WO2021201289A1 - 共役ジエン系重合体、共役ジエン系重合体の製造方法、共役ジエン系重合体組成物、及びゴム組成物 - Google Patents
共役ジエン系重合体、共役ジエン系重合体の製造方法、共役ジエン系重合体組成物、及びゴム組成物 Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
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- 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
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- 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
- C08C19/25—Incorporating silicon atoms into the molecule
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
- C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
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- 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
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a conjugated diene-based polymer, a method for producing a conjugated diene-based polymer, a conjugated diene-based polymer composition, and a rubber composition.
- the rubber material used for the tread is preferably a material having a small rolling resistance, that is, a low hysteresis loss property.
- the tire material is required to have sufficient breaking strength for practical use from the viewpoint of safety.
- Examples of the rubber material that meets the above-mentioned requirements include a rubber composition containing a rubber-like polymer and a reinforcing filler such as carbon black and silica.
- the dispersibility of silica in the rubber composition is improved by introducing a functional group having affinity or reactivity with silica into the molecular terminal portion of the highly motile rubber-like polymer. Attempts have been made to improve and reduce the motility of the molecular end of the rubbery polymer to reduce hysteresis loss while improving wear resistance and breaking strength.
- Patent Documents 1 to 3 disclose a composition of a modified conjugated diene polymer and silica obtained by reacting an amino group-containing alkoxysilane with an active terminal of a conjugated diene polymer. Further, Patent Document 4 discloses a low vinyl modified conjugated diene polymer.
- the present invention provides a conjugated diene-based polymer having excellent processability during vulcanization, and the vulcanized product having excellent wear resistance and low hysteresis loss, a method for producing a conjugated diene-based polymer, and a conjugated diene-based weight. It is an object of the present invention to provide a coalesced composition and a rubber composition.
- the present inventors have contained a portion derived from an aromatic vinyl compound in a predetermined ratio, and the degree of branching (Bn) and a specific vinyl bond amount are within a predetermined range. It has been found that the conjugated diene-based polymer is excellent in processability at the time of vulcanization, and the vulcanized product is excellent in abrasion resistance and low hysteresis loss property, and has completed the present invention.
- the present invention is as follows.
- GPC with viscosity detector-The degree of branching by the light scattering method is 7 or more.
- the amount of bound aromatic vinyl is 1% by mass or more and 32% by mass or less.
- the amount of vinyl bond in the bonded conjugated diene is 11 mol% or more and 35 mol% or less.
- the amount of the bonded aromatic vinyl is 1% by mass or more and 30% by mass or less.
- the conjugated diene-based polymer according to [1], wherein the amount of vinyl bond in the bonded conjugated diene is 11 mol% or more and 30 mol% or less.
- [3] The conjugated diene-based polymer according to [1] or [2], which has a nitrogen atom.
- [4] The conjugated diene-based polymer according to any one of [1] to [3], which has a silicon atom.
- [5] The conjugated diene-based polymer according to any one of [1] to [4], which has a modifying group.
- the modifying group has a nitrogen atom and The conjugated diene polymer according to [5], wherein the modification rate of the conjugated diene polymer is 70% by mass or more.
- At least one of the above-mentioned portions derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is a portion derived from a compound represented by the following formula (1) or (2).
- Conjugate diene polymer (In the formula (1), R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.
- R 2 and R 3 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.
- X 1 each independently represents a halogen atom
- m indicates an integer of 0 to 2
- n indicates an integer of 0 to 3
- l indicates an integer of 0 to 3, and so on.
- the sum of m, n, and l is 3.
- R 2 , R 3 , R 4 , and R 5 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and are branched into a part thereof. May have a structure X 2 and X 3 each independently represent a halogen atom, m indicates an integer of 0 to 2, n indicates an integer of 0 to 3, l indicates an integer of 0 to 3, and so on.
- At least one of the above-mentioned portions derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is a portion derived from a compound in which R 1 is a hydrogen atom and m is 0 in the above formula (1).
- At least one of the above-mentioned portions derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is a portion derived from a compound in which m is 0 and b is 0 in the above formula (2).
- R 1 is a hydrogen atom
- m is 0, and l is 0 in the above formula (1).
- the conjugated diene polymer according to [9] which is a portion derived from a compound in which n is 3.
- At least one of the above-mentioned portions derived from the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group has m as 0, l as 0, n as 3, and a in the formula (2).
- Composition [17] It contains a rubber component and a filler of 5.0 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the rubber component.
- the rubber component is the conjugated diene polymer according to any one of [1] to [13] or the conjugated diene polymer according to [16] with respect to 100 parts by mass of the total amount of the rubber component. Containing 10 parts by mass or more of the composition, Rubber composition.
- a coalesced composition and a rubber composition can be provided.
- the present embodiment will be described in detail.
- the following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments.
- the present invention can be appropriately modified and carried out within the scope of the gist thereof.
- the conjugated diene polymer of the present embodiment has a branching degree (Bn) of 7 or more and a bound aromatic vinyl amount of 1% by mass or more and 32% by mass or less by the GPC-light scattering method measurement method with a viscosity detector.
- the amount of vinyl bond in the bonded conjugated diene is 11 mol% or more and 35 mol% or less.
- the conjugated diene-based polymer of the present embodiment is a copolymer of at least one conjugated diene compound and at least one aromatic vinyl compound.
- the lower limit of the amount of bound aromatic vinyl is 1% by mass, preferably 2% by mass, and more preferably 3% by mass with respect to the entire conjugated diene polymer. It is more preferably 5% by mass.
- the lower limit may be 7% by mass.
- the upper limit of the amount of bound aromatic vinyl is 32% by mass, preferably 31% by mass, and more preferably 30% by mass.
- the upper limit of the amount of bound aromatic vinyl may be 29% by mass, 28% by mass, 27% by mass, or 26% by mass.
- the amount of the bonded aromatic vinyl may be within the range in which the above upper limit value and the lower limit value are arbitrarily combined, and may be, for example, 1% by mass or more and 30% by mass or less.
- the amount of bonded aromatic vinyl means the content of the portion derived from the aromatic vinyl compound with respect to the whole conjugated diene polymer.
- the amount of the bonded conjugated diene is preferably 50% by mass or more and 99% by mass or less, and more preferably 55% by mass or more and 98% by mass or less with respect to the entire conjugated diene-based polymer. Yes, more preferably 60% by mass or more and 95% by mass or less.
- the amount of the bonded conjugated diene is within the above range, the vulcanized product of the conjugated diene-based polymer becomes more excellent in wear resistance and low hysteresis loss.
- the amount of bound conjugated diene may be 99% by mass or less, 98% by mass or less, 97% by mass or less, 95% by mass or less, or 93% by mass or less within the above range. Within the above range, the amount of bound conjugated diene is 65% by mass or more, 68% by mass or more, 69% by mass or more, 70% by mass or more, 71% by mass or more, 72% by mass or more, 73% by mass or more, or 74% by mass. It may be% or more. The amount of bound conjugated diene may be within a range in which the above upper limit value and lower limit value are arbitrarily combined. In addition, in this specification, a "bonded conjugated diene amount" means the content of the portion derived from a conjugated diene compound with respect to the whole conjugated diene-based polymer.
- the amount of vinyl bond in the bonded conjugated diene (hereinafter, also simply referred to as “vinyl bond amount”) is 11 mol% or more and 35 mol% or less with respect to the entire bonded conjugated diene. It is preferably 12 mol% or more and 34 mol% or less, more preferably 13 mol% or more and 33 mol% or less, and further preferably 15 mol% or more and 30 mol% or less.
- the conjugated diene-based polymer is more excellent in abrasion resistance because the linearity of the structure of the conjugated diene portion is enhanced and the entanglement of the polymer chains is strengthened.
- the vinyl bond amount when the vinyl bond amount is in the above range, the vulcanized product becomes more excellent in low hysteresis loss property.
- the vinyl bond amount may be within a range in which the above upper limit value and lower limit value are arbitrarily combined, and may be, for example, 11 mol% or more and 30 mol% or less.
- the "amount of vinyl bond in the conjugated conjugated diene” means the ratio of the portion having a vinyl bond to the portion derived from the conjugated diene compound (hereinafter, referred to as "bonded conjugated diene"). ..
