KR20070024836A - Organophilic layered silicates containing polystyrenenic copolymer and preparing method thereof - Google Patents

Abstract

An alumino silicate layered inorganic material containing a polystyrene copolymer structure and a method for manufacturing the same are provided to expand an interlayer distance and improve thermal stability at a high temperature. An organic high molecules introduced into a space between layers of alumino silicate layered inorganic material is polystyrene co-polymer have an onium base represented by a chemical formula 2. In the chemical formula 2, m and n are integers ranged from 1 to 300, and R is selected from a first amine, a second amine, a third amine, and an aromatic amine.

Description

Organic aluminosilicate-based layered inorganic material containing polystyrene copolymer structure and method for manufacturing thereof {Organophilic Layered Silicates containing Polystyrenenic Copolymer and Preparing method}

1 is the introduction of the repeat unit of 4-vinyl benzyl chloride (4-chloromethyl styrene) and styrene of the copolymers (CMS-5, CMS-10 and CMS-20) synthesized according to Synthesis Examples 1 to 3 NMR spectrum measured to find out.

2 is a wide-angle X-ray diffraction diagram of the lipophilic layered silicate (MMT-20P) prepared in Preparation Example 3 and the lipophilic layered silicate (SWN-20P) prepared in Preparation Example 11. FIG.

3 is an IR spectrum of the lipophilic layered silicate (MMT-20P) prepared in Preparation Example 3 and the lipophilic layered silicate (SWN-20P) prepared in Preparation Example 11.

4 is a TEM photograph of a lipophilic layered silicate (MMT-20P) according to Preparation Example 3. FIG.

The present invention relates to an organic aluminosilicate layered inorganic material containing a polystyrene structure and a method of manufacturing the same, and more particularly, to a polystyrene copolymer and an amine having a chloromethyl group introduced between layers of an aluminosilicate layered inorganic material. Onium group containing a polystyrene structure formed by the reaction is inserted into the organic layered aluminosilicate layered inorganic material containing a novel polystyrene structure having a large interlayer distance, excellent thermal stability, improved compatibility with polystyrene and It relates to a manufacturing method thereof.

In general, as one of methods for improving the mechanical and thermal properties of organic polymers, a method of complexing an organic polymer and a layered inorganic material is widely used. At this time, the layered inorganic material to be used is required to be modified to the surface of the layered inorganic material to the organic matter because the excellent compatibility with the organic polymer should be a prerequisite.

The first attempt at organicizing the surface of layered inorganic materials requires the development of new modifiers. In other words, as an attempt for the organic property of the surface of the layered inorganic material, the introduction of a lipophilic group instead of metal ions (Na) between the layers of the layered inorganic material, as a result of which not only increases the degree of lipophilic of the layered inorganic material but also the interlayer of the material It has been reported that this can lead to an enlargement of the distance.

However, the previously reported lipophilic layered inorganic material having an alkyl group or an aryl group having 6 or more carbon atoms as a side chain has a problem of low compatibility with nonpolar polymers such as polysiloxane, polyoxyalkylene and polypropylene. In addition, the alkyl group introduced into the layered structure shows a significant decrease in the heat resistance inherent in the inorganic layer, and as a result, it is difficult to complex by melt mixing above 200 ℃.

In addition, Japanese Patent Application Laid-Open No. Hei 198645 discloses a method for preparing an organic layered inorganic material by introducing an onium group at the polyolefin end as a method for increasing compatibility with nonpolar organic polymers. The reaction of introducing onium groups poses a problem in practical applications. In addition, Japanese Patent Application Laid-Open No. 19898645 has reported a method of dispersing an organic layered inorganic material at a molecular level in a polymer material such as polysiloxane and mixing it with another polymer, but this also has a disadvantage in process.

In addition, Korean Patent No. 10-435512 discloses a method for manufacturing a polysiloxane lipophilic layered inorganic material having excellent heat resistance, but has a problem in compatibility with general-purpose polymers such as polystyrene and polypropylene.

The present inventors have made an effort to produce a high heat-resistant organic layered silicate having excellent thermal stability even at high temperature and excellent compatibility with polystyrene resins.

As a result, when a functional group capable of cation exchange reaction is introduced into the side chain of polystyrene and the organic inorganic agent is used to modify the layered inorganic material by cation exchange reaction, the content of the aromatic cyclic compound in the layered inorganic material is increased to improve heat resistance. As a result, it was found that the interlayer distance was extended to complete the present invention.

Accordingly, an object of the present invention is to provide an organic aluminosilicate layered inorganic material containing a highly heat-resistant polystyrene structure modified with a polystyrene-based copolymer having an onium group, and a method of manufacturing the same.

In the present invention, in the organic layered inorganic material in which the organic polymer is introduced between the layers of the aluminosilicate layered inorganic material, the organic polymer introduced between the layers of the aluminosilicate layered inorganic material is represented by the following formula (2): An organic aluminosilicate-based layered inorganic material which is a polystyrene-based copolymer having an onium group.

