CN105440297A - High-impact chitin composite gel preparation method - Google Patents
High-impact chitin composite gel preparation method Download PDFInfo
- Publication number
- CN105440297A CN105440297A CN201510188570.2A CN201510188570A CN105440297A CN 105440297 A CN105440297 A CN 105440297A CN 201510188570 A CN201510188570 A CN 201510188570A CN 105440297 A CN105440297 A CN 105440297A
- Authority
- CN
- China
- Prior art keywords
- chitin
- gel
- impact
- preparation
- aqueous solution
- 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
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to a high-impact chitin composite gel preparation method. The composite gel preparation method comprises: dissolving preprecessed biomass materials such as shrimp shell, dried small shrimps, crab shell, and the like into a solvent, forming gel after crosslinking, and introducing polyethylene glycol and needles nano calcium carbonate in situ in the synthesis process. The gel disclosed by the present invention is stable in a form, has excellent impact resistance and biocompatibility, and can be widely used in the field of biological tissue engineering.
Description
Technical field
The invention belongs to the preparation method of biomass gel, particularly relate to a kind of preparation method with the biomass gel of excellent impact resistibility.
Background technology
High-molecular gel refers to the macromolecular compound of three-dimensional net structure and the system of solvent composition, polymer wherein with Van der Waals force, chemical bond force, physical entanglement power, the connections such as hydrogen bond force.Because it is a kind of three-dimensional network three-dimensional arrangement, therefore it by dissolution with solvents, can not disperse in a solvent simultaneously and can keep certain shape.Although solvent can not by the macromolecule dissolution of tridimensional network, in macromolecular compound, solvophilic radical moiety can be made polymer swelling by solvent action, and this is also the reason forming high-molecular gel.
Shear thickening refers to that the viscosity occurred when the shear-stress (strain) suffered by material increases time increases, " solidification " behavior that material changes software strategy into software-hardware strategy.Shearing retrogradation phenomenon is found in particle suspension system the earliest, and as mud, starch dispersion liquid etc., system comprises dispersion medium if viscous liquid and dispersion are as micro-nano particle, has all found shear thickening phenomenon in present solid composite material and gelatinous material.Over nearly 20 years, shear thickening phenomenon is by extensive concern, and existing multiple dispersed particle and dispersion medium collocation thereof constitute the suspension with shear thickening phenomenon, and typical particle comprises inorganic particulate as SiO
2, CaCO
3, Fe
2o
3, glass fibre etc., organic filler such as starch, compound particle comprise polymethylmethacrylate (PMMA) microballoon, polystyrene (PS) microballoon, polystyrene graft vinylformic acid (PS-g-AA) microballoon, polydimethyl propionic acid amide-vinylformic acid (P(DMAA-AA)) microballoon etc., dispersion medium comprises water, polyoxyethylene glycol, glycerine, different chain length aliphatic hydrocarbon etc.When particulate in suspension system reaches certain volume mark, there is shear thickening phenomenon immediately.
At present, shear thickening phenomenon is general only to be realized in suspension, realizes the then very rare of this phenomenon in gel.Biomass gel has excellent potentiality because the biocompatibility of its excellence has application in biological medicine, especially can in plant human body as tissue engineering material.But at present still to have strength ratio lower for biomass gel, easily breaks in vivo, thus significantly limit its application in organizational project.As shear thickening behavior introduced in biomass gel, can available protecting when there is deformation, the application of biomass gel in tissue engineering material will be improved greatly undoubtedly.
