CN103254599A - Method for preparing chitosan oligosaccharide modified biodegradable composite - Google Patents
Method for preparing chitosan oligosaccharide modified biodegradable composite Download PDFInfo
- Publication number
- CN103254599A CN103254599A CN2013102129084A CN201310212908A CN103254599A CN 103254599 A CN103254599 A CN 103254599A CN 2013102129084 A CN2013102129084 A CN 2013102129084A CN 201310212908 A CN201310212908 A CN 201310212908A CN 103254599 A CN103254599 A CN 103254599A
- Authority
- CN
- China
- Prior art keywords
- oligochitosan
- pcl
- polycaprolactone
- preparation
- ldpe
- 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
Images
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, refer to specifically that by earlier synthetic a kind of oligochitosan graft copolymer medical or synthesized polymer material melt blending prepares the method for biodegradable composite with oligochitosan graft copolymer and other with the traditional material method for processing forming then.
Background technology
Most polymers all is to derive from this non-renewable energy of oil.Adopt natural polymer to prepare problems such as biodegradable sheet material, pellet and mould material are classified as the biological degradation field by world many countries research emphasis as component raw material and synthetic polymer blend.(claim high-pressure polyethylene again, LDPE), LDPE is widely used in the life Low Density Polyethylene.LDPE has good forming process, is fit to many technologies of thermoplastic molding's processing, as injection moulding, blowing, extrusion molding, rotoforming, coating, foam process, thermo-welding etc.The LDPE main application is to make the film series products, because it is nontoxic in preparation process, so how thin for industrial packaging film and food product pack, food packaging film is as candy, vegetables, frozen product, milk, bean curd, soymilk etc.; Agricultural film is as ground coating film, green house of vegetables film etc.LDPE also is used for injection-molded item, as small containers, lid, medical apparatus etc.; Extruded material is as tubing, profiled material etc.; Blowing slush molding goods are as medicine, cosmetics containers etc.But LDPE degradation property in environment is very slow; easily cause white pollution; therefore, in the face of the environmental pollution of global energy crisis and sustainable growth, LDPE is carried out modification, and to produce novel biodegradable composite be one of research focus of current polymeric material field.The LDPE degradation material of preparation is mainly used in food packaging film at present, the agricultural film aspect, the preparation method is mainly by adding the purpose that additives such as treated starch and photosensitizers are realized degraded in the LDPE matrix, but because treated starch can not fusion, therefore poor with the consistency of LDPE matrix, the mechanical properties decrease of the matrix material of feasible preparation, material is low work-ing life, and limited it at the preparation injection-molded item, the application of degradable plastic product aspects such as extruded product, particularly because the composition of additive can not be accomplished nontoxicly, it is used in medical field be subjected to bigger restriction.
Chitosan is the product of the N-deacetylation of chitin, is to occupy second natural reproducible resource.Oligochitosan (CSO) is the product after the chitosan depolymerization, have the advantages that molecular weight is little, viscosity is little and easily be absorbed and used, it has the incomparable superiority of chitosan, as better water solubility, biological degradability, germ resistance and antitumor, priming cancer cell death etc., these biological natures more and more cause people's interest.But because the amino (NH in the oligochitosan molecular structure
2) or hydroxyl (interaction of hydrogen bond makes oligochitosan and chitosan, chitin the same OH), has not both had specific fusing point, also is insoluble to ordinary organic solvents, and its application is restricted.Particularly the preparation at present all kinds of bibliographical informations contains in the matrix material of chitosan or oligochitosan, all can not fusion owing to chitosan or oligochitosan, make the consistency of itself and matrix resin bad, thereby influence its dispersion in matrix, finally cause mechanical properties decrease.
