KR100605516B1 - Diene copolymer modified polar siloxyalkyl ammonium, and dien rubber nanocomposites using them - Google Patents

Abstract

The present invention relates to a diene copolymer modified with a polar siloxyalkylammonium and a diene-based nanocomposite using the same, and more particularly, to a novel diene copolymer having a polar siloxyalkylammonium bonded thereto, and to the new diene copolymer described above. The masterbatch prepared by mixing the inorganic layered compound and the nanobatch having excellent physical properties such as mechanical strength, thermal stability, weather resistance, etc., which are prepared by mixing the masterbatch and the diene rubber in a predetermined content ratio and vulcanizing the mixture. It is about.

Polar siloxyalkylammonium, modified, diene copolymers, inorganic layered compounds, nanocomposites

Description

Diene copolymer modified with polar siloxyalkylammonium and diene-based nanocomposite using the same {Diene copolymer modified polar siloxyalkyl ammonium, and dien rubber nanocomposites using them}

1 is an XRD showing the interlayer distance between the nanocomposite (a) and the conventional nanocomposite (b) of the present invention.

The present invention relates to a diene copolymer modified with a polar siloxyalkylammonium and a diene-based nanocomposite using the same, and more particularly, to a novel diene copolymer having a polar siloxyalkylammonium bonded thereto, and to the new diene copolymer described above. The masterbatch prepared by mixing the inorganic layered compound and the nanobatch having excellent physical properties such as mechanical strength, thermal stability, weather resistance, etc., which are prepared by mixing the masterbatch and the diene rubber in a predetermined content ratio and vulcanizing the mixture. It is about.

Butadiene rubbers represented as diene rubbers may include acrylonitrile-butadiene rubber (hereinafter abbreviated as 'NBR') and styrene-butadiene rubber (hereinafter abbreviated as 'SBR'). SBR is a copolymer made by polymerizing butadiene and styrene. It has the advantages of abrasion resistance, aging resistance, and heat resistance compared to natural rubber, and is easy to process and stable in vulcanization characteristics. It is one of the most widely used synthetic rubbers that can be used in rubber products, accounting for 80% of the demand for synthetic rubber. SBR is divided into emulsion polymerization SBR and solution polymerization SBR according to the preparation method. In the case of emulsion polymerization SBR, the styrene content is about 23%, butadiene structure is 18% cis-1,4 structure, trans-1,4 structure is 65%, vinyl structure 17%. SBR produced by emulsion polymerization is classified into two types according to the polymerization temperature. There are a hot rubber which is polymerized at 50 ° C. or higher and a cold rubber which is polymerized at around 10 ° C.

SBR is a non-crystalline polymer due to chemical irregularities, it is difficult to obtain the required physical properties without a large amount of reinforcing fillers, lack of adhesiveness and shrinkage rate is difficult to Karena processing, extrusion processing is difficult. The most excellent reinforcing filler for increasing the physical properties such as strength and weather resistance of SBR is carbon black, which can improve aging resistance and abrasion resistance by heat of SBR. As such, rubber has been increased in strength by adding a large amount of heterogeneous fillers such as carbon black and metal ceramics to about 30 to 50 parts by weight, but by adding a large amount of heterogeneous materials, the weight of the material is greatly increased, and workability is reduced and economical. There is a problem.

Korean Patent No. 108956 discloses that 100 parts by weight of styrene resin composed of 20 to 70 parts by weight of amorphous polystyrene resin and 80 to 30 parts by weight of rubber-modified styrene resin are added, and 0.3 to 1.0 parts by weight of polysiloxane and glass fiber are added. Styrene-based resin compositions are described. However, the patent relates to an organic polymer composite prepared by dispersing polysiloxane in a styrene resin, and there is no chemical bond between the polysiloxane and the polymer, so that phase separation easily occurs, and there is a problem in compatibility with the inorganic filler, and thus the physical properties of the composite There is a limit to improvement.

Therefore, in order to improve compatibility between the polysiloxane and the polymer and increase the compatibility with the inorganic filler, the form in which the siloxane group is substituted with the polymer has been studied. For example, poly (isoprene) block copolymers substituted with pentamethyldisiloxane have been published [Gabor, Allen H .; Lehner, Eric A .; Mao, Guoping; Schneggenburger, Lizabeth A .; Ober, Christopher K., Chem. Mater . (1994), 6 (7), 927--34. However, the copolymer has a disadvantage of low interaction with the inorganic filler because the siloxane itself does not have a polar group portion.

Accordingly, the present inventors have made efforts to solve the above problems in the prior art, and as a result, by introducing a polar siloxyalkylammonium in a diene copolymer having a specific range of molecular weight, a novel modification with excellent inorganic layered compound Synthesized diene copolymer, and mixed with the synthesized new diene copolymer inorganic layer compound to prepare a master batch, and using a prepared master batch with excellent compatibility with the diene rubber in a certain content ratio inorganic layer phase The present invention was completed by knowing that it is easy to insert the diene rubber into the interlayer of the compound, thereby increasing the compatibility between the diene rubber and the inorganic layered compound to prepare a nanocomposite having improved tensile strength, thermal stability, and weather resistance. .

