Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/04—Polymeric products of isocyanates or isothiocyanates with vinyl compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/22—Incorporating nitrogen atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
  • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

• the present invention relates to a modified conjugated diene polymer, a method for producing the same, a rubber composition and a tire using the polymer, and particularly relates to a rubber composition excellent in low heat buildup and fracture characteristics (crack growth resistance). It is.
• Modified high cis polybutadiene rubber introduced with a functional group that interacts with the filler is known to have superior fracture characteristics compared to unmodified high cis polybutadiene rubber, and improves the low loss effect of the rubber composition. There is a need for modified high-cis polybutadiene rubbers that can be used.
• the modified high-cis polybutadiene rubber introduced with a functional group that interacts with the filler improves the low-loss property and fracture characteristics of the rubber composition. Is raised. However, the reaction efficiency between the polymer terminal and the modifier is still low, and there is a limit to improving the low loss effect by increasing the reaction efficiency.
• the present inventors examined the functional group introduced into the polymer terminal, and by introducing an amino group having an active hydrogen having an extremely high affinity with carbon black into the polymer terminal, an unprecedented level. Thus, it was found that the low loss effect can be improved. Further investigations have also revealed that introduction of a primary amino group at the polymer end brings about a remarkable low-loss effect compared to introduction of a secondary amino group or a tertiary amino group.
• the present inventors have (1) reacted a compound having two or more predetermined functional groups with a predetermined conjugated diene polymer having an active end, and (2) Furthermore, a modified conjugated diene polymer having a specific cis-1,4 bond amount, vinyl bond amount and primary amino group is obtained by reacting the resulting product with a compound having a primary amino group.
• the present invention has found that the use of the modified conjugated diene polymer as a rubber component and further applying a rubber composition containing a specific filler to a tire can greatly improve low heat buildup and fracture characteristics. It came to complete.
• the rubber composition of the present invention contains 10% by mass or more of a modified conjugated diene polymer having a cis-1,4 bond amount of 90% or more and a vinyl bond amount of 1.2% or less and having a primary amino group. It is characterized by blending 10 to 100 parts by mass of an inorganic filler and / or carbon black with respect to 100 parts by mass of the rubber component.
• the cis-1,4 bond amount is the ratio of cis-1,4 bond in the conjugated diene compound unit in the polymer, and the vinyl bond amount is the vinyl bond in the conjugated diene compound unit in the polymer. It is a ratio.
• the modified conjugated diene polymer preferably has a vinyl bond content of 0.8% or less.
• the carbon black preferably has a nitrogen adsorption specific surface area of 20 to 180 m 2 / g, and more preferably 20 to 100 m 2 / g.
• the rubber component contains 10 to 90% by mass of the modified conjugated diene polymer and 90 to 10% by mass of a diene polymer other than the modified conjugated diene polymer.
• natural rubber is preferred as the diene polymer other than the modified conjugated diene polymer.
• the rubber composition of the present invention is preferably sulfur crosslinkable.
• the tire of the present invention is characterized by using the above rubber composition for any of the tire members.
• the method for producing the modified conjugated diene polymer of the present invention comprises (1) a conjugated diene polymer having a cis-1,4 bond content of 90% or more and a vinyl bond content of 1.2% or less and having an active terminal. And reacting a compound X having a functional group A reactive to the active terminal and at least one reactive functional group B (provided that the functional group A and the functional group B may be the same). Obtaining a primary modified conjugated diene polymer, (2) The primary modified conjugated diene polymer has a functional group C that is reactive with the reactive functional group B, and at least one primary amino group or protected primary amino group. A compound Y (provided that the functional group C may be a primary amino group or a protected primary amino group) to obtain a secondary modified conjugated diene polymer; It is characterized by including.
• the conjugated diene polymer preferably has a vinyl bond content of 0.8% or less.
• the secondary modified conjugated diene polymer is hydrolyzed to remove the protected primary amino group derived from the compound Y. Including the step of protecting.
• the conjugated diene polymer is synthesized using a rare earth metal as a catalyst.
• the compound X is polymethylene polyphenyl polyisocyanate
• the compound Y is hexamethylene diamine
• modified conjugated diene polymer of the present invention is characterized by being produced by the above method.
• a compound having two or more predetermined functional groups is reacted with a predetermined conjugated diene polymer having an active end, and (2) a primary amino group is further added to the resulting product.
