KR100750291B1 - Polystyrenic nanocomposite and its preparing method - Google Patents

Abstract

Provided are a polystyrene-based nanocomposite which is improved in compatibility and heat resistance, and a method for preparing the polystyrene-based nanocomposite. A polystyrene-based nanocomposite is prepared from an aluminosilicate layered inorganic material and a polystyrene-based resin, wherein the aluminosilicate layered inorganic material is an organized aluminosilicate layered inorganic material comprising a polystyrene-based copolymer having an amine salt represented by a formula 2 introduced into the interlayer of an aluminosilicate layered inorganic material. In the formula 2, m is an integer of 1-100; x is an integer of 2-200; and X is F, Cl, Br or I.

Description

Polystyrene nanocomposite and its preparation method {Polystyrenic nanocomposite and its preparing method}

1 shows the number average molecular weights ( M _n ) of Synthesis Examples 5 and 11,

2 shows the FT-IR spectra of Preparation Examples 5 and 11;

3 shows EDS spectra of Preparation Examples 5 and 11;

Figure 4 shows the X-ray diffraction diagrams of Preparation Examples 5 and 11.

5 is a TEM image comparing Preparation Example 8 with sodium montmorillonite (MMT), which is a layered silicate.

FIG. 6 shows X-ray diffraction diagrams comparing Examples 5 to 8 with Comparative Example 1, and MMT (sodium montmorillonite) which is a layered silicate.

The present invention relates to an organic aluminosilicate layered inorganic material containing a polystyrene structure and a method for preparing the same, and more particularly, to a polystyrene copolymer and an amine chloride in which a pyridine group is introduced between layers of an aluminosilicate layered inorganic material. An onium group containing a polystyrene structure formed by the reaction is inserted into an organic aluminosilicate layered inorganic material containing a novel polystyrene structure having a large interlayer distance, excellent thermal stability, and improved compatibility with a polystyrene resin. And it relates to a manufacturing method thereof.

Polystyrene resin produced using styrene as a monomer is a material having excellent properties for the price and has the advantage of facilitating attractive molded parts by a wide range of molding technologies. In addition, it has a relatively low absorption rate and no toxicity. Polystyrene is mainly used for household goods such as toys and packaging containers. In addition, there are various uses such as signs, billboards, lighting fixtures, and aquariums.

Another technical field related to the present invention is the field of polymer nanocomposites, and recently, a method for nanocompositing an inorganic layered silicate material in an organic polymer as a method for improving the mechanical, thermal, and gas barrier properties of the organic polymer material. This has been applied in various ways. In other words, many studies have been conducted to prepare polymer nanocomposites having excellent properties over the properties of existing polymers by peeling each plate of inorganic layered silicate and uniformly dispersing it in a polymer medium. Representative methods of preparing such polymer-based nanocomposites include direct polymerization, solution mixing, and melt mixing, and these methods disperse particle sizes of conventional inorganic fillers / reinforcements to nanometer units. It aims to compensate for the shortcomings of the filler composites.

However, in order to secure dispersibility, which is the final goal in the production of polystyrene nanocomposites using the concept of nanocomposites, a method of using a compatibilizer such as styrene-maleic anhydride copolymer (PS-MA), an lipophilic layered inorganic material To prepare a nanocomposite by intercalating in a low molecular weight polystyrene solution to make a masterbatch, followed by melt mixing. 2002-0050493], A method for producing a nanocomposite by direct polymerization from a layered inorganic material lipophilic with a polymerizable modifier [Korea Patent Publication; 10-2004-0087651, M. Okamoto, S. Morita, H. Taguchi, Y. H. Kim, T. Kotaka, H. Tateyama, Polymer, 41, 3887 (2000).

However, patents and papers to date have not been successful in confirming the increase in physical properties through complete exfoliation of the nanocomposite by direct solution mixing or melt mixing without using additives such as compatibilizers.

Therefore, the present inventors have studied to solve the above problems, and as a result, by introducing a functional group capable of cation exchange reaction in the side chain of polystyrene and using this as an organic agent to modify the layered inorganic material by cation exchange reaction, Increased content of aromatic cyclic compounds improves heat resistance, extends the interlayer distance, and when mixed and dispersed with polystyrene-based resins to nanocomposite, polystyrene directly without using a compatibilizer or a process of preparing a master batch. The present invention was completed by knowing that nanocomposite of a resin and a layered inorganic material is possible.

Accordingly, the present invention provides a method for producing a polystyrene-based nanocomposite having excellent dispersibility, high transparency and excellent thermal stability by using a simple method without using a compatibilizer or omitting a process for preparing a master batch, and the method The object is to provide a polystyrene-based nanocomposite.

In addition, another object of the present invention is to provide a polystyrene-based nanocomposite having excellent haze properties, which is a disadvantage of the general layered inorganic polymer nanocomposite.

In addition, another object of the present invention to provide a method for producing a polystyrene-based layered inorganic nanocomposite having excellent thermal stability and haze characteristics.

The present invention provides a polystyrene-based nanocomposite prepared by nanocompositing an aluminosilicate layered inorganic material and a polystyrenic resin,

The aluminosilicate layered inorganic material is characterized in that the polystyrene-based nanocomposite which is an organic aluminosilicate layered inorganic material in which a polystyrene copolymer having an amine salt represented by the following formula (2) is introduced between the layers;

[Formula 2]

또는

으로 표시되는 화합물이며, x는 2 ~ 200 사이의 정수이다. 또한, X는 F, Cl, Br, I를 포함하는 할로겐계 원소 중에서 선택된 것이다. In Chemical Formula 2, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200. X is selected from halogen-based elements including F, Cl, Br, and I.

In addition, the present invention includes a method for producing a polystyrene-based nanocomposite having excellent dispersibility, high transparency, and excellent thermal stability by a simple method without using a compatibilizer or omitting a process for preparing a master batch.

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

In the present invention, a polystyrene-based copolymer having a pyridine group and an onium group containing a polystyrene structure formed by an amine chloride reaction are inserted between layers of an aluminosilicate layered inorganic material, thereby increasing the interlayer distance and providing excellent thermal stability. The present invention relates to an organic aluminosilicate layered inorganic material containing a novel polystyrene structure having improved compatibility with polystyrene resins and a method for producing the same.

The polystyrene-based nanocomposite of the present invention is characterized in that the nano-composite is mixed and dispersed with a polystyrenic resin and an organic aluminosilicate layered inorganic material modified with a polystyrene copolymer.

Polystyrene resins used in the present invention is a conventional polystyrene, high impact polystyrene (HIPS), poly (acrylonitrile-butadiene-styrene) that is generally applied in the art [poly (acrylonitril-butadiene- styrene), ABS], and the like.

On the other hand, the organic aluminosilicate layered inorganic material modified with the polystyrene-based copolymer is produced by reacting a polystyrene-based copolymer having a pyridine group represented by the following formula (1) and various kinds of amines between the layers of the aluminosilicate layered inorganic material The ammonium salt introduced polymer represented by the formula (2) is inserted.

[Formula 1]

또는

으로 표시되는 화합물이며, x는 2 ~ 200 사이의 정수이다.In Chemical Formula 1, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200.

In the present invention, the polystyrene-based copolymer having an amine salt as an organic polymer introduced between the layers of the aluminosilicate-based layered inorganic material is reacted with various types of aqueous hydrogen halide solutions to the polystyrene-based copolymer having a pyridine group represented by the formula (1). To produce a copolymer represented by the formula (2).

The following Reaction Scheme 1 illustrates a process of producing a polystyrene copolymer having an amine salt represented by Formula 2 by reacting a polystyrene copolymer having a pyridine group represented by Formula 1 with an aqueous hydrogen halide solution.

Scheme 1

In Reaction Scheme 1, m, x, R and X are as defined in Formula 2, respectively.

The following scheme 2 shows a process in which the polystyrene-based copolymer having a pyridine group represented by the formula (1) is introduced into the layered silicate by reacting with an aqueous hydrogen halide solution.

Scheme 2

In Reaction Scheme 2, m, x, R and X are as defined in Formula 2, respectively.

Polystyrene-based copolymer having an amine salt represented by the formula (2) can be used as a very low polar lipophilic modifier, having a functional group content of 1 ~ 7 mmeq / g greatly increases the hydrophilicity of the aluminosilicate layered inorganic material In addition to reducing the number average molecular weight of 500 ~ 60,000g / mol has the property to significantly increase the interlayer distance of the aluminosilicate-based inorganic layer material. In addition, the polystyrene-based copolymer in which the amine salt represented by Chemical Formula 2 is introduced has a number average molecular weight in the range of 3000 to 100,000, more preferably the number average molecular weight is adjusted in the range of 3,000 to 60,000, most preferably The number average molecular weight is adjusted in the range of 12,000 to 15,000. At this time, if the number average molecular weight is less than 3,000 there is a problem that can not secure sufficient heat resistance, if it exceeds 100,000, the relative molecular weight is large is disadvantageous to the cation exchange reaction is not preferable.

