KR20100130803A

KR20100130803A - Polymer composite, method for preparing thereof, composition and polymer separation membrane comprising the same

Info

Publication number: KR20100130803A
Application number: KR1020090049505A
Authority: KR
Inventors: 김종학; 고주환; 박정태; 서진아; 강용수; 강상욱
Original assignee: 연세대학교 산학협력단
Priority date: 2009-06-04
Filing date: 2009-06-04
Publication date: 2010-12-14

Abstract

The present invention is an amphiphilic polymer matrix; And a polymer composite including metal halide nanoparticles dispersed in the polymer matrix, a method for preparing the same, a composition comprising the above, and a separator, according to the present invention, which is uniformly dispersed in a hydrophilic region of an amphiphilic polymer matrix. By providing a polymer composite comprising the metal halide nanoparticles present, the membrane prepared using the same does not need to activate the metal halide nanoparticles, and there is no fear of reduction, so it is excellent as an olefin-promoting transport membrane without the addition of other additives. It may have selectivity and transmittance.

Description

Polymer composite, method for preparing the same, composition and polymer separation membrane comprising the above

The present invention relates to a polymer composite, a preparation method thereof, a composition comprising the same, and a polymer separation membrane.

Alkene hydrocarbons are often produced mainly by high temperature pyrolysis of naphtha obtained from crude oil refining process.Alkenes such as ethane and propane are often used in the production of alkene hydrocarbons that are very important industrially and form the basis of modern petrochemical industry. Since the hydrocarbons are also produced, separation of alkene hydrocarbons and alkanes hydrocarbons is an important process technology in the related industry.

Conventionally, classical distillation has been mainly used for the separation of mixtures of alkenes / alkanes such as ethylene / ethane and propylene / propane. However, in the case of the mixture of alkenes / alkanes, the size of the molecules to be separated are similar, and the physical properties such as relative volatility, etc., have a disadvantage in that the separation of these mixtures requires large-scale equipment investment and high energy costs.

For example, in the conventional distillation method, a 120-160 stage distillation column is operated at a temperature of -30 ° C and a high pressure of about 20 atm for separation of ethylene / ethane, and a 180-200 stage distillation column is used for separation of propylene / propane. Operating at a temperature of -30 ° C and water pressure so that the reflux ratio was above 10 required large facility investment and high energy costs. Therefore, the development of a new separation process that can replace the existing distillation method is constantly required.

A separation process using a separation membrane is drawing attention as a separation process that can replace the high cost problem of the distillation as described above. Membrane technology has made remarkable progress in the separation of gas mixtures, but in the case of separating mixtures with very similar molecular sizes and physical properties, such as mixtures of alkenes / alkanes hydrocarbons, satisfactory separation can be achieved using conventional gas separation membranes. No effect could be obtained.

Therefore, accelerated transport membranes have been developed that can achieve excellent separation performance for mixtures such as alkenes / alkanes. In the separation process of the mixture using a separation membrane, separation is performed according to the difference in permeability of each component constituting the mixture. The use of the facilitated transport membrane can increase the permeability and selectivity at the same time, so that the application range can be greatly increased.

If there are carriers in the membrane that can react selectively and reversibly with certain components in the mixture, these reversible reactions result in additional mass transfer. Therefore, the entire mass transfer can be expressed as the sum of mass transfer according to the concentration gradient (Fick's law) and the mass transfer by the carrier, and accordingly, selectivity and permeability can increase together. do.

As a membrane that was manufactured using the concept of accelerated transport, a supported liquid membrane was developed, which dissolves a carrier in a solvent such as water to promote the movement of a substance, and then It is prepared by filling in a porous thin film. In addition, a method has been devised by Kimura et al. (US Pat. No. 4,318,714) that has a facilitative transporting capability by substituting appropriate ions in the ion exchange resin.

However, the separation membrane using the supporting liquid membrane or the ion exchange resin has a property of exhibiting accelerated transport phenomenon only in a wet state, so that solvents are lost and separation performance decreases over time, and thus the initial permeation separation performance cannot be sustained for a long time. I had.

In addition, Kraus et al. Developed a facilitated transport separation membrane using a method of plasticizing using silver glycerol after replacing silver ions in an ion exchange membrane such as Nafion (US Pat. No. 4,614,524). However, the ion exchange membrane as described above also had a problem in the selectivity of ethylene / ethane when dry feed was used. In addition, when the plasticizer was not used, the ion exchange membrane not only showed no selectivity but also lost plasticizer over time. There was a problem that is difficult to use.

The present invention is to provide a polymer composite having excellent electrical and mechanical properties, including agglomeration due to external conditions, including metal halide nanoparticles uniformly dispersed in the hydrophilic region of the amphiphilic polymer matrix.

