WO2006006746A1 - Particules polymeres et procede de fabrication - Google Patents

Particules polymeres et procede de fabrication Download PDF

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Publication number
WO2006006746A1
WO2006006746A1 PCT/KR2004/001697 KR2004001697W WO2006006746A1 WO 2006006746 A1 WO2006006746 A1 WO 2006006746A1 KR 2004001697 W KR2004001697 W KR 2004001697W WO 2006006746 A1 WO2006006746 A1 WO 2006006746A1
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WO
WIPO (PCT)
Prior art keywords
fluid
spinning
collector
polymer particles
polymer
Prior art date
Application number
PCT/KR2004/001697
Other languages
English (en)
Inventor
Hak-Yong Kim
Jong-Cheol Park
Original Assignee
Hak-Yong Kim
Jong-Cheol Park
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hak-Yong Kim, Jong-Cheol Park filed Critical Hak-Yong Kim
Priority to PCT/KR2004/001697 priority Critical patent/WO2006006746A1/fr
Publication of WO2006006746A1 publication Critical patent/WO2006006746A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1629—Organic macromolecular compounds
    • A61K9/1641—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poloxamers
    • A61K9/1647—Polyesters, e.g. poly(lactide-co-glycolide)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1682—Processes
    • A61K9/1694—Processes resulting in granules or microspheres of the matrix type containing more than 5% of excipient