That is, the present invention increases the miscibility between the organic polymer and the inorganic layered compound by making the masterbatch used for the production of the diene-based nanocomposite chemically have a structure similar to that of the diene rubber, in particular the inorganic layered compound and the organic polymer uniformly By being dispersed, the diene-based nanocomposites can exhibit more excellent mechanical strength and weather resistance.

It is therefore an object of the present invention to provide novel diene copolymers modified with polar siloxyalkylammonium.

Another object of the present invention is to provide a diene-inorganic layered compound master batch prepared by mixing the new diene copolymer and the inorganic layered compound.

In addition, the present invention is another object to provide a nanocomposite with improved mechanical properties by combining the master batch and the diene-based rubber is excellent in the dispersion properties of organic-inorganic.

The present invention is characterized by a diene copolymer modified by combining a polar siloxyalkylammonium represented by the following formula (1).

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; X represents an alkylene group or a phenyl group having 1 to 10 carbon atoms; p represents an integer from 2 to 6; q represents 0 or the integer of 1-6.

The present invention also includes a master batch of a diene-inorganic layered compound containing 40 to 99.9% by weight of the modified diene copolymer and 0.1 to 60% by weight of the inorganic layered compound.

In addition, the present invention includes a nanocomposite prepared by melting, vulcanizing and compression molding by mixing the diene-inorganic layered compound master batch 1 to 30% by weight and diene rubber 70 to 99% by weight.

Referring to the present invention in more detail as follows.

The present invention relates to a novel modified diene copolymer having improved compatibility with the inorganic layered compound by modifying the diene copolymer with the polar siloxyalkylammonium represented by Formula 1, wherein the modified diene copolymer The nanocomposite prepared by mixing diene rubber in the diene-inorganic layered master batch after melting, vulcanization and compression molding because of its excellent miscibility with the compound can easily insert the diene rubber between the layers of the inorganic layered compound. By being able to be evenly dispersed at a level, it is possible to obtain an effect of improved physical properties, such as mechanical strength, thermal stability, weather resistance, compared to the composite material prepared only with conventional diene rubber and inorganic layered compound.

That is, the present invention was modified by introducing a polar siloxyalkylammonium represented by the formula (1) to the diene copolymer in order to increase the compatibility between the organic compound and the inorganic layer compound of the diene copolymer, the modified diene copolymer The dispersibility with the inorganic layered compound is increased to show a significantly improved physical properties compared to the conventional diene-based nanocomposites.

The diene copolymers used for the modification of the present invention are conventional polymers commercially available from Aldrich et al., And there is no particular limitation in their selection. Specific examples of the diene copolymer described above include styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene copolymer, and ethylene-propylene-diene-based polymer. It is also possible to use polymers in which the aforementioned copolymers are partially hydrogenated, epoxidized or brominated. However, it is preferable to use a number average molecular weight of 500 ~ 15000 of the diene copolymer to be used. If the molecular weight is less than 500, it is difficult to obtain effective improvement of thermal stability and mechanical properties, and if it exceeds 15000, it is chemically modified and purified. This is because the process is complicated and the compatibility with the inorganic layer compound is low.

The present invention uses a polar siloxane alkylammonium represented by the formula (1) as a modifier of the diene copolymer. In the siloxyalkylammonium represented by Formula 1, preferably, R ₁ , R ₂ , R ₃ , and R ₄ each represent a hydrogen atom or a methyl group, and R ₅ , R ₆ , and R ₇ each represent a hydrogen atom. Or an alkyl group having 5 to 20 carbon atoms, X represents an alkylene group or phenyl group having 1 to 3 carbon atoms, p represents an integer of 2 to 6, and q represents 0 or an integer of 1 to 6; Specific examples of the above-described siloxyalkylammonium include tetramethyldisiloxyethyl dimethyl octyl ammonium, tetramethyldisiloxyethylbenzyl dimethyl octyl ammonium, tetramethyldisiloxyethylbenzyl dimethyl dodecyl ammonium, tetramethyldisiloxane Cethyl ethyl benzyl dimethyl octadecyl ammonium, tetramethyl disiloxy undecyl dimethyl ammonium, etc. can be used.

The process for producing the modified diene copolymer according to the present invention will be described in detail for each process as follows.

The disiloxane compound represented by the following formula (2) and the alkenyl halide compound represented by the following formula (3) are reacted under a platinum catalyst to prepare a disiloxane alkyl halide compound represented by the following formula (4).

In the above, R ₁ , R ₂ , R ₃ , R ₄ , X, p, and q are as defined in the formula (1), respectively, Y represents a halogen atom.

