CN102120871A - Preparation method of chitosan fiber reinforced polylactic acid composite material - Google Patents
Preparation method of chitosan fiber reinforced polylactic acid composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a chitosan fiber reinforced polylactic acid composite material, which comprises the following steps: dissolving a purified polylactic acid in a solvent, adding purified chitosan fibers, fully infiltrating the chitosan fibers in the polylactic acid, and carrying out vacuum drying after the volatilization of the solvent to obtain a chitosan fiber/polylactic acid mixture; and placing the mixture in a mold in random orientation or uniaxial orientation or 0-degree/90-degree orientation or 0-degree/+45-degree/-45-degree/0-degree orientation, and carrying out compression molding on a vacuum flat-plate vulcanizing machine under the conditions of 20-230 DEG C, 1-200MPa and 0.01-100000Pa to obtain the composite material. The preparation method has the advantages that the quality of the raw materials is improved, the chitosan/polylactic acid composite material with good interface compatibility can be obtained without adding interface compatilizer or carrying out other interface processing, and the negative effects possibly caused by multicomponent and multiprocessing steps can be avoided.
Description
Technical field
The invention belongs to field of compound material, relate to a kind of material and preparation method of orthopedic fixation device spare, particularly a kind of chitin fiber strengthens the preparation method of lactic acid composite material.
Background technology
Traditional orthopedic fixation device spare mainly adopts titanium alloy and stainless steel and other metal materials.This metalloid material device stable mechanical property, shape retention is good, and fracture is accurately resetted, and promotes knitting, be treatment fracture at present mainly select device for use.But long-term Clinical Laboratory finds that this metalloid material device has many deficiencies.Using biodegradable medical macromolecular materials device to replace the metallic substance device is main development trend.Be used in clinical biodegradable polymer at present and mainly comprise poly(lactic acid), polyglycolic acid, polymeric polyglycolide-polylactide, polycaprolactone, poly-dioxane etc.
Wherein poly(lactic acid) orthopedic fixation device spare is owing to have excellent biological compatibility, nontoxic, no antigen, non-carcinogenesis, can degrade fully, need not advantages such as second operation taking-up, clinical application decades is main biodegradable medical macromolecular materials devices of current use.But its initial mechanical intensity is not high, and perhaps early stage degradation speed is fast, can only be used for the internal fixing of non-bearing bone, and can not be used for the internal fixing of load bone such as limb long tubular bone.The internal fixation material of simultaneously pure poly(lactic acid) preparation also has the passivity possibility of infection.The mechanical strength of solution poly(lactic acid) internal fixation material is not high and avoid acidity to become this type of material focus of research at present excessively by force.
The chitin fiber biocompatibility is good, can biological degradation, have certain intensity, and chitosan aqueous solution presents slight alkalinity, carry out chitin fiber and poly(lactic acid) compound, wish both can strengthen the acidity that produces in the time of to cushion the poly-lactic acid material degraded again to poly-lactic acid material.Literature search is found: Chinese patent: " fibre-reinforced polylactic acid composition " application number: 01107011.0, publication number: CN1362447, this patent has used chitin fiber to strengthen lactic acid composite material, its moulding technique is that chitin fiber and poly(lactic acid) are mixing even on mixing roll more earlier, carry out conventional compression molding again, prepared chitin fiber strengthens the lactic acid composite material flexural strength can reach 161.3MPa.Chinese patent: " modified chitin fiber reinforcement lactic acid composite material and preparation method thereof " application number: 03150485.X, publication number: CN1488673, this patent has been used modified chitin fiber reinforcement lactic acid composite material, its moulding technique carries out conventional compression molding with prepreg again for making prepreg earlier, it is 78.76MPa that prepared unmodified chitin fiber strengthens the lactic acid composite material flexural strength, and modified chitin fiber reinforcement lactic acid composite material flexural strength is 114.72MPa.Chinese patent: " a kind of hone lamella that is used for; nail; the preparation methods of bone piece " application number: 200710032725.9; publication number: CN101209355; this patent has been used poly(lactic acid); chitin fiber; modified chitosan; hydroxyapatite; modified hydroxylapatite; polycomponent compound systems such as compatilizer; its moulding technique is first extruding pelletization or melt extrudes or torque rheometer blend or solution blending etc.; carry out conventional injection moulding or conventional compression molding or precise injection molding again; gained lactic acid composite material flexural strength can reach 165.3-297.7MPa, and the main effect of chitin fiber is the aseptic inflammation that acid product causes when relaxing the poly(lactic acid) degraded.