Chitosan or oligochitosan are carried out modification seem very important, because oligochitosan highly crystalline, therefore oligochitosan is carried out physically modified does not have effect substantially, mainly be to adopt the graft copolymerization technology that oligochitosan is carried out chemical modification, namely introduce some group or pass through chemical copolymerization with other monomer at the tegument oligonucleotide chain, form the oligochitosan graft copolymer, can reduce the degree of crystallinity of oligochitosan, thereby improve its solvability in organic solvent.On this basis, if with biodegradable polymer graft to the oligochitosan chain, the performance of oligochitosan is improved, and can guarantee the completely biodegradable of superpolymer.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, it has excellent mechanical property and good medicine trafficability characteristic, biocompatibility and the nontoxicity of processing characteristics (similar to polyolefine), often be used to fields such as medicine controlled releasing, surgical stapling, organizational project in biomedical materials field, obtained widespread use clinically.But because poor, the degree of crystallinity height of its surface hydrophilicity makes degradation time very long.For oligochitosan, polycaprolactone is flexible macromolecular chain, therefore adopt oligochitosan g-polycaprolactone technology that the macromolecular chain of flexibility is grafted to the oligochitosan g-polycaprolactone multipolymer that obtains on the oligochitosan chain of rigidity, has meltbility, can carry out forming process, thereby overcome the shortcoming that oligochitosan can not fusion, shortened 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.
Perfect along with the enhancing of environmental consciousness and environmental regulation, the market of biodegradable material will increase rapidly, particularly in the application in fields such as plastics film, wrapping material, medical material.The oligochitosan g-polycaprolactone is the macromolecular material of a class fully biodegradable, in the pharmaceutical carrier application facet and manufacture and have a extensive future aspect the environment-friendly materials exploitation, can obtain tangible economic and social benefit, be the quantity of plastics of raw material for solving the pollution of waste plastic to physical environment, reducing with petroleum resources, have important practical significance.
At present, adding the oligochitosan biomaterial in the LDPE matrix prepares degradation material and yet there are no report.Oligochitosan grafting PCL and LDPE, PCL blend be yet there are no report at home and abroad to prepare hot biological degradable composite material.The copolymer blended matrix material of LDPE/ thermoplastic graft copolymer has biological degradability, nontoxic, has potential using value at aspects such as substituting traditional nondegradable medical soup packing bag, disposable injection device, intravenous tube, will the improve the ecological environment situation of deteriorations, solution energy shortage, petroleum resources shortage of its application.
Summary of the invention
Goal of the invention
The invention provides a kind of preparation method of oligochitosan modification biodegradable composite, purpose is that carrying out graft copolymerization by oligochitosan prepares oligochitosan grafting PCL multipolymer, overcoming oligochitosan can not fusion and the shortcoming bad with the macromolecular material consistency, then with itself and LDPE, PCL melt blending with the biological degradability that strengthens LDPE, the mechanical property that improves LDPE, this matrix material has biological degradability simultaneously.
Technical scheme
A kind of preparation method of oligochitosan modification biodegradable composite is characterized in that: this method steps is as follows:
(1) preparation of oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material
With oligochitosan in vacuum drying oven dry 48 hours, deviate from its surperficial planar water, put into moisture eliminator and store, standby;
Oligochitosan, Tetra hydro Phthalic anhydride are put into N successively, in the dinethylformamide solvent, reaction is 7 hours under 90 ℃ of oil bath conditions, reaction solution is poured into sedimentation in the frozen water, with sedimentation gained throw out usefulness ethanol repetitive scrubbing 3 times, usefulness acetone repetitive scrubbing 3 times, filter, place 45 ℃ of baking ovens to dry to constant weight then, obtain brown ceramic powder shape product N-phthaloyl oligochitosan reaction intermediate;
Dried N-phthaloyl oligochitosan is dissolved in the dry pyridine solvent, pours in the there-necked flask, again there-necked flask is put into 120 ℃ oil bath, and in there-necked flask, add the 6-caprolactone monomer; Lead to nitrogen then in there-necked flask, moisture and oxygen impurities in the flask are removed in the degassing, dehydration 2 hours;
Stannous octoate is put into dry pyridine, and to be configured to mass concentration be 20% pyridine solution, and under nitrogen protection, the pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths; Reacted product is precipitated with methyl alcohol, and the product after the filtration extracted 48 hours at apparatus,Soxhlet's with toluene, and the gained brown powder namely obtains the oligochitosan g-polycaprolactone thermoplastic material 40 ℃ of vacuum-dryings;
(2) preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
With the logical nitrogen of there-necked flask to remove in the flask behind the moisture and oxygen impurities, add 6-caprolactone, stannous octoate is put into dry pyridine, and to be configured to mass concentration be 20% pyridine solution, under nitrogen protection, pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths; Reacted product is precipitated with methyl alcohol, and the gained white powder namely gets required polycaprolactone 40 ℃ of vacuum-dryings;
2. oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone blend preparing diaphragm
More than 100 ℃ of following dry 6h of blast drier, PHCSO-g-PCL and PCL are more than 50 ℃ of following dry 6h of vacuum drying oven with Low Density Polyethylene (LDPE);
Take by weighing oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and polycaprolactone (PCL), wherein the oligochitosan g-polycaprolactone thermoplastic material accounts for 40%, the raw material that weighs up is put into beaker respectively, pour in the tetrahydrofuran solvent again, stirring and dissolving mixes, then solution is poured on the polyfluortetraethylene plate, dries, make the diaphragm of PHCSO-g-PCL/PCL binary blend;
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Difference weighing LDPE, binary blend diaphragm (PHCSO-g-PCL/PCL), wherein LDPE accounts for 70-100%, respectively each component is added in the small-sized internal mixer, melt blending 10-15min, blending temperature is 160-180 ℃, extrude the LDPE/PHCSO-g-PCL/PCL intermingling material after, put it into constant voltage 10min in the vulcanizing press immediately, be pressed into the thick thin plate of 1 ~ 4mm, take out thin plate after dropping to room temperature, re-use omnipotent sampling machine and make the standard batten.
