KR101142001B1

KR101142001B1 - Method to control morphology of polymer structure using organic salts

Info

Publication number: KR101142001B1
Application number: KR1020100018821A
Authority: KR
Inventors: 김해원; 신원상
Original assignee: 단국대학교 산학협력단
Priority date: 2010-03-03
Filing date: 2010-03-03
Publication date: 2012-05-17
Also published as: KR20110099850A

Abstract

The present invention relates to a method for producing a polymer structure, and more particularly, by selecting an organic salt having a polymer and a counter anion as appropriate, to prepare a three-dimensional porous structure as well as a particulate structure, morphology such as pores, patterns, particle diameter It is possible to control, the polymer structure thus prepared is applicable to the field of cell carriers, support for bone tissue engineering, drug carriers and the like.

Description

METHODO TO CONTROL MORPHOLOGY OF POLYMER STRUCTURE USING ORGANIC SALTS}

The present invention relates to a method for controlling the morphology of a polymer structure by controlling the types of polymers and organic salts to prepare polymer structures of various types of particulates and pores, and to control morphologies such as pores, patterns, and particle diameters.

Modern medicine is spurring the development of cells or artificial organs, not just drug treatment. Since the cells themselves do not guarantee stability as a therapeutic agent, a support that can support and grow cells and stabilize them in allografts is used for cell regeneration and growth.

The research on these scaffolds has given birth to a new field of tissue engineering. Tissue engineering involves attaching cells isolated and cultured from a patient's tissue to a structure (scaffold) made of a biodegradable polymer material, or transplanting them for a period of time to create new biological tissue or regenerating tissue, and further restoring organs. It is a discipline that makes possible. Currently, artificial skin, cartilage, and bone are commercially available using tissue engineering, and long-term regeneration technologies such as bladder, myocardium, liver, and nerves are being actively researched.

Cell culture constructs used in the field of tissue engineering must be made to make the cells feel more like a living environment, so the culture of three-dimensional structures may be more important than the two-dimensional structures. Accordingly, various three-dimensional structures have been manufactured, and not only the structural aspects but also the material researches are in progress.

The three-dimensional structure has been studied in various fields such as tissue engineering as well as materials such as membranes and gas reservoirs, drug delivery, and various electronic materials.

As a method for producing a three-dimensional structure, a method of mainly adding a metal salt, freeze drying, phase separation due to a change in concentration, and polymerization is used. However, these methods have a problem in that the three-dimensional dispersion of the patterns is uneven, not only the lack of interconnections (channels) of the patterns, but also the difficulty in controlling the shape and size of the patterns.

Accordingly, the present inventors have made studies to prepare a polymer structure using organic salts, not metal salts, and to control the morphology of the finally obtained polymer structure by appropriately controlling the properties of the organic salt and the polymer used.

Organic salts are organic salts with physical properties that exist in the liquid state in a certain temperature range of -100 ~ 300 ℃ even though they are composed of ions such as cations and anions. In general, when a cation and an anion are combined, they exist in a solid state by a very strong attraction force, but in some organic salts (ie ionic liquids), they exist in a liquid phase at a specific temperature depending on the selection of a specific cation and anion. do.

Since the organic salt is composed of ions, the ionic conductivity is high and thermal and electrochemical stability is excellent. In addition, since it does not contain a molecular solvent, it is nonvolatile and has a very high flame retardancy. Therefore, it is in the spotlight as a material that can replace the lithium secondary battery electrolyte which has been exploding in recent years, and a lot of research is underway.

Yeon et al. Are ionic based on N- (2-hydroxyethyl) -N-methyl morpholinium tetrafluoroborate and N- (2-hydroxyethyl) -N-methyl morpholinium hexafluorophosphate. A poly (vinylidene fluoride) -hexafluoropropylene-ionic liquid gel was prepared using a liquid, and the morphology thereof was observed after film production using the liquid, showing a two-dimensional structure [Yeon, S.- h .; Kim, K.-s .; Choi, S.-j .; Cha, J.-H .; Lee, H. J. Phys. Chem. B 2005, 109, 17928. In this document, for the final synthesis of conductive polymer gels, the ionic liquid used is also limited to two, and is not related to the morphology control technique proposed in the present invention.

