JP2016132764A - Modified conjugated diene polymer, manufacturing method of modified conjugated diene polymer and composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified conjugated diene polymer exhibiting excellent fuel saving property in a vulcanizate and excellent in processability during making the vulcanizate and a composition thereof.SOLUTION: There is provided a modified conjugated diene polymer expressed by the formula (1) or (2). (1), (2), where Pto Pare each independently a (co)polymer of a conjugated diene compound or a copolymer of the conjugated diene compound and an aromatic vinyl compound, Rand Rare each independently a C1 to C20 hydrocarbon group, Xis a halogen atom or a C1 to 20 alkoxy group, n is an integer of 1 to 2, m is an integer of 1 to 2, n+m=3, q is an integer of 0 to 2, r is an integer of 1 to 3, q+r=3 and sum of the number of Pto Pis 5 or more.SELECTED DRAWING: None

Description

  The present invention relates to a modified product of a conjugated diene compound (co) polymer or a copolymer of a conjugated diene compound and an aromatic vinyl compound (hereinafter collectively referred to as a “conjugated diene polymer”). In particular, the present invention relates to a novel modified conjugated diene polymer and a composition containing the same.

  In recent years, there has been an increasing demand for reducing the burden on the environment, and even for automobile tires, a material with improved fuel economy, that is, low rolling resistance, is expected without exception.

  Conventionally, carbon black, silica, or the like is used as a rubber reinforcing filler in the tire tread portion. When silica is used as the reinforcing filler, there is an advantage that fuel economy is improved.

  On the other hand, compared to carbon black on the hydrophobic surface, silica on the hydrophilic surface has a low affinity with the conjugated diene rubber and also has a property of agglomerating silica with each other. There were drawbacks.

  In order to overcome the disadvantage of poor dispersibility, attempts have been made to introduce functional groups that interact with or react with the silica surface at the ends of the conjugated diene polymer. By doing so, the free end of the polymer having high mobility interacts with the silica surface, the end mobility is suppressed, the hysteresis loss is reduced, and the fuel saving is improved.

For example, Patent Document 1 proposes a modified diene rubber obtained by reacting a modifier having a glycidylamino group with a polymer active terminal. Patent Documents 2 to 4 propose a modified diene rubber obtained by reacting an alkoxysilane containing an amino group with a polymer active terminal, and a composition of these with silica.

International Publication No. 01/23467 Pamphlet JP-A-11-189616 JP 2003-171418 A Special table 2008-527150 gazette

  However, since a functional group that interacts with the silica surface is introduced at the end of the conjugated diene polymer, the viscosity increases during the kneading process with silica, making it difficult to knead, resulting in deterioration of workability. It was. The modified diene rubbers disclosed in Patent Documents 1 to 4 also have room for improvement in processability, and not only improvement in fuel efficiency but also improvement in both processability and fuel efficiency is required.

  In view of the above circumstances, an object of the present invention is to provide a modified conjugated diene polymer having improved fuel efficiency and improved processability when used as a vulcanizate.

  As a result of diligent research and studies to solve the above problems, the present inventors have determined that the modification is characterized by a specific structure having a carbonyl group or a hydroxyl group and an alkoxy or halogenated silyl group in the molecule of the conjugated diene polymer. The present inventors have found that the above problems can be solved by using a conjugated diene polymer and a composition containing the polymer, and have completed the present invention.

The present invention is as follows.
[1] A modified conjugated diene polymer represented by the following formula (1) or (2).
(In the formulas (1) and (2), P ¹ , P ² and P ³ are independently a (co) polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound,
R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms,
X ¹ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3,
q is an integer of 0 to 2, r is an integer of 1 to 3, and satisfies q + r = 3,
When a plurality of P ¹ , P ² , P ³ , R ¹ , R ² , X ¹ , q and r are present, they may be the same or different. )
[2] The modified conjugated diene polymer according to [1], wherein in the formulas (1) and (2), the total number of P ¹ , P ² and P ³ is 5 or more.
[3] The modified conjugated diene polymer according to [1] or [2], wherein in formulas (1) and (2), n is 1 and m is 2.
[4] The modified conjugated diene polymer according to any one of [1] to [3], wherein in formulas (1) and (2), q is 1 and r is 2.
[5] A polymerization step of (co) polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound using an alkali metal or alkaline earth metal compound as a polymerization initiator, and
The manufacturing method of the modified conjugated diene type polymer including the modification | denaturation process of making the compound shown by following formula (3) react with the polymer obtained by the said polymerization process.
(In formula (3), R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms,
A ¹ is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
X ¹ , X ² , and X ³ are each independently a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3,
When a plurality of R ¹ , R ² , X ¹ , X ² , X ³ and A ¹ are present, they may be the same or different. )
[6] The method for producing a modified conjugated diene polymer according to [5], wherein in formula (3), n is 1 and m is 2.
[7] A modified conjugated diene polymer obtained by the method according to [5] or [6].
[8] The molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement has at least two peaks, and the peak top molecular weight of the peak with the largest peak area is the peak of the peak with the smallest peak top molecular weight. The modified conjugated diene polymer according to any one of [1] to [4] and [7], which is 2.6 to 5.0 times the top molecular weight.
[9] There is only one peak in the molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement, and the polystyrene-equivalent number average molecular weight (Mn) of the peak is 150,000 to 1,000,000. The modified conjugated diene polymer according to any one of [1] to [4] and [7].
[10] 100 parts by mass of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer according to any one of [1] to [4], [7], [8] and [9], and
A modified conjugated diene polymer composition comprising 0.5 to 300 parts by mass of a silica-based inorganic filler.

  According to the present invention, it is possible to provide a modified conjugated diene polymer and a composition thereof that exhibit excellent low heat build-up, that is, fuel efficiency when made into a vulcanized rubber, and are excellent in processability.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The modified conjugated diene polymer of the present embodiment is a modified conjugated diene polymer represented by the following formula (1) or (2).

In formulas (1) and (2),
P ¹ , P ² , and P ³ are each independently a (co) polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound,
R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms,
X ¹ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3,
q is an integer of 0 to 2, r is an integer of 1 to 3, and satisfies q + r = 3,
When a plurality of P ¹ , P ² , P ³ , R ¹ , R ² , X ¹ , q and r are present, they may be the same or different.

In the formulas (1) and (2), P ¹ , P ² , and P ³ are independently a (co) polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound.
The conjugated diene compound for forming the (co) polymer is not particularly limited. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3 -Methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of availability.
These may be used alone (polymer) or in combination of two or more (copolymer).

  The aromatic vinyl compound for forming the copolymer is not particularly limited, and examples thereof include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is preferable from the viewpoint of availability. These may be used alone or in combination of two or more.

