CN102030882A - Method for preparing biodegradable polyurethane material with pH responsiveness - Google Patents
Method for preparing biodegradable polyurethane material with pH responsiveness Download PDFInfo
- Publication number
- CN102030882A CN102030882A CN2010105112255A CN201010511225A CN102030882A CN 102030882 A CN102030882 A CN 102030882A CN 2010105112255 A CN2010105112255 A CN 2010105112255A CN 201010511225 A CN201010511225 A CN 201010511225A CN 102030882 A CN102030882 A CN 102030882A
- Authority
- CN
- China
- Prior art keywords
- responsiveness
- aminoderivative
- diisocyanate
- biodegradable polyurethane
- under
- 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
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a method for preparing a biodegradable polyurethane material with pH responsiveness. Diisocyanate compounds and amino derivatives of polyhydroxyl compounds or amino derivatives of polyhydroxyl polymers serve as raw materials, and a conventional in-situ reaction method in solution polymerization is adopted to prepare the material in the presence of a catalyst. The invention has the advantages that: the preparation method is simple, is easy to operate and is suitable for industrial production, the raw materials are readily available, and the product efficiency is high; the prepared multi-block polyurethane material has a special characteristic of pH sensitivity, can be assembled into the needed structure and shape, has an alternating block structure and a plurality of reactivity points, is easily subjected to macromolecular modification, and is introduced with functional groups to realize structural and functional diversity. For instance, the material is combined with targeting molecules in the field of medicines to serve as a targeted release carrier material and the like; meanwhile, the material has biodegradability, meets the environmentally-friendly requirement of society, and can be widely applied to the fields of materials science, biology, medical science and the like.
Description
Technical field
The invention belongs to pH responsiveness macromolecular material technology of preparing, be specifically related to a kind of preparation method of biodegradable multi-block polyurethane material of the pH of having responsiveness.
Background technology
So-called pH responsiveness macromolecular material is meant the variation because of the pH value, material molecule can with the H in the solution
+In conjunction with separate, this combination with separate, its microcosmic change of molecular structure can cause the variation of its volume or form, this variation is based on the stimulating responsive of molecular level and macromole level.Because this special nature has caused the attention of Chinese scholars, and has prepared the type material of a series of pH of having responsivenesss.
The macromolecular material with pH responsiveness of report has following a few class at present:
1, pH responsiveness high-molecular gel: as the pH responsiveness polymer gel fiber of early discovery, Katchalasky etc. alternately add bronsted lowry acids and bases bronsted lowry to polyacrylic fibre or polymethyl acrylic acid fiber, find that reversible pucker ﹠ bloat (Advances In Polymer Science all can take place for it, 1987,86:1-46);
2, pH responsiveness polymeric membrane: as Bayramov etc. by poly-nitrogen vinyl pyrrolidone, polyoxyethylene glycol, methacrylic acid are discovered with the mixture of the multipolymer of ethyl propenoate formation, the film that this mixture forms has responsiveness at pH5.6-7.4, its pH be 5.6 o'clock the most stable, and be 7.4 o'clock Film Fractionation (Polymer International at pH, 2008,57 (5), 785-790);
3, polyelectrolyte macromolecular material: Khan etc. adopt sol-gel method, the organism polyaniline is added drop-wise in the phosphoric acid solution of tin, prepare a kind of polyelectrolyte macromolecular material, the stability of the membrane electrode that this material forms, be subjected to influence (the Sensors and Actuators B-Chemical of environment pH size, 2006,120 (1), 10-18);
4, polymer responsiveness matrix material: Cao etc. carry out copolymerization to vinylbenzene and maleic anhydride sodium salt, form a kind of new material that meets, by this multipolymer is discovered, this material has the favorable mechanical performance, and between pH5.0-8.2, has a good sensitivity (Polymer International, 2009,58 (5), 545-551).
PH responsiveness macromolecular material is because of its unique environmental stimulus responsiveness, can in different field, be widely used, in drug delivery system, people such as Zhang find, in influencing medicine degraded and rate of release factor in vivo, the big effect of lifting in the textural property of medicine early stage itself, and later stage pharmaceutical carrier (the J.Pharm Sci 2010 that plays a decisive role itself, 99 (11), 4678-4690).Have macromolecular material various in style of pH responsiveness, its preparation method adopts the method for graft copolymerization mostly, introduces the group with pH responsiveness, normal group of introducing such as carboxyl etc.
