CN103254599B - Method for preparing chitosan oligosaccharide modified biodegradable composite - Google Patents
Method for preparing chitosan oligosaccharide modified biodegradable composite Download PDFInfo
- Publication number
- CN103254599B CN103254599B CN201310212908.4A CN201310212908A CN103254599B CN 103254599 B CN103254599 B CN 103254599B CN 201310212908 A CN201310212908 A CN 201310212908A CN 103254599 B CN103254599 B CN 103254599B
- Authority
- CN
- China
- Prior art keywords
- oligochitosan
- pcl
- polycaprolactone
- ldpe
- preparation
- 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.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention mainly relates to a method for preparing a chitosan oligosaccharide modified biodegradable composite. The method comprises the steps of: firstly, with N,N-dimethyl formamide as a solvent, protecting amino of chitosan oligosaccharide by using phthalic anhydride to prepare a N-methyl o-acyl chitosan oligosaccharide reaction intermediate; secondly, dropwise adding pyridine solution of stannous octoate under protection of nitrogen, initiating an epsilon-caprolactone monomer to carry out ring opening polymerization so that polycaprolactone is grafted on hydroxyl of N-methyl o-acyl chitosan oligosaccharide, so as to generate a chitooligo saccharide-grafted polycaprolactone thermoplastic material; and finally melting and blending LDPE (low-density polyethylene), chitooligo saccharide-grafted caprolactone and polycaprolactone to prepare the biodegradable composite. The blended composite has biological degradability, and is free of poison and wide in application range; deterioration of an ecological environment is effectively improved; and the situations of energy crisis and petroleum resource shortage are solved.
Description
Technical field
The present invention relates to chemical industry, material and biomedical sector, oligochitosan graft copolymer and other medical or synthesized polymer material melt blending, by first synthesizing a kind of oligochitosan graft copolymer, are then prepared the method for biodegradable composite by concrete finger with traditional material method for processing forming.
Background technology
Most polymers is all derive from this non-renewable energy of oil.Natural polymer is adopted to be classified as the research emphasis in biological degradation field by world many countries as problems such as component raw material and the biodegradable sheet material of the blended preparation of synthetic polymer, pellet and mould materials.Low Density Polyethylene (also known as high-pressure polyethylene, LDPE), LDPE has been widely used in life.The molding processibility that LDPE has had, is applicable to many techniques of thermoplastic molding's processing, as injection moulding, blowing, extrusion molding, rotoforming, coating, foam process, thermo-welding etc.LDPE main application makes film series products because it is nontoxic in preparation process, so be used for industrial packaging film and food product pack thin, food packaging film, as candy, vegetables, frozen product, milk, bean curd, soymilk etc.; Agricultural film, as covered ground film, green house of vegetables film etc.LDPE also for injection-molded item, as small containers, lid, medical apparatus etc.; Extruded material, as tubing, profiled material etc.; Blowing slush molding goods, as medicine, cosmetics containers etc.But LDPE in the environment degradation property is very slow; easily cause white pollution; therefore, in the face of the environmental pollution of global energy crisis and sustainable growth, carrying out modification to produce novel biodegradable matrix material to LDPE is one of study hotspot of current polymeric material field.The LDPE degradation material of current preparation is mainly used in food packaging film, agricultural film aspect, preparation method realizes the object of degraded mainly through adding the additive such as treated starch and photosensitizers in LDPE matrix, but because treated starch can not melting, therefore with the poor compatibility of LDPE matrix, make the mechanical properties decrease of the matrix material prepared, the materials'use life-span is low, and limit it and preparing injection-molded item, the application of the degradable plastic product aspects such as extruded product, particularly because the composition of additive can not be accomplished nontoxic, it is made to be subject to larger restriction in medical field application.
Chitosan is the product of the N-deacetylation of chitin, be occupy second natural reproducible resource.Oligochitosan (CSO) is the product after chitosan depolymerization, have the advantages that molecular weight is little, viscosity is little and be easily absorbed and used, it has the incomparable superiority of chitosan, as water-soluble, biological degradability, germ resistance preferably and antitumor, priming cancer cell is dead, these biological natures more and more cause the interest of people.But due to the amino (-NH in oligochitosan molecular structure
2) or hydroxyl (-OH) between the interaction of hydrogen bond make oligochitosan and chitosan, chitin the same, both there is no specific fusing point, be insoluble to ordinary organic solvents yet, and made it apply and be restricted.Particularly contain in the matrix material of chitosan or oligochitosan in the preparation of current all kinds of bibliographical information, all because chitosan or oligochitosan can not meltings, make the consistency of itself and matrix resin bad, thus affect its dispersion in the base, finally cause mechanical properties decrease.
