CN109251497A - A kind of polylactic acid/hydroxy apatite composite material and preparation method thereof that acid fiber by polylactic is strengthened - Google Patents
A kind of polylactic acid/hydroxy apatite composite material and preparation method thereof that acid fiber by polylactic is strengthened Download PDFInfo
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- CN109251497A CN109251497A CN201811263131.3A CN201811263131A CN109251497A CN 109251497 A CN109251497 A CN 109251497A CN 201811263131 A CN201811263131 A CN 201811263131A CN 109251497 A CN109251497 A CN 109251497A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention belongs to the preparations and application technology of the new functional macromolecule material of high molecular material in new material, are related to modified plastics technical field, a kind of preparation method for the polylactic acid/hydroxy apatite composite material that specifically acid fiber by polylactic is strengthened.The present invention extracts active constituent as natural antibacterial agent from radix scutellariae, honeysuckle first；Then by polylactic acid, natural antibacterial agent, gallic acid, Chinese medicine antibacterial acid fiber by polylactic is handled to obtain through electrostatic spinning；Recycle chitosan, Ca (NO3)2, H3PO4And silicon dioxide gel is prepared into hydroxy phosphorus Calx-chitosan-SiO as raw material2Hybrid collosol crushes to obtain hydroxy phosphorus Calx-chitosan-SiO after freeze-dried2Hybrid；It finally will be by antibacterial polylactic acid fiber, hydroxy phosphorus Calx-chitosan-SiO2After hybrid mixes, it is prepared into master batch after extruding pelletization, the polylactic acid/hydroxy apatite composite material that acid fiber by polylactic reinforcing is prepared in modification then is carried out to master batch surface using polylactic acid.
Description
Technical field
The invention belongs to the preparations and application technology of the new functional macromolecule material of high molecular material in new material, are related to
Modified plastics technical field, a kind of polylactic acid/hydroxy apatite composite material that specifically acid fiber by polylactic is strengthened and its
Preparation method.
Background technique
Polylactic acid (PLA), also referred to as polylactide, by its excellent degradability and biocompatibility and it is nontoxic,
It is nonirritant, it receives and is widely applied in biological medicine industry.But there is also mechanical strength deficiency, drops for polylactic acid
The aobvious acidity of the product of solution, can cause intracorporal inflammatory reaction.Hydroxyapatite (HA) is the host inorganic group of skeleton tissue
At ingredient, the growth of bone can be induced, is good bone defect healing packing material.But due to its mechanical strength, resist it is tired
Labor intensity is poor, and brittleness is big, and intensity is insufficient, and poor toughness, easy fracture causes it to be difficult to bear high load capacity or thump.This limitation
The application of hydroxy phosphorus Calx.It is compound by carrying out PLA and HA, the toughness and rigidity of composite material both can be improved, assigned
Composite material bone bioactivity, but can buffer polylactic acid degrade acid product generated, slow down the degradation speed of polylactic acid, increase
The biocompatibility of strong composite material and tissue, so that material is with a wide range of applications.
But the toughness of poly-lactic acid material is inadequate, it is therefore desirable to further increase the toughness of material with further expansion material
Application range.Therefore, prepare high tenacity biodegradable polylactic acid/hydroxy apatite composite material still have it is important
Meaning.
