JP2013213144A - Reinforcing agent for rubber or plastic, method of producing the same, and rubber composition and plastic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reinforcing agent capable of improving characteristics of a rubber composition or a plastic composition, and a method of producing the reinforcing agent.SOLUTION: A reinforcing agent for rubber or plastic is produced by: fixing a silicon compound having an alkoxysilyl group and a living radical polymerization initiating group to the surface of a solid material; and performing living radical polymerization of a radically polymerizable monomer using the living radical polymerization initiating group as a polymerization starting point. A compound represented by general formula (1) is used as the silicon compound. (In the formula: A is a group capable of initiating radical polymerization; Zand Zare each independently a bivalent group including at least a carbon atom; Rand Rare each independently a 1-3C alkyl group; and n is an integer of 1 to 3).

Description

  The present invention relates to a reinforcing agent blended in a rubber composition or a plastic composition, and a method for producing the same. The present invention also relates to a rubber composition and a plastic composition containing the reinforcing agent.

  Conventionally, it is known to add a reinforcing agent (also referred to as a reinforcing filler) in a rubber composition or a plastic composition. For example, in the rubber composition for tires, development of a low heat-generating rubber composition is required due to the increasing demand for low fuel consumption performance, and silica as a reinforcing agent is one of the compounding methods that satisfy this. It is blended. However, since the surface of the silica particles is highly polar, the interaction with the diene rubber used as the rubber component in the rubber composition for tires is low, and the reinforcing property is low as compared with carbon black. Silane coupling agents are used for the purpose of improving the reinforcing properties of silica, but are not satisfactory. On the other hand, Patent Document 1 below discloses a method in which silica is impregnated with a vinyl monomer and then coated with a polymer by radical polymerization. However, since silica and a polymer are based on physical bonds, Is not always satisfactory.

  In addition, in the case of using fine particles or fine fibers other than silica as a reinforcing agent, the surface of the solid material as the reinforcing agent is modified in order to improve the dispersibility in the rubber matrix or the plastic matrix or to enhance the reinforcing property. It may be required to quality.

  The following Patent Documents 2 to 4 and Non-Patent Document 1 disclose grafting a polymer from the surface of a solid substance by living radical polymerization. In these documents, (2-bromo-2-methyl) propionyloxyhexyltriethoxysilane (BHE) is used as a polymerization initiator, BHE is immobilized on the particle surface of a solid substance in advance, and the monomer is then subjected to living radical polymerization. It is generated on the particle surface. However, these documents do not suggest the use as a reinforcing agent for rubber or plastic.

JP 2006-213661 A WO2005 / 108451 JP 2006-213661 A JP 2007-008859 A

Kohji Ohno et al., “Synthesis of Monodisperse Silica Particles Coated with Well-Defined, High-Density Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization”, Macromolecules, Vol. 38, No. 6, p.2137-2142, 2005

  An object of the present invention is to provide a reinforcing agent for rubber or plastic that can improve the properties of a rubber composition or a plastic composition by modifying the surface, and a method for producing the same.

In the method for producing a rubber or plastic reinforcing agent according to the first aspect of the present invention, a silicon compound represented by the following general formula (1) is fixed to the surface of a solid substance, and the living radical polymerization initiating group thereof is a polymerization initiation point. As a radical polymerization, a monomer capable of radical polymerization is subjected to living radical polymerization.

In the formula, A is a living radical polymerization initiating group, Z ¹ and Z ² are each independently a divalent group containing at least a carbon atom, and R ¹ and R ² are each independently an alkyl having 1 to 3 carbon atoms. It is a group. n is an integer of 1 to 3.

  The reinforcing agent for rubber or plastic according to the second aspect of the present invention is obtained by the production method, and the amount of the polymer graft chain on the surface of the solid substance is 5 to 1000 parts by mass with respect to 100 parts by mass of the solid substance. It is characterized by being.

  The rubber composition according to the third aspect of the present invention contains 1 to 200 parts by mass of the reinforcing agent with respect to 100 parts by mass of the rubber component.

  The plastic composition according to the fourth aspect of the present invention contains 1 to 200 parts by mass of the reinforcing agent with respect to 100 parts by mass of the plastic component.

  According to the present invention, a polymer graft chain is formed on the surface of a solid material by living radical polymerization of the monomer starting from the living radical polymerization initiating group of the silicon compound fixed on the surface of the solid material. Bonding with a substance can be strengthened. Therefore, as a reinforcing agent for a rubber composition or a plastic composition, it is possible to improve dispersibility in a rubber matrix or a plastic matrix and improve their properties.

  Hereinafter, matters related to the implementation of the present invention will be described in detail.

  The reinforcing agent for rubber or plastic according to the present embodiment is a monomer capable of radical polymerization by fixing a silicon compound having an alkoxysilyl group and a living radical polymerization initiating group to the surface of a solid substance and using the living radical polymerization initiating group as a polymerization initiation point. Is obtained by living radical polymerization.

  As the silicon compound, a silicon compound represented by the following general formula (1) having an alkoxysilyl group and a living radical polymerization initiating group (that is, a group having a living radical polymerization ability) in the molecule can be used.

In formula (1), A is a living radical polymerization initiating group, Z ¹ and Z ² are each independently a divalent group containing at least a carbon atom, and R ¹ and R ² are each independently a group having 1 to 1 carbon atoms. 3 is an alkyl group, and n is an integer of 1 to 3.

  Since the silicon compound of the formula (1) has an unpaired electron in the sulfur atom of the thioether group in the structure, it has high affinity with metals, inorganic substances, and polymer substances, and does not have it. Compared to the case, it is considered that the adhesiveness to the surface of the solid substance is high and the dispersibility to a matrix such as plastic or rubber is improved.

  Regarding the living radical polymerization initiating group of A, the reaction mode of the living radical polymerization may be atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), iniferter method, reversible chain transfer catalytic polymerization (RTCP). Etc.) and the like are not particularly limited.

  Examples of the group having the ability to initiate atom transfer radical polymerization include a haloalkyl group, a haloester group, a haloalkylphenyl group, a haloketone group, a halonitrile group, a halogenated sulfonyl group, and a dithiocarbamate group. A haloester group and a haloalkylphenyl group are preferable. In this case, radicals are generated in the presence of a transition metal complex such as a copper chloride / amine complex, and the polymerization reaction proceeds. Examples of the group having reversible addition-cleavage chain transfer polymerization ability include a dithioester group, a trithiocarbonate group, a xanthate group, and a dithiocarbamate group. In this case, an azo compound or an organic peroxide is used as a polymerization catalyst. Examples of iniferters include dithiocarbamate groups. An example of reversible chain transfer catalyzed polymerization (RTCP) is an alkyl iodide group. In this case, radicals are generated in the presence of a radical generator and an iodide catalyst, and the polymerization reaction proceeds.