• a compound having two or more predetermined functional groups is reacted with a predetermined conjugated diene polymer having an active end, and (2) a primary amino group is further added to the resulting product.
• the compound has a specific cis-1,4 bond amount, vinyl bond amount and primary amino group, and imparts low heat buildup and fracture characteristics (crack growth resistance) to the rubber composition.
• the modified conjugated diene polymer it is possible to provide a rubber composition and a tire excellent in low heat buildup and fracture characteristics (crack growth resistance).
• the rubber composition of the present invention comprises a rubber component containing 10% by mass or more of a modified conjugated diene polymer having a primary amino group and a cis-1,4 bond content of 90% or more and a vinyl bond content of 1.2% or less. It is characterized by blending 10 to 100 parts by mass of an inorganic filler and / or carbon black with respect to 100 parts by mass.
• the modified conjugated diene polymer used as the rubber component of the rubber composition of the present invention has a cis-1,4 bond content of 90% or more and a vinyl bond content of 1.2% or less. It is the polymer shown.
• Such modified conjugated diene polymers generally have a low reaction efficiency with a modifier.
• the modified conjugated diene polymer used as the rubber component of the rubber composition of the present invention has a primary amino group introduced therein, and has a very high affinity for fillers such as inorganic fillers and carbon black, The filler can be effectively dispersed even with a low reaction efficiency.
• the rubber composition of the present invention has improved fracture characteristics due to the stretched crystallinity of the modified conjugated diene polymer, and further improved the low exothermicity by improving the dispersibility of the filler. It can also be made.
• the method for producing a modified conjugated diene polymer used as a rubber component in the rubber composition of the present invention will be described in detail below.
• the rubber component of the rubber composition of the present invention needs to contain 10% by mass or more of the modified conjugated diene polymer.
• the proportion of the modified conjugated diene polymer in the rubber component is less than 10% by mass, the effect of improving the dispersibility of the filler is particularly small, and the low exothermic property of the rubber composition cannot be obtained sufficiently.
• the modified conjugated diene polymer may be used in combination with a rubber component other than the modified conjugated diene polymer.
• rubber components other than the modified conjugated diene polymer include natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), Examples include ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene rubber (NBR), and among these, natural rubber is particularly preferable. Rubber components other than these modified conjugated diene polymers may be used alone or in a blend of two or more.
• a diene polymer other than a modified conjugated diene polymer such as natural rubber is combined with the modified conjugated diene polymer, 10 to 90% by mass of the modified conjugated diene polymer and other than the modified conjugated diene polymer
• a rubber component containing 90 to 10% by mass of a diene polymer is preferable.
• the rubber composition of the present invention contains 10 to 100 parts by mass of an inorganic filler and / or carbon black as a filler with respect to 100 parts by mass of the rubber component. If the blending amount of the inorganic filler and / or carbon black is less than 10 parts by mass with respect to 100 parts by mass of the rubber component, the fracture characteristics of the rubber composition are reduced. There is a risk of exothermic deterioration.
• the carbon black is not particularly limited, but the nitrogen adsorption specific surface area is preferably in the range of 20 to 180 m 2 / g, more preferably in the range of 20 to 100 m 2 / g. Carbon black having a nitrogen adsorption specific surface area in the range of 20 to 180 m 2 / g has a large particle diameter and an extremely high effect of improving low heat generation.
• the carbon black is preferably of the grade below HAF, and examples thereof include HAF, FF, FEF, GPF, SRF, and FT grades. From the viewpoint of fracture characteristics, HAF, FEF, A GPF grade is particularly preferred.
• examples of the inorganic filler include silica, talc, and aluminum hydroxide. In addition, these fillers may be used individually by 1 type, and 2 or more types may be mixed and used for them.
• the rubber composition of the present invention comprises, in addition to inorganic fillers and / or carbon black, compounding agents commonly used in the rubber industry, such as softeners, stearic acid, anti-aging agents, zinc white, A sulfur accelerator, a vulcanizing agent, and the like can be appropriately selected and blended within a range not impairing the object of the present invention, and kneaded, heated, extruded, and the like.
• the rubber composition of the present invention is preferably sulfur crosslinkable, and sulfur or the like is preferably used as a vulcanizing agent.
• the amount of the vulcanizing agent used is preferably 0.1 to 10.0 parts by weight, more preferably 1.0 to 5.0 parts by weight, based on 100 parts by weight of the rubber component.
