WO2007097489A1

WO2007097489A1 - Method of manufacturing for a porous membrane and the porous membrance manufactured thereby

Info

Publication number: WO2007097489A1
Application number: PCT/KR2006/000964
Authority: WO
Inventors: Hak-Yong Kim
Original assignee: Industrial Cooperation Foundation Chonbuk National University
Priority date: 2006-02-20
Filing date: 2006-03-16
Publication date: 2007-08-30

Abstract

Disclosed are a method of manufacturing a porous membrane and a porous membrane manufactured thereby. A polymer spinning dope in a spinning dope supply container (1) is electrically spun onto a solution (B), which is contained in a collector container (6) with a high voltage applied thereto, and whose surface is disposed within a jet stream (4) of an electrospun polymer spinning dope, through spinning nozzles (2) with a high voltage applied thereto, thereby forming a porous membrane on the surface of the solution (B). The prepared porous membrane has pores having an average diameter of 0.02 to 10//m uniformly formed thereon. It is possible to prepare a porous membrane with pores of a given size uniformly formed thereon by a more simple procedure.

Description

METHOD OF MANUFACTURING FOR A POROUS MEMBRANE AND THE POROUS MEMBRANCE MANUFACTURED THEREBY

TECHNICAL FIELD The present invention relates to a method of manufacturing a

porous membrane, and a porous membrane manufactured thereby, and

more particularly, to a method of easily manufacturing a porous

membrane with pores of a given size uniformly formed thereon using an

electrospinning method.

Porous membranes are widely used as material for giving the

moisture permeability and water resistance function to leisure clothes,

shoes, etc., or as filter material.

BACKGROUND ART

As a conventional technique for preparing a porous membrane, the

U.S. Patent No. 5,910,277 proposes a process of making a porous

polytetrafluoroethylen (PTFE) membrane by mixing a fine powder of

polytetrafluoroethylene with a liquid lubricant, molding the mixture into

a sheet by an extrusion method and the like, removing the liquid

lubricant by a heating method, and stretching this sheet in the machine

direction,

Meanwhile, the U.S. Patent No. 6,017,455 discloses a process of

preparing a porous aromatic polyether ketone membrane by dissolving an aromatic polyether ketone in an approximately 88% sulfuric acid

solvent, preparing it into a film on a glass plate, coagulating the prepared

film in 73% sulfuric acid, and then removing the residual sulfuric acid

solution left on the film using water, alcohol, etc. The thus-prepared

porous aromatic polyether ketone membrane has a crystallinity of 10% or

less. The membrane surface contacted with the glass plate has open

pores having an average pore diameter of 1.2μm at an open pore ratio of

50%, while the membrane surface not contacted with the glass plate has

open pores having an average pore diameter of 1. 1 μm at an open pore

ratio of 50%.

And, the U.S. Patent No. 6,284, 138 discloses a process of

preparing a porous membrane having pores of 0.1 to 0.2/iπι by dissolving

a polymer with polyacrylsulfone (PAS) and polyethersulfone (PES) mixed

at a predetermined ratio in dimethylaceteamide (DMAc), coating this

solution at a predetermined thickness by use of a plate, coagulating it in

a coagulating solvent of dimethylaceteamide (DMAc) and water to prepare

a membrane, and then removing the residual solvent.

The aforementioned conventional techniques have problems

including the complexity of the procedures, the non-uniformity of the size and distribution density of pores formed on the prepared porous

membrane and so on because the coagulating solution has to be used or

it has to be removed after mixing organic particles or organic /inorganic

particles therein when preparing the porous membrane. It is an object of the present invention to provide a process of preparing a porous membrane with pores of a given size uniformly formed thereon using an electrospinning method by a simple procedure.

DETAILED DESCRIPTION QF THE INVENTION TECHNICAL PROBLEMS

The present invention is intended to provide a method of manufacturing a porous membrane with pores of a given size uniformly formed thereon using an electrospinning method by a simple procedure. Additionally, the present invention is intended to provide a porous membrane which is prepared using an electrospinning method, and which has pores having an average diameter of 0.02 to 10//m uniformly formed thereon.