- the amount of vinyl bond in the bonded conjugated diene can be controlled by appropriately adjusting the reaction temperature, the amount of the polar compound added described later, and the like in the polymerization reaction for obtaining the conjugated diene-based polymer. Specifically, when the reaction temperature in the polymerization reaction for obtaining a conjugated diene polymer is increased, the amount of vinyl bond tends to be reduced. Further, when the addition amount of the polar compound described later is reduced, the vinyl bond amount tends to be reduced. More specifically, by using the production method described later, a conjugated diene polymer having a vinyl bond amount in the above range can be easily obtained.
- the relationship between the value of the above-mentioned bonded aromatic vinyl amount represented by mass% and the value of the above-mentioned vinyl bond amount expressed in mol% is not particularly limited, and even if the amount of bound aromatic vinyl is larger. Often, the vinyl bond amount may be larger or about the same. From the viewpoint of further enhancing the tensile strength and abrasion resistance of the conjugated diene polymer or its vulcanized product, the value of the amount of the above-mentioned bonded aromatic vinyl represented by mass% is the above-mentioned vinyl represented by mol%. It is preferably larger than the value of the binding amount.
- the value of the above-mentioned amount of bound aromatic vinyl may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more larger than the value of the above-mentioned vinyl bond amount.
- the amount of bound aromatic vinyl can be calculated by measuring the ultraviolet absorption of the phenyl group possessed by the portion derived from the aromatic vinyl compound of the conjugated diene polymer (hereinafter, referred to as "bonded aromatic vinyl"). ..
- the conjugated diene polymer is composed of a bonded aromatic vinyl and a bonded conjugated diene
- the amount of the bonded conjugated diene can also be obtained from the amount of the bonded aromatic vinyl obtained as described above. Specifically, the measurement may be performed by the method described in Examples described later.
- the conjugated diene polymer is a copolymer of butadiene and styrene
- vinyl in the bonded butadiene is prepared by Hampton's method (RR Hampton, Analytical Chemistry, 21,923 (1949)).
- the amount of binding (1,2-bonding amount) may be obtained. Specifically, the measurement may be performed by the method described in Examples described later.
- the conjugated diene polymer of the present embodiment preferably has a small number or no blocks in which 30 or more bonded aromatic vinyl units are linked.
- the copolymer is a butadiene-styrene copolymer
- the content of the block in which 30 or more bonded aromatic vinyl units are linked in such a conjugated diene polymer is determined by the method of Kolthoff (IM KOLTHOFF, The copolymer is decomposed by the method described in et al., J. Polym. Sci. 1,429 (1946)), and the amount of polystyrene insoluble in methanol can be measured by a known method.
- the content of the block in which 30 or more bonded aromatic vinyl units are linked as measured by such a method is preferably 5.0% by mass or less with respect to the total amount of the conjugated diene-based polymer, which is more preferable. Is 3.0% by mass or less.
- the conjugated diene polymer of the present embodiment preferably has a large proportion of the bonded aromatic vinyl unit alone.
- the copolymer is a butadiene-styrene copolymer
- the copolymer is decomposed by the method of Tanaka et al. (Polymer, 22, 1721 (1981)) using ozone decomposition, and gel permeation chromatography (Gel permeation chromatography) is performed.
- the amount of isolated styrene is preferably 40% by mass or more, and preferably 8 or more styrene chains, based on the total amount of bound styrene.
- the chained styrene structure is 5.0% by mass or less.
- the vulcanized product is more excellent in low hysteresis loss property.
- the amount of bound aromatic vinyl, the amount of bound conjugated diene, and the amount of vinyl bond also affect the glass transition temperature (hereinafter, also referred to as "Tg") of the conjugated diene polymer. Therefore, it is preferable to set the amount of the bonded aromatic vinyl, the amount of the bonded conjugated diene, and the amount of the vinyl bond within the above ranges from the viewpoint that the vulcanized product is more excellent in low hysteresis loss property.
- Tg glass transition temperature
- the glass transition temperature (Tg) of the conjugated diene polymer of the present embodiment is preferably ⁇ 85 ° C. or higher, more preferably ⁇ 80 ° C. or higher, still more preferably ⁇ 75 ° C. or higher. When the glass transition temperature is within the above range, the processability at the time of vulcanization is further excellent.
- the glass transition temperature is preferably ⁇ 35 ° C. or lower, more preferably ⁇ 38 ° C. or lower.
- the glass transition temperature may be ⁇ 40 ° C. or lower, or ⁇ 45 ° C. or lower.
- the glass transition temperature When the glass transition temperature is within the above range, the wear resistance and the low hysteresis loss property of the vulcanized product of the conjugated diene polymer become further excellent.
- the glass transition temperature may be within a range in which the above upper limit value and lower limit value are arbitrarily combined.
- the glass transition temperature of the conjugated diene polymer and the conjugated diene polymer is measured according to ISO 22768: 2017. More specifically, the DSC curve is recorded by measuring the differential scanning calorimetry (DSC) while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as the glass transition temperature. Specifically, the measurement may be performed by the method described in Examples described later.
- the conjugated diene polymer of the present embodiment has a degree of branching (Bn) by the GPC-light scattering method with a viscosity detector (hereinafter, simply "branched”).
- Degree (Bn) ”,“ branching degree ”or“ Bn ”) is 7 or more.
- the degree of branching (Bn) of 7 or more means that the conjugated diene polymer of the present embodiment has 7 or more side chain polymer chains with respect to the substantially longest polymer main chain. means.
- the degree of branching (Bn) is an index expressing the branching structure of a polymer.
- the longest polymer main chain in the case of a general 4-branched star-shaped polymer (a polymer in which four polymer chains (however, those having no additional side chains) are connected in the center), the longest polymer main chain.
- two arms (side chains) of the polymer chain are bonded to each other, and the degree of branching (Bn) is evaluated as 2.
- the conjugated diene polymer of the present embodiment has a degree of branching (Bn) of 7 or more, which means that when the conjugated diene polymer has a star-shaped polymer structure, the number of branches is 9 or more. It means that there is.
- branch means one formed by binding another polymer chain to one polymer chain.
- the "branching degree (Bn)” is the number of polymer chains that are directly or indirectly bonded to each other with respect to the longest polymer main chain. That is, not only the side chain bonded to the longest polymer chain but also the number of branches of the side chain when the side chain is further branched are taken into consideration. Therefore, when one polymer chain is bound as a side chain to the longest polymer chain and another polymer chain is further bound to the side chain, the degree of branching is 2.
- the contraction factor (g') has the following values.
- a polymer having a branch tends to have a smaller molecular size when compared with a linear polymer having the same absolute molecular weight.
- the "molecule size” is a volume substantially occupied by the molecule.
- the contraction factor (g') is a relative representation of the size of the molecule of the target polymer, and is the size of the molecule of the linear polymer having the same absolute molecular weight as the target polymer. It is an index of the ratio of the molecular weight of the target polymer to the above. That is, when the degree of branching of the polymer is large, the size is relatively small, so that the contraction factor (g') tends to be small.
- the shrinkage factor (g') is calculated as the ratio of the intrinsic viscosity in the present embodiment. That is, the shrinkage factor (g') is the ratio of the intrinsic viscosity [ ⁇ ] of the target polymer to the intrinsic viscosity [ ⁇ 0] of the linear polymer having the same absolute molecular weight as the target polymer. It is calculated as ([ ⁇ ] / [ ⁇ 0]).
- M is the absolute molecular weight. Therefore, the shrinkage factor (g') and the degree of branching (Bn) are obtained by measuring the absolute molecular weight M and the intrinsic viscosity [ ⁇ ] of the target polymer by the GPC-light scattering method with a viscosity detector. be able to.
- the calculated degree of bifurcation (Bn) accurately represents the number of polymer chains that are directly or indirectly bonded to each other with respect to the longest polymer main chain.
- the "absolute molecular weight” means the molecular weight measured by the light scattering method.