• the tire of the present invention is characterized by using the rubber composition as a tire member.
• the tire member include a tire tread, an under tread, a carcass, a sidewall, a bead portion, and the like.
• the tire of the present invention is obtained by forming each tire member using the rubber composition in an unvulcanized state, forming a raw tire according to a conventional method, and vulcanizing the raw tire.
• a tire in which the rubber composition is applied to any tire member is excellent in fracture characteristics (crack growth resistance) and low heat buildup.
• inert gas such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.
• the method for producing a modified conjugated diene polymer of the present invention comprises (1) a conjugated diene polymer having an cis-1,4 bond content of 90% or more and a vinyl bond content of 1.2% or less and having an active terminal.
• a compound X having at least one reactive functional group B and a functional group A that is reactive to the active terminal is allowed to react to form a primary product.
• a step of obtaining a modified conjugated diene polymer (primary modification reaction), and (2) a functional group C that is reactive to the reactive functional group B in the primary modified conjugated diene polymer, and at least one A compound Y having a primary amino group or a protected primary amino group (provided that the functional group C may be a primary amino group or a protected primary amino group)
• a step of obtaining a secondary modified conjugated diene polymer (secondary modification reaction).
• secondary modification reaction A step of obtaining a secondary modified conjugated diene polymer (secondary modification reaction).
• the modified conjugated diene polymer obtained by the above steps (1) and (2) or the modified conjugated diene polymer obtained by the above steps (1), (2) and (3) is cis-1, Since the amount of 4-bond is 90% or more and the amount of vinyl bond is 1.2% or less and has a primary amino group, it can be used as a modified conjugated diene polymer of the above rubber composition. The fracture characteristics and low heat buildup of the rubber composition are greatly improved.
• a compound having reactivity with the active terminal of the conjugated diene polymer and having a primary amino group is not commercially available at present, and the primary amino group is added to the conjugated diene polymer in one step. Since it is difficult to introduce, in the production method of the present invention, two modification reactions (primary modification reaction and secondary modification reaction) are performed in order to obtain a modified conjugated diene polymer.
• the modified conjugated diene polymer of the present invention needs to have a cis-1,4 bond content of 90% or more, but if the cis-1,4 bond content is less than 90%, low loss in the rubber composition is required. The effect cannot be obtained sufficiently.
• the modified conjugated diene polymer of the present invention requires a vinyl bond content of 1.2% or less, and preferably 0.8% or less. This is because the crystallinity of the polymer decreases when the vinyl bond content exceeds 1.2%.
• the modified conjugated diene polymer of the present invention has a primary amino group or a protected primary amino group in the molecule. Therefore, when the modified conjugated diene polymer of the present invention has a primary amino group in the molecule, the polymer is directly used as a rubber component, and the modified conjugated diene polymer of the present invention is incorporated in the molecule. When it has a protected amino group, the low exothermic property of the rubber composition obtained can be significantly improved by using the polymer deprotected through the step (3) as a rubber component.
• the number average molecular weight (Mn) of the modified conjugated diene polymer of the present invention is not particularly limited, and the problem of low molecular weight does not occur in the production process described below.
• the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.
• the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).
• the Mooney viscosity [ML 1 + 4 (100 ° C.)] of the modified conjugated diene polymer of the present invention is preferably 10 to 100, more preferably 20 to 80. If the Mooney viscosity [ML 1 + 4 (100 ° C)] is less than 10, rubber properties such as fracture characteristics tend to be reduced. On the other hand, if it exceeds 100, workability is deteriorated and kneaded with a compounding agent. It may be difficult to do.
• the conjugated diene polymer used in the above step (1) has a cis-1,4 bond amount of 90% or more and a vinyl bond amount of 1.2% or less, and has an active end.
• limiting in particular about the manufacturing method of such a conjugated diene type polymer Although the manufacturing method using a conventionally well-known polymerization reaction can be used, the manufacturing method using coordination polymerization is preferable.
• the solvent used may be inert in the polymerization reaction.
• the temperature of the polymerization reaction is preferably in the range of ⁇ 30 ° C. to 200 ° C., more preferably in the range of 0 ° C. to 150 ° C.
• the polymerization mode is not particularly limited, and may be batch type or continuous type.
• the conjugated diene polymer is preferably a homopolymer of a conjugated diene compound or a copolymer of an aromatic vinyl compound and a conjugated diene compound.