In addition, another object of the present invention is to provide a method for producing a polymer composite that can control the growth and final size of the nanoparticles as well as uniformly disperse the metal halide nanoparticles in the polymer matrix as described above.

In addition, another object of the present invention to provide a composition that can be used for the production of a polymer membrane, including the polymer composite.

In addition, another object of the present invention is to provide a polymer separation membrane which can be usefully used for the promotion of olefins by coating the composition on a porous support.

The present invention as a means for solving the above problems, an amphiphilic polymer matrix; And it provides a polymer composite comprising a metal halide nanoparticles dispersed in the polymer matrix.

In addition, the present invention as another means for solving the above problems, the first step of producing a polymer molded body using an amphipathic polymer matrix; And it provides a method for producing the polymer composite comprising a second step of dispersing the metal halide nanoparticles in the polymer molded body.

In addition, the present invention provides a polymer membrane composition comprising the polymer composite as another means for solving the above problems.

In addition, the present invention is another means for solving the above problems, a porous support; And a coating layer formed on the porous support and including a coating layer formed using the composition.

According to the present invention, by including the metal halide nanoparticles uniformly dispersed in the hydrophilic region of the amphiphilic polymer matrix, not only has excellent compatibility, but also agglomeration due to external conditions such as heat, pressure, atmosphere, etc. And it can provide a polymer composite having excellent mechanical properties.

In addition, according to the method of manufacturing a polymer composite according to the present invention, since the polymer molded body is first prepared during the preparation of the polymer composite, the metal halide nanoparticles are dispersed so that the growth and final size of the nanoparticles can be easily controlled. .

In addition, since the polymer membrane according to the present invention is prepared using the composition including the polymer composite, it may exhibit excellent olefin selectivity and permeability without any other additives, and may provide a more stable olefin-promoted transport membrane.

Hereinafter, the polymer composite of the present invention will be described in more detail.

The polymer composite according to the present invention, as described above, an amphiphilic polymer matrix; And metal halide nanoparticles dispersed in the polymer matrix.

The amphiphilic polymer matrix forms a complex in which metal halide nanoparticles can be stably and uniformly dispersed, and may include both amphiphilic polymers having both a hydrophilic region and a hydrophobic region. Although not particularly limited, for example, a polymer in which a hydrophilic polymer side chain is bonded to a hydrophobic polymer main chain; Alternatively, the polymer may be a hydrophobic polymer side chain bonded to a hydrophilic polymer main chain.

Here, the hydrophobic region and the hydrophilic region refer to a portion showing hydrophobicity and a portion showing hydrophilicity, respectively, and the hydrophobic region means a region in which a hydrophobic polymer is formed, and the hydrophilic region means a region in which a hydrophilic polymer is formed. It may be.

In addition, the meaning that the metal halide nanoparticles are dispersed in the polymer matrix means that the metal halide nanoparticles and the amphiphilic polymer matrix are not simply mixed, but as the interactions between them occur, the metal halide nanoparticles are dispersed in the polymer matrix. It means that it is stable and uniformly dispersed in the.

Therefore, in the polymer composite according to the present invention, the metal halide nanoparticles may be uniformly dispersed in the hydrophilic region of the amphiphilic polymer matrix in which the hydrophobic region and the hydrophilic region are microphase separated.

The metal halide nanoparticles have excellent compatibility with the polymer matrix, and are not aggregated by external conditions such as heat, pressure, and atmosphere, and thus, the polymer composite including the same has excellent electrical and mechanical properties.

For example, in the amphiphilic polymer, the hydrophobic polymer formed in the hydrophobic region may include a nonpolar atomic group having a low affinity with water and a high affinity with oil, and the kind thereof is particularly limited. However, for example, the hydrophobic polymer may include at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated alkyls and organosilicones.

More specifically, the hydrophobic polymer may be a chlorine-based polymer; Or a polymer including a repeating unit represented by Formula 1 or Formula 2 below.

Where

R ₁ to R ₃ are each independently hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms,

R ₄ is hydrogen, a halogen, a cyano group, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or -C (O) -X,

X is an alkoxy group or amino group having 1 to 8 carbon atoms,

R ₅ is hydrogen or an alkyl group having 1 to 4 carbon atoms,

n is an integer of 1-4.

Here, the "chlorine-based polymer" refers to a hydrophobic polymer containing a chlorine atom.

More specifically, the hydrophobic polymer is polyvinyl chloride, polyvinylidene fluoride-co-chlorotrifluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoromethane, polyvinylidenedichloride, polystyrene, polyalkyl Copolymers containing styrene, polymethacrylate, polyacrylate, polyisoprene, polybutadiene, polyacrylamide, polyvinyl ether and the like alone or in combination of two or more thereof may be used.