In addition, since the aromatic content is higher than the lipophilic alumino layered silicate inorganic material modified by the conventional low molecular weight alkyl group, the heat resistance is excellent, and thus the poor heat resistance problem of the lipophilic alumino layered silicate layered inorganic material can be solved. have.

In the present invention, the organic layered inorganic material is

Polyvinyl copolymer solution was prepared by dissolving 4-vinylpyridine or 2-vinylpyridine and styrene in a polar solvent in the presence of an inert gas, and then adding a reaction initiator while maintaining the temperature in the range of 40 to 80 ° C. Precipitation, washing and drying to prepare a polystyrene copolymer having a pyridine group represented by Formula 1;

Preparing a polystyrene-based copolymer having an amine salt represented by the following Formula 2 by amine salting the polystyrene copolymer into which the pyridine group is introduced; And

Preparing an organic aluminosilicate layered inorganic material by modifying the aluminosilicate layered inorganic material and the polystyrene copolymer having the amine salt in water, a polar solvent or a mixed solvent thereof.

It is prepared to include;

[Formula 1]

또는

으로 표시되는 화합물이며, x는 2 ~ 200 사이의 정수이다.In Chemical Formula 1, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200.

[Formula 2]

또는

으로 표시되는 화합물이며, x는 2 ~ 200 사이의 정수이다. 또한, X는 F, Cl, Br, I를 포함하는 할로겐계 원소 중에서 선택된 것이다. In Chemical Formula 2, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200. X is selected from halogen-based elements including F, Cl, Br, and I.

First, 4-vinylpyridine or 2-vinylpyridine purified using styrene purified through extraction and distillation under reduced pressure and disposable prepacked columns as inhibitor remover. ) Is a 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) initiator recrystallized from methanol (MeOH) under a nitrogen atmosphere for 3 to 24 hours at a temperature of 100 ~ 160 ℃ A copolymer solution of 1-20% of this controlled reactant concentration is prepared.

The copolymer solution thus prepared is precipitated in methanol, and the copolymer powder obtained is dried in a vacuum oven. Gas chromatography (GC) was used to determine the repeating units of 2-vinylpyridine and styrene in the copolymer prepared by the above method, and gel permeation chromatography (gel) The number average molecular weight was measured using permeation chromatography (GPC). The polystyrene-based copolymer having an amine salt represented by Formula 2 may have a number average molecular weight in the range of 3000 ~ 100,000.

Hereinafter, the manufacturing method of the organic-ized aluminosilicate type layered inorganic material containing the polystyrene structure of this invention is demonstrated in detail as an embodiment.

The present invention provides a method for preparing an organic layered inorganic material in which an organic polymer is introduced between layers of an aluminosilicate layered inorganic material, preparing a polystyrene copolymer having 4-vinylpyridine or 2-vinylpyridine introduced therein. Amine chloride step of the polystyrene copolymer in which -vinylpyridine or 2-vinylpyridine is introduce | transduced, and thereby organicizing an aluminosilicate based layered inorganic material.

In order to prepare a lipophilic layered silicate using a polystyrene-based copolymer having an amine salt, a polystyrene-based copolymer having an amine group represented by Formula 1 was slowly passed through a nitrogen gas through a reactor equipped with a stirrer, a nitrogen injection device, and a condenser. The reaction was performed with bromic acid and layered silicate at 3 ° C. for 24 h. Through this, the polystyrene-based copolymer having an amine salt represented by the formula (2) was modified by a cation exchange reaction using an organic agent to lipophilic the layered silicates.

The layered silicate is commonly used in the art, but is not particularly limited. Specifically, kaolinite, spentine, talc, pyropyllite, synthetic mica, Layered silicates selected from montmoillonite, hectolite, smectite and saponite may be used.

The polystyrene-based copolymer used as the organic agent of the present invention performs a cation exchange reaction within the range of 1 to 50% by weight with respect to the layered silicate, and if the content is less than 1% by weight, the amount thereof is insignificant so that the lipophilic group of the layered silicate inorganic material is used. If it is not possible to obtain a ignition effect and exceeds 50% by weight, the overall physical properties are lowered.

The layered silicate, the polystyrene-based copolymer organic agent having an amine salt represented by the formula (2) is a cation for 1 to 20 hours at a temperature of 30 ~ 80 ℃ using water, a polar solvent or a mixed solvent of water and a polar solvent It is modified by an exchange reaction to exhibit lipophilic properties. In this case, the polar solvent is one selected from chloroform (CHCl ₃ ), toluene, xylene, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethylformamide (DMF) Or two or more kinds.

The lipophilic polystyrene-based layered inorganic material of the present invention prepared by the manufacturing method as described above has a layered structure having a layer thickness of 5 to 50 micrometers and a length of 1000 to 5000 micrometers, and an interlayer distance is disordered and about 50 to 200 Å. In addition, the lipophilic polystyrene-based layered inorganic material of the present invention is obtained in powder form and has excellent heat resistance as the pyrolysis temperature is about 300 to 450 ° C.

In the present invention, by mixing and dispersing the organic aluminosilicate layered inorganic material modified with a polystyrene copolymer having the above characteristics and the polystyrene resin, it is excellent in compatibility with the polystyrene resin, so that a separate compatibilizer It is possible to produce a polystyrene-based nanocomposite having excellent dispersibility and excellent transparency and thermal properties without using.

In order to achieve the above object, the present invention deals with nanocomposite production method by the solution mixing and melt mixing method.

First, according to the solution mixing method, a polystyrene-based resin in pellet form is dissolved in a polar organic solvent to form a transparent homogeneous solution, and then completely mixed with a solvent in which the layered inorganic material is dispersed, thereby completely exfoliating the layered inorganic material. After preparing a polystyrene / layered inorganic material solution in a uniform state, and coating it on a substrate and dried to produce a nanocomposite film, the polystyrene-based nanocomposite film has excellent dispersibility and improved thermal stability. It is done.

In addition, the melt-mixing method is characterized by a polystyrene-based nanocomposite obtained through melt mixing using a layered inorganic material and a brabender, wherein the polystyrene-based resin in pellet form is modified with a polystyrene-based copolymer having excellent compatibility.

Hereinafter, the respective components of the polystyrene-based nanocomposite according to the present invention will be described in detail.

Polystyrene is a common polymer commonly applied in the art.

The polar organic solvent according to the present invention is selected from chloroform (CHCl ₃ ), toluene, xylene, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF) and the like. Use at least one polar solvent selected.

In the polystyrene nanocomposite film prepared from the polar organic solvent, the styrene polymer is preferably contained in an amount of 85 to 99.5% by weight and the layered inorganic material in a range of 0.5 to 15% by weight. When the content of polystyrene is less than 85% by weight, that is, when the amount of the layered silicate is used in excess of 15% by weight, complete peeling of the layered silicate does not occur, resulting in lowered transparency. On the other hand, when the content of the polystyrene polymer is used in excess of 99.5% by weight, that is, when the layered silicate is used in less than 0.5% by weight, the effect of increasing the thermal stability by the layered silicate is not expressed.

In addition, the layered silicate used in the production of the polystyrene nanocomposite film of the present invention used a lipophilic layered silicate surface-modified with a polystyrene copolymer.

In order to prepare a polystyrene nanocomposite solution for the polystyrene nanocomposite film according to the present invention, the lipophilic layered silicate is dispersed in a polar solvent such as chloroform, and a polystyrene solution of 1 to 20% by weight is prepared in a separate container. The mixture, and stirred sufficiently at 100 ~ 3000 rpm with a mechanical stirrer at room temperature to prepare a polystyrene nanocomposite solution. The obtained polystyrene nanocomposite solution was coated on a glass substrate with a thickness of 100 to 110 μm, dried at room temperature for 1 to 10 hours, and then heated to a temperature of 60 to 120 ° C. for 1 to 12 hours. All.