Definitions

  • the present invention relates to polymer particles and a method for manufacturing the same. More particularly, the present invention relates to a method for manufacturing polymer particles using electric spinning and polymer particles manufactured by the same.
  • polymer particles are made of a polymer and include polymer particles without hollows or fine holes formed thereon, polymer particles with hollows formed thereon, polymer particles with a plurality of fine holes formed thereon, and polymer particles with both of hollows and a plurality of fine holes formed thereon.
  • Polymer particles are utilized as various industrial materials, such as filters, gene carriers, drug carriers, catalysts, reinforcing materials of composites, additives of cosmetics and the like.
  • No. 5,945,126 discloses a method in which a dispersion phase is prepared by dissolving a poly ⁇ L-lactide-co-glycolide) (PLGA) copolymer in methylene chloride and dissolving leuprolide acetate as an agent in methanol and mixing them, a continuous phase is prepared by dissolving polyvinyl alcohol) in distilled water and then the continuous phase and the dispersion phase are mixed to manufacture spherical particles.
  • PLGA poly ⁇ L-lactide-co-glycolide
  • U.S. Patent No. 6,048,551 discloses a method in which spheres are formed via a water-oil-emulsion method by dissolving poly(L-lactide-co-glycolide) in methylene chloride and placing a gene transfer vector therein, namely, an adenovirus, then the gene transfer vector is encapsulated using a solution comprising water as a solvent, such as polyvinyl alcohol, and then spheres including the gene transfer vector are prepared by removing the polyvinyl alcohol by isopropyl alcohol and drying.
  • a method for manufacturing spherical particles by an emulsion method has been generally employed as a conventional method for manufacturing polymer particles.
  • FIG. 1 is a schematic view of a process for manufacturing polymer particles by a horizontal electric spinning method according to the present invention
  • FIG. 2 is a schematic view of a process for manufacturing polymer particles by a downward electric spinning method according to the present invention
  • FIG. 3 is a schematic view of a process for manufacturing polymer particles by an upward electric spinning method according to the present invention.
  • overflow solution recovery tank 6 nozzle (spinneret)
  • 10a fluid-supply nozzle tube for horizontal electric spinning
  • 10b fluid-supply nozzle tube for upward electric spinning
  • the present invention provides a method in which polymer particles can be made by a process which is simpler than emulsion methods, namely, by an electric spinning method through which mass production is possible.
  • Polymer particles are very useful in various fields including filters, clothing, genes, chemical carriers, cosmetics, dyes, catalysts, etc. because they have a large surface area for filtering.
  • An object of the present invention is to manufacture polymer particles in large quantity by a simple process and utilizing simplistic facilities. (TECHNICAL SOLUTION)
  • polymer particles are prepared by electrically spinning a polymer spinning solution in a spinning solution main tank 1 on a fluid existing on the surface of a conductor collector 11 with a high voltage applied thereto via nozzles 6 with a high voltage applied thereto, and then separating and drying the prepared polymer particles.
  • the electric spinning method employed in the present invention may be a downward electric spinning method, as shown in FIG. 2, in which nozzles 6 are located on an upper part of a conductor collector 11, may be an upward electric spinning method, as shown in FIG. 3, in which nozzles 6 are located at a lower part of a conductor collector 11 , or may be a horizontal electric spinning method, as shown in FIG. 1, in which nozzles 6 and a conductor collector 11 are horizontal or are maintained at an angle close to horizontal.
  • FIG. 1 is a schematic view of a process for manufacturing polymer particles via a horizontal electric spinning method according to the present invention.
  • FIG. 2 is a schematic view of a process for manufacturing polymer particles by a downward electric spinning method according to the present invention.
  • FIG. 3 is a schematic view of a process for manufacturing polymer particles by an upward electric spinning method according to the present invention. Among these, the horizontal electric spinning method of FIG. 1 will be described concretely.
  • a solution for electric spinning is supplied through a spinning solution main tank 1 and maintained at a constant level in a subsidiary tank 3, and the electric spinning solution is supplied to a nozzle block 4 through a spinning solution dropper 2 for preventing solution flow.
  • Solution overflowing the nozzle block 4 is recovered to the main tank 1 through an overflow solution recovery tank 5 and is subsequently reused.
  • a fluid in a fluid tank 8 is supplied to a
  • the spinning solution supplied to the nozzle block 4 is electrically spun through the nozzle 6 on the fluid flowing on the surface of the conductor collector 11 with a high voltage
  • a filter a centrifugal separator, a dehydrator or the like is used.
  • a solution for electric spinning is supplied through a spinning solution main tank 1 and maintained at a constant level in a subsidiary tank 3, and the electric spinning solution is supplied to a nozzle block 4 through a spinning solution dropper 2 for preventing solution flow.
  • Solution overflowing the nozzle block 4 is recovered to the main tank 1 through an overflow solution recovery tank 5 and is subsequently reused.
  • a fluid in a fluid tank 8 is supplied to a focusing device 13 through a fluid-supply quantitative pump 9 so that a conductor collector 11 may be submerged in the fluid, thus trapping the fluid on the conductor collector.
  • the spinning solution supplied to the nozzle block 4 is electrically spun through the nozzle 6 on the surface of the fluid spaced a constant distance from the conductor collector 11 with a high voltage applied thereto, thereby forming polymer particles 7.
  • the distance between the fluid surface and the top surface of the conductor collector 11 is 0.01 to 200mm, in view of production efficiency.
  • the fluid and polymer particles focused onto the focusing device 13 are separated to collect only pure polymer particles.
  • a filter, a centrifugal separator, a dehydrator or the like is used.
  • a solution for electric spinning is supplied through a spinning solution main tank 1 and maintained at a constant level in a subsidiary tank 3, and the electric spinning solution is supplied to a nozzle block 4 through a spinning solution dropper 2 for preventing solution flow.
  • Solution overflowing the nozzle block 4 is recovered to the main tank 1 through an overflow solution recovery tank 5 and is subsequently reused.
  • a film 15 is continuously supplied to the surface of a conductor collector 11 by a film supply roller 14a, a fluid in a fluid tank 8 is supplied to a fluid supply nozzle 10b through a fluid-supply quantitative pump 9, and thereafter a proper amount of the fluid is applied to the film by spraying or the like.
  • the supply of the fluid is controlled so that the fluid applied to the film may be adhered
  • the spinning solution supplied to the nozzle block 4 is electrically spun through the nozzle 6 on the surface of the fluid applied to the film passing over the conductor collector 11 with a high voltage applied thereto, thereby forming polymer particles 7.
  • the polymer particles 7 formed on the film 15 are separated and recovered to a focusing device 13 via a recovery knife 16, and then the film 15 is wound around a film take-up roller 14b.
