CN102391415A - Preparation method of thermo-sensitive hydrogel by taking baicalin as template - Google Patents
Preparation method of thermo-sensitive hydrogel by taking baicalin as template Download PDFInfo
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- CN102391415A CN102391415A CN2011103051001A CN201110305100A CN102391415A CN 102391415 A CN102391415 A CN 102391415A CN 2011103051001 A CN2011103051001 A CN 2011103051001A CN 201110305100 A CN201110305100 A CN 201110305100A CN 102391415 A CN102391415 A CN 102391415A
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- IPQKDIRUZHOIOM-UHFFFAOYSA-N Oroxin A Natural products OC1C(O)C(O)C(CO)OC1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC=CC=1)O2 IPQKDIRUZHOIOM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- IKIIZLYTISPENI-ZFORQUDYSA-N baicalin Chemical compound O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC=CC=1)O2 IKIIZLYTISPENI-ZFORQUDYSA-N 0.000 title claims abstract description 66
- 229960003321 baicalin Drugs 0.000 title claims abstract description 66
- AQHDANHUMGXSJZ-UHFFFAOYSA-N baicalin Natural products OC1C(O)C(C(O)CO)OC1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC=CC=1)O2 AQHDANHUMGXSJZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000000017 hydrogel Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000499 gel Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000010382 chemical cross-linking Methods 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
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- 238000013019 agitation Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- FCZRAAJZTGOYIC-UHFFFAOYSA-N 2,4-dimethylpent-2-enamide Chemical compound CC(C)C=C(C)C(N)=O FCZRAAJZTGOYIC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 claims description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- 102100040409 Ameloblastin Human genes 0.000 claims description 2
- ADQIFLCRXCDJNL-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(CC)C1=CC=CC=C1 Chemical compound C(C(=C)C)(=O)OCCCC(CC)C1=CC=CC=C1 ADQIFLCRXCDJNL-UHFFFAOYSA-N 0.000 claims description 2
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
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- 239000011259 mixed solution Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- -1 alkyl acrylamide class Chemical class 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000083 poly(allylamine) Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241001274660 Modulus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 241000207923 Lamiaceae Species 0.000 description 1
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- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
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- SZMVKWFJCYTPOI-UHFFFAOYSA-N baicaline Natural products N1CCC2=C3OCOC3=C(OC)C3=C2C1CC1=C3C=C(OC)C(OC)=C1 SZMVKWFJCYTPOI-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of thermo-sensitive hydrogel by taking baicalin as a template. The hydrogel is prepared from the baicalin, thermo-sensitive monomers, a chemical cross-linking agent, an initiator and an organic solvent according to the ratio by weight percent of (0.1-0.9%):(5-10%):(0.85-5%):(0.05-0.1%):(84-94%). The preparation method comprises the following steps: 1) dissolving the baicalin in the organic solvent; 2) sequentially adding the thermo-sensitive monomers, the chemical cross-linking agent and the initiator into mixed solution in the step 1), and performing free radical polymerization at high temperature after sealing to get yellow gel; and 3) cutting the yellow gel into pieces, soaking and removing impurities. The product according to the invention has thermo-sensitive property, the baicalin plays a role of the template in the gel, the pore size, the thermo-sensitive property and the mechanical properties of the product can be regulated through the using amount of the baicalin, and the product can be used in biological medicine, tissue engineering, protection against drought, anti-waterlogging property, chemical separation and other fields.
Description
Technical field
The present invention relates to pharmaceutical prepn and intelligent macromolecule material field, being specifically related to a kind of is the preparation method of the temperature-sensitive hydrogel of template with the baicalin.
Background technology
Hydrogel (hydrogels) is a kind of wetting ability but water-fast high molecular polymer can be processed into different shape, like column, porous spongy, fibrous, tubulose, hollow form, membranaceous and spherical etc.Intelligent aqueous gel capable is one type stimulates (like temperature, pH, light, electric field, magnetic field, pressure etc.) can produce the hydrogel of responsive response to external world.The temperature-responsive hydrogel that receives common concern at present is an alkyl acrylamide class hydrogel; Particularly gather (N-NSC 11448) (PNIPAM), in biological medicine, organizational project, take precautions against drought waterlogging-resistant and field such as chemical separation has demonstrated good prospects for application.
