CN100388970C - Method for preparing polylactic porous microball - Google Patents
Method for preparing polylactic porous microball Download PDFInfo
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- CN100388970C CN100388970C CNB2004100529810A CN200410052981A CN100388970C CN 100388970 C CN100388970 C CN 100388970C CN B2004100529810 A CNB2004100529810 A CN B2004100529810A CN 200410052981 A CN200410052981 A CN 200410052981A CN 100388970 C CN100388970 C CN 100388970C
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- polylactic acid
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- microsphere
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000011806 microball Substances 0.000 title description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 49
- 239000004626 polylactic acid Substances 0.000 claims abstract description 49
- 239000004005 microsphere Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229940094933 n-dodecane Drugs 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000012074 organic phase Substances 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 5
- 238000013270 controlled release Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 10
- 229920001432 poly(L-lactide) Polymers 0.000 description 10
- 229940068984 polyvinyl alcohol Drugs 0.000 description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000935 solvent evaporation Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
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- Medicinal Preparation (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention discloses a method for preparing a porous polylactic acid microsphere, which comprises the following steps: 1, polylactic acid is dissolved in solvent of methylene chloride, and then, poor solvent is added into the solvent and is mixed evenly; 2, polyvinyl alcohol dissolved in deionized water is prepared into solution in which the polylactic acid solution in the state of being stirred is poured; 3, organic solvent is volatilized, filtered and washed so as to obtain a porous polylactic acid microsphere. The method of the present invention has the advantages of simple operating technology and mild implementing condition. The obtained porous polylactic acid microsphere can be widely used as a cell microcarrier in controlled release systems of medicine and cell engineering and can be used as an adhered microsphere support bracket in tissue engineering.
Description
Technical field
The present invention relates to prepare the method for porous polylactic acid microball.
Background technology
PLA has good physical and mechanical properties, avirulence, easy absorbability in processing forming, biological degradability and the body, and therefore important use value arranged in a plurality of fields, especially as the carrier of tissue engineering material and drug delivery and controlled release.In biomedical materials field, adopt various process technologies, PLA can be prepared to bar, nail, suture, medicine microcarrier and the microballoon etc. of inner tight, or the support of loose and porous inner surface, nonwoven and hollow microsphere etc.Wherein, microballoon is with the popularity of the polytropy of the particularity of its structure, performance, application and in biomedical materials field crucial status is arranged.For example, can in multiple treatment of diseases, play a significant role as the carrier of embedding, transmission and the controlled release of medicine, gene, polypeptide and albumen; The microballoon that the surface is modified through specificity can improve the culture density of cell as the microcarrier in the cell engineering, keeps the normal physiological function of cell; The microcarrier of compound cell can be injected directly into defect, carries out tissue repair; By the further assembling between microballoon and integrated, can obtain three-dimensional porous rack, be used for the regeneration of cell guiding and tissue.
The preparation method of solid microsphere mainly contains phase separation method, emulsification-solvent evaporation method, freezing and spray-on process etc.Wherein the application of emulsification-solvent evaporation method is the most extensive.Emulsification-solvent evaporation method be with polymer dissolution in organic solvent, under agitation in the aqueous solution, carry out emulsification then, along with the volatilization of solvent, polymer microballoon slowly forms.Because the drop of organic solvent can shrink in the solvent evaporates process, the microballoon of therefore emulsification usually-solvent evaporation method preparation is solid microsphere.As implants in vivo such as drug carrier system or cell carrier, the degraded of microballoon can produce a large amount of acidic materials, mainly is lactic acid.Local high concentration acidity easily causes the aseptic inflammation reaction of peripheral organs and tissue, produces the red and swollen even downright bad of tissue.Therefore, when guaranteeing the microballoon function, the consumption that as far as possible reduces PLA is one of best solution.Porous microsphere can reduce the content of PLA in the microballoon significantly under the situation that guarantees medicine carrying amount and support overall mechanical strength.At present, the preparation method of porous microsphere mainly contains quick removal solvent method, pore-foaming agent method and two emulsion methods etc.The operating process of these methods and implementing process more complicated, influence factor is more, and the loose structure of microballoon is wayward, so the repeatability of gained porous microsphere and the difficult assurance of quality.