[Formula 2]

In Formula 2, m and n are each an integer between 1 and 300, wherein R is selected from primary amines, secondary amines, tertiary amines and aromatic amines.

Hereinafter, the present invention will be described in detail.

The present invention has been proposed for the production of a lipophilic layered silicate having excellent thermal stability at high temperatures and excellent compatibility with polystyrene resins, and a polystyrene copolymer having a chloromethyl group introduced between layers of an aluminosilicate layered inorganic material. An onium group containing a polystyrene structure formed by the reaction of an amine with an organic aluminosilicate layered layer containing a novel polystyrene structure having a large interlayer distance, excellent thermal stability, and improved compatibility with polystyrene. It is about inorganic material.

The present invention relates to a lipophilic layered silicate in which the layered silicate inorganic material is cation exchanged and modified by the polystyrene-based copolymer represented by Formula 2, and a method for preparing the same.

In the present invention, the organic polymer introduced between the layers of the aluminosilicate layered inorganic material, the polystyrene-based copolymer on which the onium group is introduced is reacted with the polystyrene-based copolymer having a chloromethyl group represented by the formula (1) and various kinds of amines It is a polymer represented by the above formula (2).

In Formula 2, R is selected from primary amine, secondary amine, tertiary amine, and aromatic amine. Specifically, the primary amine may be selectively selected from N-ethylamine, N-propylamine, N-butylamine, and the like. The secondary amine can be optionally used among N, N-dimethyl amine, N, N-diethylamine, N-ethyl-N-methylamine, and the like. As the tertiary amine, trimethylamine, triethyl It can be selectively used among amine and diethylmethylamine and the like, and aromatic amines include pyridine, 4-methylpyridine, aniline, N-methylaniline, N-ethylaniline, N, N-dimethylaniline, N, N-diethyl Aniline, p-toluidine and the like can optionally be used.

Scheme 1 shows a polystyrene-based copolymer having an onium group represented by the following Chemical Formula 2 (m and n are integers between 1 and 300, respectively) and having a chloromethyl group represented by the following formula: It shows as an example the process of generating.

Scheme 1

In Scheme 1, m, n, and R are as defined above, respectively.

The polystyrene-based copolymer in which the onium group represented by Chemical Formula 2 is introduced may be used as a very low lipophilic modifier, and has a functional group content of 1 to 7 mmeq / g, thus greatly increasing the hydrophilicity of the aluminosilicate layered inorganic material. Since the weight average molecular weight is 500 to 60,000 g / mol, the interlayer distance of the aluminosilicate layered inorganic material can be significantly increased. In addition, the polystyrene-based copolymer into which the onium group represented by Chemical Formula 2 is introduced has a number average molecular weight in the range of 3000 to 100,000, and more preferably, the number average molecular weight is adjusted within the range of 3,000 to 60,000. 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 layered aluminosilicate inorganic material modified by the conventional low molecular weight alkyl group and excellent in heat resistance, it is possible to solve the poor heat resistance problem of the conventional lipophilic aluminosilicate layered inorganic material.

Hereinafter, a method for producing an organic aluminosilicate layered inorganic material containing a polystyrene structure of the present invention will be described in more 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, the method comprising the steps of preparing a polystyrene copolymer having a chloromethyl group, and a polystyrene copolymer having the chloromethyl group introduced therein. Aminating step and thereby organicizing the aluminosilicate-based layered inorganic material.

First, a polystyrene copolymer having a chloromethyl group introduced therein is prepared. Specifically, 4-vinylbenzyl chloride and styrene are dissolved in a polar solvent in the presence of an inert gas, and then a polystyrene copolymer solution is prepared by preparing a polystyrene copolymer solution by adding a reaction initiator while maintaining the temperature in the range of 60 to 90 ° C. Precipitation, washing and drying produce a polystyrene copolymer having chloromethyl group introduced therein.

More specifically, 4-chloromethyl styrene purified using styrene purified through extraction and vacuum distillation and disposable prepacked columns as inhibitor remover is recrystallized from ethanol. One AIBN (2,2'-azobisisobutyronitrile) initiator is used to react the toluene as a reaction solvent for 3 to 24 hours at 50 to 80 ℃ under nitrogen atmosphere to control the molecular weight. And a reactant concentration of 20% copolymer solution is prepared.

The copolymer thus prepared is precipitated in methanol (MeOH), and the copolymer powder obtained is dried in a vacuum oven. Hydrogen nuclear magnetic resonance spectroscopy was used to determine the repeating units of 4-vinylbenzyl chloride (4-chloromethyl styrene) and styrene in the copolymer prepared by the above method, and the number average molecular weight was determined using GPC. Measure

Next, the polystyrene copolymer into which the chloromethyl group is introduced is aminated to prepare a polystyrene copolymer having an onium group.