Summary of the invention
In order to which the toughness for solving traditional poly-lactic acid material is inadequate, biodegradable polylactic acid/hydroxyl of the high tenacity provided
Base apatite composite material.Of the invention provides a kind of polylactic acid/hydroxy apatite composite material that acid fiber by polylactic is strengthened
And preparation method thereof.In order to achieve the above objectives, the present invention will use following technology:
A kind of polylactic acid/hydroxy apatite composite material and preparation method thereof that acid fiber by polylactic is strengthened, which is characterized in that including
Following steps:
(1) will radix scutellariae, honeysuckle it is dry after crushed respectively two kinds of herb powders are mixed after 60 meshes after through microwave treatment 10-
After 15min, after herb powder is mixed with ethanol-water mixture by the mass volume ratio (g/mL) of 1:15-20, at 50-65 DEG C
Under the conditions of filter after refluxing extraction 2-4h, filtrate is crossed into ultrafiltration membrane, pulverizes and sieves after being spin-dried for, obtains natural antibacterial agent；
(2) polylactic acid, natural antibacterial agent, gallic acid, N,N-dimethylformamide, ethyl acetate are prepared into after mixing
To fiber spinning solution, after electrostatic spinning is handled, Chinese medicine antibacterial acid fiber by polylactic is obtained after 45-55 DEG C of vacuum drying 6-8h；
(3) Chitosan powder is dissolved in 3-5wt% acetic acid aqueous solution, after obtaining 7-10wt% chitosan solution, Ca is added
(NO3)2Acetic acid solution and 55-65%(v/v) dense H3PO42h is stirred at room temperature in aqueous solution, obtains uniform polymer
After colloidal sol, after the silicon dioxide gel of 3-5wt% is added, 30min is mixed, hydroxy phosphorus Calx-chitosan-SiO is obtained2Hydridization is molten
Glue crushed 40 meshes up to hydroxy phosphorus Calx-chitosan-SiO after being freeze-dried colloidal sol2Hybrid；
(4) by antibacterial polylactic acid fiber, hydroxy phosphorus Calx-chitosan-SiO2Hybrid is transferred to twin-screw after mixing and squeezes
Out in machine, polylactic acid/hydroxy apatite composite material master batch is prepared after extruding pelletization；
(5) polylactic acid/hydroxy apatite composite material master batch is placed in the chloroformic solution of polylactic acid, impregnates 1-2h at room temperature
Afterwards, the polylactic acid/hydroxy apatite composite material for being drying to obtain acid fiber by polylactic reinforcing is taken out.
Further, radix scutellariae and quality of Flos Lonicerae ratio are 1:0.5-2 in herb powder as described in step (1).
Further, the volume fraction of ethyl alcohol is 45-60% in ethanol-water mixture as described in step (1)；Described
The molecular cut off of ultrafiltration membrane is 8000.
Further, polylactic acid described in step (2), natural antibacterial agent, gallic acid, n,N-Dimethylformamide,
Ethyl acetate is figured by mass parts when mixing and is followed successively by: 10-15 parts, 0.1-0.2 parts, 0.05-0.1 parts, 35-50 parts, 35-55
Part.
Further, Ca (NO described in step (3)3)2Acetic acid solution in acetic acid concentration be 0.1-0.2%；It is described
Ca (NO3)2With H3PO4When addition by the molar ratio of P and Ca be 1:1.6-1.8.
Further, silicon dioxide gel described in step (3) the preparation method comprises the following steps: by tetraethyl orthosilicate, acetic acid,
After water is by the molar ratio mixing of 1:0.2:8,25-30min is stirred under the conditions of 800-1000rpm up to silicon dioxide gel.
Further, antibacterial polylactic acid fiber described in step (4), hydroxy phosphorus Calx-chitosan-SiO2Hybrid is mixed
When mass ratio be 1:0.4-0.6.
Further, the concentration of polylactic acid is 2-8wt% in the chloroformic solution of polylactic acid described in step (5).
In addition, the polylactic acid/hydroxy apatite composite material that acid fiber by polylactic is strengthened, made by above-mentioned preparation method
It is standby.
Compared with prior art, the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic of the invention is strengthened
Preparation method have following the utility model has the advantages that extracting natural antibacterial of the active skull cap components as composite material using alcohol reflux
Agent not only strengthens the anti-microbial property of material, while not using artificial synthesized antibacterial agent, so that material is safer；By hydroxyl
Base phosphorus lime and chitosan, SiO2It carries out compound preparing hydroxy phosphorus Calx-chitosan-SiO2Hybrid significantly improves hydroxyl
The mechanical properties such as mechanical strength, fatigue resistance and the brittleness of phosphorus lime；It is multiple to polylactic acid/hydroxy apatite using polylactic acid
Condensation material is modified, and the toughness of material is further enhanced.The polylactic acid/hydroxy apatite being prepared through the present invention is compound
Material not only easily biological-degradable but also anti-microbial property is good, toughness is strong, excellent shock resistance and safe and non-toxic.
