CN106046400A - Preparation method of dialdehyde cellulose cross-linked chitosan film - Google Patents

Preparation method of dialdehyde cellulose cross-linked chitosan film Download PDF

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Publication number
CN106046400A
CN106046400A CN201610439210.XA CN201610439210A CN106046400A CN 106046400 A CN106046400 A CN 106046400A CN 201610439210 A CN201610439210 A CN 201610439210A CN 106046400 A CN106046400 A CN 106046400A
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dialdehyde
cellulose
preparation
film
dialdehyde cellulose
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田秀枝
蒋学
闫德东
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Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a preparation method of a dialdehyde cellulose cross-linked chitosan film, and belongs to the field of natural macromolecule modification. Microcrystalline cellulose is used as raw materials; water-soluble dialdehyde cellulose is respectively prepared through concentrated sulfuric acid hydrolysis and sodium periodate selective oxidization; then, the dialdehyde cellulose water solution is directly mixed with chitosan-acetic acid solution; vacuum defoaming and room temperature casting drying film formation are performed. Compared with a pure chitosan film, the dialdehyde cellulose cross-linked chitosan film prepared by the method provided by the invention has the advantages that the mechanical performance is obviously improved; the swelling degree in the water is obviously reduced.

Description

A kind of preparation method of the cellulose crosslinked chitosan film of dialdehyde
Technical field
The present invention relates to the preparation method of the cellulose crosslinked chitosan film of a kind of dialdehyde, belong to the modification of natural polymer Field.
Background technology
Chitin is widely present in the carapace of insecticide and Crustaceans, and in the cell wall of some fungus, is certainly So in boundary, reserves are only second to the biopolymer of cellulose.Chitosan is the deacetylation derivative of chitin, has good Film property, biocompatibility, biodegradability and antibacterial, stop blooding and promote the functions such as wound healing.At present, chitosan film The most noticeable in the application of the aspects such as food fresh keeping, drug controlled release, hemodialysis and wound dressing.But, relatively low Wet strength limit the chitosan film extensive application in packaging for foodstuff and biomedical materials field.It is reported, by changing Learn cross-linking method and can significantly improve the mechanical strength of chitosan film.Existing chemical cross-linking agent (glutaraldehyde, toluene diisocynate Ester, epoxychloropropane, Ethylene glycol diglycidyl ether, difunctional anhydride etc.) often there is cytotoxicity and biocompatibility The problems such as difference.Therefore, the natural biological cross-linking agent of these safety non-toxics such as genipin, vanillin, Cys, dialdehyde polysaccharide Of increasing concern.
Dialdehyde cellulose has been used for the preparation of cross-linked collagen film etc., but there is no the cellulose crosslinked shell of relevant dialdehyde and gather Report in terms of sugar film.The present invention uses microcrystalline Cellulose to be raw material, respectively through concentrated sulphuric acid hydrolysis, sodium metaperiodate selective oxidation Prepare dialdehyde cellulose aqueous solution, afterwards dialdehyde cellulose aqueous solution directly mix with chitosan-acetic acid solution, vacuum defoamation, room Temperature curtain coating drying and forming-film.
Summary of the invention
It is an object of the invention to provide the preparation method of the cellulose crosslinked chitosan film of a kind of dialdehyde.There is provided according to the present invention Technical scheme, the preparation method of the cellulose crosslinked chitosan film of described dialdehyde, feature is, formula proportion is counted by weight, Comprise the following steps:
(1) 1 part of microcrystalline Cellulose joins in the concentrated sulphuric acid of 20 part 64% (w/v), 45 DEG C, machinery stirs under 600r/min Mix 1h, high speed centrifugation under 9000～10000r/min, collect upper strata white colloidal, after dialysing 3 days, add the hydroxide of 0.1N The pH of sodium solution regulation colloid is 6.5；
(2) 6～7 parts of sodium metaperiodates join in the white colloidal prepared by step (1), 40～60 DEG C, under lucifuge anti- Answer 2～6h；Add 3～10 parts of glycol reaction 1h and dialyse 5 days, obtaining dialdehyde cellulose aqueous solution；
(3) chitosan solution of acetum preparation 1% (w/w) of 1% (v/w), 1～20 part of step are used under room temperature (2) the dialdehyde cellulose aqueous solution prepared by and the chitosan solution mixing of 100 part 1%, be cast in polytetrafluoro after vacuum defoamation In ethylene mould, drying at room temperature film forming.
It is an advantage of the current invention that: dialdehyde cellulose is soluble in water, thus ensure that in acetum dialdehyde cellulose with The uniform mixing of chitosan, institute's film forming crosslinks reaction between the two because of two and has higher mechanical strength.Dialdehyde cellulose And the preparation process of crosslinked chitosan film is simple, energy consumption is low, pollutes few.Dialdehyde cellulose crosslinked chitosan film biocompatibility Good, biodegradable.
Accompanying drawing explanation
Fig. 1 Cellulose nanocrystal body and transmission electron microscope (TEM) photo (the a-Cellulose nanocrystal body of dialdehyde cellulose；b- Dialdehyde cellulose)