Polyurethane material is a kind of type material, because it has good physical and mechanical properties and biocompatibility, especially its Biodegradable, for the mankind provide new possibility in the research and development of bio-medical type material, and most of pH responsiveness macromolecular materials are as biomaterial the time, biocompatibility is not good, and degraded is incomplete or degraded product is harmful to health.The research report of at present relevant polyurethane material, urethane is as a kind of special synthetic materials, because of it has excellent elasticity, tensile strength and wear resisting property, can be widely used in modern industry, as as caking agent, material contracting with heat elastomerics, isolator, sealing agent, coating and foam materials etc., and passed through the authentication of food and drug administration.Urethane is easier to prepare by the polymerization ratio of vulcabond with polyvalent alcohol, because its excellent biological compatibility and mechanical property are used as biomaterial broad research (JPolym Sci A:Polym Chem, 2004,42,271; Acta Biomaterialia 2008,4,1263-1274; Polym Biomater1994,233-244; Colloid Polym Sci 1989,267,757-785; Biomaterials 2000,21, and 161-171), and the preparation research of pH responsiveness urethane does not appear in the newspapers.
Summary of the invention
The objective of the invention is to provides a kind of preparation method of biodegradable multi-block polyurethane material of the pH of having responsiveness at the above-mentioned state of the art, and this preparation method is simple, raw material is cheap, easy handling, technical maturity, be beneficial to industrialization.
Technical scheme of the present invention:
A kind of have a pH responsiveness biodegradable polyurethane preparation methods, with the aminoderivative of diisocyanate compound and polyol or the aminoderivative of polyhydroxylated polymer is raw material, adopt the reaction in method preparation in the conventional solution polymerization under catalyst action, step is as follows:
1) aminoderivative of the aminoderivative of polyol or polyhydroxylated polymer being dissolved in volume ratio is to make solution in the 50-80 solvent doubly, under nitrogen protection, adopts component distillation to dewater and carries out guaranteeing to be reflected under the anhydrous condition;
2) be under 60 ℃ of conditions in temperature, in above-mentioned solution in molar ratio-NCO :-OH=1.1: 1 adds diisocyanate cpd, adds catalyzer, under the nitrogen protection, is warming up to solvent boiling point, refluxes 8 hours;
3) be cooled to 50-60 ℃, under the nitrogen protection, add end-capping reagent, stir reaction down 1 hour;
4) treat solution cooling after, stop to stir and nitrogen protection, do precipitation agent with ether, separate out product, be products therefrom after the drying.
Described diisocyanate compound is L-lysine methyl ester vulcabond, L-ethyl ester of lysine vulcabond, the own ester vulcabond of L-Methionin, tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), trimethylammonium 1,6-hexamethylene diisocyanate, isophorone diisocyanate (IPDI), cyclohexanedimethyleterephthalate vulcabond, 4,4 dicyclohexyl methane diisocyanates or 1,4 cyclohexyl diisocyanate.
Polyol in the aminoderivative of described polyol or polymkeric substance is trolamine (TEA), to hydroxyethyl piperazine (HEP), polyoxyethylene glycol, polypropylene glycol, PTMG, polycaprolactone dibasic alcohol, poly-valerolactone dibasic alcohol, poly(lactic acid) dibasic alcohol; Polymkeric substance in the aminoderivative of described polyol or polymkeric substance is any two or three multipolymer by arbitrary proportion copolymerization formation in polyoxyethylene glycol, polypropylene glycol, PTMG, polycaprolactone dibasic alcohol, poly-valerolactone dibasic alcohol and the poly(lactic acid) dibasic alcohol, the aminoderivative number-average molecular weight 300-5000 of polyhydroxylated polymer.
Described solvent is toluene or ethyl acetate.
Described catalyzer is dibutyl tin laurate or stannous octoate, and the weight percent consumption of catalyzer is 0.5% of a reactant.
Described end-capping reagent methyl alcohol, ethanol or propyl alcohol, particular methanol, the consumption mol ratio of end-capping reagent be-NCO 10%.