Can see that from above patent situation single chitin fiber of use or single modified chitin fiber strengthen poly(lactic acid), its flexural strength is not high, do not reach the flexural strength 176-205MPa of human body cortex bone, limited the use range of lactic acid composite material.If use the polycomponent compound system, though can reach or surpass flexural strength, the mechanism of its moulding and degraded and the practical function effect more complicated of human body cortex bone.
Existing preparation method belongs to conventional Process Technology of Polymer method basically, and prepared goods can only reach the compound of O-level mostly, and certain reinforced effects is arranged, but the performance increase rate is smaller.From microtexture, the matrix resin poly(lactic acid) in its goods does not form extended-chain lamellae, fibrous crystal and shish-kebab, and perhaps its quantity is fewer, and perhaps its arrangement is random, does not perhaps form good synergy with chitin fiber.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art with not enough, provide a kind of chitin fiber to strengthen the preparation method of lactic acid composite material, use single chitin fiber or single modified chitin fiber that poly(lactic acid) is strengthened, reach than higher flexural strength, enlarge the use range of lactic acid composite material.
Purpose of the present invention is achieved through the following technical solutions:
A kind of chitin fiber strengthens the preparation method of lactic acid composite material, may further comprise the steps:
(1) be that the poly(lactic acid) of 20-95% and chitin fiber that weight percent is 5-80% are respectively at vacuum tightness 0.01-100000Pa with weight percent, under the temperature 20-160 ℃ of condition vacuum-drying 0.5-1000 hour, remove free water content and impurity, the purifying poly(lactic acid), chitin fiber, poly(lactic acid) is dissolved in the solvent, add chitin fiber then, make poly(lactic acid) fully soak into chitin fiber, after the solvent evaporates further at vacuum tightness 0.01-100000Pa, remove free water content and impurity in vacuum-drying 0.5-1000 hour under the temperature 20-160 ℃ of condition, make chitin fiber/poly-lactic acid mixture;
(2) chitin fiber/poly-lactic acid mixture that step (1) is obtained is according to die size and moulding requirement, put into mould with random orientation or uniaxial orientation or 0 °/90 ° orientations or 0 ° /+45 °/-45 °/0 ° orientation, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness: carry out compression molding under the 0.01-100000Pa condition, obtain chitin fiber and strengthen lactic acid composite material.
Described chitin fiber is that deacetylation is chitin fiber or chitin fiber fabric or the modified chitosan fiber of 0-100%, and viscosity-average molecular weight is 50,000-1,000,000.
Described poly(lactic acid) is Poly-L-lactic acid or dextrorotation poly(lactic acid) or poly-dl-lactide or their blend, and viscosity-average molecular weight is 50,000-1,000,000.
Described solvent is chloroform, acetonitrile, tetrahydrofuran (THF), methylene dichloride, dioxan or their mixed solvent.
The mass concentration that described poly(lactic acid) is dissolved in back poly(lactic acid) in the solvent is 0.5-70%.
Mechanism of the present invention is: chitin fiber soaks in poly(lactic acid) solution, control condition well, make particularly its noncrystalline domain generation swelling to a certain degree of chitin fiber, make things convenient for the polylactic acid molecule chain end of the chain to enter the top layer or the nexine of chitin fiber, after solvent evaporates, there are the polylactic acid molecule chain segment of some amount and the molecular chain of chitin fiber that winding has taken place, stay in the chitin fiber, its remaining segment and other polylactic acid molecule chains twine, attached to the surface of chitin fiber.