Modification is carried out to chitosan or oligochitosan and seems very important, due to oligochitosan highly crystalline, therefore physically modified is carried out to oligochitosan and substantially there is no effect, graft copolymerization technology is mainly adopted to carry out chemical modification to oligochitosan, namely on tegument oligonucleotide chain, introduce some group or pass through chemical copolymerization with other monomer, form oligochitosan graft copolymer, the degree of crystallinity of oligochitosan can be reduced, thus improve its solvability in organic solvent.On this basis, if by biodegradable polymer graft on oligochitosan chain, the performance of oligochitosan not only can be made to improve, and the completely biodegradable of superpolymer can be ensured.The aliphatic polyester amphipathic graft copolymer of oligochitosan, has become one of focus of degradable material research.Polycaprolactone is a kind of crystalline biodegradable polymer, the medicine that it has excellent mechanical property excellent with processing characteristics (similar to polyolefine) passes through property, biocompatibility and nontoxicity, often be used to the fields such as medicine controlled releasing, surgical stapling, organizational project in biomedical materials field, be applied widely clinically.But because its surface hydrophilicity is poor, degree of crystallinity is high, make degradation time very long.For oligochitosan, polycaprolactone is flexible macromolecular chain, therefore oligochitosan g-polycaprolactone technology is adopted the macromolecular chain of flexibility to be grafted to the oligochitosan g-polycaprolactone multipolymer that the oligochitosan chain of rigidity obtains, there is meltbility, forming process can be carried out, thus overcome oligochitosan can not the shortcoming of melting, shorten the degradation time of polycaprolactone simultaneously.In addition, through the oligochitosan of graft modification, with the consistency of general-purpose plastics be improved significantly, the mechanical property of material increases.
Along with the enhancing of environmental consciousness and the perfect of environmental regulation, the market of biodegradable material will increase rapidly, particularly in the application in the fields such as plastics film, wrapping material, medical material.Oligochitosan g-polycaprolactone is the macromolecular material of a class fully biodegradable, have a extensive future in pharmaceutical carrier application aspect and manufacturing in environment-friendly materials exploitation, obvious economic and social benefit can be obtained, for solve waste plastic to the pollution of physical environment, to reduce with petroleum resources be the quantity of plastics of raw material, have important practical significance.
At present, in LDPE matrix, add oligochitosan biomaterial prepare degradation material and have not been reported.At home and abroad have not been reported blended to oligochitosan grafting PCL and LDPE, PCL to prepare hot biological degradable composite material.LDPE/ thermoplastic graft copolymer blended compound material has biological degradability, nontoxic, in alternative traditional nondegradable medical liquid medicine packing bag, disposable injection device, intravenous tube etc., have potential using value, its application is by deterioration of improving the ecological environment, the situation solving energy shortage, petroleum resources shortage.
Summary of the invention
Goal of the invention
The invention provides a kind of preparation method of oligochitosan modification biodegradable composite, object is that carrying out graft copolymerization by oligochitosan prepares oligochitosan grafting PCL multipolymer, overcoming oligochitosan can not melting and the shortcoming bad with macromolecular material consistency, then by itself and LDPE, PCL melt blending to strengthen the biological degradability of LDPE, to improve the mechanical property of LDPE, this matrix material has biological degradability simultaneously.