Specific embodiment
[embodiment 1]
A kind of preparation method for the polylactic acid/hydroxy apatite composite material that acid fiber by polylactic is strengthened, which is characterized in that including with
Lower step:
(1) will radix scutellariae, honeysuckle it is dry after crushed mix two kinds of herb powders by the mass ratio of 1:1 after 60 meshes respectively after
After microwave treatment 10min, herb powder is mixed with 50% ethanol-water mixture by the mass volume ratio (g/mL) of 1:15 afterwards
It after conjunction, is filtered after refluxing extraction 3h under the conditions of 65 DEG C, filtrate is crossed into the ultrafiltration membrane that molecular cut off is 8000, is crushed after being spin-dried for
Sieving, obtains natural antibacterial agent；
(2) by 12 parts of polylactic acid, 0.15 part of natural antibacterial agent, 0.05 part of gallic acid, 40 parts of N,N-dimethylformamides, 47.8
Fiber spinning solution is prepared in part ethyl acetate after mixing, after electrostatic spinning is handled, after 45 DEG C of vacuum drying 8h must in
Medicine antibacterial polylactic acid fiber；
(3) Chitosan powder is dissolved in 4wt% acetic acid aqueous solution, after obtaining 8wt% chitosan solution, Ca (NO is added3)2
Acetic acid solution and 55-65%(v/v) dense H3PO4Aqueous solution, after the molar ratio for guaranteeing the P being added and Ca is 1:1.6-1.8
2h is stirred at room temperature, after obtaining uniform polymer sol, after the silicon dioxide gel of 3.5wt% is added, mixes 30min, obtains
To hydroxy phosphorus Calx-chitosan-SiO2Hybrid collosol crushed 40 meshes up to hydroxy phosphorus Calx-after being freeze-dried colloidal sol
Chitosan-SiO2Hybrid；
(4) by antibacterial polylactic acid fiber, hydroxy phosphorus Calx-chitosan-SiO2Hybrid presses the mass ratio of 1:0.5 after mixing
It is transferred in double screw extruder, polylactic acid/hydroxy apatite composite material master batch is prepared after extruding pelletization；
(5) polylactic acid/hydroxy apatite composite material master batch is placed in the chloroformic solution of polylactic acid of 4wt%, is impregnated at room temperature
After 1h, the polylactic acid/hydroxy apatite composite material for being drying to obtain acid fiber by polylactic reinforcing is taken out.
[embodiment 2]
A kind of preparation method for the polylactic acid/hydroxy apatite composite material that acid fiber by polylactic is strengthened, which is characterized in that including with
Lower step:
(1) two kinds of herb powders are mixed by the mass ratio of 1:1.2 after 60 meshes will be crushed respectively after radix scutellariae, honeysuckle drying
After microwave treatment 12min, after the mass volume ratio (g/mL) that the ethanol-water mixture of herb powder and 45% is pressed to 1:17
It after mixing, is filtered after refluxing extraction 3h under the conditions of 65 DEG C, filtrate is crossed into the ultrafiltration membrane that molecular cut off is 8000, is spin-dried for rear powder
Broken sieving, obtains natural antibacterial agent；
(2) by 15 parts of polylactic acid, 0.15 part of natural antibacterial agent, 0.1 part of gallic acid, 44 parts of N,N-dimethylformamides, 40.75
Fiber spinning solution is prepared in part ethyl acetate after mixing, after electrostatic spinning is handled, after 45 DEG C of vacuum drying 8h must in
Medicine antibacterial polylactic acid fiber；
(3) Chitosan powder is dissolved in 5wt% acetic acid aqueous solution, after obtaining 7wt% chitosan solution, Ca (NO is added3)2
Acetic acid solution and H55-65%(v/v) dense H3PO4Aqueous solution, after the molar ratio for guaranteeing the P being added and Ca is 1:1.6-1.8
2h is stirred at room temperature, after obtaining uniform polymer sol, after the silicon dioxide gel of 3wt% is added, mixes 30min, obtains
Hydroxy phosphorus Calx-chitosan-SiO2Hybrid collosol crushed 40 meshes up to hydroxy phosphorus Calx-shell after being freeze-dried colloidal sol
Glycan-SiO2Hybrid；
(4) by antibacterial polylactic acid fiber, hydroxy phosphorus Calx-chitosan-SiO2Hybrid is uniformly mixed by the mass ratio of 1:0.45
After be transferred in double screw extruder, polylactic acid/hydroxy apatite composite material master batch is prepared after extruding pelletization；
(5) polylactic acid/hydroxy apatite composite material master batch is placed in the chloroformic solution of polylactic acid of 5wt%, is impregnated at room temperature
After 1h, the polylactic acid/hydroxy apatite composite material for being drying to obtain acid fiber by polylactic reinforcing is taken out.