When putting into mould and carry out vacuum compression molding, polylactic acid molecule chain terminated carboxyl, the hydroxyl stayed in the fortifying fibre may form covalent bonds with generation chemical crosslink reactions to a certain degree such as free carboxyl, amino, hydroxyl and amide group on the chitin fiber, the small molecules that is produced is detached rapidly under vacuum environment, other unreacted polylactic acid molecule chains and chitin fiber molecular chain may twine mutually and form the combination that comprises non covalent bonds such as hydrogen bond, Van der Waals force, are adhering to chitin fiber and are being in the same place.Another section polylactic acid molecule chain outside the chitin fiber surface and other polylactic acid molecule chains that twine with this part polylactic acid molecule chain generation, the edge direction parallel with chitin fiber fully stretches easily under the effect of molten state and external pressure, forms extended-chain lamellae, fibrous crystal or shish-kebab.Poly(lactic acid) away from the chitin fiber surface then may form fibrous crystal and shish-kebab under mobile and strain inducing, its direction of extension also is the edge direction parallel with chitin fiber.Possibility polylactic acid molecule chain does not enter the upper layer of fortifying fibre yet, on chitin fiber surface and chitin fiber winding has to a certain degree taken place just, when putting into mould and carry out the automatic vacuum compression molding, may above-mentioned crystalline orientation process take place on the chitin fiber surface, formed extended-chain lamellae, fibrous crystal and shish-kebab equally.
Electron microscopic observation finds that poly(lactic acid) on the chitin fiber surface tangible crystalline orientation has taken place, and has formed extended-chain lamellae, fibrous crystal and shish-kebab, makes the flexural strength of various chitin fiber/lactic acid composite materials that raising in various degree arranged.
The present invention uses single chitin fiber or single modified chitosan fiber that poly(lactic acid) is strengthened, reach than higher flexural strength, initial flexural strength is about 163-256.5MPa, enlarged the use range of lactic acid composite material, the preparation method is simple, practical, realize suitability for industrialized production easily.
The present invention compared with prior art has the following advantages: 1. effectively purifying poly(lactic acid), chitin fiber raw material, improved the quality of raw material.2. need not add interfacial compatibilizer or carry out other interface processing, just can obtain the chitosan/lactic acid composite material of good interface compatibility, the negative impact of having avoided polycomponent and multiprocessing step to bring.3. the chitin fiber that suitable complete processing makes strengthens lactic acid composite material and has mechanical property preferably, has enlarged the use range of matrix material.4. can avoid lactic acid composite material acidity strong excessively, reduce the incidence that passivity infects.
Description of drawings
The chitin fiber of Fig. 1 embodiment 1 preparation strengthens lactic acid composite material Electronic Speculum figure (amplifying 103 times)
The chitin fiber of Fig. 2 embodiment 1 preparation strengthens lactic acid composite material Electronic Speculum figure (amplifying 1000 times)
Best embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
Be positioned over the poly-dl-lactide (viscosity-average molecular weight 200,000) of weight percent 20% and the chitin fiber (deacetylation 75%, viscosity-average molecular weight 150,000) of weight percent 80% in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), chitin fiber raw material, poly(lactic acid) is dissolved in the dichloromethane solvent, and the mass concentration of poly(lactic acid) is 20%.Add chitin fiber, make poly(lactic acid) fully soak into chitin fiber, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes chitin fiber/poly-lactic acid mixture.
With chitin fiber/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with the random orientation arrangement architecture, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 131.7MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 145.3MPa, and the 10000Pa flexural strength can reach 150.2MPa, and the 0.01Pa flexural strength can reach 163MPa.
The chitin fiber that obtains is strengthened lactic acid composite material carry out electron microscopic observation, the results are shown in accompanying drawing 1, Fig. 2, Fig. 2 can find that chitin fiber/poly(lactic acid) stretches out to the lower right corner, every chitin fiber is axle center (chitin fiber shown in Figure 2 is solid part), polylactic resin is superimposed with each other with stratiform and is wrapped in the chitin fiber outside, every layer thickness has very big difference, little near the thickness of chitin fiber, may be at nano level, and also the density of layer is big, close and numerous, polylactic resin layer thickness away from the fiber axle center increases gradually, and two fiber intermediary thickness maximums have about 10 microns.This structure helps the matrix material batten and bears bigger load.