For these purposes, the present invention provides a process of preparing a porous membrane by disposing the surface of a solution (hereinafter, referred to as a "collector solution") contained in a collector container within a jet stream region of a polymer spinning dope formed during an electrospinning process, such that the jet stream and the collector solution are contacted with each other.

TECHNICAL SOLUTIONS

The method of manufacturing a porous membrane according to the present invention is characterized in that: a polymer spinning dope in a spinning dope supply container 1 is electrically spun onto a solution (B),

which is contained in a collector container 6 with a high voltage applied

thereto, and whose surface is disposed within a jet stream 4 of an

electrospun polymer spinning dope, through spinning nozzles 2 with a

high voltage applied thereto, thereby forming a porous membrane on the

surface of the solution (B) .

Furthermore, the porous membrane prepared in the present invention has pores having an average diameter of 0.02 to 10/aiι

uniformly formed over the entire membrane.

Hereinafter, the present invention will be described in detail with

reference to the accompanying drawings.

Typically, when a polymer spinning dope is electrically spun

through nozzles 2, the electrospun polymer spinning dope forms a tailor

cone 3 as shown in FI G.2. The tailor cone is transformed into the jet

stream 4 by an electric power, and polymer chains of a given size are

separated in an incomplete region where the polymer chains and solvent contained in the jet stream are separated from each other, thereby

forming nano fibers 5. FIG.2 is a schematic perspective view showing

the step of forming nano fibers using an electrospinning method.

In the present invention, in an electrospinning process, a porous

membrane is prepared by contacting a solvent, such as water, with the jet

stream region before the formation of nano fibers. More specifically, the

present invention relates to a process of preparing a porous membrane with pores of a given size uniformly formed thereon by contacting a solvent, such as water, with the jet stream before nano fibers are formed as polymer chains and the solvent both contained in the jet stream are separate from each other, and then volatilizing the solvent from the polymer solution as the jet stream is spread on the surface of the solvent.

Hereinafter, the present invention is described in detail with reference to FIG. l.

FIG. l is a schematic view of a process of preparing a porous membrane according to the present invention. A (+) charge is applied to a polymer spinning supply container 1 through a high voltage generator (A), and a predetermined amount of a polymer spinning dope is discharged through nozzles 2 attached to the polymer spinning dope supply container 1. The spinning dope discharged through the nozzles 2 forms a tailor cone 3 at first, and then is transformed into a jet stream 4 by an electric power. The formed jet stream 4 is immersed in a solution (hereinafter, referred to as a "collector solution") contained in a collector container 6 with a high voltage applied thereto. The collector container 6 is charged to a (-) or (+) voltage from the high voltage generator (A). The immersed jet stream 4 becomes incomplete, and forms a uniform membrane on the surface of the collector solution composed of water and various kinds of solvents. Simultaneously with the formation of a membrane, the solvent is spread, and as the solvent is spread, the polymer and the solvent are separated from each other and pores are formed on the membrane, thereby preparing a porous membrane.

By immersing the jet stream region (d) in the collector solution (B) composed of water and various kinds of solvents, a porous membrane can be formed. If the jet stream region is immersed in the collector solution (B) composed of water or various kinds of solvents after it is deviated from the incomplete region after the formation of a jet stream, it forms nano fibers or is transformed into a bead shape, thereby failing to prepare a membrane. A representative example of such a phenomenon

is shown in FIG.10, which is an electron micrograph of a sample prepared by Comparative Example. This shows that if the jet stream is immersed in the collector solution (B) outside of the jet stream region (d), some part forms fibers and some part forms a film but it is difficult to prepare a uniform membrane. Hence, it is clear that the distance (hereinafter, "spinning distance") between the nozzle tip and the surface of the collector solution is very important.