In gel, can obtain having the material of ordered structure as template with the small molecules tensio-active agent.(chemical journal .2009 such as Lu Cuixiang; 67 (3): be template 238) with Tego Alkanol 16 Soxylat A 25-7 (Brij58); Use N, N '-methylene-bisacrylamide (MBA) adopts photopolymerization to synthesize SEPIGEL 305 (PAAm) hydrogel of compound with regular structure as linking agent, has the small structure of homogeneous; Internal structure is more regular, orderly, and what kept the traditional water gel changes the character of response fast to the pH value.In addition, Shen Xinyu etc. (functional materials, 2004,35 (increasing): 2431) with the PAAm hydrogel as template, the biomineralization of simulation lime carbonate is carried out bionical syntheticly, obtaining diameter is the calcite type near-spherical aggregate of 10～50 μ m.And constitute the monomer size homogeneous, meticulous (50～100nm), and on secondary structure unit, show same orientation of this aggregate.Contrast the result who obtains under the no template to regulate condition, the PAAm hydrogel template is because the high-sequential structure that himself exists, and the crystallography orientation of lime carbonate and granularity, pattern are all had strict control action kou.
Baicalin (baicalin) another name baicaline is for the dry root of the dicotyledons Labiatae root of large-flowered skullcap extracts a kind of flavonoid compound that gets.Baicalin molecular formula C
21H
18O
11, molecular weight 446.37, light yellow crystalline powder; 223～225 ℃ of fusing points are soluble in N, the pyridine, dissolve in the basic solns such as sodium hydrogencarbonate, yellow soda ash, sodium hydroxide; But unstable in alkali lye, the gradual change burgundy is slightly soluble in hot Glacial acetic acid min. 99.5; Be insoluble in formic acid, acetate, acetone, water-soluble hardly, ether, benzene, chloroform etc.That baicalin has is anticancer, antibiotic, antiviral, remove oxyradical and anti-oxidant, analgesic, arrhythmia, step-down and calmness, adjusting immunologic function, suppress effects such as vascular smooth muscle cell proliferation, regulating blood fat, atherosclerosis.
Because baicalin is a small molecules, in gel preparation course, adds reaction system, reaction finishes and can from the hole of gel, ooze out through the mode of soaking, thereby forms the gel pattern of different bore hole sizes.The present invention has taken all factors into consideration the temperature sensitivity of hydrogel and the pore property of baicalin; Near utilize alkyl acrylamide class hydrogel volume phase transition temperature (VPTT), to stretch or shrink conformational change; Prepare at hydrogel and to add baicalin in the process, be dissolved in organic solvent jointly, prepare hydrogel under the high temperature; Through changing the baicalin consumption, can effectively regulate and control the internal structure and the hole form of gel.
Summary of the invention
The purpose of this invention is to provide a kind of is the preparation method of the temperature-sensitive hydrogel of template with the baicalin, and gained gel transparency is high, temperature-responsive is sensitive, bore hole size is adjustable.
The present invention is a kind of to be the preparation method of the temperature-sensitive hydrogel of template with the baicalin, comprises the steps:
1) under 20～25 ℃, the yellow powder baicalin is dissolved in the organic solvent, is mixed with the organic solvent solution that the baicalin mass concentration is 0.1-0.9%, magnetic agitation 15～30min forms yellow transparent solution;
2) under the nitrogen protection; Temperature sensitive monomer and chemical cross-linking agent are joined in the above-mentioned yellow transparent solution successively, behind magnetic agitation 20～40min, add the initiator solid particulate; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 24～36h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 65～80 ℃ after reaction finishes;
3) yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of organic solvent earlier; Take out then and be soaked in 1-2 week in the deionized water; Changed organic solvent or deionized water in every interval 5-8 hour, to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
The mass percent of described baicalin, temperature sensitive monomer, chemical cross-linking agent, initiator and organic solvent is baicalin: 0.1-0.9%; Temperature sensitive monomer: 5-10%; Chemical cross-linking agent: 0.85-5%, initiator: 0.05-0.1%, organic solvent: 84-94%.
Described baicalin can be dissolved in the organic solvent fully, in the gel-purified process, realizes the function of template through the mode of soaking.
Described organic solvent is any one in N (DMF), DMSO 99.8MIN. (DMSO) or the pyridine.
Described temperature sensitive monomer is a kind of of N-NSC 11448 or isopropyl methyl acrylic amide, owing to both contained hydrophilic amide group in the monomer whose structure, contains hydrophobic sec.-propyl or methyl group again; Thereby have volume phase transition temperature (VPTT), when being lower than this temperature, hydrophilic interaction power plays a major role; The molecular chain full extension, and when being higher than this temperature, hydrogen bond is destroyed; Hydrophobic interaction power increases, and molecular chain shrinks.
Described chemical cross-linking agent is any one in methylene-bisacrylamide (MBA), ethylene glycol dimethacrylate (EDGMA) or the two methacryloxypropyl phenyl-propane.
Described initiator is any one in Diisopropyl azodicarboxylate (AIBN), ABVN (AMBN), BPO (BPO) or the peroxo-isocaprylic acid tert-butyl ester (TBPO).