Then, the diene copolymer represented by the following formula (5) and the disiloxane alkyl halide compound represented by the formula (4) are reacted under a platinum catalyst to prepare a diene copolymer substituted with the disiloxy group represented by the following formula (6). .

In the above, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, R _7, X, p, and q are as defined in Formula 1, respectively, l and n are 28 to 78, respectively, m and o are 0.1-30, respectively, and represent l + m + n + o = 100, and Y represents a halogen atom.

Then, the diene copolymer substituted with the disiloxane group represented by Chemical Formula 6 is reacted with the amine compound represented by the following Chemical Formula 7, and the modified diene copolymer represented by the following Chemical Formula 8 having the polar siloxyalkylammonium bonded thereto To prepare.

In the above, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, R _7, X, p, and q are as defined in Formula 1, respectively, l and n are 28 to 78, respectively, m and o are 0.1-30, respectively, and represent l + m + n + o = 100, and Y represents a halogen atom.

As the silylation catalyst used during the production of the modified diene copolymer, transition metals such as croropratinic acid, palladium, rhodium, and platinum, or complex compounds of these transition metals may be used. It is commercially available from the company but can be synthesized by known methods.

The above silylation and amine substitution reaction is to be carried out in the range of -10 ℃ to 150 ℃, preferably carried out in a temperature range of 20 ℃ to 120 ℃ and nitrogen atmosphere. As the reaction solvent, organic solvents such as benzene, toluene and xylene are used and are not particularly limited. Although reaction time is not specifically limited, It is about 30 minutes-about 1 week.

The substitution rate of the polar siloxyalkylammonium represented by Chemical Formula 1 is not particularly limited, but preferably the total number of repeating units constituting the modified diene copolymer represented by Chemical Formula 8 (l + m + n + o) It is preferable to maintain the ratio of the number of repeating units (m) substituted with polar siloxyalkylammonium in the range of 0.1 to 50% relative to).

On the other hand, the present invention includes a diene-organic layered compound master batch composed of 40 to 99.9% by weight of the modified diene copolymer and 0.1 to 60% by weight of the inorganic layered compound as a scope.

Inorganic layered compounds have been commonly used in the manufacture of composites in the art, and the present invention does not place any particular limitation on the selection of the inorganic layered compound. As the inorganic layered compound, natural or synthetic clay minerals may be used, or lipophilic natural or synthetic clay minerals may be used. Specifically, it belongs to the mineralogy smectite group, and may use mica type layered silicates minerals, for example, montmorillonite, bentonite, and the like. .

On the other hand, the present invention includes the nanocomposite prepared by mixing and vulcanizing the diene-inorganic layered compound master batch 1 to 30% by weight and diene rubber 70 to 99% by weight as a right range.

The diene rubber may include styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene-diene-based polymer, and also the copolymer It is also possible to use partially hydrogenated, epoxidized or brominated polymers.

In manufacturing the nanocomposite of the present invention, if the content of the master batch is less than 1% by weight, it is difficult to obtain the effect of improving the physical properties of the nanocomposite, and if it exceeds 30% by weight in terms of aggregation and economics of the inorganic layered compound, There is a problem.

The nanocomposite of the present invention can be produced by mixing and vulcanizing by a known method. For example, in the case of manufacturing by melt processing, the diene rubber is melted in a Brabender mixer preheated at 20 ° C. to 150 ° C., and then melt mixed for 2 to 150 minutes by adding a diene-inorganic layer master master batch. Then, other additives are added thereto and melt mixed for 1 to 30 minutes. Subsequently, the melt-mixed sample by adding sulfur was placed in a mold having a thickness of 0.1 mm to 5 mm, press-molded and cooled for 2 to 150 minutes using a hot press preheated to 50 ° C to 250 ° C, and then the nanocomposite material. Can be prepared.

In the process of performing the melt processing method, a plasticizer may be further mixed and used within the range of 0.1 to 80 parts by weight based on 100 parts by weight of the nanocomposite composition, and may be prepared by adding one or more resins selected from known resins. . In addition, dyes, pigments, silica, carbon black, metal powder and ceramics may be prepared by adding additives known in the art, and as the additives for the production of conventional composite materials selected from oxidizing agents, UV stabilizers, coupling agents, flame retardants and crosslinking agents. An additive may be prepared by adding additional 0.1 to 10 parts by weight based on 100 parts by weight of the nanocomposite.

The nanocomposite of the present invention prepared by the above production method showed excellent mechanical properties with uniform dispersion of inorganic layered compound and suitable vulcanization processing conditions.

Therefore, in the present invention, the masterbatch used for the production of diene-based nanocomposites has a chemically similar structure to that of the diene rubber, thereby increasing the miscibility between the organic polymer and the inorganic layered compound, and in particular, the inorganic layered compound and the organic polymer uniformly. By being dispersed, the diene-based nanocomposite may have more excellent mechanical strength and weather resistance.

