Preparation method of magnesium/L-polylactic acid composite bone scaffold
Technical Field
The invention relates to a preparation method of a magnesium/L-polylactic acid composite bone scaffold, in particular to a method for preparing a magnesium/L-polylactic acid composite bone scaffold by improving the binding property of magnesium and L-polylactic acid by using amphiphilic phospholipid, belonging to the technical field of bone scaffold preparation.
Background
Levorotatory polylactic acid (PLLA) is a typical representative of biodegradable polymers for clinical application, and is a hot spot for research on bone implant materials due to its renewable source, controllable synthesis, and good mechanical properties and biocompatibility. Magnesium (Mg) is attracting increasing attention because it is self-degradable and absorbable in the human body and has good biomechanical compatibility with human bones. Thus, Mg/PLLA composites may have the advantages of both Materials, S.C. biofuels et al, prepare PLA/Mg composites and evaluate mechanical and thermal properties ([1] biofuels S C, Lieblich M, L Lo pez F A, et al. Effect of Mg content on the thermal stability and mechanical bearing of PLLA/Mg composites processed by the hot interaction [ J ]. Materials Science & Engineering C,2017,72: 18; [2] biofuels S C, friendly E, Benaventer, et al. Association of mechanical bearing of PLA composites for use with Mg-composites through the process of J.790. mechanical bearing of J.J.. Materials & Engineering C,2017,72: 18; [2] biofuels S C, friendly E, Benave R, 20111. analysis of mechanical bearing of PLA composites for use of Mg-composites, J.790. mechanical bearing of J.. Peng et al, introduction of Mg into PLLA to prepare fully absorbable PLLA/Mg Composites ([3] Peng Wan, Chen Yuan, LiLi Tan, et al, simulation of bioorganic PLLA/magnesium and PLLA/magnesium fluoride Composites for organic displays [ J ]. Composites Science and Technology,2014,98: 36-43.). On the basis of complete degradation, the biodegradable polyester film also has the characteristics of adjustable degradation performance, acid-base neutralization of a degradation microenvironment and the like. However, the physical and chemical properties of metal Mg and polymer PLLA are greatly different, so that strong interface combination is difficult to form between the Mg and the PLLA, and the mechanical property of the composite material is reduced.
Disclosure of Invention
Aiming at the problem that in the process of preparing the magnesium/L-polylactic acid composite bone scaffold material in the prior art, due to the fact that the physical and chemical properties of metal Mg and polymer PLLA are greatly different, the interface bonding capacity between the metal Mg and the polymer PLLA is weak, and the mechanical property of the composite material is reduced.
In order to realize the technical purpose, the invention provides a preparation method of a magnesium/levorotatory polylactic acid composite bone scaffold, which comprises the steps of mixing PLLA powder, Mg powder and amphiphilic Phospholipid (PL) powder through liquid phase, carrying out solid-liquid separation, drying and grinding solid to obtain composite powder; the composite powder is used for preparing the composite bone scaffold by a selective laser sintering technology.
The technical scheme of the invention is characterized in that the interface binding capacity between Mg and a PLLA matrix is improved by using PL, the PL simultaneously comprises a hydrophilic group and a hydrophobic group, the hydrophilic group has better binding capacity with Mg, the hydrophobic carbon chain tail has better binding capacity with PLLA, and the PL plays a role in enhancing the binding capacity between Mg and the PLLA matrix, so that metal Mg particles can be well fixed and dispersed in the PLLA matrix, the mechanical property of the composite bone scaffold is greatly improved, the biological activity of metal Mg is fully exerted, and the biological property of the composite bone scaffold is improved.
The PL of the invention also plays a role in promoting the dispersion of Mg particles in a liquid phase in the liquid phase mixing process, polar groups are adsorbed on the surfaces of the Mg particles, while nonpolar groups are dispersed in an organic solvent, so that the dispersity of the Mg particles in an organic liquid phase can be improved, the Mg particles are prevented from settling in the liquid phase mixing process, and meanwhile, mixed powder of Mg powder and PLLA powder which are uniformly mixed can be obtained.
In a preferred scheme, the composite powder comprises the following components in percentage by mass: PL 1% -7%; mg 2-14 percent; and (7) PLLA 79-97%. When the content of PL relative to Mg is too low, the PL cannot modify Mg, and when the content of PL relative to Mg is too high, redundant PL forms suspended particles in the liquid phase mixing process and cannot act on Mg particles.
In a preferred scheme, the particle size of the PLLA powder is 1-3 mu m, and the melting point is 178-180 ℃.