Summary of the invention
The object of the invention is the preparation method in order to provide a kind of biomass water gel, a kind of preparation method with the biomass gel of excellent impact resistibility is especially provided.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for high-impact chitin plural gel, its process is:
(1): biological material will be reclaimed and to remove after impurity by Mechanical Crushing to 200-400 order, rear employing steam explosion process, thick chitin is obtained;
(2): thick chitin to be positioned over quality be the concentration of its 100%-150% is soak 3-5 hour under 40-60 ° of C in the hydrochloric acid of 10-20wt% and oxalic acid mixed acid aqueous solution, wherein the mass ratio of hydrochloric acid and oxalic acid is 4:1, neutralize and dewater after chitin thick after process is taken out, dry, obtain refining chitin, for subsequent use;
(3): after certain mass being refined chitin input 8wt%NaOH/4w% urea/88w% aqueous solution, stir 5-10 minute, after being refrigerated to-20 ° of C to-30 ° of C, be incubated 4 hours, stir to 20 ° of C and thaw, repeat this freeze-thaw process 3-4 time, obtain transparent chitin water soluble liquid, wherein the massfraction of refining chitin is between 1-2.5%;
(4): in chitin water soluble liquid obtained in (3), add a certain amount of epoxy chloropropane (ECH) and a certain amount of needle-like nano calcium carbonate and polyoxyethylene glycol, under 60 ° of C, ultrasonic vibration is after 5 minutes, react 0.5-1.5 hour under being positioned over 60 ° of C, obtain gel;
(5): by gel repeatedly with water rinse, to remove unreacted monomer in gel, after gel is placed 1-3 hour in 90 ° of C, obtain final gel product;
Wherein, the add-on of epoxy chloropropane is 0.1-0.2ml/g chitin, the consumption of needle-like nano calcium carbonate is between the 35%-49% of its volume volume of water in (3) middle aqueous solution, the 13-24% adding quality quality in (3) middle aqueous solution of polyoxyethylene glycol.
Further, described recovery biomass material is shrimp shell, crab shell.The content of its chitin is more than 95%.
Further, described steam explosion pressure is between 8-16Mpa, and the residence time is between 10-15s.
Further, the length of described needle-like nano calcium carbonate is between 50-500nm, and length-to-diameter ratio is between 5:1-8:1.The introducing of needle-like nano calcium carbonate can produce obvious shear thickening effect in Aqueous Solutions of Polyethylene Glycol, namely when meeting with impact, because the interphase interaction of particle is assembled, and realizes impact resistant.Acicular particles can produce the impact resistant better compared with spherical particle.
Further, the relative molecular mass of described polyoxyethylene glycol is between 12000-30000.This polyoxyethylene glycol is water insoluble at low temperatures, dissolves after being added to 90 ° of C.
Beneficial effect of the present invention is: introduce cheap in the dissolving of chitin and gel polymerization process situ, the nano-calcium carbonate of abundance, introduce polyoxyethylene glycol to improve the microenvironment viscosity in gel simultaneously, thus in chitin hydrogel, realize shear thickening effect.
Accompanying drawing explanation
Fig. 1 is the relation schematic diagram of hydrogel 20 degree time between shearing rate and viscosity of preparation in embodiment 1.
Fig. 2 is the relation schematic diagram of hydrogel 20 degree time between shearing rate and viscosity of preparation in embodiment 2.
Embodiment
Below in conjunction with the embodiment of specific embodiment form, foregoing of the present invention is further elaborated again, but should not be construed as following each embodiment is restriction to scope involved by the above-mentioned theme of the present invention, and all technology realized based on foregoing of the present invention all belong to the scope of the invention.
Embodiment 1
A preparation method for high-impact chitin plural gel, its process is:
(1) will reclaim biological material to remove after impurity by Mechanical Crushing to 200-400 order, the process of rear employing steam explosion, obtains thick chitin;
(2) thick chitin is positioned over quality for its 120% concentration be soak 4 hours under 50 ° of C in 15wt% hydrochloric acid and oxalic acid mixed acid aqueous solution, wherein the mass ratio of hydrochloric acid and oxalic acid is 4:1, and rear neutralization is also dewatered, and drying, obtains refining chitin, for subsequent use;
(3) after the refining chitin after certain mass process being dropped into 8wt%NaOH/4w% urea/88w% aqueous solution, stir 8 minutes, after being refrigerated to-25 ° of C, be incubated 4 hours, stir to 20 ° of C and thaw, repeat this freeze-thaw process 3 times, obtain transparent chitin water soluble liquid, wherein the massfraction of refining chitin is 2%;
(4) a certain amount of epoxy chloropropane (ECH) and a certain amount of needle-like nano calcium carbonate and polyoxyethylene glycol is added in obtained in (3) chitin water soluble liquid, in 60 degree of lower ultrasonic vibration after 5 minutes, react 1 hour under being positioned over 60 ° of C, obtain gel;
(5) by gel repeatedly with water rinse, to remove unreacted monomer in gel, after gel is placed 2 hours in 90 ° of C, obtain final gel product.