Described is to be yellow after the temperature-sensitive hydrogel reaction of template finishes with the baicalin, is light yellow after the immersion, and near the water white transparency shape.
According to preferable methods of the present invention; Earlier baicalin is added and form transparent and homogeneous solution in the organic solvent; Add function monomer and chemical cross-linking agent and other raw material again and form mixed reaction solution, last under the initiator effect high temperature radical polymerization preparation to obtain with the baicalin be the temperature-sensitive hydrogel of template.
Described is that the inner hole of temperature-sensitive hydrogel of template is of a size of 50～500 μ m with the baicalin, and volume phase transition temperature (VPTT) is positioned at 30～34 ℃, demonstrates the low-temperature transparent swelling, the characteristics that high temperature bleaches and shrinks.
Of the present invention is that the bore hole size of the temperature-sensitive hydrogel of template, temperature sensitive property and mechanical property can be regulated by the baicalin consumption with the baicalin.No matter the baicalin mass percent is in any numerical value of 0.1-0.9%, and its volume phase transition temperature is all about 32 ℃, but temperature response speed increases with content of baicalin and improves; When no baicalin, about 70～100 μ m of hydrogel bore hole size, 15 ℃ of storage moduluss are about 1.6MPa; When the baicalin mass percent is 4%; Hydrogel hole chi is up to 400 μ m, and 15 ℃ of storage moduluss are about 6MPa, and this has important reference for the form and the performance regulation and control of hydrogel from now on application.
Description of drawings
Fig. 1 is the electron scanning micrograph of the hydrogel of template for the hydrogel of no baicalin with the baicalin.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Under 22 ℃, the 0.02g baicalin is dissolved in the 10mL DMSO 99.8MIN., magnetic agitation 20min forms yellow transparent solution;
Under the nitrogen protection; 0.90g NSC 11448 and 0.18g methylene-bisacrylamide are joined in the above-mentioned yellow transparent solution successively, behind the magnetic agitation 25min, add the 0.009g ABVN; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 30h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 70 ℃ after reaction finishes;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of DMSO 99.8MIN. earlier; Take out then and be soaked in 1 week in the deionized water; DMSO 99.8MIN. or deionized water were changed in 8 hours in every interval, and to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
Adopt sem, DSC and dynamic thermomechanometry test, gained hydrogel bore hole size is 80 μ m, and the volume phase transition temperature is 32.0 ℃, and storage modulus is 3.7MPa.
Embodiment 2
Under 23 ℃, the 0.04g baicalin is dissolved in the 10mL N, magnetic agitation 25min forms yellow transparent solution;
Under the nitrogen protection; 1.0g NSC 11448 and 0.2g methylene-bisacrylamide are joined in the above-mentioned yellow transparent solution successively, behind the magnetic agitation 30min, add the 0.01g Diisopropyl azodicarboxylate; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 32h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 73 ℃ after reaction finishes;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of N earlier; Take out then and be soaked in 1 week in the deionized water; N or deionized water were changed in 7 hours in every interval, and to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
Adopt sem, DSC and dynamic thermomechanometry test, gained hydrogel bore hole size is 400 μ m, and the volume phase transition temperature is 31.8 ℃, and storage modulus is 6.3MPa.
Embodiment 3
Under 25 ℃, the 0.06g baicalin is dissolved in the 11mL pyridine, magnetic agitation 30min forms yellow transparent solution;
Under the nitrogen protection; 0.95g isopropyl methyl acrylic amide and 0.19g ethylene glycol dimethacrylate are joined in the above-mentioned yellow transparent solution successively, behind the magnetic agitation 35min, add the 0.0095g peroxo-isocaprylic acid tert-butyl ester; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 34h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 75 ℃ after reaction finishes;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of N earlier; Take out then and be soaked in 2 weeks in the deionized water; Pyridine or deionized water were changed in 6 hours in every interval, and to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
Adopt sem, DSC and dynamic thermomechanometry test, gained hydrogel bore hole size is 460 μ m, and the volume phase transition temperature is 31.6 ℃, and storage modulus is 7.1MPa.
Embodiment 4
Under 23 ℃, the 0.08g baicalin is dissolved in the 12mL N, magnetic agitation 30min forms yellow transparent solution;
Under the nitrogen protection; 1.1g NSC 11448 and 0.2g ethylene glycol dimethacrylate are joined in the above-mentioned yellow transparent solution successively, behind the magnetic agitation 40min, add the 0.010g BPO; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 36h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 75 ℃ after reaction finishes;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of N earlier; Take out then and be soaked in 2 weeks in the deionized water; N or deionized water were changed in 5 hours in every interval, and to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
Adopt sem, DSC and dynamic thermomechanometry test, gained hydrogel bore hole size is 510 μ m, and the volume phase transition temperature is 31.2 ℃, and storage modulus is 5.6MPa.