- a polymer having a branch tends to have a smaller molecular size when compared with a linear polymer having the same absolute molecular weight. Therefore, in the GPC measurement method, which is a method of determining the molecular weight by sieving the polymer by the molecular size and making a relative comparison with a standard polystyrene sample, the molecular weight of the polymer having a branched structure tends to be underestimated. be.
- the light scattering method the molecular weight is measured by directly observing the molecule. Therefore, the light scattering method can accurately measure the molecular weight without being affected by the influence of the polymer structure or the interaction with the column packing material.
- the absolute molecular weight may be measured by the method described in Examples.
- the "intrinsic viscosity” ideally means the viscosity [ ⁇ ] obtained by the following formula (I).
- ⁇ 1 indicates the viscosity of the polymer of interest when dissolved in a solvent at a concentration c
- ⁇ 2 indicates the viscosity of the solvent.
- the value measured by the method described in Examples is used as the intrinsic viscosity.
- the conjugated diene polymer of the present embodiment has a branching degree (Bn) of 7 or more, it is extremely excellent in processability at the time of vulcanization, and the vulcanized product is excellent in abrasion resistance and fracture strength.
- Bn branching degree
- the conjugated diene polymer of the present embodiment has a degree of branching (Bn) of 7 or more, an increase in viscosity during vulcanization due to an increase in absolute molecular weight is significantly suppressed. Therefore, for example, it can be sufficiently mixed with a filler such as silica in the kneading step, and silica can be sufficiently dispersed in the polymer. That is, the conjugated diene polymer of the present embodiment has good processability. As a result, for example, the average molecular weight of the conjugated diene polymer can be further increased, and the wear resistance and fracture strength can be improved. Further, since silica can be satisfactorily dispersed in the polymer by sufficient kneading, it has a practically sufficient low hysteresis loss property.
- Bn degree of branching
- the degree of branching (Bn) of the conjugated diene polymer of the present embodiment is 7 or more, preferably 8 or more, and more preferably 9 or more. When the degree of branching (Bn) is within the above range, the conjugated diene polymer is more excellent in processability at the time of vulcanization.
- the degree of bifurcation (Bn) may be 10 or more, 11 or more, 12 or more, or 13 or more.
- the upper limit of the degree of bifurcation (Bn) is not particularly limited and may be equal to or higher than the detection limit.
- the degree of bifurcation (Bn) is preferably 84 or less, more preferably 80 or less, still more preferably 64 or less, and even more preferably 57 or less.
- the upper limit of the degree of bifurcation (Bn) may be 50, 40, 30, 30, 25, 20, or 18. You may.
- the degree of branching of the conjugated diene polymer may be controlled by appropriately adjusting the amount of the branching agent added, which will be described later. May be controlled by adjusting. Specifically, the degree of branching is controlled by the number of functional groups of the branching agent and the coupling modifier, the amount of the branching agent and the coupling modifier added, and the timing of addition of the branching agent and the coupling modifier. be able to. More specifically, by using the method for producing a conjugated diene polymer described later, the degree of branching can be more easily set within the above range.
- the conjugated diene-based polymer of the present embodiment is a copolymer of at least one conjugated diene compound and at least one aromatic vinyl compound. Therefore, the conjugated diene-based polymer may be a copolymer of one or more conjugated diene compounds and one or more aromatic vinyl compounds.
- the conjugated diene compound is not particularly limited, but for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1 , 3-Hexadiene, and 1,3-Heptadiene.
- 1,3-butadiene and isoprene are preferable from the viewpoint of effectively and surely exerting the effect of the present embodiment.
- These conjugated diene compounds may be used alone or in combination of two or more.
- the aromatic vinyl compound is not particularly limited, and examples thereof include styrene, p-methylstyrene, ⁇ -methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is preferable from the viewpoint of effectively and surely exerting the effect of the present embodiment. These aromatic vinyl compounds may be used alone or in combination of two or more.
- the conjugated diene-based polymer of the present embodiment preferably has a modifying group.
- “Modifying group” means a specific functional group having an affinity or binding reactivity with a filler. Since the conjugated diene polymer has such a modifying group, the interaction with the filler is further improved. Therefore, when the conjugated diene polymer composition containing the conjugated diene polymer and the filler is prepared. In addition, the mechanical strength of the composition is further improved. From the same viewpoint, the conjugated diene polymer of the present embodiment more preferably has a modifying group having an atom other than a carbon atom and a hydrogen atom, and more preferably has a modifying group having a silicon atom or a nitrogen atom. However, even more preferably, it has a modifying group having a nitrogen atom.
- the conjugated diene-based polymer of the present embodiment can be modified by reacting a copolymer of a conjugated diene compound and an aromatic vinyl compound with a modifier.
- the conjugated diene polymer is preferably modified with a coupling modifier described later.
- Such modified conjugated diene-based polymers not only have a specific functional group having an affinity or binding reactivity with the filler, but also tend to have a higher degree of branching (Bn). Further, from the viewpoint of further enhancing the affinity or the binding reactivity with the filler, it is preferable that at least one end of the conjugated diene polymer is modified with a nitrogen atom-containing group.
- the term "modification rate" refers to the case where a mixture of a modified conjugated diene polymer and an unmodified conjugated diene polymer can be obtained by modifying the conjugated diene polymer with a modifier.
- conjugated diene polymer or modified conjugated diene polymer described in parallel
- conjugated diene conjugated diene
- system polymer includes an unmodified conjugated diene-based polymer and a modified conjugated diene-based polymer.
- conjugated diene polymer means an unmodified conjugated diene polymer. ..
- the modifier containing the nitrogen atom can be used.
- the modification rate is the mass ratio of the modified conjugated diene polymer having the resulting nitrogen atom-containing functional group to the total amount of the conjugated diene polymer.
- conjugated diene polymer of the present embodiment is modified with a functional group containing a nitrogen atom.
- a modified conjugated diene-based polymer is more excellent in processability when a filler or the like is blended into a composition, and wear resistance, fracture strength, and low hysteresis when the composition is made into a vulcanized product. It is even more lossy.
- the modification rate of the conjugated diene polymer of the present embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, based on the total amount of the conjugated diene polymer. It is particularly preferably 80% by mass or more.
- the upper limit of the modification rate is not particularly limited, but may be, for example, 100% by mass, 98% by mass, 95% by mass, or 90% by mass. Further, when comparing conjugated diene-based polymers having the same glass transition point, the higher the modification rate, the better the low hysteresis loss property tends to be.
- the modification rate can be measured by chromatography capable of separating the functional group-containing modified component and the non-modified component.
- chromatography capable of separating the functional group-containing modified component and the non-modified component.
- a column for gel permeation chromatography using a polar substance such as silica that adsorbs a specific functional group as a filler is used, and an internal standard of a non-adsorbed component is used for comparison and quantified. (Column adsorption GPC method) can be mentioned.
- the modification rate is determined from the difference between the chromatogram obtained by measuring the sample and the sample solution containing the low molecular weight internal standard polystyrene on a polystyrene gel column and the chromatogram measuring the sample solution on a silica column. It can be obtained by calculating the amount of adsorption to the system column. More specifically, the modification rate may be measured by the method described in Examples.
- the modification rate can be controlled by adjusting the amount of the modifying agent added and the reaction method between the conjugated diene compound and the modifying agent.
- a method of polymerizing using an organic lithium compound having at least one nitrogen atom in the molecule as a polymerization initiator, a method of copolymerizing a monomer having at least one nitrogen atom in the molecule, and a method of copolymerizing may be combined.
- the conjugated diene polymer of the present embodiment preferably has a star-shaped polymer structure having three or more branches. Such conjugated diene-based polymers tend to have a high degree of bifurcation. From the same viewpoint, the conjugated diene polymer has a star-shaped polymer structure having more preferably 4 branches or more, further preferably 6 branches or more, and particularly preferably 7 branches or more.
- star-shaped polymer structure refers to a structure in which three or more polymer chains (arms) are bonded to one central branch point.
- the "central bifurcation point” refers to a portion derived from the modifier when three or more polymer chains are bonded to the portion (atom or group) derived from the modifier. Therefore, the modified conjugated diene polymer modified by the coupling modifier described later has three or more conjugated diene polymers with the portion (atom or atomic group) derived from the coupling modifier as the central branch point. It has a bonded star-shaped polymer structure.