In addition, melt mixing is prepared in a range from 85 to 99.5% by weight of polystyrene pellets and from 0.5 to 15% by weight of lipophilic layered silicates using a brabender at 210 to 240 ° C. The styrene polymer is preferably contained in the range of 85 to 99.5% by weight. The reason is as specified in the solution mixing method.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

Synthesis Example: Synthesis of Copolymer Using 2-vinylpyridine or 4-vinylpyridine and Styrene

Synthesis Example 1: Copolymer of 2-vinylpyridine and styrene (2VP-a)

For purification of styrene, hydroquinone, a polymerization inhibitor, was extracted and removed several times using a 10% by weight aqueous sodium hydroxide (NaOH) solution and a separatory funnel. The weight ratio of styrene and 10% by weight of sodium hydroxide (NaOH) aqueous solution extracted with a separatory funnel was 1: 1. The styrene obtained in this way was removed with water using magnesium sulfate (MgSO ₄₎ and distilled under reduced pressure at 40 ℃ to obtain a clear liquid purified styrene monomer. In order to purify 2-vinylpyridine, 4-tert-butylcatechol, a polymerization inhibitor, was removed using a disposable prepacked columns as inhibitor remover. 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) used as an initiator was recrystallized from methanol (MeOH) and used as 2,2,6,6-tetramethylpiperidine-1-oxyl ( 2,2,6,6-tetramethylpiperidin-1-oxyl) was used without purification. In order to adjust the molecular weight by calculating the degree of reaction by gas chromatography (GC), anisole was added with 10% by weight of the total monomer content. To synthesize a copolymer of purified styrene and 2-vinylpyridine (2COP), styrene was added to a 500 ml reactor flask equipped with a stirrer, a temperature controller, and a nitrogen injection system. ) (107.02 g, 1.02 mol), 2-vinylpyridine (5.52 g, 0.05 mol), 2,2,6,6-tetramethylpiperidine-1-oxyl (2,2,6,6 -tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2'-azobisisobutyronitrile (0.13 g, 0.78 mmol) in solid phase ) Was added. In order to calculate the molecular weight of the reactants, sampling of the initial reactants was performed by gas chromatography. Liquid nitrogen and isopropylalcohol (isopropylalcohol) are prepared respectively, and freeze-pump-thaw is performed three times to degassing. After degassing was completed, the reactor was filled with nitrogen, and then synthesized using a living radical polymerization method at 138 ° C. Gas chromatography was measured every 20 minutes while maintaining the temperature of the solution at 138 ° C. to terminate the reaction when the desired molecular weight (14,000 g / mol) was polymerized. Upon completion of the reaction, the mixture was diluted with anhydrous tetrahydrofuran, precipitated in anhydrous methanol, and washed three times. Thereafter, the resultant was dried in a vacuum oven at 60 ° C. for 24 hours to prepare a copolymer (2VP-a) [yield 25%].

[Formula 1-1]

In Chemical Formula 1-1, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2899 (CH stretching), 1575 ~ 1615 (C = C and C = N), 1252 (CH in plane)

Integral ratio was calculated by NMR in order to determine the repeating units of 2-vinylpyridine and styrene in the copolymer (2VP-a) prepared by the above method, and gel permeation chromatography (gel) Copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index (PDI)) are shown in Table 1 using permeation chromatography.

Synthesis Example 2 Copolymer of 2-vinylpyridine and Styrene (2VP-b)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (105.12g, 1.01mol), 2-vinylpyridine (7.45g, 0.07mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. A copolymer (2VP-b) was prepared by the above method [yield 27%].

[Formula 1-2]

In Chemical Formula 1-2, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3210 (CH stretching), 2906 (CH stretching), 1570 ~ 1615 (C = C and C = N), 1249 (CH in plane)

Integral ratios were calculated by NMR in order to determine the repeating units of 2-vinylpyridine and styrene in the copolymer (2VP-b), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 3: Copolymer of 2-vinylpyridine and styrene (2VP-c)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (101.29g, 0.97mol), 2-vinylpyridine (11.3g, 0.1mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. The copolymer (2VP-c) was produced by the above method [yield 25%].

[Formula 1-3]

In Formula 1-3, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2900 (CH stretching), 1570 ~ 1615 (C = C and C = N), 1250 (CH in plane)

Integral ratio was calculated by NMR in order to determine the repeating units of 2-vinylpyridine and styrene in the copolymer (2VP-c), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 4 Copolymer of 2-vinylpyridine and Styrene (2VP-d)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (98.55g, 0.94mol), 2-vinylpyridine (14.08g, 0.12mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. A copolymer (2VP-d) was prepared by the above method [yield 23%].

[Formula 1-4]

In Formula 1-4, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2910 (CH stretching), 1570 ~ 1610 (C = C and C = N), 1250 (CH in plane)

Integral ratios were calculated by NMR in order to determine the repeating units of 2-vinylpyridine and styrene in the copolymer (2VP-d), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 5 Copolymer of 2-vinylpyridine and Styrene (2VP-e)

The reaction sequence was the same as in Synthesis Example 1, and the monomer was styrene (90.11 g, 0.86 mol), 2-vinylpyridine (22.53 g, 0.2 mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.31 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.79 mmol) was added. A copolymer (2VP-e) was prepared by the above method [yield 22%].

[Formula 1-5]

In Formula 1-5, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2903 (CH stretching), 1568 ~ 1609 (C = C and C = N), 1252 (CH in plane)

Integral ratios were calculated by NMR in order to determine the repeating units of 2-vinylpyridine and styrene in the copolymer (2VP-e), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 and FIG. 1, respectively.

Synthesis Example 6 Copolymer of 2-vinylpyridine and Styrene (2VP-f)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (85.82g, 0.82mol), 2-vinylpyridine (26.81g, 0.24mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.31 mL of anisole and 2,2'-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.79 mmol) was added. A copolymer (2VP-f) was prepared by the above method [yield 20%].

[Formula 1-6]

In Formula 1-6, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2900 (CH stretching), 1572 ~ 1620 (C = C and C = N), 1253 (CH in plane)

Integral ratios were calculated by NMR in order to determine the repeating units of 2-vinylpyridine and styrene in the copolymer (2VP-f), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 7: Copolymer of 4-vinylpyridine and styrene (4VP-a)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (107.02g, 1.02mol), 4-vinylpyridine (5.52g, 0.05mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. The copolymer (4VP-a) was produced by the above method [yield 28%].

[Formula 1-7]

In Chemical Formula 1-7, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2905 (CH stretching), 1572 ~ 1618 (C = C and C = N), 1251 (CH in plane)

Integral ratio was calculated by NMR to determine the repeating units of 4-vinylpyridine and styrene in the copolymer (4VP-a), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 8 Copolymer of 4-vinylpyridine and Styrene (4VP-b)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (105.12g, 1.01mol), 4-vinylpyridine (7.45g, 0.07mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. A copolymer (4VP-b) was prepared by the above method [yield 26%].

[Formula 1-8]

In Formula 1-8, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2905 (CH stretching), 1570 ~ 1617 (C = C and C = N), 1252 (CH in plane)

Integral ratio was calculated by NMR in order to determine the repeat units of 4-vinylpyridine and styrene in the copolymer (4VP-b), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 9: Copolymer of 4-vinylpyridine and styrene (4VP-c)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (101.29g, 0.97mol), 4-vinylpyridine (11.3g, 0.1mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. The copolymer (4VP-c) was produced by the above method [yield 26%].

[Formula 1-9]

In Formula 1-9, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2904 (CH stretching), 1567 ~ 1615 (C = C and C = N), 1249 (CH in plane)

Integral ratio was calculated by NMR in order to determine the repeating units of 4-vinylpyridine and styrene in the copolymer (4VP-c), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 10 Copolymer of 4-vinylpyridine and styrene (4VP-d)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (98.55g, 0.94mol), 4-vinylpyridine (14.08g, 0.12mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.3 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.78 mmol) was added. A copolymer (4VP-d) was prepared by the above method [yield 25%].

[Formula 1-10]

In Formula 1-10, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2901 (CH stretching), 1572 ~ 1613 (C = C and C = N), 1250 (CH in plane)

Integral ratios were calculated by NMR in order to determine the repeat units of 4-vinylpyridine and styrene in the copolymer (4VP-d), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Synthesis Example 11: Copolymer of 4-vinylpyridine and styrene (4VP-e)

The reaction sequence was the same as in Synthesis Example 1, and the monomer was styrene (90.11 g, 0.86 mol), 4-vinylpyridine (22.53 g, 0.2 mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.31 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2'-azobisisobutyronitrile) (0.13 g, 0.79 mmol) was added. A copolymer (4VP-e) was prepared by the above method [yield 24%].

[Formula 1-11]

In Formula 1-11, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2901 (CH stretching), 1571 ~ 1617 (C = C and C = N), 1250 (CH in plane)

Integral ratio was calculated by NMR in order to determine the repeat units of 4-vinylpyridine and styrene in the copolymer (4VP-e), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 and FIG. 1, respectively.

Synthesis Example 12 Copolymer of 4-vinylpyridine and Styrene (4VP-f)

The reaction sequence is the same as in Synthesis Example 1, the monomer is styrene (85.82g, 0.82mol), 4-vinylpyridine (26.81g, 0.24mol), 2,2,6,6-tetra Methylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidin-1-oxyl) (0.3 g, 0.19 mmol), 11.31 mL of anisole and 2,2′-azobisisobutyl in solid form Nitrile (2,2′- azobisisobutyronitrile) (0.13 g, 0.79 mmol) was added. A copolymer (4VP-f) was prepared by the above method [yield 24%].