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

Synthesis Example: Preparation of Modified Diene Copolymer

Synthesis Example 1 Synthesis of Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-octyl-ammonium (PB-TMDSEB-DMOA)

1) 1- [2- (4-chloromethyl-phenyl) -ethyl] -1,1,3,3-tetramethyl-disiloxane synthesis

A 1000 mL three-necked round bottom flask was equipped with a magnetic stirrer, a nitrogen gas suction tube, and a condenser, and 4-vinylbenzyl chloride (70 g, 0.46 mol) was dissolved in anhydrous toluene (500 mL), followed by platinum (0) -1, 3-divinyl-1,1,3,3-tetramethylsilane catalyst (xylene solution) (0.5 mL) was added and stirred at room temperature for 10 minutes. 1,1,3,3-tetramethyldisiloxane (92,4 g, 0.69 mol) was added dropwise to this mixed solution. The reaction mixture was slowly heated, stirred at 80 ° C. for 12 hours, and then the temperature was lowered to room temperature. Activated carbon was added to remove the platinum catalyst, stirred for 4 hours, filtered through Celite, and then the solvent was removed under reduced pressure to remove 1- [2- (4-chloromethyl-phenyl) -ethyl] -1, 1,3,3-tetramethyl-disiloxane was prepared.

¹ H NMR (300 MHz, CDCl ₃ ) δ-0.08 to 0.08 (m, 12H), 0.18 (m, 2H), 2.54 (m, 2H), 4.39 (s, 2H), 7.05 to 7.17 (m, 4H) .

2) Polybutadiene 1- [2- (4 - chloromethyl-phenyl) -ethyl] -1,1,3,3-tetramethyl-disiloxane synthesis

A 1000 mL three-necked round bottom flask was equipped with a magnetic stirrer, a nitrogen gas inlet tube, and a condenser, followed by dissolving polybutadiene (50 g, 0.92 mol) in anhydrous toluene (300 mL), followed by platinum (0) -1,3-di Vinyl-1,1,3,3-tetramethylsilane catalyst (xylene solution) (0.5 mL) was added and stirred at room temperature for 10 minutes. 1- [2- (4-chloromethyl-phenyl) -ethyl] -1,1,3,3-tetramethyl-disiloxane (26.52 g, 0.09 mol) was added dropwise to this mixed solution. The reaction mixture was slowly heated, stirred at 80 ° C. for 12 hours, and then the temperature was lowered to room temperature. Activated carbon was added to remove the platinum catalyst, stirred for 4 hours, filtered through celite, and then the solvent was removed under reduced pressure to remove polybutadiene-1- [2- (4-chloromethyl-phenyl) -ethyl] -1,1 , 3,3-tetramethyl-disiloxane was prepared.

¹ H NMR (300 MHz, CDCl ₃ ) δ-0.1 to 0.1 (m, 12H), 0.79 (m, H), 1.27 (m, H), 1.87 to 2.21 (m, H), 2.56 (m, 2H) , 4.46 (s, 2H), 4.89 (m, H), 5.21-5.69 (m, H), 7.06-7.13 (m, 4H).

3) Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-octyl-ammonium synthesis

A 1000 mL three-necked round bottom flask was equipped with a magnetic stirrer, a nitrogen gas suction tube and a condenser, and then polybutadiene-1- [2- (4-chloro methyl-phenyl) -ethyl] -1,1,3,3- Tetramethyl-disiloxane (50 g) was dissolved in anhydrous tetrahydrofuran (60 mL), dimethyloctylamine (8.65 g) was added thereto, stirred at 70 ° C for 24 hours, and the temperature was lowered to room temperature. The solvent was removed under reduced pressure to prepare polybutene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-octyl-ammonium (55 g, 95% yield). .

¹ H NMR (300 MHz, CDCl ₃ ) δ-0.10 to 0.1 (m, 12H), 0.79 (m, H), 1.02 to 1.24 (m, H), 1.75 to 2.21 (m, H), 2.56 (m, 2H), 3.24 (s, 6H), 4.92 (m, H), 5.21-5.69 (m, H), 7.06-7.13 (m, 4H).

Synthesis Example 2 Synthesis of Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-dodecyl-ammonium (PB-TMDSEB-DMDDA)

A 1000 mL three-necked round bottom flask was equipped with a magnetic stirrer, a nitrogen gas suction tube, and a condenser, and then polybutadiene-1- [2- (4-chloromethyl-phenyl) -ethyl]-of Synthesis Example 1-2)- Dissolve 1,1,3,3-tetramethyl-disiloxane (50 g) in anhydrous terahydrofuran (60 mL), add dimethyldodecylamine (9.82 g), and stir at 70 ° C. for 24 hours. Lowered to room temperature. The solvent was removed under reduced pressure to prepare polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-dodecyl-ammonium (54 g, 92% yield). It was.

