CN1958081A - Method for preparing 3D porous bracket of chitosan - copolymer of poly lactic acid - Google Patents
Method for preparing 3D porous bracket of chitosan - copolymer of poly lactic acid Download PDFInfo
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- CN1958081A CN1958081A CN 200610016189 CN200610016189A CN1958081A CN 1958081 A CN1958081 A CN 1958081A CN 200610016189 CN200610016189 CN 200610016189 CN 200610016189 A CN200610016189 A CN 200610016189A CN 1958081 A CN1958081 A CN 1958081A
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Abstract
A 3D porous chitosan-polylactic acid scaffold is prepared through dissolving chitosan in lactic acid, adding sodium (or potassium) chloride, stirring while heating, loading it in mould, drying in oven, heating while vacuum copolymerizing, extracting in methanol or chloroform, drying, washing with deionized water, and freeze drying.
Description
Technical field
The present invention relates to a kind of chitosan-copolymer of poly lactic acid method for preparing 3 D porous bracket, belong to the tissue engineering bracket technology of preparing.
Background technology
The material that is used for tissue engineering bracket mainly contains natural macromolecular material and synthesized polymer material, the former generally has cellular affinity preferably, but owing to source difference, the processing method of material do not cause properties of product to be difficult to reappear on an equal basis, the adjustable scope of its conventional physicochemical property is very limited, and opereating specification is narrower in the course of processing has also limited its application in special-shaped material; Synthesized polymer material has good processing properties and can pass through regulates the composition of product and the technological parameter in the building-up process, and its physicochemical property is regulated and control.But lack reasons such as cell recognition site owing to such material surface, influenced cell adhesion and growth in its surface.Therefore, biomedical material is carried out modification and just becoming life sciences and the common research focus of material science with cellular affinity, machinability and the Mechanical Properties that improves material.And the successful exploitation of the tissue engineering rack material of function admirable will make wound and plastic surgery enter a brand-new field.
Chitosan is unique a kind of positively charged alkaline polysaccharide that occurring in nature exists, and is nontoxic, non-stimulated, has excellent biological compatibility, biodegradability.Chondrocyte apposition growth on the chitin fiber rack is rapid, and keeps its good gene phenotype.
Polylactic acid molecule amount scalable, processing characteristics is good, and it has obtained the approval of FDA as sutures and nail etc.But its hydrophilic difference and catabolite are the use that shortcomings such as acidity have also limited polylactic acid.
For the biological activity that makes full use of chitosan and the mechanical property and the machinability of polylactic acid excellence, people utilize diverse ways to make the graft copolymer of chitosan and polylactic acid.
In our initial stage work
[1,2],, successfully made the graft copolymer thin film of chitosan and polylactic acid by the amidation process of chitosan and lactic acid and the direct condensation reaction of lactic acid.The human fibroblasts cultivation results shows, makes chitosan-polylactic acid graft copolymer by direct condensation reaction and has the good cell affinity.
By the ion-type initiator system, methods such as direct polycondensation or coupling all can make the graft polymers of chitosan and polylactic acid, but up to the present all reports all are the synthetic of relevant polymer and characterize, and making product is powder or thin film.Relevant chitosan-copolymer of poly lactic acid is made three-dimensional porous rack, particularly prepare chitosan-copolymer of poly lactic acid porous support, yet there are no reported in literature by formed in situ.
List of references:
[1]Fanglian?Yao，Wei?Chen，Hao?Wang，Haifeng?Liu，Kangde?Yao.A?study?on?cytocompatiblepoly(chitosan-g-L-lactic?acid).polymer，2003，44：6435-6441
[2] Yao Kangde, Yao Fanglian, Liu Chang, Chen Wei. the preparation method of chitosan-polylactic acid graft copolymer. Chinese invention patent, CN02155475.7
Summary of the invention
The object of the present invention is to provide a kind of chitosan-copolymer of poly lactic acid method for preparing 3 D porous bracket, it is controlled to have a pore size with the prepared three-dimensional tissue of the method porous support materials, the characteristics of good mechanical properties.
