CN102432774A - Biodegradable temperature response hydrogel and preparation method thereof - Google Patents
Biodegradable temperature response hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN102432774A CN102432774A CN2011102561721A CN201110256172A CN102432774A CN 102432774 A CN102432774 A CN 102432774A CN 2011102561721 A CN2011102561721 A CN 2011102561721A CN 201110256172 A CN201110256172 A CN 201110256172A CN 102432774 A CN102432774 A CN 102432774A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polycaprolactone
- monomethyl ether
- glycol monomethyl
- biodegradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Medicinal Preparation (AREA)
- Polyethers (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses biodegradable temperature response hydrogel and a preparation method thereof. The method comprises the following steps of: (1) reacting terminal hydroxyl group of polycaprolactone dihydric alcohol with crylic acid (or methacrylic acid) to prepare polycaprolactone macromolecule cross-linking agent; (2) reacting singe terminal hydroxyl group of polyethylene glycol monomethyl ether and acryloyl chloride (or methacryloylchloride) to prepare a polyethylene glycol monomethyl ether macromolecule monomer; and (3) copolymerizing the polycaprolactone macromolecule cross-linking agent, the polyethylene glycol monomethyl ether macromolecule monomer and N-isopropylamide according to a certain ratio to obtain the biodegradable temperature response hydrogel. Compared with the traditional hydrogel, the hydrogel disclosed by the invention has the advantages of being rapid in response speed, good in mechanical strength, biodegradable and good in biocompatibility; therefore, the hydrogel is hopeful to be applied in the drug slow release field.
Description
Technical field
The invention belongs to field of functional materials, particularly a kind of hydrogel that can be used for drug release is specifically related to based on the temperature-responsive hydrogel N-NSC 11448 and biodegradable and preparation method thereof.
Background technology
The drug release drug delivery system is through methods such as physics, chemistry, makes medicine at the fixed time, be released to effect organ or particular target tissue by a certain speed, and makes the drug level long period maintain one type of preparation or device in the effective concentration.The medicine sustained release generally is to utilize carrier or the medium of polymkeric substance as medicine; Process certain formulation; Thereby the control medicine is in the intravital rate of release of people; Make the dosage of medicine, in the time range that requires, slowly discharge in vivo, to reach the purpose of efficient treatment by certain speed according to design.
Macromolecule hydrogel is a kind of material with three-dimensional crosslinked network structure that large quantity of moisture still is not dissolved in water that absorbs.Most hydrogels can hold the water of sole mass several times and even hundreds of times, and its ability of holding water with around environmental change change, be the environmental response hydrogel.That common environmental response hydrogel can be divided into is temperature sensitive, acid-sensitive, salt is quick, photosensitive etc. several types, shape memory hydrogel, electric field response hydrogel etc. are arranged in addition.These hydrogels can be made response through the variation to environment, thereby also are called as intelligent macromolecule material.Be that the hydrogel that monomer prepares is the most representative temperature-sensitive hydrogel wherein with the N-NSC 11448.This type of hydrogel has lowest critical solution temperature (LCST); N-sec.-propyl propionic acid amide chain contains hydrophilic amido and hydrophobic sec.-propyl; To be lower than LCSTN-sec.-propyl propionic acid amide chain be main with hydrogen bonded when temperature in water; Show as hydrophilicly, hydrogen bond weakens and shows as hydrophobic when temperature is higher than LCST.But traditional N-sec.-propyl propionic acid amide hydrogel is owing to LCST lower (being about 32 ℃), and response speed is slow, and mechanical strength difference and not biodegradable has limited its application in the medicine controlled releasing field.
Polyoxyethylene glycol is nontoxic, nonirritant; Has good water-solubility; And the organic polymer of good intermiscibility is arranged with many organic matter components; Have excellent lubrication in the practical application, preserve moisture, bonding and dispersing property, in industries such as makeup, pharmacy, chemical fibre, rubber, plastics, papermaking, paint, plating, agricultural chemicals, metal processing and food-processing, all have very widely and use.In recent years, about being that the research of feedstock production hydrogel emerges in an endless stream with the polyoxyethylene glycol, the hydrogel that with the polyoxyethylene glycol is feedstock production is at mechanical strength, biocompatibility, and all there is excellent performance aspects such as syringeability.