Beneficial effect of the present invention:
1) multi-block polyurethane material provided by the invention has the special property of pH susceptibility, contains in the molecular structure to be easy to H
+In conjunction with and isolating group, adjustable environmental PH can be assembled into needed structure and form, provides a novel method for material design from the microcosmic of molecular water sane level or macromole levels;
2) polyurethane material of the pH of having responsiveness provided by the invention has the alternate type block structure because of it, have a plurality of reactive behavior points, carrying out macromole easily modifies, the access function group, implementation structure and functional diversities, as be applied on the medical field and combine, the solid support material that discharges as target etc. with targeted molecular;
3) a series of biodegradable multi-block polyurethane material of pH responsiveness that has provided by the invention, differing materials is in different pH value scopes, has abundant aggregated structure, variation according to application target environment pH value, needed material shape structure is designed, enlarge the scope of optional material, further satisfied planner's demand;
4) a series of pH of having responsiveness multi-block polyurethane material provided by the invention has biological degradability, satisfies the demand of society to environmental protection;
5) a series of methods with pH responsiveness multi-block polyurethane material of preparation provided by the invention adopt reaction in, have reduced the production of by product, have improved the utilising efficiency of product;
6) preparation method provided by the invention is simple, raw material is cheap, easy handling, technical maturity, be beneficial to industrialization, can be widely used in fields such as materialogy, biology, medical science.
Description of drawings
Fig. 1 is the change curve of the ultraviolet transmittance of HEP-LDI-B with different pH values.
Fig. 2 is the change curve of the particle diameter of HEP-LDI-B with different pH values.
Fig. 3 is 2 o'clock scanning electron microscope picture (SEM) in the pH value for HEP-LDI-B.
Fig. 4 is 7 o'clock scanning electron microscope picture (SEM) at pH value for HEP-LDI-B.
Fig. 5 is the change curve of the ultraviolet transmittance of TEA-LDI-M with different pH values.
Fig. 6 is the change curve of the particle diameter of TEA-LDI-M with different pH values.
Fig. 7 is 3 o'clock scanning electron microscope picture (SEM) in the pH value for TEA-LDI-M.
Fig. 8 is 8 o'clock scanning electron microscope picture (SEM) in the pH value for TEA-LDI-M.
Embodiment
Example given below is that the present invention is done concrete elaboration; it is to be noted that following example only is used for that the present invention is further described; can not be interpreted as limiting the scope of the invention; the ordinary person relevant with this field; some nonessential adjustment and improvement to the present invention carries out still belong to protection scope of the present invention.
Embodiment 1:
Get hydroxyethyl piperazine (HEP) 3g and 80ml toluene are placed the 150ml there-necked flask; and adding 10ml methylene dichloride (solubility promoter); after treating the PEG dissolving, the mixed solution 28ml that component distillation goes out hydration toluene under the nitrogen protection adds 4.8gL-Methionin butyl ester vulcabond (LDI-B) and 0.04g dibutyl tin laurate and makes catalyzer to remove the water in the reaction system; under the nitrogen protection; be warming up to solvent boiling point, refluxed 8 hours, be cooled to 60 ℃; add 0.1g methyl alcohol end-blocking; reacted 1 hour, and after the cooling, used ether sedimentation; separate out light yellow solid; with methylene dichloride dissolving, ether sedimentation, repeat 3 times after; dry 6.2g product, the productive rate 80% of getting.
Get the 5mg product, be dissolved among the 5mlDMF, dialysed 48 hours, be mixed with the solution of 1mg/ml.Measure the transmittance and the particle diameter of different pH values, 4.5-6.5 has the pH responsiveness in the pH value, change with pH, its particle diameter and transmittance change as shown in Figure 1 and Figure 2: as seen from the figure, in pH≤4.5 and pH 〉=6.5 o'clock, particle diameter and transmittance do not change substantially with the variation of pH, and be between the 4.5-6.5 at pH, transmittance and particle diameter are all undergone mutation, and transmittance matches with the variation with pH of the variation of pH and particle diameter: when particle diameter increased, transmittance diminished; When particle diameter diminished, its transmittance increased.Fig. 3 is scanning electron microscope (SEM) picture of this urethane when pH=2: this moment polymkeric substance water-soluble entirely, particle diameter is little, under the scanning electron microscope for becoming membrane stage; Fig. 4 is scanning electron microscope (SEM) picture of this material when pH=7: this moment is water insoluble, is the spheroidal particle about diameter 480nm under the scanning electron microscope; Scanning electron microscope picture under these 2 kinds of different pH of Fig. 3 Fig. 4 matches with Fig. 1 Fig. 2 particle diameter and the transmittance variation tendency with pH, illustrates that this urethane has good pH responsiveness at pH value 4.5-6.5.
