CN100406632C - Nanometer grade diameter biodegradable fiber non-woven fabric and preparation method - Google Patents
Nanometer grade diameter biodegradable fiber non-woven fabric and preparation method Download PDFInfo
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- CN100406632C CN100406632C CNB200610023425XA CN200610023425A CN100406632C CN 100406632 C CN100406632 C CN 100406632C CN B200610023425X A CNB200610023425X A CN B200610023425XA CN 200610023425 A CN200610023425 A CN 200610023425A CN 100406632 C CN100406632 C CN 100406632C
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- butyric ester
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Abstract
The present invention relates to nanometer fiber non-woven cloth of polyhydroxy butyrate ester biodegradable polymers and a preparing method thereof. The average diameter of nanometer fiber approximately ranges from 1 nm to 200 nm, and the diameter is distributed within a narrow range. The polyhydroxy butyrate ester superpolymers and a small quantity of additives are dissolved in organic solvents so as to prepare a transparent homogeneous solution. The solution is used for electrostatic spinning so as to obtain the polyhydroxy butyrate ester fiber non-woven cloth which can be biologically degraded and has the diameter at a nanometer level. The method used by the present invention has the advantages of simplicity, easy implementation and low equipment requirement. The products of nanometer fiber non-woven cloth of polyhydroxy butyrate ester biodegradable polymers can be extensively used in the fields of medicine, health, tissue engineering, etc.
Description
Technical field
The present invention relates to the preparation field of organic nanofibers, particularly relate to method of electrostatic spinning and prepare nanofiber and preparation method.
Background technology
The diameter of traditional general fibre material mostly is the scope of 5～50 μ m.The superfine Denier fibre diameter of up-to-date exploitation can reach 0.4～4 μ m.When diameter when micron is contracted to sub-micron or nanometer, polymer fiber is compared with corresponding fibrous material, can show several surprising characteristics.Its characteristic mainly comprises: the fento effect, electric property, and mechanical property such as very large specific area (its specific area be micrometer fibers nearly a hundred times), flexible and superpower mechanical behavior (as hardness and tensile strength), these excellent characteristics make nanofiber be suitable for many important purposes.And electrostatic spinning technique has the potentiality that can conveniently prepare nano-scale fiber just and extremely the various countries researcher pay close attention to.Spin the fibre diameter that obtains scope in tens nanometers to tens micron by static.Because the different and selected solvent of various organic matter self properties is different with additive, have only seldom a part of macromolecule can spin to fibre diameter below 100 nanometers.
Poly butyric ester (PHB) and copolymer thereof are a kind of abundant raw material, and the natural macromolecular material of excellent biological compatibility and Bioabsorbable is arranged.Preparing tissue engineering bracket as bioabsorbable material in recent years paid close attention to by people.Since the broad research of electrostatic spinning technique carry out the characteristics that can prepare nanoscale and micron-sized fiber with it.The PHB base polymer also is used to the static type of being spun into and prepares fabric nonwoven cloth.In the hope of when obtaining nanometer grade diameter, obtain better characteristic.
But at present, also the PHB base polymer is not prepared into bibliographical information (Seong OkHan, Won Keun Son, Dongwhan Cho, Polymer Degradation and Stability, 86 (2004) 257-262s of average diameter less than 200nm; Jae Shin Choi, Sung Won Lee, Lim Jeong, Su-Hyun Bae, Bum Chan Min.J
1Ho Youk, Won Ho Park, International Journal of Biological Macromolecules34 (2004) 249-256) wait PHB class Biodegradable material electrostatic spinning fiber average diameter that some documents report all more than 200nm and wider distribution.
Summary of the invention
The purpose of this invention is to provide poly butyric ester (PHB) the class Biodegradable nano level fabric nonwoven cloth of a kind of average diameter at 1-200 nanometer (nm).
Another object of the present invention provides the preparation method of a kind of average diameter at poly butyric ester (PHB) the class Biodegradable nano level fabric nonwoven cloth of 1-200 nanometer (nm).
The present invention is poly butyric ester (PHB) the class Biodegradable nano level fabric nonwoven cloth of a kind of average diameter at 1-200 nanometer (nm).Described biodegradable polyesters fiber is the copolymer of poly butyric ester or hydroxybutyric acid and other carboxylic acids.Described biodegradable polyesters fiber molecule amount is 20,000 to 1,500,000, and wherein butyric ester accounts for 40%～100% of total monomer mole in the copolymer.