  Examples of the haloalkyl group include trichloromethyl, bromodichloromethyl, and the like. Examples of the haloalkylphenyl group include chloromethylphenyl, bromomethylphenyl, iodomethylphenyl, (1-chloroethyl) phenyl, (1-bromoethyl) phenyl, (1-iodoethyl) phenyl, and the like. Examples of the haloketone group include trichloroethanoyl, dichloroethanoyl and the like. Examples of the halonitrile group include chlorocyanomethyl, bromocyanomethyl, iodocyanomethyl, and the like. Examples of the halogenated sulfonyl group include chlorosulfonyl and the like.

The radical polymerization initiating group of A is preferably an α-haloester group represented by the following general formula (2).

In the formula (2), R ³ , R ⁴ and R ⁵ are each independently a structure composed of at least one selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, halogen and sulfur, and R ³ , At least one of R ⁴ and R ⁵ is halogen. As the halogen, chlorine, bromine or iodine is preferable, and bromine is more preferable. R ³ , R ⁴ and R ⁵ are each basically hydrogen, a hydrocarbon group or halogen, but at least selected from the group consisting of oxygen, nitrogen and sulfur as long as the radical polymerization initiating ability is not impaired. You may have a substituent containing one hetero atom. Preferably, R ³ is halogen, and R ⁴ and R ⁵ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Provided that R ⁴ and R ⁵ are not both hydrogen. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms. The aryl group is more preferably a phenyl group and a methylphenyl group. The arylalkyl group is more preferably a benzyl group and a phenethyl group. A particularly preferred example of R ⁴ and R ⁵ is a methyl group.

It is also a preferred embodiment that the radical polymerization initiating group of A is a thiocarbonylthio group represented by the following general formula (3).

In formula (3), R ⁶ is a structure composed of at least one selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, halogen, and sulfur. Here, when R ⁶ is a hydrocarbon group, it is a dithioester group. When R ⁶ is R ⁹ -S- (wherein R ⁹ is a hydrocarbon), it is a trithiocarbonate group. When R ⁶ is R ⁹ —O— (provided that R ⁹ is a hydrocarbon), it is a xanthate group. When R ⁶ is R ¹⁰ R ¹¹ N— (wherein R ¹⁰ and R ¹¹ are each independently hydrogen or a hydrocarbon group), it is a dithiocarbamate group. These thiocarbonylthio groups may have a substituent containing at least one heteroatom selected from the group consisting of oxygen, nitrogen and halogen as long as radical polymerization initiation ability is not impaired. More preferably, in the case of a dithioester group, R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and particularly preferably a phenyl group. . In the case of a trithiocarbonate group and a xanthate group, R ⁹ is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, particularly preferably. It is a C1-C12 alkyl group. In the case of a dithiocarbamate group, R ¹⁰ and R ¹¹ are preferably each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably R ¹⁰ is an alkyl group. , R ¹¹ is an aryl group. R ¹⁰ and R ¹¹ may combine with each other to form a ring with N.

In Formula (1), Z ¹ is a divalent group that binds the radical polymerization initiating group of A and a thioether group represented by -S-, and preferably has 2 to 20 carbon atoms. The organic group may contain an ether bond, and may have a substituent containing at least one heteroatom selected from the group consisting of oxygen, nitrogen, halogen and sulfur. More preferably, ^{Z 1} is an alkylene group having 3 to 11 carbon atoms.

In Formula (1), Z ² is a divalent group that binds a thioether group and an alkoxysilyl group represented by —Si (0R ¹ ) _n (R ² ) _3-n , and preferably has a carbon number Is a divalent organic group in which 1 to 20, the organic group may include an ether bond, and a substituent including at least one heteroatom selected from the group consisting of oxygen, nitrogen, halogen, and sulfur You may have. More preferably, ^{Z 2} is an alkylene group having 1 to 3 carbon atoms.

In the formula (1), R ¹ is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group. When a plurality of R ¹ are present in one molecule, they may be the same or different. R ² is an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group or an ethyl group. When ^two or more R ² are present in one molecule, they may be the same or different. N is an integer of 1 to 3, preferably n = 3. That is, the alkoxysilyl group represented by ^{-Si (0R 1) n (R} 2) 3-n is preferably a trialkoxysilyl group, more preferably a triethoxysilyl group or a trimethoxysilyl group.

As the silicon compound used in the present embodiment, those represented by the following general formula (4) are particularly preferable. This has an α-haloester group as a radical polymerization initiating group.

In formula (4), X is a halogen, preferably chlorine, bromine or iodine, more preferably bromine. R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, preferably each independently a methyl group or an ethyl group. R ⁷ and R ⁸ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, but are not both hydrogen. R ⁷ and R ⁸ are each preferably a methyl group or an ethyl group, more preferably a methyl group. a is an integer of 3 to 11, and m is an integer of 1 to 3. n is an integer of 1 to 3, and particularly preferably n = 3.

  The silicon compound as described above can be synthesized by reacting a compound having a living radical polymerization initiating group and a carbon-carbon double bond in the molecule with a silane coupling agent having a mercapto group. Specifically, a silicon compound represented by the following general formula (5) can be produced by reacting a compound represented by the following general formula (6) with a compound represented by the following general formula (7). it can. The silicon compound represented by the formula (5) has an α-haloester group represented by the above general formula (2) as a radical polymerization initiating group in the above general formula (1). Although the production method will be described in detail, the production method of the silicon compound may have another radical polymerization initiating group even when it has a thiocarbonylthio group represented by the above general formula (3) as the radical polymerization initiating group. Even if it has, it can carry out similarly.

In formulas (5) to (7), R ¹ , R ² , Z ¹ , Z ² and n are the same as those in the above formula (1). R ³ , R ⁴ and R ⁵ are the same as in the above formula (2). Z ³ is a divalent group containing a carbon atom, preferably a divalent organic group having 1 to 18 carbon atoms, and the organic group may contain an ether bond, oxygen, nitrogen And a substituent containing at least one heteroatom selected from the group consisting of halogen and sulfur. More preferably, Z ³ is an alkylene group having 1 to 9 carbon atoms, and is a group having 2 fewer carbon atoms than Z ¹ .

  The compound represented by the formula (6) is a compound having a radical polymerization initiating group and a double bond in the molecule, and the compound represented by the formula (7) is a silane coupling agent having a mercapto group. In this reaction, the mercapto group of the compound of the formula (7) is bonded to the ene-thiol reaction with respect to the double bond of the compound of the formula (6).

  In the reaction, a radical generator is used as a reaction catalyst. Examples of the radical generator include azo compounds and organic peroxides, and those that generate radicals by heat and those that generate radicals by light irradiation are included. Examples of the azo compound include azobisisobutyronitrile (AIBN), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), and the like. Examples of the organic oxide include di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, and methyl ethyl ketone peroxide. When such a radical generator is used, generally speaking, it is considered that the compound of the formula (6) is polymerized by the vinyl bond, but actually, the ene-thiol reaction proceeds preferentially, and the formula It was found that the silicon compound represented by (5) was produced. More specifically, the reaction is performed by mixing a compound represented by the formula (6), a compound represented by the formula (7), and a radical generator together with an organic solvent such as toluene to generate radicals. It is possible to carry out by holding.

