CN105088414A - Preparation method of chitobiose derivative crosslinking fibers - Google Patents
Preparation method of chitobiose derivative crosslinking fibers Download PDFInfo
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- CN105088414A CN105088414A CN201510534301.7A CN201510534301A CN105088414A CN 105088414 A CN105088414 A CN 105088414A CN 201510534301 A CN201510534301 A CN 201510534301A CN 105088414 A CN105088414 A CN 105088414A
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Abstract
The invention discloses a preparation method of chitobiose derivative crosslinking fibers. The preparation method of the chitobiose derivative crosslinking fibers comprises the following steps of performing grafting modification on chitobiose through ring-opening reaction to obtain chitobiose derivative with polymerization reaction activity; adding photoinitiator to perform miscibility and then performing low-temperature freezing crystallization; performing irradiance crosslinking polymerization at low temperature; and removing a solvent by freeze drying to obtain a chitobiose derivative crosslinking fiber material. By the preparation method, the chitobiose derivative crosslinking fiber material with high mechanical property and mechanical strength is obtained. In a preparation process, a reagent for changing characteristics of chitobiose is not added, original excellent properties of the chitobiose serving as natural polymers are not changed, and the crosslinking chitobiose derivative fiber material can be widely used for various fields of medicine release systems, wound healing materials, sewage treatment, heavy metal recycling, membrane separation, daily-use chemical industry and the like.
Description
Technical field
The present invention relates to natural polyelectrolyte fibrous material field, particularly relate to a kind of method being prepared chitosan derivatives cross filament by photopolymerization reaction.
Background technology
Shitosan (chitosan), also known as chitosan, is that the chitin (chitin) extensively existed by nature obtains through deacetylation, and chemical name is Chitosan (1-4)-2-amino-B-D glucose.From 1859, after first Frenchman Rouget obtains shitosan, the premium properties such as the biological functionality of this natural polymer and compatibility, blood compatibility, security, microbic resolvability, by all trades and professions extensive concern, achieve major progress in the application study of the numerous areas such as medicine, food, chemical industry, cosmetics, water treatment, METAL EXTRACTION and recovery, biochemistry and biomedical engineering.For patient, shitosan reducing blood lipid, hypoglycemic effect have research report.Meanwhile, shitosan is listed in state food additive use standard GB-2760 by as thickener, fruit glaze agent.
The method preparing fiber at present mainly contains super super drawing melt spinning process, sea-island-type composite spun method, matrix polymerization method, method of electrostatic spinning and being separated.Super super drawing melt spinning process is that polymer prepares long filament type superfine fibre through super super drawing, although the method cost is lower, but only have the polymeric material that can bear tremendous strains likely could be prepared into nanofiber, and the method is prepared in the process of superfine fibre and is easily produced lousiness.Sea-island-type composite spun method is the method adopting blend melt spinning, and two kinds of immiscible polymer are prepared blended fiber by twin-screw extrusion to the distribution plate of particular design and spinnerets.Matrix polymerization method prepares the method for nanofiber or hollow Nano fiber in use, the method polymerizing condition is easy to control, polymerization influence factor is few, the nano-scale polymer product of various structure can be obtained, reacted rear pattern plate easily to remove, major defect is exactly very consuming time.Method of electrostatic spinning is a kind of a kind of method that ratio is easier to the nanofiber preparing the various pattern of continuous print, and the diameter of prepared fiber is less than 100nm, and length can reach a few km, and its shortcoming is difficult to carry out large-scale production.Phase separation method is the process that dissolving, gelation, extraction, condensation and drying obtain nanoporous foam, and the polyalcohol stephanoporate nanofiber diameter obtained is between 300 ~ 900nm, and aperture is 1 ~ 120nm.Its shortcoming needs cost long time to make polymer conversion be nanoporous foam.