- n-branched star-shaped polymer structure (n is a natural number) means a structure in which n polymer chains are bonded to the central branch point, and here, the bonded polymer chains. It doesn't matter if is further branched or not. Therefore, the degree of branching (Bn) of the n-branched star-shaped polymer structure in which n unbranched polymer chains are bonded to the central branch point is n-2.
- the above star-shaped polymer structure can be obtained by modifying the conjugated diene polymer with a denaturing agent, more preferably a coupling denaturing agent described later. That is, when the conjugated diene polymer is reacted with the coupling modifier, a plurality of polymer chains, which are the conjugated diene polymers, are bonded to each other with the coupling modifier as the central branch point, whereby the star-shaped polymer is formed.
- a modified conjugated diene polymer having a structure can be obtained.
- the number of branches of the star-shaped polymer structure can be controlled by adjusting the number of functional groups of the coupling modifier and the amount of the polymerization initiator and the coupling modifier added.
- the conjugated diene-based polymer of the present embodiment preferably has at least one branched chain having a star-shaped polymer structure further branched.
- Such conjugated diene-based polymers tend to have a higher degree of bifurcation (Bn).
- the conjugated diene polymer of the present embodiment preferably has more than half of the branched chains of the star-shaped polymer structure further branched, and more preferably the star-shaped polymer. All of the branched chains of the structure are further branched.
- the conjugated diene polymer in the conjugated diene polymer, at least one branched chain of the star-shaped polymer structure more preferably has two or more branched points, and more preferably three or more branched points.
- the conjugated diene polymer is preferably a branch point having 4 or more polymer chains at the branch point in the branch chain of the star-shaped polymer structure, and is a branch having 5 or more polymer chains. It is more preferably a point, and further preferably a branch point having 6 or more polymer chains.
- the conjugated diene polymer of the present embodiment for example, when the conjugated diene polymer is polymerized, a branched conjugated diene polymer or a branched chain having a star-shaped polymer structure is branched by adding a branching agent described later. A further branched conjugated diene polymer can be obtained.
- the number of branching points generated by adding the branching agent and the number of branching points are determined by the number of functional groups of the branching agent, the amount of the polymerization initiator and the branching agent added, and the timing of addition of the branching agent. It can be controlled by adjusting.
- the branching point generated by adding the branching agent preferably contains a nitrogen atom or a silicon atom. That is, the conjugated diene-based polymer of the present embodiment preferably has a nitrogen atom or a silicon atom, and branching occurs at a portion having a nitrogen atom or a silicon atom.
- the conjugated diene-based polymer of the present embodiment preferably has at least one moiety derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group. However, the portion is further branched.
- the conjugated diene-based polymer of the present embodiment preferably has three or more branches, more preferably four or more branches, and further, in a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group. It preferably has 5 or more branches.
- At least one branched chain of the star-shaped polymer structure has at least one moiety derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group. Moreover, it is preferable that the portion is further branched. That is, at least one of the branch points in the branched chain of the star-shaped polymer structure is preferably a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group.
- the conjugated diene-based polymer of the present embodiment preferably has three or more branches, more preferably four or more branches, and further, in a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group. It preferably has 5 or more branches.
- the conjugated diene-based polymer of the present embodiment has a branch point at a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group.
- the conjugated diene polymer has at least one moiety derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group and the polymer chain is branched at that moiety, 29 Si-NMR.
- a peak derived from the portion is detected in the range of ⁇ 45 ppm to ⁇ 65 ppm, and more specifically, in the range of -50 ppm to -60 ppm.
- At least one of the above-mentioned portions derived from the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is represented by the following formula (1) or (2). It is preferably derived from the compound to be used. That is, at least one of the branch points in the branched chain of the star-shaped polymer structure as described above is preferably a portion derived from the compound represented by the following formula (1) or (2). From the same point of view, among the branching points in the branched chain of the star-shaped polymer structure as described above, more preferably more than half, more preferably all of them are compounds represented by the following formula (1) or (2). It is the part from which it is derived.
- R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.
- 2 and R 3 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof, and X 1 is each.
- the halogen atom is indicated
- m indicates an integer of 0 to 2
- n indicates an integer of 0 to 3
- l indicates an integer of 0 to 3
- the sum of m, n, and l is. 3.
- R 2 , R 3 , R 4 , and R 5 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and a part thereof. It may have a branched structure, where X 2 and X 3 each independently represent a halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l. Indicates an integer of 0 to 3, the sum of m, n, and l is 3, a indicates an integer of 0 to 3, b indicates an integer of 0 to 2, and c indicates 0. It indicates an integer of 3 and the sum of a, b, and c is 3. Examples of the compound represented by the formula (1) or (2) will be described later.
- At least one of the branching points in the branched chain of the star-shaped polymer structure is preferably a hydrogen atom in R 1 and 0 in m in the above formula (1). It is a part derived from a certain compound. Such conjugated diene-based polymers tend to have a higher number of branches, and wear resistance and workability are further improved.
- At least one of the branching points in the branched chain of the star-shaped polymer structure preferably has R 1 as a hydrogen atom and m in the above-mentioned formula (1). It is a portion derived from a compound which is 0, l is 0, and n is 3. Such a conjugated diene-based polymer tends to further improve the modification rate and the degree of bifurcation, and further improves fuel efficiency, wear resistance and workability.
- At least one of the branch points in the branched chain of the star-shaped polymer structure is preferably 0 in m and 0 in b in the above formula (2). It is a part derived from a certain compound.
- Such conjugated diene-based polymers tend to have a higher number of branches, and wear resistance and workability are further improved.
- At least one of the branching points in the branched chain of the star-shaped polymer structure is preferably 0 in m and 0 in l in the above formula (2). Yes, n is 3, a is 0, b is 0, and c is 3 from the compound.
- Such conjugated diene-based polymers tend to have a higher number of branches, and wear resistance and workability are further improved.
- the conjugated diene-based polymer of the present embodiment particularly preferably has a star-shaped polymer structure having three or more branches, and at least one branched chain of the star-shaped polymer structure contains an alkoxysilyl group or a halosilyl group. It is a conjugated diene-based polymer having at least one moiety derived from a vinyl-based monomer and further branched in the moiety. Such conjugated diene-based polymers tend to be more excellent in processability and wear resistance.
- the star-shaped polymer structure having three or more branches, and at least one branched chain of the star-shaped polymer structure has at least one moiety derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group.
- the following method may be used. That is, by using an organic lithium-based compound as a polymerization initiator, a conjugated diene compound and an aromatic vinyl compound are polymerized, and the conjugated diene polymer is further reacted with a branching agent described later during and / or after the polymerization.
- conjugated diene-based polymer having a branched structure Obtain a conjugated diene-based polymer having a branched structure. Then, the obtained conjugated diene polymer having a branched structure may be further reacted with a modifier described later to obtain a modified conjugated diene polymer. As specific polymerization conditions, the conditions described in the production method in Examples described later may be used.
- a modified conjugated diene polymer having a star-shaped polymer structure can be surely obtained by using the coupling modifier described later. can.
- Both the modification with the coupling modifier and the introduction of the branching agent can increase the degree of branching (Bn) of the conjugated diene polymer, but the modification with the coupling modifier is the degree of branching (Bn). ) Tends to be even larger.
- the degree of branching (Bn) can be controlled by selecting the type and amount of the coupling modifier and the branching agent, but also consider the contribution rate to the increase in the degree of branching (Bn).
- the degree of branching (Bn) can be easily controlled.
- the weight average molecular weight of the conjugated diene polymer of the present embodiment measured by the GPC measurement method is preferably 30 ⁇ 10 4 or more, more preferably 40 ⁇ 10 4 or more, and further preferably 45 ⁇ 10 4 or more, particularly preferably 60 ⁇ 10 4 or more.
- the processability at the time of vulcanization is further excellent, and the vulcanized product is further excellent in low hysteresis loss property.
- the weight average molecular weight is preferably not 300 ⁇ 10 4 or less, more preferably 250 ⁇ 10 4 or less, more preferably not more 180 ⁇ 10 4 or less, even more preferably at 0.99 ⁇ 10 4 or less be.