The mol ratio of stannous octoate and 6-caprolactone monomer is 0.05%-1% in the step (1), and the proportioning of N-phthaloyl oligochitosan and 6-caprolactone is 1:4 – 1:15(g/mL).
Described oligochitosan molecular weight is less than 1500.
The mass ratio of oligochitosan and Tetra hydro Phthalic anhydride is 1:3.5 in the step (1).
Advantage and effect
Advantage of the present invention and beneficial effect are as follows:
(1) to adopt oligochitosan be raw material in the present invention; at first the amino of oligochitosan is protected; preparation presoma Tetra hydro Phthalic anhydride oligochitosan; reduced the degree of crystallinity of oligochitosan molecule; be conducive to carry out graft copolymerization at the hydroxyl of oligochitosan, thereby realization also makes the polycaprolactone ring-opening polymerization of hydroxyl realize easily when locating grafting.Help to prepare the graft copolymer of high percentage of grafting theoretically, proportioning, temperature of reaction and the reaction times of proportioning, stannous octoate and 6-caprolactone monomer by control 6-caprolactone monomer and Tetra hydro Phthalic anhydride oligochitosan, thus good basis laid for having prepared thermoplastic shell oligosaccharide-g-polycaprolactone material.
(2) oligochitosan can not be dissolved in common organic solvent and heat and can not fusion limit its application.Thereby the present invention is incorporated into the degradation time that degree of crystallinity that the thermoplastic shell oligosaccharide-g-polycaprolactone material for preparing on the rigid backbone of oligochitosan reduced polycaprolactone has reduced polycaprolactone by chemical modification method with the polycaprolactone of flexibility, also reduced simultaneously the degree of crystallinity of oligochitosan, thereby improved the moulding processability of oligochitosan, make graft copolymer when heating can fusion, be spherulitic crystal structure during in cooling, so it is the crystalline material with better mechanical property.Because this grafts has thermoplasticity, can directly adopt melting method to prepare medical bio goods or other Biocomposite material; Its hydrophobic backbone can be used as the medicament slow release material, having a extensive future of biomaterial for medical purpose field.
(3) adopt oligochitosan g-polycaprolactone and PCL elder generation solution blending after, with the method for LDPE melt blending, be conducive to improve the consistency of each component in blended compound material again, thus the mechanical property of raising matrix material.
Description of drawings
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 fusion, just be added into as rigid particles usually and prepare matrix material in the macromolecular material, it and matrix polymer-polymer miscibility are bad, make the mechanical properties decrease of matrix material, thereby limited its widespread use in the material field.Therefore, make oligochitosan have meltbility by oligochitosan is carried out grafting, copolymerization and modification, this oligochitosan graft copolymer can be used as the consistency of compatilizer each storeroom when improving with the polymer melt blending simultaneously, thereby improves the mechanical property of matrix material.
The invention provides a kind of preparation method of oligochitosan modification biodegradable composite, at first with N, dinethylformamide is solvent, prepares N-phthaloyl oligochitosan reaction intermediate with the amino of Tetra hydro Phthalic anhydride protective shell oligosaccharides; Secondly, under nitrogen protection, dropwise add the pyridine solution of stannous octoate, cause 6-caprolactone monomer generation ring-opening polymerization, polycaprolactone is grafted on the hydroxyl of N-phthaloyl oligochitosan, generate the oligochitosan g-polycaprolactone thermoplastic material; At last, LDPE, oligochitosan g-polycaprolactone and polycaprolactone melt blending are prepared biodegradable composite.