On the other hand, the hydrophilic polymer may include an atomic group having a good affinity with water, the type of the atomic group is not particularly limited, for example, sulfo group (-SO ₃ H), carboxy group (-COOH) , Amino group (-NH ₄ ), ammonium group (-NH ₄ ), amine group (-N-) and may include one or more selected from the functional group represented by the formula (3), specifically, the preparation of metal halide nanoparticles It can contain an amine group in the point which can be made easier.

COOM 1

Wherein M ₁ is an alkali metal or NH ₄ .

More specific examples of the hydrophilic polymer include poly4-vinylpyridine, poly2-vinylpyridine, polydiethyl aminoethyl (meth) acrylate, polydiethylaminoethyl (meth) acrylate, and polydodecyl (meth) acrylic. Copolymers containing amide, poly2vinylpyridine oxide, polyaminostyrene, polyallylamine hydrochloride, polymethylvinylamine, polyethylimine, and the like alone or in combination of two or more thereof may be used.

Meanwhile, in the amphiphilic polymer matrix, the content of the hydrophobic polymer and the hydrophilic polymer is not particularly limited. For example, the amphiphilic polymer matrix may include 20 to 80 parts by weight of hydrophobic polymer and 80 to 20 parts by weight of hydrophilic polymer. can do.

If the content of the hydrophobic polymer and the hydrophilic polymer is out of the above limited numerical range, there is a fear that the thermal, mechanical and chemical stability of the polymer matrix.

In addition, the molar ratio of the hydrophobic region and the hydrophilic region is not particularly limited, but, for example, the molar ratio of the hydrophobic region and the hydrophilic region in the amphiphilic polymer matrix may be 20:80 to 80:20.

When the ratio of the hydrophobic region becomes smaller than the numerical value defined in the numerical range because the molar ratio is out of the limited numerical range, it may be difficult to control the size and shape of the metal halide nanoparticles. When the ratio of the regions is small, the mechanical strength of the separator may be weakened. In addition, in the polymer composite according to the present invention, metal halide nanoparticles having an average particle diameter of 20 to 200 nm may be dispersed in the hydrophilic region of the amphiphilic polymer matrix, and the size of the metal halide nanoparticles dispersed in the hydrophilic region is particularly limited. Although not specifically, it may be 20 to 50nm more specifically.

As such, the metal halide nanoparticles are uniformly dispersed in the hydrophilic region due to excellent compatibility with the polymer matrix, thereby preventing aggregation by external conditions, thereby greatly improving the electrical and mechanical properties of the polymer composite. .

On the other hand, in the polymer composite according to the present invention, the content of the amphiphilic polymer matrix and the metal halide nanoparticles is not particularly limited, but the content of the metal halide nanoparticles can be variously changed according to the intended use of the present invention. For example, the polymer composite may include 1 to 50 parts by weight of the metal halide nanoparticles based on 100 parts by weight of the amphipathic polymer matrix.

Here, the metal halide used as the metal halide nanoparticles is not particularly limited in kind, and various metal halides may be used. For example, the metal halide may be represented by the following formula (4).

M 2 X

Where

M ₂ is a metal selected from the group consisting of Au, Pt, Pd, Cu, Ag, Co, Fe, Ni, Mn, Sm, Nd, Pr, Gd, Ti, Zr, Si and In, including two or more of the metals To be a metal compound, an alloy of the metal or a mixture thereof,

X is F, Cl, Br or I.

In addition, the hydrophilic polymer includes an atomic group having good affinity with water such as an amine group as described above, and thus forms metal salts or metal nanoparticles through direct coordination or acid-base action. Nanoparticles can be uniformly dispersed in the hydrophilic region of the amphiphilic polymer matrix according to the present invention.

In addition, the particle size of the metal halide nanoparticles is not particularly limited, for example, the average particle diameter may be 1 to 200nm.

Meanwhile, the polymer composite according to the present invention may further include 1 to 25 parts by weight of the electron acceptor based on 100 parts by weight of the amphipathic polymer matrix.

The electron acceptor acts as a cation for the metal halide nanoparticles, the kind is not particularly limited, for example, p-benzoquinone, anthracene, azobenzene, benzophenone, ferrocene, nitrobenzene, tetracyanoqui Nodimethane, N, N, N'N'-tetramethyl-p-phenylenediamine, tetrathiafulvalene, thianthrene, tri-Np-tolylamine and the like.

In addition, the present invention comprises a first step of producing a polymer molded body using an amphipathic polymer matrix; And it relates to a method for producing a polymer composite according to the invention comprising a second step of dispersing metal halide nanoparticles in the polymer molded body.