And Biodegradable high-molecular is used for the medicine sustained release, compares with the non-biodegradation macromolecular material, has bigger advantage, does not promptly need after drug release is intact, to carry out second operation and takes out solid support material.Take with behind the medicament of Biodegradable high-molecular as the medicine controlled release carrier material, along with the degraded of solid support material, medicine also discharges thereupon, can realize the control to drug releasing rate through the degradation speed of regulating carrier matrix.In the Biodegradable high-molecular drug release material; Polycaprolactone (PCL) is a kind of typical biodegradable thermoplastic material; Can be degraded to carbonic acid gas and water voluntarily in vivo, have excellent biological compatibility simultaneously, thereby be widely used in field of medical materials.
To sum up, polyoxyethylene glycol and biodegradable controlled-release material are applied to prepare temperature-sensitive hydrogel and have good application prospects and feasibility.
Summary of the invention
In order to solve the deficiency of prior art, the preparation method of a kind of biodegradable temperature-responsive hydrogel that primary and foremost purpose of the present invention is to provide.
Another purpose of the present invention is to provide the biodegradable temperature-responsive hydrogel of method for preparing.
The object of the invention is realized through following technical proposals:
A kind of preparation method of biodegradable temperature-responsive hydrogel; This method is at 1.5～2ml 1 by 0.025～0.0333g polycaprolactone macromolecules cross-linking agent (being designated as PCLDAC), 0.0667～0.1333g poly glycol monomethyl ether macromonomer (being designated as MPEGAC) and 0.15～0.25g N-NSC 11448 and 2～4mg Diisopropyl azodicarboxylate; React in the 4-dioxane, make biodegradable temperature-responsive hydrogel.
Said reaction process is that the polycaprolactone macromolecules cross-linking agent of said consumption, poly glycol monomethyl ether macromonomer, N-NSC 11448 and Diisopropyl azodicarboxylate are added 1, dissolves in the 4-dioxane, carries out freezing then; Vacuumize; Towards nitrogen with thaw, repeats 2～3 times after closed reactor, react 24～48h in 65～80 ℃; Smash reactor drum, obtain biodegradable temperature-responsive hydrogel.
In order to realize the present invention better, the optimum amount of said reactant is: polycaprolactone macromolecules cross-linking agent 0.025g, poly glycol monomethyl ether macromonomer 0.1077g; N-NSC 11448 0.2g; Diisopropyl azodicarboxylate 3mg, 1.5ml 1, the 4-dioxane.
Said freezing; Vacuumize; Towards the nitrogen and the concrete operations of thawing be: reaction vessel is put into the liquid nitrogen that is about-190～-200 ℃ and be refrigerated to wherein that liquid solidifies; Be evacuated to reaction vessel vacuum tightness then and be lower than 0.1MPa, charging into nitrogen to reaction vessel vacuum tightness again is 100～101Mpa, under 25～35 ℃ environment, lets in the container solid separate naturally and is frozen into liquid; The said repetition is repeated freezing successively, vacuumizes inflated with nitrogen and the operation of thawing.
The structural formula of said polycaprolactone macromolecules cross-linking agent is suc as formula shown in 1, and its weight-average molecular weight is 2000, and n is 8～9.
Formula 1
The preparation method of said polycaprolactone macromolecules cross-linking agent is: get 1.5～2.5g polycaprolactone divalent alcohol and 1～2ml vinylformic acid and be dissolved in 15～25ml methylene dichloride, add 4～5g N, N-NSC 57182 and 0.06～0.12g 2-methylamino pyridine; 36～48h is stirred in airtight back; Suction filtration, will filtrate concentrates, with methanol extraction 2～3 times; Filter, obtain the agent of polycaprolactone macromolecules cross-linking.Wherein, the weight-average molecular weight of said polycaprolactone divalent alcohol is 2000; Said filtrating is concentrated into 5～10ml; Said methyl alcohol is low-temp methanol, and temperature is-15～-25 ℃.
The structural formula of said poly glycol monomethyl ether macromonomer is suc as formula shown in 2, and its weight-average molecular weight is 1000, and m is 22～23.