- the weight average molecular weight may be within a range in which the above upper limit value and the above lower limit value are arbitrarily combined.
- the weight average molecular weight of the modified conjugated diene polymer and the conjugated diene polymer described later by the GPC measurement method is specifically measured by the method described in Examples described later.
- the number average molecular weight of the conjugated diene polymer of the present embodiment measured by the GPC measurement method is preferably 20 ⁇ 10 4 or more, more preferably 25 ⁇ 10 4 or more, and further preferably 30 ⁇ 10 4 That is all.
- the number average molecular weight may be 35 ⁇ 10 4 or more.
- the number average molecular weight is preferably not 100 ⁇ 10 4 or less, more preferably 90 ⁇ 10 4 or less, more preferably not more 80 ⁇ 10 4 or less, even more preferably at 70 ⁇ 10 4 or less be.
- the number average molecular weight may be within a range in which the above upper limit value and the above lower limit value are arbitrarily combined.
- the number average molecular weight of the modified conjugated diene polymer and the conjugated diene polymer described later measured by the GPC measurement method is specifically measured by the method described in Examples described later.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) measured by the GPC measurement method to the number average molecular weight (Mn) measured by the GPC measurement method is the present embodiment. From the viewpoint of effectively and surely exerting the effect of the form, it is preferably 1.5 or more and 3.0 or less, more preferably 1.6 or more and 2.8 or less, and further preferably 1.7 or more and 2.4 or less. Is.
- the Mooney viscosity of the conjugated diene polymer of the present embodiment as measured at 100 ° C. is preferably 50 or more and 180 or less, and more preferably 70 or more and 160 or less.
- the Mooney viscosity of the modified conjugated diene polymer and the conjugated diene polymer described later can be measured by the method described in Examples described later.
- the conjugated diene-based polymer of the present embodiment preferably has a nitrogen atom or a silicon atom.
- the conjugated diene polymer is more preferably modified by using a compound represented by any of the following formulas (i) or the following formulas (A) to (D) as a coupling modifier. Examples of the compounds represented by the following formula (i) or the following formulas (A) to (D) will be described later.
- R 7 has a divalent hydrocarbon group or a polar group having an oxygen atom such as ether, epoxy, and ketone, and a sulfur atom such as thioether and thioketone. It is a divalent organic group having at least one polar group selected from a polar group and a polar group having a nitrogen atom such as a tertiary amino group and an imino group.
- the divalent hydrocarbon group is a saturated or unsaturated hydrocarbon group which may be linear, branched or cyclic, and includes an alkylene group, an alkenylene group, a phenylene group and the like.
- the divalent hydrocarbon group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.
- the divalent hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and for example, methylene, ethylene, butylene, cyclohexylene, 1,3-bis (methylene) -cyclohexane, 1,3-bis (ethylene).
- -Cyclohexane, o-phenylene, m-phenylene, p-phenylene, m-xylene, p-xylene, bis (phenylene) -methane and the like can be mentioned.
- R 8 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- R 6 represents a hydrogen atom, a monovalent or higher alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- the valence of R 6 is 1 or more, which is the same as o in the formula (i).
- R 9 is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a structure of the following formula (ii).
- R 6 and R 8 may have an annular structure connected to each other.
- R 9 is a monovalent hydrocarbon group, it may have a cyclic structure bonded to R 8 to each other. However, only if the N and R 8 bonded to R 9 are directly bonded, R 9 may be a hydrogen atom.
- o is an integer of 1 or more.
- R 1 and R 2 are synonymous with R 7 and R 8 in formula (i), respectively.
- R 12 , R 13 , R 14 , and R 15 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 16 Indicates an alkylene group having 1 to 10 carbon atoms
- R 17 indicates an alkylene group having 1 to 20 carbon atoms
- q indicates an integer of 1 or 2
- r indicates an integer of 2 or 3.
- the sum of q and r is an integer greater than or equal to 4.
- R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms.
- R 24 , R 25 , and R 26 each independently represent an alkylene group having 1 to 20 carbon atoms, and s, t, and u each independently represent an integer of 1 to 3. Shown, the sum of s, t, and u is an integer of 4 or more.
- A is a hydrocarbon group having 1 to 20 carbon atoms, or at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom.
- R 27 , R 28 , and R 29 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms, indicating an organic group having and having no active hydrogen
- R 30 , R 31 , R 32 , R 33 , and R 35 each independently represent an alkyl group having 1 to 20 carbon atoms
- R 34 and R 37 each independently represent an alkylene group having 1 to 20 carbon atoms.
- i indicates an integer of 0 to 6
- j indicates an integer of 0 to 6
- k indicates an integer of 0 to 6
- the sum of i, j, and k is an integer of 4 to 10. Is.
- R 36 represents an alkylene group having 1 to 20 carbon atoms
- R 37 , R 39 , and R 40 are independently alkyl groups having 1 to 20 carbon atoms or carbon atoms. It represents an aryl group of 6 to 20, R 38 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and z represents an integer of 1 to 3.
- the conjugated diene polymer of the present embodiment preferably contains a structure derived from a coupling modifier described later.
- the above-mentioned conjugated diene-based polymer can be produced by any method as long as a polymer having the above-mentioned constitution can be obtained, but the conjugated diene-based polymer of the present embodiment, which will be described in detail below.
- the above-mentioned conjugated diene polymer can be obtained reliably and easily.
- the method for producing a conjugated diene polymer of the present embodiment has a branched structure by adding a branching agent while polymerizing at least the conjugated diene compound and the aromatic vinyl compound using an organic lithium compound as a polymerization initiator. It has a polymerization branching step of obtaining a conjugated diene-based polymer having the above. According to such a method, a conjugated diene-based polymer in which the amount of bonded aromatic vinyl, the amount of vinyl bond in the bonded conjugated diene and the degree of branching (Bn) are in the above-mentioned ranges can be surely and easily obtained.
- the method for producing a conjugated diene-based polymer of the present embodiment is preferably modified conjugated diene by reacting a conjugated diene-based polymer having a branched structure obtained by the above-mentioned polymerization branching step with a coupling modifier. It has a coupling step of obtaining a system polymer. According to such a method, a conjugated diene-based polymer in which the weight average molecular weight, the glass transition temperature and the degree of bifurcation (Bn) are in the above-mentioned ranges can be surely and easily obtained.
- a conjugated diene-based polymer having a branched structure is obtained by adding a branching agent while polymerizing at least a conjugated diene compound and an aromatic vinyl compound using an organic lithium compound described later as a polymerization initiator. This is the process of obtaining. Therefore, in the polymerization branching step, at least the polymerization reaction of the conjugated diene compound and the aromatic vinyl compound is the main reaction before the branching agent is added, and the branching reaction is started after the branching agent is added.
- At least the polymerization reaction of the conjugated diene compound and the aromatic vinyl compound is preferably polymerization by a growth reaction by a living anionic polymerization reaction, whereby a conjugated diene-based polymer having an active terminal can be obtained.
- the branching agent when the branching agent is added, the conjugated diene polymer and the branching agent react efficiently. Further, even when the production method of the present embodiment has a coupling step described later, a highly efficient reaction tends to occur.
- the polymerization reaction mode is not limited to the following, and examples thereof include a batch type (hereinafter, also referred to as “batch type”) and a continuous type polymerization reaction mode.
- one or two or more connected reactors can be used.
- a continuous reactor for example, a tank type reactor with a stirrer or a tube type reactor is used.
- the monomer, the inert solvent described later, and the polymerization initiator described later are continuously fed to the reactor to obtain a polymer solution containing the polymer in the reactor.
- the polymer solution is continuously discharged.
- the batch reactor for example, a tank-type reactor with a stirrer is used.
- the monomer, the inert solvent described below, and the polymerization initiator described below are fed, and if necessary, the monomer is continuously or intermittently added during the polymerization in the reactor.
- a polymer solution containing the polymer is obtained, and the polymer solution is discharged after the completion of the polymerization.
- the polymer can be continuously discharged and subjected to the next reaction in a short time. It is preferable to proceed the polymerization reaction by the polymerization reaction mode of the formula.
