CN110157170B - Polylactic acid/nano-cellulose/hydroxyapatite composite material and preparation thereof - Google Patents
Polylactic acid/nano-cellulose/hydroxyapatite composite material and preparation thereof Download PDFInfo
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- CN110157170B CN110157170B CN201910485555.2A CN201910485555A CN110157170B CN 110157170 B CN110157170 B CN 110157170B CN 201910485555 A CN201910485555 A CN 201910485555A CN 110157170 B CN110157170 B CN 110157170B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a polylactic acid/nano-cellulose/hydroxyapatite composite material and a preparation method thereof, wherein the polylactic acid/nano-cellulose/hydroxyapatite composite material comprises the following components in percentage by weight: 50-90% of polylactic acid, 0.1-40% of nano cellulose and 0.1-40% of hydroxyapatite. Preparation: and melting and blending the nano-cellulose/hydroxyapatite blend and polylactic acid for 5-8min at 120-170 ℃ by using a double-screw extruder to obtain the nano-cellulose/hydroxyapatite blend. The method of the invention has simple operation, is simple and feasible, can improve the strength of the polylactic acid material, and can control the degradation time of the polylactic acid material.
Description
Technical Field
The invention belongs to the field of biodegradable medical materials and preparation thereof, and particularly relates to a polylactic acid/nano-cellulose/hydroxyapatite composite material and preparation thereof.
Background
Polylactic acid (PLA) is a biodegradable bio-based aliphatic polyester, is nontoxic and harmless, has good sustainability and biocompatibility as well as better mechanical strength, elastic modulus and thermoformability, has been applied in a plurality of fields because degradation products can permeate into human bodies to participate in metabolism, and is considered as a biodegradable high polymer material with the highest market potential so far. At present, polylactic acid and its copolymer, polylactic acid, have been widely used in the medical field, such as: drug release materials, ophthalmic materials, surgical sutures, fracture internal fixation materials, tissue engineering repair and the like. However, pure polylactic acid is hard and brittle, has poor toughness, and is a hydrophobic substance with a degradation period which is difficult to control. The above disadvantages limit the popularization and application of polylactic acid, so that it is necessary to modify it to increase its application range and route.
The nano cellulose is derived from cellulose, is rod-shaped superfine microfiber with the length of about tens to hundreds of nanometers, has excellent performances of large length-diameter ratio, high strength, high purity and the like, and has the characteristics of light weight, degradability, biocompatibility, reproducibility and the like of biological materials, so that the nano cellulose shows a huge application prospect in high-performance composite materials, and particularly shows an excellent characteristic as a reinforcing phase of the composite materials.
If the modified nano-cellulose can be selected to modify PLA, the processability of PLA can be improved, the strength of polylactic acid can be increased, meanwhile, the nano-cellulose is a hydrophilic substance and can improve the hydrophobicity of polylactic acid, and the obtained composite material belongs to a complete bio-based material and can be completely biodegraded after being discarded.
The research of cellulose modified polylactic acid has attracted a great deal of attention. Chinese patent (CN201510276530.3) discloses a polylactic acid/nano cellulose degradable material, which adopts microcrystalline cellulose, polyethylene glycol, sulfuric acid and sodium hydroxide to improve the strength of polylactic acid; chinese patent (CN103044871B) discloses a compound of modified nano-cellulose reinforced polylactic acid, wherein the nano-cellulose modified by polyethylene glycol and the polylactic acid are melted. At present, the nanocellulose is modified by mostly adopting organic compounds, and the method has the defects of complex operation, high requirement on mechanical equipment and low production efficiency. Chinese patent (CN103285428A) discloses an artificial bone material, which is prepared by adding nano-cellulose and hydroxyapatite into polylactic acid solution, stirring, blending, drying and grinding, or melting, blending, extruding and crushing the polylactic acid, the nano-cellulose and the hydroxyapatite. The solution blending method has low production efficiency, and the melt blending method has the defect of uneven mixing in the blending extrusion of an extruder.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polylactic acid/nano-cellulose/hydroxyapatite composite material and a preparation method thereof, overcoming the defect of uneven mixing in the prior art.