• conjugated diene compounds as monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. , Myrcene and the like. Among these, 1,3-butadiene and isoprene are preferable.
• examples of the aromatic vinyl compound as a monomer include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, chloromethylstyrene, vinyltoluene and the like.
• the conjugated diene polymer is preferably synthesized using a rare earth metal as a catalyst.
• the monomer is polymerized in the presence of a polymerization catalyst composition containing the following components (a) to (c) as main components. Is obtained.
• a conjugated diene polymer By producing a conjugated diene polymer by polymerization using such a catalyst (catalyst composition), a conjugated diene polymer having a narrow molecular weight distribution and a high amount of cis-1,4 bonds can be obtained. .
• this catalyst (catalyst composition) is less expensive than conventionally used metallocene catalysts and does not require a polymerization reaction at an extremely low temperature. For this reason, operation is simple and useful as an industrial production process.
• the component (a) used in the polymerization catalyst composition is a lanthanoid element-containing compound containing at least one of lanthanoid elements (rare earth elements corresponding to atomic numbers 57 to 71 in the periodic table), or the lanthanoid element-containing compound and Lewis base It is a reaction product obtained by reaction with.
• lanthanoid elements include neodymium, praseodymium, cerium, lanthanum, gadolinium, samarium and the like. Of these, neodymium is preferred.
• these lanthanoid elements may be used individually by 1 type, and may be used in combination of 2 or more type.
• the lanthanoid element-containing compound examples include carboxylates, alkoxides, ⁇ -diketone complexes, phosphates and phosphites of the above lanthanoid elements.
• carboxylate or phosphate is preferable, and carboxylate is more preferable.
• Examples of the lanthanoid element carboxylates include salts such as 2-hexylhexane, naphthenic acid, versatic acid [trade name, manufactured by Shell Chemical Co., Ltd., carboxylic acid having a carboxyl group bonded to a tertiary carbon atom].
• Specific examples of the alkoxide of the lanthanoid element include compounds represented by the general formula (II) :( R 4 O) 3 M (provided that, in the general formula (II), M is a lanthanoid element).
• R 4 is a hydrocarbon group having 1 to 20 carbon atoms).
• alkoxy group represented by “R 4 O” examples include 2-ethyl-hexylalkoxy group and benzylalkoxy group.
• Preferable examples of the ⁇ -diketone complex of the lanthanoid element include an acetylacetone complex and an ethylacetylacetone complex.
• Examples of the lanthanoid element phosphates or phosphites include bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, 2-ethylhexylphosphonate mono-2-ethylhexyl, and bis (2-ethylhexyl). ) Salts such as phosphinic acid are preferred.
• the lanthanoid element-containing compound is more preferably a neodymium phosphate or a neodymium carboxylate, and a carboxylate such as neodymium 2-ethylhexanoate or neodymium versatate. Particularly preferred.
• a reaction product obtained by mixing a lanthanoid element-containing compound and a Lewis base, or reacting a lanthanoid element-containing compound and a Lewis base It is also preferable that The amount of the Lewis base is preferably 0 to 30 mol, more preferably 1 to 10 mol, per 1 mol of the lanthanoid element.
• Lewis base examples include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, a monovalent or divalent alcohol, and the like.
• the component (a) described so far may be used alone or in combination of two or more.
• the component (b) used in the polymerization catalyst composition is an alumoxane and / or an organoaluminum compound represented by the general formula (I).
• Alumoxane also referred to as aluminoxane
• II organoaluminum compound represented by the general formula (III) or (IV).
• R 5 is a hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, isobutyl group, t- A butyl group, a hexyl group, an isohexyl group, an octyl group, an isooctyl group and the like can be mentioned. Among these, a methyl group is particularly preferable.
• n ′ is an integer of 2 or more, and preferably an integer of 4 to 100.
• alumoxane examples include methylalumoxane (MAO), ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, isohexylalumoxane and the like.
• MAO methylalumoxane
• ethylalumoxane ethylalumoxane
• n-propylalumoxane n-butylalumoxane
• isobutylalumoxane isobutylalumoxane
• t-butylalumoxane hexylalumoxane
• isohexylalumoxane and the like can be mentioned.
• Alumoxane can be produced by a known method.
• trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, xylene, and water, water vapor, water vapor-containing nitrogen gas, or copper sulfate pentahydrate or aluminum sulfate 16-hydrate. It can be produced by adding a salt having water of crystallization to react.
• alumoxane may be used individually by 1 type, and may be used in combination of 2 or more type.
• organoaluminum compound represented by the general formula (II) examples include triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride and the like.
• an organoaluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• Component (c) used in the polymerization catalyst composition is a halogen-containing compound containing at least one halogen atom in its molecular structure, such as a reaction product of a metal halide and a Lewis base, diethylaluminum chloride, Silicon tetrachloride, trimethylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, ethylaluminum dichloride, ethylaluminum sesquichloride, tin tetrachloride, tin trichloride, phosphorus trichloride, benzoyl chloride, t-butyl chloride, trimethylsilylio Dido, triethylsilyl iodide, dimethylsilyl iodide, diethylaluminum iodide, methyl iodide, butyl iodide, he
• Examples of the metal halide that can be used in the reaction product of the metal halide and the Lewis base include magnesium chloride, manganese chloride, zinc chloride, copper chloride, magnesium iodide, manganese iodide, zinc iodide, copper iodide, and the like. Are preferable.
• the Lewis base phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols and the like can be preferably used.
• Preferable examples include ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol.
• the Lewis base is preferably reacted at a rate of 0.01 mol to 30 mol, more preferably at a rate of 0.5 mol to 10 mol, per 1 mol (mol) of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
• component (a) is preferably 0.00001 mmol to 1.0 mmol, more preferably 0.0001 mmol to 0.5 mmol, relative to 100 g of monomer.
• a preferable amount of the alumoxane contained in the catalyst can be represented by a molar ratio between the component (a) and aluminum (Al) contained in the alumoxane. That is, “component (a)”: “aluminum (Al) contained in alumoxane” (molar ratio) is preferably 1: 1 to 1: 500, more preferably 1: 3 to 1: 250. 1: 5 to 1: 200 is particularly preferable.
• component (b) is an organoaluminum compound
• the preferred amount of the organoaluminum compound contained in the catalyst can be represented by the molar ratio of the component (a) to the organoaluminum compound. That is, “component (a)”: “organoaluminum compound” (molar ratio) is preferably 1: 1 to 1: 700, and more preferably 1: 3 to 1: 500.
• the preferred amount of the component (c) contained in the catalyst composition can be represented by the molar ratio of the halogen atom contained in the component (c) and the component (a). That is, (halogen atom) / (component (a)) (molar ratio) is preferably 20 to 0.1, more preferably 15 to 0.2, and particularly preferably 8 to 0.5.
• the catalyst described above may be prepared in advance using the same conjugated diene compound and / or non-conjugated diene compound as the polymerization monomer, if necessary. Also good.
• the catalyst composition can be prepared, for example, by reacting components (a) to (c) dissolved in a solvent, and a conjugated diene compound and / or a non-conjugated diene compound added as necessary. .
• the addition order of each component may be arbitrary. However, it is preferable from the viewpoints of improving polymerization activity and shortening the polymerization start induction period that each component is mixed and reacted in advance and aged.
• the aging temperature is preferably 0 ° C. to 100 ° C., more preferably 20 ° C. to 80 ° C.
• the aging time is not particularly limited. Each component may be brought into contact in the line before being added to the polymerization reactor. The aging time should be 0.5 minutes or longer.
• the prepared catalyst composition is stable for several days.
• step (1) by reacting compound X with the conjugated diene polymer having the active site, a primary modified conjugated diene polymer in which compound X is introduced into the active terminal of the conjugated diene compound is obtained. It is done.
• the compound X used in the above step (1) is a compound having a functional group A reactive to the active terminal of the conjugated diene polymer and at least one reactive functional group B.
• the functional group A and the functional group B may be the same or different, and examples thereof include a ketene group, an isocyanate group, a thioisocyanate group, and a carbodiimide group.
• the compound X In the method for producing a modified conjugated diene polymer of the present invention, it is preferable to use a heterocumulene compound having two or more isocyanate groups as the compound X, and it is particularly preferable to use polymethylene polyphenyl polyisocyanate.
• the compound X may be used individually by 1 type, and may be used in combination of 2 or more type.
• the amount of compound X used is preferably 0.02 mmol to 20 mmol, more preferably 0.1 mmol to 10 mmol, and particularly preferably 0.2 mmol to 5 mmol with respect to 100 g of monomer.