[Formula 1-12]

In Formula 1-12, x is an integer between 2 and 200.

FT-IR (cm ^-1 ): 3100 ~ 3200 (CH stretching), 2896 (CH stretching), 1571 ~ 1613 (C = C and C = N), 1251 (CH in plane)

Integral ratios were calculated by NMR in order to determine the repeating units of 4-vinylpyridine and styrene in the copolymer (4VP-f), and gel permeation chromatography was used. The copolymer composition ratio, number average molecular weight ( M _n ) and molecular weight distribution (polydispersity index; PDI) are shown in Table 1 below.

Preparation Example: Preparation of lipophilic layered silicate using copolymer

Preparation Example 1: Preparation of lipophilic layered silicate (M2VP-a)

In order to prepare the lipophilic layered silicate (M2VP-a) through ion exchange reaction, 5 g of the copolymer (2VP- After a) and 2.4 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, the temperature of the reactor was raised to 70 ° C. Then, 0.61 g of sodium montmorillonite (MMT) swelled in 11.62 g of distilled water was slowly added using a dropping funnel, followed by 250 g of dimethylformamide (DMF) at 5 hour intervals for 15 hours. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M2VP-a). .

FT-IR (cm ^-1 ): 3400 (MMT), 3100 ~ 3200 (CH stretching), 2900 (CH stretching), 1570 ~ 1615 (C = C and C = N), 1050 (MMT)

Thermal properties, interlayer distance and dispersibility of the prepared lipophilic layered silicate (M2VP-a) are shown in Table 2 below.

Preparation Example 2: Preparation of lipophilic layered silicate (M2VP-b)

In order to prepare the lipophilic layered silicate (M2VP-b) through ion exchange reaction, 5 g of the copolymer (2VP- b) and 3.2 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 0.82 g of sodium montmorillonite (MMT) swelled in 15.49 g of distilled water was slowly added using a dropping funnel, followed by 300 g of dimethylformamide (DMF) for 15 hours at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare an lipophilic layered silicate (M2VP-b). .

FT-IR (cm ^-1 ): 3398 (MMT), 3100 ~ 3200 (CH stretching), 2902 (CH stretching), 1565 ~ 1620 (C = C and C = N), 1048 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M2VP-b) are shown in Table 2 below.

Preparation Example 3: Preparation of lipophilic layered silicate (M2VP-c)

In order to produce a lipophilic layered silicate (M2VP-c) through ion exchange reaction, a 5 g copolymer (2VP- c) and 4.8 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 1.22 g of sodium montmorillonite (MMT) swelled in 23.24 g of distilled water was slowly added using a dropping funnel, followed by 400 g of dimethylformamide (DMF) for 15 hours at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M2VP-c). .

FT-IR (cm ^-1 ): 3405 (MMT), 3100 ~ 3200 (CH stretching), 2905 (CH stretching), 1571 ~ 1620 (C = C and C = N), 1052 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M2VP-c) are shown in Table 2 below.

Preparation Example 4: Preparation of lipophilic layered silicate (M2VP-d)

In order to prepare a lipophilic layered silicate (M2VP-d) through ion exchange reaction, 5g of the copolymer (2VP- d) and 6 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 1.53 g of sodium montmorillonite (MMT) swelled in 29.01 g of distilled water was slowly added using a dropping funnel, followed by 15 hours of 450 g of dimethylformamide (DMF) at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare an lipophilic layered silicate (M2VP-d). .

FT-IR (cm ^-1 ): 3400 (MMT), 3100 ~ 3205 (CH stretching), 2904 (CH stretching), 1569 ~ 1617 (C = C and C = N), 1054 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M2VP-d) are shown in Table 2 below.

Preparation Example 5 Preparation of Lipophilic Layered Silicate (M2VP-e)

In order to produce a lipophilic layered silicate (M2VP-e) through ion exchange reaction, 5 g of copolymer (2VP-) synthesized in Synthesis Example 5 was added to a 2000 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler. e) and 9.58 mL of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 2.44 g of sodium montmorillonite (MMT) swelled in 46.38 g of distilled water was gradually added using a dropping funnel, followed by 700 g of dimethylformamide (DMF) for 15 hours at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M2VP-e). .

FT-IR (cm ^-1 ): 3402 (MMT), 3100 ~ 3200 (CH stretching), 2905 (CH stretching), 1572 ~ 1618 (C = C and C = N), 1048 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M2VP-e) are shown in Table 2 below.

Preparation Example 6 Preparation of Lipophilic Layered Silicate (M2VP-f)

In order to produce a lipophilic layered silicate (M2VP-f) through ion exchange reaction, a 5 g copolymer (2VP-) synthesized in Synthesis Example 6 was added to a 2000 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel, and a cooler. f) and 11.4 mL of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 2.91 g of sodium montmorillonite (MMT) swelled in 55.2 g of distilled water was slowly added using a dropping funnel, followed by 900 g of dimethylformamide (DMF) at 5 hour intervals for 15 hours. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M2VP-f). .

FT-IR (cm ^-1 ): 3400 (MMT), 3102 ~ 3207 (CH stretching), 2902 (CH stretching), 1571 ~ 1617 (C = C and C = N), 1051 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M2VP-f) are shown in Table 2 below.

Preparation Example 7: Preparation of lipophilic layered silicate (M4VP-a)

In order to prepare a lipophilic layered silicate (M4VP-a) through ion exchange reaction, a 5 g copolymer (4VP-) synthesized in Synthesis Example 7 was added to a 1000 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel, and a cooler. After a) and 2.4 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, the temperature of the reactor was raised to 70 ° C. Then, 0.61 g of sodium montmorillonite (MMT) swelled in 11.62 g of distilled water was slowly added using a dropping funnel, followed by 250 g of dimethylformamide (DMF) at 5 hour intervals for 15 hours. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M4VP-a). .

FT-IR (cm ^-1 ): 3404 (MMT), 3100 ~ 3200 (CH stretching), 2906 (CH stretching), 1565 ~ 1614 (C = C and C = N), 1048 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M4VP-a) are shown in Table 2 below.

Preparation Example 8: Preparation of lipophilic layered silicate (M4VP-b)

In order to prepare a lipophilic layered silicate (M4VP-b) through ion exchange reaction, 5 g of the copolymer (4VP- b) and 3.2 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 0.82 g of sodium montmorillonite (MMT) swelled in 15.49 g of distilled water was slowly added using a dropping funnel, followed by 300 g of dimethylformamide (DMF) for 15 hours at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M4VP-b). .

FT-IR (cm ^-1 ): 3401 (MMT), 3100 ~ 3200 (CH stretching), 2903 (CH stretching), 1568 ~ 1615 (C = C and C = N), 1047 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M4VP-b) are shown in Table 2 below.

Preparation Example 9 Preparation of Lipophilic Layered Silicate (M4VP-c)

In order to prepare the lipophilic layered silicate (M4VP-c) through ion exchange reaction, 5 g of the copolymer (4VP-) synthesized in Synthesis Example 9 was added to a 1000 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel, and a cooler. c) and 4.8 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 1.22 g of sodium montmorillonite (MMT) swelled in 23.24 g of distilled water was slowly added using a dropping funnel, followed by 400 g of dimethylformamide (DMF) for 15 hours at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M4VP-c). .

FT-IR (cm ^-1 ): 3405 (MMT), 3100 ~ 3200 (CH stretching), 2900 (CH stretching), 1570 ~ 1616 (C = C and C = N), 1052 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M4VP-c) are shown in Table 2 below.

Preparation Example 10 Preparation of Lipophilic Layered Silicate (M4VP-d)

In order to prepare the lipophilic layered silicate (M4VP-d) through ion exchange reaction, 5g of the copolymer (4VP- d) and 6 ml of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 1.53 g of sodium montmorillonite (MMT) swelled in 29.01 g of distilled water was slowly added using a dropping funnel, followed by 15 hours of 450 g of dimethylformamide (DMF) at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M4VP-d). .

FT-IR (cm ^-1 ): 3400 (MMT), 3100 ~ 3200 (CH stretching), 2901 (CH stretching), 1563 ~ 1613 (C = C and C = N), 1049 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M4VP-d) are shown in Table 2 below.

Preparation Example 11: Preparation of lipophilic layered silicate (M4VP-e)

In order to prepare the lipophilic layered silicate (M4VP-e) through ion exchange reaction, 5 g of the copolymer (4VP- e) and 9.58 mL of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 2.44 g of sodium montmorillonite (MMT) swelled in 46.38 g of distilled water was gradually added using a dropping funnel, followed by 700 g of dimethylformamide (DMF) for 15 hours at 5 hour intervals. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M4VP-e). .