- conjugated diene compound and the aromatic vinyl compound which are the monomers used in the polymerization branching step at least one of the above-mentioned conjugated diene compound and at least one of the above-mentioned aromatic vinyl compound may be used.
- a nitrogen atom can be introduced into the conjugated diene polymer, a derivative obtained by substituting the above-mentioned conjugated diene compound or the above-mentioned aromatic vinyl compound so as to have at least one nitrogen atom in the molecule is used. You may.
- the polymerization initiator is not particularly limited, but for example, an organic lithium compound such as an organic monolithium compound can be used.
- Examples of the organic monolithium compound include a compound having a carbon-lithium bond, a compound having a nitrogen-lithium bond, and a compound having a tin-lithium bond in the bonding mode of the organic group and the lithium thereof.
- the organic monolithium compound is preferably an organic lithium compound having at least one nitrogen atom in the molecule from the viewpoint of being able to introduce a nitrogen atom into the conjugated diene-based polymer, and more preferably. It is an alkyllithium compound having a substituted amino group, or a dialkylaminolithium.
- the substituted amino group is an amino group that does not have active hydrogen in the amino group or that protects the active hydrogen in the amino group.
- the alkyllithium compound having an amino group having no such active hydrogen is not particularly limited, but for example, piperidinolithium, 3-dimethylaminopropyllithium, 3-diethylaminopropyllithium, 4- (methylpropylamino). Examples include butyllithium and 4-hexamethyleneiminobutyllithium.
- the alkyllithium compound having an amino group that protects active hydrogen is not particularly limited, and examples thereof include 3-bistrimethylsilylaminopropyllithium and 4-trimethylsilylmethylaminobutyllithium.
- the dialkylaminolithium is not particularly limited, and for example, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithiumdi-n-hexylamide, lithium diheptylamide, lithium diisopropylamide, lithium dioctylamide, lithium-.
- organic monolithium compounds having a substituted amino group are organic monoliths that are solubilized by reacting a small amount of polymerizable monomers such as 1,3-butadiene, isoprene, or styrene. It can also be used as a monolithium compound.
- the polymerization initiator When the polymerization initiator has a nitrogen atom constituting an amino group, a chain transfer reaction is likely to occur when anionic polymerization proceeds, and the amount of reaction of the coupling agent or modifier to the active terminal after the completion of polymerization tends to be low. It is in. As a result, when a polymerization initiator having a nitrogen atom constituting an amino group is used, the weight average molecular weight tends to be small. Therefore, when it is desired to set a high modification rate in a polymer having a relatively high molecular weight of 40 ⁇ 10 4 or more, 45 ⁇ 10 4 or more, or 60 ⁇ 10 4 or more in weight average molecular weight, the weight ends instead of the polymerization start end side.
- the nitrogen content of the polymer is generally 3 mass ppm to 500 mass ppm.
- an alkyllithium compound may be used as the organic monolithium compound.
- an organic monolithium compound is used, a conjugated diene-based polymer having an alkyl group at the polymerization initiation terminal can be obtained.
- the alkyllithium compound is not particularly limited, and examples thereof include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, and stillbenlithium.
- n-butyllithium and sec-butyllithium are preferable from the viewpoint of easy industrial availability and easy control of the polymerization reaction.
- organic monolithium compounds may be used alone or in combination of two or more. In addition, it may be used in combination with other organometallic compounds.
- the other organometallic compound is not particularly limited, and examples thereof include an alkaline earth metal compound, an alkali metal compound other than lithium, and other organometallic compounds.
- the alkaline earth metal compound is not particularly limited, and examples thereof include an organic magnesium compound, an organic calcium compound, and an organic strontium compound. Also included are compounds of alkaline earth metals alcoxide, sulfonate, carbonate, and amide.
- organic magnesium compound examples include dibutyl magnesium and ethyl butyl magnesium.
- organometallic compounds examples include organoaluminum compounds.
- the amount of the polymerization initiator added is preferably determined by the molecular weight of the target conjugated diene polymer or modified conjugated diene polymer.
- the number average molecular weight and / or the weight average molecular weight can be controlled by the ratio of the amount of the monomer added to the amount of the polymerization initiator added. Specifically, when the ratio of the amount of the polymerization initiator added is small, the molecular weight tends to increase, and when the ratio of the amount of the polymerization initiator added is large, the molecular weight tends to decrease.
- the polymerization branching step is preferably carried out in an inert solvent.
- an inert solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons.
- Specific hydrocarbon-based solvents are not particularly limited, but are, for example, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; and hydrocarbons consisting of mixtures thereof.
- the polymerization reaction in the polymerization branching step is described in, for example, Japanese Patent Application Laid-Open No. 59-140211.
- the following methods may be used. That is, even if a method is used in which the polymerization reaction is first started using the total amount of the aromatic vinyl compound and a part of the conjugated diene compound, and then the remaining conjugated diene compound is intermittently added in the middle of the polymerization reaction. good.
- the polymerization temperature in the polymerization reaction of the polymerization branching step is not particularly limited, but is preferably the temperature at which the living anionic polymerization proceeds. Further, from the viewpoint of improving productivity, it is more preferably 0 ° C. or higher, and further preferably 0 ° C. or higher and 120 ° C. or lower. When the polymerization temperature in the polymerization reaction is within the above range, the reactivity with the coupling modifier tends to be sufficiently enhanced in the coupling step described later. From the same viewpoint, the polymerization temperature in the polymerization reaction is even more preferably 50 ° C. or higher and 100 ° C. or lower.
- a polar compound may be added.
- a polar compound When a polar compound is added, it tends to be possible to obtain a conjugated diene-based polymer in which an aromatic vinyl compound and a conjugated diene compound are more randomly copolymerized.
- the polar compound since the polar compound has an effective randomizing effect in the copolymerization of the conjugated diene compound and the aromatic vinyl compound, it can be used as an agent for adjusting the distribution of the aromatic vinyl compound and adjusting the amount of styrene block. ..
- the polar compound can accelerate the polymerization reaction and can also be used as a vinylizing agent for controlling the microstructure of the conjugated diene-based polymer.
- the polar compound is used as a vinylizing agent, a randomizing agent, and a polymerization accelerator, for example, when the polar compound is reduced to adjust the vinylization rate and the randomization rate, the polymerization promoting effect is also reduced. It tends to end up. Therefore, in the method of adjusting the degree of branching of the polymer by reacting the polymerization termination end with a coupling modifier, when the amount of the polar compound added is reduced, the polymerization time becomes long and the proportion of the polymerization termination terminal deactivated. Will be higher. As a result, such a method tends to make it difficult for the denaturation rate to increase.
- the degree of branching of the modified conjugated diene polymer is adjusted by adjusting the addition amount of the polar compound and the coupling modifier, it tends to be difficult to control the vinylization rate and the randomization rate.
- the degree of branching of the polymer can be increased by the branching agent described later, the degree of branching can be controlled independently of the vinylization rate and the randomization rate, and the structural design of the polymer can be performed. It is advantageous.
- the polar compound is not particularly limited, and is, for example, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane.
- Ethers such as; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, and quinuclidine; potassium-tert-amylate, potassium-tert-butyrate, sodium-tert-butyrate, and Alkali metal alkoxide compounds such as sodium amylate; and phosphine compounds such as triphenylphosphine can be used. These polar compounds may be used alone or in combination of two or more.
- the amount of the polar compound added is not particularly limited, but can be adjusted according to the amount of the polymerization active terminal, that is, the amount of the polymerization initiator added.
- the amount of the polar compound added is, for example, preferably 0.010 mol or more and 1.0 mol or less, and more preferably 0.10 mol or more and 0.70 mol or less with respect to 1 mol of the polymerization initiator. preferable.
- the amount of the polar compound added may be 0.60 mol or less or 0.50 mol or less with respect to 1 mol of the polymerization initiator in the above range. Alternatively, the amount may be 0.15 mol or more or 0.20 mol or more with respect to 1 mol of the polymerization initiator.
- the amount of the polar compound added When the amount of the polar compound added is not more than the above upper limit, a conjugated diene compound having a low Tg tends to be obtained. Further, when the addition amount of the polar compound is equal to or more than the above lower limit, deactivation of the polymerization active terminal is suppressed, and the coupling rate in the coupling step described later tends to be improved.