Chitosan derivatives become the gas permeability after tunica fibrosa, moisture retention and anti-ageing, crease-resistant, beauty treatment, health-care function, to skin have no stimulation be current synthetic material incomparable.The present invention carries out suitable modification by chemical means to shitosan, make it have photopolymerizable reactive, then the miscible rear cryogenic freezing crystallization of light trigger is added, and carry out illumination cross-linked polymeric at low temperatures, removing desolventizing by freeze drying, obtain the chitosan derivatives cross filament material with excellent mechanical performances and mechanical strength.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of chitosan derivatives cross filament, rapidly and efficiently, experimental facilities is simple for preparation process, and course of reaction is easy to operation, and the tunica fibrosa of preparation has good gas permeability and moisture retention.
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for chitosan derivatives cross filament, comprises the following steps:
(1) shitosan and methyl propenoic acid glycidyl ether are obtained the chitosan derivatives with light reaction by ring-opening reaction;
(2) chitosan derivatives and light trigger with light reaction are dissolved in solvent, cryogenic freezing, UV Light under freezing state, freeze drying is except desolventizing, obtain chitosan derivatives cross filament, the mass ratio of the described chitosan derivatives and solvent with light reaction is 1:100-2000, and described light trigger is 0.001-0.1:1 with the mass ratio of the chitosan derivatives with light reaction.
As preferably, described in there is light reaction the mass ratio of chitosan derivatives and solvent be 1:1000-2000.
Particularly, the shitosan described in step (1) is chitosan, and deacetylation is 80%-95%, and weight average molecular weight is 3000-120000.
Particularly, solvent described in step (2) is the mixture of water or water and acetic acid, and the mass ratio of acetic acid and water is 1-10:100.
Particularly, light trigger described in step (2) be 2959,8700, Water Soluble Photoinitiators Thioxanthone Derivates or water miscible Benzophenone-type light initiator;
Particularly, described in step (2), cryogenic temperature is-197 DEG C-0 DEG C;
Particularly, the temperature that illumination described in step (2) is crosslinked is-197 DEG C-0 DEG C;
Particularly, described in step (2), uviol lamp light intensity is 20mW/cm
2, 30mW/cm
2, 50mW/cm
2or 100mW/cm
2, corresponding light application time is respectively 40min, 30min, 20min and 10min.
The invention has the beneficial effects as follows:
1, the chitosan derivatives cross filament mechanics of materials intensity prepared of the present invention is large, and machining property is high, is applicable to multiple fields;
2, the natural polymer chitosan derivative fibrous material very environmental protection prepared of the present invention, does not add the reagent of any change shitosan characteristic, can not change shitosan as the more original premium properties of natural polymer in preparation process;
3, preparation process rapidly and efficiently, and experimental facilities is simple, and course of reaction is easy to operation, has saved raw material and cost, has expanded the range of application of chitosan derivatives fibrous material.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the scanning electron microscope (SEM) photograph of the cross filament prepared by the preparation method of a kind of chitosan derivatives cross filament of the present invention.
Detailed description of the invention
In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, only basic structure of the present invention are described in a schematic way, and therefore it only shows the formation relevant with the present invention.
Embodiment 1
(1) by 2g shitosan (deacetylation DP=85%, weight average molecular weight Mw=3000) be dissolved in dilute solution of acetic acid, add methyl propenoic acid glycidyl ether, add thermal agitation 12h, after having reacted, obtain the chitosan derivatives of comparatively pure photopolymerization through post processing.
(2) chitosan derivatives of photopolymerization in (1) and light trigger 2959 chitosan derivatives=0.1/1 of photopolymerization (2959 with) are dissolved in (chitosan derivatives of photopolymerization and mass ratio=1/100 of water) in aqueous solvent, in 0 DEG C of cryogenic freezing, make water freezing and crystallizing, be 20mW/cm by light intensity under 0 DEG C of low temperature
2ultraviolet source illumination 40min is cross-linked, and freeze drying removing aqueous solvent, obtains cross-linked chitosan derivant fiber material.