These method concrete steps are as follows:
(1) preparation of oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material
With the oligochitosan bought in vacuum drying oven dry 48 hours, deviate from its surperficial planar water, put into moisture eliminator and store, standby;
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 the dinethylformamide solvent, the dinethylformamide solvent is as reaction medium, account for reaction vessel volume 1/3), reaction is 7 hours under 90 ℃ of oil bath conditions, reaction solution is poured into sedimentation in the frozen water, with sedimentation gained throw out usefulness ethanol repetitive scrubbing 3 times, usefulness acetone repetitive scrubbing 3 times, filter, place 45 ℃ of baking ovens to dry to constant weight then, obtain brown ceramic powder shape product N-phthaloyl oligochitosan reaction intermediate;
Dried N-phthaloyl oligochitosan is dissolved in the dry pyridine solvent, pours in the there-necked flask, again there-necked flask is put into 120 ℃ oil bath, and in there-necked flask, add the 6-caprolactone monomer; Lead to nitrogen then in there-necked flask, impurity such as moisture and oxygen in the flask is removed in the degassing, dehydration 2 hours;
Stannous octoate is put into dry pyridine, and to be configured to mass concentration be 20% pyridine solution, and under nitrogen protection, the pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths; Reacted product is precipitated with methyl alcohol, and the product after the filtration extracted 48 hours at apparatus,Soxhlet's with toluene, and the gained brown powder can obtain the oligochitosan g-polycaprolactone thermoplastic material 40 ℃ of vacuum-dryings;
(2) preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
With the logical nitrogen of there-necked flask to remove in the flask behind the impurity such as moisture and oxygen, add 6-caprolactone, stannous octoate is put into dry pyridine, and to be configured to mass concentration be 20% pyridine solution, under nitrogen protection, pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths; Reacted product is precipitated with methyl alcohol, the gained white powder 40 ℃ of vacuum-dryings get final product required polycaprolactone;
2. oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone blend preparing diaphragm
With the industrial goods Low Density Polyethylene (LDPE) bought 100 ℃ of blast driers down more than the dry 6h, the oligochitosan g-polycaprolactone thermoplastic material that PHCSO-g-PCL(step (1) obtains) and the polycaprolactone that 1. obtains of PCL(step) under 50 ℃ of vacuum drying ovens more than the dry 6h;
Accurately take by weighing oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and polycaprolactone (PCL), wherein the oligochitosan g-polycaprolactone thermoplastic material accounts for the 40%(weight ratio), the raw material that weighs up is put into beaker respectively, pour again that (mass ratio of binary blend and tetrahydrofuran (THF) is 1:10 in the tetrahydrofuran solvent into, binary blend is the mixture of oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone), stirring and dissolving mixes, then solution is poured on the polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend;
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Difference weighing LDPE, PHCSO-g-PCL/PCL binary blend diaphragm, wherein LDPE accounts for the 70-100%(weight ratio), respectively each component is added in the small-sized internal mixer, melt blending 10-15min, blending temperature is 160-180 ℃, extrude the LDPE/PHCSO-g-PCL/PCL intermingling material after, put it into constant voltage 10min in the vulcanizing press immediately, be pressed into the thick thin plate of 1 ~ 4mm, take out thin plate after dropping to room temperature, re-use omnipotent sampling machine and make the standard batten.
The mol ratio of stannous octoate and 6-caprolactone monomer is 0.05%-1% in the step (1), and the proportioning of 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 fusion in heat-processed and can crystallization in temperature-fall period, and crystal is spherocrystal.
Earlier 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 the LDPE melt blending.This matrix material has biological degradability, nontoxic, has potential using value at aspects such as substituting traditional nondegradable agricultural mulching, wrapping material and medical soup packing bag, disposable injection device, intravenous tube, will the improve the ecological environment situation of deteriorations, solution energy shortage, petroleum resources shortage of its application.