The selection of solvent and additive by the static spinning stock solution, and the accurate control of spinning parameter in the electrostatic spinning process are the PHB class Biodegradable nano level fiber of 1-200 nanometer thereby obtain mean diameter.
Average diameter of the present invention comprises the steps: in the preparation method of poly butyric ester (PHB) the class Biodegradable nano level fabric nonwoven cloth of 1-200 nanometer (nm)
1. PHB base polymer and additive through purifying are dissolved in the organic solvent, obtain the organic solution of the additive of the PHB that contains 0.01%～3% weight of transparent homogeneous and 0～5% weight.Be prepared into spinning solution.
2. carry out static with prepared spinning solution and spin, spinning solution joins in the container, is fixed on the micro-injection pump, and spout connects high-voltage positive electrode, receiving device ground connection.Thereby static is spun various parameters control collection PHB class Biodegradable nano fabric nonwoven cloth
Above-mentioned organic solvent is: N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAC), alcohol, carrene, chloroform, 1, one or more mixed solvents in 2-dichloroethanes, oxolane, ether, trichloro-ethylene, cyclohexanol, methyl-sulfoxide or the trifluoroethanol all adopt the commercially available prod.
Above-mentioned additive comprises: one or more in triethanolamine, trihydroxy ethylamine oleate soap, aliphatic amine polyoxyethylene ether, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride, benzyl tributyl ammonium chloride, DDAO or the alkylolamides phosphoric acid fat.
The above-mentioned static of controlling spins parameter and comprises: voltage 5kv～20kv, spout aperture 1 μ m～2mm, solution flow rate 1 μ l/h～10ml/h, 0～100 ℃ of environment temperature; Suggestion dash receiver and spinning head spacing 2～50cm.
Above-mentioned receiving device can be difform gathering-devices such as flat board, cylinder or metal frame.
Adopt the PHB class biodegradable fiber non-woven fabric of the nanometer grade diameter that method of the present invention prepares, the average diameter of its fiber is at 1nm～200nm.
Required raw material is general chemical reagent all in the method for the present invention, and entire method is simple.Nonwoven fabric product of the present invention can be widely used in fields such as medical and health, organizational project.
Description of drawings
The stereoscan photograph of the poly butyric ester class Biodegradable fibers of Fig. 1 average diameter 146nm;
The diameter of the poly butyric ester class Biodegradable fibers of Fig. 2 average diameter 146nm distributes;
The stereoscan photograph of the poly butyric ester class Biodegradable fibers of Fig. 3 average diameter 80nm;
The diameter of the poly butyric ester class Biodegradable fibers of Fig. 4 average diameter 80nm distributes;
The stereoscan photograph of the poly butyric ester class Biodegradable fibers of Fig. 5 average diameter 190nm;
The diameter of the poly butyric ester class Biodegradable fibers of Fig. 6 average diameter 190nm distributes.
The specific embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
The solution preparation
| PHB | Chloroform/alcohol mixed solvent | Benzyltriethylammoinium chloride | |
| Quality (g) | 1 | 88/11 | 03 |
| The source | Ningbo Tianan Biological Material Co., Ltd. | Suzhou City Linkage new material Co., Ltd | Shanghai chemical reagents corporation |
Static spins parameter control
| Voltage | The spout aperture | Solution flow rate | Dash receiver and spout spacing | Environment temperature |
| 10kv | 0.4mm | 1ml/h | 15cm | 40℃ |
With weight fraction is that 1% PHB base polymer and benzyltriethylammoinium chloride through purifying are dissolved in the organic solvent, obtain transparent homogeneous, contain the organic solution of the benzyltriethylammoinium chloride of the PHB base polymer through purifying of 1% weight and 0.3% weight, be i.e. the static spinning stock solution.
Carrying out static with prepared static spinning stock solution spins.Spinning parameter is controlled at voltage 10kv, spout aperture 0.4mm, solution flow rate 1ml/h, 40 ℃ of environment temperatures, dash receiver and spout spacing 15cm.
PHB class Biodegradable fibers average diameter 146nm wherein.Fig. 1 is a stereoscan photograph, and Fig. 2 distributes for diameter.