The preparation method of said poly glycol monomethyl ether macromonomer is: in reactor drum, poly glycol monomethyl ether 1.5～2.5g is added in 15～25ml methylene dichloride and dissolves, add 0.15～0.2ml triethylamine and 0.01～0.015g MEHQ again; 0.25～0.3ml acrylate chloride is dissolved in 4～7ml methylene dichloride, obtains the dichloromethane solution of acrylate chloride, under the condition of ice bath this drips of solution is added reactor drum; Dropwise the back closed reactor; 40～45 ℃ are stirred 24～36h, suction filtration then, and filtrating concentrates the back with petroleum ether precipitation 2～3 times; Filter, obtain the poly glycol monomethyl ether macromonomer.The weight-average molecular weight of said poly glycol monomethyl ether is 1000; Said filtrating is concentrated into 5～10ml.
A kind of biodegradable temperature-responsive hydrogel is prepared from through above-mentioned preparation method.This hydrogel has overcome the shortcoming that traditional N-NSC 11448 hydrogel is had, and has quicker response, higher mechanical strength and favorable biological degradability, and the performance flexibly changing of hydrogel.
Principle of the present invention is: at first utilize the terminal hydroxy group and vinylformic acid (or methylacrylic acid) reaction of polycaprolactone divalent alcohol; Add N, the N-NSC 57182 is a dehydrating condensation agent, can promote the esterification between hydroxyl and the carboxyl; Make the two slough a part water and generate ester bond; Consumption is 2～4 times of molar equivalents of reaction substrate, obtains polycaprolactone diacrylate (or methylacrylic acid) ester, i.e. polycaprolactone macromolecules cross-linking agent; Utilize the one-ended hydroxy and acrylate chloride (or methacrylic chloride) reaction of poly glycol monomethyl ether then, obtain poly glycol monomethyl ether vinylformic acid (or methylacrylic acid) ester, make the poly glycol monomethyl ether macromonomer; N-NSC 11448, the agent of polycaprolactone macromolecules cross-linking, poly glycol monomethyl ether macromonomer are carried out free-radical polymerized, finally obtain having the biodegradable temperature-responsive hydrogel of three-dimensional net structure.
The present invention controls the mechanical strength and the rate of water absorption of biodegradable temperature-responsive hydrogel through the content of regulating MPEGAC; Wherein the content of MPEGAC is high more; The mechanical strength of biodegradable temperature-responsive hydrogel is high more, and it is linear that rate of water absorption is tending towards more, and LCST is not obvious more.Control the mechanical strength and the biological degradability of biodegradable temperature-responsive hydrogel through the content of regulating PCLDAC, wherein the content of PCLDAC is high more, and the mechanical strength of biodegradable temperature-responsive hydrogel is strong more, and biological degradability is good more.
In addition,, can make hydrogel in the process that forms, occur being separated, form vesicular structure because polycaprolactone belongs to hydrophobic polymer; Poly glycol monomethyl ether is hydrophilic polymer, can form hydrophilic passage, and two close to mutually combine and more help the transportation of moisture in hydrogel.
The present invention compared with prior art has following advantage and beneficial effect: the present invention controls the mechanical strength and the rate of water absorption of hydrogel through the content of regulating MPEGAC; Control the mechanical strength and the biological degradability of hydrogel through the content of regulating PCLDAC; And hydrophobicity polycaprolactone polymer and hydrophilic polyglycol monomethyl ether mutually combine and more help the transportation of moisture in hydrogel; Make the hydrogel of preparation have quicker response; Higher mechanical strength and favorable biological degradability; But and the performance flexible of hydrogel, prepare the hydrogel of different in kind according to the difference of practical application object, it is had a extensive future.
Description of drawings
Fig. 1 is the H of the polycaprolactone macromolecules cross-linking agent of embodiment 1 preparation
1The NMR spectrogram.
Fig. 2 is the H of the poly glycol monomethyl ether macromonomer of embodiment 2 preparations
1The NMR spectrogram.
Fig. 3 is the infrared spectrogram of the biodegradable temperature-responsive hydrogel of embodiment 6 preparations.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Raw material in following examples is following:
Before the N-NSC 11448 uses with normal hexane recrystallization 2 times; Add the 1.5g hydrolith before methylene dichloride uses, airtight back stirring at room 18h is then 40 ℃ of following air distillations; Collecting 41～42 ℃ cut, to put into encloses container subsequent use; 1, before using, the 4-dioxane adds the 4A molecular sieve of 20g through temperature baking 3h more than 400 ℃, and for use behind the airtight then placement 30h.The unprocessed direct use of other raw materials.