Korean Patent Registration No. 10-0792619 suggests that it is possible to prepare mesoporous alumina having various shapes and crystal structures by controlling the conditions of humidification while preparing a method for preparing the ionic liquid / aluminum hydroxide composite and mesoporous alumina. have. However, mesoporous alumina produced in the patent is used as a material for use in the electrolyte of the fuel cell.

Republic of Korea Patent Registration No. 10-0844016 relates to a manufacturing method for uniformly improving the size and shape of the pores formed during the manufacture of the porous scaffold using the freeze-drying method, more specifically dry to the existing freeze-drying method The present invention relates to a method for producing a porous polymer scaffold that can be applied to a three-dimensional cell culture support, a tissue engineering support, a wound coating agent, or the like, by adding ice to a slush form.

Korea Patent Registration No. 10-0792619 Korea Patent Registration 10-0844016

Yeon, S.-h .; Kim, K.-s .; Choi, S.-j .; Cha, J.-H .; Lee, H. J. Phys. Chem. B 2005, 109, 17928

Accordingly, an object of the present invention is to provide a method of manufacturing a morphology of a polymer structure capable of manufacturing not only particulate structures but also three-dimensional porous structures and controlling morphologies such as pores, patterns, and particle diameters thereof.

In order to achieve the above object,

Selecting an organic salt having a polymer and a lower degree of hydrophilicity;

Dissolving the polymer and the organic salt in an organic solvent;

Removing the organic solvent in the obtained solution to prepare a composite gel consisting of a polymer-organic salt;

Removing organic salts in the composite gel; And

It provides a method for producing a particulate polymer structure comprising the step of drying.

In addition,

Selecting an organic salt having a polymer and a higher degree of hydrophilicity;

Dissolving the polymer and the organic salt in an organic solvent;

Removing organic salts in the composite gel; And

It provides a method for producing a porous polymer structure comprising the step of drying.

The polymer structure according to the present invention is selected in consideration of the hydrophilicity (or hydrophobicity) of organic salts, particularly counter anions of organic salts, with respect to the polymer, and channels are formed therein as well as particulate structures made of microspheres or microblocks. Various polymer structures such as three-dimensional porous structures having a structure are possible. In addition, morphologies such as pores, patterns, and particle diameters of the finally obtained polymer structure can be controlled.

Such a method is relatively simple and not only easy to industrialize, but also has an advantage in that the recovery of the organic salt used in the manufacturing process is simple and reuse thereof.

The polymer structure thus prepared is applicable to the fields of tissue engineering, ie, cell carriers capable of supporting and delivering cells, support for bone tissue engineering, as well as drug carriers, gas reservoirs, gas filters, and catalyst carriers for chemical reactions. It is possible.

1 is a flowchart showing the preparation of a polymer structure according to the type of counter anion of an organic salt.
Figure 2 is a schematic diagram showing the shape of the polymer structure according to the type of counter anion of the organic salt.
3 is a SEM image of the polymer structure prepared in Experimental Example 1, showing a change in shape according to the type of counter anion.
4 is PLDLA alone FT-IR spectrum.
5 is an FT-IR spectrum of the PLDLA-SbF ₆ particulate polymer structure prepared in Experimental Example 1. FIG.
6 is PLDLA-PF ₆ prepared in Experimental Example 1 FT-IR spectrum of the particulate polymer structure.
7 is an FT-IR spectrum of the PLDLA-NTf ₂ particulate polymer structure prepared in Experimental Example 1. FIG.
8 is an FT-IR spectrum of the PLDLA-OTf porous polymer structure prepared in Experimental Example 1. FIG.
9 is an FT-IR spectrum of the PLDLA-BF ₄ porous polymer structure prepared in Experimental Example 1. FIG.
10 is an FT-IR spectrum of the PLDLA-Cl ₄ porous polymer structure prepared in Experimental Example 1. FIG.
11 is a thermal analysis (TGA) graph of the polymer structure prepared in Experimental Example 1, wherein (a) is PLDLA alone, (b) PLDLA-SbF ₆ structure and (c) PLDLA-NTf ₂ structure.
12 is a thermal analysis (TGA) graph of the porous polymer structure prepared in Experimental Example 1, (a) PLDLA-OTf, (b) PLDLA-BF ₄ , and (c) PLDLA-Cl structure.

The polymer structure according to the present invention may have various forms such as a three-dimensional porous structure such as a channel formed therein or a honeycomb structure as well as a particulate structure such as a microsphere or a microblock.