Embodiment 2
With the dextrorotation poly(lactic acid) (viscosity-average molecular weight 1,000,000) of weight percent 95%, the chitin fiber (deacetylation 30% of weight percent 5%, viscosity-average molecular weight 600,000) be positioned in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), chitin fiber raw material are dissolved in poly(lactic acid) in the chloroform solvent, and the mass concentration of poly(lactic acid) is 20%.Add chitin fiber, make poly(lactic acid) fully soak into chitin fiber, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes chitin fiber/poly-lactic acid mixture.
With chitin fiber/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with the uniaxial orientation arrangement architecture, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 153.8MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 165.1MPa, and the 10000Pa flexural strength can reach 175.2MPa, and the 0.01Pa flexural strength can reach 213.3MPa.
Embodiment 3
With the Poly-L-lactic acid (viscosity-average molecular weight 100,000) of weight percent 50%, the chitin fiber (deacetylation 90% of weight percent 50%, viscosity-average molecular weight 100,000) be positioned in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), chitin fiber raw material are dissolved in poly(lactic acid) in the acetonitrile solvent, and the mass concentration of poly(lactic acid) is 20%.Add chitin fiber, make poly(lactic acid) fully soak into chitin fiber, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes chitin fiber/poly-lactic acid mixture.
With chitin fiber/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with 0 °/90 ° orientation arrangement structures, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 165.6MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 180.1MPa, and the 10000Pa flexural strength can reach 191.8MPa, and the 0.01Pa flexural strength reaches 233.9MPa.
Embodiment 4
With the poly-dl-lactide (viscosity-average molecular weight 100,000) of weight percent 70%, the chitin fiber (deacetylation 60% of weight percent 30%, viscosity-average molecular weight 500,000) be positioned in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), chitin fiber raw material are dissolved in poly(lactic acid) in the tetrahydrofuran solvent, and the mass concentration of poly(lactic acid) is 20%.Add chitin fiber, make poly(lactic acid) fully soak into chitin fiber, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes chitin fiber/poly-lactic acid mixture.
With chitin fiber/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with 0 ° /+45 °/-45 °/0 ° orientation arrangement structure, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D 790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 133.4MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 151.9MPa, and the 10000Pa flexural strength can reach 165.3MPa, and the 0.01Pa flexural strength reaches 186.5MPa.
Embodiment 5
With the Poly-L-lactic acid (viscosity-average molecular weight 1,000,000) of weight percent 55%, the chitin fiber fabric (deacetylation 30% of weight percent 45%, viscosity-average molecular weight 600,000) be positioned in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), chitin fiber textile are dissolved in poly(lactic acid) in the dioxan solvent, and the mass concentration of poly(lactic acid) is 20%.Add the chitin fiber fabric, make poly(lactic acid) fully soak into the chitin fiber fabric, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes chitin fiber fabric/poly-lactic acid mixture.
With chitin fiber fabric/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with 0 °/90 ° orientation arrangement structures, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D 790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 184.0MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 210.5MPa, and the 10000Pa flexural strength can reach 225.4MPa, and the 0.01Pa flexural strength can reach 256.5MPa.
Embodiment 6
With the dextrorotation poly(lactic acid) (viscosity-average molecular weight 500,000) of weight percent 75%, the chitin fiber fabric (deacetylation 20% of weight percent 25%, viscosity-average molecular weight 850,000) be positioned in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), chitin fiber textile are dissolved in poly(lactic acid) in the dichloromethane solvent, and the mass concentration of poly(lactic acid) is 20%.Add the chitin fiber fabric, make poly(lactic acid) fully soak into the chitin fiber fabric, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes chitin fiber fabric/poly-lactic acid mixture.
With chitin fiber fabric/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with 0 ° /+45 °/-45 °/0 ° orientation arrangement structure, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D 790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 165.6MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 200.5MPa, and the 10000Pa flexural strength can reach 219.3MPa, and the 0.01Pa flexural strength can reach 246.1MPa.