¹ H NMR (300 MHz, CDCl ₃ ) δ-0.10 to 0.1 (m, 12H), 0.75 (m, H), 1.02 to 1.29 (m, H), 1.77 to 2.30 (m, H), 2.56 (m, 2H), 3.31 (s, 6H), 4.97 (m, H), 5.21-5.70 (m, H), 7.06-7.13 (m, 4H).

Synthesis Example 3 Synthesis of Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-octadecyl-ammonium (PB-TMDSEB-DMODA)

A 1000 mL three-neck round bottom flask was equipped with a magnetic stirrer, a nitrogen gas suction tube, and a condenser, and then polybutadiene-1- [2- (4-chloromethyl-phenyl) -ethyl] -1 of Synthesis Example 1-2). Dissolve 1,3,3-tetramethyl-disiloxane (50 g) in anhydrous terahydrofuran (60 mL), add dimethyloctadecylamine (13.69 g), and stir at 70 ° C. for 24 hours. Lowered to room temperature. The solvent was removed under reduced pressure to prepare polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -ethyl-benzyl] -dimethyl-octadecyl-ammonium (59 g, 94% yield). It was.

¹ H NMR (300 MHz, CDCl ₃ ) δ-0.10 to 0.13 (m, 12H), 0.75 (m, H), 1.02 to 1.24 (m, H), 1.75 to 2.25 (m, H), 2.51 (m, 2H), 3.22 (s, 6H), 4.88 (m, H), 5.21-5.71 (m, H), 7.06-7.18 (m, 4H).

Synthesis Example 4 Synthesis of Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amine hydrochloride (PB-TMDSUD-DMA HCl)

1) Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amide synthesis

A polybutadiene-[(1,1,3,3-tetramethyl-di) prepared by the method of Synthesis Example 1-2 after mounting a magnetic stirrer, a nitrogen gas suction tube and a condenser in a 1000 mL three-neck round bottom flask. Dissolve siloxy) -undecanoyl chloride (50 g, 8.8 mmol) in anhydrous dichloromethane (200 mL), and then triethylamine (3.07 mL, 22 mmol) and dimethylamine hydrochloride (0.92 g, 11 mmol) at 0 ° C. Was added in. The reaction mixture was stirred at 0 ° C. for 2 hours, washed with brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by column chromatography (Hexane: EtOAc = 1; 1) to give polybutadiene-[(1, 1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amide (yield 81.5%) was prepared.

2) Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amine synthesis

Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amide (50 g, 8.8 mmol) was dissolved in tetrahydrofuran and LiAlH ₄ (1.34 g, 35.2 mmol ) Was added slowly and the reaction mixture was heated to reflux for 24 hours. After cooling to 0 ° C., methanol was slowly added, followed by addition of a small amount of brine. Ether was added and stirred at room temperature for 30 minutes, after which the solid formed was filtered and washed with dichloromethane. The filtrate and the washings were combined, concentrated under reduced pressure and purified by column chromatography (Hexane, EtOAc = 1: 3) to give polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl]- Dimethyl-amine (yield 93%) was prepared.

3) Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amine hydrochloride synthesis

Polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amine (8.8 mmol) was dissolved in dioxane and 4N-HCl / dioxane solution (1 mL) was added. The mixture was stirred at room temperature for 30 minutes and then concentrated under reduced pressure to prepare polybutadiene-[(1,1,3,3-tetramethyl-disiloxy) -undecyl] -dimethyl-amine hydrochloride (yield 99%).

In the same manner as in Synthesis Example, a modified diene copolymer represented by Chemical Formula 1 was synthesized by the reaction of the following Table 1.

Modified diene copolymer Polybutadiene Modifier (Formula 1) menstruum catalyst Response time (hours) Reaction temperature (℃) Molecular Weight mole Siloxyalkyl ammonium mole Modified copolymer 1 (Formula 8a) 5000 0.92 Siloxybenzyl dimethyl octyl ammonium 0.092 toluene PTDVT 12 80 Modified copolymer 2 (Formula 8a) 5000 0.92 0.046 toluene PTDVT 12 80 Modified copolymer 3 (Formula 8a) 1530 0.92 0.092 toluene Chroropratinic acid 12 80 Modified copolymer 4 (Formula 8b) 5000 0.92 Siloxybenzyl dimethyl dodecyl ammonium 0.092 toluene PTDVT 12 80 Modified copolymer 5 (Formula 8b) 5000 0.92 0.046 toluene PTDVT 12 80 Modified copolymer 6 (Formula 8b) 1530 0.92 0.092 toluene PTDVT 12 80 Modified copolymer 7 (Formula 8c) 5000 0.92 Siloxybenzyl dimethyl octadecyl ammonium 0.092 toluene Chroropratinic acid 12 80 Modified copolymer 8 (Formula 8c) 5000 0.92 0.046 toluene PTDVT 12 80 Modified copolymer 9 (Formula 8c) 1530 0.92 0.092 toluene PTDVT 12 80 Modified copolymer 10 (Formula 8d) 5000 092 Siloxy dimethyl undeenyl ammonium 0.092 toluene PTDVT 6 60