The preparation of such a polymer structure is possible by appropriately selecting a combination of a counter anion of a polymer and an organic salt.

a) selecting an organic salt in consideration of the polymer and its degree of hydrophilicity;

b) dissolving the polymer and organic salt in an organic solvent;

c) removing the organic solvent in the obtained solution to prepare a composite gel consisting of a polymer-organic salt;

d) removing organic salts in the composite gel; And

e) through a drying step.

Each step will be described in more detail below.

First, in step a), a polymer and an organic salt are selected.

Polymers can be applied to tissue regeneration materials, drug carriers, metal and inorganic complexes, conductive material complexes such as carbon nanotubes, gas storage and separators, filtration membranes, and catalyst support for chemical reactions. It does not specifically limit in this invention.

The polymer may be a synthetic polymer, and both thermosetting resins and thermoplastic resins may be used. Typically, polycarbonate, polyalkylene terephthalate, aromatic polyamide, polyamide, polystyrene, polyphenylene sulfide, polysulfone, polyetherimide, polyetheretherkitone, polyarylate, polymethylmethylacrylate, polyvinyl Alcohol, polypropylene, polyethylene, polyacrylonitrile butadiene styrene copolymer, polytetramethylene oxide-1,4-butanediol copolymer, fluororesin, polyvinyl chloride, polyacrylonitrile, polynorbornene, epoxy resin, Or phenol resins, without limitation.

For example, a polyester-based polymer having biodegradation properties may be used when used in the field of tissue regeneration, and polylactide (PLA), poly (D, L) lactide (PDLLA), and polyglycol are known as preferred. Lead (PGA), poly β-hydroxy butyric acid, polycaprolactone, polyorthoester, polylactide-co-glycolide (PLGA), polyethylene glycol (PEG), polylactide coglycolide (poly (lactide- co-glycolides (PLGA), polyvalerolactone, polyhydroxy butyrate, polyhydroxy valerate, and poly (lactide-co-caprolactone), and combinations thereof.

The organic salt ([X] ⁺ [Y] ^- ) according to the invention is an ionic salt consisting of a cation ([X] ⁺ ) and a counter anion ([Y] ^- ). The organic salt is removed through a subsequent process after mixing with the polymer, wherein the counter anion ([Y] ⁻ ) of the organic salt is involved in the morphology of the polymer structure, that is, the shape and size of the polymer structure.

Organic salts vary greatly in hydrophilicity and hydrophobicity according to the type of counter anion ([Y] ^- ), and polymer structures in various forms of granular or porous form due to differences in hydrophilicity (as opposed to hydrophobicity) with the polymer used. It is because it can manufacture.

Specifically, when the counter anion ([Y] ^- ) has a hydrophobic tendency and the organic salt has a low hydrophilicity (hydrophobicity) as compared to the polymer, the hydrophobicity causes uneven phase separation between the organic salt and the polymer during evaporation of the organic solvent. Relative and relatively hydrophilic polymer can be spherical to finally obtain a particulate polymer structure. In contrast, when the counter anion ([Y] ^- ) has a hydrophilic tendency and the organic salt has a higher hydrophilicity (hydrophilicity) than the polymer, the organic salt becomes spherical during phase separation due to evaporation of the organic solvent and subsequent removal process is performed. Through the porous polymer structure with pores formed inside and outside can be obtained.

Figure 2 is a schematic diagram showing the shape of the polymer structure according to the type of counter anion of the organic salt. At this time, an imidazolium salt having various counter anions ([Y] ⁻ ) was used as the organic salt.

The counter anion ([Y] ⁻ ) shown in FIG. 2 is represented by SbF ₆ <PF ₆ <NTf ₂ <OTf The hydrophilicity tends to increase in order of <BF ₄ <Cl.

Therefore, if the counter anion ([Y] ^- ) of an organic salt is SbF ₆ , PF ₆ , or NTf _2, it tends to be hydrophobic and forms a non-uniform mixture with water, minimizing its surface area when the phase is separated from the polymer PLA due to organic solvent removal. After spheroidizing in the direction, and the organic salt surrounding the polymer particles is completely removed, a particulate polymer structure of microspheres (or microblocks) is formed. The particle size of the particulated structure varies depending on the type of counter anion, that is, the degree of hydrophobicity (or hydrophilicity), and has a diameter of several μm to several hundred μm, preferably 10 to 50 μm. The larger is, the smaller the particle size tends to be.