Embodiment 2:
Get trolamine (TEA) 3g and toluene 80ml and place the 150ml there-necked flask; after the TEA dissolving; component distillation goes out the mixed solution 18ml of hydration toluene to remove the water in the reaction system under the nitrogen protection; add 0.64g lysine methyl ester vulcabond (LDI-M) and 0.02g dibutyl tin laurate and make catalyzer, under the nitrogen protection, be warming up to solvent boiling point; refluxed 8 hours; be cooled to 60 ℃, add 0.1g methyl alcohol end-blocking, reacted 1 hour; after the cooling; use ether sedimentation, separate out yellow solid, dissolve with chloroform; ether sedimentation; after repeating 4 times, dry 3.3g product, the productive rate 90.6% of getting.
Get the 5mg polymkeric substance, be dissolved among the 10mlDMF, dialysed 48 hours, be mixed with the solution of 0.5mg/ml.Survey its transmittance and particle diameter under different PH, find that its pH responsiveness is in pH value 5-7 scope, its particle diameter and transmittance change shown in Figure 6 as Fig. 5 with the pH value: as seen from the figure, in pH≤5 and pH 〉=7 o'clock, particle diameter and transmittance do not change substantially with the variation of pH, and are between the 5-7 at pH, and transmittance and particle diameter are all undergone mutation, and transmittance matches with the variation with pH of the variation of pH and particle diameter: when particle diameter increased, transmittance diminished; When particle diameter diminished, its transmittance increased.Fig. 7 is for for scanning electron microscope (SEM) picture of this polyurethane material when pH=3: this moment, polymkeric substance was water-soluble entirely, and particle diameter is little, under the scanning electron microscope for becoming membrane stage; Fig. 8 is scanning electron microscope (SEM) picture of this material when pH=8: this moment is water insoluble, is the spheroidal particle about diameter 450nm under the scanning electron microscope; Fig. 7 Fig. 8 is the scanning electron microscope picture under the different pH, matches with Fig. 5 Fig. 6 particle diameter and the transmittance variation tendency with pH, illustrates that this urethane has good pH response part at pH value 5-7.
Claims (6)
1. one kind has pH responsiveness biodegradable polyurethane preparation methods, it is characterized in that: with the aminoderivative of diisocyanate compound and polyol or the aminoderivative of polyhydroxylated polymer is raw material, adopt the reaction in method preparation in the conventional solution polymerization under catalyst action, step is as follows:
1) aminoderivative of the aminoderivative of polyol or polyhydroxylated polymer being dissolved in volume ratio is to make solution in the 50-80 solvent doubly, under nitrogen protection, adopts component distillation to dewater and carries out guaranteeing to be reflected under the anhydrous condition;
2) be under 60 ℃ of conditions in temperature, in above-mentioned solution in molar ratio-NCO :-OH=1.1: 1 adds diisocyanate cpd, adds catalyzer, under the nitrogen protection, is warming up to solvent boiling point, refluxes 8 hours;
3) be cooled to 50-60 ℃, under the nitrogen protection, add end-capping reagent, stir reaction down 1 hour;
4) treat solution cooling after, stop to stir and nitrogen protection, do precipitation agent with ether, separate out product, be products therefrom after the drying.
2. has a pH responsiveness biodegradable polyurethane preparation methods according to claim 1 is described, it is characterized in that: described diisocyanate compound is a L-lysine methyl ester vulcabond, L-ethyl ester of lysine vulcabond, the own ester vulcabond of L-Methionin, tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), trimethylammonium 1, the 6-hexamethylene diisocyanate, isophorone diisocyanate (IPDI), the cyclohexanedimethyleterephthalate vulcabond, 4,4 dicyclohexyl methane diisocyanates or 1,4 cyclohexyl diisocyanate.
3. have a pH responsiveness biodegradable polyurethane preparation methods according to claim 1 is described, it is characterized in that: the polyol in the aminoderivative of described polyol or polymkeric substance is trolamine (TEA), to hydroxyethyl piperazine (HEP), polyoxyethylene glycol, polypropylene glycol, PTMG, polycaprolactone dibasic alcohol, poly-valerolactone dibasic alcohol, poly(lactic acid) dibasic alcohol; Polymkeric substance in the aminoderivative of described polyol or polymkeric substance is any two or three multipolymer by arbitrary proportion copolymerization formation in polyoxyethylene glycol, polypropylene glycol, PTMG, polycaprolactone dibasic alcohol, poly-valerolactone dibasic alcohol and the poly(lactic acid) dibasic alcohol, the aminoderivative number-average molecular weight 300-5000 of polyhydroxylated polymer.