Technical scheme
A preparation method for oligochitosan modification biodegradable composite, is characterized in that: the method step is as follows:
(1) preparation of oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material
By oligochitosan in vacuum drying oven dry 48 hours, deviate from the planar water on its surface, put into moisture eliminator and store, for subsequent use;
Oligochitosan, Tetra hydro Phthalic anhydride are put into N successively, in dinethylformamide solvent, react 7 hours under 90 DEG C of oil bath conditions, reaction solution is poured into sedimentation in frozen water, by sedimentation gained throw out ethanol repetitive scrubbing 3 times, use acetone repetitive scrubbing 3 times, filter, be then placed in 45 DEG C of baking ovens and dry to constant weight, obtain brown powder product N-phthaloyl oligochitosan reaction intermediate;
Dried N-phthaloyl oligochitosan is dissolved in dry pyridine solvent, pours in there-necked flask, then there-necked flask is put into the oil bath of 120 DEG C, and add 6-caprolactone monomer in there-necked flask; Then logical nitrogen in there-necked flask, degassed, dehydration 2 hours, moisture and oxygen impurities in removing flask;
Stannous octoate is put into dry pyridine and be configured to the pyridine solution that mass concentration is 20%, under nitrogen protection, the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths; Precipitated by reacted product with methylalcohol, the product toluene after filtration extracts 48 hours at apparatus,Soxhlet's, and namely gained brown powder obtains oligochitosan g-polycaprolactone thermoplastic material 40 DEG C of vacuum-dryings;
(2) preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
There-necked flask is led to nitrogen to remove in flask after moisture and oxygen impurities, add 6-caprolactone, stannous octoate is put into dry pyridine and be configured to the pyridine solution that mass concentration is 20%, under nitrogen protection, the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths; Precipitated by reacted product with methylalcohol, namely gained white powder obtains required polycaprolactone 40 DEG C of vacuum-dryings;
2. oligochitosan g-polycaprolactone thermoplastic material and the preparation of polycaprolactone blend diaphragm
By Low Density Polyethylene (LDPE) dry more than 6h, PHCSO-g-PCL and PCL dry more than 6h at vacuum drying oven 50 DEG C at blast drier 100 DEG C;
Take oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and polycaprolactone (PCL), wherein oligochitosan g-polycaprolactone thermoplastic material accounts for 40%, the raw material weighed up is put into beaker respectively, pour into again in tetrahydrofuran solvent, stirring and dissolving mixes, then solution is poured on polyfluortetraethylene plate, dries, make the diaphragm of PHCSO-g-PCL/PCL binary blend;
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Weigh LDPE, binary blend diaphragm (PHCSO-g-PCL/PCL) respectively, wherein LDPE accounts for 70-100%, respectively each component is added in small-sized internal mixer, melt blending 10-15min, blending temperature is 160-180 DEG C, after extruding LDPE/PHCSO-g-PCL/PCL intermingling material, put it into constant voltage 10min in vulcanizing press immediately, be pressed into the thin plate that 1 ~ 4mm is thick, after dropping to room temperature, take out thin plate, re-use universal sampling machine and make standard batten.
In step (1), the mol ratio of stannous octoate and 6-caprolactone monomer is the proportioning of 0.05%-1%, N-phthaloyl oligochitosan and 6-caprolactone is 1:4 – 1:15(g/mL).
Described oligochitosan molecular weight is less than 1500.
In step (1), the mass ratio of oligochitosan and Tetra hydro Phthalic anhydride is 1:3.5.
Step 2. in the mass ratio of binary blend and tetrahydrofuran (THF) be 1:10.
Advantage and effect
Advantage of the present invention and beneficial effect as follows:
(1) the present invention adopts oligochitosan to be raw material; first the amino of oligochitosan is protected; prepare presoma Tetra hydro Phthalic anhydride oligochitosan; reduce the degree of crystallinity of oligochitosan molecule; be conducive to carrying out graft copolymerization at the hydroxyl of oligochitosan, thus also make the polycaprolactone ring-opening polymerization of hydroxyl easily realize while realizing location grafting.Contribute to the graft copolymer preparing high percentage of grafting theoretically, by controlling the proportioning of the proportioning of 6-caprolactone monomer and Tetra hydro Phthalic anhydride oligochitosan, stannous octoate and 6-caprolactone monomer, temperature of reaction and reaction times, thus lay good basis for having prepared thermoplastic shell oligosaccharide-g-polycaprolactone material.
(2) oligochitosan can not be dissolved in and common are machine solvent and heat and melting can not limit its application.The polycaprolactone of flexibility to be incorporated into thermoplastic shell oligosaccharide-g-polycaprolactone material prepared by the rigid backbone of oligochitosan by chemical modification method and to reduce the degree of crystallinity of polycaprolactone thus reduce the degradation time of polycaprolactone by the present invention, also reduce the degree of crystallinity of oligochitosan simultaneously, thus improve the moulding processability of oligochitosan, make graft copolymer heat time can melting, cool time be spherulitic crystal structure, therefore it is the crystalline material with better mechanical property.Because this grafts has thermoplasticity, melting method can be directly adopted to prepare medical bio goods or other Biocomposite material; Its hydrophobic backbone can be used as Thermosensitive Material Used for Controlled Releasing of Medicine, having a extensive future of biomaterial for medical purpose field.
(3) after adopting the first solution blending of oligochitosan g-polycaprolactone and PCL, then with the method for LDPE melt blending, be conducive to improving the consistency of each component in blended compound material, thus the mechanical property of raising matrix material.
Accompanying drawing explanation
Fig. 1 is the differential scanning calorimetry curve of thermoplastic shell oligosaccharide-g-polycaprolactone graft copolymer of the present invention;
Fig. 2 is the mechanical curves of oligochitosan modification biodegradable composite.