Embodiment 2
The solution preparation
| PHBV (hydroxybutyric acid valeric acid copolyesters) | Carrene/ether | Triethanolamine | |
| Quality (g) | 0.4 | 90/10 | 0.01 |
| The source | Ningbo Tianan Biological Material Co., Ltd. | Suzhou City Linkage new material Co., Ltd | Auxiliary reagent factory, Xingtai |
Static spins parameter control
| Voltage | The spout aperture | Solution flow rate | Dash receiver and spout spacing | Environment temperature |
| 16kv | 0.05mm | 007ml/h | 8cm | 50℃ |
PHB base polymer and triethanolamine through purifying are dissolved in the organic solvent, obtain the PHB base polymer through purifying transparent homogeneous, that contain 0.4% weight and the triethanolamine organic solution of 001% weight.It is the static spinning stock solution.
With weight fraction is that the triethanolamine of 0.01wt% is dissolved in the solution.
Carrying out static with prepared static spinning stock solution spins.Spinning parameter is controlled at voltage 16kv, spout aperture 0.05mm, solution flow rate 0.07ml/h, 50 ℃ of environment temperatures, dash receiver and spout spacing 8cm.
PHB class Biodegradable fibers average diameter 80nm wherein.Fig. 3 is a stereoscan photograph, and Fig. 4 distributes for diameter.
Embodiment 3
The solution preparation
| PHBV (hydroxybutyric acid valeric acid copolyesters) | Chloroform | Alkylolamides phosphoric acid fat | |
| Quality (g) | 0.3 | 99 | 1 |
| The source | Ningbo Tianan Biological Material Co., Ltd. | Suzhou City Linkage new material Co., Ltd | Shanghai chemical reagents corporation |
Static spins parameter control
| Voltage | The spout aperture | Solution flow rate | Dash receiver and spout spacing | Environment temperature |
| 20kv | 1mm | 0.4ml/h | 12cm | 30℃ |
PHB base polymer and alkylolamides phosphoric acid fat through purifying are dissolved in the organic solvent, obtain the PHB base polymer through purifying transparent homogeneous, that contain 03% weight and the alkylolamides phosphoric acid fat organic solution of 1% weight.It is the static spinning stock solution.
Carrying out static with prepared static spinning stock solution spins.Spinning parameter is controlled at voltage 20kv, spout aperture 1mm, solution flow rate 04ml/h, 30 ℃ of environment temperatures, dash receiver and spout spacing 8cm.
PHB class Biodegradable fibers average diameter 190nm wherein.Fig. 5 is a stereoscan photograph, and Fig. 6 distributes for diameter.
Claims (6)
1. the preparation method of the biodegradable polyesters fabric nonwoven cloth of a nanometer grade diameter is characterized in that adopting following steps:
(1), will be dissolved in the electrostatic spinning liquid that makes transparent homogeneous in the organic solvent through the polymer and the additive of purification poly butyric ester or hydroxybutyric acid and other carboxylic acids; The poly butyric ester or the polymer of hydroxybutyric acid and other carboxylic acids and the additive of 0～5% weight that contain 0.01%～3% weight in the described electrostatic spinning liquid; Described additive is one or more in triethanolamine, trihydroxy ethylamine oleate soap, aliphatic amine polyoxyethylene ether, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride, benzyl tributyl ammonium chloride, DDAO or the alkylolamides phosphoric acid fat;
(2), carry out electrostatic spinning with above-mentioned electrostatic spinning liquid, extrude by micro-injection pump, spout connects high-voltage positive electrode, receiving device ground connection, and it is voltage 5kv～20kv that the static of control spins parameter, spout aperture 1 μ m～2mm, solution flow rate 1 μ l/h～10ml/h, 0～100 ℃ of environment temperature is collected nano fiber non-woven fabric;
Described biodegradable polyesters fiber is the copolymer of poly butyric ester or hydroxybutyric acid and other carboxylic acids.
2. method according to claim 1 is characterized in that described biodegradable polyesters fiber molecule amount is 20,000 to 1,500,000, and wherein butyric ester accounts for 40%～100% of total monomer mole in the copolymer.
3. method according to claim 1, the average diameter that it is characterized in that fiber in the described nonwoven fabric is 1nm～200nm.