Embodiment 2
(1) by 2g shitosan (deacetylation DP=85%, weight average molecular weight Mw=5000) be dissolved in dilute solution of acetic acid, add methyl propenoic acid glycidyl ether, add thermal agitation 12h, after having reacted, obtain the chitosan derivatives of comparatively pure photopolymerization through post processing.
(2) chitosan derivatives of photopolymerization in (1) and light trigger 8700 (mass ratio=0.001/1 of the chitosan derivatives of light trigger 8700 and photopolymerization) are dissolved in (chitosan derivatives of photopolymerization and mass ratio=1/1000 of water) in aqueous solvent, in-197 DEG C of cryogenic freezings, make water freezing and crystallizing, be 30mW/cm by light intensity under-197 DEG C of low temperature
2ultraviolet source illumination 30min is cross-linked, and freeze drying removing aqueous solvent, obtains the chitosan derivatives fibrous material be cross-linked.
Embodiment 3
(1) by 2g shitosan (deacetylation DP=88%, weight average molecular weight Mw=8000) be dissolved in dilute solution of acetic acid, add methyl propenoic acid glycidyl ether, add thermal agitation 12h, after having reacted, obtain the chitosan derivatives of comparatively pure photopolymerization through post processing.
(2) chitosan derivatives of photopolymerization in (1) and Water Soluble Photoinitiators Thioxanthone Derivates (mass ratio=0.005/1 of the chitosan derivatives of Water Soluble Photoinitiators Thioxanthone Derivates and photopolymerization) are dissolved in (mass ratio=5/10000 of the mixture of the chitosan derivatives of photopolymerization and water and acetic acid in the mixture of aqueous solvent and acetic acid, the mass ratio of water and acetic acid is 100/1), in-50 DEG C of cryogenic freezings, make water and acetic acid freezing and crystallizing, be 50mW/cm by light intensity under-20 DEG C of low temperature
2ultraviolet source illumination 20min is cross-linked, and freeze drying removing aqueous solvent and acetic acid, obtain the chitosan derivatives fibrous material be cross-linked.
Embodiment 4
(1) by 2g shitosan (deacetylation DP=88%, weight average molecular weight Mw=12000) be dissolved in dilute solution of acetic acid, add methyl propenoic acid glycidyl ether, add thermal agitation 12h, after having reacted, obtain the chitosan derivatives of comparatively pure photopolymerization through post processing.
(2) by the chitosan derivatives of photopolymerization in (1) and water miscible Benzophenone-type light initiator (mass ratio=0.05/1 of the chitosan derivatives of water miscible Benzophenone-type light initiator and photopolymerization) water-soluble with (mass ratio=5/1000 of the mixture of the chitosan derivatives of photopolymerization and water and acetic acid in the mixture of acetic acid, the mass ratio of water and acetic acid is 100/5), in-100 DEG C of cryogenic freezings, make water and acetic acid freezing and crystallizing, under-10 DEG C of low temperature, use 100mW/cm
2ultraviolet source illumination 10min is cross-linked, and freeze drying removing aqueous solvent and acetic acid, obtain the chitosan derivatives fibrous material be cross-linked.
Embodiment 5
(1) by 2g shitosan (deacetylation DP=90%, weight average molecular weight Mw=20000) be dissolved in dilute solution of acetic acid, add methyl propenoic acid glycidyl ether, add thermal agitation 12h, after having reacted, obtain the chitosan derivatives of comparatively pure photopolymerization through post processing.
(2) by (mass ratio=9/10000 of the mixture of the chitosan derivatives of photopolymerization and water and acetic acid in the mixture of water-soluble to the chitosan derivatives of photopolymerization in (1) and light trigger 8700 mass ratio=0.008/1 of the chitosan derivatives of photopolymerization (8700 with) and acetic acid, the mass ratio of water and acetic acid is 100/8), in-60 DEG C of cryogenic freezings, make water and acetic acid freezing and crystallizing, be 50mW/cm by light intensity under-100 DEG C of low temperature
2ultraviolet source illumination 20min is cross-linked, and freeze drying removing aqueous solvent and acetic acid, obtain the chitosan derivatives fibrous material be cross-linked.