That is, an amination reaction is carried out to prepare a polystyrene-based copolymer having an onium group, and a polystyrene-based group having a chloromethyl group of Chemical Formula 1 while slowly passing nitrogen gas through a reactor equipped with a stirrer, a nitrogen injection device, and a condenser The copolymer is reacted with the amine at 70 ° C. for 10 hours under toluene solvent. The copolymer thus prepared is precipitated in methanol, and the obtained precipitate is dried for 24 hours.

Finally, the aluminosilicate layered inorganic material and the polystyrene copolymer having the onium group are modified in water, a polar solvent, or a mixed solvent thereof to prepare an organic aluminosilicate layered inorganic material.

That is, the layered inorganic material is modified by cation exchange reaction using the polystyrene-based copolymer having an onium group represented by Chemical Formula 2 as an organic agent to lipophilic it.

The layered inorganic material is commonly used in the art, but is not particularly limited, and specifically, kaolinite, spentine, talc, pyropyllite, synthetic mica It is more preferable to use an aluminosilicate layered inorganic material selected from montmoillonite, hectorite, smectite and saponite.

The polystyrene-based copolymer having an onium group is used in the layered inorganic material within the range of 1 to 50% by weight to perform a cation exchange reaction, and when the content is less than 1% by weight, the amount is insignificant. If the lipophilic effect is not obtained, and if it exceeds 50% by weight, the overall physical properties are lowered.

The layered inorganic material and the polystyrene-based copolymer having an onium group represented by Chemical Formula 2 may be used at a temperature of 50 to 80 ° C. using a mixed solvent of water, water / protic polar solvent or water / aprotic polar solvent. It is modified by cation exchange reaction for a period of time to lipophilate. The polar solvent may be selected from chloroform (CHCl ₃ ), toluene, xylene, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), and the like. Or mixtures of two or more thereof may be used.

The organic aluminosilicate layered inorganic material containing the polystyrene structure of the present invention prepared as described above has a layered structure having a thickness of 5 to 50 mm 3 and a length of 1000 to 5000 mm and an interlayer distance of 50 to 50 mm. 200 Å.

In addition, the organic aluminosilicate layered inorganic material containing the polystyrene structure of the present invention is obtained in powder form, and has a thermal decomposition temperature of about 200 to 350 ° C., which is excellent in heat resistance.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Synthesis Example: Synthesis of Copolymer Using 4-vinylbenzylchloride and Styrene and Amination of the Copolymer

Synthesis Example 1 Synthesis of Copolymer (CMS-5) of 4-Vinylbenzylchloride and Styrene

For purification of styrene, hydroquinone, a polymerization inhibitor, was extracted and removed several times using an aqueous solution of sodium hydroxide (NaOH) diluted with 10% by weight and a separatory funnel. When extracted with a separatory funnel, the weight ratio of styrene and 10% by weight of sodium hydroxide (NaOH) aqueous solution 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 4-vinylbenzyl chloride, 4-tert-butylcatechol and nitroparaffin, which are polymerization inhibitors, were prepared using a disposable prepacked columns as inhibitor remover. (nitroparaffin) was removed. 2,2'-azobisisobutyronitrile used as an initiator was used by recrystallization twice with ethanol (EtOH).

In order to synthesize the copolymer of purified styrene and 4-chloromethyl styrene (CMS-5), nitrogen gas was slowly added to a 500 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. While passing through, styrene (49.47 g, 0.48 mol) and 4-vinylbenzyl chloride (3.82 g, 0.03 mol) were added to toluene (213.38 g). Solid 2,2'-azobisisobutyronitrile (0.06 g, 0.35 mmol) was added while maintaining the temperature of the solution at 65 ° C. The reaction mixture was stirred at 65 ° C. for 10 hours to synthesize a copolymer (CMS-5) having a reactant concentration of 20%.

The synthesized copolymer (CMS-5) was precipitated little by little in methanol (MeOH), and the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ° C. for 24 hours. Integral ratios were calculated by NMR to determine the repeating units of 4-vinylbenzyl chloride (4-chloromethyl styrene) and styrene in the copolymer (CMS-5) synthesized by the above method. 1 is shown.

Synthesis Example 2 Copolymer of 4-vinylbenzylchloride and styrene (CMS-10)

For purification of styrene, hydroquinone, a polymerization inhibitor, was extracted and removed several times using an aqueous solution of sodium hydroxide (NaOH) diluted with 10% by weight 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 4-vinylbenzyl chloride, 4-tert-butylcatechol and nitroparaffin, which are polymerization inhibitors, were prepared using a disposable prepacked columns as inhibitor remover. (nitroparaffin) was removed. 2,2'-azobisisobutyronitrile used as an initiator was used by recrystallization twice with ethanol (EtOH).

In order to synthesize the copolymer of purified styrene and 4-chloromethyl styrene (CMS-10), nitrogen gas was slowly added to a 500 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. While passing through, styrene (46.87 g, 0.45 mol) and 4-vinylbenzyl chloride (7.63 g, 0.05 mol) were added to toluene (218.22 g). Solid 2,2'-azobisisobutyronitrile (0.06 g, 0.35 mmol) was added while maintaining the temperature of the solution at 65 ° C. The reaction mixture was stirred at 65 ° C. for 10 hours to synthesize a copolymer (CMS-10) having a reactant concentration of 20%.

