CN101401954B - Degradable synthetic polymer spherical honeycombed grain material, producing method and apparatus thereof - Google Patents

Degradable synthetic polymer spherical honeycombed grain material, producing method and apparatus thereof Download PDF

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Publication number
CN101401954B
CN101401954B CN2008102350714A CN200810235071A CN101401954B CN 101401954 B CN101401954 B CN 101401954B CN 2008102350714 A CN2008102350714 A CN 2008102350714A CN 200810235071 A CN200810235071 A CN 200810235071A CN 101401954 B CN101401954 B CN 101401954B
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synthetic polymer
degradable
grain material
degradable synthetic
honeycombed grain
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CN101401954A (en
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董寅生
毛屹
郭超
盛晓波
储成林
林萍华
浦跃朴
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Jiangsu Haijian Co., Ltd.
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Southeast University
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Abstract

The invention relates to a degradable synthetic polymer spherical porous particle material, and a method and a device for preparing the same. The method comprises the following steps: step one, preparing a dioxane solution of degradable polymer; step two, adding the solution into a material storage tank from a feed opening, wherein the pressure is between 0.08 and 0.5 MPa; the solution flows out of the material storage tank at a speed of between 10 and 60 drops per minute from a liquid guiding tube with the tube diameter between phi 0.5 and 3 millimeters; and the dioxane solution of the degradable polymer flowing out of the liquid guiding tube grows big and similar to a spherical particle with the diameter between phi 0.8 and 4 millimeters, and then drops off; after that, the dioxane solution is dripped into a condensate with a temperature between 10 and 20 DEG C below zero in a thermal insulation container to be condensed so that a dioxane spherical porous particle material of the degradable polymer is formed, which has good sphericity and uniform particle diameter; and step three, separating, freezing and drying the dioxane spherical porous particle material of the degradable polymer to obtain the degradable synthetic polymer spherical porous particle material. The spherical particle material has homogeneous particle diameter distribution, contains a large number of micropores communicated with one another therein, has higher specific surface area, and can be applied to tissue repair and medicament slow release.