  In addition, the synthesis | combining method of the compound represented by Formula (6) is not specifically limited, It can synthesize | combine by the method disclosed by the said patent documents 3 and 4. That is, for example, for a compound having a hydroxyl group at one end of the molecular chain and an addition polymerizable double bond at the other end, an acid halide in which a halogen is bonded to the carbon at the α-position is obtained in the presence of triethylamine. What is necessary is just to make it react. On the other hand, the compound represented by the formula (7) is not particularly limited, but a silane coupling agent having a mercapto group is commercially available. Of course, you may synthesize | combine by a well-known method.

  In this embodiment, in order to produce the silicon compound represented by the above formula (4), a compound represented by the following general formula (8) and a compound represented by the following general formula (9) can be reacted. That's fine.

In the formulas (8) and (9), X, R ¹ , R ² , R ³ , R ⁴ , a, m and n are the same as in the above formula (4).

  The solid substance for fixing the silicon compound is preferably fine particles or microfibers in order to disperse in a rubber matrix or plastic matrix and reinforce them. Examples of the material of the solid substance include metals, metal compounds, inorganic substances (including inorganic compounds), and polymer compounds, and those having a hydroxyl group on the surface are preferable. This is because the silicon compound has an alkoxysilyl group in the molecule, and therefore, it is easy to realize stronger fixation by reacting with a hydroxyl group on the surface of the solid substance by hydrolysis of the alkoxy group or the like.

The average particle diameter of the fine particles as a solid substance is in the range of 0.1 nm to 1 mm, preferably 1 nm to 100 μm, more preferably 1 nm to 1 μm. Here, the particle diameter of the fine particles is an average particle diameter (a 50% integrated particle diameter) obtained from a laser diffraction / scattering method. Further, when the primary particle diameter of the fine particles is in the above range but takes the form of an aggregate structure such as an aggregate, the specific surface area is evaluated by the BET method (JIS K6217-7). In this case, the BET specific surface area is in the range of ²⁰ to 1000 m ² / g, preferably 40 to 250 m ² / g. The fine fibers have an average fiber diameter of 0.1 nm to 100 μm and an average fiber length of 100 nm to 10 mm, preferably an average fiber diameter of 1 nm to 10 μm and an average fiber length of 100 nm to 1 mm. More preferably, the average fiber diameter is in the range of 1 nm to 1 μm, and the average fiber length is in the range of 100 nm to 100 μm. Here, the average fiber diameter is obtained by randomly extracting ten fibrillated fibers from a scanning electron microscope observation (SEM) image, measuring the short diameter, and taking the arithmetic average as the average fiber diameter. The average fiber length is measured according to JIS P8121 using a fiber length measuring machine (FS-200) manufactured by KAJANI.

  More preferably, the solid substance includes inorganic fine particles having a hydroxyl group on the particle surface, such as silica fine particles, zinc oxide fine particles, titanium oxide fine particles and barium titanate fine particles, and has a good chemical bond with the silicon compound having an alkoxy group. Composite fine particles that are easy to form and in which radical polymer chains are firmly bonded can be obtained. As the solid substance, silica is particularly preferable. When polymer-grafted silica, in which a polymer phase is formed by performing graft polymerization from the silica surface, is incorporated into a rubber composition, the presence of the polymer phase improves dispersibility in the rubber matrix, and the polymer chain is directly bonded to the silica. By bonding, it is considered that a hard resin phase is formed even after mixing with rubber, and the reinforcement is increased. Therefore, it is possible to achieve high elasticity while suppressing an increase in heat generation.

  The method for fixing the silicon compound to the surface of the solid substance is not particularly limited, and for example, a surface treatment method usually used for a silane coupling agent can be applied. For example, a dry treatment in which the silicon compound is dissolved as it is or in an appropriate solvent may be sprayed and mixed on a solid material, or a slurry is prepared by adding water to the solid material, and the silicon compound is added thereto. Wet processing with stirring may be used.

  Here, the fixation means that the silicon compound may be chemically bonded to the surface of the solid substance by hydrolysis of an alkoxy group, or may be a physical bond such as a hydrogen bond, or may be trapped in the pores of the solid surface. Good. As a method for confirming whether or not it is fixed, after the fixing treatment, after washing with an organic solvent or the like, whether the element in the silicon compound is present on the surface of the fixing treatment is determined by energy dispersive X-ray spectroscopy (EDX) or Measurement can be performed using X-ray electron spectroscopy (XPS) or the like.

  A monomer is living radically polymerized from the silicon compound using a solid substance to which the silicon compound is fixed. Since the silicon compound has a living radical polymerization initiating group in the molecule as described above, it is possible to perform living radical polymerization of a monomer capable of radical polymerization using the polymerization initiating group as a polymerization initiation point. Thereby, a reinforcing agent as a composite of a polymer and a solid substance, that is, a composite in which a polymer graft chain is formed on the surface of the solid substance (hereinafter sometimes referred to as a polymer graft reinforcing agent) is obtained.

  Examples of radically polymerizable monomers include vinyl monomers and diene monomers. Examples of vinyl monomers include acrylic acid monomers, methacrylic monomers, acrylamide monomers, styrene monomers, vinyl acetate, and acrylonitrile. .

  Examples of acrylic acid monomers include acrylic acid, methyl acrylate, ethyl acrylate, 2-carboxyethyl acrylate, 2- (dimethylamino) ethyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, Butyl acrylate, sodium acrylate, isobornyl acrylate, propargyl acrylate, ethylene glycol methyl ether acrylate, hexyl acrylate, lauryl acrylate, isobutyl acrylate, 2-hydroxyethyl acrylate, tert-butyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, Isodecyl acrylate, 4-hydroxybutyl acrylate, 2-naphthyl acrylate, 2-ethylhexyl Acrylate, trimethylsilyl acrylate, 2,2,2-trifluoroethyl acrylate, 4-tert-butylcyclohexyl acrylate, fluorescein o-acrylate, 9-anthracene methyl acrylate.

  Examples of the methacrylic acid monomer include 3- (acryloyloxy) -2-hydroxypropyl methacrylate, allyl methacrylate, benzyl methacrylate, butyl methacrylate, tert-butyl methacrylate, and 11- [4- (4-butylphenylazo) phenoxy]. Undecyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2- (diethylamino) ethyl methacrylate, diethylene glycol monomethyl ether methacrylate, 2- (dimethylamino) ethyl methacrylate, lauryl methacrylate, 2 -Ethoxyethyl methacrylate, ethylene glycol monoethyl ether methacrylate, ethyl methacrylate , Furfuryl methacrylate, glycidyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, hexyl methacrylate, ethylene glycol methacrylate, isobornyl methacrylate, isobutyl methacrylate, 2-isocyanatoethyl methacrylate, isopropyl methacrylate, Methacrylic acid, methyl methacrylate, 1H, 1H, 5H-perfluoropentyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, stearyl methacrylate, N-succinimide methacrylate, 3-sulfopropyl potassium methacrylate, 2 , 2,3,3-tetrafluoropropyl methacrylate, tetrahydrofurfuryl methacrylate, 2,2,6,6-the Lamethyl-4-piperidyl methacrylate, tridecyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, 2- (trimethylsilyloxy) ethyl methacrylate , 3- (tris (trimethylsilyloxy) silyl) propyl methacrylate and the like.