Embodiment 1
The preparation process of the polycaprolactone macromolecules cross-linking agent (PCLDAC) that embodiment 3～6 is used is following: get 2.5g polycaprolactone divalent alcohol and be dissolved in the 20ml methylene dichloride; Add N; N-NSC 57182 4.06g, 2-methylamino pyridine 0.1g, airtight back stirring at room 48h.The reaction back suction filtration that finishes is removed insolubles, filtrating is revolved to steam be concentrated into 5ml, pours in-20 ℃ the methyl alcohol deposition into 2 times, filters, and the agent of gained polycaprolactone macromolecules cross-linking is designated as PCLDAC.The H of PCLDAC
1The NMR spectrogram is seen Fig. 1, and test result is: δ=1.225-1.294 (m, 2H ,-CH2-); δ=1.493-1.553 (m, 4H ,-CH2CH2-); δ=2.239-2.276 (m, 2H ,-CH2CO-); δ=3.950-3.983 (t, 2H ,-O-CH2-); δ=5.568-5.699,6.278-6.324 (m, 2H ,=CH2); δ=6.145-6.186 (t, 1H ,-OCH=).
The preparation process of the poly glycol monomethyl ether macromonomer (MPEGAC) that embodiment 3～6 is used is following:
Taking polyethylene glycol monomethyl ether 2.5g is dissolved in the 20ml methylene dichloride, adds the 0.2ml triethylamine again.Acrylate chloride 0.25ml is dissolved in the dichloromethane solution that obtains acrylate chloride in the 5ml methylene dichloride, and the dichloromethane solution with acrylate chloride under condition of ice bath is added dropwise in the reactor drum, dropwises the back closed reactor; 40 ℃ of vigorous stirring 24h; Suction filtration was removed insolubles after reaction finished, and the room temperature of will filtrating is revolved to steam and is concentrated into 10ml, pours into and repeats in the sherwood oil to precipitate 2 times; Filtration obtains the poly glycol monomethyl ether macromonomer, and product is designated as MPEGAC.The H of MPEGAC
1The NMR spectrogram is seen Fig. 2, and test result is: δ=3.352 (s, 3H ,-CH3); δ=3.616-3.630 (d, 4H ,-O-CH2CH2-O-); δ=3.630-3.727 (m, 2H ,-CH2-); δ=4.276-4.300 (t, 2H ,-CH2-); δ=5.694-5.724,6.247-6.293 (m, 2H ,=CH2); δ=6.112-6.121 (t, 1H ,-OCH=); δ=3.352 (s, 3H ,-CH3).
Take by weighing PCLDAC 0.0333g, MPEGAC 0.0667g, N-NSC 11448 0.2g, Diisopropyl azodicarboxylate 3mg, be dissolved in 1.5ml 1, in the 4-dioxane; Carry out freezingly, vacuumize, inflated with nitrogen with thaw; Tube sealing after repeating 3 times, in 65 ℃ of reaction 24h, can obtain LCST is 32.7 ℃; The imbibition rate is 0.95 in the time of 35 ℃, and 5h can reach equilibrium state, and the compression mechanical strength is the biodegradable temperature-responsive hydrogel of 54.5KPa.
Take by weighing PCLDAC 0.0333g, MPEGAC 0.0857g, N-NSC 11448 0.2g, Diisopropyl azodicarboxylate 3mg, be dissolved in 1.5ml 1, in the 4-dioxane; Carry out freezingly, vacuumize, inflated with nitrogen with thaw; Tube sealing after repeating 3 times, in 70 ℃ of reaction 36h, can obtain LSCT is 33 ℃; The imbibition rate is 1.19 in the time of 35 ℃, and 5h can reach equilibrium state, and the compression mechanical strength is the biodegradable temperature-responsive hydrogel of 59.7KPa.
Take by weighing PCLDAC 0.0333g, MPEGAC 0.1333g, N-NSC 11448 0.2g, Diisopropyl azodicarboxylate 3mg, be dissolved in 1.5ml 1, in the 4-dioxane; Carry out freezingly, vacuumize, inflated with nitrogen with thaw; Tube sealing after repeating 3 times, in 80 ℃ of reaction 48h, can obtain LCST is 33.2 ℃; The imbibition rate is 1.73 in the time of 35 ℃, and 5h can reach equilibrium state, and the compression mechanical strength is the biodegradable temperature-responsive hydrogel of 43.2KPa.