Hereinafter, the method for preparing a polymer composite according to the present invention will be described in more detail step by step.

In the method of preparing a polymer composite according to the present invention, the first step comprises the steps of: (1) preparing an amphiphilic polymer matrix by polymerizing a hydrophobic polymer and a hydrophilic polymer; And (2) introducing positive charges and anions into the polymer matrix prepared in step (1).

That is, in step (1), an amphiphilic polymer matrix may be prepared by mixing a hydrophobic polymer and a hydrophilic polymer and polymerizing the polymer, wherein the hydrophobic polymer and the hydrophilic polymer may be used without limitation. have.

In addition, as a polymerization method of the hydrophobic polymer and the hydrophilic polymer, a conventional graft polymerization method known in the art may be used, and for example, hydrophilicity to the hydrophobic main chain may be used using such a known graft polymerization method. It can be prepared by introducing a side chain.

For example, controlled free radical polymerization may be used in view of selective introduction into the efficiency and hydrophilic region of the reaction, and more specifically, atomic transfer radical polymerization (ATRP) Although may be used, the polymerization method of the hydrophobic polymer and the hydrophilic polymer is not particularly limited to the illustrated polymerization method.

Here, the atomic transfer radical polymerization method is a kind of living / controlled radical polymerization method, wherein the living polymerization has only an initiation reaction and a growth reaction in the chain polymerization process, and irreversible stop reaction or chain transfer does not occur, and thus growth activity is This means a polymerization reaction maintained for a long time.

In such atomic transfer radical polymerization, the reversible oxidation / reduction reaction of a transition metal compound induces a reversible transfer between a propagating species and a dormant species, and effectively suppresses an increase in the concentration of the growth species radicals. The concentration can be kept constant. As a result, side reactions such as chain transfer, stop reaction, and pairing phenomenon are suppressed in atomic transfer radical polymerization, and the structure, molecular weight and molecular weight distribution of the target polymer can be controlled efficiently.

That is, the amphiphilic polymer matrix used in the present invention may be prepared by polymerizing the hydrophilic polymer and the hydrophobic polymer using various polymerization methods as described above.

In addition, the polymerization conditions of the hydrophobic polymer and the hydrophilic polymer are not particularly limited, and polymerization conditions commonly applied in this field may be appropriately selected and employed, for example, under a nitrogen atmosphere, The polymerization can be carried out at a temperature for 16 to 20 hours. Such polymerization conditions are also not particularly limited to the exemplified contents, and it is also possible to freely change the polymerization conditions in order to produce the polymer matrix desired in the present invention.

Furthermore, in the present invention, when the hydrophilic polymer and the hydrophobic polymer are mixed, an appropriate catalyst and a ligand may be added to allow the reaction to proceed more efficiently.

Here, the catalyst that can be used is also not particularly limited, for example, a catalyst represented by the following formula (5) can be used.

Qp-Yq

Where

Q is Cu ⁰ , Cu ¹⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ¹⁺ , Mo ²⁺ , Mo ^{3 +} , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ¹⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ¹⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ¹⁺ , Zn ²⁺ , Au ¹⁺ , Au ²⁺ , Ag ^1+, and any one transition metal ion selected from the group consisting of Ag ²⁺ ,

Y consists of halogen, alkoxy having 1 to 20 carbon atoms, SO ₄ , PO ₄ , HPO ₄ , H ₂ PO ₄ , triflate, thiocyanate, hexafluorophosphate, alkylsulfonate, benzenesulfonate and toluenesulfonate An anion formed from one selected from the group,

p represents the number of transition metal ions and q represents the coordination number.

In the method for preparing a polymer matrix used in the polymer composite according to the present invention, the type of ligand that contributes to the activation of the polymerization reaction together with the catalyst described above is not particularly limited, and any ligand which is commonly used in the art may be used without limitation. have.

Examples of such ligands include ligands comprising at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus and sulfur which can be coordinated to the transition metal via σ-bonding or 2 which can be coordinated to the transition metal via π-bonding. And ligands containing the above carbon atoms, and specific examples thereof include 2,2-bipyridine, triphenylphosphane, alkyl-2,2-bipyridine, 4,4-di (5-nonyl) -2,2 -Bipyridine, 4,4-di (5-heptyl) -2,2-bipyridine, tris (2-aminoethyl) amine, N, N, N ', N', N "-pentamethyldiethylenetriamine , 1,1,4,7,10,10-hexamethyltriethylenetetraamine and one or more selected from the group consisting of tetramethylethylenediamine, but is not limited thereto.

Meanwhile, the positive and negative charges may be introduced into the polymer matrix according to the step (2). The positive and negative ion introduction methods may be performed according to conventional methods known in the art, but are not particularly limited thereto. For example, the positive charges and anions can be introduced by reacting the polymer matrix with the halogenated alkyl.