• the amount of compound X used is less than 0.02 mmol, the progress of the primary modification reaction is not sufficient, and the functional group that reacts with compound Y may not be sufficiently introduced into the conjugated diene polymer, whereas when it exceeds 20 mmol, The number of functional groups that react with the compound Y in the conjugated diene polymer is saturated, which is economically undesirable.
• This primary denaturation reaction is preferably performed by a solution reaction.
• This solution reaction may be, for example, a solution containing unreacted monomers used when polymerizing a conjugated diene polymer.
• a solution reaction may be, for example, a solution containing unreacted monomers used when polymerizing a conjugated diene polymer.
• limiting in particular about the form of primary denaturation reaction You may carry out using a batch type reactor, and you may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer.
• the polymerization temperature of the conjugated diene polymer can be used as it is. Specifically, 0 ° C. to 120 ° C. is preferable, and 10 ° C. to 100 ° C. is more preferable. When this temperature is lowered, the viscosity of the resulting polymer (primary modified conjugated diene polymer) tends to increase. On the other hand, when the temperature is raised, the polymerization active terminal tends to be deactivated, which is not preferable.
• the time required for the primary denaturation reaction is preferably, for example, 5 minutes to 5 hours, and more preferably 15 minutes to 1 hour.
• the active terminal of the conjugated diene polymer is reacted with the functional group A of the compound X to obtain a primary modified conjugated diene polymer.
• the secondary modification reaction described later step (2)).
• at least one of the functional groups B of the compound X needs to be left unreacted.
• step (2) the secondary modification in which the compound Y is introduced into the reactive functional group B derived from the compound X by reacting the compound Y with the primary modified conjugated diene polymer obtained in the step (1).
• a conjugated diene polymer can be obtained.
• the compound Y used in the step (2) includes a functional group C that is reactive with the reactive functional group B derived from the compound X, and at least one primary amino group or protected primary amino group. It is a compound which has this.
• the functional group C include an amino group, an imino group, a mercapto group, and a hydroxyl group.
• the functional group C may be a primary amino group or a protected primary amino group.
• Compound Y includes hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, dodecamethylenediamine, decamethylenediamine, 1,5-naphthalenediamine, 1,8-naphthalenediamine, and 1,3-bis (aminomethyl) cyclohexane.
• Preferable examples include 1,4-bis (aminomethyl) cyclohexane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like.
• examples of the compound Y include hexamethyldisilazane, N-chlorohexamethyldisilazane, N-bromohexamethyldisilazane, (3-Bromopropyl) -2,2,5,5-tetramethyl-1-aza-2,5-diciacyclopentane, 1- (3-chloropropyl) -2,2,5,5-tetramethyl Preferred examples include -1-aza-2,5-diciacyclopentane.
• This secondary denaturation reaction can be carried out continuously with the above-mentioned primary denaturation reaction, and is preferably carried out by a solution reaction in the same manner as the primary denaturation reaction.
• This solution reaction may be, for example, a solution containing unreacted monomers used when polymerizing a conjugated diene polymer.
• the type of secondary denaturation reaction is not particularly limited, and may be performed using a batch type reactor as in the case of the primary denaturation reaction, or a continuous type using an apparatus such as a multistage continuous reactor or an inline mixer. You may go on. Further, it is important to carry out this secondary modification reaction after completion of the polymerization reaction and before performing various operations necessary for solvent removal treatment, water treatment, heat treatment, polymer isolation, and the like.
• the amount of compound Y used is preferably 0.02 to 20 mmol, more preferably 0.1 to 10 mmol, and particularly preferably 0.2 to 5 mmol, based on 100 g of monomer. If the amount of compound Y used is less than 0.02 mmol, the progress of the secondary denaturation reaction is not sufficient, the dispersibility with the filler is not sufficiently exhibited, and the effect of improving the fracture characteristics may not be manifested. On the other hand, if it exceeds 20 mmol, the effect of improving the dispersibility and physical properties of the filler is saturated, which is not economically preferable.
• the temperature of the secondary denaturation reaction the temperature of the primary denaturation reaction can be used as it is. Specifically, 0 ° C. to 120 ° C. is preferable, and 10 ° C. to 100 ° C. is more preferable. When this temperature is lowered, the viscosity of the resulting polymer (secondary modified conjugated diene polymer) tends to increase. On the other hand, when the temperature is raised, the polymerization active terminal tends to be deactivated, which is not preferable.