Take by weighing PCLDAC 0.025g, MPEGAC 0.1077g, N-NSC 11448 0.2g, Diisopropyl azodicarboxylate 3mg, be dissolved in 1.5ml 1, in the 4-dioxane; Carry out freezingly, vacuumize, inflated with nitrogen with thaw; Tube sealing after repeating 3 times, in 70 ℃ of reaction 36h, can obtain LCST is 34 ℃; The imbibition rate is 1.51 in the time of 35 ℃, and 5h can reach equilibrium state, and the compression mechanical strength is the biodegradable temperature-responsive hydrogel of 71.5KPa.
The infrared test result of the biodegradable temperature-responsive hydrogel of present embodiment preparation sees Fig. 3, analyzes as follows: 3436.53cm
-1The broad peak that the place occurs is in the N-NSC 11448-stretching vibration (vN-H) of NH; 2975.62cm
-1C-H stretching vibration (vCH appears in the place
3); 2935.13cm
-1C-H stretching vibration (vCH appears in the place
2); 2877.27cm
-1C-H stretching vibration (vCH) appears in the place; 1727.91cm
-1Strong and wide C=O stretching vibration (vC=O) appears in the place; 1548cm
-1The N-H flexural vibration (δ N-H) of secondary amide appear in the place; 1357.64cm
-1, 1307.50cm
-1, 1245.7cm
-1, 1114.65cm
-1And 1043.40cm
-1The C-O symmetry and the asymmetrical stretching vibration (vC-O) of ester class and polyoxyethylene glycol component appears in the place.3090～3010cm wherein
-1The C-H stretching vibration peak of two keys does not appear in the place, explains that the intact small molecule monomer of unreacted eliminates.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.As stated, can realize the present invention preferably.
Claims (10)
1. the preparation method of a biodegradable temperature-responsive hydrogel; It is characterized in that: this method is at 1.5～2ml 1 by the agent of 0.025～0.0333g polycaprolactone macromolecules cross-linking, 0.0667～0.1333g poly glycol monomethyl ether macromonomer and 0.15～0.25g N-NSC 11448 and 2～4mg Diisopropyl azodicarboxylate; React in the 4-dioxane, make biodegradable temperature-responsive hydrogel.
2. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 1; It is characterized in that comprising following operating process: the agent of polycaprolactone macromolecules cross-linking, poly glycol monomethyl ether macromonomer, N-NSC 11448 and the Diisopropyl azodicarboxylate of said consumption are added 1, dissolve in the 4-dioxane, carry out freezing then; Vacuumize; Inflated with nitrogen with thaw, repeats 2～3 times after closed reactor, in 65～80 ℃ react 24～48h after; Smash reactor drum, obtain biodegradable temperature-responsive hydrogel.
3. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 2; It is characterized in that: said freezing; Vacuumize, inflated with nitrogen and the concrete operations of thawing are: reaction vessel is put into-190～-200 ℃ of liquid nitrogen and be refrigerated to wherein that liquid solidifies fully, be evacuated to then that vacuum tightness is lower than 0.1MPa in the container; Inflated with nitrogen to vacuum tightness is 100～102MPa, solid is separated be frozen into liquid; The said repetition is repeated freezing successively, vacuumizes inflated with nitrogen and the operation of thawing.
4. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 1 is characterized in that: the structural formula of said polycaprolactone macromolecules cross-linking agent is suc as formula shown in 1, and wherein n is 8～9,
Formula 1.
5. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 4; It is characterized in that: the preparation method of said polycaprolactone macromolecules cross-linking agent is: get 1.5～2.5g polycaprolactone divalent alcohol and 1～2ml vinylformic acid and be dissolved in 15～25ml methylene dichloride, add 4～5g N, N-NSC 57182 and 0.06～0.12g 2-methylamino pyridine; Airtight back stirring at room 36～48h; Suction filtration, will filtrate concentrates, with methanol extraction 2～3 times; Filter, obtain the agent of polycaprolactone macromolecules cross-linking.
6. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 5 is characterized in that: the weight-average molecular weight of said polycaprolactone divalent alcohol is 2000; Said filtrating is concentrated into 5～10ml; Said methyl alcohol is low-temp methanol, and temperature is-15～-25 ℃.
7. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 1 is characterized in that: said poly glycol monomethyl ether macromonomer is the compound shown in the formula 2, and wherein m is 22～23,
Formula 2.
8. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 7; It is characterized in that: the preparation method of said poly glycol monomethyl ether macromonomer is: in reactor drum, with dissolving in 1.5～2.5g poly glycol monomethyl ether adding, 15～25ml methylene dichloride, add 0.15～0.2ml triethylamine and 0.01～0.015g MEHQ again; 0.25～0.3ml acrylate chloride is dissolved in 4～7ml methylene dichloride, obtains the dichloromethane solution of acrylate chloride, under the condition of ice bath this solution is added reactor drum; Closed reactor then; Stir 24～36h at 40～45 ℃, suction filtration is poured into after filtrating concentrates and is precipitated 2～3 times in the sherwood oil; Filter, obtain the poly glycol monomethyl ether macromonomer.
9. the preparation method of a kind of biodegradable temperature-responsive hydrogel according to claim 8 is characterized in that: the weight-average molecular weight of said poly glycol monomethyl ether is 1000; Said filtrating is concentrated into 5～10ml.
10. the biodegradable temperature-responsive hydrogel for preparing according to each said method of claim 1～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110256172 CN102432774B (en) | 2011-09-01 | 2011-09-01 | Biodegradable temperature response hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110256172 CN102432774B (en) | 2011-09-01 | 2011-09-01 | Biodegradable temperature response hydrogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432774A true CN102432774A (en) | 2012-05-02 |
| CN102432774B CN102432774B (en) | 2013-03-20 |
Family
ID=45981154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110256172 Expired - Fee Related CN102432774B (en) | 2011-09-01 | 2011-09-01 | Biodegradable temperature response hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432774B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304733A (en) * | 2013-06-19 | 2013-09-18 | 复旦大学 | Preparation method of degradable environmental sensitive polymer nano hydrogel and application |
| CN103421204A (en) * | 2013-08-20 | 2013-12-04 | 常州大学 | Surface-amphiphilic polyester film and preparation method thereof |
| CN104772129A (en) * | 2015-04-13 | 2015-07-15 | 南京工业大学 | Intelligent temperature responding adsorbent as well as preparation method and application thereof |
| CN105924588A (en) * | 2016-02-03 | 2016-09-07 | 临沂大学 | Novel poly N-isopropylacrylamide hydrogel, and preparation method and application thereof |
| CN106237329A (en) * | 2016-08-04 | 2016-12-21 | 佛山科学技术学院 | There is nucleocapsid structure magnetic Hydrogel Nanoparticles and the preparation method of temperature-responsive |
| CN113637182A (en) * | 2021-08-10 | 2021-11-12 | 四川大学 | CO based on dynamic covalent bond2Responsive intelligent hydrogel and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633711A (en) * | 2009-08-20 | 2010-01-27 | 中国科学院广州化学研究所 | Temperature-sensitive hydrogel containing adamantyl and preparation method and application thereof |
| CN101857666A (en) * | 2010-05-13 | 2010-10-13 | 中科院广州化学有限公司 | Cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof |
-
2011
- 2011-09-01 CN CN 201110256172 patent/CN102432774B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633711A (en) * | 2009-08-20 | 2010-01-27 | 中国科学院广州化学研究所 | Temperature-sensitive hydrogel containing adamantyl and preparation method and application thereof |
| CN101857666A (en) * | 2010-05-13 | 2010-10-13 | 中科院广州化学有限公司 | Cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QUNFENG LIU ET AL.: "Synthesis of rapid responsive gels comprising hydrophilic backbone and poly(N-isopropylacrylamide) graft chains by RAFT polymerization and end-linking processes", 《POLMER》 * |
| YOUDAO LING ET AL.: "Thermo and pH dual responsive Poly (N-isopropylacrylamide-co-itaconic acid) hydrogels prepared in aqueous NaCl solutions and their characterization", 《JOURNAL OF POLYMER RESEARCH》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304733A (en) * | 2013-06-19 | 2013-09-18 | 复旦大学 | Preparation method of degradable environmental sensitive polymer nano hydrogel and application |
| CN103304733B (en) * | 2013-06-19 | 2016-09-28 | 复旦大学 | A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel |
| CN103421204A (en) * | 2013-08-20 | 2013-12-04 | 常州大学 | Surface-amphiphilic polyester film and preparation method thereof |