  Examples of acrylamide monomers include acrylamide, 6-acrylamidohexanoic acid, 2-acrylamido-2-methylpropanesulfonic acid, (3-acrylamidopropyl) trimethylammonium chloride, N- (butoxymethyl) acrylamide, and N-tert-butyl. Acrylamide, trans-3-phenylacrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N, N-diethylacrylamide, N, N ′-(1,2-dihydroxyethylene) bisacrylamide, N, N -Dimethylacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N-dodecylacrylamide, N-ethyl-N- (4-pyridylmethyl) -2-phenylacrylamide, N- (2-hydroxy) And ethyl) acrylamide, N- (hydroxymethyl) acrylamide, N-isopropylacrylamide, N, N′-methylenebisacrylamide and the like.

  Styrene monomers include styrene, 4-aminostyrene, 4-bromo-β, β-difluorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 4-tert-butylstyrene, 4- (chloro Methyl) styrene, 4-chloro-α-methylstyrene, chloromethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,6-dichlorostyrene, 4-fluoro-α-methylstyrene, 3- Fluorostyrene, 4-fluorostyrene, 4-isopropenyltoluene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, β-methylstyrene, 4-nitrostyrene, 4 -N-octylstyrene, 2,3,4,5,6-pentafluorovinyl Styrene, alpha-(trimethylsilyloxy) styrene, beta-sodium styrene sulfonate, 2,4,6-trimethyl styrene, vinyl cyanide, 2-acetoxystyrene, 4-acetoxy styrene.

  Examples of the diene monomer include 1,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like.

  The monomers exemplified above may be used either alone or in combination of two or more.

  In the living radical polymerization, for example, when the living radical polymerization initiating group has an atom transfer radical polymerization initiating ability, a transition metal complex is used as a catalyst. As such a transition metal complex, a metal complex having an element as a central metal of Group 7, Group 8, Group 9, Group 10, or Group 11 of the periodic table is preferable, and more preferably zero-valent copper, monovalent Copper, divalent ruthenium, divalent iron or divalent nickel complex, particularly preferably a monovalent copper complex, and a copper (I) complex having an amine / imine polydentate ligand, Copper chloride / amine complexes are preferably used. Further, for example, when the living radical polymerization initiating group has reversible addition-fragmentation chain transfer polymerization ability, azo such as azobisisobutyronitrile (AIBN), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), etc. An organic peroxide such as a compound, di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide is used as a polymerization catalyst.

  In the polymer graft reinforcing agent thus obtained, the amount of the polymer graft chain on the surface of the solid substance formed by living radical polymerization of the monomer is 5 to 1000 parts by mass with respect to 100 parts by mass of the solid substance. It is preferable. The amount of the polymer graft chain is more preferably 30 to 500 parts by mass, and still more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the solid substance.

  In the polymer graft reinforcing agent, the glass transition temperature (Tg) of the polymer graft chain is not particularly limited, and can be appropriately set within a range of, for example, -100 ° C to 150 ° C. For example, when blended in a rubber composition, if the Tg of the polymer graft chain is in the vicinity of 10 to 70 ° C., tan δ in the vicinity of 60 ° C. can be effectively increased. It is suitable for energy absorbing rubbers such as anti-vibration rubbers. Further, when the Tg of the polymer graft chain is in a high temperature region of 80 ° C. or higher, it is possible to suppress an increase in tan δ near room temperature while increasing the elastic modulus. Further, when the Tg of the polymer graft chain is in a low temperature region of −10 ° C. or lower, tan δ can be increased while suppressing an increase in the elastic modulus at around 0 ° C. Therefore, a tire rubber with high grip properties can be obtained. It is also suitable as rubber for winter tires. The Tg of these polymer graft chains can be set depending on the type of monomer constituting the polymer graft chain.

  The polymer graft reinforcing agent is added to a rubber component or a plastic component and used to reinforce a rubber composition or a plastic composition. By blending the polymer graft reinforcing agent, the dispersibility of the reinforcing agent (solid substance) in the rubber matrix or the plastic matrix can be improved, and the properties of the rubber composition and the plastic composition can be improved. In addition, in the polymer graft reinforcement, the graft polymer chain is fixed on the surface of the solid material, so that the polymer graft chain can be retained even after mixing with the rubber matrix or plastic matrix, and the effect of increasing the elasticity is exhibited. Easy to be.

  According to the rubber composition according to the present embodiment, the polymer graft reinforcing agent is blended at 1 to 200 parts by mass with respect to 100 parts by mass of the rubber component. The blending amount of the polymer graft reinforcing agent is more preferably 10 to 150 parts by mass, still more preferably 20 to 100 parts by mass.

  Examples of rubber components in the rubber composition include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR ), Butyl rubber (IIR), halogenated butyl rubber (for example, brominated butyl rubber, chlorinated butyl rubber), ethylene propylene rubber (EPDM), etc., and these may be used alone or in combination of two or more. Can do. A diene rubber is preferably used as the rubber component.

  In addition to the polymer graft reinforcing agent, the rubber composition includes reinforcing fillers such as untreated silica and carbon black, silane coupling agents, oil, zinc white, stearic acid, anti-aging agents, waxes, additives. Various additives generally used in rubber compositions, such as a vulcanizing agent and a vulcanization accelerator, can be blended.

  Examples of the vulcanizing agent include sulfur and sulfur-containing compounds (for example, sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, etc.). It can be used in combination of more than one species. Although the compounding quantity of a vulcanizing agent is not specifically limited, It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of rubber components, More preferably, it is 0.5-5 mass parts.

  As the vulcanization accelerator, for example, various vulcanization accelerators such as sulfenamide-based, thiuram-based, thiazole-based, and guanidine-based compounds can be used, and any one of them can be used alone or in combination of two or more. Can do. The blending amount of the vulcanization accelerator is not particularly limited, but is preferably 0.1 to 7 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. .

  The rubber composition can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll, or other mixer. The use of the rubber composition thus obtained is not particularly limited, but can be used for various rubber compositions such as tires such as treads and sidewalls, conveyor belts, and vibration-proof rubbers. Various rubber molded bodies can be obtained by vulcanization molding at ˜200 ° C.

  According to the plastic composition according to the present embodiment, the polymer graft reinforcing agent is blended at 1 to 200 parts by mass with respect to 100 parts by mass of the plastic component. The blending amount of the polymer graft reinforcing agent is more preferably 10 to 150 parts by mass, still more preferably 20 to 100 parts by mass.

  Examples of the plastic component in the plastic composition include polyolefin, polystyrene, polyacrylate, polymethacrylate, polyester, polyamide, polyurethane, polycarbonate, polyimide, etc., and these are used alone or in combination of two or more. Can be used.

  In addition to the polymer graft reinforcing agent, the plastic composition is blended with various additives generally used in plastic compositions such as antioxidants, plasticizers, crosslinking agents, inorganic particles, glass fibers, and organic fibers. be able to.