Although the spinning distance cannot be measured indiscriminately because the length of the jet stream varies depending on the type of every polymer to be used, it is usually 5cm or less in most cases. Thus, in case of polymers having a large length of the jet stream, in particular, in case of polymers having a high conductivity, the length of the jet stream becomes greater in general. Therefore, it is preferred to adjust the spinning distance considering the conductivity of the polymer spinning dope used or the like. The spinning distance is 0.1 to 5.0cm, and more preferably, 0. 1 to 1.5cm.

In the present invention, a porous membrane formed on the

surface of the collector solution (B) is separated from the collector

solution (B) by a substrate 8 passing through the collector solution (B),

and thereafter squeezed, dried, and wound. The porous membrane

formed on the surface of the collector solution (B) is very thin, thus it is very difficult to wind it into a given form without using the substrate 8.

The substrate 8 is supplied from a substrate supply roller 7, and

separates the porous membrane formed on the surface of the collector

solution (B) from the collector solution (B) while sequentially passing

through feed rollers 9 and 10 put in the collector solution (B). The

substrate 8 includes a film or a mesh. The thus- separated porous

membrane is squeezed while passing through a squeezing roller 1 1 , being

placed on the substrate 8, and then dried while passing through a drier

12, and then wound on a winding machine 13.

Additionally, in the present invention, the surface height,

concentration, temperature, and pH of the collector solution (B) are kept

constant. Specifically, a given amount of the collector solution is

supplied into the collector container by a collector container supply

device 14, a collector solution of the same amount as the supplied

collector solution is discharged out of the collector container by a

collector solution discharge device 15, thereby keeping constant the

surface height of the collector solution (B). Besides, the concentration and pH of the collector solution (B) is kept constant by treating the

collector solution discharged out of the collector container by a solvent

removal device 16 in the collector solution such that the solvent in the

collector solution is removed, and the temperature of the collector

solution (B) is kept constant by a heating or the like.

Useable polymers of the present invention include (I) natural

polymers, such as cellulose, chitosan, etc., and copolymers or mixtures

thereof, (II) thermoplastic resins, such as polyester, nylon, fluoride resins,

etc., and copolymers or mixtures thereof, (III) thermosetting resins such

as melamine, epoxy, etc., and copolymers or mixtures thereof, and (IV)

sol-gel containing inorganic materials, such as aluminum, titanium, etc.

The solution (B) contained in the collector container 6 is one

selected from water and a solvent. The solvent is one selected from the

group consisting of methylene chloride, alcohol, benzene, toluene,

sulfuric acid and mixtures thereof. An organic or inorganic matter

serving as various kinds of additives may be added to the solvent, or a

surfactant may be added thereto.

The size of the pores formed on the porous membrane varies

depending on the concentration of polymers in the spinning dope or the

pH, temperature, and electrical conductivity of the collector solution (B).

Thus, the size of the pores can be adjusted by adjusting them.

The porous membrane prepared in the process according to the present invention has pores having an average diameter of 0.02 to 10/aii uniformly formed thereon.

ADVANTAGEOUS EFECTS

The present invention is able to prepare a porous membrane with

pores of a given size uniformly formed thereon by a simple procedure

using an electrospinning method.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a process of the present invention;

FIG.2 is a schematic perspective view showing the step of forming

nano fibers using an electrospinning method;

FIG.3 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 1 ;

FIG.4 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 2;

FIG.5 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 3;

FIG.6 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 4;

FIG.7 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 5;

FIG.8 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 6; FIG.9 is an electron micrograph of a porous polycaprolactone

membrane prepared by Example 7; and

FIG.10 is an electron micrograph of a porous polycaprolactone

membrane prepared by Comparative Example 1 ;

* Explanation of reference numerals for main components in the

drawings

A: high voltage generator B: solution contained in collector container

(collector solution)

1 : spinning dope supply container 2: nozzle

3: tailor cone 4: jet stream

5: nano fiber 6: collector container

7: substrate supply roller 8: substrate

9, 10: substrate feed roller 1 1 : squeezing roller

12: drier 13: winding roller

14: collector container supply device

15: collector solution discharge device

16: solvent removal device in collector solution

d: jet stream region

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is now understood more concretely by

comparison between examples of the present invention and comparative

examples. However, the present invention is not limited to such examples.