FT-IR (cm ^-1 ): 3401 (MMT), 3100 ~ 3200 (CH stretching), 2902 (CH stretching), 1570 ~ 1618 (C = C and C = N), 1049 (MMT)

Thermal properties, interlayer distance and dispersibility of the prepared lipophilic layered silicate (M4VP-e) are shown in Table 2 below.

Preparation Example 12 Preparation of Lipophilic Layered Silicate (M4VP-f)

In order to produce a lipophilic layered silicate (M4VP-f) through ion exchange reaction, 5 g of copolymer (4VP-) synthesized in Synthesis Example 12 was added to a 2000 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler. f) and 11.4 mL of bromic acid (1 N / L) and 45 g of dimethylformamide (DMF) were added, and the temperature of the reactor was raised to 70 ° C. Then, 2.91 g of sodium montmorillonite (MMT) swelled in 55.2 g of distilled water was slowly added using a dropping funnel, followed by 900 g of dimethylformamide (DMF) at 5 hour intervals for 15 hours. Was added in portions and stirred vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and then lyophilized for 48 hours to prepare a lipophilic layered silicate (M4VP-f). .

FT-IR (cm ^-1 ): 3402 (MMT), 3100 ~ 3203 (CH stretching), 2902 (CH stretching), 1570 ~ 1615 (C = C and C = N), 1052 (MMT)

Thermal properties, interlayer distance, and dispersibility of the prepared lipophilic layered silicate (M4VP-f) are shown in Table 2 below.

Comparative Example 1: Lipophilic Layered Silicate (Cloisite 15A)

       In order to compare with the lipophilic layered silicates synthesized in Preparation Examples 1 to 12, Cloisite 15A (Dimethyl dihydrogenated tallow ammonium), which is commercially available from Southern Clay Products, was purchased and compared to thermal properties, interlayer distance, and dispersibility. Shown in

Comparative Example 2: Lipophilic Layered Silicate (Cloisite 20A)

       In order to compare with the lipophilic layered silicates synthesized in Preparation Examples 1 to 12, Cloisite 20A (Dimethyl dihydrogenated tallow ammonium), which is commercially available from Southern Clay Products, was purchased and compared to thermal properties, interlayer distance, and dispersibility. Shown in

Comparative Example 3: Lipophilic Layered Silicate (Cloisite 30B)

       In order to compare with the lipophilic layered silicates synthesized in Preparation Examples 1 to 12, Cloisite 30B (Methyl tallow bis-2-hydroxy ethyl quarternary ammonium), which is commercially available from Southern Clay Products, was purchased to obtain thermal properties, interlayer distance, and dispersibility. The comparison is shown in Table 2 below.

As shown in Table 2, it can be seen that the organic aluminosilicate layered inorganic material containing the polystyrene structure of the present invention is excellent in dispersibility.

EXAMPLES Preparation of Polystyrene Nanocomposites Using Lipophilic Layered Silicates

Example 1 Preparation of Polystyrene Nanocomposite Film (M2VP-0.5 / PS)

The organic agent used for the synthesis of lipophilic layered silicate (M2VP) is a copolymer of 2-vinylpyridine and styrene (2VP) whose molecular weight is controlled by living radical polymerization, and has a number average molecular weight The molecular weight distribution indices are 14,000 g / mol and 1.41, respectively. 0.02 g of lipophilic layered silicate (M2VP) was added to 20 g of chloroform (chloroform) and dispersed for 3 hours by ultrasound, and then 4 g of polystyrene (PS) was added to a solution dissolved in 33.41 g of chloroform. The mixture was stirred for 1 day at 400 rpm using a mechanical stirrer. The prepared polymer solution was cast by adjusting the solid content to a thickness of 100 μm on a glass plate, dried at room temperature for 90 minutes, and then placed in a vacuum oven for 3 hours at 60 ° C. and 1 hour at 100 ° C. for a lipophilic layered silicate ( M2VP) was prepared in a polystyrene nanocomposite film (M2VP-0.5) dispersed 0.5wt%.

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M2VP-0.5) are shown in Table 3 below.

Example 2: Preparation of Polystyrene Nanocomposite Film (M2VP-1 / PS)

0.04 g of lipophilic layered silicate (M2VP) synthesized as in Example 1 was added to 20 g of chloroform and dispersed for 3 hours by ultrasound, and then 4 g of polystyrene (PS) was 33.67 g of chloroform. Was added to the solution dissolved in. Preparation of the polystyrene nanocomposite film (M2VP-1) using this mixture was carried out in the same manner as in Example 1, to prepare a polystyrene nanocomposite film (M2VP-1) in which the lipophilic layered silicate (M2VP) 1wt% dispersed. .

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M2VP-1) are shown in Table 3 below.

Example 3: Preparation of Polystyrene Nanocomposite Film (M2VP-3 / PS)

0.12 g of lipophilic layered silicate (M2VP) synthesized as in Example 1 was added to 25 g of chloroform and dispersed for 3 hours by ultrasound, and 4 g of polystyrene (PS) was 29.74 g of chloroform. Was added to the solution dissolved in. Preparation of the polystyrene nanocomposite film (M2VP-3) using this mixture was carried out in the same manner as in Example 1, to prepare a polystyrene nanocomposite film (M2VP-3) in which the lipophilic layered silicate (M2VP) 3wt% dispersed. .

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M2VP-3) are shown in Table 3 below.

Example 4: Preparation of polystyrene nanocomposite film (M2VP-5 / PS)

0.2 g of lipophilic layered silicate (M2VP) synthesized as in Example 1 was added to 25 g of chloroform (chloroform) and dispersed for 3 hours by ultrasound, and 4 g of polystyrene (PS) was 30.8 g of chloroform. Was added to the solution dissolved in. Preparation of the polystyrene nanocomposite film (M2VP-5) using this mixture was carried out in the same manner as in Example 1, to prepare a polystyrene nanocomposite film (M2VP-5) dispersed 5wt% lipophilic layered silicate (M2VP). .

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M2VP-5) are shown in Table 3 below.

Example 5: Preparation of polystyrene nanocomposite film (M4VP-0.5 / PS)

The organizing agent used for the synthesis of lipophilic layered silicate (M4VP) is a copolymer of 4-vinylpyridine and styrene (4VP), whose molecular weight is controlled by living radical polymerization, with a number average molecular weight The molecular weight distribution indices are 13,500 g / mol and 1.46, respectively. 0.02 g of lipophilic layered silicate (M4VP) was added to 20 g of chloroform (chloroform) and dispersed for 3 hours by ultrasound, and then 4 g of polystyrene (PS) was added to a solution dissolved in 33.41 g of chloroform. The mixture was stirred for 1 day at 400 rpm using a mechanical stirrer. The prepared polymer solution was cast by adjusting the solid content to a thickness of 100 μm on a glass plate, dried at room temperature for 90 minutes, and then placed in a vacuum oven for 3 hours at 60 ° C. and 1 hour at 100 ° C. for a lipophilic layered silicate ( A polystyrene nanocomposite film (M4VP-0.5) having 0.5 wt% of M4VP dispersed therein was prepared.

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M4VP-0.5) are shown in Table 3 below.

Example 6: Preparation of Polystyrene Nanocomposite Film (M4VP-1 / PS)

0.04 g of lipophilic layered silicate (M4VP) synthesized as in Example 5 was added to 20 g of chloroform and dispersed for 3 hours by ultrasound, and then 4 g of polystyrene (PS) was 33.67 g of chloroform. Was added to the solution dissolved in. Preparation of the polystyrene nanocomposite film (M4VP-1) using this mixture was carried out in the same manner as in Example 5, to prepare a polystyrene nanocomposite film (M4VP-1) in which the lipophilic layered silicate (M4VP) 1wt% dispersed. .

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M4VP-1) are shown in Table 3 below.

Example 7: Preparation of polystyrene nanocomposite film (M4VP-3 / PS)

0.12 g of lipophilic layered silicate (M4VP) synthesized as in Example 5 was added to 25 g of chloroform, and dispersed for 3 hours by ultrasonic, 4 g of polystyrene (PS) was 29.74 g of chloroform. Was added to the solution dissolved in. Preparation of the polystyrene nanocomposite film (M4VP-3) using this mixture was carried out in the same manner as in Example 5, to prepare a polystyrene nanocomposite film (M4VP-3) dispersed 3wt% lipophilic layered silicate (M4VP). .

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M4VP-3) are shown in Table 3 below.