Description

Degradable synthetic polymer spherical honeycombed grain material and preparation method thereof and device
One, technical field
The invention belongs to a kind of spherical particle material preparation technology that is applied to biomedical sector, be specifically related to a kind of preparation method of natural polymer degradable synthetic polymer spherical honeycombed grain material.
Two, background technology
Prior art: the degradable synthetic polymer material can be produced in batches with comparalive ease, and can change its characteristics according to specific use, is studied widely and uses in pharmaceuticals industry.At present, the degradable synthetic polymer material of more generally using has copolymer (PLGA) and the butyric ester (PHB) of polylactic acid (PLA), polyglycolic acid (PGA), polylactic acid and polyglycolic acid.These materials.No matter be as medicament slow release or for tissue renovation material, all obtain more research.Granular degradable synthetic polymer material not only can be used as targeted drug or sustained-release and controlled release pharmaceutical carrier, and can be used for the tissue filling reparation.
Micro-sphere material has the unexistent excellent properties of a lot of irregular particles, as being difficult for causing stress concentration etc. after high flowability, high bulk density, difficult reunion, the filling.At present, reparation, the alveolar ridge of frontal resorption increase due to the filling, periodontal disease of root canal and exodontia nest, the filling of jaw bones blister cavities, atrophic rhinitis's filling, mastoid cavity filling, shaping (such as the nasus incurvus beauty treatment) reach in the damaged filling of bone with other position of skeleton, and the microsphere particle packing material is used widely.The polymer-matrix microsphere particle has multiple preparation method, and commonly used have emulsifying-chemical crosslink technique, emulsion solvent evaporation technique and a spray drying method.The microsphere diameter distribution of using these method preparations is larger, and packed density is large, and when being applied to tissue filling, intergranular hole is very few, is unfavorable for growing into of cambium.
Three, summary of the invention
The present invention is directed to above-mentioned technological deficiency, a kind of preparation method for preparing the degradable synthetic polymer spherical honeycombed grain material with homogeneous distributed granule diameter is provided.
Technical scheme of the present invention is a kind of degradable synthetic polymer spherical honeycombed grain material, the spheroidal particle of described degradable synthetic polymer spherical honeycombed grain material, particle diameter is φ 0.8~4mm, the granule body interior is that the aperture is less than the micropore of 150 μ m, intercommunication between the micropore, the porosity of degradable synthetic polymer spherical honeycombed grain material are 75~93%.
Described degradable synthetic polymer spherical honeycombed grain material, described degradable synthetic polymer be the copolymer (PLGA) of polylactic acid (PLA), polyglycolic acid (PGA), polylactic acid and polyglycolic acid, in the poly butyric ester (PHB) any one.
A kind of preparation method for preparing degradable synthetic polymer spherical honeycombed grain material as claimed in claim 1, preparation process is:
The dioxane solution of the ratio preparation degradable polymer first step, in mass ratio degradable polymer: dioxane=1:(4~15);
Second step, the dioxane solution of the degradable polymer that the first step is prepared adds storage tank from charge door, be 0.08~0.5MPa by the pressure in Pressure gauge and the pressure-control valve control storage tank, evenly flow out take the catheter of dioxane solution from caliber as φ 0.5~3mm that the guarantee degradable polymer speed with 10~60/min.The dioxane solution of the degradable polymer that flows out from catheter is dripped behind the subsphaeroidal granule of about φ 0.8~4mm greatly mouth of pipe director, in dropping process, because capillary effect forms spherical, the temperature that then splashes in the cool-bag is condensation in the-condensed fluid of (10~20) ℃, forms the dioxane spherical honeycombed grain material of the degradable polymer of good sphericity, uniform particle diameter.
According to the surface tension formula:
mg=2πrσ
In the formula: m is drop mass; R is the extracapillary radius; σ is surface tension; G is acceleration of gravity.When density and viscosity one timing of collagen solution, under the condition without external interference, this method can be prepared the spheroidal particle of good sphericity, uniform particle diameter.
In the 3rd step, with the condensed spheroidal particle separation of second step, lyophilization, obtain degradable synthetic polymer spherical honeycombed grain material.
Wherein said degradable synthetic polymer is the copolymer (PLGA) of polylactic acid (PLA), polyglycolic acid (PGA), polylactic acid and polyglycolic acid, in the poly butyric ester (PHB) any one.Described condensed fluid is dimethicone or vegetable oil.
The device for preparing described degradable synthetic polymer spherical honeycombed grain material, formed by storage tank and cool-bag, be provided with charge door at the storage tank top, on storage tank, also be provided with Pressure gauge, Pressure gauge is connected with pressure-control valve, bottom at storage tank is provided with catheter, is provided with flow control valve at catheter, is provided with cool-bag below catheter.
Beneficial effect: the degradable synthetic polymer spherical honeycombed grain material of the present invention's preparation::
(1) contain a large amount of intercommunication micropores in the granule body interior, form three-dimensional netted stereochemical structure, this granule has higher specific surface area, is conducive to the Flow of tissue fluid of the adhesion of cell;
(2) the degradable synthetic polymer granule has the particle size distribution of homogeneous, does not need to sieve the granular materials that processing can obtain having same particle size; Because according to the surface tension formula:
mg=2πrσ
In the formula: m is drop mass; R is the extracapillary radius; σ is surface tension; G is acceleration of gravity.When density and viscosity one timing of degradable synthetic polymer dioxane solution, under the condition without external interference, this method can be prepared the spheroidal particle of good sphericity, uniform particle diameter.
(3) uniform particle diameter because of the degradable synthetic polymer spherical granular materials for preparing according to this method is good, and the spherical granular material of same particle size, the intergranular space rate is maximum after the filling, so be conducive to the migration growth of Flow of tissue fluid and cell after the degradable synthetic polymer spherical granular materials of the present invention filling.
Four, description of drawings
Fig. 1 spheroidal particle forming device schematic diagram
Device mainly is comprised of charge door 1, Pressure gauge 2, pressure-control valve 3, storage tank 4, flow control valve 5, catheter 6, condensed fluid 7 and cool-bag 8.