Embodiment
At present, because oligochitosan heating can not melting, be usually just added in macromolecular material as rigid particles and prepare matrix material, it and matrix polymer-polymer miscibility are bad, make the mechanical properties decrease of matrix material, thus limit its widespread use at Material Field.Therefore, make oligochitosan have meltbility by carrying out grafting, copolymerization and modification to oligochitosan, this oligochitosan graft copolymer can improve the consistency with each storeroom during polymer melt blending as compatilizer simultaneously, thus improves the mechanical property of matrix material.
The invention provides a kind of preparation method of oligochitosan modification biodegradable composite, is first solvent with DMF, prepares N-phthaloyl oligochitosan reaction intermediate with the amino of Tetra hydro Phthalic anhydride protective shell oligosaccharides; Secondly, dropwise add the pyridine solution of stannous octoate under nitrogen protection, cause 6-caprolactone monomer generation ring-opening polymerization, make polycaprolactone be grafted on the hydroxyl of N-phthaloyl oligochitosan, generate oligochitosan g-polycaprolactone thermoplastic material; Finally, LDPE, oligochitosan g-polycaprolactone and polycaprolactone melt blending are prepared biodegradable composite.
The method concrete steps are as follows:
(1) preparation of oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material
By the oligochitosan bought in vacuum drying oven dry 48 hours, deviate from the planar water on its surface, put into moisture eliminator and store, for subsequent use;
Oligochitosan, Tetra hydro Phthalic anhydride (mass ratio of oligochitosan and Tetra hydro Phthalic anhydride is 1:3.5) are put into N successively, (N in dinethylformamide solvent, dinethylformamide solvent is as reaction medium, account for 1/3 of reaction vessel volume), react 7 hours under 90 DEG C of oil bath conditions, reaction solution is poured into sedimentation in frozen water, by sedimentation gained throw out ethanol repetitive scrubbing 3 times, use acetone repetitive scrubbing 3 times, filter, then be placed in 45 DEG C of baking ovens to dry to constant weight, obtain brown powder product N-phthaloyl oligochitosan reaction intermediate;
Dried N-phthaloyl oligochitosan is dissolved in dry pyridine solvent, pours in there-necked flask, then there-necked flask is put into the oil bath of 120 DEG C, and add 6-caprolactone monomer in there-necked flask; Then logical nitrogen in there-necked flask, degassed, dehydration 2 hours, the impurity such as moisture and oxygen in removing flask;
Stannous octoate is put into dry pyridine and be configured to the pyridine solution that mass concentration is 20%, under nitrogen protection, the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths; Precipitated by reacted product with methylalcohol, the product toluene after filtration extracts 48 hours at apparatus,Soxhlet's, and gained brown powder can obtain oligochitosan g-polycaprolactone thermoplastic material 40 DEG C of vacuum-dryings;
(2) preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
There-necked flask is led to nitrogen to remove in flask after the impurity such as moisture and oxygen, add 6-caprolactone, stannous octoate is put into dry pyridine and be configured to the pyridine solution that mass concentration is 20%, under nitrogen protection, the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths; Reacted product with methylalcohol is precipitated, gained white powder 40 DEG C of vacuum-dryings required polycaprolactone;
2. oligochitosan g-polycaprolactone thermoplastic material and the preparation of polycaprolactone blend diaphragm
Industrial goods Low Density Polyethylene (LDPE) the oligochitosan g-polycaprolactone thermoplastic material that dry more than 6h, PHCSO-g-PCL(step (1) obtains at blast drier 100 DEG C by buying) and the polycaprolactone that 1. obtains of PCL(step) dry more than 6h at vacuum drying oven 50 DEG C;
Accurately take oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and polycaprolactone (PCL), wherein oligochitosan g-polycaprolactone thermoplastic material accounts for 40%(weight ratio), the raw material weighed up is put into beaker respectively, pour in tetrahydrofuran solvent that (mass ratio of binary blend and tetrahydrofuran (THF) is 1:10 again into, the mixture of binary blend and oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone), stirring and dissolving mixes, then solution is poured on polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend,
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Weigh LDPE, PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 70-100%(weight ratio), respectively each component is added in small-sized internal mixer, melt blending 10-15min, blending temperature is 160-180 DEG C, after extruding LDPE/PHCSO-g-PCL/PCL intermingling material, put it into constant voltage 10min in vulcanizing press immediately, be pressed into the thin plate that 1 ~ 4mm is thick, after dropping to room temperature, take out thin plate, re-use universal sampling machine and make standard batten.