On the other hand, OTf, BF ₄ , or Cl increases the hydrophilic tendency, and the phase of the organic salt in the phase separation of the polymer PL with A due to the removal of the organic solvent is mostly present outside the polymer phase and relatively hydrophobic droplet in the polymer. Form. After the organic salt is completely removed, a porous polymer structure having various pore forms is formed. At this time, the size of the pore depends on the degree of hydrophilization of the organic salt, the diameter is 1 ~ 100㎛ size. In this case, the larger the hydrophilicity of the organic salt, the larger the particle size.

The counter anion ([Y] ⁻ ) can control the morphology of the polymer structure depending on how hydrophilic (or hydrophobic) the polymer is used in combination with the hydrophilicity (or hydrophobicity).

The counter anion ([Y] ⁻ ) usable in the present invention is not particularly limited and includes all chemically possible anions.

Representatively, for example, polymers comprising an anion composed of a single element, an anion compound containing at least one anionic element of Group 13-17 elements, an oxo anion, an anion derived from an organic acid, an anion derived from an amino acid or an anion Including but not limited to compounds.

Specifically, the anion consists of a single element is _{^{N 3 -, Br -, Cl}} -, F - , and I ^- anion of a compound selected one kind available, and from the group consisting of the fullerene _{^{anion, CHB 11 H 12 -, HS}} -, ^{OCN -, SCN -, CN -} , PF 6 -, NTf 2 -, OTf - and BF ₄ ^- anion compound containing anionic one kind of element (at least one of the 13 to 17 group elements) selected from the group consisting of the possible, oxo anion is _{^{_{^{CO 3 2-, HCO 3 -,}}}} OH -, NO 3 -, NO 2 -, PO 4 3-, HPO 4 2-, H 2 PO 4 -, SO 4 2- and HSO ₄ ^- and one member can be selected from the group consisting of, specific examples of an anion derived from an organic acid is ^{R-COO -, R-SO} 4 - in (here, R is a least one functional group containing a hydroxyl group or amino group are each independently substituted or unsubstituted represents an unsubstituted alkyl group or an aryl group), C ₂ O ₄ ^2-, or HC ₂ O ₄ ^- to is not limited to including, mounds containing the anion Magnetic compounds include, but are not limited to, anions derived from RNA, anions derived from DNA, anions derived from proteins, or anions derived from cation exchange resins.

As the cation ([X] ⁺ ) usable in the present invention, an ionic salt composed of ammonium, pyrrolidinium, pyridinium, phosphonium, imidazolium cation and counter anion may be used. Select from 5 and use.

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

(In the above formulas (1) to (5), R ₁ to R ₁₆ each independently represent hydrogen or a C1 to C18 straight or branched alkyl group)

Preferably, R ₁ to R ₁₁ are C1 to C8 alkyl groups, R ₁₂ , R ₁₄ and R ₁₅ are hydrogen or C1 to C6 alkyl groups, and R ₁₃ and R ₁₆ are hydrogen or C1 to C8 alkyl groups are possible. Do.

More preferably, the ammonium salt of Formula 1 may be a tetrabutyl ammonium cation, a tetraethyl ammonium cation, a tetramethyl ammonium cation, and the pyrrolidinium salt of Formula 2 may be N-butyl-N-methylpyrrolidinium. Cation, N-ethyl-N-methylpyrrolidinium cation is possible, pyridinium salt of formula (3) is N-butylpyridinium cation, N-ethylpyridinium cation, N-methylpyridinium cation, The phosphonium salt of tetrabutyl phosphonium cation, tetraethyl phosphonium cation can be, the imidazolium salt of formula 5 is 1-ethyl-3-methyl-imidazolium cation, 1-methyl-3-propyl Imidazolium cation, 1-butyl-3-methyl-imidazolium cation, 1-methyl-3-pentyl-imidazolium cation, 1-hexyl-3-methyl-imidazolium cation, 1-heptyl-3 -Methyl-imidazolium cation, 1-methyl-3-octyl-imidazolium cation , 2,3-dimethyl-1-propyl-imidazolium cation, or 2,3-dimethyl-1-butyl-imidazolium cation is possible.