The synthesized copolymer (CMS-10) was precipitated little by little in methanol (MeOH), and the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ° C. for 24 hours. Integral ratios were calculated by NMR to determine the repeat units of 4-vinylbenzyl chloride (4-chloromethyl styrene) and styrene in the copolymer (CMS-10) synthesized by the above method. 1 is shown.

Synthesis Example 3: Copolymer of 4-vinylbenzylchloride and styrene (CMS-20)

For purification of styrene, hydroquinone, a polymerization inhibitor, was extracted and removed several times using an aqueous solution of sodium hydroxide (NaOH) diluted with 10% by weight and a separatory funnel. When extracted with a separatory funnel, the weight ratio of styrene and 10% by weight of sodium hydroxide (NaOH) aqueous solution 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 4-vinylbenzyl chloride, 4-tert-butylcatechol and nitroparaffin, which are polymerization inhibitors, were prepared using a disposable prepacked columns as inhibitor remover. (nitroparaffin) was removed. 2,2'-azobisisobutyronitrile used as an initiator was used by recrystallization twice with ethanol (EtOH).

In order to synthesize the copolymer of purified styrene and 4-chloromethyl styrene (CMS-20), nitrogen gas was slowly added to a 500 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. While passing through, styrene (41.66 g, 0.4 mol) and 4-vinylbenzyl chloride (15.26 g, 0.1 mol) were added to toluene (227.92 g). Solid 2,2'-azobisisobutyronitrile (0.06 g, 0.35 mmol) was added while maintaining the temperature of the solution at 65 ° C. The reaction mixture was stirred at 65 ° C. for 10 hours to synthesize a copolymer (CMS-20) having a reactant concentration of 20%.

The synthesized copolymer (CMS-20) was precipitated little by little in methanol (MeOH), and the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ° C. for 24 hours. Integral ratios were calculated by NMR to determine the repeat units of 4-vinylbenzyl chloride (4-chloromethyl styrene) and styrene in the copolymer (CMS-20) synthesized by the above method. 1 is shown.

Synthesis Example 4 Copolymer of 4-vinylbenzylchloride and styrene (CMS-100)

In order to purify 4-vinylbenzyl chloride, 4-tert-butylcatechol and nitroparaffin, which are polymerization inhibitors, were prepared using a disposable prepacked columns as inhibitor remover. (nitroparaffin) was removed. 2,2'-azobisisobutyronitrile (2,2'- azobisisobutyronitrile) used as an initiator was used by recrystallization twice with ethanol (EtOH).

In order to polymerize purified 4-chloromethyl styrene, 4-vinylbenzyl chloride was slowly passed through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. 55 g, 0.36 mol) was added to toluene (220.24 g). Solid 2,2'-azobisisobutyronitrile (0.06 g, 0.35 mmol) was added while maintaining the temperature of the solution at 65 ° C. The reaction mixture was stirred at 65 ° C. for 10 hours to synthesize a polymer having a reactant concentration of 20% (CMS-100). The synthesized polymer (CMS-100) was precipitated little by little in methanol (MeOH), and the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ° C. for 24 hours.

Synthesis Example 5 Amination of Copolymer (CMS-5) (ACMS-5)

In order to synthesize the aminated copolymer (ACMS-5), the copolymer synthesized in Synthesis Example 1 (CMS-) while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. 5) (3 g, 1.86 mmol) was added to toluene (30.98 g). Pyridine (0.44 g, 5.59 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give 10% by weight of an aminated copolymer (ACMS-5). ) Was synthesized.

The synthesized amination copolymer (ACMS-5) was precipitated in methanol (MeOH) little by little, the precipitated product was washed several times with methanol (MeOH), and then dried in a vacuum oven at 50 ℃ for 24 hours. The obtained amination copolymer (ACMS-5) is represented by the following formula (3).

[Formula 3]

In Formula 3, n is an integer between 2 and 40.

Synthesis Example 6 Amination of Copolymer (CMS-10) (ACMS-10)

In order to synthesize the aminated copolymer (ACMS-10), the copolymer synthesized in Synthesis Example 2 (CMS-) while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. 10) (3 g, 3.62 mmol) was added to toluene (34.72 g). Pyridine (0.86 g, 10.84 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give 10% by weight of an aminated copolymer (ACMS-10). ) Was synthesized.

The synthesized amination copolymer (ACMS-10) was precipitated in methanol (MeOH) little by little, the precipitated product was washed several times with methanol (MeOH), and then dried in a vacuum oven at 50 ℃ for 24 hours. The obtained amination copolymer (ACMS-10) is represented by the following formula (4).

[Formula 4]

In Formula 4, n is an integer between 4 and 80.