Fig. 2 is polylactic acid spherical honeycombed grain photo.
Fig. 3 is the internal void photo of polylactic acid spherical honeycombed grain.
Five, specific embodiments:
Embodiment 1:
(1) mass ratio of pressing polylactic acid (PLLA, Shandong medical device research institute, mean molecule quantity 100,000) and dioxane is 1:15 preparation polylactic acid dioxane solution;
(2) as shown in Figure 1, the polylactic acid dioxane solution for preparing adds storage tank 4 from charge door 1, the pressure of controlling in the storage tanks 4 by pressure-control valve 3 is 0.08~0.5MPa, guaranteeing that the polylactic acid dioxane solution evenly flows out from φ 0.5~3mm catheter 6, be that the speed of 10~60/min evenly flows out by flow control valve 5 coutroi velocities.Behind the subsphaeroidal granule of φ 0.8~4mm, drip greatly mouth of pipe director from the polylactic acid dioxane solution that catheter 6 flows out, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-(10~20) ℃, condensed fluid is dimethicone, forms spheroidal particle.
(3) condensed microsphere separates, and process 8~24h in the-temperature lyophilization of (5~10) ℃, obtain the polylactic acid spherical honeycombed grain material, as shown in Figure 2, the good sphericity of the polylactic acid spherical honeycombed grain material that obtains, uniform particle diameter, as shown in Figure 3, interior porosity is high, has formed three-dimensional netted stereochemical structure.
Embodiment 2:
(1) mass ratio of pressing polyglycolic acid (PGA, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, mean molecule quantity 80,000) and dioxane is 1:8 preparation polyglycolic acid dioxane solution;
(2) the polyglycolic acid dioxane solution for preparing adds storage tank 4 from charge door 1, is 0.08~0.5MPa by the pressure in the control storage tank 4, evenly flows out from φ 0.5~3mm catheter 6 to guarantee the polyglycolic acid dioxane solution.Behind the subsphaeroidal granule of φ 0.8~4mm, drip greatly mouth of pipe director from the polyglycolic acid dioxane solution that catheter 6 flows out, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-(10~20) ℃, condensed fluid is vegetable oil, forms spheroidal particle.
(3) condensed microsphere separates, and processes 8~24h, obtain the polyglycolic acid spherical honeycombed grain material in the-temperature lyophilization of (5~10) ℃.
Embodiment 3:
(1) pressing the copolymer (PLGA (75/25), Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, mean molecule quantity 8.2 ten thousand) of polylactic acid and polyglycolic acid and the mass ratio of dioxane is the 1:12 obtain solution;
(2) copolymer solution for preparing adds storage tank 4 from charge door 1, is 0.08~0.5MPa by the pressure in the control storage tank 4, evenly flows out from φ 0.5~3mm catheter 6 with the dioxane solution that guarantees polylactic acid and co-glycolic acid.The dioxane solution of the polylactic acid that flows out from catheter 6 and the copolymer of polyglycolic acid is dripped behind the subsphaeroidal granule of φ 0.8~4mm greatly mouth of pipe director, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-(10~20) ℃, form spheroidal particle.
(3) condensed microsphere separates, and processes 8~24h, obtain the copolymer spherical honeycombed grain material of polylactic acid and polyglycolic acid in the-temperature lyophilization of (5~10) ℃.
Embodiment 4:
(1) mass ratio of pressing poly butyric ester (PHB, Jiangsu group of Nan Tian, mean molecule quantity 1,100,000) and dioxane is the 1:5 obtain solution;
(2) the poly butyric ester solution for preparing adds storage tank 4 from charge door 1, is 0.08~0.5MPa by the pressure in the control storage tank 4, evenly flows out from φ 0.5~3mm catheter 6 to guarantee the poly butyric ester dioxane solution.Behind the subsphaeroidal granule of φ 0.8~4mm, drip greatly mouth of pipe director from the poly butyric ester dioxane solution that catheter 6 flows out, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-(10~20) ℃, form spheroidal particle.
(3) condensed microsphere separates, and processes 8~24h, obtain the poly butyric ester spherical honeycombed grain material in the-temperature lyophilization of (5~10) ℃.
Embodiment 5:
(1) mass ratio of pressing polylactic acid (PLLA, Shandong medical device research institute, mean molecule quantity 100,000) and dioxane is 1:4 preparation polylactic acid dioxane solution;
(2) the polylactic acid dioxane solution for preparing adds storage tank 4 from charge door 1, the pressure of controlling in the storage tanks 4 by pressure-control valve 3 is 0.08MPa, guaranteeing that the polylactic acid dioxane solution evenly flows out from φ 0.5mm catheter 6, be that the speed of 10/min evenly flows out by flow control valve 5 coutroi velocities.Behind the subsphaeroidal granule of φ 0.8mm, drip greatly mouth of pipe director from the polylactic acid dioxane solution that catheter 6 flows out, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-10 ℃, forms spheroidal particle.
(3) condensed microsphere separates, and processes 8h-5 ℃ temperature lyophilization, obtains the polylactic acid spherical honeycombed grain material, and particle diameter is 0.8mm, and porosity is 75%.
Embodiment 6:
(1) mass ratio of pressing polylactic acid (PLLA, Shandong medical device research institute, mean molecule quantity 100,000) and dioxane is 1:8 preparation polylactic acid dioxane solution;
(2) the polylactic acid dioxane solution for preparing adds storage tank 4 from charge door 1, the pressure of controlling in the storage tanks 4 by pressure-control valve 3 is 0.15MPa, guaranteeing that the polylactic acid dioxane solution evenly flows out from φ 1.5mm catheter 6, be that the speed of 40/min evenly flows out by flow control valve 5 coutroi velocities.Behind the subsphaeroidal granule of φ 1.5mm, drip greatly mouth of pipe director from the polylactic acid dioxane solution that catheter 6 flows out, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-15 ℃, forms spheroidal particle.
(3) condensed microsphere separates, and processes 16h-7 ℃ temperature lyophilization, obtains the polylactic acid spherical honeycombed grain material.
Embodiment 7:
(1) mass ratio of pressing polylactic acid (PLLA, Shandong medical device research institute, mean molecule quantity 100,000) and dioxane is 1:15 preparation polylactic acid dioxane solution;
(2) the polylactic acid dioxane solution for preparing adds storage tank 4 from charge door 1, the pressure of controlling in the storage tanks 4 by pressure-control valve 3 is 0.5MPa, guaranteeing that the polylactic acid dioxane solution evenly flows out from φ 3mm catheter 6, be that the speed of 60/min evenly flows out by flow control valve 5 coutroi velocities.Behind the subsphaeroidal granule of φ 4mm, drip greatly mouth of pipe director from the polylactic acid dioxane solution that catheter 6 flows out, in dropping process, because capillary effect forms spherical, then splash into condensation in the condensed fluid 7 in the cool-bag 8, the temperature of condensed fluid is-20 ℃, forms spheroidal particle.
(3) condensed microsphere separates, and processes 24h-10 ℃ temperature lyophilization, obtains the polylactic acid spherical honeycombed grain material.