Example 8 Preparation of Polystyrene Nanocomposite Film (M4VP-5 / PS)

0.2 g of lipophilic layered silicate (M4VP) synthesized as in Example 5 was added to 25 g of chloroform and dispersed for 3 hours by ultrasound, and then 4 g of polystyrene (PS) was 30.8 g of chloroform. Was added to the solution dissolved in. Preparation of the polystyrene nanocomposite film (M4VP-5) using this mixture was carried out in the same manner as in Example 5, to prepare a polystyrene nanocomposite film (M4VP-5) dispersed 5wt% lipophilic layered silicate (M4VP). .

Dispersibility, optical and thermal properties of the prepared polystyrene nanocomposite film (M4VP-5) are shown in Table 3 below.

Example 9 Preparation of HIPS Nanocomposite Film (M2VP-1 / HIPS)

As in Example 2, 0.04 g of lipophilic layered silicate (M2VP) was added to 20 g of chloroform and dispersed for 3 hours by ultrasound, followed by 4 g of High-Impact polystyrene (HIPS) of 33.67 g. It was added to the solution dissolved in chloroform. Preparation of HIPS nanocomposite film (M2VP-1) using this mixture was carried out in the same manner as in Example 2, HIPS nanocomposite film (M2VP-1 / HIPS) in which the lipophilic layered silicate (M2VP) 1wt% dispersed Prepared.

Dispersibility, optical and thermal properties of the prepared HIPS nanocomposite film (M2VP-1 / HIPS) are shown in Table 3 below.

Example 10 Preparation of HIPS Nanocomposite Film (M2VP-3 / HIPS)

As in Example 3, 0.12 g of lipophilic layered silicate (M2VP) was added to 25 g of chloroform and dispersed for 3 hours by ultrasound, followed by 4 g of High-Impact polystyrene (HIPS) of 29.74 g. It was added to the solution dissolved in chloroform. HIPS nanocomposite film (M2VP-3 / HIPS) using this mixture was prepared in the same manner as in Example 3, HIPS nanocomposite film (M2VP-3) dispersed 3wt% lipophilic layered silicate (M2VP) Prepared.

Dispersibility, optical and thermal properties of the prepared HIPS nanocomposite film (M2VP-3) are shown in Table 3 below.

Example 11 Preparation of HIPS Nanocomposite Film (M4VP-1 / HIPS)

As in Example 6, 0.04 g of lipophilic layered silicate (M4VP) was added to 20 g of chloroform and dispersed for 3 hours by ultrasound, followed by 4 g of High-Impact polystyrene (HIPS) of 33.67 g. It was added to the solution dissolved in chloroform. The preparation of HIPS nanocomposite film (M4VP-1 / HIPS) using this mixture was carried out in the same manner as in Example 6, HIPS nanocomposite film (M4VP-1) in which the lipophilic layered silicate (M4VP) 1wt% dispersed Prepared.

Dispersibility, optical and thermal properties of the prepared HIPS nanocomposite film (M4VP-1) are shown in Table 3 below.

Example 12 Preparation of Polystyrene Nanocomposite Film (M4VP-3 / PS)

0.12 g of lipophilic layered silicate (M4VP) synthesized as in Example 7 was added to 25 g of chloroform, and dispersed for 3 hours by ultrasound. 4 g of High-Impact polystyrene (HIPS) was 29.74 g of chloroform. It was added to the solution dissolved in (chloroform). HIPS nanocomposite film (M4VP-3 / HIPS) using this mixture was prepared in the same manner as in Example 7, the lipophilic layered silicate (M4VP) HIPS nanocomposite film (M4VP-3) dispersed 3wt% Prepared.

Dispersibility, optical and thermal properties of HIPS nanocomposite film (M4VP-3) are shown in Table 3 below.

Example 13: Preparation of ABS Nanocomposite Film (M2VP-1 / ABS)

As in Example 2, 0.04 g of lipophilic layered silicate (M2VP) was added to 20 g of chloroform and dispersed for 3 hours by ultrasonic, then 4 g of ABS was dissolved in 33.67 g of chloroform. To the solution. Preparation of the ABS nanocomposite film (M2VP-1 / ABS) using this mixture was carried out in the same manner as in Example 2, the ABS nanocomposite film (M2VP-1) in which the lipophilic layered silicate (M2VP) 1wt% dispersed Prepared.

 Dispersibility, optical and thermal properties of the ABS nanocomposite film (M2VP-1) are shown in Table 3 below.

Example 14 Preparation of ABS Nanocomposite Film (M2VP-3 / ABS)

0.12 g of lipophilic layered silicate (M2VP) synthesized as in Example 3 was added to 25 g of chloroform (chloroform) and dispersed for 3 hours by ultrasound, and 4 g of ABS was dissolved in 29.74 g of chloroform. Was added. Preparation of the ABS nanocomposite film (M2VP-3ABS) using this mixture was carried out in the same manner as in Example 3, to prepare an ABS nanocomposite film (M2VP-3ABS) dispersed 3wt% lipophilic layered silicate (M2VP). .

Dispersibility, optical and thermal properties of the ABS nanocomposite film (M2VP-3ABS) are shown in Table 3 below.

Example 15 Preparation of ABS Nanocomposite Film (M4VP-1 / ABS)

0.04 g of lipophilic layered silicate (M4VP) synthesized as in Example 6 was added to 20 g of chloroform and dispersed for 3 hours by ultrasound, and then 4 g of ABS was dissolved in 33.67 g of chloroform. Was added. Preparation of ABS nanocomposite film (M4VP-1 / ABS) using this mixture was carried out in the same manner as in Example 6, ABS nanocomposite film (M4VP-1 / ABS in which the lipophilic layered silicate (M4VP) 1wt% dispersed ) Was prepared.

Dispersibility, optical and thermal properties of the ABS nanocomposite film (M4VP-1 / ABS) are shown in Table 3 below.

Example 16: Preparation of ABS Nanocomposite Film (M4VP-3 / ABS)

As in Example 7, the synthesized 0.12 g of lipophilic layered silicate (M4VP) was added to 25 g of chloroform (chloroform) and dispersed for 3 hours by ultrasound, and then 4 g of ABS was dissolved in 29.74 g of chloroform. To the solution. Preparation of ABS nanocomposite film (M4VP-3 / ABS) using this mixture was carried out in the same manner as in Example 7, ABS nanocomposite film (M4VP-3 / ABS) dispersed 3wt% lipophilic layered silicate (M4VP) ) Was prepared.

Dispersibility, optical and thermal properties of the ABS nanocomposite film (M4VP-3 / ABS) are shown in Table 3 below.

Example 17 Preparation of Polystyrene Nanocomposite Sheet (M2VP-S-0.5 / PS)

0.02g of synthetic lipophilic layered silicate (M2VP) and 4g of polystyrene were added to 93.4g of chloroform in 250ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. The prepared powder was dried in a vacuum oven at 50 ° C. for 48 hours, and then prepared into a fine powder using a pellet mixer, and then put in a vacuum oven again and dried at 50 ° C. for 3 hours. The dried 5.205g nanocomposite powder was added with 0.0104g of antioxidant Irganox 1076 with 0.2% solids content and then brazed internal mixer for 5 minutes at 240 ° C at 600 rpm. Melt kneading. The melt-kneaded polystyrene nanocomposite composition was made of a polystyrene nanocomposite sheet (M2VP-S-0.5) in which 0.5 wt% of an lipophilic layered silicate (M2VP) was dispersed at 240 ° C. using a hot press. Polystyrene nanocomposite sheet (M2VP-S-0.5) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M2VP-S-0.5) are shown in Table 3 below.

Example 18 Preparation of Polystyrene Nanocomposite Sheet (M2VP-S-1 / PS)

0.04 g of synthetic lipophilic layered silicate (M2VP) and 4 g of polystyrene were added to 93.7 g of chloroform in a 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and the preparation of the polystyrene nanocomposite sheet (M2VP-S-1) using the same were carried out in the same manner as in Example 9, polystyrene nanocomposite sheet (M2VP) dispersed 1wt% of the lipophilic layered silicate (M2VP) -S-1) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M2VP-S-1) are shown in Table 3 below.

Example 19 Preparation of Polystyrene Nanocomposite Sheets (M2VP-S-3 / PS)

0.12 g of synthetic lipophilic layered silicate (M2VP) and 4 g of polystyrene were added to 94.7 g of chloroform in 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and preparation of the polystyrene nanocomposite sheet (M2VP-S-3) using the same were carried out in the same manner as in Example 9, and polystyrene nanocomposite sheet (M2VP) in which 3 wt% of the lipophilic layered silicate (M2VP) was dispersed. -S-3) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M2VP-S-3) are shown in Table 3 below.

Example 20 Preparation of Polystyrene Nanocomposite Sheets (M2VP-S-5 / PS)

0.2g of lipophilic layered silicate (M2VP) and 4g of polystyrene in 95.8g of chloroform were mixed in a 250ml round bottom flask with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and the preparation of the polystyrene nanocomposite sheet (M2VP-S-5) using the same were carried out in the same manner as in Example 9, polystyrene nanocomposite sheet (M2VP) dispersed 5wt% lipophilic layered silicate (M2VP) -S-5) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M2VP-S-5) are shown in Table 3 below.