Embodiment 7
With the Poly-L-lactic acid (viscosity-average molecular weight 600,000) of weight percent 60%, the acetylated chitosan sugar fiber (deacetylation 0% of weight percent 40%; viscosity-average molecular weight 1,000,000) be positioned in the vacuum drying oven respectively; vacuum tightness 0.06Pa; 40 ℃ of temperature; removed free water content and impurity in 48 hours; purifying poly(lactic acid), acetylated chitosan sugar fibrous material are dissolved in poly(lactic acid) in the chloroform solvent, and the mass concentration of poly(lactic acid) is 20%.Add acetylated chitosan sugar fiber; make poly(lactic acid) fully soak into acetylated chitosan sugar fiber; further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes acetylated chitosan sugar fiber/poly-lactic acid mixture.
With the acetylated chitosan that obtains sugar fiber/poly-lactic acid mixture according to die size and moulding requirement; put into mould with 0 °/90 ° orientation arrangement structures; on the evacuated flat panel vulcanizer in temperature: 20-230 ℃; pressure: 1-200MPa; vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D 790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 167.3MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 185.6MPa, and the 10000Pa flexural strength can reach 195.3MPa, and the 0.01Pa flexural strength reaches 238.7MPa.
Embodiment 8
With the poly-dl-lactide (viscosity-average molecular weight 500,000) of weight percent 45%, the glutaraldehyde modified chitosan fiber (deacetylation 100% of weight percent 55%, viscosity-average molecular weight 400,000) be positioned in the vacuum drying oven respectively, vacuum tightness 0.06Pa, 40 ℃ of temperature, removed free water content and impurity in 48 hours, purifying poly(lactic acid), glutaraldehyde modified chitosan fiber raw material are dissolved in poly(lactic acid) in the acetonitrile solvent, and the mass concentration of poly(lactic acid) is 20%.Add chitin fiber, make poly(lactic acid) fully soak into chitin fiber, further vacuum-drying after the solvent evaporates (vacuum tightness 0.06Pa, 40 ℃ of temperature were removed free water content and impurity in 48 hours) makes glutaraldehyde modified chitosan fiber/poly-lactic acid mixture.
With glutaraldehyde modified chitosan fiber/poly-lactic acid mixture of obtaining according to die size and moulding requirement, put into mould with 0 °/90 ° orientation arrangement structures, on the evacuated flat panel vulcanizer in temperature: 20-230 ℃, pressure: 1-200MPa, vacuum tightness 0.01-100000Pa carries out compression molding, obtains chitin fiber and strengthens lactic acid composite material.Use day island proper Tianjin AG-1 electronic universal tester and German ZWick universal testing machine, with reference to standards such as ASTM D 790, ISO 178, adopt the three-point bending testing method, establishing rate of bending is 2mm/min, and span 30mm. carries out the bending property test of matrix material.Normal pressure counterdie press-bending Qu Qiangdu can reach 171.2MPa (contrast), and vacuum tightness 100000Pa flexural strength can reach 198MPa, and the 10000Pa flexural strength can reach 217.4MPa, and the 0.01Pa flexural strength reaches 247.3MPa.
Comparative Examples 1
Raw material only adopts poly-dl-lactide (viscosity-average molecular weight 200,000), all the other preparation methods are with embodiment one, material normal pressure counterdie press-bending Qu Qiangdu can reach 102.3MPa (contrast), vacuum tightness 100000Pa flexural strength can reach 105.4MPa, the 10000Pa flexural strength can reach 107.5MPa, and the 0.01Pa flexural strength reaches 113.8MPa.
