Calcium phosphate bone induction biological ceramic stent based on photocuring 3D printing technology and preparation method thereof

Abstract

The invention discloses a calcium phosphate bone induction biological ceramic stent based on a photocuring 3D printing technology and a preparation method thereof, and belongs to the field of biomedical materials. Through the method, ceramic paste which is high in content of solid, low in viscosity and good in dispersity and fluidity can be effectively prepared. Through the photocuring 3D printingtechnology and follow-up degreasing sintering, the bone induction porous calcium phosphate ceramic stent with an internal penetrating pore structure can be prepared, wherein the shape, size, porosityand macroscopic morphology of the bone induction porous calcium phosphate ceramic stent can be accurately controlled, and the bone induction porous calcium phosphate ceramic stent is used for bone tissue repairing and filling and individualized repairing.

Description

technical field

[0001] The invention belongs to the technical field of biomedical materials, in particular to a calcium phosphate osteoinductive bioceramic scaffold based on photocuring 3D printing technology and a preparation method thereof. technical background

[0002] For a long time, bone defects caused by trauma, tumors, metabolic diseases, etc. have been a major clinical problem, often resulting in partial or complete loss of bone function in patients, seriously affecting the quality of life. For bone defects smaller than 1 cm, autogenous repair can be used, while for bone defects larger than 1 cm, only interventional treatment can be used.

[0003] Although autologous bone grafting is still regarded as the "gold standard" for the treatment of large bone defects, it still faces risks such as limited sources, secondary surgical trauma, and unknown complications. Allogeneic bone and animal-derived xenografts have the characteristics of "natural bone" or "osteolike", bu...

Examples

Embodiment 1

[0040] (1) Preparation of photosensitive resin premix: select 50wt% epoxy acrylate as oligomer, 44wt% TMPTA as reactive diluent, 5wt% 819 as photoinitiator, 1wt% EDB as sensitizer, Mix well with a magnetic stirrer for 20 min.

[0041] (2) Use hydroxyapatite with a purity of 99.9% (60% by mass), the prepared photosensitive resin premix (37% by mass), and KH-570 silane coupling agent as a dispersant (60% by mass) 3%) was placed in a ball mill at a speed of 150r / min, and ball milled for 10 hours to obtain a ceramic-resin slurry.

[0042] (3) Put the ceramic-resin slurry under the DLP light curing machine for printing, the wavelength is 405nm, the printing layer thickness is 50μm, the light time is 5s / layer, and the layers are stacked and accumulated to form a ceramic green body.

[0043] (4) After removing the support from the printed ceramic green body, place it in a muffle furnace for sintering and degreasing. Raise the temperature at a rate of 5°C / min, raise the temperature ...

Embodiment 2

[0046] (1) Preparation of photosensitive resin premix: select 59wt% epoxy acrylate as oligomer, 35wt% TMPTA as reactive diluent, 5wt% 819 as photoinitiator, 1wt% EDB as sensitizer, Mix well with a magnetic stirrer for 20 min.

[0047] (2) Same as step (2) in Example 1.

[0048] (3) Same as step (3) in Example 1.

[0049] (4) After removing the support from the printed ceramic green body, place it in a muffle furnace for sintering and degreasing. Raise the temperature at a rate of 5°C / min, raise the temperature to 800°C and keep it for 3 hours, then raise the temperature at a rate of 5°C / min to 1200°C, keep it for 5 hours, and then cool down with the furnace to obtain a porous calcium phosphate ceramic support with a ceramic porosity of 65. %.

[0050] The content of the reactive diluent in this embodiment selects the lowest value of the optional mass fraction range, and the sample can be successfully printed.

Embodiment 3

[0052] (1) Same as step (1) in Example 1.

[0053] (2) Use hydroxyapatite with a purity of 99.9% (50% by mass), the prepared photosensitive resin premix (47% by mass), and KH-570 silane coupling agent as a dispersant (proportion by mass 3%) was placed in a ball mill at a speed of 150r / min, and ball milled for 10 hours to obtain a ceramic-resin slurry.

[0054] (3) Same as step (3) in Example 1.