  • the fluid and polymer particles focused onto the focusing device 13 are separated to collect only pure polymer particles.
  • a filter, a centrifugal separator, a dehydrator or the like is used.
  • the fluid is present on the surface of the conductor collector 11 , with the fluid being applied to the film passing over the conductor collector 11.
  • pores and/ or hollows can be formed on the polymer particles more efficiently.
  • pores and hollows can be formed more efficiently on the formed polymer particles.
  • the fluid water, an organic solvent, a surfactant and a polymer solution containing a polymer are used.
  • Suitable organic solvents include methanol, ethanol, propanols, toluene, methylene chloride, benzene or acetic acid.
  • Suitable surfactants include cationic surfactants, anionic surfactants, zwitterionic surfactants and non-ionic surfactant.
  • Such a surfactant can be variously selected and used according to the charge distribution of the polymer.
  • polymer particles to be prepared are ketonic acids, which are cationic polymers
  • polymer particles having pores and/ or hollows can be prepared more efficiently.
  • nano-fibers can be manufactured simply by controlling the concentration of a polymer solution, and filaments or the like can be easily manufactured simply by a focusing device, for example, by using an air focusing device or removing the nano-fibers from the fluid surface and passing them through a focusing roller.
  • thermoplastic resin a natural polymer, a copolymer thereof, a mixture thereof, or a sol-gel containing a metal composition may be used.
  • the polymer spinning solution of the present invention may include polyester resins, nylon resins, polysulfone resins, polylactic acids, ketonic acids, collagen, cellulose, fibrinogen, copolymera thereof, a mixture thereof or a sol-gel containing a metal composition.
  • polymer particles composed of a mixture of two or more polymer compositions can be manufactured more easily.
  • polymer particles composed of a mixture of two or more polymer compositions can be manufactured by electrically spinning polymer spinning solutions of two or more kinds on the same fluid through respective nozzles in different nozzle blocks via two ore more nozzle blocks, or electrically spinning polymer particles composed of a mixture of two or more polymer compositions on the same fluid through respective nozzles arranged in the same nozzle block by using one nozzle block, in which nozzles for spinning polymer spinning solutions of two or more different polymers are combined therein.
  • porous or hollow polymer particles as a fluid enters into the polymer particles during the process in which polymer particles electrically spun on the fluid present on the conductor collector 11 are coagulated and the fluid escapes during the coagulation and drying process, pores and/ or hollows are formed on the polymer particles. Especially, when a flowing fluid is heated, such a phenomenon can be controlled more freely.
  • polymer particles optionally having hollows and/ or pores can be manufactured using a simple process and simple facilities.
  • Polymer particles made in the present invention are useful as materials for various fields including various industrial filters, drug carriers, gene carriers, various composition filling materials, secondary cell electrode materials, carriers for hydrogen storage, catalysts, cosmetic additives and the like.
  • a polymer solution was prepared by dissolving 2% by weight of nylon 66 manufactured by BASF having a relative viscosity of 2.7 in formic acid.
  • the prepared spinning solution had a viscosity of 45 centipoises (cPs), which was measured using a rheometer DV-III (Brookfield Co., USA), and an electric conductivity of 0.286 mS/m, which was measured using a conductivity meter CM-40G (TOA electronics Co., Japan).
  • Electric spinning was performed by a horizontal electric spinning method as shown in FIG. 1 using such a solution (spinning solution).
  • the polymer solution (spinning solution) was supplied to a main tank 1 , the supplied solution (spinning solution) passed through a spinning solution dropper (continuous flow prevention device) 2 so as to prevent a continuous flow of the polymer solution, a subsidiary tank 3 for preventing excessive flow of a spinning solution was installed on a spinning plate nozzle block 4 so as to control supply of the spinning solution using an atmospheric pressure, and a level around nozzles arranged for maintaining a smooth spinning efficiency was maintained at a predetermined position.
  • the nozzles 6 was spun at 30 kV, supplied by a high voltage generator 12, to the surface of the collector 11.
  • the distance between the nozzles and the collector where water flows was 12cm.
  • particles 7 of nylon 66 were prepared on the water surface due to such high voltage, and these particles 7 were dropped along with naturally flowing water, water and the particles were focused on a focusing device 13, collected by a filter, and dried, thereby obtaining particles.
  • the average size of the spherical particles of nylon 66 thus
  • Embodiment 2 A polymer solution (spinning solution) having a concentration of 1% by weight was prepared by dissolving poly (L-lactide) (PLLA) manufactured by Boerhringer Ingelheim having a molecular weight of 650,000 in methylene chloride.
  • the prepared spinning solution had a viscosity of 20 centipoises (cPs), which was measured using a rheometer DV-III (Brookfield Co., USA), and an electric conductivity of 0.01 mS/m, which was measured by a conductivity meter CM-40G (TOA electronics Co., Japan). Electric spinning was performed by a downward electric spinning method as shown in FIG. 2 using such a solution (spinning solution).
  • the polymer solution (spinning solution) was supplied to a main tank 1 , the supplied solution (spinning solution) was passed through a spinning solution dropper (continuous flow prevention device) 2 so as to prevent a continuous flow of the polymer solution, a subsidiary tank 3 for controlling a flow of an excessive spinning solution due to a rapid supply was installed on a spinning plate nozzle block 4 so as to control the supply of the spinning solution using an atmospheric pressure, and a level around nozzles arranged for maintaining a smooth spinning efficiency was maintained at a predetermined position. An overflow generated from the nozzle block to control the predetermined position of the solution naturally flowed down the nozzle block. The recovered solution was recovered to the spinning solution main tank 1 through the solution recovery tank 5 and was reused.
  • a spinning solution dropper continuous flow prevention device
  • the solution (spinning solution) discharged through the nozzles 6 was spun at 30 kV, supplied from a high voltage generator 12, to the surface of the collector 11.
  • the distance between the nozzles and the collector where water flows was 15cm.
  • a predetermined amount of water was supplied to the surface of the collector through a fluid-supply quantitative pump 9 from a separate water tank 8, and electric spinning was performed on the surface.
  • the collector was installed at a distance of 5cm from the water surface.
  • particles 7 of poly(L-lactide) (PLLA) were prepared on the water surface by a high voltage, and these particles 7 fell into the water.
  • the fallen particles were removed from the water, collected by a filter and dried, thus obtaining particles of poly (L-lactide) (PLLA).
  • the average diameter of the obtained poly(L-lactide) particles was 31 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