The organic salt according to the present invention containing the above cation and the counter anion ([Y] ⁻ ) may be selected by an appropriate combination of the counter anion and the cation of the formula (1-5) as described above.

Preferably, the organic salt is tetramethyl ammonium chloride (Me ₄ NCl), tetraethyl ammonium chloride (Et ₄ NCl), trimethylcetyl ammonium chloride (Me ₃ (C ₁₆ H ₃₅ ) NCl based on ammonium of formula (1). ), Tetraoctyl ammonium chloride ((C ₈ H ₁₇ ) ₄ NCl) and 1-octyl-3-methyl-imidazolium based on imidazolium of formula 5 (1-octyl-3-methyl-imidazolium) Chloride (Cl ⁻ ), 1-octyl-3-methyl-imidazolium (1-octyl-3-methyl-imidazolium) tetrachloroaluminate (AlCl ₄ ⁻ ), 1-octyl-3-methyl-imidazolium ( borate in 1-octyl-3-methyl- imidazolium) tetrafluoroborate (BF ₄ ^-), 1- octyl-3-methyl-imidazolium (1-octyl-3-methyl -imidazolium) phosphate (PF ₆ hexafluoro ^- ) also 1-octyl-3-methyl-imidazolium (1-octyl-3-methyl -imidazolium) antimonate hexafluorophosphate (SbF ₆ ^- a) 1-butyl-3-methyl-imidazolium (1 -butyl-3-methyl-imidaz olium) chloride (Cl ^-), 1- butyl-3-methyl-imidazolium (1-butyl-3-methyl -imidazolium) tetrachloro aluminate (AlCl ₄ ^-), 1- butyl-3-methyl-imidazolidin imidazolium (1-butyl-3-methyl -imidazolium) tetrafluoroborate (BF ₄ ^-), 1- butyl-3-methyl-imidazolium (1-butyl-3-methyl -imidazolium) hexafluorophosphate (PF _⁶ and the like) may be used ^-) or 1-butyl-3-methyl-imidazolium (1-butyl-3-methyl -imidazolium) hexafluoroantimonate (SbF _6.

The above-described organic salt is selected from the counter anion in consideration of the degree of hydrophilicity (or hydrophobicity) with the polymer to secure the shape of the polymer structure to be finally obtained, and in the case of the porous polymer structure, the cation of the organic salt By considering the size, the polymer structure having pores of various shapes and sizes can be obtained.

Next, in step b), the polymer and the organic salt selected in step a) are dissolved in an organic solvent.

The polymer: organic salt: organic solvent is preferably mixed in a mass ratio of 1: 2: 50 to 1:10:50.

The organic salt is removed by a non-solvent in a subsequent step to form a specific pattern in the polymer structure, wherein the mass ratio is limited to control the size, number and shape of the pores.

If the mass ratio is out of the above range, the number or size of particles or pores may be too large or too small to control the physical properties and morphology of the polymer structure and thus may not be used as the structure.

The organic solvent according to the present invention uses a polymer and an organic salt can be dissolved at the same time, the lower the vaporization temperature is advantageous. Typically, usable organic solvents include dichloromethane, chloroform, acetone, ethyl acetate, diethyl ether, trifluoroethanol, tetrahydrofuran, 1,4-dioxane, hexane, cyclohexane, benzene, toluene and mixtures thereof One selected from the group consisting of solvents is preferred.

Next, in step c) to remove the organic solvent in the mixed solution obtained in step b) to prepare a composite gel consisting of a polymer-organic salt.

The mixed solution obtained in the previous step b) is viscous and is converted to a more viscous gel-like complex consisting only of polymer and organic salt with the removal of the organic solvent.

Removal of the organic solvent is not particularly limited in the present invention, it can be carried out by a commonly used method, for example, the evaporation method.

Next, in step d), the organic salt in the composite gel obtained in step c) is removed.

Removal of organic salts in the composite gel may be a non-solvent treatment method. The non-solvent used for the organic salt removal may be one selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol and mixed solvents thereof.

At this time, the expensive organic salts removed (eg, ionic liquids) can be recovered separately and reused through simple treatment.

Next, in step e), the complex obtained by removing the organic salt in step d) is dried to obtain a polymer structure according to the present invention.

Subsequently, the obtained polymer structure may be subjected to various methods of drying such as normal temperature atmospheric pressure drying, hot air drying, and vacuum drying.