4. method according to claim 1, it is characterized in that described organic solvent is N, dinethylformamide, N, N-dimethylacetylamide, alcohol, carrene, chloroform, 1, one or more mixed solvents in 2-dichloroethanes, oxolane, ether, trichloro-ethylene, cyclohexanol, methyl-sulfoxide or the trifluoroethanol.
5. method according to claim 1 is characterized in that described receiving device is the gathering-device of flat board, cylinder or metal frame.
6. method according to claim 1 is characterized in that described receiving device and spout spacing 2～50cm.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200610023425XA CN100406632C (en) | 2006-01-18 | 2006-01-18 | Nanometer grade diameter biodegradable fiber non-woven fabric and preparation method |
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| CNB200610023425XA CN100406632C (en) | 2006-01-18 | 2006-01-18 | Nanometer grade diameter biodegradable fiber non-woven fabric and preparation method |
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| CN1800474A CN1800474A (en) | 2006-07-12 |
| CN100406632C true CN100406632C (en) | 2008-07-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2612959A1 (en) * | 2010-08-30 | 2013-07-10 | National University Corporation Okayama University | Nanofiber exerting excellent biodegradability and biocompatibility, and method for producing said nanofiber |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327345B (en) * | 2008-07-21 | 2012-10-24 | 南开大学 | Superfine fibre porous membrane material and preparation method thereof |
| CN105214520A (en) * | 2015-10-21 | 2016-01-06 | 宁波聿丰新材料科技有限公司 | A kind of liquid medicine filtering membrane and preparation method thereof |
| CN112898550B (en) * | 2021-01-27 | 2022-10-18 | 江苏睿安应用生物技术股份有限公司 | Biodegradable polyester and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0454075A2 (en) * | 1990-04-26 | 1991-10-30 | B.A.T. Cigarettenfabriken GmbH | Process for manufacturing cigarette filters |
| DE4013293A1 (en) * | 1990-04-26 | 1991-11-07 | Bat Cigarettenfab Gmbh | Cigarette filter contg. irregularly oriented fibres - comprises spun poly:hydroxybutyric acid or copolymer of hydroxybutyric acid and poly:hydroxy:valeric acid |
| CN1493719A (en) * | 2003-07-02 | 2004-05-05 | 东华大学 | Spinning solution and its preparation and application |
| CN1715463A (en) * | 2004-06-30 | 2006-01-04 | 东华大学 | Static spinning device and its industrial use |
-
2006
- 2006-01-18 CN CNB200610023425XA patent/CN100406632C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0454075A2 (en) * | 1990-04-26 | 1991-10-30 | B.A.T. Cigarettenfabriken GmbH | Process for manufacturing cigarette filters |
| DE4013293A1 (en) * | 1990-04-26 | 1991-11-07 | Bat Cigarettenfab Gmbh | Cigarette filter contg. irregularly oriented fibres - comprises spun poly:hydroxybutyric acid or copolymer of hydroxybutyric acid and poly:hydroxy:valeric acid |
| CN1493719A (en) * | 2003-07-02 | 2004-05-05 | 东华大学 | Spinning solution and its preparation and application |
| CN1715463A (en) * | 2004-06-30 | 2006-01-04 | 东华大学 | Static spinning device and its industrial use |
Non-Patent Citations (4)
| Title |
|---|
| PHBV电纺纤维结构与形态的研究. 方壮熙，张璐，韩涛，胡平.高分子学报，第4期. 2004 |
| PHBV电纺纤维结构与形态的研究. 方壮熙，张璐，韩涛，胡平.高分子学报，第4期. 2004 * |
| 生物降解性纤维. 山中敬雄，著，刘辅庭，译.国外纺织技术，第11期. 2004 |
| 生物降解性纤维. 山中敬雄，著，刘辅庭，译.国外纺织技术，第11期. 2004 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2612959A1 (en) * | 2010-08-30 | 2013-07-10 | National University Corporation Okayama University | Nanofiber exerting excellent biodegradability and biocompatibility, and method for producing said nanofiber |
| EP2612959A4 (en) * | 2010-08-30 | 2014-01-22 | Tmt Machinery Inc | Nanofiber exerting excellent biodegradability and biocompatibility, and method for producing said nanofiber |
| US9321208B2 (en) | 2010-08-30 | 2016-04-26 | Tmt Machinery, Inc. | Nanofibers with excellent biodegradability and biocompatibility and method for producing the same |
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| CN1800474A (en) | 2006-07-12 |
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