[embodiment 3]
A kind of preparation method for the polylactic acid/hydroxy apatite composite material that acid fiber by polylactic is strengthened, which is characterized in that including with
Lower step:
(1) two kinds of herb powders are mixed by the mass ratio of 1:0.8 after 60 meshes will be crushed respectively after radix scutellariae, honeysuckle drying
After microwave treatment 12min, after the mass volume ratio (g/mL) that the ethanol-water mixture of herb powder and 55% is pressed to 1:17
It after mixing, is filtered after refluxing extraction 3h under the conditions of 65 DEG C, filtrate is crossed into the ultrafiltration membrane that molecular cut off is 8000, is spin-dried for rear powder
Broken sieving, obtains natural antibacterial agent；
(2) by 15 parts of polylactic acid, 0.15 part of natural antibacterial agent, 0.1 part of gallic acid, 35 parts of N,N-dimethylformamides, 49.75
Fiber spinning solution is prepared in part ethyl acetate after mixing, after electrostatic spinning is handled, after 45 DEG C of vacuum drying 8h must in
Medicine antibacterial polylactic acid fiber；
(3) Chitosan powder is dissolved in 4.5wt% acetic acid aqueous solution, after obtaining 8.5wt% chitosan solution, Ca is added
(NO3)2Acetic acid solution and 55-65%(v/v) dense H3PO4Aqueous solution guarantees that the molar ratio of the P being added and Ca is 1:1.6-
2h is stirred at room temperature after 1.8, after obtaining uniform polymer sol, after the silicon dioxide gel of 4wt% is added, mixing
30min obtains hydroxy phosphorus Calx-chitosan-SiO2Hybrid collosol crushed 40 meshes up to hydroxyl after being freeze-dried colloidal sol
Phosphorus lime-chitosan-SiO2Hybrid；
(4) by antibacterial polylactic acid fiber, hydroxy phosphorus Calx-chitosan-SiO2Hybrid is uniformly mixed by the mass ratio of 1:0.45
After be transferred in double screw extruder, polylactic acid/hydroxy apatite composite material master batch is prepared after extruding pelletization；
(5) polylactic acid/hydroxy apatite composite material master batch is placed in the chloroformic solution of polylactic acid of 6wt%, is impregnated at room temperature
After 1h, the polylactic acid/hydroxy apatite composite material for being drying to obtain acid fiber by polylactic reinforcing is taken out.
For the ordinary skill in the art, specific embodiment is only exemplarily described the present invention,
Obviously the present invention specific implementation is not subject to the restrictions described above, as long as use the inventive concept and technical scheme of the present invention into
The improvement of capable various unsubstantialities, or not improved the conception and technical scheme of the invention are directly applied to other occasions
, it is within the scope of the present invention.