The polylactic acid/nano-cellulose/hydroxyapatite composite material is characterized by comprising the following components in percentage by weight: 50-90% of polylactic acid, 0.1-40% of nano cellulose and 0.1-40% of hydroxyapatite.
The components by weight percentage are as follows: 65% of polylactic acid, 22% of nano fiber and 13% of hydroxyapatite.
The components by weight percentage are as follows: 74% of polylactic acid, 18% of nano-fiber and 8% of hydroxyapatite.
The components by weight percentage are as follows: 85% of polylactic acid, 10% of nano fiber and 5% of hydroxyapatite.
The invention relates to a preparation method of a polylactic acid/nano-cellulose/hydroxyapatite composite material, which comprises the following steps:
(1) adding calcium hydroxide into the nano-cellulose solution, and heating and stirring at 60-70 ℃ to form a suspension; then, dropwise adding phosphoric acid into the suspension to obtain a mixed solution, keeping the pH value above 10.5, stirring for 1-2h, cooling to room temperature, standing for 24-48h, filtering, washing, drying and grinding to obtain nano-cellulose/hydroxyapatite; wherein the mass ratio of the nano-cellulose to the calcium hydroxide is 1:20-1: 30;
(2) preparing a polylactic acid/nano-cellulose/hydroxyapatite composite material by a melt blending method: and melting and blending the nano-cellulose/hydroxyapatite and polylactic acid for 5-8min at the temperature of 120-170 ℃ by a double-screw extruder to obtain the polylactic acid/nano-cellulose/hydroxyapatite composite material.
The preferred mode of the above preparation method is as follows:
the method for preparing the nano-cellulose by the acidolysis method in the step (1) comprises the following steps: adding sulfuric acid into cellulose, stirring to obtain a suspension, diluting to stop the acidolysis reaction, stirring at a super high speed (the speed range is 10000-12000r/min) for more than 30min to remove redundant acid and centralize the cellulose; centrifuging the precipitate with deionized water for 2-4 times, dialyzing the centrifuged precipitate with water to pH 5-6, and treating the suspension with ultrasonic wave to obtain nanometer cellulose solution.
The cellulose is microcrystalline cellulose with a particle size of 250 μm (product number C104844, Shanghai Aladdin Biotechnology Co., Ltd.).
The volume percentage concentration of the sulfuric acid is 65%.
The stirring is carried out at the temperature of 50-60 ℃ and at the speed of more than 700 r/min; diluting to 10 times;
the volume percentage concentration of the phosphoric acid in the step (1) is 17%.
Maintaining the pH above 10.5 in step (1): the ammonia solution was added so that the pH of the mixture was above 10.5.
In the step (1), the filtration is to separate white precipitate substances by vacuum filtration; the washing is twice with distilled water and ethanol.
The drying in the step (1) comprises the following steps: freeze-drying, and then drying at 100-110 ℃ for 3-6 h.
The step (2) of melt blending is carried out by a double-screw extruder.
The weight average molecular weight of the polylactic acid in the step (2) is 8.9 multiplied by 105(Ingeo 6201D，NatureWorks)。
The polylactic acid/nano cellulose/hydroxyapatite composite material greatly improves the mechanical strength of the material. The polylactic acid/nano cellulose/hydroxyapatite composite material can be used for preparing oral cavity materials, orthopedic scaffolds and other biological materials with excellent mechanical properties and biocompatibility. The system can be customized by combining a 3D printing technology to meet personalized requirements.
Advantageous effects
The preparation method is simple in preparation process, green and environment-friendly;
the polylactic acid/nano-cellulose/hydroxyapatite biological composite material prepared by the invention has good thermal stability and excellent mechanical property;
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Microcrystalline cellulose having a particle size of 250 μm (product No. C104844, Shanghai Aladdin Biotechnology Ltd.)