- the amount of the polar compound added may be within a range in which the above upper limit value and lower limit value are arbitrarily combined.
- the production method of the present embodiment may include a step of removing impurities before the polymerization branching step.
- the production method of the present embodiment is a step of removing impurities before the polymerization branching step. It is preferable to have.
- the step of removing such impurities is not particularly limited, and examples thereof include a step of treating with an organometallic compound.
- an organometallic compound is not particularly limited, and examples thereof include an organolithium compound, and examples of the organolithium compound include, but are not limited to, n-butyllithium.
- the branching reaction is started in the conjugated diene polymer by adding a branching agent described later. After the branching agent is added, the polymerization reaction in which the conjugated diene polymer grows and the branching reaction in which the conjugated diene polymer branches compete with each other in the reaction system. Therefore, the weight average molecular weight, the number average molecular weight, the ratio (Mw / Mn) of these, and the ratio (Mw / Mn) of the conjugated diene polymer obtained in the polymerization branching step, depending on the type and amount of the branching agent added and the timing of adding the branching agent. It is possible to control the absolute molecular weight, the degree of branching of the conjugated diene polymer, the number of branching points, and the number of branching points at the branching points.
- the total amount of active terminals of the conjugated diene polymer in the reaction system can be reduced as compared with the amount of the polymerization initiator added. Even if the amount of the polar compound added is small, the reaction at the initial stage of polymerization can be promoted and the activity of the polymerization active terminal can be maintained. As a result, with respect to the conjugated diene-based polymer of the present embodiment in which the amount of bound aromatic vinyl and the amount of vinyl bonded are within the above-mentioned predetermined ranges, the coupling rate and / or the modification rate at the end of polymerization can be easily improved. be able to.
- the degree of branching (Bn) of the conjugated diene polymer tends to be easily increased by using a coupling modifier having a multi-branched structure as the denaturing agent. It is in.
- the conjugated diene polymer of the present embodiment does not necessarily have to react with a coupling agent or a denaturing agent.
- the amount of the polar compound added can be adjusted for the purpose of controlling the microstructure such as the amount of bound aromatic vinyl and the amount of vinyl bond.
- the amount of the polar compound usually used to bring the amount of bound aromatic vinyl and the amount of vinyl bonded within the above-mentioned predetermined ranges is such that the active terminal of the conjugated diene polymer in the reaction system is not added when the branching agent is not added. It is insufficient from the viewpoint of maintaining, and it is not easy to sufficiently maintain the activity of the polymerization active terminal.
- the randomizing ability for the aromatic vinyl compound and the conjugated diene compound is not sufficiently high, and the bound aromatic vinyl amount and the vinyl bond amount are within the above-mentioned predetermined ranges.
- the polymerization terminal tends to be an aromatic vinyl compound. In such a state, it tends to be difficult to obtain a conjugated diene-based polymer having a high coupling rate or a modification rate, and therefore it tends to be difficult to sufficiently increase the degree of bifurcation (Bn).
- the timing of adding the branching agent in the branching step is not particularly limited, and can be appropriately selected depending on the application of the conjugated diene polymer to be produced and the like.
- the timing of adding the branching agent is the timing when the raw material conversion rate is 20% or more after the addition of the polymerization initiator. It is preferably 40% or more, more preferably 50% or more, further preferably 65% or more, and particularly preferably 75% or more. That is, the timing of adding the branching agent is preferably the timing at which the polymerization reaction is sufficiently stable.
- the branching agent is not particularly limited, but for example, a compound represented by the following formula (1) or formula (2) can be used.
- R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.
- 2 and R 3 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof, and X 1 is each.
- the halogen atom is indicated
- m indicates an integer of 0 to 2
- n indicates an integer of 0 to 3
- l indicates an integer of 0 to 3
- the sum of m, n, and l is. It is 3.
- R 2 , R 3 , R 4 , and R 5 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and a part thereof. It may have a branched structure, where X 2 and X 3 each independently represent a halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 3, and l. Indicates an integer of 0 to 3, the sum of m, n, and l is 3, a indicates an integer of 0 to 3, b indicates an integer of 0 to 2, and c indicates 0. It indicates an integer of 3 and the sum of a, b, and c is 3.
- the bifurcation agent is a compound in which R 1 is a hydrogen atom and m is 0 in the above formula (1) from the viewpoint of suppressing inhibition of the polymerization reaction and improving the degree of bifurcation. It is preferable to have.
- the bifurcation agent is preferably a compound in which m is 0 and b is 0 in the above-mentioned formula (2) from the viewpoint of improving the degree of bifurcation.
- the branching agent has R 1 as a hydrogen atom, m as 0, and l as 0 in the above formula (1). It is more preferable that the compound has n of 3.
- the branching agent has m being 0, l being 0, n being 3, and a being 0 in the above formula (2). It is preferably a compound in which b is 0 and c is 3.
- the compound represented by the formula (1) is not particularly limited, and is, for example, trimethoxy (4-vinylphenyl)silane, triethoxy (4-vinylphenyl)silane, tripropoxy (4-vinylphenyl)silane, and tributoxy (4).
- -Vinylphenyl) silane triisopropoxy (4-vinylphenyl) silane, trimethoxy (3-vinylphenyl) silane, triethoxy (3-vinylphenyl) silane, tripropoxy (3-vinylphenyl) silane, tributoxy (3-vinyl) Phenyl) silane, triisopropoxy (3-vinylphenyl) silane, trimethoxy (2-vinylphenyl) silane, triethoxy (2-vinylphenyl) silane, tripropoxy (2-vinylphenyl) silane, tributoxy (2-vinylphenyl) Silane, triisopropoxy (2-vinylphenyl) silane, dimethoxymethyl (4-vinylphenyl) silane, diethoxymethyl (4-vinylphenyl) silane, dipropoxymethyl (4-vinylphenyl) silane, dibutoxymethyl (4) -Vinylpheny
- the compound represented by the formula (2) is not limited to the following, and is, for example, 1,1-bis (4-trimethoxysilylphenyl) ethylene and 1,1-bis (4-triethoxysilylphenyl) ethylene. , 1,1-bis (4-tripropoxycysilylphenyl) ethylene, 1,1-bis (4-tripentoxysilylphenyl) ethylene, 1,1-bis (4-triisopropoxysilylphenyl) ethylene, 1 , 1-bis (3-trimethoxysilylphenyl) ethylene, 1,1-bis (3-triethoxysilylphenyl) ethylene, 1,1-bis (3-tripropoxycysilylphenyl) ethylene, 1,1-bis (3-Tripentoxysilylphenyl) ethylene, 1,1-bis (3-triisopropoxysilylphenyl) ethylene, 1,1-bis (2-trimethoxysilylphenyl) ethylene, 1,1-bis (2-) Tri
- 1,1-bis (4-trimethoxysilylphenyl) ethylene 1,1-bis (4-triethoxysilylphenyl) ethylene, 1,1-bis (4-tripropoxysilylphenyl) ethylene , 1,1-bis (4-tripentoxysilylphenyl) ethylene, and 1,1-bis (4-triisopropoxysilylphenyl) ethylene are preferable, and 1,1-bis (4-trimethoxysilylphenyl) ethylene is preferable. Is more preferable.
- the amount of such a branching agent added is not particularly limited and may be appropriately selected depending on the intended use of the conjugated diene polymer to be produced, etc., but 0.020 mol with respect to 1 mol of the polymerization initiator. It is preferably 0.50 mol or more, more preferably 0.030 mol or more and 0.40 mol or less, and further preferably 0.040 mol or more and 0.25 mol or less.
- the amount of the branching agent added may be 0.050 mol or more or 0.060 mol or more with respect to 1 mol of the polymerization initiator in the above range. Alternatively, the amount may be 0.20 mol or less or 0.18 mol or less with respect to 1 mol of the polymerization initiator.
- the amount of the branching agent added may be within a range in which the above upper limit value and lower limit value are arbitrarily combined.
- the reaction temperature may or may not be changed after the branching agent is added.