Described oligochitosan g-polycaprolactone thermoplastic material can fusion under heating condition, can directly be processed into corresponding degradable biomaterial goods by traditional forming polymer working method (as injection molding, extrusion moulding and compression moulding).In addition, the oligochitosan g-polycaprolactone thermoplastic material is except preparing degradable composite material by the melt blending mode with the LDPE that mentions in this patent, and then adopt traditional forming polymer working method to produce outside the degradable product, also can be used on and thermoplastic starch or synthetic polymer such as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), polybutylene terephthalate (PBT), polypropylene, high density polyethylene(HDPE) adopts traditional forming polymer working method (as injection molding by melt blending, extrusion moulding and compression moulding) prepare the degradable product.
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1
1. the preparation of oligochitosan g-polycaprolactone thermoplastic material
(1) preparation of N-phthaloyl oligochitosan
With the oligochitosan bought in vacuum drying oven dry 48 hours, deviate from its surperficial planar water, put into moisture eliminator and store, standby.
With 1g oligochitosan, 2g Tetra hydro Phthalic anhydride and 30ml N; dinethylformamide adds in the there-necked flask successively; reaction is 7 hours under 90 ℃ of oil bath conditions; then reaction solution is poured into sedimentation in the frozen water; with throw out usefulness ethanol repetitive scrubbing 3 times, usefulness acetone repetitive scrubbing 3 times, filter, place 45 ℃ of baking ovens to dry to constant weight then; obtain brown ceramic powder shape product N-phthaloyl oligochitosan reaction intermediate, productive rate is 67.85%.
(2) preparation of N-phthaloyl oligochitosan g-polycaprolactone
Be dissolved in the 1g N-phthaloyl oligochitosan of drying in the dry pyridine solvent and 4ml 6-caprolactone monomer is poured (there-necked flask is put into 120 ℃ oil bath) in the there-necked flask into; in there-necked flask, lead to nitrogen; impurity such as moisture and oxygen in the flask is removed in the degassing, dehydration 2 hours.0.15g stannous octoate (mol ratio that stannous octoate accounts for the 6-caprolactone monomer is 0.5%) is put into dry pyridine, and to be configured to concentration be 20% pyridine solution; under nitrogen protection, join in the above-mentioned there-necked flask stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths.Reacted product is precipitated with methyl alcohol, and the product after the filtration extracted 48 hours at apparatus,Soxhlet's with toluene, and the gained brown powder can obtain the oligochitosan g-polycaprolactone thermoplastic material 40 ℃ of vacuum-dryings.
2. the preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
With the logical nitrogen of there-necked flask to remove in the flask behind the impurity such as moisture and oxygen; add 6 ml 6-caprolactones; 0.068g stannous octoate (mol ratio that stannous octoate accounts for the 6-caprolactone monomer is 0.3%) is put into dry pyridine, and to be configured to concentration be 20% pyridine solution; under nitrogen protection; pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask; stirring reaction is 26 hours in 120 ℃ of oil baths; reacted product is precipitated with methyl alcohol, the gained white powder 40 ℃ of vacuum-dryings get final product required polycaprolactone.
2. oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone blend preparing diaphragm
LDPE is more than 100 ℃ of following dry 6h of blast drier, and PHCSO-g-PCL and PCL are more than 50 ℃ of following dry 6h of vacuum drying oven.
Accurately take by weighing 4g oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and 6g polycaprolactone (PCL), the raw material that weighs up is put into beaker respectively, pour 100 ml tetrahydrofuran solvents again into, stirring and dissolving mixes, then solution is poured on the polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend.
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Difference weighing 42.5g LDPE and 7.5g PHCSO-g-PCL/PCL binary blend diaphragm, wherein LDPE accounts for the 85%(weight ratio), respectively each component is added in the small-sized internal mixer, at 160 ℃ of following melt blending 10-15min, then the LDPE/PHCSO-g-PCL/PCL intermingling material is put it into immediately in the vulcanizing press at 160 ℃ of following constant voltage 10min, be pressed into the thick thin plate of 2mm, take out thin plate after dropping to room temperature, re-use omnipotent sampling machine cutting, make the standard batten.
Fig. 1 for thermoplastic shell oligosaccharide-g-polycaprolactone graft copolymer among the embodiment 1 that obtains by technical scheme of the present invention respectively at the differential scanning calorimetry curve of 10 ℃ of intensifications and rate of temperature fall, the curve at A point place is the heating curve of differential scanning calorimetry among Fig. 1, the A point is 55.82 ℃ for the fusing point of oligochitosan g-polycaprolactone graft copolymer, show that this graft copolymer can fusion in temperature-rise period, thereby have thermoplasticity; The curve at B point place is the temperature lowering curve of differential scanning calorimetry, and the B point shows that for the Tc of oligochitosan g-polycaprolactone graft copolymer is 22.49 ℃ this graft copolymer can crystallization in temperature-fall period.