In step (1), the mol ratio of stannous octoate and 6-caprolactone monomer is the proportioning of 0.05%-1%, N-phthaloyl oligochitosan and 6-caprolactone is 1:4 – 1:15(g/mL).
1. the middle stannous octoate of step (2) and the mol ratio of 6-caprolactone monomer are 0.05%-1%.
Above-mentioned oligochitosan molecular weight is less than 1500.
Above-mentioned oligochitosan g-polycaprolactone thermoplastic material has thermoplasticity, can melting and can crystallization in temperature-fall period in heat-processed, and crystal is spherocrystal.
First oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone are prepared binary blend by solution blending in the preparation process of this blended compound material, and then prepare biodegradable composite with LDPE melt blending.This matrix material has biological degradability, nontoxic, in alternative traditional nondegradable agricultural mulching, wrapping material and medical liquid medicine packing bag, disposable injection device, intravenous tube etc., have potential using value, its application is by deterioration of improving the ecological environment, the situation solving energy shortage, petroleum resources shortage.
Described oligochitosan g-polycaprolactone thermoplastic material can melting under heating condition, directly can be processed into corresponding degradable biomaterial goods by traditional Polymer moulding method (as injection molding, extrusion moulding and compression moulding).In addition, oligochitosan g-polycaprolactone thermoplastic material is except preparing degradable composite material with the LDPE that mentions in this patent by melt blending mode, and then adopt traditional Polymer moulding method to produce outside degradable product, also can be used on thermoplastic starch or synthetic polymer as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), polybutylene terephthalate (PBT), polypropylene, high density polyethylene(HDPE) passes through melt blending, adopt traditional Polymer moulding method (as injection molding, extrusion moulding and compression moulding) prepare degradable product.
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1
1. the preparation of oligochitosan g-polycaprolactone thermoplastic material
(1) preparation of N-phthaloyl oligochitosan
By the oligochitosan bought in vacuum drying oven dry 48 hours, deviate from the planar water on its surface, put into moisture eliminator and store, for subsequent use.
By 1g oligochitosan, 2g Tetra hydro Phthalic anhydride and 30ml N; dinethylformamide adds in there-necked flask successively; react 7 hours under 90 DEG C of oil bath conditions; then reaction solution is poured into sedimentation in frozen water; by throw out ethanol repetitive scrubbing 3 times, use acetone repetitive scrubbing 3 times, filter, be then placed in 45 DEG C of baking ovens and dry to constant weight; obtain brown powder product N-phthaloyl oligochitosan reaction intermediate, productive rate is 67.85%.
(2) preparation of N-phthaloyl oligochitosan g-polycaprolactone
The 1g N-phthaloyl oligochitosan of drying is dissolved in dry pyridine solvent and pours (there-necked flask puts into the oil bath of 120 DEG C) in there-necked flask into 4ml 6-caprolactone monomer; logical nitrogen in there-necked flask; degassed, dehydration 2 hours, removing flask in the impurity such as moisture and oxygen.0.15g stannous octoate (mol ratio that stannous octoate accounts for 6-caprolactone monomer is 0.5%) is put into dry pyridine and be configured to the pyridine solution that concentration is 20%; join in above-mentioned there-necked flask under nitrogen protection, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths.Precipitated by reacted product with methylalcohol, the product toluene after filtration extracts 48 hours at apparatus,Soxhlet's, and gained brown powder can obtain oligochitosan g-polycaprolactone thermoplastic material 40 DEG C of vacuum-dryings.
2. the preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
There-necked flask is led to nitrogen to remove in flask after the impurity such as moisture and oxygen; add 6 ml 6-caprolactones; 0.068g stannous octoate (mol ratio that stannous octoate accounts for 6-caprolactone monomer is 0.3%) is put into dry pyridine and be configured to the pyridine solution that concentration is 20%; under nitrogen protection; the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask; stirring reaction 26 hours in 120 DEG C of oil baths; reacted product with methylalcohol is precipitated, gained white powder 40 DEG C of vacuum-dryings required polycaprolactone.
2. oligochitosan g-polycaprolactone thermoplastic material and the preparation of polycaprolactone blend diaphragm
LDPE is dry more than 6h, PHCSO-g-PCL and PCL dry more than 6h at vacuum drying oven 50 DEG C at blast drier 100 DEG C.
Accurately take 4g oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and 6g polycaprolactone (PCL), the raw material weighed up is put into beaker respectively, pour 100 ml tetrahydrofuran solvents again into, stirring and dissolving mixes, then solution is poured on polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend.
