CN100532394C - Method of modifying elastin by atom transition free radical polymerization reaction - Google Patents
Method of modifying elastin by atom transition free radical polymerization reaction Download PDFInfo
- Publication number
- CN100532394C CN100532394C CNB2007100565083A CN200710056508A CN100532394C CN 100532394 C CN100532394 C CN 100532394C CN B2007100565083 A CNB2007100565083 A CN B2007100565083A CN 200710056508 A CN200710056508 A CN 200710056508A CN 100532394 C CN100532394 C CN 100532394C
- Authority
- CN
- China
- Prior art keywords
- elastin
- free radical
- radical polymerization
- polymerization reaction
- transition free
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a modified elastic protein polymerized by atom transmitted free radical, which is characterized by the following: adopting elastic protein to bromidize to produce elastic protein of macromolecular atom-transmitted free radical polymeric trigger; using CuCl/2 as trigger under 2-dipyridine catalytic system; synthesizing elastic protein and polymethacrylic acid-beta-hydroxy carbethoxy grafted polymer; improving hydrophobicity for elastic protein; reducing heat stability.
Description
Technical field
The present invention relates to a kind of material modified method of atom transition free radical polymerization reaction of utilizing, more particularly, relate to a kind of method of utilizing the atom transition free radical polymerization reaction modifying elastin.
Background technology
Elastin (elastin) is insoluble in the extracellular matrix, high crosslinked macromole fibrous protein, can combine with microfibril in vivo and form spandex fiber, major function is passively to stretch, give place tissue and organ with retractility and reversible deformability.At present, domestic and international research to elastin mainly concentrates on the hydrolysate α-elastin and the K-elastin that utilize elastin and prepares aspects such as synthesizing of tissue engineering bracket and biological degradation elastomerics and genetic engineered product class silk elastin polymkeric substance and application, and elastin is because highly insoluble, highly hydrophobic and highly crosslinkable, not easy-to-use chemistry and physical method are processed, are produced and be difficult to machine-shaping, have greatly limited its application.
In recent years, surface modification has become traditional material and has been converted into one of most popular method of the novel material with programmable specified property.In numerous surface modifying methods, (atom trnsfer radical polymerization ATRP) can prepare narrow molecular weight distribution polymer, functional end-group polymkeric substance, random and gradient copolymer, segmented copolymer, radial copolymer, grafting and comb shaped polymer, hyperbranched polymer etc. with it to atom transfer radical polymerization; Also can introduce halogenated alkyl hydrocarbon initiator on surface, spherical molecule and macromole surface, then further at its surperficial initiated polymerization, can obtain having the polymer brush of different compositions, the polymerization degree and shape, and have reaction process in polyreaction and control easily, advantage such as equipment is simple and receiving much attention.Existing at present research of using the atom transfer radical polymerization technology to the surface modification of inorganic silica, Mierocrystalline cellulose, jute fibre, chitosan particle, starch particulate, Wang resin, polypeptide and partial synthesis polymkeric substance etc., but do not see the research report of this technology to elastin modification aspect.
Summary of the invention
The objective of the invention is to utilize macromole evocating agent to cause atom transfer radical polymerization (ATRP) polymerization process, hydrophilic polymethyl acrylic acid-beta-hydroxy ethyl ester is incorporated into the elastin surface, be intended to not change under the condition of elastin 26S Proteasome Structure and Function (spring function), synthetic polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance, elastin is carried out surface modification, explore the preparation method and the performance study thereof of elastin sill.
A kind of method of utilizing the atom transition free radical polymerization reaction modifying elastin of the present invention, carry out according to following steps:
(1) elastin under protection of inert gas and anhydrous condition with Organohalogen compounds and triethylamine prepared in reaction macromole atom transition free radical polymerization reaction initiator;
(2) in (1), add methacrylic acid-beta-hydroxy ethyl ester and anhydrous methanol in the macromole atom transition free radical polymerization reaction initiator of preparation under protection of inert gas and anhydrous condition; utilize CuCl/2, the catalyst system of 2-dipyridyl prepares polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance.
Described elastin passes through the dimethyl sulfoxide (DMSO) swelling in advance, and the mass ratio of dimethyl sulfoxide (DMSO) and elastin is 1～50, and swelling time is 10～24h.
Described macromole atom transition free radical polymerization reaction initiator passes through the dimethyl sulfoxide (DMSO) swelling in advance before initiated polymerization, the mass ratio of dimethyl sulfoxide (DMSO) and elastin is 1～50, and swelling time is 10～24h.