The weight average molecular weight of the polylactic acid is 8.9X 105(Ingeo 6201D，NatureWorks)
Example 1
The polylactic acid/nano-cellulose/hydroxyapatite composite material comprises the following components in percentage by weight: 65% of polylactic acid, 22% of nano fiber and 13% of hydroxyapatite.
The method comprises the following specific steps:
(1) preparing nano-cellulose by an acidolysis method: placing cellulose into a round-bottom flask, adding 100-120ml of sulfuric acid, mixing the mixture with water 10: 1, mixing and stirring at a high speed at a proper temperature; the cellulose is obtained by crushing microcrystalline cellulose; the sulfuric acid is prepared by diluting concentrated sulfuric acid with water to 65%; the appropriate temperature is 55 ℃; the high-speed stirring is 800 r/min.
(2) Diluting the suspension prepared in the step (1) to 10 times by using deionized water to stop the acidolysis reaction, stirring at 10000r/min for 40min to remove redundant acid and centralize cellulose; the precipitated material was centrifuged again 4 times with deionized water.
(3) Dialyzing the sediment obtained by centrifugation in the step (2) with water until the pH value meets the requirement, and treating the suspension with ultrasonic waves to obtain a nano cellulose solution; the pH was 5.5.
(4) Preparing a nano-cellulose/hydroxyapatite composite material: adding calcium hydroxide into the nano-cellulose solution obtained in the step (3), heating at 65 ℃ and stirring to form a suspension; the mass ratio of the nano-cellulose to the calcium hydroxide is 1: 30.
(5) Will contain 17% of H3PO4Phosphoric acid was added dropwise to the suspension obtained in (4) while maintaining the pH of the mixture at 11 by adding an ammonia solution.
(6) The solution was stirred for an additional 2 hours. It was cooled to room temperature and left for another 48 hours. The white precipitated material was isolated by vacuum filtration and washed twice with distilled water and ethanol and freeze-dried.
(7) The filter cake was dried in an oven at 110 ℃ for 6h and ground using a mortar and pestle to obtain a nanocellulose/hydroxyapatite powder.
(8) Preparing a polylactic acid/nano-cellulose/hydroxyapatite composite material by a melt blending method: and (3) melting and blending the nano-cellulose/hydroxyapatite blend obtained in the step (7) and polylactic acid for 7min at 160 ℃ by using a double-screw extruder to obtain the polylactic acid/nano-cellulose/hydroxyapatite composite material. The melt blending method is that two-phase raw materials are blended by a double-screw extruder in a high-temperature melting state to obtain a uniformly dispersed blend.
Example 2:
the polylactic acid/nano-cellulose/hydroxyapatite composite material comprises the following components in percentage by weight: 74% of polylactic acid, 18% of nano-fiber and 8% of hydroxyapatite.
The method comprises the following specific steps:
(1) preparing nano-cellulose by an acidolysis method: placing cellulose into a round-bottom flask, adding 100-120ml of sulfuric acid, mixing the mixture with water 10: 1, mixing and stirring at a high speed at a proper temperature; the cellulose is obtained by crushing microcrystalline cellulose; the sulfuric acid is prepared by diluting concentrated sulfuric acid with water to 65%; the appropriate temperature is 55 ℃; the high-speed stirring is 800 r/min.
(2) Diluting the suspension prepared in the step (1) to 10 times by using deionized water to stop the acidolysis reaction, stirring at 10000r/min for 40min to remove redundant acid and centralize cellulose; the precipitated material was centrifuged again 4 times with deionized water.
(3) Dialyzing the sediment obtained by centrifugation in the step (2) with water until the pH value meets the requirement, and treating the suspension with ultrasonic waves to obtain a nano cellulose solution; the pH was 5.5.