  The plastic composition can be prepared by kneading according to a conventional method using a mixer such as a commonly used mixer or kneader. The use of the plastic composition thus obtained is not particularly limited, but can be used for various plastic compositions of films, containers, coating agents, adhesives, automobile parts, and heat insulating materials. Various plastic moldings can be obtained by compression molding or the like.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Synthesis of silicon compounds>
[Synthesis Example 1]
Synthesis of 6- (3- (triethoxysilyl) propylthio) hexyl 2-bromo-2-methylpropanoate:
5-Hexen-1-ol (42.6 g), triethylamine (45.8 g) and tetrahydrofuran (0.8 L) were mixed and then ice-cooled, and 2-bromoisobutyryl bromide (100 g) was added dropwise. Thereafter, the reaction solution was stirred at 4 ° C. for 3 hours and then stirred at room temperature for 15 hours. The reaction solution was filtered, concentrated with an evaporator, and then dissolved in diethyl ether (300 mL). It was dissolved in 1N hydrochloric acid solution (2 × 300 mL), saturated sodium bicarbonate solution (2 × 300 mL), and distilled water (2 × 300 mL). ) In this order. Thereafter, the organic layer is dried over sodium sulfate, filtered, concentrated by an evaporator, purified by a silica gel column (developing solvent: hexane / ethyl acetate = 15/1), concentrated, and then expressed by the following chemical formula. 74.2 g of hexenyl 2-bromo-2-methylpropanate (Compound 1) was obtained.

  Next, Compound 1 (10.1 g), 3-mercaptopropyltriethoxysilane (9.58 g: “3-mercaptopropyltriethoxysilane” manufactured by Tokyo Chemical Industry Co., Ltd.), AIBN (0.194 g), and toluene (20 g) was mixed, and after bubbling with nitrogen gas for 30 minutes, the reaction solution was held at 70 ° C. for 3 hours, concentrated with an evaporator, and then 6- (3- (triethoxysilyl) propylthio represented by the following chemical formula. ) 17.2 g of hexyl 2-bromo-2-methylpropanate (compound 2) was obtained (yield: 88%).

From the following NMR results, it was identified that the product was a compound represented by the following chemical formula. ¹ H-NMR (400 MHz, TMS standard = 0.0 ppm): 1.93 (s, 6H, (CH ₃ ) ₂ BrC—), 4.17 (t, 2H, — (O═C) —O—CH ₂ —), 1.70 (m, 2H,-(O = C) -O-CH ₂ -C H _2- ), 1.43 (t, 4H,-(O = C) -O-CH ₂ -CH ₂ -C H ₂ -C H _{2 -), 1.60 (t,} 2H, O = CO-CH 2 -CH 2 -CH 2 -CH 2 -C H 2 -), 2.5 (t, 2H, -C H 2 -S-CH 2 -), 2.53 (t, 2H, -CH ₂ -SC H _2- ), 1.69 (m, 2H, -CH ₂ -S-CH ₂ -C H _2- ), 0.74 (t, 2H, -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 3.82 (q, 6H, -CH ₂ -Si- (OC H ₂ -CH ₃ ) ₃ , 1..23 (t, 9H, -CH ₂ -Si- (O -CH ₂ -C H ₃ ) ₃ .
¹³ C-NMR (400MHz, TMS standard = 0.0ppm): 30.9 ((C H 3) 2 BrC -), 55.9 ((CH 3) 2 Br C -), 171.5 (- (O = C) -O-CH _2- ), 65.9 (-(O = C) -O- C H _2- ), 28.3 (-(O = C) -O-CH ₂ - C H _2- ), 25.9 (-(O = C)- O-CH ₂ -CH ₂ - C H _2- ), 28.4 (-(O = C) -O-CH ₂ -CH ₂ -CH ₂ - C H _2- ), 29.6 (-(O = C) -O _{-CH 2 -CH 2 -CH 2 --CH 2} - C H 2 -), 32.0 (- C H 2 -S-CH 2 -), 35.3 (-CH 2 -S- C H 2 -), 23.2 ( -CH ₂ -S-CH ₂ - C H _2- ), 10.3 ( -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 58.4 (-CH ₂ -Si- (O- C H _2- CH ₃ ) ₃ , 18.3 (-CH ₂ -Si- (O-CH ₂ - C H ₃ ) ₃ .

[Synthesis Example 2]
3- (3- (triethoxysilyl) propylthio) propyl 2-bromo-2-methylpropanoate:
Allyl 2- (2-bromo-2-methyl) propionate (1.5 g: Sigma-Aldrich), 3-mercaptopropyltriethoxysilane (1.73 g), AIBN (0.036 g), and toluene (20 g) And then bubbling with nitrogen gas for 30 minutes, the reaction solution was held at 70 ° C. for 3 hours, concentrated with an evaporator, and then 3- (3- (triethoxysilyl) propylthio) propyl 2 represented by the following chemical formula. -2.95g of bromo-2-methylpropanate (compound 3) was obtained (yield: 91%). The obtained compound 3 is a polymerization initiator capable of living radical polymerization as in the case of compound 2, and has a triethoxysilyl group capable of reacting with a silanol group on the silica surface. Was usable.

From the following NMR results, it was identified that the product was a compound represented by the following chemical formula. ¹ H-NMR (400 MHz, TMS standard = 0.0 ppm): 1.93 (s, 6H, (CH ₃ ) ₂ BrC—), 4.27 (t, 2H, — (O═C) —O—CH ₂ —), 1.97 (m, 2H,-(O = C) -O-CH ₂ -C H _2- ), 2.61 (t, 2H, -C H ₂ -S-CH _2- ), 2.55 (t, 2H, -CH ₂ -SC H _2- ), 1.71 (m, 2H, -CH ₂ -S-CH ₂ -C H _2- ), 0.74 (t, 2H, -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 3.82 (q, 6H, -CH ₂ -Si- (OC H ₂ -CH ₃ ) ₃ , 1..23 (t, 9H, -CH ₂ -Si- (O-CH ₂ -C H ₃ ) ₃ .
¹³ C-NMR (400 MHz, TMS standard = 0.0 ppm): 30.8 (( C H ₃ ) ₂ BrC-), 55.9 ((CH ₃ ) ₂ Br C- ), 171.5 (-(O = C ) -O-CH _2- ), 64.6 (-(O = C) -O- C H _2- ), 28.6 (-(O = C) -O-CH ₂ - C H _2- ), 28.3 ( -C H ₂ -S- CH _2- ), 35.2 (-CH ₂ -S- C H _2- ), 23.2 (-CH ₂ -S-CH ₂ - C H _2- ), 9.94 ( -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 58.4 (-CH ₂ -Si- (O- C H ₂ -CH ₃ ) ₃ , 18.4 (-CH ₂ -Si- (O-CH ₂ - C H ₃ ) ₃ .

[Synthesis Example 3]
11- (3- (triethoxysilyl) propylthio) undecyl 2-bromo-2-methylpropanoate:
10-Undecen-1-ol was used instead of 5-hexen-1-ol in Synthesis Example 1, and 10-undecenyl 2-bromo-2-methylpropanate (compound) represented by the following chemical formula was used in the same procedure. 4) was obtained.