Fig. 2 is the stress-strain curve of oligochitosan modified degradable bio-medical composition among Low Density Polyethylene (LDPE) and the embodiment 1.A is LDPE, and 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 higher than LDPE, and σ is 10.24MPa, and elongation is lower than LDPE, and ε is 347%.
1. the mol ratio of stannous octoate and 6-caprolactone monomer is that the proportioning of 1%, N-phthaloyl oligochitosan and 6-caprolactone is 1:15(g/ mL in the preparation of oligochitosan g-polycaprolactone thermoplastic material, step (1)), all the other conditions are with embodiment 1;
2. the preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL) (mol ratio that stannous octoate accounts for the 6-caprolactone monomer is 0.05%, and preparation condition is with embodiment 1).
2. oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone blend preparing diaphragm
LDPE is more than 100 ℃ of following dry 6h of blast drier, and PHCSO-g-PCL and PCL are more than 50 ℃ of following dry 6h of vacuum drying oven.
Accurately take by weighing 4g oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and 6g polycaprolactone (PCL), the raw material that weighs up is put into beaker respectively, pour 100 ml tetrahydrofuran solvents again into, stirring and dissolving mixes, then solution is poured on the polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend.
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Difference weighing 40g LDPE and 10g PHCSO-g-PCL/PCL binary blend diaphragm, wherein LDPE accounts for the 80%(weight ratio), respectively each component is added in the small-sized internal mixer, at 180 ℃ of following melt blending 10-15min, then the LDPE/PHCSO-g-PCL/PCL intermingling material is put it into immediately in the vulcanizing press at 160 ℃ of following constant voltage 10min, be pressed into the thick thin plate of 4mm, take out thin plate after dropping to room temperature, re-use omnipotent sampling machine cutting, make the standard batten.
Embodiment 3
1. the preparation of oligochitosan g-polycaprolactone thermoplastic material; the mol ratio of stannous octoate and 6-caprolactone monomer is 0.05% in the step (1); 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 of polycaprolactone (PCL) (mol ratio that stannous octoate accounts for the 6-caprolactone monomer is 1%, and preparation condition is with embodiment 1).
2. oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone blend preparing diaphragm
LDPE is more than 100 ℃ of following dry 6h of blast drier, and PHCSO-g-PCL and PCL are more than 50 ℃ of following dry 6h of vacuum drying oven.
Accurately take by weighing 4g oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and 6g polycaprolactone (PCL), the raw material that weighs up is put into beaker respectively, pour 100 ml tetrahydrofuran solvents again into, stirring and dissolving mixes, then solution is poured on the polyfluortetraethylene plate, dry, make the diaphragm of certain thickness PHCSO-g-PCL/PCL binary blend.
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Difference weighing 45g LDPE and 5g PHCSO-g-PCL/PCL binary blend diaphragm, wherein LDPE accounts for the 90%(weight ratio), respectively each component is added in the small-sized internal mixer, at 170 ℃ of following melt blending 12min, then the LDPE/PHCSO-g-PCL/PCL intermingling material is put it into immediately in the vulcanizing press at 160 ℃ of following constant voltage 10min, be pressed into the thick thin plate of 1mm, take out thin plate after dropping to room temperature, re-use omnipotent sampling machine cutting, make the standard batten.
Embodiment 4
Step is 3. in the LDPE/PHCSO-g-PCL/PCL blend preparation, weighing 35g LDPE and 15g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for the 70%(weight ratio), all the other conditions are with embodiment 1.