Described rare gas element is at least a in nitrogen, helium and the argon gas.
Described Organohalogen compounds are α-bromine isobutyl acylbromide.
The triethylamine in the described step (1) and the mol ratio of Organohalogen compounds are 0.8-1.2, and temperature of reaction is 15～35 ℃, and the reaction times is 12～24h.
The solvent that adopts in the described step (2) is any one in anhydrous methanol, dimethyl sulfoxide (DMSO) and the dimethyl formamide.
The solvent in the described step (2) and the volume ratio of methacrylic acid-beta-hydroxy ethyl ester are 1:1～5:1, macromole atom transition free radical polymerization reaction initiator, cuprous chloride and 2, the mol ratio of 2-dipyridyl is 1～1.5:1～1.5:1～1.5:1, reaction times is 10～96h, and temperature of reaction is 15～50 ℃.
Infrared (FTIR) and x-ray photoelectron power spectrum (XPS), thermogravimetric analysis (TGA), scanning electron microscope (SEM) and dynamic contact angle characterize modifying elastin.The result shows: PHEMA has been keyed on the elastin and (has seen accompanying drawing 2,3a, 3b and 3c); SEM shows after the graft modification that the surface ratio of elastin becomes smooth before unmodified and (sees accompanying drawing 6a-6f), and reduced the thermostability of elastin to a certain extent, initial heat decomposition temperature 307.0 ℃ before by modification become 265 ℃, and maximum weight loss rate temperature drops to 316.76 ℃ (seeing accompanying drawing 4a and 4b) by 347 ℃; Sample had good hydrophilicity after the dynamic contact angle experiment showed graft modification, advancing angle 130.45 ° before by grafting drop to 29.80 ° behind the reaction 72h, improved the wetting ability of elastin, advancing angle drops to 29.80 ° by 130.45 ° of modification proelastin behind the atom transition free radical polymerization reaction 72h, and contact angle hysteresis becomes 29.80 ° (seeing accompanying drawing 5) by 70.42 °.
Behind this method modifying elastin, the hydrophobic performance of elastin be improved significantly, and reduced its thermostability.The elastin modification is the basis of elastin in the bionical study on the synthesis work of biological medical polymer material, and provides theoretical foundation for its further application in medicine sustained release, bioelastomer, organizational project.
Description of drawings
Fig. 1 is the synthetic route chart of ATRP method modifying elastin.
Fig. 2 is the infrared spectrogram of the elastin polymkeric substance of elastin, bromo isobutyl acidylate elastin, polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 3 a is that the x-ray photoelectron of elastin can spectrogram.
Fig. 3 b is that the x-ray photoelectron of bromo isobutyl acidylate elastin can spectrogram.
Fig. 3 c is that the x-ray photoelectron of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified can spectrogram.
Fig. 4 a is the thermogravimetric curve figure of the elastin polymkeric substance of elastin and polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 4 b is the differential thermogravimetric graphic representation of the elastin polymkeric substance of elastin and polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 5 is the graphic representation that the dynamic advancing contact angle of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified changes with polymerization time.
Fig. 6 a is the electron scanning micrograph (100 *) of elastin.
Fig. 6 b is the electron scanning micrograph (1000 *) of elastin.
Fig. 6 c is the electron scanning micrograph (100 *) of bromo isobutyl acidylate elastin.
Fig. 6 d is the electron scanning micrograph (1000 *) of bromo isobutyl acidylate elastin.