Embodiment 6
(1) by 2g shitosan (deacetylation DP=95%, weight average molecular weight Mw=120000) be dissolved in dilute solution of acetic acid, add methyl propenoic acid glycidyl ether, add thermal agitation 12h, after having reacted, obtain the chitosan derivatives of comparatively pure photopolymerization through post processing.
(2) by (mass ratio=1/1000 of the mixture of the chitosan derivatives of photopolymerization and water and acetic acid in the mixture of water-soluble to the chitosan derivatives of photopolymerization in (1) and light trigger 2959 mass ratio=0.01/1 of the chitosan derivatives of photopolymerization (2959 with) and acetic acid, the mass ratio of water and acetic acid is 100/10), in-30 DEG C of cryogenic freezings, make water and acetic acid freezing and crystallizing, under-40 DEG C of low temperature with light intensity be 100mW/cm2 ultraviolet source illumination 10min be cross-linked, freeze drying removing aqueous solvent and acetic acid, obtain the chitosan derivatives fibrous material be cross-linked.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.
Claims (8)
1. a preparation method for chitosan derivatives cross filament, comprises the following steps:
(1) shitosan and methyl propenoic acid glycidyl ether are obtained the chitosan derivatives with light reaction by ring-opening reaction;
(2) chitosan derivatives and light trigger with light reaction are dissolved in solvent, cryogenic freezing, UV Light under freezing state, freeze drying is except desolventizing, obtain chitosan derivatives cross filament, the mass ratio of the described chitosan derivatives and solvent with light reaction is 1:100-2000, and described light trigger is 0.001-0.1:1 with the mass ratio of the chitosan derivatives with light reaction.
2. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, is characterized in that: described in there is light reaction the mass ratio of chitosan derivatives and solvent be 1:1000-2000.
3. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, it is characterized in that: the shitosan described in step (1) is chitosan, deacetylation is 80%-95%, and weight average molecular weight is 3000-120000.
4. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, is characterized in that: solvent described in step (2) is the mixture of water or water and acetic acid, and the mass ratio of acetic acid and water is 1-10:100.
5. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, is characterized in that: light trigger described in step (2) is 2959,8700, Water Soluble Photoinitiators Thioxanthone Derivates or water miscible Benzophenone-type light initiator.
6. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, is characterized in that: described in step (2), cryogenic temperature is-197 DEG C-0 DEG C.
7. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, is characterized in that: the temperature that illumination described in step (2) is cross-linked is-197 DEG C-0 DEG C.
8. the preparation method of a kind of chitosan derivatives cross filament according to claim 1, is characterized in that: described in step (2), uviol lamp light intensity is 20mW/cm
2, 30mW/cm
2, 50mW/cm
2or 100mW/cm
2, corresponding light application time is respectively 40min, 30min, 20min and 10min.
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| CN108992670A (en) * | 2018-07-24 | 2018-12-14 | 武汉理工大学 | Preparation and application of near-infrared light polymerization injectable hydrogel |
| CN112940318A (en) * | 2021-03-15 | 2021-06-11 | 深圳市通产丽星科技集团有限公司 | Method for producing organic-inorganic composite film and organic-inorganic composite film |
| CN115088736A (en) * | 2022-07-20 | 2022-09-23 | 安徽江淮汽车集团股份有限公司 | Antibacterial agent and preparation method and application thereof |
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| CN115088736A (en) * | 2022-07-20 | 2022-09-23 | 安徽江淮汽车集团股份有限公司 | Antibacterial agent and preparation method and application thereof |
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Application publication date: 20151125 |