The copolymer may be a random copolymer or a block copolymer. Moreover, you may have a branched structure.
Preferred cases P ^1, P ^2, and preferably a vinyl bond content in the conjugated diene bond units in the P ³ and a copolymer of P ^1, P ^2, and P ³ is a conjugated diene compound and an aromatic vinyl compound The content of the aromatic vinyl unit is the same as that in the modified conjugated diene polymer described later.
The polystyrene-converted weight average molecular weights of P ¹ , P ² , and P ³ are each preferably 20,000 to 1,000,000, more preferably 50,000 to 800,000, and 80,000 to 500,000. Is more preferable.

R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² are preferably alkylene groups, preferably 2 to 7 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples of R ¹ and R ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a dodecylene group.

X ¹ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and the halogen atom of X ¹ is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkoxy group of X ^1, the number of carbon atoms is preferably 1 to 10, 1 to 2 is more preferred. Specific examples when X ¹ is an alkoxy group include a methoxy group, an ethoxy group, a propyl group, a butoxy group, a pentoxy group, a heptoxy group, an octoxy group, a dodeoxy group, and the like.

  The content of the aromatic vinyl compound unit in the modified conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 1 to 50% by mass, more preferably 10 to 45% by mass, and 20 -40 mass% is still more preferable. When the aromatic vinyl compound unit amount is in the above range, a vulcanizate having a further excellent balance between fuel economy and wet skid resistance can be obtained.

The amount of vinyl bonds in the conjugated diene compound unit is not particularly limited, but is preferably 10 to 75 mol%, more preferably 25 to 65 mol%. When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between fuel economy and wet skid resistance can be obtained. The vinyl bond amount refers to the 1,2-vinyl bond amount (conjugated diene compound unit incorporated in the polymer by 1,2-bond) and 3,4-vinyl bond amount (with respect to all conjugated diene compound units). The total ratio of the conjugated diene compound unit incorporated in the polymer by 3,4-bonds. (However, when 1,3-butadiene is used as the conjugated diene compound unit, it means the ratio of the 1,2-vinyl bond amount to the total conjugated diene compound unit.)
Here, when the modified conjugated diene-based polymer is a copolymer of 1,3-butadiene and styrene, butadiene is analyzed by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The vinyl bond amount (1,2-bond amount) in the bond unit can be determined.

  When two or more peaks are present in the molecular weight distribution curve obtained when gel permeation chromatography (GPC) measurement is performed on the modified conjugated diene polymer of the present embodiment, the peak area in the peak is The peak top molecular weight of the largest peak is in the range of 2.6 to 5.0 times the peak top molecular weight of the peak having the smallest peak top molecular weight, which improves the balance between rolling resistance and workability. From the viewpoint, it is preferably in the range of 2.8 to 4.5 times, more preferably 2.8 to 4.2 times.

The molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement preferably has 2 to 5 peaks, and more preferably 2 peaks.
The area of the peak having the largest peak area is preferably 35 to 95%, more preferably 50 to 95%, and more preferably 70 to 95%, assuming that the area of the entire peak is 100%. Further preferred. Further, the peak area of the peak having the smallest peak top molecular weight is preferably 5 to 50%, more preferably 5 to 40%, more preferably 5 to 30% when the area of the entire peak is 100%. More preferably.

Furthermore, the polystyrene-equivalent number average molecular weight (Mn) (when there are a plurality of peaks as described above, the total number average molecular weight (Mn) as described above) is 10,000 to 1,000,000. The range is preferably 100,000 to 800,000, more preferably 250,000 to 500,000. Fuel economy can be improved by setting it as the molecular weight more than the said lower limit, and workability can be improved by setting it as the molecular weight below the said upper limit.
The peak top molecular weight of the peak having the smallest peak top molecular weight is preferably 10,000 to 500,000, more preferably 50,000 to 300,000, and 50,000 to 200,000. More preferably it is.

  The modified conjugated diene polymer having two or more peaks in the molecular weight distribution curve is prepared by adjusting the ratio of the modifying agent described later to the anionic polymerization initiator to 0.05 to 5.0, for example, by batch polymerization. can get.

When only one peak is present in the molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement, the number average molecular weight (Mn) in terms of polystyrene obtained is 10,000 to 1,000,000. The range is preferably 150,000 to 1,000,000, more preferably 250,000 to 500,000. Rolling resistance can be improved by setting the molecular weight to be equal to or higher than the lower limit value, and workability can be improved by setting the molecular weight to be equal to or lower than the upper limit value.
At this time, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.00 to 3.50, more preferably 1.10 to 3.00. More preferably, it is .10 to 2.70.
A modified conjugated diene polymer having only one peak in the molecular weight distribution curve can be obtained, for example, by producing it by a continuous polymerization method described later.

From the viewpoint of processability, the total number of P ¹ , P ² and P ³ contained in one molecule is preferably 5 or more. More preferably, it is 6 or more. The upper limit of the total of P ¹ , P ² and P ³ is preferably 7 or less.
Further, from the viewpoint of workability, q is preferably 1 and r is 2. From the viewpoint of fuel economy, it is preferable that n is 1 and m is 2.

  Next, a method for producing the modified conjugated diene polymer of this embodiment will be described. The modified conjugated diene polymer of the present embodiment includes, for example, (co) polymerization of a conjugated diene compound or co-polymerization of a conjugated diene compound and an aromatic vinyl compound using an alkali metal or alkaline earth metal compound as a polymerization initiator. It can be obtained by the method for producing a modified conjugated diene polymer according to this embodiment, which includes a polymerization step for polymerization and a modification step for reacting a compound obtained by the polymerization step with a compound represented by the following formula (3).

In formula (3), R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms, A ¹ is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and X ¹ , X ² and X ³ are each independently a halogen atom or an alkoxy group having 1 to 20 carbon atoms, n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3 , R ¹ , R ² , X ¹ , X ² , X ³ and A ¹ may be the same or different when there are a plurality of R ¹ , R ² , X ¹ , X ² , X ³ and A ¹ .

As the polymerization initiator, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound.
The organic alkali metal compound used as the polymerization initiator is not particularly limited, but an organic lithium compound is preferable. Examples of organolithium compounds include low molecular weight compounds, solubilized oligomeric organolithium compounds, compounds having a carbon-lithium bond in the lithium bond mode as an organic group, compounds having a nitrogen-lithium bond, and compounds having a tin-lithium bond. Is mentioned.

  Examples of the low molecular lithium compound include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, phenyl lithium, and still lithium.

  Examples of the compound having a nitrogen-lithium bond include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, and lithium. Examples include heptamethylene imide and lithium morpholide.