Synthesis Example 7: Amination of Copolymer (CMS-20) (ACMS-20)

In order to synthesize the aminated copolymer (ACMS-20), the copolymer synthesized in Synthesis Example 3 while gradually passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser was used. 20) (3 g, 6.45 mmol) was added to toluene (40.78 g). After adding pyridine (1.53 g, 19.35 mmol) while raising the temperature of the solution to 70 ° C., the reaction mixture was stirred at 70 ° C. for 10 hours to give 10% by weight of an aminated copolymer (ACMS-20). ) Was synthesized.

The synthesized amination copolymer (ACMS-20) was precipitated in methanol (MeOH) little by little, the precipitated product was washed several times with methanol (MeOH), and then dried in a vacuum oven at 50 ℃ for 24 hours. The structural formula of the obtained amination copolymer (ACMS-20) is shown in FIG. The obtained amination copolymer (ACMS-20) is represented by the following formula (5).

[Formula 5]

In Chemical Formula 5, n is an integer between 6 and 120.

Synthesis Example 8: Amination of 4-Vinylbenzylchloride Polymer (CMS-100) (ACMS-100)

4 was synthesized in Synthesis Example 4 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser for the synthesis of the aminated 4-vinylbenzyl chloride (ACMS-100) polymer. 4-vinylbenzyl chloride (CMS-100) (2.3 g, 15.07 mmol) polymer was charged to toluene (52.89 g). Pyridine (3.58 g, 45.21 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give a solid content of 10% by weight of aminated 4-vinylbenzyl chloride ( 4-vinylbenzyl chloride) (ACMS-100) was synthesized. The synthesized aminated 4-vinylbenzyl chloride (ACMS-100) was gradually precipitated in ethyl ether, and the precipitated product was washed several times with ethyl ether. It was dried for 24 hours in a vacuum oven at 50 ℃. The obtained amination copolymer (ACMS-100) is represented by the following formula (6).

[Formula 6]

In Chemical Formula 6, n is an integer between 12 and 260.

Synthesis Example 9 Amination of Copolymer (CMS-5) (ACMS-5-TEA)

In order to synthesize the aminated copolymer (ACMS-5-TEA), the copolymer synthesized in Synthesis Example 1 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser ( CMS-5) (3 g, 1.86 mmol) was added to toluene (32.13 g). Triethylamine (0.57 g, 5.59 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give 10% by weight of an aminated copolymer (ACMS). -5-TEA) was synthesized.

The synthesized copolymer (ACMS-5-TEA) was precipitated in methanol (MeOH) little by little, the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ℃ for 24 hours.

Synthesis Example 10 Amination of Copolymer (CMS-10) (ACMS-10-TEA)

In order to synthesize the aminated copolymer (ACMS-10-TEA), the copolymer synthesized in Synthesis Example 2 (CMS) was gradually passed while passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser. -10) (3 g, 3.62 mmol) was added to toluene (36.9 g). Triethylamine (1.1 g, 10.86 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give 10% by weight of an aminated copolymer (ACMS). -10-TEA) was synthesized.

The synthesized copolymer (ACMS-10-TEA) was precipitated in methanol (MeOH) little by little, the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ℃ for 24 hours.

Synthesis Example 11: Amination of Copolymer (CMS-20) (ACMS-20-TEA)

In order to synthesize the aminated copolymer (ACMS-20-TEA), the copolymer synthesized in Synthesis Example 3 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser ( CMS 20) (3 g, 6.45 mmol) was added to toluene (44.64 g). Triethylamine (1.96 g, 19.35 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give 10% by weight of an aminated copolymer (ACMS). -20-TEA) was synthesized.

The synthesized copolymer (ACMS-20-TEA) was precipitated in methanol (MeOH) little by little, the precipitated product was washed several times with methanol (MeOH) and dried in a vacuum oven at 50 ℃ for 24 hours.

Synthesis Example 12: Amination of 4-Vinylbenzylchloride Polymer (CMS-100) (ACMS-100-TEA)

Synthesis of Synthesis Example 4 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer, a nitrogen injection device, and a condenser to synthesize an aminated 4-vinylbenzyl chloride (ACMS-100-TEA) polymer. One 4-vinylbenzylchloride (CMS-100) (2.3 g, 15.07 mmol) polymer was charged to toluene (61.83 g). Triethylamine (4.57 g, 45.21 mmol) was added while raising the temperature of the solution to 70 ° C., and then the reaction mixture was stirred at 70 ° C. for 10 hours to give a solid content of 10% by weight of aminated 4-vinylbenzyl. Chloride (CMS-100) (ACMS-100-TEA) was synthesized.

The synthesized aminated 4-vinylbenzyl chloride (ACMS-100-TEA) was gradually precipitated in ethyl ether, and the precipitated product was washed several times with ethyl ether. Then, it was dried for 24 hours in a vacuum oven at 50 ℃.