  Next, by reacting 10-undecenyl 2-bromo-2-methylpropanate and 3-mercaptopropyltriethoxysilane in the same procedure as in Synthesis Example 1, 11- (3- (triethoxy Silyl) propylthio) undecyl 2-bromo-2-methylpropanate (compound 5) was obtained. The obtained compound 5 is a polymerization initiator capable of living radical polymerization like the compound 2, and has a triethoxysilyl group capable of reacting with a silanol group on the silica surface. Was usable.

From the following NMR results, it was identified that the product was a compound represented by the following chemical formula. ¹ H-NMR (400 MHz, TMS standard = 0.0 ppm): 1.92 (s, 6H, (CH ₃ ) ₂ BrC—), 4.16 (t, 2H, — (O═C) —O—CH ₂ —), 1.28 ~1.38 (m, 16H, - ( O = C) -O-CH 2 - (C H 2) 8 -), 1.56 (m, 16H, - (O = C) -O-CH 2 - (CH 2) ₈ -C H _2- ), 2.5 (t, 2H, -C H ₂ -S-CH _2- ), 2.53 (t, 2H, -CH ₂ -SC H _2- ), 1.70 (m, 2H, -CH ₂ -S-CH ₂ -C H _2- ), 0.73 (t, 2H, -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 3.82 (q, 6H, -CH ₂ -Si- ( OC H ₂ -CH ₃ ) ₃ , 1..23 (t, 9H, -CH ₂ -Si- (O-CH ₂ -C H ₃ ) ₃ .
¹³ C-NMR (400MHz, TMS standard = 0.0ppm): 30.8 ((C H 3) 2 BrC -), 56.4 ((CH 3) 2 Br C -), 172.1 (- (O = C) -O-CH _{2 -), 66.2 (- (} O = C) -O- C H 2 -), 29.0~29.5 (- (O = C) -O-CH 2 - (C H 2) 8 -), 29.8 (- ( O = C) -O-CH _2- (CH ₂ ) ₈ - C H ₂ ), 32.0 ( -C H ₂ -S-CH _2- ), 35.3 (-CH ₂ -S- C H _2- ), 23.3 (-CH ₂ -S-CH ₂ -C H _2- ), 9.7 ( -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 58.4 (-CH ₂ -Si- (O- C H ₂ -CH ₃ ) ₃ , 18.4 (-CH ₂ -Si- (O-CH ₂ - C H ₃ ) ₃ .

[Synthesis Example 4]
Synthesis of 6- (3- (triethoxysilyl) propylthio) hexyl 2-iodo-2-methylpropanoate:
6- (3- (Triethoxysilyl) propylthio) hexyl 2-bromo-2-methylpropanate (5 g), sodium iodide (20 g) obtained by the procedure of Synthesis Example 1 and 100 mL of dry acetone were mixed, and nitrogen was added. The reaction was carried out at 75 ° C. for 10 hours under an atmosphere. After the reaction, extraction was performed to obtain 6- (3- (triethoxysilyl) propylthio) hexyl 2-iodo-2-methylpropanate (Compound 6) represented by the following chemical formula. The obtained compound 6 is a polymerization initiator capable of living radical polymerization like the compound 2, and has a triethoxysilyl group capable of reacting with a silanol group on the silica surface. Was usable.

From the following NMR results, it was identified that the product was a compound represented by the following chemical formula. ¹ H-NMR (400 MHz, TMS standard = 0.0 ppm): 2.2 (s, 6H, (CH ₃ ) ₂ IC—), 4.17 (t, 2H, — (O═C) —O—CH ₂ —), 1.70 (m, 2H,-(O = C) -O-CH ₂ -C H _2- ), 1.43 (t, 4H,-(O = C) -O-CH ₂ -CH ₂ -C H ₂ -C H _{2 -), 1.60 (t,} 2H, O = CO-CH 2 -CH 2 -CH 2 -CH 2 -C H 2 -), 2.5 (t, 2H, -C H 2 -S-CH 2 -), 2.53 (t, 2H, -CH ₂ -SC H _2- ), 1.69 (m, 2H, -CH ₂ -S-CH ₂ -C H _2- ), 0.74 (t, 2H, -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 3.82 (q, 6H, -CH ₂ -Si- (OC H ₂ -CH ₃ ) ₃ , 1..23 (t, 9H, -CH ₂ -Si- (O -CH ₂ -C H ₃ ) ₃ .
¹³ C-NMR (400MHz, TMS standard = 0.0ppm): 27.5 ((C H 3) 2 IC -), 57.4 ((CH 3) 2 Br C -), 171.5 (- (O = C) -O -CH _2- ), 65.9 (-(O = C) -O- C H _2- ), 28.3 (-(O = C) -O-CH ₂ - C H _2- ), 25.9 (-(O = C ) -O-CH ₂ -CH ₂ - C H _2- ), 28.4 (-(O = C) -O-CH ₂ -CH ₂ -CH ₂ - C H _2- ), 29.6 (-(O = C) -O-CH ₂ -CH ₂ -CH ₂ --CH ₂ - C H _2- ), 32.0 ( -C H ₂ -S-CH _2- ), 35.3 (-CH ₂ -S- C H _2- ), 23.2 (-CH ₂ -S-CH ₂ -C H _2- ), 10.3 ( -C H ₂ -Si- (O-CH ₂ -CH ₃ ) ₃ , 58.4 (-CH ₂ -Si- (O- C H ₂ -CH ₃ ) ₃ , 18.3 (-CH ₂ -Si- (O-CH ₂ - C H ₃ ) ₃ .

<Synthesis of polymer graft reinforcement>
[Example 1]
Silica (35 g: “Nippal AQ” manufactured by Tosoh Silica Co., Ltd., BET specific surface area = 205 m ² / g), 28 mass% ammonia water (66 g), and ethanol 1000 mL were mixed and stirred for 1 hour, then compound 2: 6- (3- (triethoxysilyl) propylthio) hexyl 2-bromo-2-methylpropanate (10 g) was added dropwise and stirred at room temperature for 16 hours. Silica was collected from the obtained solution by a centrifugal separator and washed with ethanol and anisole to obtain 28 g of silica (polymerization initiator-introduced silica) having Compound 2 fixed on the particle surface.

  Next, the obtained polymerization initiator-introduced silica (22.9 g), benzyl methacrylate (200 g), ethyl 2-bromobutyrate (1.14 g), 4,4′-dinonyl-2,2′-bipyridyl (4. 54 g) and anisole (300 g) were mixed, and after bubbling with nitrogen for 1.5 hours, copper (I) chloride (0.56 g) was added to the reaction solution and maintained at 50 ° C. for 5 hours. The obtained solution was centrifuged to separate the solid phase, washed with anisole and dried, and then polymer graft silica (43 g) was obtained as reinforcing agent 1.

[Examples 2 to 4]
Reinforcing agents 2 to 4 were obtained in the same manner as in Example 1 except that the charging ratio (molar ratio) of the monomer (benzyl methacrylate) to the polymerization initiator was changed as shown in Table 1 below.

[Example 5]
The type of monomer was changed from benzyl methacrylate to methyl methacrylate, and the others were polymer grafted silica as reinforcing agent 5 in the same manner as in the synthesis of reinforcing agent 1.