  In addition to the above monoorganolithium compound, polymerization can also be carried out using a polyfunctional organolithium compound in combination. Examples of the polyfunctional organolithium compound include 1,4-dilithiobutane, a reaction product of sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiobenzene, n-butyllithium and 1,3-butadiene, and the like. Examples thereof include a reaction product of divinylbenzene, a reaction product of n-butyllithium and a polyacetylene compound. Further, known organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. Can be used.

As the organic lithium compound, n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and ease of control of the polymerization reaction.
These organolithium compounds may be used alone or in combination of two or more.

Examples of other organic alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, alkoxides such as lithium, sodium, and potassium, sulfonates, carbonates, amides, and the like can be given.
These organoalkali metal compounds may be used in combination with other organometallic compounds.

Examples of the alkaline earth metal compound used as the polymerization initiator include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used.
These organic alkaline earth metal compounds may be used in combination with alkali metal compounds or other organic metal compounds.

  In the present embodiment, the conjugated diene polymer is a polymer having an active terminal obtained by a growth reaction by an anionic polymerization reaction using the above-described alkali metal compound and / or alkaline earth metal compound as a polymerization initiator. preferable. In particular, the conjugated diene polymer is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.

  The polymerization mode employed in the polymerization step is not particularly limited, but can be performed by a polymerization mode such as a batch type (also referred to as “batch type”) or a continuous type. In the continuous mode, one or two or more connected reactors can be used. The reactor may be a tank type with a stirrer, a tube type or the like.

  The polymerization reaction of the conjugated diene polymer is preferably performed in a solvent. Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include hydrocarbons composed of a mixture thereof. Treatment of allenes and acetylenes, which are impurities, with an organometallic compound before being subjected to a polymerization reaction tends to yield a polymer having a high concentration of active terminals, and a high modification rate is achieved. It is preferable because of its tendency.

  In the polymerization reaction of the conjugated diene polymer, a polar compound may be added. An aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene portion. It is also effective in promoting the polymerization reaction.

  The polar compound is not particularly limited, and examples thereof include tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl) propane, and the like. Ethers; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-tert-amylate, potassium-tert-butylate, sodium-tert-butyrate, sodium amylate Alkali metal alkoxide compounds such as phosphine compounds such as triphenylphosphine can be used. . These polar compounds may be used alone or in combination of two or more.

  The polymerization temperature is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, the polymerization temperature is preferably 0 ° C. or more, and a sufficient reaction amount of the modifier with respect to the active terminal after the polymerization is ensured. From the viewpoint of achieving this, it is preferably 120 ° C. or lower.

  In the polymerization step, a polyfunctional aromatic vinyl compound such as divinylbenzene for controlling branching may be used from the viewpoint of preventing cold flow of the conjugated diene polymer.

  After obtaining a conjugated diene polymer having an active end by the method as described above, the active end is reacted with a compound represented by the following formula (3) (hereinafter sometimes referred to as “modifier”). By performing the modification step, the modified conjugated diene polymer of this embodiment can be obtained.

In formula (3), R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms, A ¹ is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 20 carbon atoms, X ¹ , X ² and X ³ are each independently a halogen atom or an alkoxy group having 1 to 20 carbon atoms, n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3, When there are a plurality of R ¹ , R ² , X ¹ , X ² , X ³ , and A ¹ , they may be the same or different.

R ¹ and R ² are preferably alkylene groups, preferably 2 to 7 carbon atoms, more preferably 3 to 5 carbon atoms.

The halogen atom for X ¹ , X ² , X ³ , and A ¹ is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As X < ¹ >, X < ² > and X < ³ >, an alkoxy group is preferable, C1-C10 is preferable and 1-2 is more preferable from a reactive viewpoint.

A ¹ is preferably an alkoxy group, preferably having 1 to 5 carbon atoms, and more preferably 1 to 2 from the viewpoint of reactivity. Specific examples when A ¹ is an alkoxy group include a methoxy group, an ethoxy group, a propyl group, a butoxy group, a pentoxy group, a heptoxy group, an octoxy group, a dodeoxy group, and the like.
R ¹ and R ^2, are, like are preferably used as R ^1, R ² expressed by the aforementioned equations (1) and ^{(2), X 1, X} 2, X 3 is the aforementioned equations (1) and The same as X ^{1 in} (2) is preferably used.