Example 1

A polymer spinning dope was prepared by dissolving a poly(ε-caprolactone) polymer (purchased from Aldrich Chemical Company) having a number average molecular weight of 80,000 in a mixed solvent of methylene chloride/ N, N'-dimethyl formamide (volume ratio: 70/30) at a concentration of 8% by weight. The polymer spinning dope had a surface tension of 31 mN/m, a solution viscosity of 200 centipoise at an ambient temperature, and an electrical conductivity of 0.021 mS/m. Then, as shown in FIG. 1, the thusly-prepared polymer spinning dope was electrically spun onto a solution (B), which is contained in a collector container 6 with a high voltage applied thereto, and whose surface is disposed within a jet stream 4 of an electrospun polymer spinning dope, through spinning nozzles 2 with a high voltage applied thereto, thereby forming a porous membrane on the surface of the solution (B) . The porous membrane was separated from the solution (B) by use of a substrate 8 passing through the solution (B), squeezed by a squeezing roller 11, dried by a drier 12, and then wound by a winding machine 13. The diameter of the nozzles used was 0.8 mm, the nozzles were arranged at 2cm intervals, and a unit block where 50 nozzles are arranged for a length of 110cm in the width direction was used. A nozzle plate consisting of 10 unit blocks was used, and the nozzles arranged on the 10 unit blocks were uniformly and diagonally arranged in the membrane traveling direction (machine direction), thereby acquiring the

uniformity of a membrane to be formed. The electrospinning distance

was 0.2 cm, and a solution having a pH of 3.0 was used as the collector

solution. In order to acquire the uniformity of the thickness of the

membrane, the membrane was prepared by reciprocating the 10 unit

blocks at lcm/min in the width direction. A predetermined amount of

the solution (B) was supplied into the collector container by a collector

solution supply device 14 so that the height of the surface of the solution

(B) in the collector container is kept constant, and simultaneously a

predetermined amount of the solution (B) is discharged from the collector

container by the collector solution discharge device 15, the temperature,

concentration, and pH in the discharged solution (B) were adjusted by a

solvent removal device 16 for the collector solution, and then the solution

(B) was re-supplied to the collector container. A polypropylene membrane having a thickness of 500μm was used as the substrate 8, and

the substrate was supplied into the collector solution at a velocity of 50

m/min through feed rollers 9 and 10. The pressure of the squeezing roller

1 1 was lkg/ cm², the drier 12 performed drying using a 35 ^°C air, and the

winding velocity was 50 cm/min. The prepared porous film had open

pores having a size of 1.98/inι at an open pore ratio of 54.4%, and an

electron micrograph thereof was as shown in FIG.3.

Example 2 A porous membrane was prepared under the same conditions as in Example 1 except that a solution having a pH of 5 was used as the solution (B) contained in the collector container 4.

The prepared porous membrane had open pores having a size of 5 2.65_//m at an open pore ratio of 60.1%, and an electron micrograph

thereof was as shown in FIG.4.

Example 3

A porous membrane was prepared under the same conditions as in K) Example 1 except that a solution having a pH of 7 was used as the solution (B) contained in the collector container 4.

The prepared porous membrane had open pores having a size of 9.78_//m at an open pore ratio of 38.6%, and an electron micrograph thereof was as shown in FIG.5. 15

Example 4

A porous membrane was prepared under the same conditions as in

Example 1 except that a solution having a pH of 9 was used as the solution (B) contained in the collector container 4.