Fig. 6 e is the electron scanning micrograph (100 *) of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 6 f is the electron scanning micrograph (1000 *) of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Embodiment
Further specify technical scheme of the present invention below in conjunction with embodiment
Example 1
(1) the 2g elastin is under nitrogen protection; the triethylamine and the alpha-brominated isobutyl acylbromide of 2.4g that add 0.8gg react 12h down at 20 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) under nitrogen protection, add 12mL methacrylic acid-beta-hydroxy ethyl ester and 60mL anhydrous methanol; add 0.09gCuCl, 0.21g 2 then successively; 2-dipyridyl and 1.5g bromo isobutyl acidylate elastin; 20 ℃ are reacted 15h down; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Example 2
(1) the 4g elastin is under the helium protection; the triethylamine and the alpha-brominated isobutyl acylbromide of 54g that add 20g react 16h down at 35 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) under the helium protection, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 100mL dimethyl sulfoxide (DMSO); add 1gCuCl, 2g 2 then successively; 2-dipyridyl and 3g bromo isobutyl acidylate elastin; 40 ℃ are reacted 25h down; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Example 3
(1) the 5g elastin is under argon shield; the triethylamine and the alpha-brominated isobutyl acylbromide of 68.15g that add 30g react 20h down at 30 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) under argon shield, add 100mL methacrylic acid-beta-hydroxy ethyl ester and 100mL dimethyl formamide; add 0.95g CuCl, 1.5g 2 then successively; 2-dipyridyl and 2.5g bromo isobutyl acidylate elastin; 50 ℃ are reacted 70h down; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 4
(1) the 5g elastin is under argon shield; the triethylamine and the alpha-brominated isobutyl acylbromide of 68.15g that add 30g react 12h down at 30 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) under argon shield, add 100mL methacrylic acid-beta-hydroxy ethyl ester and 300mL anhydrous methanol; add 0.95gCuCl, 1.5g 2 then successively; 2-dipyridyl and 2.5g bromo isobutyl acidylate elastin; 50 ℃ are reacted 96h down; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Example 5
(1) 4g elastin and 4g dimethyl sulfoxide (DMSO) are mixed; swelling 10h; then under the helium protection; the alpha-brominated isobutyl acylbromide of triethylamine, 54g and the elastin after the swelling that add 20g react 24h down at 15 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) 3g macromole atom transition free radical polymerization reaction initiator and 150g dimethyl sulfoxide (DMSO) are mixed; swelling 24h; under the helium protection, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 100mL dimethyl sulfoxide (DMSO) then; add 0.96gCuCl, 1.45g 2 then successively; bromo isobutyl acidylate elastin after 2-dipyridyl and the 2.5g swelling; 45 ℃ are reacted 90h down, and product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 6
(1) 4g elastin and 40g dimethyl sulfoxide (DMSO) are mixed; swelling 20h; then under the helium protection; the alpha-brominated isobutyl acylbromide of triethylamine, 54g and the elastin after the swelling that add 28.52g react 20h down at 25 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) 3g macromole atom transition free radical polymerization reaction initiator and 30g dimethyl sulfoxide (DMSO) are mixed; swelling 10h; under the helium protection, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 100mL dimethyl sulfoxide (DMSO) then; add 0.98gCuCl, 1.4g 2 then successively; bromo isobutyl acidylate elastin after 2-dipyridyl and the 2.6g swelling; 50 ℃ are reacted 80h down, and product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 7
(1) 4g elastin and 80g dimethyl sulfoxide (DMSO) are mixed; swelling 15h; then under nitrogen protection; the alpha-brominated isobutyl acylbromide of triethylamine, 54g and the elastin after the swelling that add 22g react 20h down at 20 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) 3g macromole atom transition free radical polymerization reaction initiator and 120g dimethyl sulfoxide (DMSO) are mixed; swelling 20h; under nitrogen protection, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 100mL dimethyl sulfoxide (DMSO) then; add 1g CuCl, 2g2 then successively; bromo isobutyl acidylate elastin after 2-dipyridyl and the 3g swelling; 30 ℃ are reacted 96h down, and product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 8
(1) 4g elastin and 160g dimethyl sulfoxide (DMSO) are mixed; swelling 12h; then under the helium protection; the alpha-brominated isobutyl acylbromide of triethylamine, 54g and the elastin after the swelling that add 25g react 24h down at 35 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) 3g macromole atom transition free radical polymerization reaction initiator and 30g dimethyl sulfoxide (DMSO) are mixed; swelling 24h; under the helium protection, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 150mL dimethyl sulfoxide (DMSO) then; add 1g CuCl, 2g 2 then successively; bromo isobutyl acidylate elastin after 2-dipyridyl and the 3g swelling; 50 ℃ are reacted 10h down, and product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 9
(1) 4g elastin and 4g dimethyl sulfoxide (DMSO) are mixed; swelling 10h; then under argon shield; the alpha-brominated isobutyl acylbromide of triethylamine, 54g and the elastin after the swelling that add 20g react 24h down at 20 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) 3g macromole atom transition free radical polymerization reaction initiator and 150g dimethyl sulfoxide (DMSO) are mixed; swelling 24h; under argon shield, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 200mL dimethyl sulfoxide (DMSO) then; add 1g CuCl, 2g 2 then successively; bromo isobutyl acidylate elastin after 2-dipyridyl and the 3g swelling; 15 ℃ are reacted 30h down, and product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
(1) 4g elastin and 4g dimethyl sulfoxide (DMSO) are mixed; swelling 10h; then under the helium protection; the alpha-brominated isobutyl acylbromide of triethylamine, 54g and the elastin after the swelling that add 19g react 24h down at 35 ℃; product obtains macromole atom transition free radical polymerization reaction initiator bromo isobutyl acidylate elastin through thorough washing and drying.