The modifier represented by the above formula (3) is not particularly limited, and examples thereof include N- (chlorocarbonylethyl) -N, N-bis (3-trimethoxysilylpropyl) amine and N- (chlorocarbonylethyl). -N, N-bis (3-triethoxysilylpropyl) amine, N- (chlorocarbonylpropyl) -N, N-bis (3-trimethoxysilylpropyl) amine, N- (chlorocarbonylpropyl) -N, N -Bis (3-triethoxysilylpropyl) amine, N- (chlorocarbonylethyl) -N, N-bis (3-trimethoxysilylbutyl) amine, N- (chlorocarbonylethyl) -N, N-bis (3 -Triethoxysilylbutyl) amine, N- (chlorocarbonylethyl) -N, N-bis (3-trimethoxysilylpentyl) amine, -(Chlorocarbonylethyl) -N, N-bis (3-triethoxysilylpentyl) amine, N- (chlorocarbonylpropyl) -N, N-bis (3-trimethoxysilylbutyl) amine, N- (chlorocarbonyl Propyl) -N, N-bis (3-triethoxysilylbutyl) amine, N- (chlorocarbonylpropyl) -N, N-bis (3-trimethoxysilylpentyl) amine, N- (chlorocarbonylpropyl) -N , N-bis (3-triethoxysilylpentyl) amine, N, N-bis- (chlorocarbonylethyl) -N- (3-trimethoxysilylpropyl) amine, N, N-bis- (chlorocarbonylethyl)- N- (3-triethoxysilylpropyl) amine, N, N-bis (chlorocarbonylpropyl) -N- (3-tri Toxisilylpropyl) amine, N, N-bis (chlorocarbonylpropyl) -N- (3-triethoxysilylpropyl) amine, N, N-bis (chlorocarbonylethyl) -N- (3-trimethoxysilylbutyl) Amine, N, N-bis (chlorocarbonylethyl) -N- (3-triethoxysilylbutyl) amine, N, N-bis (chlorocarbonylethyl) -N- (3-trimethoxysilylpentyl) amine, N, N-bis (chlorocarbonylethyl) -N- (3-triethoxysilylpentyl) amine, N, N-bis (chlorocarbonylpropyl) -N- (3-trimethoxysilylbutyl) amine, N, N-bis ( Chlorocarbonylpropyl) -N- (3-triethoxysilylbutyl) amine, N, N-bis (chlorocarbonylpropylene) ) Halogenated carbonyl group-containing alkoxysilyl compounds such as N) -N- (3-trimethoxysilylpentyl) amine, N, N-bis (chlorocarbonylpropyl) -N- (3-triethoxysilylpentyl) amine, N -(Methoxycarbonylethyl) -N, N-bis (3-trimethoxysilylpropyl) amine, N- (ethoxycarbonylethyl) -N, N-bis (3-triethoxysilylpropyl) amine, N- (methoxycarbonyl) Propyl) -N, N-bis (3-trimethoxysilylpropyl) amine, N- (ethoxycarbonylpropyl) -N, N-bis (3-triethoxysilylpropyl) amine, N- (methoxycarbonylethyl) -N , N-bis (3-trimethoxysilylbutyl) amine, N- (ethoxycarbonylethyl) -N, N-bis (3-triethoxysilylbutyl) amine, N- (methoxycarbonylethyl) -N, N-bis (3-trimethoxysilylpentyl) amine, N- (ethoxycarbonylethyl) -N, N -Bis (3-triethoxysilylpentyl) amine, N- (methoxycarbonylpropyl) -N, N-bis (3-trimethoxysilylbutyl) amine, N- (ethoxycarbonylpropyl) -N, N-bis (3 -Triethoxysilylbutyl) amine, N- (methoxycarbonylpropyl) -N, N-bis (3-trimethoxysilylpentyl) amine, N- (ethoxycarbonylpropyl) -N, N-bis (3-triethoxysilyl) Pentyl) amine, N, N-bis- (methoxycarbonylethyl) -N- (3-trimethoxysilylpropylene ) Amine, N, N-bis- (ethoxycarbonylethyl) -N- (3-triethoxysilylpropyl) amine, N, N-bis (methoxycarbonylpropyl) -N- (3-trimethoxysilylpropyl) amine, N, N-bis (ethoxycarbonylpropyl) -N- (3-triethoxysilylpropyl) amine, N, N-bis (methoxycarbonylethyl) -N- (3-trimethoxysilylbutyl) amine, N, N- Bis (ethoxycarbonylethyl) -N- (3-triethoxysilylbutyl) amine, N, N-bis (methoxycarbonylethyl) -N- (3-trimethoxysilylpentyl) amine, N, N-bis (ethoxycarbonyl) Ethyl) -N- (3-triethoxysilylpentyl) amine, N, N-bis (methoxycarbonylpropiyl) ) -N- (3-trimethoxysilylbutyl) amine, N, N-bis (ethoxycarbonylpropyl) -N- (3-triethoxysilylbutyl) amine, N, N-bis (methoxycarbonylpropyl) -N Examples thereof include alkoxycarbonyl group-containing alkoxysilyl compounds such as-(3-trimethoxysilylpentyl) amine and N, N-bis (ethoxycarbonylpropyl) -N- (3-triethoxysilylpentyl) amine.
Among these, from the viewpoints of fuel economy and processability, those in which n is 1 and m is 2 are preferable, and alkoxycarbonyl group-containing alkoxysilyl compounds are more preferable.

In the modification step, the active terminal of the conjugated diene copolymer obtained in the polymerization step may be reacted with the modifier represented by the above formula (3), and the action thereof is presumed as follows.
For example, when an ester group-containing alkoxysilane compound such as N- (methoxycarbonylethyl) -N or N-bis (3-trimethoxysilylpropyl) amine is used as the modifying agent represented by the above formula (3), conjugation The active terminal of the diene polymer reacts with the alkoxy group and ester group of the modifier, whereby the conjugated diene polymer terminal and the modifier are bonded via a covalent bond (see Formula (4)). However, this is only one reaction form, and the reaction form is not limited to this.
First, 4 mol of a conjugated diene polymer terminal reacts with an alkoxy group with respect to 1 mol of a modifier. Next, 1 mol of the resulting modified conjugated diene polymer and 1 mol of the conjugated diene polymer terminal may react with each other or 2 mol may occur. When 1 mol is reacted, a 5-branched modified conjugated diene copolymer is obtained. When 2 mol is reacted, a 6-branched modified conjugated diene copolymer is obtained.
The modified conjugated diene polymer of the present embodiment thus obtained has both an alkoxy group and a hydroxyl group and / or a carbonyl group. It is considered that excellent processability is exhibited when a composition or a vulcanized rubber is mixed with the above components.

(P represents a conjugated diene polymer)

  The reaction temperature and reaction time when the above modifier is reacted with the conjugated diene polymerization terminal are not particularly limited, but it is preferable to react at 0 to 120 ° C. for 30 seconds or longer.

  The amount of the modifier added is not particularly limited, but the total number (mole) of the reactive groups possessed by the modifier added in the modification step is from 0.4 to the polymerization initiator (mole) used in the polymerization step. A range of 5 times is preferable, a range of 0.55 to 3 times is more preferable, and a range of 0.7 to 1.5 times is more preferable. Here, the total number of reactive groups is such that one molecule of the conjugated diene polymerization terminal reacts with one alkoxy group / halogen atom, and a maximum of two molecules of the conjugated diene polymer react with one ester group. In the case of using the modifying agent represented by 3), (the number of alkoxy groups in the modifying agent / the number of halogen atoms (= m × 3) × 1) + (the number of ester groups in the modifying agent (n) × 2) It shall be calculated.

If it is in the range of 0.4 times or more, the modification rate and coupling rate (ratio of the modified conjugated diene polymer having 2 or more branches in the whole conjugated diene polymer obtained through the modification step) are high. Shows sufficient fuel economy and processability. Moreover, it is preferable to make it 5 times or less from a viewpoint of the cost of a modifier.
The modification rate (the total amount of the conjugated diene polymer modified (reacted with the modifier of formula (3)) with respect to the total amount of the conjugated diene polymer) is 20 to 95% by mass from the viewpoint of fuel economy. Preferably, it is 50 to 95%, more preferably 60 to 95% by mass. The modification rate can be measured by the method described in Examples below.

The modified conjugated diene polymer shown in the formula (1), the modified conjugated diene polymer shown in the formula (2), or these through the polymerization step and the modification step using the modifier represented by the formula (3) A mixture is obtained.
The number of branches of the modified conjugated diene copolymer obtained in this case (the number of conjugated diene polymers that react with one molecule of the modifier) is the number of polymerization initiators used in the polymerization step and the modifier added in the modification step. It is possible to control from the amount added.
Specifically, in order to obtain a modified conjugated diene polymer in which q is 1 and r is 2 in the above formula (1) and / or (2), the total number of reactive groups possessed by the modifier is determined by starting polymerization. The range which is 0.3-3 times with respect to an agent is preferable, the range which is 0.5-2 times is more preferable, and it is still more preferable that it is 0.7-1.2 times. The closer the total number of reactive groups to the polymerization initiator is, the higher the proportion of the modified conjugated diene polymer having q = 1 and r = 2.