Embodiment 5
Step is 3. in the LDPE/PHCSO-g-PCL/PCL blend preparation, weighing 50g LDPE and 0g PHCSO-g-PCL/PCL binary blend diaphragm respectively, wherein LDPE accounts for the 100%(weight ratio), all the other conditions are with embodiment 1.(content of binary blend is zero in this blend sample, and reality is pure LDPE diaphragm, can be used as other blended compound material performance test with reference to sample)
Conclusion: the oligochitosan g-polycaprolactone thermoplastic material for preparing among the present invention has enlarged the use range of oligochitosan, can be used as interface coupling agent, the agricultural chemicals control release capsule solid support material of chitosan, oligochitosan, various starch and polycaprolactone blend, also can directly under melting condition, be processed into relevant biologic material products; The matrix material of the present invention's preparation is nontoxic, is having broad application prospects aspect the medical materials such as preparation degradable plastic product, agricultural mulching, wrapping material and medical soup packing bag, disposable injection device, intravenous tube.In addition, method of the present invention also provides theoretical foundation for the blend of oligochitosan and other macromolecular material with research and the application for preparing biodegradable composite.
Claims (5)
1. the preparation method of an oligochitosan modification biodegradable composite, it is characterized in that: this method steps is as follows:
(1) preparation of oligochitosan g-polycaprolactone (PHCSO-g-PCL) thermoplastic material
With oligochitosan in vacuum drying oven dry 48 hours, deviate from its surperficial planar water, put into moisture eliminator and store, standby;
Oligochitosan, Tetra hydro Phthalic anhydride are put into N successively, in the dinethylformamide solvent, reaction is 7 hours under 90 ℃ of oil bath conditions, reaction solution is poured into sedimentation in the frozen water, with sedimentation gained throw out usefulness ethanol repetitive scrubbing 3 times, usefulness acetone repetitive scrubbing 3 times, filter, place 45 ℃ of baking ovens to dry to constant weight then, obtain brown ceramic powder shape product N-phthaloyl oligochitosan reaction intermediate;
Dried N-phthaloyl oligochitosan is dissolved in the dry pyridine solvent, pours in the there-necked flask, again there-necked flask is put into 120 ℃ oil bath, and in there-necked flask, add the 6-caprolactone monomer; Lead to nitrogen then in there-necked flask, moisture and oxygen impurities in the flask are removed in the degassing, dehydration 2 hours;
Stannous octoate is put into dry pyridine, and to be configured to mass concentration be 20% pyridine solution, and under nitrogen protection, the pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths; Reacted product is precipitated with methyl alcohol, and the product after the filtration extracted 48 hours at apparatus,Soxhlet's with toluene, and the gained brown powder namely obtains the oligochitosan g-polycaprolactone thermoplastic material 40 ℃ of vacuum-dryings;
(2) preparation of oligochitosan modification biodegradable composite
1. the preparation of polycaprolactone (PCL)
With the logical nitrogen of there-necked flask to remove in the flask behind the moisture and oxygen impurities, add 6-caprolactone, stannous octoate is put into dry pyridine, and to be configured to mass concentration be 20% pyridine solution, under nitrogen protection, pyridine solution with 20% dropwise joins in the above-mentioned there-necked flask, stirring reaction stopped reaction after 26 hours in 120 ℃ of oil baths; Reacted product is precipitated with methyl alcohol, and the gained white powder namely gets required polycaprolactone 40 ℃ of vacuum-dryings;
2. oligochitosan g-polycaprolactone thermoplastic material and polycaprolactone blend preparing diaphragm
More than 100 ℃ of following dry 6h of blast drier, PHCSO-g-PCL and PCL are more than 50 ℃ of following dry 6h of vacuum drying oven with Low Density Polyethylene (LDPE);
Take by weighing oligochitosan g-polycaprolactone thermoplastic material (PHCSO-g-PCL) and polycaprolactone (PCL), wherein the oligochitosan g-polycaprolactone thermoplastic material accounts for 40%, the raw material that weighs up is put into beaker respectively, pour in the tetrahydrofuran solvent again, stirring and dissolving mixes, then solution is poured on the polyfluortetraethylene plate, dries, make the diaphragm of PHCSO-g-PCL/PCL binary blend;
3. LDPE/PHCSO-g-PCL/PCL blend preparation
Difference weighing LDPE, binary blend diaphragm (PHCSO-g-PCL/PCL), wherein LDPE accounts for 70-100%, respectively each component is added in the small-sized internal mixer, melt blending 10-15min, blending temperature is 160-180 ℃, extrude the LDPE/PHCSO-g-PCL/PCL intermingling material after, put it into constant voltage 10min in the vulcanizing press immediately, be pressed into the thick thin plate of 1 ~ 4mm, take out thin plate after dropping to room temperature, re-use omnipotent sampling machine and make the standard batten.