Example  One : Modified Dien  Copolymer and Organic  Preparation of Master Batch Using Montmorillonite

Lipophilic montmorillonite (OMMT; Southern Clay Company, Model 6A, 2.5 g) was added to 20 mL of tetrahydrofuran and stirred to form a suspension, followed by polybutadiene-[(1,1,3,3-tetramethyl-disiloxy 20 mL of tetrahydrofuran solution containing 5 g of) -ethyl-benzyl] -dimethyl-octyl-ammonium was added thereto, stirred at room temperature for 2 hours, and then reacted with an ultrasonicator for 2 hours. The film was prepared by bar coating on a glass plate and then dried at room temperature and dried in a vacuum oven to obtain a modified polybutene-organized montmorillonite master batch.

In the same manner as in Example 1, a master batch was prepared using polybutene and montmorillonite modified as shown in Table 2 below.

Diene-Inorganic Layered Compound Masterbatch Modified Polybutene (Weight) Inorganic Layered Compound (Weight) Masterbatch 1 Modified Copolymer 1 (5 g) Na-MMT ^a) (2.5 g) Masterbatch 2 Modified Copolymer 2 (10 g) Na-MMT (5 g) Masterbatch 3 Modified Copolymer 1 (10 g) VBDOA-MMT ^b) (5 g) Masterbatch 4 Modified Copolymer 1 (10 g) VBDDA-MMT ^c) (5 g) Masterbatch 5 Modified Copolymer 1 (10 g) VBDODA-MMT ^d0 (5 g) Masterbatch 6 Modified Copolymer 2 (10 g) VBDOA-MMT (5 g) Masterbatch 7 Modified Copolymer 2 (10 g) VBDDA-MMT (5 g) Masterbatch 8 Modified Copolymer 2 (10 g) VBDODA-MMT (5 g) Masterbatch 9 Modified Copolymer 4 (10 g) VBDOA-MMT (5 g) Masterbatch 10 Modified Copolymer 4 (10 g) VBDDA-MMT (5 g)  Masterbatch 11 Modified Copolymer 4 (10 g) VBDODA-MMT (5 g) Masterbatch 12 Modified Copolymer 5 (10 g) VBDOA-MMT (5 g)  Masterbatch 13 Modified Copolymer 5 (10 g) VBDDA-MMT (5 g)  Masterbatch 14 Modified Copolymer 5 (10 g) VBDODA-MMT (5 g)  Masterbatch 15 Modified Copolymer 7 (5 g) VBDOA-MMT (2.5 g)  Masterbatch 16 Modified Copolymer 7 (5 g) VBDDA-MMT (2.5 g)  Masterbatch 17 Modified Copolymer 7 (5 g) VBDODA-MMT (2.5 g) Masterbatch 18 Modified Copolymer 8 (5 g) VBDOA-MMT (2.5 g)  Masterbatch 19 Modified Copolymer 8 (5 g) VBDDA-MMT (2.5 g)  Masterbatch 20 Modified Copolymer 8 (5 g) VBDODA-MMT (2.5 g)  Masterbatch 21 Modified Copolymer 3 (10 g) VBDOA-MMT (5 g)  Masterbatch 22 Modified Copolymer 3 (10 g) VBDDA-MMT (5 g)  Masterbatch 23 Modified Copolymer 3 (10 g) VBDOA-MMT (5 g) Masterbatch 23 Modified Copolymer 10 (10 g) VBDOA-MMT (5 g) Masterbatch 24 Modified Copolymer 10 (10 g) VBDOA-MMT (2.5 g) Masterbatch 25 Modified Copolymer 10 (10 g) VBDDA-MMT (5 g)  a) Na-MMT: sodium montmorillonite layered compound b) VBDOA-MMT: montmorillonite organicated with vinylbenzyldimethyloctylamine. c) VBDDA-MMT: Montmorillonite organicated with vinylbenzyldimethyldodecylamine. d) VBDODA-MMT: Montmorillonite organicated with vinylbenzyldimethyloctadecylamine.

Example 2 Preparation of Diene Nanocomposites

The modified polybutadiene-organized montmorillonite master batch and diene rubber and other additives prepared in Example 1 were placed in a preheated Brabender mixer and melt kneaded. 1.5 parts by weight of stearic acid and 3 parts by weight of zinc oxide were added to 100 parts by weight of the total composition of the melt kneaded product, followed by further kneading for 10 minutes. Finally, 1.5 parts by weight of sulfur was added and kneaded for 5 minutes. The obtained sample was placed in a mold having a thickness of 2 mm, compression molded for 30 minutes using a press preheated to 150 ° C., and then cooled for 5 minutes to obtain a nanocomposite sheet.

By the method of Example 2, a diene-based nanocomposite sheet was obtained under the conditions shown in Table 3 below.