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Weigh 42.5g LDPE and 7.5g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 85%(weight ratio), respectively each component is added in small-sized internal mixer, melt blending 10-15min at 160 DEG C, then LDPE/PHCSO-g-PCL/PCL intermingling material to be put it into immediately in vulcanizing press constant voltage 10min at 160 DEG C, be pressed into the thin plate that 2mm is thick, after dropping to room temperature, take out thin plate, re-use universal sampling machine cutting, make standard batten.
Fig. 1 is that in the embodiment 1 obtained by technical scheme of the present invention, thermoplastic shell oligosaccharide-g-polycaprolactone graft copolymer heats up and the differential scanning calorimetry curve of rate of temperature fall at 10 DEG C respectively, in Fig. 1, the curve at A point place is the heating curve of differential scanning calorimetry, A point is the fusing point of oligochitosan g-polycaprolactone graft copolymer is 55.82 DEG C, show that this graft copolymer can melting in temperature-rise period, thus there is thermoplasticity; The curve at B point place is the temperature lowering curve of differential scanning calorimetry, and B point is the Tc of oligochitosan g-polycaprolactone graft copolymer is 22.49 DEG C, shows that this graft copolymer can crystallization in temperature-fall period.
Fig. 2 is the stress-strain curve of oligochitosan modified degradable bio-medical composition in Low Density Polyethylene (LDPE) and embodiment 1.A is LDPE, b is oligochitosan modified degradable bio-medical composition.As can be seen from Figure 2, the tensile strength σ of pure LDPE is 9.34MPa, and elongation at break ε is 550%; The tensile strength of the oligochitosan modification biodegradable composite of preparation is 10.24MPa higher than LDPE, σ, and elongation is 347% lower than LDPE, ε.
embodiment 2
1. the preparation of oligochitosan g-polycaprolactone thermoplastic material, in step (1), the mol ratio of stannous octoate and 6-caprolactone monomer is the proportioning of 1%, N-phthaloyl oligochitosan and 6-caprolactone is 1:15(g/ mL), all the other conditions are with embodiment 1;
2. the preparation of oligochitosan modification biodegradable composite
1. the preparation (mol ratio that stannous octoate accounts for 6-caprolactone monomer is 0.05%, and preparation condition is with embodiment 1) of polycaprolactone (PCL).
2. oligochitosan g-polycaprolactone thermoplastic material and the preparation of polycaprolactone blend diaphragm
LDPE is dry more than 6h, PHCSO-g-PCL and PCL dry more than 6h at vacuum drying oven 50 DEG C at blast drier 100 DEG C.
Accurately take 4g oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and 6g polycaprolactone (PCL), the raw material weighed up is put into beaker respectively, pour 100 ml tetrahydrofuran solvents again into, stirring and dissolving mixes, then solution is poured on polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend.
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Weigh 40g LDPE and 10g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 80%(weight ratio), respectively each component is added in small-sized internal mixer, melt blending 10-15min at 180 DEG C, then LDPE/PHCSO-g-PCL/PCL intermingling material to be put it into immediately in vulcanizing press constant voltage 10min at 160 DEG C, be pressed into the thin plate that 4mm is thick, after dropping to room temperature, take out thin plate, re-use universal sampling machine cutting, make standard batten.
embodiment 3
1. the preparation of oligochitosan g-polycaprolactone thermoplastic material; in step (1), the mol ratio of stannous octoate and 6-caprolactone monomer is 0.05%; the proportioning of N-phthaloyl oligochitosan and 6-caprolactone is 1:6(g/ mL), all the other conditions are with embodiment 1.
2. the preparation of oligochitosan modification biodegradable composite
1. the preparation (mol ratio that stannous octoate accounts for 6-caprolactone monomer is 1%, and preparation condition is with embodiment 1) of polycaprolactone (PCL).
2. oligochitosan g-polycaprolactone thermoplastic material and the preparation of polycaprolactone blend diaphragm
LDPE is dry more than 6h, PHCSO-g-PCL and PCL dry more than 6h at vacuum drying oven 50 DEG C at blast drier 100 DEG C.
Accurately take 4g oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and 6g polycaprolactone (PCL), the raw material weighed up is put into beaker respectively, pour 100 ml tetrahydrofuran solvents again into, stirring and dissolving mixes, then solution is poured on polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend.