The present invention is realized that by following technical proposals a kind of chitosan-copolymer of poly lactic acid method for preparing 3 D porous bracket is characterized in that comprising following process:
(1) in mass ratio is 1: 1.5～1: 4 ratio, chitosan is dissolved among L-lactic acid, D-lactic acid or the DL-lactic acid, stirred 0.5～1 hour, to settled solution.In the mass ratio of porogen and chitosan is that 1: 1～1: 4 ratio adds sodium chloride or potassium chloride in settled solution, mechanical agitation 1-5 hour, serosity.
(2) serosity that step (1) is made stirs and is heated to 40～70 ℃, stops after 5～30 minutes stirring, and pours in the mould, leaves standstill under room temperature 12～48 hours.The mould that mixture will be housed is put into baking oven again, 30～60 ℃ of following constant pressure and dries 36～96 hours, then at 0.04～0.1MPa, makes the solids intensification copolymerization of drying and moulding under 35～100 ℃ of conditions.
(3) solids that will take out from mould places vacuum drying oven with methanol or chloroform continuously or be interrupted extracting after 24～80 hours again, at 25 ℃, and 0.08～0.1MPa dry 48 hours down.
(4) dried solids is carried out washing by soaking with deionized water, changed a deionized water every 24 hours, till the existence that detects in the deionized water after washing less than porogen, obtain the hygrometric state support.
(5) with the hygrometric state support-30～-50 ℃ of following lyophilizations, obtain chitosan-copolymer of poly lactic acid porous support.
Innovation part of the present invention is by add a certain amount of porogen in polymerization reaction system, polyreaction and rack forming are carried out simultaneously, avoided the use of organic solvent and catalyst, saved the post forming process, the intensity of gained support, porosity and pore-size distribution can be well controlled.
The prepared chitosan of the present invention-polylactic acid graft copolymer three-dimensional porous rack when keeping both excellent biological compatibility, biological activity and mechanical property, by polylactic acid is grafted on the chitosan main chain, has improved drawing abillity.Simultaneously, the catabolite of chitosan is alkalescence, can in and the acidity of polylactic acid catabolite.So preparation polylactic acid/chitosan composite is expected to improve the polylactic acid hydrophilic and overcomes owing to the polylactic acid catabolite is the acid problem that causes aseptic inflammation to take place.
Material source of the present invention is extensive, and is with low cost.By regulating the particle diameter and the use amount of porogen, can prepare three-dimensional porous rack, and the connectedness in hole is stronger with suitable aperture and porosity.Prepared porous support can be widely used for the reconstruction or the reparation of multiple tissues such as skin, cartilage, bone or organ.
Description of drawings
Fig. 1 is according to the SEM photo of the support of the preparation method preparation of embodiment 3.
The specific embodiment
Embodiment 1:
Take by weighing the 1.5g chitosan, it be dissolved among the 2.25g DL-lactic acid, stir 0.5 hour to dissolving fully.Weighing 2.5g sodium chloride adds so far in the solution, mechanical agitation 3 hours, to be mixed evenly, 50 ℃ of heating 10 minutes down.Solution is poured in the mould of plastics, under room temperature, was left standstill 24 hours, after put into 40 ℃ of following constant pressure and dries of baking oven 96 hours.Divided for three steps made the copolymerization that under vacuum condition, heats up of the solids of drying and moulding:
1. 40-50 ℃, 0.06MPa heated 1.5 hours
2. 75-80 ℃, 0.08MPa heated 2-3 hour
3. 85-95 ℃, 0.1MPa heated 2-3 hour
The solids of taking out is put into vacuum drying oven with the continuous extracting of 500mL methanol after 24 hours, and further drying is 48 hours under room temperature, 0.1MPa, with the residual methanol of Ex-all.Again solids is steeped in the deionized water, changed water once every 24 hours, clean 10 times repeatedly after, detect existence in the deionized water after the washing less than sodium chloride, obtain the hygrometric state support.The hygrometric state support-30 ℃ of following lyophilizations, is prepared into porous support.It is 95.9% that the support that obtains records porosity with density bottle, and pore diameter range is 5～50 microns.