• the time required for the secondary denaturation reaction is preferably, for example, 5 minutes to 5 hours, and more preferably 15 minutes to 1 hour.
• a catalyst that promotes the reaction between the functional group B derived from the compound X of the primary modified conjugated diene polymer and the functional group C of the compound Y.
• the functional group B derived from the compound X of the primary modified conjugated diene polymer and the functionality of the compound Y It is preferable to add a catalyst (addition reaction catalyst) that promotes the reaction with the group C.
• an addition reaction catalyst it contains a compound containing a tertiary amino group or one or more elements belonging to any of groups 4A, 2B, 3B, 4B and 5B in the periodic table More preferably, the compound contains one or more elements of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), or tin (Sn).
• the compound constituting the catalyst is particularly preferably an alkoxide, a carboxylate, or an acetylacetonate complex.
• addition reaction catalyst examples include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetra i-propoxy titanium, tetra n-butoxy titanium, tetra n-butoxy titanium oligomer, tetra sec-butoxy titanium, tetra tert-butoxytitanium, tetra (2-ethylhexyl) titanium, bis (octanediolate) bis (2-ethylhexyl) titanium, tetra (octanediolate) titanium, titanium lactate, titanium dipropoxybis (triethanolamate), titanium Dibutoxybis (triethanolaminate), titanium tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipro Xybis (acetylacetonate), titanium tripropoxyethyl acetoacetate, titanium propoxyacetylacetonate bis (e
• addition reaction catalyst examples include tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, and tris (linoleate).
• bis (n-octanoate) tin bis (2-ethylhexanoate) tin, bis (laurate) tin, bis (naphthoate) tin, bis (stearate) tin, bis ( Oleate) tin, dibutyltin diacetate, dibutyltin di-n-octanoate, dibutyltin di-2-ethylhexanoate, dibutyltin dilaurate, dibutyltin malate, dibutyltin bis (benzyl malate), dibutyltin bis (2-ethylhexylmalate), din -Octyltin diacetate, di-n-octyltin di-n-octanoate, di-n-octyltin di-2-ethylhexanoate, di-n-octyltylt
• the amount of the addition reaction catalyst used is such that the number of moles of the compound exemplified as the addition reaction catalyst is 0.1 to 10 as the molar ratio relative to the total of the unreacted functional group A and functional group B present in the reaction system. Is more preferable, and 0.5 to 5 is more preferable. When the molar ratio is less than 0.1, the modification reaction (specifically, the secondary modification reaction) does not proceed sufficiently. On the other hand, when it exceeds 10, the effect as an addition reaction catalyst is saturated, which is economically preferable. Absent.
• the modified conjugated diene polymer of the present invention is obtained by adding a polymerization terminator or a polymerization stabilizer to the reaction system as necessary after the steps (1) and (2) are completed. It can collect
• the (3) secondary modified conjugated diene polymer is further hydrolyzed. It is preferable to perform a step of deprotecting the protected primary amino group derived from compound Y. Thereby, a modified conjugated diene polymer having a primary amino group is obtained, and can be used as a modified conjugated diene polymer of the rubber composition described above.
• a normal method can be used for a hydrolysis.
• the Mooney viscosity [ML 1 + 4 (100 ° C.)] was 18 and the molecular weight distribution (Mw / Mn) was 2.2.
• Mooney viscosity [ML 1 + 4 (100 ° C)] According to JIS K6300, using an L rotor, the preheating was performed for 1 minute, the rotor operation time was 4 minutes, and the temperature was 100 ° C.
• Polymer B Polymerization was carried out in the same manner as in the above Production Example of Polymer A, and then the polymer solution was kept at a temperature of 60 ° C. to obtain polymethylene polyphenyl polyisocyanate (trade name “PAPI * 135”, manufactured by Dow Chemical Japan) ( A toluene solution of (hereinafter also referred to as “cMDI”) (4.16 mmol in terms of isocyanate group (NCO)) was added and reacted for 15 minutes (primary modification reaction). Subsequently, a toluene solution of hexamethylenediamine (hereinafter also referred to as “HMDA”) (2.08 mmol) was added and reacted for 15 minutes (secondary modification reaction).