Example 21 Preparation of Polystyrene Nanocomposite Sheets (M4VP-S-0.5 / PS)

0.02 g of synthetic lipophilic layered silicate (M4VP) and 4 g of polystyrene were added to 93.4 g of chloroform in 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. The prepared powder was dried in a vacuum oven at 50 ° C. for 48 hours, and then prepared into a fine powder using a pellet mixer, and then put in a vacuum oven again and dried at 50 ° C. for 3 hours. The dried 5.205g nanocomposite powder was added with 0.0104g of antioxidant Irganox 1076 with 0.2% solids content and then brazed internal mixer for 5 minutes at 240 ° C at 600 rpm. Melt kneading. The melt-kneaded polystyrene nanocomposite composition was made of a polystyrene nanocomposite sheet (M4VP-S-0.5) in which 0.5 wt% of an lipophilic layered silicate (M4VP) was dispersed at 240 ° C. using a hot press. Polystyrene nanocomposite sheet (M4VP-S-0.5) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M4VP-S-0.5) are shown in Table 3 below.

Example 22 Preparation of Polystyrene Nanocomposite Sheets (M4VP-S-1 / PS)

94 g of chloroform and 0.04 g of synthetic lipophilic layered silicate (M4VP) and 4 g of polystyrene were placed in a 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and preparation of the polystyrene nanocomposite sheet (M4VP-S-1) using the same were carried out in the same manner as in Example 13, and the polystyrene nanocomposite sheet (M4VP) in which 1 wt% of the lipophilic layered silicate (M4VP) was dispersed. -S-1) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M4VP-S-1) are shown in Table 3 below.

Example 23 Preparation of Polystyrene Nanocomposite Sheet (M4VP-S-3 / PS)

0.12 g of synthetic lipophilic layered silicate (M4VP) and 4 g of polystyrene were added to 94.7 g of chloroform in 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and preparation of the polystyrene nanocomposite sheet (M4VP-S-3) using the same were carried out in the same manner as in Example 13. The polystyrene nanocomposite sheet (M4VP) in which 3 wt% of the lipophilic layered silicate (M4VP) was dispersed. -S-3) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M4VP-S-3) are shown in Table 3 below.

Example 24 Preparation of Polystyrene Nanocomposite Sheets (M4VP-S-5 / PS)

0.2g of lipophilic layered silicate (M4VP) and 4g of polystyrene in 95.8g of chloroform were mixed in a 250ml round bottom flask with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and preparation of the polystyrene nanocomposite sheet (M4VP-S-5) using the same were carried out in the same manner as in Example 13. The polystyrene nanocomposite sheet (M4VP) in which 5 wt% of the lipophilic layered silicate (M4VP) was dispersed. -S-5) was prepared.

Dispersibility, Haze, and thermal properties of the polystyrene nanocomposite sheet (M4VP-S-5) are shown in Table 3 below.

Example 25 Preparation of HIPS Nanocomposite Sheet (M2VP-S-1 / HIPS)

Add 0.04 g of synthetic lipophilic layered silicate (M2VP) and 4 g of High-Impact polystyrene (HIPS) to 93.7 g of chloroform in a 250 ml round bottom flask, and use a mechanical stirrer to mix the solution. HIPS nanocomposite powder was prepared by filtering in the form of precipitate and powder. Drying of nanocomposite powder and preparation of HIPS nanocomposite sheet (M2VP-S-1HIPS) using the same were carried out in the same manner as in Example 18, HIPS nanocomposite sheet (M2VP) in which 1 wt% of lipophilic layered silicate (M2VP) was dispersed. -S-1 / HIPS) was prepared.

Dispersibility, Haze, and thermal properties of HIPS nanocomposite sheet (M2VP-S-1 / HIPS) are shown in Table 3 below.

Example 26 Preparation of HIPS Nanocomposite Sheet (M2VP-S-3 / HIPS)

0.12 g of synthetic lipophilic layered silicate (M2VP) and 4 g of High-Impact polystyrene (HIPS) were added to 94.7 g of chloroform in a 250 ml round bottom flask, and the solution was mixed with a mechanical stirrer, followed by methanol (MeOH). HIPS nanocomposite powder was prepared by filtering in the form of precipitate and powder. Drying of nanocomposite powder and preparation of HIPS nanocomposite sheet (M2VP-S-3 / HIPS) using the same were carried out in the same manner as in Example 19, HIPS nanocomposite sheet of 3% by weight of lipophilic layered silicate (M2VP) (M2VP-S-3 / HIPS) was prepared.

Dispersibility, Haze, and thermal properties of HIPS nanocomposite sheet (M2VP-S-3 / HIPS) are shown in Table 3 below.

Example 27 Preparation of HIPS Nanocomposite Sheet (M4VP-S-1 / HIPS)

Add 0.04 g of lipophilic layered silicate (M4VP) and 4 g of High-Impact polystyrene (HIPS) to 93.7 g of chloroform in a 250 ml round bottom flask, and use a mechanical stirrer to mix the solution. HIPS nanocomposite powder was prepared by filtering in the form of precipitate and powder. Drying of nanocomposite powder and preparation of HIPS nanocomposite sheet (M4VP-S-1 / HIPS) using the same were carried out in the same manner as in Example 22, HIPS nanocomposite sheet in which 1 wt% of lipophilic layered silicate (M4VP) was dispersed. (M4VP-S-1 / HIPS) was prepared.

Dispersibility, Haze, and thermal properties of HIPS nanocomposite sheet (M4VP-S-1 / HIPS) are shown in Table 3 below.

Example 28 Preparation of HIPS Nanocomposite Sheet (M4VP-S-3 / HIPS)

0.12 g of synthetic lipophilic layered silicate (M4VP) and 4 g of High-Impact polystyrene (HIPS) were added to 94.7 g of chloroform in a 250 ml round bottom flask, and the solution was mixed with a mechanical stirrer, followed by methanol (MeOH). HIPS nanocomposite powder was prepared by filtering in the form of precipitate and powder. Drying of nanocomposite powder and preparation of HIPS nanocomposite sheet (M4VP-S-3 / HIPS) using the same were carried out in the same manner as in Example 23, HIPS nanocomposite sheet of 3% by weight of lipophilic layered silicate (M4VP) dispersed (M4VP-S-3 / HIPS) was prepared.

Dispersibility, Haze, and thermal properties of HIPS nanocomposite sheet (M4VP-S-3 / HIPS) are shown in Table 3 below.

Example 29 Preparation of ABS Nanocomposite Sheet (M2VP-S-1 / ABS)

Add 0.04 g of synthetic lipophilic layered silicate (M2VP) and 4 g of ABS to 250 ml round bottom flask in 93.7 g of chloroform, mix the solution with a mechanical stirrer, precipitate in methanol (MeOH), filter in powder state ABS nanocomposite powder was prepared. Drying of the nanocomposite powder and preparation of the ABS nanocomposite sheet (M2VP-S-1 / ABS) using the same were carried out in the same manner as in Example 18, and the ABS nanocomposite sheet in which 1 wt% of the lipophilic layered silicate (M2VP) was dispersed. (M2VP-S-1 / ABS) was prepared.

Dispersibility, Haze, and thermal properties of the ABS nanocomposite sheet (M2VP-S-1 / ABS) are shown in Table 3 below.

Example 30 Preparation of ABS Nanocomposite Sheet (M2VP-S-3 / ABS)

0.12 g of synthetic lipophilic layered silicate (M2VP) and 4 g of ABS were added to 94.7 g of chloroform in 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. ABS nanocomposite powder was prepared. Drying of the nanocomposite powder and preparation of the ABS nanocomposite sheet (M2VP-S-3 / ABS) using the same were carried out in the same manner as in Example 19, and the ABS nanocomposite sheet in which 3 wt% of the lipophilic layered silicate (M2VP) was dispersed. (M2VP-S-3 / ABS) was prepared.

Dispersibility, Haze, and thermal properties of the ABS nanocomposite sheet (M2VP-S-3 / ABS) are shown in Table 3 below.

Example 31 Preparation of ABS Nanocomposite Sheet (M4VP-S-1 / ABS)

0.04 g of synthetic lipophilic layered silicate (M4VP) and 4 g of ABS were added to 93.7 g of chloroform in 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. To prepare a polystyrene nanocomposite powder. Drying of the nanocomposite powder and preparation of the ABS nanocomposite sheet (M4VP-S-1 / ABS) using the same were carried out in the same manner as in Example 22, and the ABS nanocomposite sheet in which 1 wt% of the lipophilic layered silicate (M4VP) was dispersed. (M4VP-S-1 / ABS) was prepared.