Comparative Examples 2
Raw material is with embodiment one, and the preparation method adopts conventional injection moulding, and the material bending intensity that obtains reaches 110 ± 5MPa.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. the preparation method of a chitin fiber enhancing lactic acid composite material is characterized in that, may further comprise the steps:
(1) be that the poly(lactic acid) of 20-95% and chitin fiber that weight percent is 5-80% are respectively at vacuum tightness 0.01-100000Pa with weight percent, under the temperature 20-160 ℃ of condition vacuum-drying 0.5-1000 hour, then poly(lactic acid) is dissolved in the solvent, add chitin fiber, make poly(lactic acid) fully soak into chitin fiber, after the solvent evaporates further at vacuum tightness 0.01-100000Pa, under the temperature 20-160 ℃ of condition vacuum-drying 0.5-1000 hour, make chitin fiber/poly-lactic acid mixture;
(2) chitin fiber/poly-lactic acid mixture that step (1) is obtained is put into mould with random orientation or uniaxial orientation or 0 °/90 ° orientations or 0 ° /+45 °/-45 °/0 ° orientation, on the evacuated flat panel vulcanizer in 20-230 ℃, 1-200MPa, 0.01-100000Pa carry out compression molding under the condition, obtain chitin fiber and strengthen lactic acid composite material.
2. strengthen the preparation method of lactic acid composite material according to the described a kind of chitin fiber of claim 1, it is characterized in that: described chitin fiber is that deacetylation is chitin fiber or chitin fiber fabric or the modified chitosan fiber of 0-100%, and viscosity-average molecular weight is 50,000-1,000,000.
3. strengthen the preparation method of lactic acid composite material according to the described a kind of chitin fiber of claim 1, it is characterized in that: described poly(lactic acid) is Poly-L-lactic acid or dextrorotation poly(lactic acid) or poly-dl-lactide or their blend, and viscosity-average molecular weight is 50,000-1,000,000.
4. strengthen the preparation method of lactic acid composite material according to the described a kind of chitin fiber of claim 1, it is characterized in that: described solvent is chloroform, acetonitrile, tetrahydrofuran (THF), methylene dichloride, dioxan or their mixed solvent.
5. strengthen the preparation method of lactic acid composite material according to the described a kind of chitin fiber of claim 1, it is characterized in that: the mass concentration that described poly(lactic acid) is dissolved in back poly(lactic acid) in the solvent is 0.5-70%.
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| CN109157679A (en) * | 2018-10-26 | 2019-01-08 | 广州润虹医药科技股份有限公司 | A kind of preparation method of nanometer hydroxyapatite-chitosan artificial bone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703807A (en) * | 2009-11-17 | 2010-05-12 | 暨南大学 | Polylactic acid/chitosan composite nano fiber scaffold, preparation method and application thereof |
| CN101792580A (en) * | 2010-03-26 | 2010-08-04 | 暨南大学 | Modified chitosan fiber and polylactic acid composite material and preparation method thereof |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703807A (en) * | 2009-11-17 | 2010-05-12 | 暨南大学 | Polylactic acid/chitosan composite nano fiber scaffold, preparation method and application thereof |
| CN101792580A (en) * | 2010-03-26 | 2010-08-04 | 暨南大学 | Modified chitosan fiber and polylactic acid composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《厦门大学学报（自然科学版）》 20100331 胡晓兰等 生物医用聚乳酸纤维增强壳聚糖棒材 293-296 1-5 第49卷, 第2期 2 * |
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| CN109157679A (en) * | 2018-10-26 | 2019-01-08 | 广州润虹医药科技股份有限公司 | A kind of preparation method of nanometer hydroxyapatite-chitosan artificial bone |
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| CN110172180B (en) * | 2019-04-12 | 2021-07-09 | 西安理工大学 | Inorganic fiber/silicon dioxide nano material and preparation method and application thereof |
| CN113398325A (en) * | 2021-06-11 | 2021-09-17 | 叶川 | Fibrous membrane for enhancing screw stability and inducing bone regeneration and preparation method thereof |
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| CN113969498A (en) * | 2021-12-07 | 2022-01-25 | 吉林大学 | Modified carbon fiber, preparation method and carbon fiber reinforced resin matrix composite material with modified electro-generated interface |
| CN113969498B (en) * | 2021-12-07 | 2023-10-20 | 吉林大学 | Modified carbon fiber, preparation method and carbon fiber reinforced resin matrix composite material modified by electrointerface |
| CN115594871A (en) * | 2022-10-18 | 2023-01-13 | 湖南科技大学（Cn） | Preparation method of full-biodegradable wood-plastic composite light high-strength material |
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