  In the method for producing the modified conjugated diene polymer of the present embodiment, a deactivation agent, a neutralizing agent, and the like may be added to the copolymer solution as necessary after the modification reaction. The quenching agent is not particularly limited, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol. The neutralizing agent is not particularly limited, and examples thereof include carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of carboxylic acids having 9 to 11 carbon atoms, mainly 10 and having many branches); inorganic Acid aqueous solution; carbon dioxide gas and the like.

  Moreover, it is preferable to add the stabilizer for rubber | gum to the modified conjugated diene type polymer of this embodiment from a viewpoint which prevents the gel production | generation after superposition | polymerization, or a viewpoint which improves the stability at the time of a process. The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 4,6-bis (octylthiomethyl) -o-cresol, 3- (3,5-di-tert-butyl Antioxidants such as octadecyl-4-hydroxyphenyl) propanoate and 2,6-di-tert-butyl-4-hydroxytoluene (BHT) are preferred. These may be used alone or in combination of two or more.

  Moreover, in order to further improve the workability of the modified conjugated diene polymer of the present embodiment, an extending oil can be added to the modified conjugated diene copolymer as necessary. The method of adding the extending oil to the modified conjugated diene polymer is not particularly limited, but a method of adding the extending oil to the polymer solution and mixing to remove the solvent from the oil-extended copolymer solution is preferable. . Examples of the extending oil include aroma oil, naphthenic oil, paraffin oil, and the like. Among these, from the viewpoint of environmental safety, oil bleed prevention and wet grip characteristics, an aromatic substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less by the IP346 method is preferable. Examples of the aroma substitute oil include TDAE (Treated Distillate Aromatic Extracts) shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), MES (Mil Extraction Solvate), etc., and R e s, e. Although the addition amount of extending oil is not specifically limited, Usually, it is 10-60 mass parts with respect to 100 mass parts of modified conjugated diene polymers, and 20-37.5 mass parts is preferable.

  As a method for obtaining the modified conjugated diene polymer of the present embodiment from the polymer solution, a known method can be used. For example, after separating the solvent by steam stripping or the like, the polymer is filtered off, further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. The method, the method of devolatilizing directly with a drum dryer etc. are mentioned.

  The modified conjugated diene polymer of this embodiment is suitably used as a vulcanizate. For example, the vulcanized product may be a modified conjugated diene polymer of this embodiment, an inorganic filler such as a silica-based inorganic filler or carbon black, if necessary, or a rubber other than the modified conjugated diene polymer of this embodiment. After mixing with a polymer, a silane coupling agent, a rubber softener, a vulcanizing agent, a vulcanization accelerator / auxiliary, etc., a modified conjugated diene polymer composition is heated and vulcanized. Can be obtained.

Next, the modified conjugated diene polymer composition of this embodiment will be described.
The modified conjugated diene-based polymer of the present embodiment is mixed with a silica-based inorganic filler and a rubber component other than the modified conjugated diene-based polymer of the present embodiment as necessary, and a modified conjugated diene-based polymer composition It is preferable to do.
The modified conjugated diene polymer composition includes 100 parts by mass of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer of the present embodiment, and 0.5 to 300 parts by mass of a silica-based inorganic filler. Is more preferable.

Dispersing the silica-based inorganic filler in the modified conjugated diene-based polymer of the present embodiment provides an excellent balance between fuel economy and wet skid resistance when used as a vulcanizate, and is practically sufficient. It can have wear resistance and breaking strength, and can provide excellent workability.
Even when the modified conjugated diene polymer composition of the present embodiment is used for vulcanized rubber applications such as tires, automobile parts such as vibration-proof rubber, and shoes, it is preferable that a silica-based inorganic filler is included.

  In the conjugated diene polymer composition, a rubbery polymer that is a rubber component other than the modified conjugated diene polymer of the present embodiment can be used in combination with the modified conjugated diene polymer of the present embodiment. The rubbery polymer is not particularly limited, and for example, a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof, or a conjugated diene compound. And a block copolymer of a vinyl aromatic compound or a hydrogenated product thereof, a non-diene polymer, and natural rubber.

  Specifically, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene block copolymerized Examples thereof include styrene-based elastomers such as coalescence or hydrogenated products thereof, acrylonitrile-butadiene rubber, or hydrogenated products thereof.

  Examples of the non-diene polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and other olefin elastomers, butyl rubber, brominated butyl rubber, Acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber and the like can be mentioned.

Various rubber-like polymers other than the modified conjugated diene polymer of the present embodiment described above may be modified rubbers having a functional group having a polarity such as a hydroxyl group or an amino group. The weight average molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 1,500,000, from the viewpoint of the balance between performance and processing characteristics. Also, so-called liquid rubber having a low molecular weight can be used.
These rubber-like polymers may be used individually by 1 type, and may use 2 or more types together.

When the modified conjugated diene polymer of the present embodiment is combined with the above-described rubber-like polymer to form a modified conjugated diene polymer composition, the blending ratio (mass ratio) thereof is the modified ratio of the present embodiment. The conjugated diene polymer / rubbery polymer is preferably 20/80 to 100/0, more preferably 30/70 to 90/10, and still more preferably 50/50 to 80/20.
That is, in 100 parts by mass of the total rubber component in the composition, the modified conjugated diene polymer is preferably contained in an amount of 20 to 100 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 50 to 80 parts by mass. preferable. When the blending ratio of the modified conjugated diene polymer / rubber-like polymer is within the above range, a vulcanizate having a further excellent balance between fuel economy and wet skid resistance and further satisfying wear resistance and breaking strength. Can be obtained.

The silica-based inorganic filler is not particularly limited and known ones can be used, but solid particles containing SiO ₂ or Al ₂ (SiO ₃ ) ₃ as a structural unit are preferred, and SiO ₂ or Al ₂ More preferably, (SiO ₃ ) ₃ is the main component of the structural unit. Here, a main component means the component contained in a silica type inorganic filler 50 mass% or more, Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more.

  Specific examples of the silica-based inorganic filler include inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. Among these, silica and glass fiber are preferable from the viewpoints of strength, wear resistance, and the like, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable from the viewpoint of an excellent balance between the effect of improving fracture characteristics and wet skid resistance.

In the modified conjugated diene polymer composition, from the viewpoint of obtaining practically good wear resistance and fracture characteristics, the nitrogen adsorption specific surface area required by the BET adsorption method of the silica-based inorganic filler is 100 to 300 m ² / g. It is preferable that it is 170-250 m < ² > / g. Further, if necessary, the specific surface area is relatively small (for example, a silica-based inorganic filler having a specific surface area of 200 m ² / g or less) and the specific surface area is relatively large (for example, a silica-based inorganic material having a specific surface area of 200 m ² / g or more). And a filler) can be used in combination. Thereby, it is possible to highly balance good wear resistance, fracture characteristics and fuel saving performance.