Nanocomposite Masterbatch (% by weight) Butadiene rubber (% by weight) Other additives (parts by weight) ^ㅁ) Melting temperature (℃) Melt time (min) Nanocomposites 1 Masterbatch 1 (10) SSBR ^b) (90) - 120 6 Nanocomposites 2 Masterbatch 1 (5) SSBR (95) - 120 10 Nanocomposites 3 Masterbatch 2 (10) SSBR (90) Irganox ^e) (0.5) 100 6 Nanocomposites 4 Masterbatch 2 (15) SSBR (85) Irganox (0.5) 120 6 Nanocomposites 5 Masterbatch 3 (10) SSBR (90) Silica (10) 100 6 Nanocomposites 6 Masterbatch 3 (5) SBR ^c) (95) - 120 15 Nanocomposites 7 Masterbatch 4 (3) SSBR (97) - 120 5 Nanocomposites 8 Masterbatch 4 (15) NBR ^d) (85) - 60 6 Nanocomposites 9 Masterbatch 5 (10) SSBR (90) - 100 8 Nanocomposites 10 Masterbatch 5 (20) SSBR (80) Irganox (0.25) 120 6 Nanocomposites 11 Masterbatch 6 (5) SBR (95) - 120 20 Nanocomposites 12 Masterbatch 6 (7) NBR (93) - 80 6 Nanocomposites 13 Masterbatch 7 (12) SSBR (88) Silica (20) 120 6 Nanocomposites 14 Masterbatch 7 (10) SSBR (90) - 100 15 Nanocomposites 15 Masterbatch 8 (3) SSBR (97) Irganox (0.25) 120 5 Nanocomposites 16 Masterbatch 8 (5) SSBR (95) - 120 6 Nanocomposites 17 Masterbatch 23 (5) SSBR (97) Irganox (0.25) 100 5 Nanocomposites 18 Masterbatch 24 (5) SSBR (97) - 110 10 Nanocomposites 19 Masterbatch 25 (5) NBR (93) - 90 15 a) parts by weight: amount of additive added based on the weight of butadiene rubber b) SSBR: styrene-butadiene rubber synthesized by solution polymerization c) SBR: styrene-butadiene-block copolymer d) NBR: acrylonitrile-butadiene rubber f Irganox: Antioxidants (Ciba Specialty Chemcials)

Comparative Example: Preparation of Composite of Unmodified Butadiene Rubber

In the present invention, montmorillonite and butadiene-based rubbers are prepared by mixing the diene copolymer and the inorganic layered compound to prepare a master batch, and then mixing the diene rubber and the master batch to prepare a nanocomposite. The composite sheet was prepared by melt mixing and compression processing in the method of 2. Comparative composites prepared in this Comparative Example are shown in Table 4 below.

Composite Butadiene Rubber Inorganic fillers (wt%) Comparative Composite 1 SBR - Comparative Composite 2 SBR 15A ^a) (5) Comparative Composite 3 NBR - Comparative Composite 4 NBR 15A (5) ^a) Montmorillonite substituted with dimethylhydrochloride tallow chloride salt produced from Southern Clay.

Test Example

Physical properties of the composite prepared in Example 2 and Comparative Example were measured by the following method.

(1) Chemical structure: The chemical structure of the synthesized material was confirmed by ¹ H NMR spectroscopy.

(2) Interlayer distance: The interlayer distance of the inorganic layered compound is measured by using XRD (X-ray diffraction).

(3) Mechanical Properties: Tensile properties (tensile strength, tensile modulus, elongation, etc.) of nanocomposites are measured by ASTM D412.

(4) Morphology of nanocomposites: The prepared nanocomposites were cryo-ultramicrotomed and cut to a thickness of 70-100 nm and measured using transmission electron microscopy (TEM).

division Tensile Strength (kgf / cm ² ) Tensile Modulus (kgf / cm ² ) Elongation (%) Interlayer Silicate Interlayer Distance (nm) Nanocomposites 1 135 120 865 3.2 Nanocomposites 2 129 115 788 3.3 Nanocomposites 3 142 125 654 3.5 Nanocomposites 4 138 119 677 2.9 Nanocomposites 5 250 180 695 2.7 Nanocomposites 6 180 175 658 4.5 Nanocomposites 7 183 169 676 4.2 Nanocomposites 8 202 178 616 4.8 Nanocomposites 9 196 154 786 4.3 Nanocomposites 10 188 142 670 3.9 Nanocomposites 11 190 146 649 2.8 Nanocomposites 12 210 178 696 3.1 Nanocomposites 13 245 185 651 2.5 Nanocomposites 14 192 153 682 4.9 Nanocomposites 15 220 176 704 2.2 Nanocomposites 16 232 162 632 2.9 Nanocomposites 17 172 138 788 3.5 Nanocomposites 18 189 146 756 3.2 Nanocomposites 19 159 130 689 3.0 Comparative Composite 1 65 100 780 1.1 Comparative Composite 2 78 120 690 1.3 Comparative Composite 3 68 68 834 1.1 Comparative Composite 4 80 116 684 1.8

Figure 1 is an XRD showing the interlayer distance between the nanocomposite (a) and the conventional nanocomposite (b) of the present invention, 2θ of the nanocomposite of the present invention exhibits a lower value than the 2θ of the conventional nanocomposite, the interlayer distance Was found to have increased significantly.