In a preferable scheme, the particle size of the Mg powder is 400-600 nm, and the purity is more than 99.9%.
In a preferable scheme, the particle size of the PL powder is 3-15 nm, and the melting point is 234-238 ℃.
In the preferred scheme, stirring and ultrasonic dispersion modes are adopted in the liquid phase mixing process, the magnetic stirring time is 40-60 min, and the speed is 200-400 r/min; the ultrasonic dispersion time is 10-30 min, and the temperature is 40-60 ℃.
In the preferred scheme, the selective laser sintering process parameters are as follows: the laser power is 2.3-2.7W, the scanning speed is 100-120 mm/min, the scanning interval is 0.8-1.2 mm, and the spot diameter is 0.3-0.7 mm.
The method for preparing the Mg/PLLA composite bone scaffold comprises the following main steps:
(1) respectively weighing PLLA, Mg and PL powder according to a proportion, mixing the powder with the PLLA, Mg and PL powder in a beaker, placing the beaker in absolute ethyl alcohol for ultrasonic stirring to obtain PLLA/Mg/PL suspension, and then carrying out magnetic stirring, filtering and constant-temperature drying treatment to obtain uniformly dispersed PLLA/Mg/PL mixed powder; the content of amphiphilic PL and Mg in the mixed powder was 5 wt.% and 10 wt.%, respectively; the ultrasonic dispersion time is 20min, the temperature is 50 ℃, the magnetic stirring time is 50min, and the magnetic stirring speed is 300 r/min;
(2) the mixed powder is placed on a selective laser sintering system by adopting a preset powder laying process, and the composite powder is selectively scanned by using laser under the conditions of laser power of 2.5W, scanning speed of 110mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the designed structural requirements.
Compared with the prior art, the technical scheme of the invention has the following positive effects:
1) the invention adopts PL to improve the binding capacity between metal Mg and PLLA, the PL comprises a hydrophobic carbon chain tail and a hydrophilic molecular head, the hydrophilic molecular head and Mg have better binding effect, and the hydrophobic carbon chain tail and PLLA have better compatibility, thereby improving the interface binding capacity between Mg and PLLA through PL, realizing the dispersion distribution of metal Mg in PLLA matrix, better playing the role of Mg, not only being used as a reinforcing phase to improve the mechanical property of the bone scaffold, but also improving the adhesion, proliferation and differentiation of osteoblasts and the mechanical property of the composite bone scaffold by Mg ions generated by metal Mg.
2) The invention utilizes the selective laser sintering technology to prepare the composite bone scaffold, can realize customized appearance, and can control the size, distribution and connectivity of holes.
3) The alkaline products formed by Mg degradation neutralize the acidic products of PLLA degradation, reducing the inflammatory response.
Detailed Description
The following further describes embodiments of the present invention with reference to specific examples, but the present invention is not limited thereto.
Comparative example 1
And (3) utilizing three-dimensional design software to design the personalized appearance and the internal porous structure of the composite bone scaffold, and importing the designed three-dimensional data model into a computer to perform layered slicing processing to obtain the section profile information of each layer. 4.25 g of PLLA powder and 0.75 g of Mg powder are respectively weighed and sequentially added into a beaker filled with 30ml of absolute ethyl alcohol, and the mixture is uniformly mixed by ultrasonic dispersion and magnetic stirring. And filtering the mixed suspension by using filter paper, drying in an electrothermal blowing drying oven, grinding the dried mixed powder, placing the ground mixed powder in a selective laser sintering system for sintering experiment, and selectively sintering the mixed powder by using laser and preparing the PLLA/Mg composite bone scaffold under the conditions of laser power of 2.5W, scanning speed of 110mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the pre-designed structural requirements. At this time, the tensile strength of the composite bone scaffold material was measured to be 3.84MPa and the compressive strength was measured to be 21.31 MPa. Indicating that the metallic Mg bonds poorly to PLLA and the compressive strength is low without the addition of PL powder.
Example 1
And (3) utilizing three-dimensional design software to design the personalized appearance and the internal porous structure of the composite bone scaffold, and importing the designed three-dimensional data model into a computer to perform layered slicing processing to obtain the section profile information of each layer. 4.25 g of PLLA powder, 0.50 g of Mg powder and 0.25 g of PL powder are respectively weighed, and the three are sequentially added into a beaker filled with 30ml of absolute ethyl alcohol, and are uniformly mixed by ultrasonic dispersion and magnetic stirring. And filtering the mixed suspension by using filter paper, drying in an electrothermal blowing drying oven, grinding the dried mixed powder, placing the ground mixed powder in a selective laser sintering system for sintering experiment, and selectively sintering the mixed powder by using laser and preparing the PLLA/Mg composite bone scaffold under the conditions of laser power of 2.5W, scanning speed of 110mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the pre-designed structural requirements. At this time, the tensile strength of the composite bone scaffold material was measured to be 3.05MPa, and the compressive strength was measured to be 101.24 MPa.