20 The prepared porous membrane had open pores having a size of

0.39_/mi at an open pore ratio of 27.1%, and an electron micrograph

thereof was as shown in FIG.6. Example 5

A porous membrane was prepared under the same conditions as in Example 1 except that a solution having a pH of 11 was used as the solution (B) contained in the collector container 4. The prepared porous membrane had open pores having a size of

0.82/ΛΠ at an open pore ratio of 31.6%, and an electron micrograph thereof was as shown in FIG.7.

Example 6 A porous membrane was prepared under the same conditions as in

Example 1 except that the concentration of polymer in the polymer spinning dope was changed to 9% by weight.

The prepared porous membrane had open pores having a size of 1.99/zm at an open pore ratio of 70.2%, and an electron micrograph thereof was as shown in FIG.8.

Example 7

A porous membrane was prepared under the same conditions as in Example 1 except that the concentration of polymer in the polymer spinning dope was changed to 10% by weight.

The prepared porous membrane had open pores having a size of 3.23_/zm at an open pore ratio of 17.5%, and an electron micrograph thereof was as shown in FIG.9. Comparative Example 1

The polymer spinning dope of Example 1 was electrically spun onto a solution (B), which is contained in a collector container 6 with a high voltage applied thereto, and whose surface is disposed within a jet stream

4 of an electrospun polymer spinning dope, through spinning nozzles 2 with a high voltage applied thereto, thereby forming a porous membrane.

The electrospinning distance (S) was 2cm, and a solution having a PH of

3.0 was used as the collector solution. In this case, the collector solution is disposed outside of the jet stream region, and the electrospun polymer spinning dope is contacted with the collector solution after the formation of nano fibers, which makes it difficult to form a porous membrane. An electron micrograph of the prepared porous membrane was as shown in FIG.10.

INDUSTRIAL APPLICABILITY

The porous membrane of the present invention is used as material for giving the moisture permeability and water resistance function to leisure clothes, shoes, etc., or as filter material.

Claims

WHAT IS CLAIMED IS:

1. A method of manufacturing a porous membrane, characterized in that: a polymer spinning dope in a spinning dope supply container 1 is electrically spun onto a solution (B), which is contained in a collector container 6 with a high voltage applied thereto, and whose surface is disposed within a jet stream 4 of an electrospun polymer spinning dope, through spinning nozzles 2 with a high voltage applied thereto, thereby forming a porous membrane on the surface of the solution (B) .

2. The method of claim 1, wherein the solution (B) contained in the collector container 6 is one selected from water and a solvent.

3. The method of claim 2, wherein the solvent is one selected from the group consisting of methylene chloride, alcohol, benzene, toluene, sulfuric acid and mixtures thereof.

4. The method of claim 1, wherein the size of pores are controlled by adjusting at least one of the polymer concentration in the spinning dope and the temperature, pH, and electrical conductivity of the solution (B) contained in the collector container 6.

5. The method of claim 1, wherein the distance (spinning distance) between the lower end of the nozzles 2 and the surface of the solution (B) contained in the collector container 6 is 0.1 to 5.0cm.

6. The method of claim 5, wherein the distance (spinning distance) between the lower end of the nozzles 2 and the surface of the solution (B) contained in the collector container 6 is 0.1 to 1.5cm.

7. The method of claim 1, wherein the porous membrane formed on the surface of the solution (B) contained in the collector container 6 is separated from the solution (B) by a substrate 8 passing through the solution (B), and then squeezed, dried, and wound.

8. The method of claim 7, wherein the substrate 8 is a film or mesh.

9. The method of claim 1 , wherein a predetermined amount of the solution (B) is supplied into the collector container so that the height of the surface of the solution (B) in the collector container is kept constant, and simultaneously a predetermined amount of the solution (B) is discharged from the collector container, the temperature, concentration, and pH in the discharged solution (B) are adjusted, and then the solution (B) is re-supplied to the collector container.

10. A porous membrane which is manufacturede in the process of claim 1, and has pores having an average diameter of 0.02 to lO/zni

uniformly formed thereon.