According to the method for preparing a polymer composite according to the present invention, after preparing a polymer molded body using the polymer matrix as described above, metal halide nanoparticles are added to the amphiphilic polymer matrix by dispersing and growing a metal halogen precursor in the polymer molded body. It is possible to produce a dispersed polymer composite.

Herein, the shape of the polymer molded body is not particularly limited, and various shapes may be selected according to the purpose and use of the polymer composite according to the present invention. For example, appropriate shapes among conventional substrate films known in the art may be appropriate. It may be a polymer film formed by applying a base film and applying it on the base film and then drying.

In addition, the method for producing the polymer molded article is not particularly limited, but may be prepared by, for example, applying and drying a solution containing the polymer matrix on a suitable substrate using a casting method.

At this time, the type of the solvent for dissolving the polymer matrix is not particularly limited. For example, tetrahydrofuran (THF), toluene, dimethylformamide (DMF) or chloroform (CHCl ₃ ) may be used. Any solvent that can be used conventionally in the art can be used without limitation.

More specifically, the second step may include the steps of: a) mixing the polymer molded body and the metal halogen precursor solution to disperse the metal halogen precursor in the polymer molded body; And b) growing metal halogen nanoparticles in the polymer molded body obtained in step a).

As described above, in the manufacturing method of the polymer composite according to the present invention, after the polymer molded body is manufactured, the growth and the final size of the nanoparticles can be easily controlled by introducing a metal halogen precursor into the polymer molded body, Because of the fine phase separation into the hydrophobic region, the metal halide precursor can be more uniformly dispersed without aggregation.

The type of the metal halide precursor is not particularly limited, and according to the type of nanoparticles to be introduced, conventional precursors known in the art may be selected and used without limitation, but for example, as described above, May be a metal halide element, wherein M is any selected from the group consisting of Au, Pt, Pd, Cu, Ag, Co, Fe, Ni, Mn, Sm, Nd, Pr, Gd, Ti, Zr, Si and In One metal element, X may be a halogen element, such as F, Cl, Br, I.

In addition, the metal halogen precursor may include any one component selected from the group consisting of two or more intermetallic compounds of the metal elements, alloys of two or more components of the metal elements, and mixtures thereof, salts thereof, or oxides thereof. have.

On the other hand, the present invention also relates to a composition for polymer membrane comprising a polymer composite as described above.

That is, the composition for the polymer separator includes the polymer composite, and may include all of the compositions that may be used to prepare the polymer membrane, and the form is not particularly limited, for example, the polymer composite and It may include a suitable solvent capable of dissolving the polymer composite.

In addition, the present invention also provides a porous support; And a coating layer formed on the porous support and including a coating layer formed using the composition.

Herein, the porous support means a support on which a plurality of pores are formed, and may include all porous supports generally used to form a polymer separator in this field, and the kind thereof is not particularly limited.

In addition, the method of forming a coating layer using the composition is not particularly limited, and as a method of coating the composition on a support to form a polymer separation membrane, conventional methods known in the art may be used without limitation.

The polymer membrane thus prepared is a membrane for various gases, and exhibits excellent permeability and selectivity, such as a mixture of alkene / alkane hydrocarbons, even when the size and physical properties of the molecules are very similar, the olefin having excellent both permeability and selectivity. It can be used as a separator for promoting transportation.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these examples.

Preparation Example 1 Preparation of Polymer Composite

1. Preparation of Amphiphilic Polymer Matrix

3 g of polyvinyl chloride (PVC, Poly (vinyl chloride, Aldrich)) was dissolved in 75 ml of 1-methyl-2-pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone, Aldrich) at 70 ° C.

After cooling the solution to room temperature, 9 ml of 4-vinylpyridine (4VP, 4-vinyl pyridine, Aldrich) and 0.24 g of copper chloride (CuCl, Copper chloride, Aldrich), 0.66 ml of 1,1,4,7,10 , 10-hexamethyl triethylene tetraamine (HMTETA, 1,1,4,7,10,10-hexamethyl triethylene tetramine, Aldrich) was added.

Nitrogen was injected for 30 minutes with stirring until the mixed solution became uniform, and then placed in an oil bath preheated to 90 ° C., and reacted for 4 hours. The polymer solution after the reaction was precipitated in diethyl ether (Aldrich) and filtered to recover the polymer. After removing the solvent in the drying oven for 24 hours in the recovered polymer, polyvinyl chloride-poly-4-vinylpyridine (PVC-g-P4VP) was prepared by completely removing the remaining solvent in a vacuum oven.