4. have a pH responsiveness biodegradable polyurethane preparation methods according to claim 1 is described, it is characterized in that: described solvent is toluene or ethyl acetate.
5. have a pH responsiveness biodegradable polyurethane preparation methods according to claim 1 is described, it is characterized in that: described catalyzer is dibutyl tin laurate or stannous octoate, and the weight percent consumption of catalyzer is 0.5% of a reactant.
6. have a pH responsiveness biodegradable polyurethane preparation methods according to claim 1 is described, it is characterized in that: described end-capping reagent methyl alcohol, ethanol or propyl alcohol, particular methanol, the consumption mol ratio of end-capping reagent be-NCO 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105112255A CN102030882B (en) | 2010-10-19 | 2010-10-19 | Method for preparing biodegradable polyurethane material with pH responsiveness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105112255A CN102030882B (en) | 2010-10-19 | 2010-10-19 | Method for preparing biodegradable polyurethane material with pH responsiveness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102030882A true CN102030882A (en) | 2011-04-27 |
| CN102030882B CN102030882B (en) | 2012-11-21 |
Family
ID=43884383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105112255A Expired - Fee Related CN102030882B (en) | 2010-10-19 | 2010-10-19 | Method for preparing biodegradable polyurethane material with pH responsiveness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102030882B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875772A (en) * | 2012-10-19 | 2013-01-16 | 中国科学院长春应用化学研究所 | Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel |
| CN104945587A (en) * | 2015-06-17 | 2015-09-30 | 常州大学 | Degradation rate controllable polyurethane and synthetic method thereof |
| CN106349457A (en) * | 2016-09-30 | 2017-01-25 | 河北大学 | Temperature-responsive polyurethane material and preparation method thereof |
| CN106366285A (en) * | 2016-09-09 | 2017-02-01 | 福州维亚生物科技有限公司 | Method for preparing and using vascular stent |
| CN107163893A (en) * | 2017-04-24 | 2017-09-15 | 深圳光华伟业股份有限公司 | A kind of hot-fusible pressure-sensitive adhesive |
| CN108641089A (en) * | 2018-05-07 | 2018-10-12 | 程桂平 | A kind of synthetic method of the material containing selenium |
| CN112709083A (en) * | 2021-02-08 | 2021-04-27 | 魔力薇薇(上海)服饰科技有限公司 | Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1477173A (en) * | 2002-07-31 | 2004-02-25 | 罗姆和哈斯公司 | Trigger response compositioin |
| US20080274190A1 (en) * | 2007-05-03 | 2008-11-06 | Sungkyunkwan University Foundation For Corporate Collaboration | TEMPERATURE AND pH - SENSITIVE BLOCK COPOLYMER HAVING EXCELLENT GEL STRENGTH, METHOD OF PREPARING THE SAME, AND DRUG DELIVERY SYSTEM USING THE SAME |
| CN101450991A (en) * | 2008-11-27 | 2009-06-10 | 上海交通大学 | Method for preparing temperature and pH double responsiveness hyper branched polymer |
| CN101775119A (en) * | 2010-02-08 | 2010-07-14 | 湖南科技大学 | Preparation method of environmental sensitivity polyurethane film |
-
2010
- 2010-10-19 CN CN2010105112255A patent/CN102030882B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1477173A (en) * | 2002-07-31 | 2004-02-25 | 罗姆和哈斯公司 | Trigger response compositioin |
| US20080274190A1 (en) * | 2007-05-03 | 2008-11-06 | Sungkyunkwan University Foundation For Corporate Collaboration | TEMPERATURE AND pH - SENSITIVE BLOCK COPOLYMER HAVING EXCELLENT GEL STRENGTH, METHOD OF PREPARING THE SAME, AND DRUG DELIVERY SYSTEM USING THE SAME |
| CN101450991A (en) * | 2008-11-27 | 2009-06-10 | 上海交通大学 | Method for preparing temperature and pH double responsiveness hyper branched polymer |
| CN101775119A (en) * | 2010-02-08 | 2010-07-14 | 湖南科技大学 | Preparation method of environmental sensitivity polyurethane film |
Non-Patent Citations (1)
| Title |
|---|
| 唐黎明，戴彧: "pH响应性聚氨酯薄膜的制备", 《应用化学》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875772A (en) * | 2012-10-19 | 2013-01-16 | 中国科学院长春应用化学研究所 | Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel |
| CN104945587A (en) * | 2015-06-17 | 2015-09-30 | 常州大学 | Degradation rate controllable polyurethane and synthetic method thereof |
| CN106366285A (en) * | 2016-09-09 | 2017-02-01 | 福州维亚生物科技有限公司 | Method for preparing and using vascular stent |
| CN106349457A (en) * | 2016-09-30 | 2017-01-25 | 河北大学 | Temperature-responsive polyurethane material and preparation method thereof |
| CN107163893A (en) * | 2017-04-24 | 2017-09-15 | 深圳光华伟业股份有限公司 | A kind of hot-fusible pressure-sensitive adhesive |
| CN107163893B (en) * | 2017-04-24 | 2023-08-04 | 深圳光华伟业股份有限公司 | Hot-melt pressure-sensitive adhesive |
| CN108641089A (en) * | 2018-05-07 | 2018-10-12 | 程桂平 | A kind of synthetic method of the material containing selenium |
| CN112709083A (en) * | 2021-02-08 | 2021-04-27 | 魔力薇薇(上海)服饰科技有限公司 | Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102030882B (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102030882B (en) | Method for preparing biodegradable polyurethane material with pH responsiveness | |
| Qu et al. | Biocompatible conductive hydrogels based on dextran and aniline trimer as electro-responsive drug delivery system for localized drug release | |
| CN102181060B (en) | Polyvinyl alcohol-polypeptide-polyethylene glycol graft copolymer and preparation method thereof | |
| Shao et al. | A self-healing cellulose nanocrystal-poly (ethylene glycol) nanocomposite hydrogel via Diels–Alder click reaction | |
| CN102181061B (en) | Polyurethane-polypeptide graft copolymer and preparation method thereof | |
| Dayananda et al. | pH-and temperature-sensitive multiblock copolymer hydrogels composed of poly (ethylene glycol) and poly (amino urethane) | |
| CN102174163B (en) | Side chain functionalized amphiphilic polyurethane and preparation method and application thereof | |
| CN101522788B (en) | Biocompatible polymer compositions | |
| Li et al. | Control of hyperbranched structure of polycaprolactone/poly (ethylene glycol) polyurethane block copolymers by glycerol and their hydrogels for potential cell delivery | |
| Shababdoust et al. | Controlled curcumin release from nanofibers based on amphiphilic-block segmented polyurethanes | |
| Qu et al. | Synthesis and characterization of a new biodegradable polyurethanes with good mechanical properties | |
| EP2222754B1 (en) | Thermoresponsive arginine-based hydrogels as biologic carriers | |
| CN101503501A (en) | Biodegradable nontoxic amphipathic multi-block polyurethane material and preparation thereof | |
| CN101541849A (en) | Bioresorbable polymers | |
| CN102336913A (en) | Poly(N-isopropyl acrylamide)-polyurethane-polypeptide block-graft copolymer and preparation method thereof | |
| Krogman et al. | The influence of side group modification in polyphosphazenes on hydrolysis and cell adhesion of blends with PLGA | |
| CN101255234B (en) | Thermo-sensitive tri-block polymer as well as preparation method and use thereof | |
| CN101215377A (en) | Aliphatic polyester-polyamino acid Y-type three-arm block copolymers and synthetic method thereof | |
| CN101812227A (en) | Micelle based on non-linear polyethylene glycol-polylactic acid block copolymer and preparation method thereof | |
| CN1995099A (en) | Degradable chemically-crosslinked aquagel and its preparation method | |
| Zhang et al. | Loading dependent swelling and release properties of novel biodegradable, elastic and environmental stimuli-sensitive polyurethanes | |
| Jaiswal et al. | Synthesis and characterization of positively charged interpenetrating double-network hydrogel matrices for biomedical applications | |
| CN101255235A (en) | Thermo-sensitive tri-block copolymer having sol-gel conversion characteristic and preparation thereof | |
| Vijayakumar et al. | Diisocyanate mediated polyether modified gelatin drug carrier for controlled release | |
| CN101288782A (en) | Preparation method of high intensity biodegradable supramolecule hydrogel |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121121 Termination date: 20131019 |