As described above, the present invention prepared a new modified diene copolymer having improved compatibility with the inorganic layered compound by modifying the diene copolymer with a polar siloxyalkylammonium, to the novel modified diene copolymer The masterbatch prepared by mixing the inorganic layered compound in a certain content ratio has excellent mechanical properties and thermal stability and is excellent in solubility in a container solvent, and thus can be used in various modifiers, adhesives, dispersants, and the like. In addition, the masterbatch of the present invention can be produced as a nanocomposite by the melt processing method, the nanocomposite has the effect of improving the thermal stability, mechanical properties and the like due to the improved affinity of the modified diene copolymer with the inorganic layered compound. You can get it.

Claims (10)

Modified diene copolymer, characterized in that the diene copolymer, the polar siloxyalkylammonium represented by the following formula (1) is bonded: [Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; X represents an alkylene group or a phenyl group having 1 to 10 carbon atoms; p represents an integer from 2 to 6; q represents 0 or the integer of 1-6. The compound of claim 1, wherein R ₁ , R ₂ , R ₃ , and R ₄ each represent a hydrogen atom or a methyl group; R ₅ , R ₆ , and R ₇ each represent a hydrogen atom or an alkyl group having 5 to 20 carbon atoms; X represents an alkylene group or a phenyl group having 1 to 3 carbon atoms; p represents an integer from 2 to 6; q is a modified diene copolymer, characterized in that 0 or an integer from 1 to 6. 2. The diene copolymer according to claim 1, wherein the diene copolymer is a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, an acrylate-butadiene rubber, an acrylonitrile-butadiene-styrene copolymer, an ethylene-propylene-diene-based polymer, or A modified diene copolymer, characterized in that the copolymer is selected from among partially hydrogenated, epoxidized or brominated polymers. 40 to 99.9% by weight of the modified diene copolymer of claim 1, and 0.1 to 60% by weight of the inorganic layered compound diene-organic layered compound master batch. The master batch of the inorganic layered compound according to claim 4, wherein the inorganic layered compound is a natural or synthetic clay mineral or an lipophilic natural or synthetic clay mineral. Nanocomposite, characterized in that prepared using 1 to 30% by weight of the diene-inorganic layered compound master batch of claim 4 and 70 to 99% by weight of diene rubber. The method of claim 6, wherein the diene-inorganic layered masterbatch and the diene rubber are mixed and melt processed at a temperature of 20 ° C to 150 ° C, followed by compression molding at a temperature of 50 ° C to 250 ° C by adding sulfur. Nanocomposite, characterized in that. 7. The diene rubber according to claim 6, wherein the diene rubber is a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, an acrylate-butadiene rubber, an acrylonitrile-butadiene-styrene copolymer, an ethylene-propylene-diene-based polymer, or A nanocomposite characterized in that one copolymer is selected from partially hydrogenated, epoxidized or brominated polymers. The nanocomposite according to claim 6, wherein the nanocomposite further comprises an additive for preparing a conventional composite and an organic solvent selected from an oxidizing agent, a coupling agent, a UV stabilizer, a crosslinking agent, and a flame retardant. Preparing a disiloxane alkyl halide compound represented by Formula 4 by reacting a disiloxane compound represented by Formula 2 with an alkenyl halide compound represented by Formula 3 under a platinum catalyst;

In the above, R ₁ , R ₂ , R ₃ , R ₄ , X, p, and q are as defined in Formula 1, respectively, Y represents a halogen atom, A process of preparing a diene copolymer substituted with a disiloxy group represented by Formula 6 by reacting a diene copolymer represented by Formula 5 with a disiloxane alkyl halide compound represented by Formula 4 under a platinum catalyst;

In the above, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, R _7, X, p, and q are as defined in Formula 1, respectively, l and n are 28 to 78, respectively, m and o are 0.1-30, respectively, and represent l + m + n + o = 100, and Y represents a halogen atom. A diene copolymer substituted with a disiloxane group represented by Chemical Formula 6 is reacted with an amine compound represented by Chemical Formula 7 to prepare a modified diene copolymer represented by Chemical Formula 8, in which a polar siloxyalkylammonium is bonded. Manufacturing method characterized in that it comprises a process to:

In the above, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6 ,} R _{7 ,} X, p, and q are as defined in Formula 1, respectively, l and n are 28 to 78, respectively, m and o are 0.1-30, respectively, and represent l + m + n + o = 100, and Y represents a halogen atom.

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