamide, dimethyl sulfoxide (DMSO) or the N-methyl-pyrrolidone.
6. temperature sensitive saper branched polyether is characterized in that the temperature sensitive saper branched polyether that adopts each described preparation method of claim 1～5 to obtain, and its molecular weight is 2,000～7730, and lowest critical solution temperature is 0～100 ℃.
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| CN101450991B (en) * | 2008-11-27 | 2011-02-09 | 上海交通大学 | Method for preparing temperature and pH double responsiveness hyper branched polymer |
| CN106220840B (en) * | 2016-08-18 | 2018-05-22 | 浙江大学 | A kind of synthetic method of hyperbranched poly tetrahydrofuran |
| CN106636211A (en) * | 2016-12-23 | 2017-05-10 | 北京化工大学 | Method for constructing hyperbranched gene vector with antibacterial performance on basis of ring-opening reaction |
| CN107261868B (en) * | 2017-06-28 | 2020-12-22 | 安庆师范大学 | Temperature-sensitive amphiphilic polymer modified paper-based filter membrane and preparation method thereof |
| CN109880000B (en) * | 2019-03-01 | 2021-01-29 | 西南民族大学 | Temperature stimulation response type intelligent hyperbranched scale inhibitor and application thereof |
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| CN1328067A (en) * | 2001-06-29 | 2001-12-26 | 清华大学 | Process for preparing temp-sensitive porous poly(N-isopropyl acrylamide) aqueogel |
| CN1586706A (en) * | 2004-07-08 | 2005-03-02 | 东华大学 | Method for preparing quick temperature response semi-interpenetration network hydrogel |
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| CN1328067A (en) * | 2001-06-29 | 2001-12-26 | 清华大学 | Process for preparing temp-sensitive porous poly(N-isopropyl acrylamide) aqueogel |
| CN1586706A (en) * | 2004-07-08 | 2005-03-02 | 东华大学 | Method for preparing quick temperature response semi-interpenetration network hydrogel |
Non-Patent Citations (1)
| Title |
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| 用氧阴离子聚合方法制备新型温度/PH响应聚合物 倪沛红等，科学通报，第21期 2001 * |
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