Figure 1a schematically shows the synthesis process of the polyvinyl chloride-poly-4-vinylpyridine, Figure 1b is a graph showing the results of NMR synthesis of the polyvinyl chloride-poly-4-vinylpyridine.

2. Preparation of N-alkylated Positive Charge Copolymers (N-PVC-g-P4VP)

1.5 g of the polyvinyl chloride-poly-4-vinylpyridine copolymer and 1.5 ml of 1-bromohexane (Aldrich) synthesized above were prepared using 1-methyl-2-pyrrolidinone (NMP, 1-methyl-). 2-pyrrolidinone, Aldrich) was dissolved in 70 ml.

The solution was then placed in an oil bath preheated to 60 ° C. with stirring and reacted for 24 hours. After the reaction, the polymer solution was precipitated in diethyl ether (Aldrich) and filtered to recover the alkylated polymer. The polymer solution was dried at room temperature to synthesize an N-alkylated positive charge copolymer.

Figure 2 schematically shows the synthesis of the N-alkylated positive charge copolymer.

3. Preparation of Nanocomposite (AgBr / PVC-g-P4VP)

1.5 g of the N-alkylated positive charge copolymer prepared above was dissolved in 60 ml of 1-methyl-2-pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone, Aldrich).

Separately, 1.5 g of silver para toluene sulfonate (AgPTS, Silver p-toluene sulfonate, Aldrich) was dissolved in 18 ml of dimethyl sulfoxide (DMSO, dimethyl sulfoxide, Aldrich). The silver para toluene sulfonate solution was mixed with the N-alkylated positive charge copolymer by dropping it dropwise for 10 minutes into a solution stirred at a stirring speed of 700 rpm, and the mixed solution was stirred at room temperature for 1 hour. .

After the reaction was completed, the polymer mixture solution was precipitated in diethyl ether (Aldrich), filtered, and dried at room temperature for 1 day to prepare a nanocomposite (AgBr / PVC-g-P4VP).

Figure 3 schematically shows the synthesis process of the nanocomposite, Figure 4a is a photograph of a transmission electron microscope of the final nanocomposite (transmission electron microscope), Figure 4b shows the dispersion according to the particle diameter of the metal halide nanoparticles. .

As a result, as shown in Figure 4b, it was confirmed that the silver bromide nanoparticles are stabilized without agglomeration with each other in the size of the average size of 10 to 50nm.

Preparation Example 2 Preparation of Polymer Composite

1. Preparation of Amphiphilic Polymer Matrix

3 g of poly (vinylidene fluoride-chlorotrifluoroethylene) (P (VDF-co-CTFE), poly (vinylidene fluoride-co-chlorotrifluoroethylene), Solvay) at 1 atm. It was dissolved in 75 ml of pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone, Aldrich).

After cooling the solution to room temperature, 18 ml of 4-vinylpyridine (4VP, 4-vinyl pyridine, Aldrich) and 0.24 g of copper chloride (CuCl, Copper chloride, Aldrich), 0.66 ml of 1,1,4,7,10 , 10-hexamethyl triethylene tetraamine (HMTETA, 1,1,4,7,10,10-hexamethyl triethylene tetramine, Aldrich) was added.

Nitrogen was injected for 30 minutes with stirring until the mixed solution became uniform, and then placed in an oil bath preheated to 120 ° C., and reacted for 6 hours. After the reaction, the polymer solution was precipitated in methanol (methanol, Aldrich) and filtered to recover the polymer.

The polymer was dried in a drying oven for 24 hours to remove the solvent, and then put in a vacuum oven to completely remove the remaining solvent, thereby removing poly (vinylidene fluoride-chlorotrifluoroethylene) -poly-4-vinylpyridine (P (VDF-co-CTFE) -g-P4VP) was prepared.

2. Preparation of N-alkylated Positive Charge Copolymers (N-P (VDF-co-CTFE) -g-P4VP)

0.15 g of poly (vinylidene fluoride-chlorotrifluoroethylene) -poly-4-vinylpyridine and 0.1 ml of 1-bromohexane (Aldrich) synthesized above were dimethyl sulfoxide (DMSO, dimethyl sulfoxide). , Aldrich) was dissolved in 10 ml.

The solution was placed in an oil bath preheated to 60 ° C. with stirring and reacted for 24 hours. After the reaction, the polymer solution was precipitated in diethyl ether (Aldrich) and filtered to recover an N-alkylated positive charge copolymer. The polymer solution containing the N-alkylated positive charge copolymer was dried at room temperature.

3. Preparation of Nanocomposites

0.1 g of the N-alkylated positive charge copolymer (NP (VDF-co-CTFE) -g-P4VP) prepared above was prepared with 1 ml of dimethyl sulfoxide (DMSO, dimethyl sulfoxide, Aldrich) and 1 ml of tetrahydrofuran (THF, Tetrahydrofuran, Aldrich) solution.