(4) Preparing a nano-cellulose/hydroxyapatite composite material: adding calcium hydroxide into the nano-cellulose solution obtained in the step (3), heating at 65 ℃ and stirring to form a suspension; the mass ratio of the nano-cellulose to the calcium hydroxide is 1: 30.
(5) Will contain 17% of H3PO4Phosphoric acid was added dropwise to the suspension obtained in (4) while maintaining the pH of the mixture at 11 by adding an ammonia solution.
(6) The solution was stirred for an additional 2 hours. It was cooled to room temperature and left for another 48 hours. The white precipitated material was isolated by vacuum filtration and washed twice with distilled water and ethanol and freeze-dried.
(7) The filter cake was dried in an oven at 110 ℃ for 6h and ground using a mortar and pestle to obtain a nanocellulose/hydroxyapatite powder.
(8) Preparing a polylactic acid/nano-cellulose/hydroxyapatite composite material by a melt blending method: and (3) melting and blending the nano-cellulose/hydroxyapatite blend obtained in the step (7) and polylactic acid for 7min at 160 ℃ by using a double-screw extruder to obtain the polylactic acid/nano-cellulose/hydroxyapatite composite material. The melt blending method is that two-phase raw materials are blended by a double-screw extruder in a high-temperature melting state to obtain a uniformly dispersed blend.
Example 3:
the polylactic acid/nano-cellulose/hydroxyapatite composite material comprises the following components in percentage by weight: 99% of polylactic acid, 0.8% of nano fiber and 0.2% of hydroxyapatite.
The method comprises the following specific steps:
(1) preparing nano-cellulose by an acidolysis method: placing cellulose into a round-bottom flask, adding 100-120ml of sulfuric acid, mixing the mixture with water 10: 1, mixing and stirring at a high speed at a proper temperature; the cellulose is obtained by crushing microcrystalline cellulose; the sulfuric acid is prepared by diluting concentrated sulfuric acid with water to 65%; the appropriate temperature is 55 ℃; the high-speed stirring is 800 r/min.
(2) Diluting the suspension prepared in the step (1) to 10 times by using deionized water to stop the acidolysis reaction, stirring at 12000r/min for 40min to remove redundant acid and centralize cellulose; the precipitated material was centrifuged again 4 times with deionized water.
(3) Dialyzing the sediment obtained by centrifugation in the step (2) with water until the pH value meets the requirement, and treating the suspension with ultrasonic waves to obtain a nano cellulose solution; the pH was 5.5.
(4) Preparing a nano-cellulose/hydroxyapatite composite material: adding calcium hydroxide into the nano-cellulose solution obtained in the step (3), heating at 65 ℃ and stirring to form a suspension; the mass ratio of the nano-cellulose to the calcium hydroxide is 1: 30.
(5) Will contain 17% of H3PO4Phosphoric acid was added dropwise to the suspension obtained in (4) while maintaining the pH of the mixture at 11 by adding an ammonia solution.
(6) The solution was stirred for an additional 2 hours. It was cooled to room temperature and left for another 48 hours. The white precipitated material was isolated by vacuum filtration and washed twice with distilled water and ethanol and freeze-dried.
(7) The filter cake was dried in an oven at 110 ℃ for 6h and ground using a mortar and pestle to obtain a nanocellulose/hydroxyapatite powder.
(8) Preparing a polylactic acid/nano-cellulose/hydroxyapatite composite material by a melt blending method: and (3) melting and blending the nano-cellulose/hydroxyapatite blend obtained in the step (7) and polylactic acid for 7min at 160 ℃ by using a double-screw extruder to obtain the polylactic acid/nano-cellulose/hydroxyapatite composite material. The melt blending method is that two-phase raw materials are blended by a double-screw extruder in a high-temperature melting state to obtain a uniformly dispersed blend.