Les particules polymères classiques utilisées dans divers matériaux industriels tels que filtres, vecteurs de gènes, véhicules pour médicaments, catalyseurs, matériaux de renfort ou additifs pour produits cosmétiques présentent une aire spécifique réduite, nécessitent l'emploi de processus et d'installations de fabrication complexes et se prêtent mal à une production de masse. Avec la présente invention, les particules polymères peuvent être produites à grande échelle au moyen de processus et d'installations simples par électrofilature d'une solution polymère filable dans un réservoir principal contenant une solution filable (1) sur un fluide présent à la surface d'un collecteur conducteur (11), avec application d'une haute tension à des filières, puis séparation et séchage des particules polymères ainsi formées.
PCT/KR2004/001697 2004-07-09 2004-07-09 Particules polymeres et procede de fabrication WO2006006746A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2004/001697 WO2006006746A1 (fr) 2004-07-09 2004-07-09 Particules polymeres et procede de fabrication

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2004/001697 WO2006006746A1 (fr) 2004-07-09 2004-07-09 Particules polymeres et procede de fabrication

Publications (1)

Publication Number Publication Date
WO2006006746A1 true WO2006006746A1 (fr) 2006-01-19

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Application Number Title Priority Date Filing Date
PCT/KR2004/001697 WO2006006746A1 (fr) 2004-07-09 2004-07-09 Particules polymeres et procede de fabrication

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5695905A (en) * 1979-11-27 1981-08-03 Kanegafuchi Chem Ind Co Ltd Preparation of coagulated latex
US5945126A (en) * 1997-02-13 1999-08-31 Oakwood Laboratories L.L.C. Continuous microsphere process
US6048551A (en) * 1997-03-27 2000-04-11 Hilfinger; John M. Microsphere encapsulation of gene transfer vectors
KR20020082212A (ko) * 2000-01-28 2002-10-30 스미스클라인 비참 코포레이션 전기방사 약제학적 조성물
KR20030048765A (ko) * 2001-12-13 2003-06-25 주식회사 라이지오케미칼코리아 극세 무기섬유 및 그의 제조방법
JP2004002410A (ja) * 2002-05-07 2004-01-08 Xerox Corp ポリマー微小球の生成法
KR20040108525A (ko) * 2003-06-17 2004-12-24 (주)삼신크리에이션 전기화학소자용 복합막, 그 제조방법 및 이를 구비한전기화학소자

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5695905A (en) * 1979-11-27 1981-08-03 Kanegafuchi Chem Ind Co Ltd Preparation of coagulated latex
US5945126A (en) * 1997-02-13 1999-08-31 Oakwood Laboratories L.L.C. Continuous microsphere process
US6048551A (en) * 1997-03-27 2000-04-11 Hilfinger; John M. Microsphere encapsulation of gene transfer vectors
KR20020082212A (ko) * 2000-01-28 2002-10-30 스미스클라인 비참 코포레이션 전기방사 약제학적 조성물
KR20030048765A (ko) * 2001-12-13 2003-06-25 주식회사 라이지오케미칼코리아 극세 무기섬유 및 그의 제조방법
JP2004002410A (ja) * 2002-05-07 2004-01-08 Xerox Corp ポリマー微小球の生成法
KR20040108525A (ko) * 2003-06-17 2004-12-24 (주)삼신크리에이션 전기화학소자용 복합막, 그 제조방법 및 이를 구비한전기화학소자

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