Embodiment 2:
Take by weighing the 1.5g chitosan, it be dissolved among the 6g L-lactic acid, stir 0.5 hour to dissolving fully.Weighing 2.5g sodium chloride adds so far in the solution, mechanical agitation 1 hour, to be mixed evenly, 50 ℃ of heating 5 minutes down.Solution is poured in the mould of plastics, under room temperature, was left standstill 24 hours, after put into 30 ℃ of following constant pressure and dries of baking oven 96 hours.The vacuum polymerization process is the same.The support that takes out is put into vacuum drying oven with the continuous extracting of 500mL methanol after 40 hours, and further drying is 48 hours under room temperature, 0.1MPa, with the residual methanol of Ex-all.Again support is steeped in the deionized water, changed water once every 24 hours, clean 14 times repeatedly after, detect existence in the deionized water after the washing less than sodium chloride, obtain the hygrometric state support.The hygrometric state support-50 ℃ of following lyophilizations, is prepared into porous support.It is 89.1% that the support that obtains records porosity with density bottle, and pore diameter range is 5～50 microns.
Embodiment 3:
Take by weighing the 1.5g chitosan and be dissolved among the 3g lactic acid, stir 1 hour to dissolving fully.Weighing 1.5g potassium chloride adds so far in the solution, mechanical agitation 3 hours, to be mixed evenly, 40 ℃ of heating 10 minutes down.Solution is poured in the plastic culture dish, in room temperature, was left standstill 12 hours, after put into 60 ℃ of following constant pressure and dries of baking oven 36 hours.The vacuum polymerization process is the same.The support that takes out is put into vacuum drying oven with the continuous extracting of 500mL methanol after 40 hours, and further drying is 48 hours under room temperature, 0.08MPa, with the residual methanol of Ex-all.Again support is steeped in the deionized water, changed water once every 24 hours, clean 14 times repeatedly after, detect existence in the deionized water after the washing less than potassium chloride, obtain the hygrometric state support.The hygrometric state support-50 ℃ of following lyophilizations, is prepared into porous support.It is 92.0% that the support that obtains records porosity with density bottle, and pore diameter range is 5～30 microns.See Fig. 1.
Embodiment 4:
Take by weighing the 1.5g chitosan and be dissolved among the 3g lactic acid, stir 0.5 hour to dissolving fully.Weighing 4.5g sodium chloride adds so far in the solution, mechanical agitation 5 hours, to be mixed evenly, 50 ℃ of heating 30 minutes down.Solution is poured in the plastic culture dish, in room temperature, was left standstill 48 hours, after put into 40 ℃ of following constant pressure and dries of baking oven 72 hours.The vacuum polymerization process is the same.The support that takes out is put into vacuum drying oven with the continuous extracting of 600mL chloroform after 80 hours, and further drying is 48 hours under room temperature, 0.1MPa, with the residual chloroform of Ex-all.Again support is steeped in the deionized water, changed water once every 24 hours, clean 14 times repeatedly after, detect existence in the deionized water after the washing less than sodium chloride, obtain the hygrometric state support.The hygrometric state support-40 ℃ of following lyophilizations, is prepared into porous support.It is 95.7% that the support that obtains records porosity with density bottle, and pore diameter range is 5～30 microns.