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Weigh 45g LDPE and 5g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 90%(weight ratio), respectively each component is added in small-sized internal mixer, melt blending 12min at 170 DEG C, then LDPE/PHCSO-g-PCL/PCL intermingling material to be put it into immediately in vulcanizing press constant voltage 10min at 160 DEG C, be pressed into the thin plate that 1mm is thick, after dropping to room temperature, take out thin plate, re-use universal sampling machine cutting, make standard batten.
embodiment 4
Step is 3. in the preparation of LDPE/PHCSO-g-PCL/PCL blend, and weigh 35g LDPE and 15g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 70%(weight ratio), all the other conditions are with embodiment 1.
embodiment 5
Step is 3. in the preparation of LDPE/PHCSO-g-PCL/PCL blend, and weigh 50g LDPE and 0g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 100%(weight ratio), all the other conditions are with embodiment 1.(in this blended sample, the content of binary blend is zero, and reality is pure LDPE diaphragm, can be used as the reference sample of other blended compound material performance test)
Conclusion: the oligochitosan g-polycaprolactone thermoplastic material prepared in the present invention expands the use range of oligochitosan, can be used as the interface coupling agent of chitosan, oligochitosan, various starch and polycaprolactone blend, agricultural chemicals Co ntrolled release capsule carrier material, also directly can be processed into relevant biologic material products under melting condition; Matrix material prepared by the present invention is nontoxic, has broad application prospects preparing in the medical materials such as degradable plastic product, agricultural mulching, wrapping material and medical liquid medicine packing bag, disposable injection device, intravenous tube.In addition, method of the present invention also provides theoretical foundation for oligochitosan and the blended of other macromolecular material with the investigation and application preparing biodegradable composite.
Claims (3)
1. a preparation method for oligochitosan modification biodegradable composite, is characterized in that: the method step is as follows:
(1) preparation of oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material
By oligochitosan in vacuum drying oven dry 48 hours, deviate from the planar water on its surface, put into moisture eliminator and store, for subsequent use;
Oligochitosan, Tetra hydro Phthalic anhydride are put into N successively, in dinethylformamide solvent, react 7 hours under 90 DEG C of oil bath conditions, reaction solution is poured into sedimentation in frozen water, by sedimentation gained throw out ethanol repetitive scrubbing 3 times, use acetone repetitive scrubbing 3 times, filter, be then placed in 45 DEG C of baking ovens and dry to constant weight, obtain brown powder product N-phthaloyl oligochitosan reaction intermediate;
Dried N-phthaloyl oligochitosan is dissolved in dry pyridine solvent, pours in there-necked flask, then there-necked flask is put into the oil bath of 120 DEG C, and add 6-caprolactone monomer in there-necked flask; Then logical nitrogen in there-necked flask, degassed, dehydration 2 hours, moisture and oxygen impurities in removing flask;
Stannous octoate is put into dry pyridine and be configured to the pyridine solution that mass concentration is 20%, under nitrogen protection, the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths; Precipitated by reacted product with methylalcohol, the product toluene after filtration extracts 48 hours at apparatus,Soxhlet's, and namely gained brown powder obtains oligochitosan g-polycaprolactone thermoplastic material 40 DEG C of vacuum-dryings;
(2) preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
There-necked flask is led to nitrogen to remove in flask after moisture and oxygen impurities, add 6-caprolactone, stannous octoate is put into dry pyridine and be configured to the pyridine solution that mass concentration is 20%, under nitrogen protection, the pyridine solution of 20% is dropwise joined in above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 DEG C of oil baths; Precipitated by reacted product with methylalcohol, namely gained white powder obtains required polycaprolactone 40 DEG C of vacuum-dryings;
2. oligochitosan g-polycaprolactone thermoplastic material and the preparation of polycaprolactone blend diaphragm
By Low Density Polyethylene (LDPE) dry more than 6h at blast drier 100 DEG C, oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material and PCL dry more than 6h at vacuum drying oven 50 DEG C;
Take oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material and polycaprolactone (PCL), wherein oligochitosan g-polycaprolactone thermoplastic material accounts for 40% weight ratio, the raw material weighed up is put into beaker respectively, pour into again in tetrahydrofuran solvent, stirring and dissolving mixes, then solution is poured on polyfluortetraethylene plate, dries, make the diaphragm of PHCSO-g-PCL/PCL binary blend;
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Weigh LDPE, PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for 70-100% weight ratio, respectively each component is added in small-sized internal mixer, melt blending 10-15min, blending temperature is 160-180 DEG C, after extruding LDPE/PHCSO-g-PCL/PCL intermingling material, put it into constant voltage 10min in vulcanizing press immediately, be pressed into the thin plate that 1 ~ 4mm is thick, after dropping to room temperature, take out thin plate, re-use universal sampling machine and make standard batten; Described oligochitosan molecular weight is less than 1500; Step 2. in the mass ratio of binary blend and tetrahydrofuran (THF) be 1:10.