Preparation Example: Preparation of organic layered silicate using aminated 4-vinylbenzyl chloride and styrene copolymer

Preparation Example 1 Preparation of Organic Layered Silicate (MMT-5P)

After adding 0.74 g of copolymer (synthesis 5) and 6.63 g of dimethylformamide (DMF) synthesized in Synthesis Example 5 to a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, the reactor was added. The temperature of was heated up to 70 degreeC. Add 0.19 g of sodium montmorillonite to 3.52 g of water, and slowly add a solution dispersed at 70 ° C. for 24 hours using a dropping funnel. Then, add 24 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-5P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 2 Preparation of Organic Layered Silicate (MMT-10P)

Into a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel, and a cooler, the reactor was added with 0.79 g of copolymer (ACMS-10) and 7.13 g of dimethylformamide (DMF) synthesized in Synthesis Example 6. The temperature of was heated up to 70 degreeC. Add 0.37 g of sodium montmorillonite to 7.03 g of water, and slowly add a solution dispersed at 70 ° C. for 24 hours using a dropping funnel, and then add 25 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-10P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 3 Preparation of Organic Layered Silicate (MMT-20P)

After adding 0.95 g of copolymer (ACMS-20) and 8.54 g of dimethylformamide (DMF) synthesized in Synthesis Example 7 to a 250 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, the reactor was added. The temperature of was heated up to 70 degreeC. To this, add 0.74 g of sodium montmorillonite in 14.06 g of water and slowly add a solution dispersed at 70 ° C. for 24 hours using a dropping funnel, and then add 92.5 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-20P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 4 Preparation of Organic Layered Silicate (MMT-100P)

After adding 0.81 g of copolymer (ACMS-100) and 7.27 g of dimethylformamide (DMF) synthesized in Synthesis Example 8 to a 500 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, the reactor was added. The temperature of was heated up to 70 degreeC. 1.48 g of sodium montmorillonite was added to 28.12 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 160 g of dimethylformamide (DMF) for 12 hours. Stir vigorously. The precipitated product was washed twice with dimethylformamide (DMF) at 70 ° C. using a centrifuge, washed several times with distilled water, and lyophilized for 48 hours. The organic layered silicate (MMT-100P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 5 Preparation of Organic Layered Silicate (MMT-5TEA)

Into a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.74 g of copolymer (ACMS-5-TEA) synthesized in Synthesis Example 9 and 6.63 g of dimethylformamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. Add 0.19 g of sodium montmorillonite to 3.52 g of water, and slowly add a solution dispersed at 70 ° C. for 24 hours using a dropping funnel. Then, add 24 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-5TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 6 Preparation of Organic Layered Silicate (MMT-10TEA)

To a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.79 g of copolymer (ACMS-10-TEA) synthesized in Synthesis Example 10 and 7.13 g of dimethylformamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. Add 0.37 g of sodium montmorillonite to 7.03 g of water and slowly add the solution dispersed at 70 ° C. for 24 hours using a dropping funnel. Then, add 25 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-10TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 7 Preparation of Organic Layered Silicate (MMT-20TEA)

To a 250 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.95 g of copolymer (ACMS-20-TEA) synthesized in Synthesis Example 11 and 8.54 g of dimethylformamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. To this, add 0.74 g of sodium montmorillonite in 14.06 g of water and slowly add the solution dispersed at 70 ° C. for 24 hours using a dropping funnel, and then add 92.5 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-20TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 8 Preparation of Organic Layered Silicate (MMT-100TEA)

To a 500 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.81 g of copolymer (ACMS-100-TEA) synthesized in Synthesis Example 12 and 7.27 g of dimethyl formamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. 1.48 g of sodium montmorillonite was added to 28.12 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 160 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (MMT-100TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 9 Preparation of Organic Layered Silicate (SWN-5P)

The reactor after adding 0.51 g of copolymer (ACMS-5) and 4.6 g of dimethylformamide (DMF) synthesized in Synthesis Example 5 was added to a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler. The temperature of was heated up to 70 degreeC. 0.19 g of synthetic smectite (SWN) was added to 3.52 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 21 g of dimethylformamide (DMF). Stir 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. The organic layered silicate (SWN-5P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 10 Preparation of Organic Layered Silicate (SWN-10P)

Into a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.55 g of the copolymer (ACMS-10) synthesized in Synthesis Example 6 and 4.95 g of dimethylformamide (DMF) were added. The temperature of was heated up to 70 degreeC. Then, 0.37 g of synthetic smectite (SWN) was added to 7.03 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 25 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (SWN-10P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 11 Preparation of Organic Layered Silicate (SWN-20P)

After adding 0.66 g of copolymer (ACMS-20) and 5.93 g of dimethylformamide (DMF) synthesized in Synthesis Example 7 to a 250 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, the reactor was added thereto. The temperature of was heated up to 70 degreeC. Here, 0.74 g of synthetic smectite (SWN) was added to 14.06 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 92.5 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (SWN-20P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 12 Preparation of Organic Layered Silicate (SWN-100P)