Wherein, the add-on of epoxy chloropropane is 0.15ml/g chitin, the consumption of needle-like nano calcium carbonate for its volume be in (3) in aqueous solution volume of water 45%, the add-on of polyoxyethylene glycol be 18% of quality in (3) middle aqueous solution.
Described recovery biomass material is shrimp shell.
Described steam explosion pressure is 12Mpa, and the residence time is 12s.
The length of described needle-like nano calcium carbonate is between 50-500nm, and length-to-diameter ratio is between 6:1-7:1.
The relative molecular mass of described polyoxyethylene glycol is between 15000-20000.
Embodiment 2
A preparation method for high-impact chitin plural gel, its process is:
(1) will reclaim biological material to remove after impurity by Mechanical Crushing to 200-400 order, the process of rear employing steam explosion, obtains thick chitin;
(2) thick chitin is positioned over quality for its 130% concentration be soak 4 hours under 50 ° of C in 18wt% hydrochloric acid and oxalic acid mixed acid aqueous solution, wherein the mass ratio of hydrochloric acid and oxalic acid is 4:1, and rear neutralization is also dewatered, and drying, obtains refining chitin, for subsequent use;
(3) after the refining chitin after certain mass process being dropped into 8wt%NaOH-4w% urea/88w% aqueous solution, stir 8 minutes, after being refrigerated to-27 ° of C, be incubated 4 hours, stir to 20 ° of C and thaw, repeat this freeze-thaw process 4 times, obtain transparent chitin water soluble liquid, wherein the massfraction of chitin is 1.8%;
(4) a certain amount of epoxy chloropropane (ECH) and a certain amount of needle-like nano calcium carbonate and polyoxyethylene glycol is added in obtained in (3) chitin water soluble liquid, in 60 degree of lower ultrasonic vibration after 5 minutes, react 1 hour under being positioned over 60 ° of C, obtain gel;
(5) by gel repeatedly with water rinse, to remove unreacted monomer in gel, after gel is placed 2 hours in 90 ° of C, obtain final gel product.
Wherein, the add-on of epoxy chloropropane is 0.18ml/g chitin, the consumption of needle-like nano calcium carbonate for its volume be in (3) in aqueous solution volume of water 47%, the add-on of polyoxyethylene glycol be 20% of quality in (3) middle aqueous solution.
Described recovery biomass material is crab shell.
Described steam explosion pressure is 15Mpa, and the residence time is 10s.
The length of described needle-like nano calcium carbonate is between 50-500nm, and length-to-diameter ratio is between 5:1-7:1.
The relative molecular mass of described polyoxyethylene glycol is between 15000-25000.