2. the preparation method of a kind of oligochitosan modification biodegradable composite according to claim 1; it is characterized in that: in step (1), the mol ratio of stannous octoate and 6-caprolactone monomer is the proportioning g/mL of 0.05%-1%, N-phthaloyl oligochitosan and 6-caprolactone is 1:4 – 1:15.
3. the preparation method of a kind of oligochitosan modification biodegradable composite according to claim 1, is characterized in that: in step (1), the mass ratio of oligochitosan and Tetra hydro Phthalic anhydride is 1:3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310212908.4A CN103254599B (en) | 2013-05-31 | 2013-05-31 | Method for preparing chitosan oligosaccharide modified biodegradable composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310212908.4A CN103254599B (en) | 2013-05-31 | 2013-05-31 | Method for preparing chitosan oligosaccharide modified biodegradable composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103254599A CN103254599A (en) | 2013-08-21 |
| CN103254599B true CN103254599B (en) | 2015-04-29 |
Family
ID=48958832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310212908.4A Active CN103254599B (en) | 2013-05-31 | 2013-05-31 | Method for preparing chitosan oligosaccharide modified biodegradable composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103254599B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885182B (en) * | 2016-07-01 | 2018-05-18 | 许仙福 | A kind of medical bio macromolecule degradable material and preparation method thereof |
| CN107321318A (en) * | 2017-07-12 | 2017-11-07 | 浙江大学 | A kind of preparation method of N phthalic acids substitution chitosan oligosaccharide sorbing material and its derivative |
| CN111607207B (en) * | 2020-06-29 | 2022-04-19 | 无锡会通轻质材料股份有限公司 | Expandable biodegradable particles and biodegradable foaming beads with antibacterial function |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN101857649A (en) * | 2010-03-18 | 2010-10-13 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7238748B2 (en) * | 2003-08-20 | 2007-07-03 | Dupont Performance Elastomers L.L.C. | Process aid for metallocene catalyzed linear low density polyethylene polymers |
-
2013
- 2013-05-31 CN CN201310212908.4A patent/CN103254599B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN101857649A (en) * | 2010-03-18 | 2010-10-13 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103254599A (en) | 2013-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102666619A (en) | Biodegradable polyester | |
| CN103992517A (en) | Continuously-produced full-degradable starch-based plastic alloy and preparation method thereof | |
| CN103965598B (en) | Polydactyl acid and preparation method thereof | |
| CN100406498C (en) | Blend material of vinol/polylactic acid graft copolymer and starch, their prepn. and application | |
| CN106674923B (en) | A kind of controllable PBAT/PLA composite membranes and preparation method thereof of degrading | |
| CN101367986A (en) | Coupling and capacity increasing technique for coblended interface of biodegradation polylactic acid/starch composite material | |
| CN104072957A (en) | Food grade biodegradable polylactic acid-based composite material and application thereof | |
| CN103254599B (en) | Method for preparing chitosan oligosaccharide modified biodegradable composite | |
| CN101824229A (en) | Thermoplastic plant fiber/polylactic acid blending material and preparation method thereof | |
| CN107522904A (en) | A kind of Starch Based Biodegradable Plastics applied to packaging for foodstuff | |
| CN109456487A (en) | A kind of preparation method and application of cellulose derivative grafted polylactic acid | |
| CN101857649A (en) | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material | |
| CN105131542A (en) | Blended composite material prepared from lactide surface grafted bamboo powder and polylactic acid, and preparation method and applications thereof | |
| CN104877352A (en) | Compatibilizer-containing fibroin/polylactic acid blended material and preparation method thereof | |
| CN103193890A (en) | Functionalized starch nano-crystals and preparation method thereof | |
| CN101851424B (en) | Thermoplastic plant protein/polylactic acid blend material and preparation method thereof | |
| CN101168616A (en) | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material | |
| CN104530670A (en) | Fibroin/polylactic acid blend material and melt-blending preparation method thereof | |
| Wang et al. | Chitosan-graft poly (p-dioxanone) copolymers: preparation, characterization, and properties | |
| CN108864628A (en) | A kind of preparation method of high temperature resistant biological plastics | |
| CN102617969B (en) | Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material | |
| CN106751568B (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| CN108559067A (en) | Long-chain branched polymer type processing aid and preparation method thereof and its application | |
| CN102030892B (en) | Preparation method of glutinous rice flour grafted polycaprolactone thermoplastic material | |
| CN108752956A (en) | The preparation method and application of polylactic acid crystal nucleating agent and material based on humic acid |
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 |