The FT-IR of Fig. 2 dialdehyde cellulose and crosslinked chitosan film thereof composes (a-chitosan；B-dialdehyde cellulose；C-dialdehyde is fine Dimension element cross-linked chitosan)
Specific implementation method
The present invention divides three steps:
(1) preparation of Cellulose nanocrystal body (CNC) colloid；
(2) preparation of dialdehyde cellulose (DAC) aqueous solution；
(3) preparation of DAC crosslinked chitosan film.
The properties of CNC, DAC and DAC crosslinked chitosan film of the present invention can use following index to detect:
(1) structural analysis measures: FT-IR analyzes and uses NICOLET NEXUS 470 Fourier transform infrared spectrometer, light Spectrometer resolution is 4cm-1, scanning times is 32.
(2) tensile property test: DAC crosslinked chitosan film is put in thermostatic constant wet chamber (temperature is 25 DEG C, relative humidity It is 65%) balance 48h, and it is cut into the strip of a width of 1cm；On strip film, 5 test films of averaging are extracted with film thickness gauge Thickness, and the tensile break strength of universal testing machine (WDW-20 Shanghai Hua Long test instrunment company) survey film is controlled with microcomputer And percentage elongation, test clip is away from being set to 5cm, and draw speed is 50mm/min.
(3) swelling behavior test: DAC crosslinked chitosan film is dried to constant weight.Weigh (Wd, g) after immerse deionized water In enough long-time, take out film and also blot its surface moisture content with filter paper, weigh (W immediatelys,g).The Equilibrium swelling ratio (Q, %) of film Computing formula is:
Q = [ W s - W d W d ] × 100 %
Detailed description of the invention
Embodiment 1
(1) 1 part of microcrystalline Cellulose joins in the concentrated sulphuric acid of 20 part 64% (w/v), 45 DEG C, machinery stirs under 600r/min Mix 1h, high speed centrifugation under 10000r/min, collect upper strata white CNC colloid, the sodium hydroxide adding 0.1N after dialysing 3 days is molten The pH of liquid regulation colloid is 6.5；
(2) 6.3 parts of sodium metaperiodates join in the CNC colloid prepared by step (1), 45 DEG C, react 4h under lucifuge；Add Enter 3 parts of glycol reaction 1h and dialyse 5 days, obtaining dialdehyde cellulose aqueous solution；
(3) chitosan solution of acetum preparation 1% (w/w) of 1% (v/w), 1 part of step (2) institute are used under room temperature The dialdehyde cellulose aqueous solution of preparation and the chitosan solution mixing of 100 part 1%, be cast after vacuum defoamation in politef mould In tool, drying at room temperature film forming.
Embodiment 2
(1) 1 part of microcrystalline Cellulose joins in the concentrated sulphuric acid of 20 part 64% (w/v), 45 DEG C, machinery stirs under 600r/min Mix 1h, high speed centrifugation under 10000r/min, collect upper strata white CNC colloid, the sodium hydroxide adding 0.1N after dialysing 3 days is molten The pH of liquid regulation colloid is 6.5；
(2) 6.3 parts of sodium metaperiodates join in the CNC colloid prepared by step (1), 45 DEG C, react 4h under lucifuge；Add Enter 3 parts of glycol reaction 1h and dialyse 5 days, obtaining dialdehyde cellulose aqueous solution；
(3) chitosan solution of acetum preparation 1% (w/w) of 1% (v/w), 3 parts of step (2) institutes are used under room temperature The dialdehyde cellulose aqueous solution of preparation and the chitosan solution mixing of 100 part 1%, be cast after vacuum defoamation in politef mould In tool, drying at room temperature film forming.
Embodiment 3
(1) 1 part of microcrystalline Cellulose joins in the concentrated sulphuric acid of 20 part 64% (w/v), 45 DEG C, machinery stirs under 600r/min Mix 1h, high speed centrifugation under 10000r/min, collect upper strata white CNC colloid, the sodium hydroxide adding 0.1N after dialysing 3 days is molten The pH of liquid regulation colloid is 6.5；
(2) 6.3 parts of sodium metaperiodates join in the CNC colloid prepared by step (1), 45 DEG C, react 4h under lucifuge；Add Enter 3 parts of glycol reaction 1h and dialyse 5 days, obtaining dialdehyde cellulose aqueous solution；
(3) chitosan solution of acetum preparation 1% (w/w) of 1% (v/w), 5 parts of step (2) institutes are used under room temperature The dialdehyde cellulose aqueous solution of preparation and the chitosan solution mixing of 100 part 1%, be cast after vacuum defoamation in politef mould In tool, drying at room temperature film forming.
Embodiment 4
(1) 1 part of microcrystalline Cellulose joins in the concentrated sulphuric acid of 20 part 64% (w/v), 45 DEG C, machinery stirs under 600r/min Mix 1h, high speed centrifugation under 10000r/min, collect upper strata white CNC colloid, the sodium hydroxide adding 0.1N after dialysing 3 days is molten The pH of liquid regulation colloid is 6.5；
(2) 6.3 parts of sodium metaperiodates join in the CNC colloid prepared by step (1), 45 DEG C, react 4h under lucifuge；Add Enter 3 parts of glycol reaction 1h and dialyse 5 days, obtaining dialdehyde cellulose aqueous solution；
(3) chitosan solution of acetum preparation 1% (w/w) of 1% (v/w), 7 parts of step (2) institutes are used under room temperature The dialdehyde cellulose aqueous solution of preparation and the chitosan solution mixing of 100 part 1%, be cast after vacuum defoamation in politef mould In tool, drying at room temperature film forming.
The mechanical performance of the cellulose crosslinked chitosan film of a kind of dialdehyde prepared by the present invention and water swelling degree such as table 1 institute Show:

Claims (3)

1. a preparation method for the cellulose crosslinked chitosan film of dialdehyde, comprises the following steps that (formula proportion is by weight Meter):
(1) 1 part of microcrystalline Cellulose joins in the concentrated sulphuric acid of 20 part 64% (w/v), 45 DEG C, mechanical agitation under 600r/min 1h, high speed centrifugation under 9000～10000r/min, collect upper strata white colloidal, after dialysing 3 days, add the sodium hydroxide of 0.1N The pH of solution regulation colloid is 6.5；
(2) 6～7 parts of sodium metaperiodates join in the white colloidal prepared by step (1), 40～60 DEG C, react under lucifuge 2～ 6h；Add 3～10 parts of glycol reaction 1h and dialyse 5 days, obtaining dialdehyde cellulose aqueous solution；
(3) chitosan solution of acetum preparation 1% (w/w) of 1% (v/w), 1～20 part of step (2) institute are used under room temperature The dialdehyde cellulose aqueous solution of preparation and the chitosan solution mixing of 100 part 1%, be cast after vacuum defoamation in politef mould In tool, drying at room temperature film forming.
The dialdehyde cellulose that the most according to claim 1, prepared by method.
The cellulose crosslinked chitosan film of dialdehyde that the most according to claim 1, prepared by method.
CN201610439210.XA 2016-06-20 2016-06-20 Preparation method of dialdehyde cellulose cross-linked chitosan film Withdrawn CN106046400A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928375A (en) * 2017-04-05 2017-07-07 江南大学 A kind of preparation method of aquagel
CN107698784A (en) * 2017-10-23 2018-02-16 广西大学 A kind of preparation method of dialdehyde nano-cellulose and chitosan complex film
CN108165518A (en) * 2018-02-12 2018-06-15 山东建筑大学 A kind of two-dimensional/three-dimensional cell culturing rack material
CN112029756A (en) * 2020-07-21 2020-12-04 南京工业大学 Method for catalytically synthesizing phytosterol ester compound by using magnetic immobilized lipase
CN113412104A (en) * 2019-01-25 2021-09-17 雷诺尼尔性能纤维有限责任公司 Improved absorption properties by cross-linking cellulose with glyoxal

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434072A (en) * 2003-01-27 2003-08-06 武汉大学 High-strength antimicrobial dialdehyde starch crosslinked chitosan membane and preparation method and use thereof
CN105670016A (en) * 2016-02-03 2016-06-15 江南大学 Preparation method of cellulose nanocrystal and chitosan composite membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434072A (en) * 2003-01-27 2003-08-06 武汉大学 High-strength antimicrobial dialdehyde starch crosslinked chitosan membane and preparation method and use thereof
CN105670016A (en) * 2016-02-03 2016-06-15 江南大学 Preparation method of cellulose nanocrystal and chitosan composite membrane

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928375A (en) * 2017-04-05 2017-07-07 江南大学 A kind of preparation method of aquagel
CN107698784A (en) * 2017-10-23 2018-02-16 广西大学 A kind of preparation method of dialdehyde nano-cellulose and chitosan complex film
CN108165518A (en) * 2018-02-12 2018-06-15 山东建筑大学 A kind of two-dimensional/three-dimensional cell culturing rack material
CN113412104A (en) * 2019-01-25 2021-09-17 雷诺尼尔性能纤维有限责任公司 Improved absorption properties by cross-linking cellulose with glyoxal
CN112029756A (en) * 2020-07-21 2020-12-04 南京工业大学 Method for catalytically synthesizing phytosterol ester compound by using magnetic immobilized lipase
CN112029756B (en) * 2020-07-21 2022-11-25 南京工业大学 Method for catalytically synthesizing phytosterol ester compound by using magnetic immobilized lipase

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