Dispersibility, Haze, and thermal properties of the ABS nanocomposite sheet (M4VP-S-1 / ABS) are shown in Table 3 below.

Example 32 Preparation of ABS Nanocomposite Sheet (M4VP-S-3 / ABS)

0.12 g of synthetic lipophilic layered silicate (M4VP) and 4 g of ABS were added to 94.7 g of chloroform in 250 ml round bottom flask, mixed with a mechanical stirrer, precipitated in methanol (MeOH), and filtered in a powder state. ABS nanocomposite powder was prepared. Drying of the nanocomposite powder and preparation of the ABS nanocomposite sheet (M4VP-S-3 / ABS) using the same were carried out in the same manner as in Example 23, and the ABS nanocomposite sheet in which 3 wt% of the lipophilic layered silicate (M4VP) was dispersed. (M4VP-S-3 / ABS) was prepared.

Dispersibility, Haze, and thermal properties of the ABS nanocomposite sheet (M4VP-S-3 / ABS) are shown in Table 3 below.

Comparative Example 1: Preparation of Polystyrene Film (PS)

1 g of polystyrene was dissolved in 19 g of chloroform using a mechanical stirrer, and then cast on a glass plate by adjusting the solid content to have a thickness of 100 μm, dried at room temperature for 90 minutes, and then placed in a vacuum oven at 3 ° C. for 60 hours at 100 ° C. Treatment at 1 ° C. for 1 hour yielded a polystyrene film. Dispersibility, Haze, and thermal properties of the prepared polystyrene film (PS) are shown in Table 3 below.

Comparative Example 2: Preparation of Polystyrene Nanocomposite Film

1 g of polystyrene and 0.05 g of claspite 10A (Closite 10A) were dissolved in 19 g of chloroform using a mechanical stirrer, and then cast on a glass plate by adjusting the solid content to a thickness of 100 μm. Put and treated for 3 hours at 60 ℃, 1 hour at 100 ℃ to prepare a polystyrene film.

Dispersibility, haze and thermal properties of the prepared polystyrene film are shown in Table 3 below.

Comparative Example 3: Preparation of Polystyrene Sheet (PS-S)

Polystyrene powder was prepared by adding 5.2 g of polystyrene to a 250 ml round bottom flask in 91.19 g of chloroform, mixing the solution with a mechanical stirrer, precipitating to methanol (MeOH), and filtering the powder. The prepared powder was dried in a vacuum oven at 50 ° C. for 48 hours, and then prepared into a fine powder using a pellet mixer, and then put in a vacuum oven again and dried at 50 ° C. for 3 hours. The dried 5.2g powder was melt-kneaded at 240 rpm at 600 rpm for 5 minutes using Brabender Internal Mixer by adding 0.0104g of antioxidant Irganox 1076 with 0.2% solids content. It was. The melt-kneaded polystyrene was prepared as a polystyrene sheet at 240 ° C. using a hot press, and the dispersibility, Haze, and thermal properties of the prepared polystyrene sheet (PS-S) are shown in Table 3 below.

Comparative Example 4: Preparation of Polystyrene Nanocomposite Sheet

91.19 g of chloroform, 5.2 g of polystyrene, and 0.26 g of cladite 10A (Cloisite 10A) were added to a 250 mL round bottom flask, mixed with a mechanical stirrer, precipitated in methanol, and filtered to prepare a polystyrene powder.

The prepared polystyrene powder was treated in the same manner as in Comparative Example 3 to prepare a polystyrene nanocomposite sheet, and the dispersibility, haze and thermal properties of the prepared polystyrene nanocomposite sheet are shown in Table 3 below.

Test Example: Measurement of Physical Properties

The physical properties of the polystyrene nanocomposite film prepared according to Examples 1 to 20, the polystyrene nanocomposite sheet prepared according to Examples 21 to 40, and the polystyrene film and sheet prepared according to Comparative Examples 1 to 4 were as follows. It was measured and the results are shown in Table 3 below.

1) Particle Dispersibility: The dispersibility of the nanoparticles in the polymer matrix was evaluated using wide-angle X-ray experiments and transmission electron microscopy, and classified according to whether peaks attributable to the interlayer distance of the layered particles were observed in the wide-angle X-ray experiments. It was.

2) Haze (Haze): Haze is a ratio of the amount of light scattered more than 2.5 degrees with respect to the total incident light amount is represented by the following equation (1).

[Equation 1]

3) Thermal Characteristics: The initial decomposition temperature was measured using a thermogravimetric analyzer.

As shown in Table 3, the nanocomposite according to the present invention was very excellent in dispersibility, while the nanocomposites of Comparative Examples 1 to 4 were not excellent in dispersibility.

In addition, if the nanocomposite according to the present invention maintained a high transparency, the thermal stability was also excellent.

As described above, according to the present invention, a polystyrene nanocomposite in which the layered inorganic material is dispersed is a simple manufacturing method without using a compatibilizer and does not go through a master batch manufacturing process, and has excellent dispersibility and maintains high transparency. It is possible to provide a polystyrene-based nanocomposite having improved thermal stability.

According to the present invention, it is possible to provide a polystyrene-based nanocomposite capable of maintaining high transparency by improving haze characteristics, which is a disadvantage of conventional layered inorganic polymer nanocomposites.

Therefore, the polystyrene-based nanocomposite of the present invention can be effectively used in household goods such as toys, packaging containers, industrial transparent materials and the like by effectively dispersing the layered inorganic material to the polystyrene base material evenly.

Claims (10)

In the polystyrene-based nanocomposite prepared by nanocompositing the aluminosilicate-based layered inorganic material and polystyrenic resin, The aluminosilicate layered inorganic material is a polystyrene-based nanocomposite, characterized in that the polystyrene-based copolymer having an amine salt represented by the following formula (2) is an organic aluminosilicate layered inorganic material introduced between the layers: [Formula 2]

In Chemical Formula 2, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200. X is selected from halogen-based elements including F, Cl, Br, and I. The polystyrene-based nanocomposite according to claim 1, wherein the polystyrene-based copolymer having an amine salt has a weight average molecular weight (Mw) of 500 to 60,000 g / mol. The polystyrene-based nanocomposite according to claim 1, wherein the polystyrene-based copolymer having an amine salt has a number average molecular weight (Mn) of 3000 to 100,000. The polystyrene-based nanocomposite of claim 1, wherein the polystyrene-based copolymer having an amine salt is included in an amount of 1 to 50% by weight in the layered inorganic material. The polystyrene-based nanocomposite according to claim 1, wherein the polystyrene-based copolymer having an amine salt comprises a functional group of 1 to 7 meq / g. The polystyrene-based nanocomposite of claim 1, wherein the polystyrenic resin is selected from polystyrene, high impact sugar polystyrene (HIPS), and acrylonitrile-butadiene-styrene (ABS). In the method of producing a polystyrene-based nanocomposite by dissolving a polystyrene resin and a layered inorganic material in a polar organic solvent in the presence of a compatibilizer, by a solution mixing method, The nano-composite of the organic aluminosilicate layered inorganic material in which the polystyrene resin and the polystyrene copolymer having an amine salt represented by the following formula (2) is introduced between the layers is performed in a state in which a compatibilizer is excluded Method for producing nanocomposites: [Formula 2]

In Chemical Formula 2, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200. X is selected from halogen-based elements including F, Cl, Br, and I. In the method for producing a polystyrene-based nanocomposite by a melt mixing method comprising a master batch manufacturing step of the nanocomposite powder obtained by dissolving a polystyrene-based resin and a layered inorganic material in a polar organic solvent and drying, Nanocomposite of the organic aluminosilicate layered inorganic material in which the polystyrene-based resin and the polystyrene-based copolymer having an amine salt represented by the following Chemical Formula 2 is introduced between the layers is performed in a state in which a master batch manufacturing step is excluded. Method for producing polystyrene-based nanocomposites: [Formula 2]

In Chemical Formula 2, m is an integer between 1 and 100 (more preferably, an integer between 1 and 50, respectively), and R is

or

It is a compound represented by and x is an integer between 2 and 200. X is selected from halogen-based elements including F, Cl, Br, and I. The method according to claim 7 or 8, wherein the nanocompositing is performed in a ratio of 85 to 99.5% by weight of the polystyrene resin and 0.5 to 15% by weight of the layered inorganic material. The method of claim 7 or 8, wherein the polar organic solvent is chloroform (CHCl ₃ ), toluene, xylene, N-methyl-2-pyrrolidone (NMP), N, N- dimethylacetamide (DMAc) and dimethyl A method for producing a polystyrene-based nanocomposite, characterized in that one or two or more selected from formamide (DMF).

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