| CN104772129A (en) * | 2015-04-13 | 2015-07-15 | 南京工业大学 | Intelligent temperature responding adsorbent as well as preparation method and application thereof |
| CN105924588A (en) * | 2016-02-03 | 2016-09-07 | 临沂大学 | Novel poly N-isopropylacrylamide hydrogel, and preparation method and application thereof |
| CN105924588B (en) * | 2016-02-03 | 2018-06-29 | 临沂大学 | A kind of poly-N-isopropyl acrylamide hydrogel and its preparation method and application |
| CN106237329A (en) * | 2016-08-04 | 2016-12-21 | 佛山科学技术学院 | There is nucleocapsid structure magnetic Hydrogel Nanoparticles and the preparation method of temperature-responsive |
| CN106237329B (en) * | 2016-08-04 | 2019-10-11 | 佛山科学技术学院 | Core-shell structure magnetic Hydrogel Nanoparticles and preparation method with temperature-responsive |
| CN113637182A (en) * | 2021-08-10 | 2021-11-12 | 四川大学 | CO based on dynamic covalent bond2Responsive intelligent hydrogel and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432774B (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432774A (en) | Biodegradable temperature response hydrogel and preparation method thereof | |
| Ramin et al. | Low molecular weight hydrogels derived from urea based-bolaamphiphiles as new injectable biomaterials | |
| CN101952348B (en) | Thermoresponsive arginine-based hydrogels as biologic carriers | |
| JP5671024B2 (en) | Process for making polymers, preferably (alkyl) acryloyl polycarbonates, resulting polymers and (alkyl) acryloyl polycarbonates, and biodevices comprising the same | |
| CN104892871A (en) | Hydrogel with self-repairing function and preparation method of hydrogel | |
| CN104877087B (en) | A kind of temperature-sensitive hydrogel with bioactivity and preparation method thereof | |
| CN102827293B (en) | Alkynyl hydroxypropyl cellulose and preparation method and application of temperature-sensitive hydrogel of alkynyl hydroxypropyl cellulose | |
| CN105555832A (en) | Bioelastomers and applications thereof | |
| Zhang et al. | Biocompatible and pH-sensitive PEG hydrogels with degradable phosphoester and phosphoamide linkers end-capped with amine for controlled drug delivery | |
| CN107286326B (en) | The Ratio-type fluorescence imaging high molecular nanometer carrier and its preparation of quick penetration cell membrane and environment-responsive intracellular and application | |
| Yiğitoğlu et al. | Microwave-assisted synthesis of alginate-g-polyvinylpyrrolidone copolymer and its application in controlled drug release | |
| US9815935B2 (en) | Biodegradable side chain liquid crystal elastomers: smart responsive scaffolds (SRS) for tissue regeneration | |
| CN106589355A (en) | Non-viral gene transfection vector material based on cationic helical peptide | |
| CN111218011B (en) | Polyethylene glycol-based hydrogel and preparation method and application thereof | |
| Wu et al. | Enzymatically degradable oxidized dextran–chitosan hydrogels with an anisotropic aligned porous structure | |
| CN102924653B (en) | Poly (N- isopropyl acrylamide)- poly (crylic acid or acrylic acid derivative) copolymer and preparation method thereof | |
| KR20120090709A (en) | Polyethyleneglycol/polyester block copolymers with side functional group as biocompatible thermo-sensitive materials and manufacturing method thereof | |
| CN108610491A (en) | Thermo-sensitive graft polymers, the hydrogel that cell can be carried and preparation method and application | |
| CN108641092B (en) | Preparation method of supramolecular polymer composite micelle based on hydrogen bond | |
| CN105175750B (en) | A kind of preparation method of hydrogel microsphere | |
| CN102898635B (en) | Amphipathic high polymer material and method for preparing same | |
| CN102167818A (en) | Poly(gamma-propynyl-L-glutamate) block copolymer and preparation method and hydrogel thereof | |
| CN108752530A (en) | It can the temperature-sensitive hydrogel materials of load cells, temperature-sensitive hydrogel and the preparation method and application thereof | |
| CN108201636A (en) | A kind of preparation method of the controllable natural polymer subbase 3D porous compound support frames in aperture | |
| CN108822299B (en) | Hydroxylamino-terminated polyethylene glycol block polymer, preparation method thereof, hydrogel containing polyethylene glycol block polymer, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130320 Termination date: 20150901 |
|
| EXPY | Termination of patent right or utility model |