(2) 3g macromole atom transition free radical polymerization reaction initiator and 15g dimethyl sulfoxide (DMSO) are mixed; swelling 24h; under the helium protection, add 50mL methacrylic acid-beta-hydroxy ethyl ester and 250mL dimethyl sulfoxide (DMSO) then; add 1.05gCuCl, 1.5g 2 then successively; bromo isobutyl acidylate elastin after 2-dipyridyl and the 2.5g swelling; 45 ℃ are reacted 85h down, and product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Claims (5)
1. a method of utilizing the atom transition free radical polymerization reaction modifying elastin is characterized in that, carries out according to following steps:
(1) elastin under protection of inert gas and anhydrous condition with Organohalogen compounds and triethylamine prepared in reaction macromole atom transition free radical polymerization reaction initiator, the mol ratio of described triethylamine and Organohalogen compounds is 0.8～1.2, temperature of reaction is 15～35 ℃, reaction times is 12～24h, and described Organohalogen compounds are α-bromine isobutyl acylbromide;
(2) in (1), add methacrylic acid-beta-hydroxy ethyl ester and solvent in the macromole atom transition free radical polymerization reaction initiator of preparation under protection of inert gas and anhydrous condition; utilization is by CuCl and 2; the catalyst system that the 2-dipyridyl is formed prepares polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance; the volume ratio of described solvent and methacrylic acid-beta-hydroxy ethyl ester is 1:1～5:1; macromole atom transition free radical polymerization reaction initiator; cuprous chloride and 2; the mol ratio of 2-dipyridyl is 1～1.5:1～1.5:1～1.5; reaction times is 10～96h, and temperature of reaction is 15～50 ℃.
2. a kind of method of utilizing the atom transition free radical polymerization reaction modifying elastin according to claim 1, it is characterized in that, described elastin passes through the dimethyl sulfoxide (DMSO) swelling in advance, and the mass ratio of dimethyl sulfoxide (DMSO) and elastin is 1～50, and swelling time is 10～24h.
3. a kind of method of utilizing the atom transition free radical polymerization reaction modifying elastin according to claim 1, it is characterized in that, described macromole atom transition free radical polymerization reaction initiator is before initiated polymerization, pass through the dimethyl sulfoxide (DMSO) swelling in advance, the mass ratio of dimethyl sulfoxide (DMSO) and elastin is 1～50, and swelling time is 10～24h.
4. a kind of method of utilizing the atom transition free radical polymerization reaction modifying elastin according to claim 1 is characterized in that, described rare gas element is at least a in nitrogen, helium and the argon gas.
5. a kind of method of utilizing the atom transition free radical polymerization reaction modifying elastin according to claim 1 is characterized in that, the solvent that adopts in the described step (2) is any one in anhydrous methanol, dimethyl sulfoxide (DMSO) and the dimethyl formamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100565083A CN100532394C (en) | 2007-01-23 | 2007-01-23 | Method of modifying elastin by atom transition free radical polymerization reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100565083A CN100532394C (en) | 2007-01-23 | 2007-01-23 | Method of modifying elastin by atom transition free radical polymerization reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016335A CN101016335A (en) | 2007-08-15 |
| CN100532394C true CN100532394C (en) | 2009-08-26 |
Family
ID=38725575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100565083A Expired - Fee Related CN100532394C (en) | 2007-01-23 | 2007-01-23 | Method of modifying elastin by atom transition free radical polymerization reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100532394C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186718B (en) * | 2007-11-22 | 2010-07-14 | 天津大学 | Method for modifying elastin by utilizing layer assembling technique and product thereof |
| CN109971269B (en) * | 2019-04-08 | 2020-11-06 | 沈阳顺风新材料有限公司 | Environment-friendly hydrophobic coating |
-
2007
- 2007-01-23 CN CNB2007100565083A patent/CN100532394C/en not_active Expired - Fee Related
Non-Patent Citations (9)
| Title |
|---|
| Cysteine-Reactive Polymers Synthesized by Atom Transfer Radical Polymerization for Conjugation to Proteins. Debora Bontempo,Karina L. Heredia, Benjamin A. Fish and Heather D. Maynard.Journal of American Chemistry Society,Vol.126 No.47. 2004 |