Embodiment 5
Under 25 ℃, the 0.10g baicalin is dissolved in the 13mL DMSO 99.8MIN., magnetic agitation 30min forms yellow transparent solution;
Under the nitrogen protection; 0.90g NSC 11448 and 0.20g ethylene glycol dimethacrylate are joined in the above-mentioned yellow transparent solution successively, behind the magnetic agitation 30min, add the 0.009g BPO; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 32h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 76 ℃ after reaction finishes;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of N earlier; Take out then and be soaked in 1 week in the deionized water; Organic solvent or deionized water were changed in 5 hours in every interval, and to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
Adopt sem, DSC and dynamic thermomechanometry test, gained hydrogel bore hole size is 610 μ m, and the volume phase transition temperature is 32.3 ℃, and storage modulus is 6.7MPa.
Claims (10)
1. the present invention is a kind of is the preparation method of the temperature-sensitive hydrogel of template with the baicalin, comprises the steps:
1) under 20～25 ℃, the yellow powder baicalin is dissolved in the organic solvent, is mixed with the organic solvent solution that the baicalin mass concentration is 0.1-0.9%, magnetic agitation 15～30min forms yellow transparent solution;
2) under the nitrogen protection; Temperature sensitive monomer and chemical cross-linking agent are joined in the above-mentioned yellow transparent solution successively, behind magnetic agitation 20～40min, add the initiator solid particulate; Behind the restir 20min reaction solution is poured in the glass article; Be positioned over after the sealing that 24～36h carries out radical polymerization in the constant temperature oven, control reaction temperature obtains yellow gel at 65～80 ℃ after reaction finishes;
3) yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is; Be soaked in 1 week of organic solvent earlier; Take out then and be soaked in 1-2 week in the deionized water; Changed organic solvent or deionized water in every interval 5-8 hour, to remove unreacted monomer, linking agent and various impurity, obtaining described is the temperature-sensitive hydrogel of template with the baicalin.
2. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin; It is characterized in that; The mass percent of described baicalin, temperature sensitive monomer, chemical cross-linking agent, initiator and organic solvent is baicalin: 0.1-0.9%, temperature sensitive monomer: 5-10%, chemical cross-linking agent: 0.85-5%; Initiator: 0.05-0.1%, organic solvent: 84-94%.
3. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin, it is characterized in that described baicalin can be dissolved in the organic solvent fully, in the gel-purified process, realize the function of template through the mode of soaking.
4. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin, it is characterized in that described organic solvent is any one in N (DMF), DMSO 99.8MIN. (DMSO) or the pyridine.
5. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin, it is characterized in that the temperature sensitive monomer in the said step 2 is a kind of of N-NSC 11448 or isopropyl methyl acrylic amide.
6. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin; It is characterized in that the chemical cross-linking agent in the said step 2 is any one in methylene-bisacrylamide (MBA), ethylene glycol dimethacrylate (EDGMA) or the two methacryloxypropyl phenyl-propane.
7. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin; It is characterized in that the initiator in the said step 2 is any one in Diisopropyl azodicarboxylate (AIBN), ABVN (AMBN), BPO (BPO) or the peroxo-isocaprylic acid tert-butyl ester (TBPO).
8. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin, it is characterized in that described is to be yellow after the temperature-sensitive hydrogel reaction of template finishes with the baicalin, is light yellow after the immersion, and near the water white transparency shape.
9. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin; It is characterized in that; According to preferable methods of the present invention; Earlier baicalin is added and forms transparent and homogeneous solution in the organic solvent, add function monomer and chemical cross-linking agent and other raw material again and form mixed reaction solution, last under the initiator effect high temperature radical polymerization prepare that to obtain with the baicalin be the temperature-sensitive hydrogel of template.
10. according to claim 1 a kind of be the preparation method of the temperature-sensitive hydrogel of template with the baicalin; It is characterized in that; Described is that the inner hole of temperature-sensitive hydrogel of template is of a size of 50～500 μ m with the baicalin; Volume phase transition temperature (VPTT) is positioned at 30～34 ℃, demonstrates the low-temperature transparent swelling, the characteristics that high temperature bleaches and shrinks.
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| CN104138350A (en) * | 2013-05-06 | 2014-11-12 | 上海中医药大学 | Baicalein temperature-sensitive gel, preparing method thereof and applications of the gel |
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| CN101824123A (en) * | 2009-12-23 | 2010-09-08 | 天津大学 | High-strength temperature-sensitive hydrogel as well as preparation method and application thereof |
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| CN104138350A (en) * | 2013-05-06 | 2014-11-12 | 上海中医药大学 | Baicalein temperature-sensitive gel, preparing method thereof and applications of the gel |
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