[0055] (4) After removing the support from the printed ceramic green body, place it in a muffle furnace for sintering and degreasing. Raise the temperature at a rate of 5°C / min, raise the temperature to 800°C and keep it for 3 hours, then raise the temperature at a rate of 5°C / min to 1200°C, keep it for 5 hours, and then cool down with the furnace to obtain a porous calcium phosphate ceramic support with a ceramic porosity of 73 %.

[0056] In this embodiment, the mass ratio (solid content) of hydroxyapatite is selected from the lowest value in the optional range, and the sample ca...

technical field

[0001] The invention belongs to the technical field of biomedical materials, in particular to a calcium phosphate osteoinductive bioceramic scaffold based on photocuring 3D printing technology and a preparation method thereof. technical background

[0002] For a long time, bone defects caused by trauma, tumors, metabolic diseases, etc. have been a major clinical problem, often resulting in partial or complete loss of bone function in patients, seriously affecting the quality of life. For bone defects smaller than 1 cm, autogenous repair can be used, while for bone defects larger than 1 cm, only interventional treatment can be used.

[0003] Although autologous bone grafting is still regarded as the "gold standard" for the treatment of large bone defects, it still faces risks such as limited sources, secondary surgical trauma, and unknown complications. Allogeneic bone and animal-derived xenografts have the characteristics of "natural bone" or "osteolike", bu...

Examples

Embodiment 1

[0040] (1) Preparation of photosensitive resin premix: select 50wt% epoxy acrylate as oligomer, 44wt% TMPTA as reactive diluent, 5wt% 819 as photoinitiator, 1wt% EDB as sensitizer, Mix well with a magnetic stirrer for 20 min.

[0041] (2) Use hydroxyapatite with a purity of 99.9% (60% by mass), the prepared photosensitive resin premix (37% by mass), and KH-570 silane coupling agent as a dispersant (60% by mass) 3%) was placed in a ball mill at a speed of 150r / min, and ball milled for 10 hours to obtain a ceramic-resin slurry.

[0042] (3) Put the ceramic-resin slurry under the DLP light curing machine for printing, the wavelength is 405nm, the printing layer thickness is 50μm, the light time is 5s / layer, and the layers are stacked and accumulated to form a ceramic green body.

[0043] (4) After removing the support from the printed ceramic green body, place it in a muffle furnace for sintering and degreasing. Raise the temperature at a rate of 5°C / min, raise the temperature ...

Embodiment 2

[0046] (1) Preparation of photosensitive resin premix: select 59wt% epoxy acrylate as oligomer, 35wt% TMPTA as reactive diluent, 5wt% 819 as photoinitiator, 1wt% EDB as sensitizer, Mix well with a magnetic stirrer for 20 min.

[0047] (2) Same as step (2) in Example 1.

[0048] (3) Same as step (3) in Example 1.

[0049] (4) After removing the support from the printed ceramic green body, place it in a muffle furnace for sintering and degreasing. Raise the temperature at a rate of 5°C / min, raise the temperature to 800°C and keep it for 3 hours, then raise the temperature at a rate of 5°C / min to 1200°C, keep it for 5 hours, and then cool down with the furnace to obtain a porous calcium phosphate ceramic support with a ceramic porosity of 65. %.

[0050] The content of the reactive diluent in this embodiment selects the lowest value of the optional mass fraction range, and the sample can be successfully printed.

Embodiment 3

[0052] (1) Same as step (1) in Example 1.

[0053] (2) Use hydroxyapatite with a purity of 99.9% (50% by mass), the prepared photosensitive resin premix (47% by mass), and KH-570 silane coupling agent as a dispersant (proportion by mass 3%) was placed in a ball mill at a speed of 150r / min, and ball milled for 10 hours to obtain a ceramic-resin slurry.

[0054] (3) Same as step (3) in Example 1.

[0055] (4) After removing the support from the printed ceramic green body, place it in a muffle furnace for sintering and degreasing. Raise the temperature at a rate of 5°C / min, raise the temperature to 800°C and keep it for 3 hours, then raise the temperature at a rate of 5°C / min to 1200°C, keep it for 5 hours, and then cool down with the furnace to obtain a porous calcium phosphate ceramic support with a ceramic porosity of 73 %.

[0056] In this embodiment, the mass ratio (solid content) of hydroxyapatite is selected from the lowest value in the optional range, and the sample ca...

Images