The polymer structure manufactured through the above-described steps may be obtained in a variety of forms from three-dimensional particulate form to three-dimensional porous form. The morphology can be controlled by not merely selecting complicated parameters but by simply using hydrophilicity of the polymer and organic salts, and controlling various ions by selecting anions of organic salts.

In addition, the process of the above steps b) to e) is very simple, it is possible to reuse the used organic salt is very economically advantageous, there is an advantage that can be mass-produced.

The polymer structure thus prepared is applicable to the field of tissue engineering, that is, cell carriers capable of supporting and delivering cells, support for bone tissue engineering, drug carriers, gas reservoirs, gas filters, and catalyst carriers for chemical reactions. .

In Experimental Example 1 of the present invention, morphological control of the polymer structure according to the type of counter anion of organic salt was confirmed.

Imidazolium salt is used as the cation of the organic salt, and SbF ₆ <PF ₆ <NTf ₂ <OTf Anions having a tendency to increase the degree of hydrophilicity in order of <BF ₄ <Cl were used to prepare a PLDLA polymer structure by selecting counter anions. As a result, SbF _6, PF _6, has a counter anion of an organic salt which is relatively NTf ₂ has a low degree of hydrophilic, were prepared for the particle diameter of the particulate polymer structures 10 ~ 50㎛, for OTf, BF _4, or Cl Organic salts having a counter anion have a relatively high degree of hydrophilicity to prepare a porous structure having pores with a diameter of 1 ~ 100㎛. These results show that the morphology of the polymer structure can be easily controlled only by adjusting the counter anion.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are merely illustrative of the invention and the present invention is not limited by these examples.

[Example]

Experimental Example 1 Control of Polymer Structure Morphology by Counter Anions of Organic Salts

PLDLA, one of the biodegradable biopolymers as a polymer, dichloromethane (CH ₂ Cl ₂ ) as the organic solvent, 1-butyl-3-methyl-imidazolium as the cation, and the counter anion Cl, OTf, BF ₄ , SbF ₆ , PF ₆ , and NTf ₂ were used, respectively.

(1) Preparation of Polymer Structure

Dichloromethane (10 ml) was added to the reactor, and PLDLA (200 mg) and organic salt (1 g) were added thereto, followed by stirring to make a uniform solution. In the obtained mixed solution, the dichloromethane was fully removed at room temperature and normal pressure (25 degreeC) in the state which removed the stirrer, and the composite gel was obtained. 70% ethanol (20 ml) in the obtained composite gel was added to remove the organic salt in the composite gel, and then dried at room temperature for 24 hours to prepare a PLDLA polymer structure.

(2) structural form analysis

After measuring the shape of the PLDLA polymer structure prepared in the above by using a SEM photometer, Table 1 summarizes the shape of the polymer structure according to the type of the counter anion, Figure 3 according to the type of the counter anion of Experimental Example 1 SEM images showing the structure morphology are shown.

number Counter anion Polymer structure form Pore size Particle size One SbF ₆ Particulate Structure (Microsphere) - 10 to 20 μm 2 PF ₆ Particulate Structure (Microsphere) - 20 ～ 30 ㎛ 3 NTf ₂ Particulate Structure (Microsphere) - 30-50 μm 4 OTf 3D porous structure 20 ～ 30 ㎛ - 5 BF ₄ 3D porous structure 30 ～ 70 ㎛ - 6 Cl 3D porous structure 50-100 μm -

As shown in Figure 3 and Table 1, it can be seen that the polymer structure can be changed in various forms only by the type of the counter anion. In addition, as the counter anion was higher in hydrophilicity than the polymer, a porous structure having a large pore size could be manufactured.

(3) FT-IR analysis

In order to confirm the characteristic peak of the PLDLA polymer structure prepared above, the spectrum was obtained by using an infrared spectroscopy (FT-IR spectrometry).

4 is an FT-IR spectrum of PLDLA alone, and FIGS. 5 to 10 are FT-IR spectra of the polymer structure prepared in Experimental Example 1. FIG.

When 4 to refer to Figure 10, to determine the CH peak of C = O peak at 1748 ~ 1750cm ^-1, a peak CO at 1183cm ^-1, 1081 ~ 1084cm ^-1, 2996cm ^-1 in the manufactured in Experimental Example 1 It was confirmed that the polymer structure consists of PLDLA polymer.