  As described above, the compounding amount of the silica-based inorganic filler in the modified conjugated diene polymer composition is set to 0.000 parts by mass with respect to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer of the present embodiment. It is preferable that it is 5-300 mass parts, 5-200 mass parts is more preferable, and 20-100 mass parts is still more preferable. The compounding amount of the silica-based inorganic filler is preferably 0.5 parts by mass or more from the viewpoint of developing the effect of adding the inorganic filler, and the inorganic filler is sufficiently dispersed to improve the workability of the composition and the machine. From the viewpoint of making the strength practically sufficient, it is preferably set to 300 parts by mass or less.

  Carbon black may be contained in the modified conjugated diene polymer composition. The carbon black is not particularly limited, and for example, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m 2 / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g is preferable.

  The blending amount of carbon black is preferably 0.5 to 100 parts by weight, more preferably 3 to 100 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the rubber component containing the modified conjugated diene polymer of the present embodiment. Part is more preferred. The blending amount of the carbon black is preferably 0.5 parts by mass or more from the viewpoint of expressing performances required for tires such as dry grip performance and conductivity, and 100 parts by mass from the viewpoint of dispersibility. The following is preferable.

  In addition to the silica-based inorganic filler and carbon black, the modified conjugated diene-based polymer composition may contain a metal oxide or a metal hydroxide. The metal oxide refers to solid particles having a chemical unit MxOy (M represents a metal atom, and x and y each represent an integer of 1 to 6) as a main component of a structural unit, such as alumina or titanium oxide. Magnesium oxide, zinc oxide, or the like can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used. The metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

  The modified conjugated diene polymer composition may contain a silane coupling agent. The silane coupling agent has a function to close the interaction between the rubber component and the silica-based inorganic filler, and has an affinity or binding group for each of the rubber component and the silica-based inorganic filler. In general, a compound having a sulfur bond portion and an alkoxysilyl group and / or silanol group portion in one molecule is used. Specifically, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -ethyl ] -Tetrasulfide etc. are mentioned.

  0.1-30 mass parts is preferable with respect to 100 mass parts of silica type inorganic fillers mentioned above, as for the compounding quantity of a silane coupling agent, 0.5-20 mass parts is more preferable, and 1-15 mass parts is. Further preferred. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent can be made more remarkable.

  In order to improve processability, the modified conjugated diene polymer composition may contain a rubber softener. As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable. The mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain. A paraffin chain having 50% or more of the total number of carbon atoms is called a paraffin type, a naphthene ring having 30 to 45% of the total carbon number is naphthenic, and an aromatic carbon number of 30% of the total carbon. Those that exceed are called aromatic. As the rubber softener used together with the modified conjugated diene-aromatic vinyl copolymer of the present embodiment, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer.

  The blending amount of the rubber softening agent is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, with respect to 100 parts by weight of the rubber component containing the modified conjugated diene polymer of the present embodiment. 90 parts by mass is more preferable. If the blending amount of the rubber softener exceeds 100 parts by mass with respect to 100 parts by mass of the rubber component, bleeding out tends to occur, and the composition surface may become sticky.

  About the method of mixing the modified conjugated diene polymer of this embodiment and other rubbery polymers, silica-based inorganic fillers, carbon black and other fillers, silane coupling agents, rubber softeners and the like Is not particularly limited. For example, a melt kneading method using a general blender such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc., each component is dissolved and mixed, and then the solvent is heated The method of removing etc. are mentioned. Of these, a melt kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoint of productivity and good kneading properties. In addition, any of a method of kneading the modified conjugated diene polymer and various compounding agents at a time and a method of mixing in multiple times can be applied.

  The modified conjugated diene polymer composition may be a vulcanized composition that has been vulcanized with a vulcanizing agent. As the vulcanizing agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds can be used. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like. The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. . As the vulcanization method, a conventionally known method can be applied, and the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

  In vulcanization, a vulcanization accelerator may be used as necessary. As the vulcanization accelerator, conventionally known materials can be used. For example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate And the like. Further, as the vulcanization aid, zinc white, stearic acid or the like can be used. The amount of the vulcanization accelerator used is usually 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. preferable.

  The modified conjugated diene-based polymer composition includes other softeners and fillers other than those described above, as well as heat stabilizers, antistatic agents, weathering stabilizers, and aging, as long as the purpose of the present embodiment is not impaired. Various additives such as an inhibitor, a colorant, and a lubricant may be used. As other softeners, known softeners can be used. Specific examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. Known materials can be used as the above heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, colorant, and lubricant.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
In addition, the analysis of Examples 1-3 and the polymer of Comparative Examples 1 and 2 was performed by the method shown below.

(1) Amount of bound styrene A 100 mg sample was diluted to 100 mL with chloroform and dissolved to prepare a measurement sample. The amount of bound styrene (% by mass) was measured by absorption at 254 nm by the phenyl group of styrene (manufactured by Shimadzu Corporation, spectrophotometer “UV-2450”).

(2) Microstructure of butadiene moiety (1,2-vinyl bond content)
A sample of 50 mg was dissolved in 10 mL of carbon disulfide to prepare a measurement sample. Using a solution cell, the infrared spectrum was measured in the range of 600 to 1000 cm −1, and the microstructure of the butadiene portion was determined from the absorbance at a predetermined wave number according to the formula of the Hampton method (manufactured by JASCO Corporation, Fourier transform red Outer spectrophotometer "FT-IR230").

(3) Mooney viscosity The Mooney viscosity was measured using a Mooney viscometer ("VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) according to JIS K6300 (ISO289-1) and ISO289-4. The measurement temperature was 100 ° C. First, after preheating the sample for 1 minute, the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain the Mooney viscosity (ML1 + 4).

(4) Glass transition temperature (Tg)
In accordance with ISO 22768: 2006, a DSC curve was recorded using a differential scanning calorimeter “DSC3200S” manufactured by Mac Science, while increasing the temperature from −100 ° C. to 20 ° C./min under a flow of helium at 50 mL / min. The peak top (Inflection point) of the DSC differential curve was taken as the glass transition temperature.

(5) Molecular weight Using a GPC measuring apparatus in which three columns using polystyrene gel as a filler were connected, the chromatogram was measured, and the weight average molecular weight (Mw) and number based on a calibration curve using standard polystyrene. The average molecular weight (Mn) was determined. Tetrahydrofuran (THF) was used as the eluent. As the column, guard column: TSK guard column Super H-H manufactured by Tosoh Corporation, column: TSK gel Super H 5000, TSK gel Super H 6000, TSK gel Super H 7000 manufactured by Tosoh Corporation were used. An RI detector (manufactured by Tosoh Corporation, “HLC8020”) was used under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. 10 mg of a sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 200 μL of the measurement solution was injected into a GPC measurement device and measured.