Summary of the invention
The purpose of this invention is to provide the method for preparing porous polylactic acid microball that a kind of operating process and implementing process are simple, can control microsphere porous structure.
The method for preparing porous polylactic acid microball of the present invention may further comprise the steps:
1) PLA is dissolved in the methylene chloride, adds poor solvent then, mix, the bulking value concentration of PLA in the mixed solvent of carrene and poor solvent is 3～8%; The volume ratio of carrene and poor solvent is 10: 0～8: 2 in the mixed solvent;
2) polyvinyl alcohol is dissolved in the deionized water, be prepared into bulking value concentration and be 0.3～0.8% solution, low whipping speed is under 300～800 rev/mins of situations, and PLA solution is poured in the poly-vinyl alcohol solution, and the volume ratio of water and organic facies is 5: 1～10: 1;
3) vapor away organic solvent under 10～40 ℃, filter, washing obtains porous polylactic acid microball.
Among the present invention, said poor solvent can be n-hexane, normal heptane, normal octane, isooctane or n-dodecane.
The inventive method operating procedure is simple, implementation condition is gentle.Prepare porous polylactic acid microball with emulsification-solvent evaporation method with the molten method that combines that is separated that causes, can regulate and control the particle size of polylactic acid microsphere, the porosity of microballoon and the size of internal capillary by the mixed proportion of mixing speed, PLA concentration, polyethylene of dispersing agent determining alcohol, good solvent carrene and poor solvent and the ratio of organic facies and water.The inventive method provides a kind of new method of simple possible for the preparation porous polylactic acid microball.The gained porous polylactic acid microball can be widely used in cell microcarrier in medicine controlled releasing system, the cell engineering and the microballoon adhesion type support in the organizational project.
Description of drawings
Fig. 1 is that the particle diameter of example 1 porous polylactic acid microball distributes;
Fig. 2 is the configuration of surface and the internal structure of example 1 porous polylactic acid microball; Fig. 2 a, Fig. 2 b are the configuration of surface stereoscan photograph of porous polylactic acid microball, and multiplication factor is respectively 100 times and 230 times; Fig. 2 c is the cross sectional photograph of porous polylactic acid microball; Fig. 2 d is the internal structure photo of porous polylactic acid microball;
Fig. 3 is that the particle diameter of example 2 porous polylactic acid microball distributes;
Fig. 4 is the configuration of surface and the internal structure of example 2 porous polylactic acid microball; Fig. 4 a, Fig. 4 b are the configuration of surface stereoscan photograph of porous polylactic acid microball, and multiplication factor is respectively 50 times and 150 times; Fig. 4 c is the cross sectional photograph of porous polylactic acid microball; Fig. 4 d is the internal structure photo of porous polylactic acid microball;
Fig. 5 is that the particle diameter of example 3 porous polylactic acid microball distributes;
Fig. 6 is the configuration of surface and the internal structure of example 3 porous polylactic acid microball; Fig. 6 a, Fig. 6 b are the configuration of surface stereoscan photograph of porous polylactic acid microball, and multiplication factor is respectively 100 times and 180 times; Fig. 6 c is the cross sectional photograph of porous polylactic acid microball; Fig. 6 d is the internal structure photo of porous polylactic acid microball;
Fig. 7 is the configuration of surface and the internal structure of example 4 PLLA porous microspheres; Fig. 7 a is the configuration of surface of PLLA porous microsphere; Fig. 7 b is the cross sectional photograph of PLLA porous microsphere;
Fig. 8 is the configuration of surface and the internal structure of example 5 PLLA porous microspheres; Fig. 8 a is the configuration of surface of PLLA porous microsphere; Fig. 8 b is the cross sectional photograph of PLLA porous microsphere;
The specific embodiment
Example 1: the 0.5g PLA is dissolved in the 9ml carrene, adds the 1ml n-hexane, mix, standby.Adding bulking value concentration is 0.8% polyvinyl alcohol water solution 100ml in the beaker of 200ml.Start and stir, mixing speed is 500 rev/mins, pours the carrene/hexane solution of PLA into.Temperature is 25 ℃, stirs 24h, makes the organic solvent volatilization fully.After stopping to stir, microballoon is suspended in solution surface, filters, and uses the deionized water cyclic washing, collects the back in 35 ℃ of following vacuum drying 3 days.Yield is 98%, and microballoon number average bead diameter d=290 micron is seen Fig. 1; Apparent density is 0.2891g/cm
3, inner average pore size is 16 ± 3 microns, sees Fig. 2 a～Fig. 2 d.