In addition, the presence or absence of imidazolium salt can be confirmed, for example, 1464 cm ^-1 and 1571 cm ^-1 peaks by C = C and C = N from 3161 cm ^-1 , aromatic imidazolium ring of sp ² CH It can not be seen that the alcohol is almost completely removed.

(4) TGA analysis

In order to confirm the thermal decomposition characteristics of the PLDLA polymer structure prepared above, it was measured using a thermogravimetric analyzer (TGA).

11 and 12 are TGA results of the polymer structure obtained in Experimental Example 1, wherein (a) of FIG. 11 is PLDLA alone, (b) PLDLA-SbF ₆ , and (c) PLDLA-NTf ₂ structure, and FIG. 12. (A) PLDLA-OTf, (b) PLDLA-BF ₄ , and (c) PLDLA-Cl constructs.

11 and 12, all PLDLA polymer structures started to decompose at 300 to 390 ° C. This decomposition curve was slightly different depending on the shape of the PLDLA polymer structure, and in the form of particles from 300 ~ 310 ℃, the porous porosity was found to be 220 ~ 280 ℃. In addition, the secondary decomposition curve by the organic salt was not seen, it was confirmed that the organic salt is almost removed.

(5) Porosity Analysis

In order to confirm the pore characteristics of the porous polymer structure of the prepared PLDLA polymer structure was measured by the BET method, the results obtained are shown in Table 2 below.

Polymer Structure Code Organic salt Porosity (%) PLDLA-OTf [bmim] OTf 13.3 PLDLA-BF ₄ [bmim] BF ₄ 78.3 PLDLA-Cl [bmim] Cl 79.2

Referring to Table 2, as a result of analyzing the porosity of the porous polymer structure, it can be seen that as the hydrophilicity of the counter anion of the organic salt increases, the porosity value also increases.

Through the results of (1) to (5), it can be seen that in the present invention, the morphology (structural form, pore characteristics) of the polymer structure can be controlled only by controlling the hydrophilicity / hydrophobicity of the organic salt by changing the counter anion of the organic salt. have.

The polymer structure according to the present invention is applicable to the field of tissue engineering, that is, cell carriers capable of supporting and delivering cells, scaffolds for bone tissue engineering, drug carriers and the like.

Claims

Selecting a polyester polymer and an organic salt having a lower hydrophilicity than the polymer, wherein the organic salt has a cation ([X] ⁺ ) and a counter anion ([Y] ⁻ ) represented by Formula 5 below;
Dissolving the polyester polymer and the organic salt in an organic solvent;
Removing the organic solvent in the obtained solution to prepare a composite gel consisting of a polymer-organic salt;
Removing organic salts in the composite gel; And
Method for producing a particulate polymer structure comprising the step of drying:
[Chemical Formula 5]

(In Formula 5, R ₁₂ to R ₁₆ each independently represent hydrogen or a C1-C18 linear or branched alkyl group.)

delete

The method of claim 1, wherein the polyester polymer is polylactide (PLA), poly (D, L) lactide (PDLLA), polyglycolide (PGA), poly β- hydroxy butyl acid, polycaprolactone, poly Orthoesters, polylactide-co-glycolide (PLGA), polyethylene glycol (PEG), polylactide-co-glycolides (PLGA), polyvalerolactone, polyhydroxy butyrate, poly A method for producing a particulate polymer structure comprising one type selected from the group consisting of hydroxy valerate, poly (lactide-co-caprolactone), and combinations thereof.

delete

According to claim 1, wherein the counter anion ([Y] ^-) is _{^{N 3 -, Br -, Cl}} -, F - , and I ^- anions consisting of a single element of one member selected from the group consisting of: fullerene anion, CHB ₁₁ _{^{H 12 -, HS -, OCN}} -, SCN -, CN -, PF 6 -, NTf 2 -, OTf - and BF ₄ ^- anions of one member selected from the group consisting of _{^{_{^{compounds: CO 3 2-, HCO 3 -}}}} , ^{_{^{OH -, NO 3 -, NO}}} 2 -, PO 4 3-, HPO 4 2-, H 2 PO 4 -, SO 4 2- and HSO ₄ ^- of one member selected from the group consisting of oxo anions: R-COO ^- , R-SO ₄ ^- (where, R is each independently a hydroxyl substituted with one or more functional groups comprising a lock group or an amino group or represents an unsubstituted alkyl group or an aryl group), C ₂ O ₄ ^2-, or HC ₂ O ₄ ^- an anion derived from an organic acid: an anion derived from the anionic, DNA derived from RNA, a polymer containing an anion derived from the anion, or cation exchange resins derived from proteinaceous Ions: and a process for producing a particulate polymer structure including one selected from the group consisting of.