2. according to the preparation method of the described a kind of oligochitosan modification biodegradable composite of claim 1; it is characterized in that: the mol ratio of stannous octoate and 6-caprolactone monomer is 0.05%-1% in the step (1), and the proportioning of N-phthaloyl oligochitosan and 6-caprolactone is 1:4 – 1:15(g/mL).
3. according to the preparation method of the described a kind of oligochitosan modification biodegradable composite of claim 1, it is characterized in that: described oligochitosan molecular weight is less than 1500.
4. according to the preparation method of the described a kind of oligochitosan modification biodegradable composite of claim 1, it is characterized in that: the mass ratio of oligochitosan and Tetra hydro Phthalic anhydride is 1:3.5 in the step (1).
5. according to the preparation method of the described a kind of oligochitosan modification biodegradable composite of claim 1, it is characterized in that: step 2. in the mass ratio of binary blend and tetrahydrofuran (THF) be 1:10.
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 true CN103254599A (en) | 2013-08-21 |
| CN103254599B 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885182A (en) * | 2016-07-01 | 2016-08-24 | 赵艳丽 | Medical biological polymer 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 |
| CN111607207A (en) * | 2020-06-29 | 2020-09-01 | 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 (3)
| 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 |
| US20050043456A1 (en) * | 2003-08-20 | 2005-02-24 | Oriani Steven Richard | Process aid for metallocene catalyzed linear low density polyethylene polymers |
| CN101857649A (en) * | 2010-03-18 | 2010-10-13 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material |
-
2013
- 2013-05-31 CN CN201310212908.4A patent/CN103254599B/en active Active
Patent Citations (3)
| 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 |
| US20050043456A1 (en) * | 2003-08-20 | 2005-02-24 | Oriani Steven Richard | Process aid for metallocene catalyzed linear low density polyethylene polymers |
| CN101857649A (en) * | 2010-03-18 | 2010-10-13 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885182A (en) * | 2016-07-01 | 2016-08-24 | 赵艳丽 | Medical biological polymer 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 |
| CN111607207A (en) * | 2020-06-29 | 2020-09-01 | 无锡会通轻质材料股份有限公司 | Expandable biodegradable particles and biodegradable foaming beads with antibacterial function |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103254599B (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104072957B (en) | A kind of food grade biodegradable polylactic acid based composites and application thereof | |
| CN103992517A (en) | Continuously-produced full-degradable starch-based plastic alloy and preparation method thereof | |
| CN102666619A (en) | Biodegradable polyester | |
| CN101824229B (en) | Thermoplastic plant fiber/polylactic acid blending material and preparation method thereof | |
| CN106674923B (en) | A kind of controllable PBAT/PLA composite membranes and preparation method thereof of degrading | |
| CN103965598B (en) | Polydactyl acid and preparation method thereof | |
| CN101580642A (en) | Full-biodegradation natural polymer alloy and preparation method thereof | |
| CN101495571A (en) | Thermoplastic resin composition and molded body thereof | |
| CN1834134A (en) | Blend material of vinol/polylactic acid graft copolymer and starch, their prepn. and application | |
| CN103254599B (en) | Method for preparing chitosan oligosaccharide modified biodegradable composite | |
| CN107522904A (en) | A kind of Starch Based Biodegradable Plastics applied to packaging for foodstuff | |
| CN101168616B (en) | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material | |
| CN101974136A (en) | Method for preparing high-toughness degradable material by using melt-grafting blending method | |
| CN103183936A (en) | Biodegradable composite material prepared by excessive processing materials of high-starch crops and preparation method thereof | |
| CN104877352A (en) | Compatibilizer-containing fibroin/polylactic acid blended material and preparation method thereof | |
| 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 | |
| CN102134380A (en) | Completely biodegradable composite material and preparation method thereof | |
| CN103183937B (en) | A kind of modified polylactic acid composite material and preparation method thereof | |
| CN104530670A (en) | Fibroin/polylactic acid blend material and melt-blending preparation method thereof | |
| CN102617969B (en) | Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material | |
| CN109401239A (en) | A kind of biodegradable material for crisper, crisper and preparation method thereof | |
| CN114573721B (en) | Rapidly degradable biological plastic and preparation method thereof | |
| CN106751568A (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| CN102030892B (en) | Preparation method of glutinous rice flour grafted polycaprolactone thermoplastic material |
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 |