Separately, 0.05 g of silver paratoluene sulfonate (AgPTS, Silver p-toluene sulfonate, Aldrich) was dissolved in 4 ml of a mixed solution of DMSO and THF in a volume ratio of 1: 1.

Subsequently, both the polymer solution and the silver para toluene sulfonate solution were allowed to stand at room temperature while being placed in an ice bath at 0 ° C. The silver para toluene sulfonate solution was slowly dropped dropwise to the N-alkylated positive charge copolymer solution stirred for 10 minutes at a stirring speed of 700 rpm, and the mixed solution was stirred at room temperature for 1 hour.

After the reaction, the polymer mixture solution was precipitated in diethyl ether (Aldrich), filtered, and dried at room temperature for 1 day to obtain a nanocomposite (AgBr / PP (VDF-co-CTFE) -g-P4VP). Prepared.

Example 1 Preparation of Nanocomposite Membranes

The AgBr / PVC-g-P4VP nanocomposite prepared in Preparation Example 1 was dissolved in tetrahydrofuran (THF) solvent. Then the ionic liquid 1-methyl-3-octyl-imidazolium nitrate (1-methyl-3-octylimidazolium nitrate; MOIM + NO 3 -, C-TRI) As shown in Figure 5, the content of the different Was added and stirred at a temperature of 100 ° C. for 5 hours.

The mixed solutions obtained above were coated on a polysulfone porous membrane (average pore size 70 nm, polysulfone) using RK Control Coater (Model 101, Control Coater RK Print-Coat instruments LTD, UK).

Example 2 Preparation of Nanocomposite Membrane

AgBr / PP (VDF-co-CTFE) -g-P4VP nanocomposite prepared in Preparation Example 2 was dissolved in tetrahydrofuran (THF).

Then the ionic liquid 1-methyl-3-octylimidazolium nitrate (MOIM + NO 3 -, C-TRI) As shown in FIG. 6, insert a different content was stirred at a temperature of 100 ℃ for 5 hours.

The mixed solution was coated on a polysulfone porous membrane (average pore size 70 nm, polysulfone) using RK Control Coater (Model 101, Control Coater RK Print-Coat instruments LTD, UK).

[Test Example]

1.Olefin Separation Selectivity and Permeability Measurement

The separators according to Examples 1 and 2 were stored in an oven at 100 ° C. for 24 hours for heat treatment and drying. The membrane thus prepared was measured for separation performance using a propylene / propane mixed gas (50:50 vol%) at room temperature.

The permeability of the permeated gas was measured by a bubble flow meter, and the composition ratio was measured by gas chromatography. The pressure on the upper side was 40 psig and the pressure on the permeate side was atmospheric pressure (0 psig).

The unit of gas permeability is represented by GPU [10 ^-6 cm ³ (STP) / cm ² cmHg sec], the permeability and selectivity of the separator according to Example 1 after reaching a steady state is shown in Figure 5, The permeability and selectivity of the separator according to Example 2 is shown in FIG. 6.

As a result, referring to FIG. 5, in the separation membrane according to Example 1, the separation performance of propylene / propane was about 5GPU and 4 selectivity even when there was no ionic liquid (Weight fraction of AgBr composite = 1). When the ionic liquid was added, the permeability increased to 5.7 GPU and the selectivity increased to about 6.

In addition, referring to FIG. 6, in the case of the separation membrane according to Example 2, when the ionic liquid was absent, the separation performance was shown for propylene / propane having a permeability of 4.5 GPU and a selectivity of 3.8. When added, the transmittance increased to 5.4 GPU and the selectivity to about 5.5.

Figure 1a schematically shows the synthesis process of the amphiphilic polymer matrix in the preparation of the polymer composite according to Preparation Example 1 of the present invention, Figure 1b is a graph of the NMR data of the amphiphilic polymer matrix shown in Figure 1a,

Figure 2 schematically shows the synthesis process of the N-alkylated positive charge copolymer in the preparation of the polymer composite according to Preparation Example 1 of the present invention,

3 schematically shows a process of synthesizing a nanocomposite in the preparation of a polymer composite according to Preparation Example 1 of the present invention.

Figure 4a is an electron micrograph of the nanocomposite prepared in Figure 3, Figure 4b is a graph showing the dispersion degree according to the average particle diameter of the metal halide nanoparticles in the nanocomposite prepared in Figure 3,

5 is a graph showing the results of measuring the olefin selectivity and permeability with the separator according to Example 1 of the present invention,

6 is a graph showing the results of measuring olefin selectivity and permeability with the separator according to Example 2 of the present invention.