Claims (1)
1. chitosan-copolymer of poly lactic acid method for preparing 3 D porous bracket is characterized in that comprising following process:
(1) in mass ratio is 1: 1.5～1: 4 ratio, chitosan is dissolved among L-lactic acid, D-lactic acid or the DL-lactic acid, stirred 1～3 hour, to settled solution; In the mass ratio of porogen and chitosan is that 1: 1～1: 4 ratio adds sodium chloride or potassium chloride in settled solution, mechanical agitation 0.5-5 hour, serosity;
(2) serosity that step (1) is made stirs and is heated to 40～100 ℃, stops after 5～30 minutes stirring, and pours in the mould, leaves standstill under room temperature 12～48 hours; The mould that mixture will be housed is put into baking oven again, 30～60 ℃ of following constant pressure and dries 36～96 hours, then at 0.04～0.1MPa, makes the solids intensification copolymerization of drying and moulding under 35～100 ℃ of conditions;
(3) solids that will take out from mould places vacuum drying oven with methanol or chloroform continuously or be interrupted extracting after 24～80 hours again, at 25 ℃, and 0.08～0.1MPa dry 48 hours down;
(4) dried solids is carried out washing by soaking with deionized water, changed a deionized water every 24 hours, till the existence that detects in the deionized water after washing less than porogen, obtain the hygrometric state support;
(5) with the hygrometric state support-30～-50 ℃ of following lyophilizations, obtain chitosan-copolymer of poly lactic acid porous support.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394121A (en) * | 2013-07-31 | 2013-11-20 | 苏州纳埃净化科技有限公司 | Preparation method for porous composite support material |
| CN106924173A (en) * | 2017-03-29 | 2017-07-07 | 南宁学院 | A kind of drug loading mesoporous material and preparation method thereof |
| CN110652381A (en) * | 2019-10-24 | 2020-01-07 | 深圳兰度生物材料有限公司 | Osteochondral repair scaffold and preparation method thereof |
| CN114753022A (en) * | 2022-03-23 | 2022-07-15 | 合肥工业大学 | Self-repairing waterproof polylactic acid fiber fabric with core-shell structure |
| CN115645609A (en) * | 2021-12-30 | 2023-01-31 | 盐城工业职业技术学院 | Three-dimensional porous biodegradable polymer artificial esophagus stent and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139989A (en) * | 1996-11-13 | 1998-05-26 | Ekomatetsuku Kenkyusho:Kk | Poly(lactic acid)/polysaccharide composition |
| AU3097999A (en) * | 1998-03-18 | 1999-10-11 | University Of Pittsburgh | Chitosan-based composite materials containing glycosaminoglycan for cartilage repair |
| CN1203128C (en) * | 2001-04-26 | 2005-05-25 | 暨南大学 | Polylactic acid/chitin kind of porous support materials and its preparing process |
| CN1176141C (en) * | 2002-07-11 | 2004-11-17 | 上海交通大学 | Prepn of dissolved liquid crystal of chitosan grafted polylactic acid |
| CN1204166C (en) * | 2002-12-16 | 2005-06-01 | 天津大学 | Method for preparing chitosan-polylactic acid grafted copolymer |
| CN100431624C (en) * | 2005-12-07 | 2008-11-12 | 浙江大学 | Method for preparing injectable polyletic acid micro-carrier/chitosan hydrogel composite scaffold |
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- 2006-10-23 CN CNB2006100161899A patent/CN100431623C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394121A (en) * | 2013-07-31 | 2013-11-20 | 苏州纳埃净化科技有限公司 | Preparation method for porous composite support material |
| CN106924173A (en) * | 2017-03-29 | 2017-07-07 | 南宁学院 | A kind of drug loading mesoporous material and preparation method thereof |
| CN110652381A (en) * | 2019-10-24 | 2020-01-07 | 深圳兰度生物材料有限公司 | Osteochondral repair scaffold and preparation method thereof |
| CN115645609A (en) * | 2021-12-30 | 2023-01-31 | 盐城工业职业技术学院 | Three-dimensional porous biodegradable polymer artificial esophagus stent and preparation method thereof |
| CN114753022A (en) * | 2022-03-23 | 2022-07-15 | 合肥工业大学 | Self-repairing waterproof polylactic acid fiber fabric with core-shell structure |
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| CN100431623C (en) | 2008-11-12 |
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Assignee: Tianjin Petrochemical Engineering Design Co., Ltd. Assignor: Tianjin University Contract fulfillment period: 2009.5.20 to 2014.12.31 contract change Contract record no.: 2009120000087 Denomination of invention: Method for preparing 3D porous bracket of chitosan - copolymer of poly lactic acid Granted publication date: 20081112 License type: Exclusive license Record date: 2009.7.9 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.5.20 TO 2014.12.31; CHANGE OF CONTRACT Name of requester: TIANJIN CHENXIN LANDIFICATION ENGINEERING DESIGN C Effective date: 20090709 |
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