Claims (4)
1. a preparation method for high-impact chitin plural gel, its process is:
(1): biological material will be reclaimed and to remove after impurity by Mechanical Crushing to 200-400 order, rear employing steam explosion process, thick chitin is obtained;
(2): thick chitin to be positioned over quality be the concentration of its 100%-150% is soak 3-5 hour under 40-60 ° of C in the hydrochloric acid of 10-20wt% and oxalic acid mixed acid aqueous solution, wherein the mass ratio of hydrochloric acid and oxalic acid is 4:1, neutralize and dewater after chitin thick after process is taken out, dry, obtain refining chitin, for subsequent use;
(3): after certain mass being refined chitin input 8wt%NaOH/4w% urea/88w% aqueous solution, stir 5-10 minute, after being refrigerated to-20 ° of C to-30 ° of C, be incubated 4 hours, stir to 20 ° of C and thaw, repeat this freeze-thaw process 3-4 time, obtain transparent chitin water soluble liquid, wherein the massfraction of refining chitin is between 1-2.5%;
(4): in chitin water soluble liquid obtained in (3), add a certain amount of epoxy chloropropane (ECH) and a certain amount of needle-like nano calcium carbonate and polyoxyethylene glycol, under 60 ° of C, ultrasonic vibration is after 5 minutes, react 0.5-1.5 hour under being positioned over 60 ° of C, obtain gel;
(5): by gel repeatedly with water rinse, to remove unreacted monomer in gel, after gel is placed 1-3 hour in 90 ° of C, obtain final gel product;
Wherein, the add-on of epoxy chloropropane is 0.1-0.2ml/g chitin, the consumption of needle-like nano calcium carbonate is between the 35%-49% of its volume volume of water in (3) middle aqueous solution, the 13-24% adding quality quality in (3) middle aqueous solution of polyoxyethylene glycol.
2. the preparation method of a kind of high-impact chitin plural gel according to claim 1, is characterized in that: described recovery biomass material is shrimp shell, crab shell.
3. the preparation method of a kind of high-impact chitin plural gel according to claim 1, is characterized in that: the length of described needle-like nano calcium carbonate is between 50-500nm, and length-to-diameter ratio is between 5:1-8:1.
4. the preparation method of a kind of high-impact chitin plural gel according to claim 1, is characterized in that: the relative molecular mass of described polyoxyethylene glycol is between 12000-30000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510188570.2A CN105440297B (en) | 2015-04-21 | 2015-04-21 | A kind of preparation method of high-impact chitin plural gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510188570.2A CN105440297B (en) | 2015-04-21 | 2015-04-21 | A kind of preparation method of high-impact chitin plural gel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105440297A true CN105440297A (en) | 2016-03-30 |
| CN105440297B CN105440297B (en) | 2018-01-23 |
Family
ID=55550968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510188570.2A Expired - Fee Related CN105440297B (en) | 2015-04-21 | 2015-04-21 | A kind of preparation method of high-impact chitin plural gel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105440297B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134703A (en) * | 2018-08-01 | 2019-01-04 | 农业部规划设计研究院 | A kind of method that shrimp and crab shells waste cleans comprehensive utilization |
| CN110655675A (en) * | 2019-07-08 | 2020-01-07 | 广西民族大学 | In-situ doped nano calcium carbonate chitin hydrogel as well as preparation method and application thereof |
| JP2021095551A (en) * | 2019-12-18 | 2021-06-24 | 國立台湾海洋大學Ｎａｔｉｏｎａｌ Ｔａｉｗａｎ Ｏｃｅａｎ Ｕｎｉｖｅｒｓｉｔｙ | Chitin aqueous solution, and method for acquiring the chitin aqueous solution |
| CN113307989A (en) * | 2021-06-07 | 2021-08-27 | 中山大学 | Preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895684A (en) * | 2006-06-30 | 2007-01-17 | 清华大学 | Preparation of natural-nanometer fiber-base tissue engineering cell stand |
| CN101857684A (en) * | 2010-06-10 | 2010-10-13 | 武汉大学 | Chitin hydrogel and preparation method and application thereof |
| CN103520767A (en) * | 2013-10-28 | 2014-01-22 | 山东赛克赛斯药业科技有限公司 | Anti-microbial healing-promoting hydrogel dressing and preparation method therefor |
| CN103834069A (en) * | 2014-02-21 | 2014-06-04 | 武汉大学 | Preparation method of nano-silver-containing magnetic chitin microspheres |
-
2015