Example 2: the 0.5g PLA is dissolved in the 9ml carrene, adds the 1ml normal octane, mix, standby.Adding bulking value concentration is 0.8% polyvinyl alcohol water solution 100ml in the beaker of 200ml.Start and stir, mixing speed is 300 rev/mins, pours the carrene/hexane solution of PLA into.Temperature is 25 ℃, stirs 24 hours, makes the organic solvent volatilization fully.After stopping to stir, microballoon is suspended in solution surface, filters, and uses the deionized water cyclic washing, collects the back in 35 ℃ of following vacuum drying 3 days.Yield is 97.7%, and microsphere average grain diameter d=471 micron is seen Fig. 3; Apparent density is 0.2136g/cm
3, inner average pore size is 24 ± 4 microns, sees Fig. 4 a～Fig. 4 d.
Example 3: the 0.5g PLA is dissolved in the 8ml carrene, adds the 2ml n-hexane, mix, standby.Adding bulking value concentration is 0.8% polyvinyl alcohol water solution 100ml in the beaker of 200ml.Start and stir, mixing speed is 500 rev/mins, pours the carrene/hexane solution of PLA into.Temperature is 25 ℃, stirs 24 hours, makes the organic solvent volatilization fully.After stopping to stir, microballoon is suspended in solution surface, filters, and uses the deionized water cyclic washing, collects back 35 ℃ of following vacuum drying 3 days.Yield is 99%, and microsphere average grain diameter d=413 micron is seen Fig. 5; Apparent density is 0.1726g/cm
3, inner average pore size is 30 ± 5 microns, sees Fig. 6 a～Fig. 6 d.
Example 4 is dissolved in the 0.5g PLLA in the 9ml carrene, adds the 1ml n-hexane, mixes, and is standby.Adding bulking value concentration is 0.8% polyvinyl alcohol water solution 100ml in the beaker of 200ml.Start and stir, mixing speed is 500 rev/mins, pours the carrene/hexane solution of PLLA into.Temperature is 25 ℃, stirs 24 hours, makes the organic solvent volatilization fully.After stopping to stir, visible microballoon is suspended in solution surface, filters, and uses the deionized water cyclic washing, collects back 35 ℃ of following vacuum drying 3 days.See Fig. 7 a, Fig. 7 b.
Example 5 is dissolved in the 0.5g PLLA in the 9ml carrene, adds the 1ml n-dodecane, mixes, and is standby.Adding bulking value concentration is 0.8% polyvinyl alcohol water solution 100ml in the beaker of 200ml.Start and stir, mixing speed is 500 rev/mins, pours the carrene/n-dodecane solution of PLLA into.Temperature is 25 ℃, stirs 24 hours, makes the organic solvent volatilization fully.After stopping to stir, microballoon is suspended in solution surface, filters, and uses the deionized water cyclic washing, collects back 35 ℃ of following vacuum drying 3 days.See Fig. 8 a, Fig. 8 b.
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| CNB2004100529810A CN100388970C (en) | 2004-07-15 | 2004-07-15 | Method for preparing polylactic porous microball |
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| CNB2004100529810A CN100388970C (en) | 2004-07-15 | 2004-07-15 | Method for preparing polylactic porous microball |
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| CN100388970C true CN100388970C (en) | 2008-05-21 |
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| CN109265942A (en) * | 2018-08-16 | 2019-01-25 | 张海军 | A kind of polylactic acid microsphere and the preparation method and application thereof |
| CN111298196A (en) * | 2020-03-27 | 2020-06-19 | 常州药物研究所有限公司 | Polylactic acid porous microsphere, preparation method and application thereof |
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| CN111298196A (en) * | 2020-03-27 | 2020-06-19 | 常州药物研究所有限公司 | Polylactic acid porous microsphere, preparation method and application thereof |
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