[Example 6]
The type of monomer was changed from benzyl methacrylate to tridecyl methacrylate, and polymer graft silica was obtained as the reinforcing agent 6 in the same manner as in the synthesis of the reinforcing agent 1 except for the above.

[Measurement of polymer graft amount of reinforcing agent]
From the measurement results by TGA (temperature increase rate 5 ° C./min, temperature range 50 ° C. to 500 ° C.), the polymer graft amount was calculated as shown in Table 1 based on the following formula (A).

Formula (A): P = (W _Initial -W _{500 ℃} /0.9)/(W _{500 ℃} /0.9)
P: Polymer graft mass per unit mass of silica
W _initial stage: TGA measurement charge mass (mg)
W _{500 ° C} : Mass of residue at 500 ° C (mg)
[Measurement of glass transition temperature of polymer graft chain]
DSC measurement was performed on the reinforcing agent in the range of −100 ° C. to 150 ° C. under the temperature rising rate of 20 ° C./min, and the glass transition temperature (Tg) of the polymer graft chain was determined.

  From the TGA measurement of the obtained reinforcing agent, the presence of the graft polymer chain was confirmed. Further, as shown in Table 1, the monomer charge ratio and the amount of the polymer graft chain were in a proportional relationship, indicating that the polymerization was performed in a living manner from the silica surface.

[Example 7]
Zinc oxide (100 g: “FINEX-30” manufactured by Sakai Chemical Industry Co., Ltd.), 28 mass% ammonia water (66 g), and ethanol 1000 mL were mixed and stirred for 1 hour, then compound 2: 6- (3- (Triethoxysilyl) propylthio) hexyl 2-bromo-2-methylpropanate (10 g) was added dropwise and stirred at room temperature for 16 hours. Zinc oxide was recovered from the obtained solution by a centrifugal separator and washed with ethanol and anisole to obtain 82 g of zinc oxide (polymerization initiator-introduced zinc oxide) in which compound 2 was fixed to the particle surface.

  Next, the obtained polymerization initiator-introduced zinc oxide (62 g), benzyl methacrylate (200 g), ethyl 2-bromobutyrate (1.14 g), 4,4′-dinonyl-2,2′-bipyridyl (4.54 g) ) And anisole (300 g) were mixed and nitrogen bubbling was performed for 1.5 hours, and then copper (I) chloride (0.56 g) was added to the reaction solution and kept at 50 ° C. for 5 hours. The obtained solution was centrifuged to separate the solid phase, washed with anisole, and dried to obtain polymer grafted zinc oxide (75.9 g) as reinforcing agent 7. About the obtained reinforcing agent 7, it carried out similarly to the said reinforcing agent 1, and measured the polymer graft amount. The results are shown in Table 2 below.

[Example 8]
After mixing barium titanate (100 g: “BT01” manufactured by Sakai Chemical Industry Co., Ltd.), 28 mass% ammonia water (66 g), and ethanol 1000 mL, the mixture was stirred for 1 hour, then compound 2: 6- (3- ( Triethoxysilyl) propylthio) hexyl 2-bromo-2-methylpropanate (10 g) was added dropwise and stirred at room temperature for 16 hours. Barium titanate was collected from the obtained solution by a centrifugal separator and washed with ethanol and anisole to obtain 85 g of barium titanate (polymerization initiator-introduced barium titanate) in which compound 2 was fixed to the particle surface. .

  Next, the polymerization initiator-introduced barium titanate (68 g), benzyl methacrylate (200 g), ethyl 2-bromobutyrate (1.14 g), 4,4′-dinonyl-2,2′-bipyridyl (4. 54 g) and anisole (300 g) were mixed, and after bubbling with nitrogen for 1.5 hours, copper (I) chloride (0.56 g) was added to the reaction solution and maintained at 50 ° C. for 5 hours. The obtained solution was centrifuged to separate the solid phase, washed with anisole and dried, and then polymer grafted barium titanate (82 g) was obtained as reinforcing agent 8. About the obtained reinforcing agent 8, it carried out similarly to the said reinforcing agent 1, and measured the polymer graft amount. The results are shown in Table 3 below.

<Evaluation of rubber composition>
In the following evaluation of the rubber composition, polymers C1 to C3 blended in the rubber composition of the comparative example were synthesized as follows.

[Synthesis of Polymer C1]
Benzyl methacrylate (30 g), ethyl 2-bromobutyrate (0.66 g), 4,4′-dinonyl-2,2′-bipyridyl (1.4 g), and anisole (30 g) were mixed and nitrogen was added for 1.5 hours. After bubbling, copper (I) chloride (0.17 g) was added to the reaction solution and kept at 50 ° C. for 5 hours. The resulting solution was reprecipitated in ethanol to obtain polybenzyl methacrylate (polymer C1).

[Synthesis of Polymer C2]
The kind of monomer was changed from benzyl methacrylate to methyl methacrylate, and the others were obtained in the same manner as for polymer C1 to obtain polymethyl methacrylate (polymer C2).

[Synthesis of Polymer C3]
The kind of monomer was changed from benzyl methacrylate to tridecyl methacrylate, and the others were obtained in the same manner as in polymer C1 to obtain polytridecyl methacrylate (polymer C3).

[Examples 9 and 10 and Comparative Examples 1 and 2]
Using a Banbury mixer, according to the formulation (parts by mass) shown in Table 4 below, first, in the first mixing stage, other compounding agents excluding sulfur and vulcanization accelerator are added and kneaded, and then kneaded. In the final mixing stage, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to prepare a rubber composition. Details of each component in Table 4 are as follows.

SBR: Styrene butadiene rubber, “SBR1502” manufactured by JSR Corporation
・ Silica: “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd.
Silane coupling agent: bis (3-triethoxysilylpropyl) tetrasulfide, “Si69” manufactured by Evonik Degussa
・ Zinc flower: “Zinc flower 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
Anti-aging agent: “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
・ Sulfur: Hosoi Chemical Co., Ltd. “Powder sulfur for rubber 150 mesh”
・ Vulcanization accelerator: “Noxeller CZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Secondary vulcanization accelerator: “Noxeller D” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

About each obtained rubber composition, the test piece of a predetermined shape is produced by vulcanizing at 160 ° C. for 20 minutes, and using the obtained test piece, the dynamic elastic modulus E ^* and tan δ at 25 ° C. The dynamic elastic modulus E ^* and tan δ at 60 ° C. were measured. Each measuring method is as follows.

-25 degreeC dynamic elastic modulus E ^* : Dynamic elastic modulus ^* was measured on the conditions of frequency 50Hz, static strain 10%, dynamic strain 2%, and temperature 25 degreeC using the rheometer E4000 by UBM.

-25 degreeC tan-delta: Loss coefficient tan-delta was measured on the conditions of frequency 50Hz, static strain 10%, dynamic strain 2%, and temperature 25 degreeC using the rheometer E4000 by UBM.

60 ° C. dynamic elastic modulus E ^* , 60 ° C. tan δ: The temperature was changed to 60 ° C., and the others were measured in the same manner as 25 ° C. dynamic elastic modulus E ^* and 25 ° C. tan δ.