In order to fully prove that the polylactic acid/nano-cellulose/hydroxyapatite composite material obtained by the preparation method has excellent mechanical properties, the materials prepared in the examples 1, 2 and 3 are selected and tested for tensile properties. Tensile properties were measured using a general-purpose mechanical tester (H5K-S, Hounsfield) with a gauge length of 30mm and a test speed set at 10 mm/min.
The specific test results are shown in the following table:
| item | Blank space | Example 1 | Example 2 | Example 3 |
| Tensile strength/MPa | 35 | 40 | 47 | 57 |
According to the data in the table, the tensile strength of the polylactic acid/nano cellulose/hydroxyapatite composite material is improved, and the improvement percentage is far greater than that described in the chinese patent (CN 103285428A).
The tensile properties test above was carried out in accordance with the determination of the tensile properties of the plastics of GB/T1040-.
Claims (9)
1. A preparation method of a polylactic acid/nano-cellulose/hydroxyapatite composite material comprises the following steps:
(1) adding calcium hydroxide into the nano-cellulose solution, and heating and stirring at 60-70 ℃ to form a suspension; then, dropwise adding phosphoric acid into the suspension to obtain a mixed solution, keeping the pH value above 10.5, stirring for 1-2h, cooling to room temperature, standing for 24-48h, filtering, washing, drying and grinding to obtain nano-cellulose/hydroxyapatite; wherein the mass ratio of the nano-cellulose to the calcium hydroxide is 1:20-1: 30;
(2) and melting and blending the nano-cellulose/hydroxyapatite and polylactic acid at the temperature of 120-170 ℃ for 5-8min to obtain the polylactic acid/nano-cellulose/hydroxyapatite composite material.
2. The method according to claim 1, wherein the nanocellulose solution in step (1) is prepared by: adding sulfuric acid into cellulose, stirring to obtain a suspension, diluting, stirring, centrifuging, washing, dialyzing, and performing ultrasonic treatment to obtain a nano cellulose solution.
3. The method according to claim 1, wherein the pH is maintained at 10.5 or more in the step (1): the ammonia solution was added so that the pH of the mixture was above 10.5.
4. The method according to claim 1, wherein the drying in the step (1) is: freeze-drying, and then drying at 100-110 ℃ for 3-6 h.
5. The polylactic acid/nano-cellulose/hydroxyapatite composite material prepared by the method of claim 1 is characterized by comprising the following components in percentage by weight: 50-90% of polylactic acid, 0.1-40% of nano cellulose and 0.1-40% of hydroxyapatite.
6. The composite material according to claim 5, characterized in that the components comprise, in weight percent: 65% of polylactic acid, 22% of nano fiber and 13% of hydroxyapatite.
7. The composite material according to claim 5, characterized in that the components comprise, in weight percent: 74% of polylactic acid, 18% of nano-fiber and 8% of hydroxyapatite.
8. The composite material according to claim 5, characterized in that the components comprise, in weight percent: 85% of polylactic acid, 10% of nano fiber and 5% of hydroxyapatite.
9. The application of the polylactic acid/nano cellulose/hydroxyapatite composite material prepared by the method of claim 1 in biological materials.
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| CN113845652A (en) * | 2021-12-01 | 2021-12-28 | 北京石墨烯技术研究院有限公司 | Modified polylactic acid material, polylactic acid composite material and preparation method thereof |
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| CN103285428B (en) * | 2013-04-26 | 2015-01-28 | 珠海市红旌发展有限公司 | Artificial bone material and preparation method thereof |
| CN103285427B (en) * | 2013-04-26 | 2014-11-05 | 中国国旅贸易有限责任公司 | Artificial bone material and preparation method thereof |
| WO2016004222A1 (en) * | 2014-07-01 | 2016-01-07 | Georgia Regents University | Bio-compatible radiopaque dental fillers for imaging |
| CN104292481B (en) * | 2014-10-07 | 2017-02-15 | 桂林理工大学 | Method for preparing synergetic enhanced polylactic acid biological composite material |
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