After adding 0.56 g of copolymer (ACMS-100) and 5.05 g of dimethylformamide (DMF) synthesized in Synthesis Example 8 to a 500 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, the reactor was added. The temperature of was heated up to 70 degreeC. 1.48 g of synthetic smectite (SWN) was added to 28.12 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel. Then, 150 g of dimethylformamide (DMF) was added thereto for 12 hours. Stir 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. The organic layered silicate (SWN-100P) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 13 Preparation of Organic Layered Silicate (SWN-5TEA)

To a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.51 g of copolymer (ACMS-5-TEA) synthesized in Synthesis Example 9 and 4.6 g of dimethylformamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. 0.19 g of synthetic smectite (SWN) was added to 3.52 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 21 g of dimethylformamide (DMF). Stir 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. The organic layered silicate (SWN-5TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 14 Preparation of Organic Layered Silicate (SWN-10TEA)

To a 100 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.55 g of copolymer (ACMS-10-TEA) synthesized in Synthesis Example 10 and 4.95 g of dimethylformamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. Then, 0.37 g of synthetic smectite (SWN) was added to 7.03 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 25 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (SWN-10TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 15 Preparation of Organic Layered Silicate (SWN-20TEA)

To a 250 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler was added 0.66 g of copolymer (ACMS-20-TEA) synthesized in Synthesis Example 11 and 5.93 g of dimethylformamide (DMF). After that, the temperature of the reactor was raised to 70 ° C. Here, 0.74 g of synthetic smectite (SWN) was added to 14.06 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel, followed by 92.5 g of dimethylformamide (DMF) for 12 hours. Stir 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. The organic layered silicate (SWN-20TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

Preparation Example 16 Preparation of Organic Layered Silicate (SWN-100TEA)

To a 500 ml reactor equipped with a stirrer, a temperature controller, a dropping funnel and a cooler, 0.56 g of copolymer (ACMS-100-TEA) synthesized in Synthesis Example 12 and 5.05 g of dimethylformamide (DMF) were added. After that, the temperature of the reactor was raised to 70 ° C. 1.48 g of synthetic smectite (SWN) was added to 28.12 g of water, and the solution dispersed at 70 ° C. for 24 hours was slowly added using a dropping funnel. Then, 150 g of dimethylformamide (DMF) was added thereto for 12 hours. Stir 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. The organic layered silicate (SWN-100TEA) was prepared by filtering the particles into small particles using a 325 mesh sieve.

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

In order to compare with the organic layered silicates prepared in Preparation Examples 1 to 16, a closet 15A (Cloisite 15A, Dimethyl dihydrogenated tallow ammonium), which is commercially available from Southern Clay Products, was purchased and thermal characteristics, interlayer distance, Acidity was compared.

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

In order to compare with the organic layered silicates prepared in Preparation Examples 1 to 16, the closet 20 (Closite 20A, Dimethyl dihydrogenated tallow ammonium), which is commercially available from Southern Clay Product, was purchased and thermal characteristics, interlayer distance, Acidity was compared.

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

In order to compare with the organic layered silicates prepared in Preparation Examples 1 to 16, a closet 30B (Cloisite 30B, Methyl tallow bis-2-hydroxy ethyl quarternary ammonium), which is commercially available from Southern Clay Products, was purchased and thermally prepared. The characteristics, interlayer distance, and dispersibility were compared.

Experimental Example: Comparison of Thermal and Physical Properties

Using the organic layered silicate prepared in Preparation Examples 1 to 16 and the organic layered silicate of Comparative Examples 1 to 3, the thermal properties were confirmed by specifying an initial pyrolysis temperature and a maximum minute temperature using a thermogravimetric analyzer, and the interlayer distance was wide. Measured by X-ray experiments and transmission electron microscopy, dispersion stability 1.0g of the prepared lipophilic layered silicate was dispersed in 10ml of chloroform solvent and left for 1 week at room temperature and then visually observed.

The thermal properties, interlayer distance, and dispersibility measured as described above are compared and the results are shown in Table 1 below.