Claims (9)
1. a kind of preparation method for the polylactic acid/hydroxy apatite composite material that acid fiber by polylactic is strengthened, which is characterized in that including
Following steps:
(1) will radix scutellariae, honeysuckle it is dry after crushed respectively two kinds of herb powders are mixed after 60 meshes after through microwave treatment 10-
After 15min, after herb powder is mixed with ethanol-water mixture by the mass volume ratio (g/mL) of 1:15-20, at 50-65 DEG C
Under the conditions of filter after refluxing extraction 2-4h, filtrate is crossed into ultrafiltration membrane, pulverizes and sieves after being spin-dried for, obtains natural antibacterial agent；
(2) polylactic acid, natural antibacterial agent, gallic acid, N,N-dimethylformamide, ethyl acetate are prepared into after mixing
To fiber spinning solution, after electrostatic spinning is handled, Chinese medicine antibacterial acid fiber by polylactic is obtained after 45-55 DEG C of vacuum drying 6-8h；
(3) Chitosan powder is dissolved in 3-5wt% acetic acid aqueous solution, after obtaining 7-10wt% chitosan solution, Ca is added
(NO3)2Acetic acid solution and 55-65%(v/v) dense H3PO42h is stirred at room temperature in aqueous solution, obtains uniform polymer
After colloidal sol, after the silicon dioxide gel of 3-5wt% is added, 30min is mixed, hydroxy phosphorus Calx-chitosan-SiO is obtained2Hydridization is molten
Glue crushed 40 meshes up to hydroxy phosphorus Calx-chitosan-SiO after being freeze-dried colloidal sol2Hybrid；
(4) by antibacterial polylactic acid fiber, hydroxy phosphorus Calx-chitosan-SiO2Hybrid is transferred to twin-screw extrusion after mixing
In machine, polylactic acid/hydroxy apatite composite material master batch is prepared after extruding pelletization；
(5) polylactic acid/hydroxy apatite composite material master batch is placed in the chloroformic solution of polylactic acid, impregnates 1-2h at room temperature
Afterwards, the polylactic acid/hydroxy apatite composite material for being drying to obtain acid fiber by polylactic reinforcing is taken out.
2. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that radix scutellariae and quality of Flos Lonicerae ratio are 1:0.5-2 in herb powder as described in step (1).
3. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that the volume fraction of ethyl alcohol is 45-60% in ethanol-water mixture as described in step (1)；Described is super
The molecular cut off of filter membrane is 8000.
4. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that polylactic acid, natural antibacterial agent, gallic acid, n,N-Dimethylformamide, second described in step (2)
Acetoacetic ester is figured by mass parts when mixing and is followed successively by: 10-15 parts, 0.1-0.2 parts, 0.05-0.1 parts, 35-50 parts, 35-55 parts.
5. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that Ca (NO described in step (3)3)2Acetic acid solution in acetic acid concentration be 0.1-0.2%；Described
Ca(NO3)2With H3PO4When addition by the molar ratio of P and Ca be 1:1.6-1.8.
6. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that silicon dioxide gel described in step (3) the preparation method comprises the following steps: by tetraethyl orthosilicate, acetic acid,
After water is by the molar ratio mixing of 1:0.2:8,25-30min is stirred under the conditions of 800-1000rpm up to silicon dioxide gel.
7. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that antibacterial polylactic acid fiber described in step (4), hydroxy phosphorus Calx-chitosan-SiO2Hybrid is mixed
When mass ratio be 1:0.4-0.6.
8. the preparation for the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic according to claim 1 is strengthened
Method, which is characterized in that the concentration of polylactic acid is 2-8wt% in the chloroformic solution of polylactic acid described in step (5).
9. the polylactic acid/hydroxy apatite composite material that a kind of acid fiber by polylactic is strengthened, by according to claim 1-8 any one
Prepared by preparation method described in.
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Cited By (6)
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| CN111005056A (en) * | 2019-12-24 | 2020-04-14 | 宁波革创新材料科技有限公司 | Composite long-life conductive hook for PCB electroplating and preparation method thereof |
| CN111472093A (en) * | 2020-04-08 | 2020-07-31 | 武汉理工大学 | Nano-hydroxyapatite/polylactic acid composite fiber membrane and preparation method thereof |
| CN112813528A (en) * | 2020-12-30 | 2021-05-18 | 浪莎针织有限公司 | Degradable flame-retardant polylactic acid elastic fiber and preparation method thereof |
| CN114621563A (en) * | 2022-03-09 | 2022-06-14 | 营口东盛实业有限公司 | Antibacterial full-degradable plastic material and preparation method thereof |
| CN115068693A (en) * | 2021-03-11 | 2022-09-20 | 东北林业大学 | Bone repair foaming composite material and preparation method thereof |
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