  The results are as shown in Table 4. Compared with Comparative Example 1 as a control, in Comparative Example 2, the addition of the resin (polymer C1) increased the dynamic elastic modulus and tan δ value. On the other hand, in Example 9 in which the reinforcing agent 1 which is polymer graft silica was blended, the dynamic elastic modulus and the tan δ value were significantly increased as compared with Comparative Example 1. Further, in Example 10 in which the total amount of the reinforcing filler was the reinforcing agent 2 that was polymer-grafted silica, the dynamic elastic modulus further increased from that in Example 9. In Comparative Example 2, Example 9 and Example 10, the silica component and the polybenzyl methacrylate component (polybenzyl methacrylate grafted in the reinforcing agents 1 and 2) are almost the same in the rubber compounding. Polybenzyl methacrylate is considered to exist as an isolated phase, whereas in Examples 9 and 10, all the polybenzyl methacrylate is bonded to silica, so that the dynamic elastic modulus and tan δ are efficiently increased. doing. Such a rubber exhibiting a large energy loss at around 60 ° C. is suitable for a tread rubber blend that requires high grip properties and an energy absorbing rubber.

[Example 11 and Comparative Example 3]
Using a Banbury mixer, according to the composition (parts by mass) shown in Table 5 below, a rubber composition was prepared in the same manner as in Example 9, and a test piece prepared from each of the obtained rubber compositions was used at 25 ° C. The dynamic elastic modulus E ^* and tan δ were measured.

  The results are as shown in Table 5. Compared with Comparative Example 1 as a control, in Comparative Example 3, the dynamic elastic modulus was increased by blending polymethyl methacrylate (polymer C2). In Example 11 in which the reinforcing agent 5 was added, the dynamic elastic modulus further increased. On the other hand, since the glass transition temperature of polymethylmethacrylate is in the high temperature region, the increase in the tan δ value near the room temperature was suppressed. Therefore, the rubber composition of Example 11 is suitable for a fuel-efficient tire rubber or the like.

[Example 12 and Comparative Example 4]
Using a Banbury mixer, according to the composition (parts by mass) shown in Table 6 below, a rubber composition was prepared in the same manner as in Example 9, and a test piece prepared from each of the obtained rubber compositions was used at 0 ° C. The dynamic elastic modulus E ^* and tan δ at 25 ° C. and the dynamic elastic modulus E ^* and tan δ at 25 ° C. were measured. The dynamic elastic modulus E ^* and tan δ at 0 ° C. were measured in the same manner as the 25 ° C. dynamic elastic modulus E ^* and 25 ° C. tan δ except that the temperature was changed to 0 ° C.

  The results are as shown in Table 6. Compared with Comparative Example 1 which is a control, in Comparative Example 4, the tan δ value in the low temperature region is increased by adding polytridecyl methacrylate (Polymer C3). In Example 12 in which the reinforcing agent 6 which is graft silica was blended, the tan δ value could be further increased. In addition, since the glass transition temperature of polytridecyl methacrylate exists in the low temperature region, it was possible to increase the tan δ value in the low temperature region while suppressing an increase in the dynamic elastic modulus. Therefore, the rubber composition of Example 12 is suitable for high grip rubber for tires, rubber for winter tires, and the like.

  The above results indicate that the dynamic viscoelasticity of the rubber composition can be efficiently and arbitrarily controlled by selecting the polymer (monomer to be used) to be grafted to the reinforcing agent. Of course, the graft polymer may be a copolymer or block copolymer of two or more types, and two or more types of reinforcing agents may be blended in the rubber component.

<Evaluation of plastic composition>
[Example 13 and Comparative Examples 5 and 6]
Using a biaxial kneader (manufactured by Plastics Engineering Laboratory), the mixture was melt kneaded and pelletized according to the formulation (parts by mass) shown in Table 7. The obtained pellets were T-die molded into a film having a width of 350 mm and a thickness of 0.2 mm using a single screw extruder. Details of the components in Table 7 are as follows.

・ Polyester: Toyobo "Perprene P30B"
・ Silica: “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd.
About each obtained film, the air permeability coefficient was measured with the following method.

Air permeability coefficient: In accordance with JIS K7126-1, using a gas permeability measuring device “BT-3” manufactured by Toyo Seiki Seisakusho Co., Ltd., test gas: air, test temperature: air permeability coefficient at 80 ° C. Was measured and displayed as an index with the air permeability coefficient of the film of Comparative Example 5 as 100. The smaller the index, the smaller the air permeability coefficient and the better the gas barrier property.

  A result is as showing in Table 7, and the air permeability coefficient fell in Example 13 which added the reinforcing agent 1 with respect to the comparative example 6 which mixed the silica and polymer C1 in polyester. This is because, in the reinforcing agent 1, the polymer is grafted on the silica, so that the high-dispersion in the polyester matrix effectively lengthens the air molecule permeation path. On the other hand, in Comparative Example 6 in which silica was added alone, there was an effect of lengthening the permeation path of air molecules, but the dispersibility reached Example 13, which is considered to be limited. Such a plastic composition can be applied to containers, packaging materials, and the like.

Claims (7)

For rubber or plastics characterized in that a silicon compound represented by the following general formula (1) is fixed to the surface of a solid substance, and a radical-polymerizable monomer is subjected to living radical polymerization using the living radical polymerization initiating group as a polymerization initiation point. A method of manufacturing a reinforcing agent.

(In the formula, A is a living radical polymerization initiating group, Z ¹ and Z ² are each independently a divalent group containing at least carbon atoms, and R ¹ and R ² are each independently a group having 1 to 3 carbon atoms. (It is an alkyl group. N is an integer of 1 to 3.) The method according to claim 1, wherein A is a compound represented by the following general formula (2) or general formula (3).

(Wherein R ³ , R ⁴ and R ⁵ are each independently a structure composed of at least one selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, halogen and sulfur, and R ³ , R ⁴ And at least one of R ⁵ is halogen.)

(Wherein R ⁶ is a structure composed of at least one selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, halogen and sulfur.) The said silicon compound is a compound represented by following General formula (4), The manufacturing method of Claim 1 characterized by the above-mentioned.

(In the formula, X is a halogen, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms. R ⁷ and R ⁸ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms. A is an integer from 3 to 11, m is an integer from 1 to 3, and n is an integer from 1 to 3.   It is obtained by the manufacturing method of any one of Claims 1-3, The quantity of the polymer graft chain of the said solid substance surface is 5-1000 mass parts with respect to 100 mass parts of said solid substances. Reinforcing agent for rubber or plastic.   The rubber or plastic reinforcing agent according to claim 4, wherein the solid substance is at least one selected from the group consisting of silica fine particles, zinc oxide fine particles, titanium oxide fine particles and barium titanate fine particles.   A rubber composition comprising 1 to 200 parts by mass of the reinforcing agent according to claim 4 or 5 with respect to 100 parts by mass of a rubber component.   A plastic composition comprising 1 to 200 parts by mass of the reinforcing agent according to claim 4 or 5 with respect to 100 parts by mass of the plastic component.