Example 2
And (3) utilizing three-dimensional design software to design the personalized appearance and the internal porous structure of the composite bone scaffold, and importing the designed three-dimensional data model into a computer to perform layered slicing processing to obtain the section profile information of each layer. 4.25 g of PLLA powder, 0.63 g of Mg powder and 0.12 g of PL powder are respectively weighed, and the three are sequentially added into a beaker filled with 30ml of absolute ethyl alcohol, and are uniformly mixed by ultrasonic dispersion and magnetic stirring. And filtering the mixed suspension by using filter paper, drying in an electrothermal blowing drying oven, grinding the dried mixed powder, placing the ground mixed powder in a selective laser sintering system for sintering experiment, and selectively sintering the mixed powder by using laser and preparing the PLLA/Mg composite bone scaffold under the conditions of laser power of 2.5W, scanning speed of 110mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the pre-designed structural requirements. At this time, the tensile strength and compressive strength of the composite bone scaffold material were measured to be 3.44MPa and 54.49MPa, respectively.
Example 3
And (3) utilizing three-dimensional design software to design the personalized appearance and the internal porous structure of the composite bone scaffold, and importing the designed three-dimensional data model into a computer to perform layered slicing processing to obtain the section profile information of each layer. 4.25 g of PLLA powder, 0.12 g of Mg powder and 0.63 g of PL powder are respectively weighed, and the three are sequentially added into a beaker filled with 30ml of absolute ethyl alcohol, and are uniformly mixed by ultrasonic dispersion and magnetic stirring. And filtering the mixed suspension by using filter paper, drying in an electrothermal blowing drying oven, grinding the dried mixed powder, placing the ground mixed powder in a selective laser sintering system for sintering experiment, and selectively sintering the mixed powder by using laser and preparing the PLLA/Mg composite bone scaffold under the conditions of laser power of 2.5W, scanning speed of 110mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the pre-designed structural requirements. At this time, the tensile strength of the composite bone scaffold material was measured to be 2.60MPa and the compressive strength was measured to be 63.51 MPa.
Example 5
And (3) utilizing three-dimensional design software to design the personalized appearance and the internal porous structure of the composite bone scaffold, and importing the designed three-dimensional data model into a computer to perform layered slicing processing to obtain the section profile information of each layer. 4.25 g of PLLA powder, 0.50 g of Mg powder and 0.25 g of PL powder are respectively weighed, and the three are sequentially added into a beaker filled with 30ml of absolute ethyl alcohol, and are uniformly mixed by ultrasonic dispersion and magnetic stirring. And filtering the mixed suspension by using filter paper, drying in an electrothermal blowing drying oven, grinding the dried mixed powder, placing the ground mixed powder in a selective laser sintering system for sintering experiment, and selectively sintering the mixed powder by using laser and preparing the PLLA/Mg composite bone scaffold under the conditions of laser power of 2.3W, scanning speed of 120mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the pre-designed structural requirements. At this time, the tensile strength of the composite bone scaffold material was measured to be 2.87MPa and the compressive strength was measured to be 80.73 MPa.
Example 6
And (3) utilizing three-dimensional design software to design the personalized appearance and the internal porous structure of the composite bone scaffold, and importing the designed three-dimensional data model into a computer to perform layered slicing processing to obtain the section profile information of each layer. 4.25 g of PLLA powder, 0.50 g of Mg powder and 0.25 g of PL powder are respectively weighed, and the three are sequentially added into a beaker filled with 30ml of absolute ethyl alcohol, and are uniformly mixed by ultrasonic dispersion and magnetic stirring. And filtering the mixed suspension by using filter paper, drying in an electrothermal blowing drying oven, grinding the dried mixed powder, placing the ground mixed powder in a selective laser sintering system for sintering experiment, and selectively sintering the mixed powder by using laser and preparing the PLLA/Mg composite bone scaffold under the conditions of laser power of 2.7W, scanning speed of 100mm/min, scanning interval of 1mm and spot diameter of 0.5mm according to the pre-designed structural requirements. At this time, the tensile strength of the composite bone scaffold material was measured to be 2.76MPa and the compressive strength was measured to be 76.54 MPa.