Claims

Amphiphilic polymer matrix; And

A polymer composite comprising metal halide nanoparticles dispersed in the polymer matrix.

The method of claim 1,

Amphiphilic polymer matrix is a polymer having a hydrophilic polymer side chain bonded to a hydrophobic polymer backbone; Or a polymer in which a hydrophobic polymer side chain is bonded to a hydrophilic polymer main chain.

The method of claim 2,

Hydrophobic polymer is a polymer composite, characterized in that it comprises at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated alkyl and organosilicon.

The method of claim 2,

Hydrophobic polymers are chlorine-based polymers; Or a polymer comprising a repeating unit represented by Formula 1 or Formula 2 below:

[Formula 1]

[Formula 2]

Where

X is an alkoxy group or amino group having 1 to 8 carbon atoms,

R ₅ is hydrogen or an alkyl group having 1 to 4 carbon atoms,

n is an integer of 1-4.

The method of claim 2,

Hydrophobic polymers include polyvinyl chloride, polyvinylidene fluoride-co-chlorotrifluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoromethane, polyvinylidenedichloride, polystyrene, polyalkylstyrene, polymethacryl Polymer composite, characterized in that it comprises at least one selected from the group consisting of latex, polyacrylate, polyisoprene, polybutadiene, polyacrylamide and polyvinyl ether.

The method of claim 2,

The hydrophilic polymer is a polymer composite comprising at least one selected from the group consisting of a sulfo group, a carboxyl group, an amino group, an ammonium group, an amine group and a functional group represented by the following general formula (3):

(3)

COOM ₁

Wherein M ₁ is an alkali metal or NH ₄ .

The method of claim 2,

Hydrophilic polymers include poly4-vinylpyridine, poly2-vinylpyridine, polydiethyl aminoethyl (meth) acrylate, polydiethylaminoethyl (meth) acrylate, polydodecyl (meth) acrylamide, poly2vinylpyridine Polymer composite, characterized in that it comprises at least one selected from the group consisting of oxides, polyaminostyrene, polyallylamine hydrochloride, polymethylvinylamine and polyethylimine.

The method of claim 2,

The amphiphilic polymer matrix comprises 20 to 80 parts by weight of hydrophobic polymer and 80 to 20 parts by weight of hydrophilic polymer.

The method of claim 2,

Polymer composite, characterized in that the molar ratio of the hydrophobic region and the hydrophilic region is 20:80 to 80:20.

The method of claim 2,

A polymer composite, wherein metal halide nanoparticles having an average particle diameter of 20 to 200 nm are dispersed in a hydrophilic region of an amphiphilic polymer matrix.

The method of claim 1,

A polymer composite comprising 1 to 50 parts by weight of metal halide nanoparticles based on 100 parts by weight of an amphipathic polymer matrix.

The method of claim 1,

The metal halogen is a polymer composite, characterized in that represented by the following formula (4):

[Formula 4]

M ₂ X

Where

X is F, Cl, Br or I.

The method of claim 1,

A polymer composite further comprising 1 to 25 parts by weight of an electron acceptor based on 100 parts by weight of an amphipathic polymer matrix.

The method of claim 13,

Electron acceptors are p-benzoquinone, anthracene, azobenzene, benzophenone, ferrocene, nitrobenzene, tetracyanoquinomimethane, N, N, N'N'-tetramethyl-p-phenylenediamine, tetrathiafulvalene, Polymer composite, characterized in that selected from the group consisting of thianthrene and tri-Np-tolylamine.

A first step of preparing a polymer molded body using an amphipathic polymer matrix; And

The method of manufacturing a polymer composite according to any one of claims 1 to 14, comprising a second step of dispersing metal halide nanoparticles in the polymer molded body.

The method of claim 15,

The first step is

Polymerizing a hydrophobic polymer and a hydrophilic polymer to prepare an amphiphilic polymer matrix (1); And

Method (2) of introducing a positive charge and an anion into the polymer matrix prepared in step (1).

The method of claim 16,

In the step (2), a positive charge and an anion are introduced by reacting the polymer matrix with a halogenated alkyl.

The method of claim 15,

The second step is

a) mixing a polymer molded product and a metal halogen precursor solution to disperse the metal halogen precursor in the polymer molded product; And

b) growing a metal halogen nanoparticle in the polymer molded body obtained in step a).

A composition for polymer separation membrane comprising the polymer composite according to any one of claims 1 to 14.

Porous support; And

A polymer separation membrane formed on the porous support, comprising a coating layer formed using the composition according to claim 19.

The method of claim 20,

Polymer separation membrane, characterized in that the separation membrane for olefin promoted transport.