(6) Denaturation rate It measured by applying the characteristic which the component modified | denatured adsorb | sucks to the GPC column which used the silica type gel as the filler. Specifically, a sample solution containing a sample and a low molecular weight internal standard polystyrene was measured by measuring the amount of adsorption on the silica column from the difference between the chromatogram measured with the polystyrene gel column and the chromatogram measured with the silica column, and the denaturation rate. Asked.
・ Sample solution preparation:
A sample solution was prepared by dissolving 10 mg of a sample and 5 mg of standard polystyrene in 20 mL of THF.
-GPC measurement conditions using a polystyrene column:
Using THF as an eluent, 200 μL of the sample solution was injected into the apparatus for measurement. As the column, guard column: TSK guard column Super H-H manufactured by Tosoh Corporation, column: TSK gel Super H 5000, TSK gel Super H 6000, TSK gel Super H 7000 manufactured by Tosoh Corporation were used. A chromatogram was obtained by measurement using a RI detector (HLC8020 manufactured by Tosoh Corporation) under conditions of a column oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.
-GPC measurement conditions using a silica column:
Using THF as an eluent, 200 μL of sample was injected into the apparatus for measurement. As the column, guard column: DIOL 4.6 × 12.5 mm 5 micron, column: Zorbax PSM-1000S, PSM-300S, PSM-60S were used. CCP8020 series build-up type GPC system manufactured by Tosoh Corporation with column oven temperature of 40 ° C. and THF flow rate of 0.5 ml / min: AS-8020, SD-8022, CCPS, CO-8020, RI-8021, using RI detector To obtain a chromatogram.
・ Method of calculating denaturation rate:
The peak area P1 of the sample and the peak area P2 of the standard polystyrene were calculated with the total peak area of the chromatogram using the polystyrene column as 100. Further, the peak area P3 of the sample and the peak area P4 of the standard polystyrene were calculated with the total peak area of the chromatogram using the silica column as 100. Using these values, the modification rate (%) was determined from the following formula.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100
(However, P1 + P2 = P3 + P4 = 100)

[Example 1]
An autoclave having an internal volume of 5 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance, 1670 g of normal hexane, 83 g of styrene, 236 g of 1,3-butadiene, and 2,2 as a polar substance. -Bis (2-oxolanyl) propane 2.25mmol was put into the reactor, and when the inside of the reactor was 52 ° C, 3.75mmol of a polymerization initiator n-butyllithium was added to initiate polymerization. Immediately after the start of polymerization, the temperature in the reactor increased, and when a decrease in temperature was confirmed after reaching the peak temperature, the modifier N- (methoxycarbonylethyl) -N, N-bis (3-trimethoxysilylpropyl) ) 0.41 mmol of amine (MCEBTMSPA-1) was added, and the mixture was further stirred for 30 minutes. 3.75 mmol of ethanol was added as a polymerization terminator to stop the reaction, and a modified conjugated diene polymer-containing polymer solution was obtained.

After adding 0.64 g of 2,6-di-tert-butyl-4-hydroxytoluene as an antioxidant to the resulting polymerization solution, the solvent is removed by steam stripping, and after vacuum drying, a modified conjugated diene is obtained. A copolymer A was obtained. The analysis results of A are shown in Table 1.
The obtained modified conjugated diene copolymer A is a mixture of modified conjugated diene polymers corresponding to the formulas (1) and (2), and the amount of the polymerization initiator used in the polymerization process and the modification process. Since the ratio of the addition amount of the modifiers (n = 1, m = 2 in the formula (3)) used in (1) was about 0.87, the modified conjugated diene in which q is 1 and r is 2 is mainly used. A system polymer was obtained.

[Example 2]
The modifier is changed from N- (methoxycarbonylethyl) -N, N-bis (3-trimethoxysilylpropyl) amine to N- (ethoxycarbonylpropyl) -N, N-bis (3-triethoxysilylbutyl) amine (ECEBTESPA). The modified conjugated diene polymer B was obtained in the same manner as in Example 1 except that the above was changed. The analysis results of B are shown in Table 1.
The obtained modified conjugated diene copolymer B is a mixture of modified conjugated diene polymers corresponding to the formulas (1) and (2), and the amount of the polymerization initiator used in the polymerization process and the modification process. The ratio of the addition amount of the modifiers used in (n = 1, m = 2) was about 0.87 times, so that a modified conjugated diene polymer in which q is 1 and r is 2 is mainly obtained. It was.

[Example 3]
The modifier is changed from N- (methoxycarbonylethyl) -N, N-bis (3-trimethoxysilylpropyl) amine to N, N-bis (methoxycarbonylethyl) -N- (3-trimethoxysilylpropyl) amine (MCEBTMSPA). -2) A modified conjugated diene polymer C was obtained in the same manner as in Example 1, except for changing to -2. The analysis results of C are shown in Table 1.
The obtained modified conjugated diene copolymer C is a mixture of modified conjugated diene polymers corresponding to the formulas (1) and (2), and the amount of the polymerization initiator used in the polymerization process and the modification process. The ratio of the addition amount of the modifiers (n = 2, m = 1) used in Example 1 was about 0.77, so that mainly modified conjugated diene polymers having q = 1 and r = 2 were obtained. It was.

[Comparative Example 1]
An autoclave having an internal volume of 5 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance, 1670 g of normal hexane, 83 g of styrene, 236 g of 1,3-butadiene, and 2,2 as a polar substance. -2.65 mmol of bis (2-oxolanyl) propane was put into the reactor, and when the inside of the reactor was 56 ° C, 3.54 mmol of a polymerization initiator n-butyllithium was added to initiate polymerization. Immediately after the start of the polymerization, the temperature in the reactor was increased, and when a decrease in temperature was confirmed after reaching the peak temperature, the modifier bis (3-trimethoxysilylpropyl) -N-methylamine (BTMSA) 0.64 mmol Added and stirred for an additional 30 minutes. 3.54 mmol of ethanol was added as a polymerization terminator to stop the reaction, and a modified conjugated diene polymer-containing polymer solution was obtained.

  After adding 160 mg of 2,6-di-tert-butyl-4-hydroxytoluene as a stabilizer to the polymerization solution obtained, the solvent was removed by steam stripping, vacuum drying was performed, and the modified conjugated diene-based copolymer was then removed. Polymer D was obtained. The analysis results of D are shown in Table 1.

[Comparative Example 2]
An autoclave having an internal volume of 5 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance, 1670 g of normal hexane, 83 g of styrene, 236 g of 1,3-butadiene, and 2,2 as a polar substance. -2.65 mmol of bis (2-oxolanyl) propane was put into the reactor, and when the inside of the reactor was 56 ° C, 3.54 mmol of a polymerization initiator n-butyllithium was added to initiate polymerization. Immediately after the start of the polymerization, the temperature in the reactor increased, and when a decrease in temperature was confirmed after reaching the peak temperature, 0.41 mmol of the modifier hexachlorodisilane (HCDS) was added and further stirred for 30 minutes. 3.54 mmol of ethanol was added as a polymerization terminator to stop the reaction, and a modified conjugated diene polymer-containing polymer solution was obtained.