division Thermal properties Interlayer Distance (Å) Dispersion stability IDT ^(a) T _max ^(b) Residual content (%) ^(c) Preparation Example 1 MMT-5P 305 420 15.9 > 150 ○ Preparation Example 2 MMT-10P 312 418 23.2 > 150 ○ Preparation Example 3 MMT-20P 338 386 35.4 > 150 ○ Preparation Example 4 MMT-100P 326 394 40.1 > 150 ○ Preparation Example 5 MMT-5TEA 306 413 16.2 > 150 ○ Preparation Example 6 MMT-10TEA 307 399 23.8 > 150 ○ Preparation Example 7 MMT-20TEA 309 404 30.5 > 150 ○ Preparation Example 8 MMT-100TEA 302 426 34.9 > 150 ○ Preparation Example 9 SWN-5P 299 394 14.8 > 150 ○ Preparation Example 10 SWN-10P 301 372 19.4 > 150 ○ Preparation Example 11 SWN-20P 316 388 25.8 > 150 ○ Preparation Example 12 SWN-100P 304 382 33.2 > 150 ○ Preparation Example 13 SWN-5TEA 301 384 15.3 > 150 ○ Preparation Example 14 SWN-10TEA 306 381 24.1 > 150 ○ Preparation Example 15 SWN-20TEA 302 382 31.6 > 150 ○ Preparation Example 16 SWN-100TEA 298 379 38.9 > 150 ○ Comparative Example 1 Cloisite 15A 203 324 51.3 31.5 × Comparative Example 2 Cloisite 20A 199 327 54.8 24.2 △ Comparative Example 3 Cloisite 30B 197 328 57.2 18.5 △ ^(a) : initial pyrolysis temperature (° C); ^(b) : maximum pyrolysis temperature (° C.); ^(c) : Residue content (%) at 800 ° C. ○: very good; Δ: normal; ×: not excellent

As shown in Table 1, it can be seen that the organic aluminosilicate layered inorganic material containing the polystyrene structure of the present invention is excellent in dispersibility.

In addition, the thermal decomposition is about 300 ℃ in the case of the organic commercial aluminosilicate-based layered inorganic material containing the polystyrene structure of the present invention, compared to the conventional commercial products Comparative Examples 1 to 3 starting from about 200 ℃ In the case of the existing commercially available Comparative Examples 1 to 3 it can be confirmed that the organic aluminosilicate layered inorganic material containing the polystyrene structure of the present invention is about 370 ~ 470 ℃, the polystyrene structure of the present invention It can be seen that the thermal properties such as heat resistance of the organic aluminosilicate layered inorganic material containing the improved.

As described above, the organic layered aluminosilicate layered inorganic material containing the polystyrene structure of the present invention has an extended interlayer distance and excellent thermal stability even at high temperatures.

In addition, the organic aluminosilicate layered inorganic material containing the polystyrene structure of the present invention exhibits an excellent compatibility with the polystyrene resin.

Claims (8)

 In the organic layered inorganic material in which an organic polymer is introduced between the layers of the aluminosilicate layered inorganic material, Organic aluminosilicate-based layered inorganic material, characterized in that the organic polymer introduced between the layers of the aluminosilicate layered inorganic material is a polystyrene copolymer having an onium group represented by the following formula (2): [Formula 2]

In Formula 2, m and n are each an integer between 1 and 300, wherein R is selected from primary amines, secondary amines, tertiary amines and aromatic amines. The organic aluminosilicate layered inorganic material according to claim 1, wherein the polystyrene-based copolymer having an onium group represented by Chemical Formula 2 has a weight average molecular weight (Mn) of 500 to 60,000 g / mol. The polystyrene-based copolymer having an onium group represented by Chemical Formula 2, wherein R is a primary amine selected from N-ethylamine, N-propylamine and N-butylamine, N, N-dimethyl Tertiary amines selected from amines, N, N-diethylamine and N-ethyl-N-methylamine, trimethylamine, triethylamine and diethylmethylamine, pyridine, 4-methylpyridine, aniline, An organic aluminosilicate layered inorganic material, characterized in that selected from aromatic amines selected from N-methylaniline, N-ethylaniline, N, N-dimethylaniline, N, N-diethylaniline, and p-toluidine. The organic aluminosilicate layered inorganic material according to claim 1, wherein the polystyrene-based copolymer having an onium group represented by Chemical Formula 2 is included in an amount of 1 to 50% by weight in the layered inorganic material. The organic aluminosilicate layered inorganic material according to claim 1, wherein the polystyrene-based copolymer having an onium group represented by Chemical Formula 2 includes a functional group of 1 to 7 meq / g.  In the method for producing an organic layered inorganic material in which an organic polymer is introduced between the layers of an aluminosilicate layered inorganic material, Dissolve 4-vinylbenzyl chloride and styrene in a polar solvent in the presence of an inert gas, add a reaction initiator while maintaining the temperature in the range of 40 to 80 ℃ to prepare a polystyrene copolymer solution, and then precipitate, wash and dry the polystyrene copolymer. Preparing a polystyrene copolymer into which chloromethyl groups are introduced, Preparing a polystyrene-based copolymer having an onium group by amination of the polystyrene copolymer into which the chloromethyl group is introduced, and Preparing an organic aluminosilicate layered inorganic material by modifying the aluminosilicate layered inorganic material and the polystyrene copolymer having the onium group in water, a polar solvent or a mixed solvent thereof. Method for producing an organic aluminosilicate-based layered inorganic material comprising a. The polar solvent of claim 6, wherein the polar solvent is chloroform (CHCl ₃ ), toluene, xylene, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethylformamide (DMF). Method for producing a polystyrene nanocomposite, characterized in that one or a mixture of two or more selected from. The method of claim 6, wherein the polystyrene-based copolymer having an onium group is included in an amount of 1 to 50 wt% in the layered inorganic material.

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