The method of claim 1, wherein the organic salt is 1-butyl-3-methyl-imidazolium chloride, 1-butyl-3-methyl-imidazolium trifluoromethane sulfonate, 1-butyl-3-methyl-imi A method for producing a particulate polymer structure comprising one type selected from the group consisting of dazolium tetrafluoroborate, and combinations thereof.

The method of claim 1, wherein the organic solvent is dichloromethane, chloroform, acetone, ethyl acetate, diethyl ether, trifluoroethanol, tetrahydrofuran, 1,4-dioxane, hexane, cyclohexane, benzene, toluene and their Method for producing a particulate polymer structure comprising one selected from the group consisting of a mixed solvent.

The method of claim 1, wherein the polymer: organic salt: organic solvent is mixed at a mass ratio of 1: 2: 50 to 1:10:50.

Selecting a polyester polymer and an organic salt having a higher hydrophilicity than the polymer, wherein the organic salt has a cation ([X] ⁺ ) and a counter anion ([Y] ⁻ ) represented by Formula 5 below;
Dissolving the polyester polymer and the organic salt in an organic solvent;
Removing the organic solvent in the obtained solution to prepare a composite gel consisting of a polymer-organic salt;
Removing organic salts in the composite gel; And
Method for producing a porous polymer structure comprising the step of drying:
[Chemical Formula 5]

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The method of claim 10, wherein the polyester polymer is polylactide (PLA), poly (D, L) lactide (PDLLA), polyglycolide (PGA), poly β- hydroxy butyl acid, polycaprolactone, poly Orthoesters, polylactide-co-glycolide (PLGA), polyethylene glycol (PEG), polylactide-co-glycolides (PLGA), polyvalerolactone, polyhydroxy butyrate, poly A method for producing a porous polymer structure comprising one type selected from the group consisting of hydroxy valerate, poly (lactide-co-caprolactone), and combinations thereof.

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Of claim 10 wherein the counter anion ([Y] ^-) is _{^{N 3 -, Br -, Cl}} -, F - , and I ^- anions consisting of a single element of one member selected from the group consisting of: fullerene anion, CHB ₁₁ _{^{H 12 -, HS -, OCN}} -, SCN -, CN -, PF 6 -, NTf 2 -, OTf - and BF ₄ ^- anions of one member selected from the group consisting of _{^{_{^{compounds: CO 3 2-, HCO 3 -}}}} , ^{_{^{OH -, NO 3 -, NO}}} 2 -, PO 4 3-, HPO 4 2-, H 2 PO 4 -, SO 4 2- and HSO ₄ ^- of one member selected from the group consisting of oxo anions: R-COO ^- , R-SO ₄ ^- (where, R is each independently a hydroxyl substituted with one or more functional groups comprising a lock group or an amino group or represents an unsubstituted alkyl group or an aryl group), C ₂ O ₄ ^2-, or HC ₂ O ₄ ^- an anion derived from an organic acid: an anion derived from the anionic, DNA derived from RNA, a polymer containing an anion derived from the anion, or cation exchange resins derived from proteinaceous Ions: and a process for producing a porous polymer structure comprising one member selected from the group consisting of.

The method of claim 10, wherein the organic salt is 1-butyl-3-methyl-imidazolium chloride, 1-butyl-3-methyl-imidazolium trifluoromethane sulfonate, 1-butyl-3-methyl-imi Dazolium tetrafluoroborate, and a method for producing a porous polymer structure containing one selected from the group consisting of a combination thereof.

The method of claim 10, wherein the organic solvent is dichloromethane, chloroform, acetone, ethyl acetate, diethyl ether, trifluoroethanol, tetrahydrofuran, 1,4-dioxane, hexane, cyclohexane, benzene, toluene and their Method for producing a porous polymer structure containing one selected from the group consisting of a mixed solvent.

The method of claim 10, wherein the polymer: organic salt: organic solvent is mixed in a mass ratio of 1: 2: 50 to 1:10:50.