  After adding 0.64 g of 2,6-di-tert-butyl-4-hydroxytoluene as an antioxidant to the obtained polymerization solution, the solvent was removed by steam stripping, and after vacuum drying, the modified conjugate Diene copolymer E was obtained. The analysis results of E are shown in Table 1.

[Examples 4-6, Comparative Examples 3-4]
Using the modified conjugated diene polymers A to E (samples A to E) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 as raw rubber, each raw rubber is contained according to the formulation shown below. A rubber composition was obtained.
Modified conjugated diene polymer (samples A to E): 100.0 parts by mass Silica (Evonik Degussa, “Ultrasil 7000 GR”, nitrogen adsorption specific surface area 170 m 2 / g): 75.0 parts by mass Carbon black (Tokai Carbon) “Seast KH (N339)”): 5.0 parts by mass Silane coupling agent (Evonik Degussa, “Si75”, bis (triethoxysilylpropyl) disulfide): 6.0 parts by mass S-RAE oil (Manufactured by JX Nippon Oil & Energy Corporation, “Process NC140”): 30.0 parts by mass Zinc white: 2.5 parts by mass Stearic acid: 2.0 parts by mass Anti-aging agent (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine): 2.0 parts by mass Sulfur: 1.7 parts by mass Vulcanization accelerator (N-cyclohexyl-2-benzothia Rusuru namides): 1.7 parts by mass Vulcanization accelerator (diphenylguanidine): 2.0 parts by weight Sum: 227.9 parts by weight

The above materials were kneaded by the following method to obtain a rubber composition.
Using a closed kneader (with an internal volume of 0.3 L) equipped with a temperature control device, raw rubber (samples A to E) under the conditions of a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm as the first stage kneading , Filler (silica, carbon black), silane coupling agent, process oil, zinc white, and stearic acid were kneaded. At this time, the temperature of the closed mixer was controlled, and a rubber composition (compound) was obtained at a discharge temperature of 155 to 160 ° C.

  Next, as the second stage kneading, the blend obtained above was cooled to room temperature, an anti-aging agent was added, and kneaded again to improve silica dispersion. Also in this case, the discharge temperature of the blend was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer. After cooling, as a third stage of kneading, sulfur and a vulcanization accelerator were added and kneaded with an open roll set at 70 ° C. Thereafter, it was molded and vulcanized with a vulcanization press at 160 ° C. for 20 minutes. After vulcanization, the physical properties of the rubber composition were measured. The physical property measurement results are shown in Table 2.

The physical properties of the rubber composition were measured by the following methods.
(1) Compound Mooney Viscosity Using a Mooney viscometer, after preheating at 130 ° C. for 1 minute in accordance with JIS K6300-1, the viscosity after rotating the rotor at 2 revolutions per minute for 4 minutes Was measured. It shows that it is excellent in workability, so that a value is small.

(2) Viscoelastic parameters Viscoelastic parameters were measured in a torsion mode using a viscoelasticity tester “ARES” manufactured by Rheometrics Scientific. Each measured value was indexed with the value of the rubber composition of Comparative Example 4 as 100. Tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel economy. A smaller value indicates better fuel economy.

From Table 2, the rubber compositions (modified conjugated diene polymer compositions) of Examples 4 to 6 are comparable to the rubber composition of Comparative Example 3 with no difference in tan δ at 50 ° C. It was confirmed that the compound Mooney viscosity value was small and excellent in workability while exhibiting fuel economy. In addition, the rubber compositions (modified conjugated diene polymer compositions) of Examples 4 to 6 are comparable in processability with no difference in the value of the compound Mooney viscosity as compared with the rubber composition of Comparative Example 4. It was confirmed that the value of tan δ at 50 ° C. was small and excellent in fuel efficiency.
From these results, it was confirmed that the modified conjugated diene polymer compositions of Examples 4 to 6 were excellent in the balance between fuel economy and processability.

  The modified conjugated diene polymer according to the present invention exhibits excellent fuel economy when used as a vulcanized rubber, and is processable when mixed with other components to form a composition or vulcanized rubber. It can also be suitably used as a material for various members such as tire treads, footwear, and industrial articles.

Claims (10)

A modified conjugated diene polymer represented by the following formula (1) or (2).
(In the formulas (1) and (2), P ¹ , P ² and P ³ are independently a (co) polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound,
R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms,
X ¹ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3,
q is an integer of 0 to 2, r is an integer of 1 to 3, and satisfies q + r = 3,
When a plurality of P ¹ , P ² , P ³ , R ¹ , R ² , X ¹ , q and r are present, they may be the same or different. ) ^2. The modified conjugated diene polymer according to claim 1, wherein in the formulas (1) and (2), the total number of P ¹ , P ² and P ³ is 5 or more.   The modified conjugated diene polymer according to claim 1 or 2, wherein n is 1 and m is 2 in the formulas (1) and (2).   The modified conjugated diene polymer according to any one of claims 1 to 3, wherein, in the formulas (1) and (2), q is 1 and r is 2. A polymerization step of (co) polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound, using an alkali metal or alkaline earth metal compound as a polymerization initiator; and
The manufacturing method of the modified conjugated diene type polymer including the modification | denaturation process of making the compound shown by following formula (3) react with the polymer obtained by the said polymerization process.
(In formula (3), R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms,
A ¹ is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
X ¹ , X ² , and X ³ are each independently a halogen atom or an alkoxy group having 1 to 20 carbon atoms,
n is an integer of 1 to 2, m is an integer of 1 to 2, and satisfies n + m = 3,
When a plurality of R ¹ , R ² , X ¹ , X ² , X ³ and A ¹ are present, they may be the same or different. )   The method for producing a modified conjugated diene polymer according to claim 5, wherein n is 1 and m is 2 in the formula (3).   A modified conjugated diene polymer obtained by the method according to claim 5 or 6.   The molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement has at least two peaks, and the peak top molecular weight of the peak with the largest peak area is the peak top molecular weight of the peak with the smallest peak top molecular weight. The modified conjugated diene polymer according to any one of claims 1 to 4 and 7, which is 2.6 to 5.0 times.   There is only one peak in the molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement, and the polystyrene-equivalent number average molecular weight (Mn) of the peak is 150,000 to 1,000,000. The modified conjugated diene polymer according to any one of claims 1 to 4 and 7. 100 parts by mass of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer according to any one of claims 1 to 4, 7, 8, and 9, and
A modified conjugated diene polymer composition comprising 0.5 to 300 parts by mass of a silica-based inorganic filler.