Claims (5)

1. degradable synthetic polymer spherical honeycombed grain material, it is characterized in that described degradable synthetic polymer spherical honeycombed grain material, particle diameter is φ 0.8~4mm, the granule body interior is that the aperture is less than the micropore of 150 μ m, intercommunication between the micropore, the porosity of degradable synthetic polymer spherical honeycombed grain material are 75~93%; Described degradable synthetic polymer is the copolymer of polylactic acid, polyglycolic acid, polylactic acid and polyglycolic acid, in the poly butyric ester any one.
2. a preparation method for preparing degradable synthetic polymer spherical honeycombed grain material as claimed in claim 1 is characterized in that, preparation process is:
The first step, in mass ratio degradable polymer: dioxane=1: the dioxane solution of the ratio preparation degradable polymer of (4~15);
Second step, the dioxane solution of the degradable polymer that the first step is prepared is the pipe of φ 0.5~3mm from caliber, evenly flows out with the speed of 10~60/min, splashes into temperature for condensation in the-condensed fluid of (10~20) ℃, forms spheroidal particle;
In the 3rd step, with the condensed spheroidal particle separation of second step, lyophilization, obtain degradable synthetic polymer spherical honeycombed grain material.
3. the preparation method of degradable synthetic polymer spherical honeycombed grain material as claimed in claim 2 is characterized in that described degradable synthetic polymer is the copolymer of polylactic acid, polyglycolic acid, polylactic acid and polyglycolic acid, in the poly butyric ester any one.
4. the preparation method of degradable synthetic polymer spherical honeycombed grain material as claimed in claim 2 is characterized in that, described condensed fluid is dimethicone or vegetable oil.
5. the device for preparing degradable synthetic polymer spherical honeycombed grain material as claimed in claim 1, it is characterized in that, described device is comprised of storage tank (4) and cool-bag (8), be provided with charge door (1) at storage tank (4) top, on storage tank (4), also be provided with Pressure gauge (2), Pressure gauge (2) is connected with pressure-control valve (3), be provided with catheter (6) in the bottom of storage tank (4), be provided with flow control valve (5) at catheter (6), below catheter, be provided with cool-bag (8).
CN2008102350714A 2008-11-07 2008-11-07 Degradable synthetic polymer spherical honeycombed grain material, producing method and apparatus thereof Expired - Fee Related CN101401954B (en)

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CN104277234A (en) * 2014-10-31 2015-01-14 华东理工大学 Method of preparing polymer porous beads based on liquid drop settling and freezing technology
GB201702475D0 (en) * 2017-02-15 2017-03-29 Locate Therapeutics Ltd Tissue scaffold and scaffold composition
CN110448724B (en) * 2019-07-23 2022-03-18 广东省医疗器械研究所 Degradable polymer microsphere with surface pits and preparation method and application thereof
CN110404115B (en) * 2019-07-23 2022-03-18 广东省医疗器械研究所 Carbonate/degradable polymer microsphere with surface pits and preparation method and application thereof

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