| Cysteine-Reactive Polymers Synthesized by Atom Transfer Radical Polymerization for Conjugation to Proteins. Debora Bontempo,Karina L. Heredia, Benjamin A. Fish and Heather D. Maynard.Journal of American Chemistry Society,Vol.126 No.47. 2004 * |
| In Situ Preparation of Protein-"Smart" Polymer Conjugateswith Retention of Bioactivity. Karina L. Heredia et.al.Jorunal of American Chemical Society,Vol.127 No.48. 2005 |
| In Situ Preparation of Protein-"Smart" Polymer Conjugateswith Retention of Bioactivity. Karina L. Heredia et.al.Jorunal of American Chemical Society,Vol.127 No.48. 2005 * |
| Solid-Phase ATRP Synthesis of Peptide-Polymer Hybrids. Ying Mei et.al.Journal of American Chemical Society,Vol.126 No.11. 2004 |
| Solid-Phase ATRP Synthesis of Peptide-Polymer Hybrids. Ying Mei et.al.Journal of American Chemical Society,Vol.126 No.11. 2004 * |
| Streptavidin as a Macroinitiator for PolymerizationL In SituProtein-Polymer Conjugate Formation. Debora Bontempo and Heather D. Maynard.Journal of American Chemistry Society,Vol.127 No.18. 2005 |
| Synthesis of protein-polymer conjugates. Karina L. Heredia and Heather D. Maynard.Organic & Biomolecular Chemistry,Vol.5 No.1. 2007 |
| Synthesis of Uniform Protein-Polymer Conjugates. Bhalchandra S. Lele, Hironobu Murata, KrzysztofMatyjaszewski and Alan J. Russell.Biomacromolecules,Vol.6 No.6. 2005 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101016335A (en) | 2007-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Thakur et al. | Synthesis, swelling and adsorption studies of a pH-responsive sodium alginate–poly (acrylic acid) superabsorbent hydrogel | |
| CN101230539B (en) | Method for preparing functional real silk | |
| Li et al. | Synthesis and properties of clay-based superabsorbent composite | |
| Gürdağ et al. | Cellulose graft copolymers: synthesis, properties, and applications | |
| Oktay et al. | Immobilization of α-amylase onto poly (glycidyl methacrylate) grafted electrospun fibers by ATRP | |
| CN106928413A (en) | A kind of method of styrene maleic anhydride copolymer graft modification Graphene | |
| Rodrigues et al. | Chitosan-graft-poly (acrylic acid)/rice husk ash based superabsorbent hydrogel composite: preparation and characterization | |
| CN110092921B (en) | Preparation method of high-strength lignin hydrogel with adjustable mechanical properties | |
| CN101492520A (en) | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof | |
| CN103408683A (en) | Preparation method of physical/chemical crosslinking photo-thermal response hydrogel | |
| CN100532394C (en) | Method of modifying elastin by atom transition free radical polymerization reaction | |
| Soliman et al. | Preparation of carboxymethyl cellulose-g-poly (acrylic acid-2-acrylamido-2-methylpropane sulfonic acid)/attapulgite superabsorbent composite | |
| CN100532393C (en) | Method of modifying elastin by initiation transition termination agent | |
| Li et al. | Enhanced mechanical performance of xylan-based composite hydrogel via chain extension and semi-interpenetrating networks | |
| CN101623613A (en) | Preparation method of amino polyphosphazene microspheres | |
| CN101880425B (en) | Method for preparing green natural flax fiber reinforced polypropylene resin-based composite material | |
| Hao et al. | Synthesis and property of superabsorbent polymer based on cellulose grafted 2-acrylamido-2-methyl-1-propanesulfonic acid | |
| Feng et al. | Facile and rapid synthesis of flexible PEG porous polymers as substrates for functional materials by thiol-ene click chemistry | |
| Assem et al. | Synthesis of acrylate-modified cellulose via raft polymerization and its application as efficient metal ions adsorbent | |
| KR100992557B1 (en) | Preparation Method of Ion Selective Fibrous Nano-form using Hyperbranched Polystyrene with Reactive Acrylic Resin | |
| CN105294934B (en) | A kind of high intensity anti-bacterial hydrogel and preparation method thereof | |
| Akgün et al. | Synthesis and properties of chitosan-modified poly (vinyl butyrate) | |
| Kalaleh et al. | Preparation of poly (sodium acrylate-co-acrylamide) superabsorbent copolymer via alkaline hydrolysis of acrylamide using microwave irradiation | |
| CN114456318B (en) | Chitosan-bentonite-acrylic acid water-absorbent resin and preparation method thereof | |
| Volynets et al. | Preparation and characterization of poly (2-hydroxyethyl methacrylate) grafted bacterial cellulose using atom transfer radical polymerization |
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: 20090826 Termination date: 20100223 |