- 2015-04-21 CN CN201510188570.2A patent/CN105440297B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895684A (en) * | 2006-06-30 | 2007-01-17 | 清华大学 | Preparation of natural-nanometer fiber-base tissue engineering cell stand |
| CN101857684A (en) * | 2010-06-10 | 2010-10-13 | 武汉大学 | Chitin hydrogel and preparation method and application thereof |
| CN103520767A (en) * | 2013-10-28 | 2014-01-22 | 山东赛克赛斯药业科技有限公司 | Anti-microbial healing-promoting hydrogel dressing and preparation method therefor |
| CN103834069A (en) * | 2014-02-21 | 2014-06-04 | 武汉大学 | Preparation method of nano-silver-containing magnetic chitin microspheres |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134703A (en) * | 2018-08-01 | 2019-01-04 | 农业部规划设计研究院 | A kind of method that shrimp and crab shells waste cleans comprehensive utilization |
| CN110655675A (en) * | 2019-07-08 | 2020-01-07 | 广西民族大学 | In-situ doped nano calcium carbonate chitin hydrogel as well as preparation method and application thereof |
| CN110655675B (en) * | 2019-07-08 | 2022-05-03 | 广西民族大学 | In-situ doped nano calcium carbonate chitin hydrogel as well as preparation method and application thereof |
| JP2021095551A (en) * | 2019-12-18 | 2021-06-24 | 國立台湾海洋大學Ｎａｔｉｏｎａｌ Ｔａｉｗａｎ Ｏｃｅａｎ Ｕｎｉｖｅｒｓｉｔｙ | Chitin aqueous solution, and method for acquiring the chitin aqueous solution |
| CN113307989A (en) * | 2021-06-07 | 2021-08-27 | 中山大学 | Preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material |
| CN113307989B (en) * | 2021-06-07 | 2022-07-29 | 中山大学 | Preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105440297B (en) | 2018-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nascimento et al. | Nanocellulose nanocomposite hydrogels: technological and environmental issues | |
| Pu et al. | A comprehensive review of polysaccharide biopolymers for enhanced oil recovery (EOR) from flask to field | |
| Noremylia et al. | Recent advancement in isolation, processing, characterization and applications of emerging nanocellulose: A review | |
| Li et al. | pH-responsive water-based drilling fluids containing bentonite and chitin nanocrystals | |
| Qureshi et al. | Polysaccharide based superabsorbent hydrogels and their methods of synthesis: A review | |
| Roman et al. | Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose | |
| Chiellini et al. | Ulvan: A versatile platform of biomaterials from renewable resources | |
| Barikani et al. | Preparation and application of chitin and its derivatives: a review | |
| Donati et al. | Material properties of alginates | |
| Kabir et al. | Alginate/polymer-based materials for fire retardancy: Synthesis, structure, properties, and applications | |
| Quong et al. | DNA protection from extracapsular nucleases, within chitosan‐or poly‐L‐lysine‐coated alginate beads | |
| CN105440297A (en) | High-impact chitin composite gel preparation method | |
| Jiang et al. | Preparation and characterization of hybrid double network chitosan/poly (acrylic amide-acrylic acid) high toughness hydrogel through Al3+ crosslinking | |
| CN101445609B (en) | Hydroscopic cellulose hydrogel and preparation method thereof | |
| Wang et al. | Effects of cellulose nanofibrils on dialdehyde carboxymethyl cellulose based dual responsive self-healing hydrogel | |
| CN104387597A (en) | Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof | |
| Gou et al. | Novel biodegradable graft-modified water-soluble copolymer using acrylamide and konjac glucomannan for enhanced oil recovery | |
| CN101857684A (en) | Chitin hydrogel and preparation method and application thereof | |
| CN103396570A (en) | Chitin nano-fiber/polyaniline composite film preparation method | |
| CN102876312A (en) | Acrylamide graft copolymer oil-displacing agent and preparation method thereof | |
| CN104624130A (en) | Method for preparing regenerated chitin microspheres | |
| Zhang et al. | Preparation and characterization of tamarind gum/sodium alginate composite gel beads | |
| Wei et al. | Nanocellulose-Strengthened Particle Gel for Conformance Control in Fractured Tight Formations. Part I: Preparation and Mechanical Stability | |
| Xu et al. | Hemicellulose-based hydrogels for advanced applications | |
| Im et al. | Effects of malonic acid crosslinked starch for soil strength improvement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180123 Termination date: 20180421 |