• cMDI polymethylene polyphenyl polyisocyanate
• NCO isocyanate group
• HMDA hexamethylenediamine
• Polymer C Polymerization was carried out in the same manner as in Production Example for Polymer A, and then the polymer solution was kept at a temperature of 60 ° C. and a toluene solution of 4,4′-bis (diethylamino) benzophenone (2.08 mmol) was added for 15 minutes. Reacted. Thereafter, it was extracted into a methanol solution containing 1.3 g of 2,4-di-tert-butyl-p-cresol, the polymerization was stopped, the solvent was removed by steam stripping, and the product was dried with a roll at 110 ° C. Got. The polymer C thus obtained was measured by the above method.
• the Mooney viscosity [ML 1 + 4 (100 ° C.)] was 24, the molecular weight distribution (Mw / Mn) was 2.0, and the cis- The amount of 1,4 bonds was 96.0%, and the amount of 1,2-vinyl bonds was 0.58%.
• Polymer D Polymerization was carried out in the same manner as in Production Example for Polymer A, and then the polymer solution was kept at a temperature of 60 ° C., and a toluene solution of trimethylolpropane tris [(3- (1-aziridinyl)) propionate] (2.08 mmol). was added and allowed to react for 15 minutes. Thereafter, it was taken out in a methanol solution containing 1.3 g of 2,4-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and the polymer D was dried by a roll at 110 ° C. Got. The polymer D thus obtained was measured by the above method.
• the Mooney viscosity [ML 1 + 4 (100 ° C.)] was 33, the molecular weight distribution (Mw / Mn) was 2.2, and cis- The amount of 1,4 bonds was 96.3%, and the amount of 1,2-vinyl bonds was 0.62%.
• the polymer solution was kept at a temperature of 50 ° C., cMDI (0.84 mmol in terms of isocyanate group (NCO)) was added and reacted for 15 minutes, and then HMDA (0.42 mmol) was reacted. Thereafter, it was extracted into a methanol solution containing 1.3 g of 2,4-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and the polymer E was dried with a roll at 110 ° C. Got. The polymer E thus obtained was measured by the above method.
• the Mooney viscosity [ML 1 + 4 (100 ° C.)] was 42, the molecular weight distribution (Mw / Mn) was 1.70, and cis- The amount of 1,4 bonds was 45.1%, and the amount of 1,2-vinyl bonds was 18.33%.
• Polymer F Polymer F Polymerization was carried out in the same manner as in the production example of the polymer A, and then the polymer solution was kept at 60 ° C. and 1-trimethylsilyl-2-methylchloro-1-aza-2-silacyclopentane (2.08 mmol) in toluene. The solution was added and allowed to react for 15 minutes. Thereafter, it was extracted into a methanol solution containing 1.3 g of 2,4-di-tert-butyl-p-cresol, the polymerization was stopped, the solvent was removed by steam stripping, and the polymer F was dried by a roll at 110 ° C. (Modified conjugated diene polymer) was obtained. The polymer F thus obtained was measured by the above method.
• the Mooney viscosity [ML 1 + 4 (100 ° C.)] was 26
• the molecular weight distribution (Mw / Mn) was 2.1
• cis- The amount of 1,4 bonds was 96.4%
• the amount of 1,2-vinyl bonds was 0.62%.
• the rubbers of Examples 1 to 4 containing a modified conjugated diene polymer having a primary amino group and a cis-1,4 bond content of 90% or more and a vinyl bond content of 1.2% or less.
• the composition has a cis-1,4 bond content of 90% or more and a vinyl bond content of 1.2% or less, but contains a conjugated diene polymer having no primary amino group. It can be seen that the crack growth resistance and the low heat buildup can be greatly improved as compared with the rubber composition of No. 3. Further, from the results of Examples 1 to 4, the effect of improving crack growth resistance and low exothermicity is greatly improved when carbon black having a nitrogen adsorption specific surface area of 20 to 180 m 2 / g is blended. I understand that I can do it. In addition, since the rubber composition of the comparative example 4 has low cis-1,4 bond amount of the blended polymer E, it can be seen that although the low heat buildup is improved, the crack growth resistance is greatly reduced.
• Comparative Example 5 in which the rubber composition of Example 1 in which the polymer B into which the primary amino group was introduced was blended with the polymer C and the polymer D into which the tertiary amino group had been introduced was blended. It can be seen that the crack growth resistance and the low heat buildup can be greatly improved as compared with the rubber compositions of 6 to 6.

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