- the monomer of the conjugated diene polymer may be further added, and then the branching agent may be additionally added, and the branching agent and the simple compound may be further added. The additional addition of the polymer may be repeated.
- the monomer to be added is not particularly limited, but from the viewpoint of improving the modification rate in the coupling step, it is preferable to add the same monomer that was first added as the monomer in the polymerization branching step.
- the amount of the monomer to be added may be 1.0% or more, 5.0% or more, or 10% or more of the total amount used as the monomer of the conjugated diene polymer. It may be 15% or more, or 20% or more.
- the amount of the monomer to be added may be 50% or less, 40% or less, or 35% or less.
- the amount of the monomer to be added is within the above range, the molecular weight between the branch point generated by adding the branching agent and the branch point generated by adding the coupling modifier becomes long, so that the linearity is linear. It tends to be easy to take a high molecular structure.
- the obtained conjugated diene polymer have such a structure, the entanglement of the molecular chains of the conjugated diene polymer increases when it is made into a vulcanized product, resulting in wear resistance, steering stability and fracture strength. It tends to be easy to obtain excellent vulcanized products.
- the production method of the present embodiment preferably obtains a modified conjugated diene polymer by reacting the conjugated diene polymer having a branched structure obtained by the above polymerization branching step with a coupling modifier. Has a ring process.
- the conjugated diene-based polymer having a branched structure obtained by the polymerization branching step can be modified with a specific functional group having affinity or binding reactivity with the filler.
- a conjugated diene-based polymers can be coupled, a conjugated diene-based polymer having a high degree of branching (Bn) can be obtained reliably and easily. Therefore, the production method having such a coupling step can more reliably and easily obtain the conjugated diene-based polymer of the present embodiment described above.
- the reactivity having a specific functional group having an affinity or binding reactivity with the filler and having two or more functional groups capable of reacting with the active terminal of the conjugated diene polymer is not particularly limited.
- Examples of such a coupling modifier include a coupling modifier having a group containing a nitrogen atom and / or a silicon atom. From the viewpoint of effectively and surely exerting the effect of the present embodiment, the coupling modifier has preferably 3 or more, more preferably 4 or more functional groups capable of reacting with the active terminal of the conjugated diene polymer.
- the coupling modifier having a group containing a silicon atom is not particularly limited, and for example, a halogenated silane compound, an epoxidized silane compound, a vinylized silane compound, an alkoxysilane compound, and an alkoxysilane compound containing a nitrogen-containing group. Can be mentioned.
- the halogenated silane compound is not particularly limited, and is, for example, methyltrichlorosilane, tetrachlorosilane, tris (trimethylsiloxy) chlorosilane, tris (dimethylamino) chlorosilane, hexachlorodisilane, bis (trichlorosilyl) methane, 1,2-bis.
- examples thereof include (trichlorosilyl) ethane, 1,2-bis (methyldichlorosilyl) ethane, 1,4-bis (trichlorosilyl) butane, and 1,4-bis (methyldichlorosilyl) butane.
- the epoxidized silane compound is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and epoxy-modified silicone. Can be mentioned.
- the alkoxysilane compound is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, triphenoxymethylsilane, 1,2-bis (triethoxysilyl) ethane, and methoxy-substituted polyorganosiloxane.
- the coupling modifier having a group containing a nitrogen atom is not particularly limited, and is, for example, an isocyanato compound, an isothiocyanate compound, an isocyanuric acid derivative, a nitrogen atom-containing carbonyl compound, a nitrogen atom-containing vinyl compound, and a nitrogen atom-containing agent.
- examples thereof include an epoxy compound and a nitrogen atom-containing alkoxysilane compound.
- Examples of the amine compound having no active hydrogen include a tertiary amine compound.
- the isocyanate compound is not particularly limited, and is, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polypeptide type diphenylmethane diisocyanate (C-MDI), phenyl.
- the isocyanuric acid derivative is not particularly limited, and is, for example, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (3-triethoxysilylpropyl) isocyanurate, 1. , 3,5-tri (oxylan-2-yl) -1,3,5-triazinan-2,4,6-trione, and 1,3,5-tris (isocyanatomethyl) -1,3,5- Examples thereof include triazinan-2,4,6-trione and 1,3,5-trivinyl-1,3,5-triazinan-2,4,6-trione.
- the nitrogen atom-containing carbonyl compound is not particularly limited, and is, for example, 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3- (2-).
- the nitrogen atom-containing vinyl compound is not particularly limited, and is, for example, N, N-dimethylacrylamide, N, N-dimethylmethacrylicamide, N-methylmaleimide, N-methylphthalimide, N, N-bistrimethylsilylacrylamide, and morpholinoacrylamide.
- the nitrogen atom-containing epoxy compound is not particularly limited, and examples thereof include a hydrocarbon compound containing an epoxy group bonded to an amino group. Further, the hydrocarbon compound may further have an epoxy group bonded to an ether group. Such a nitrogen atom-containing epoxy compound is not particularly limited, and examples thereof include a compound represented by the formula (i).
- R 7 has a divalent hydrocarbon group or a polar group having an oxygen atom such as ether, epoxy, and ketone, and a sulfur atom such as thioether and thioketone. It is a divalent organic group having at least one polar group selected from a polar group and a polar group having a nitrogen atom such as a tertiary amino group and an imino group.
- the divalent hydrocarbon group is a saturated or unsaturated hydrocarbon group which may be linear, branched or cyclic, and includes an alkylene group, an alkenylene group, a phenylene group and the like.
- the divalent hydrocarbon group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.
- the divalent hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and for example, methylene, ethylene, butylene, cyclohexylene, 1,3-bis (methylene) -cyclohexane, 1,3-bis (ethylene).
- -Cyclohexane, o-phenylene, m-phenylene, p-phenylene, m-xylene, p-xylene, bis (phenylene) -methane and the like can be mentioned.
- R 8 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- R 6 represents a hydrogen atom, a monovalent or higher alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- the valence of R 6 is 1 or more, which is the same as o in the formula (i).
- R 9 is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a structure of the following formula (ii).
- R 6 and R 8 may have an annular structure connected to each other.
- R 9 is a monovalent hydrocarbon group, it may have a cyclic structure bonded to R 8 to each other. However, only if the N and R 8 bonded to R 9 are directly bonded, R 9 may be a hydrogen atom.
- o is an integer of 1 or more.
- R 1 and R 2 are synonymous with R 7 and R 8 in formula (i), respectively.
- the nitrogen atom-containing epoxy compound is preferably a nitrogen atom-containing epoxy compound having one or more diglycidylamino groups in the molecule and one or more glycidoxy groups.
- the nitrogen atom-containing epoxy compound is not particularly limited, and is, for example, N, N-diglycidyl-4-glycidoxyaniline, 1-N, N-diglycidylaminomethyl-4-glycidoxy-cyclohexane, 4- (4- (4-).
- Glycydoxyphenyl)-(N, N-diglycidyl) aniline 4- (4-glycidoxyphenoxy)-(N, N-diglycidyl) aniline, 4- (4-glycidoxybenzyl)-(N, N -Diglycidyl) aniline, 4- (N, N'-diglycidyl-2-piperazinyl) -glycidoxybenzene, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N '-Tetraglycidyl-m-xylene diamine, 4,4-methylene-bis (N, N-diglycidylaniline), 1,4-bis (N, N-diglycidylamino) cyclohexane, N, N, N', N'-tetraglycidyl-p-phenylenediamine, 4,4'-bis (diglycidylamino) benzophenone, 4- (4
- the nitrogen atom-containing alkoxysilane compound is not particularly limited, and for example, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-Piperidinopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane, 3- (4-methyl-1-piperazino) propyltriethoxysilane, 1- [3- (triethoxysilyl) -propyl] -3-Methylhexahydropyrimidine, 3- (4-trimethylsilyl-1-piperazino) propyltriethoxysilane, 3- (3-triethylsilyl-1-imidazolidinyl) propylmethyldiethoxysilane, 3- (3-trimethylsilyl-1)
- nitrogen atom-containing alkoxysilane compounds are not particularly limited, but for example, tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3-tripropoxysilylpropyl).
- examples of the protected amine compound in which active hydrogen is substituted with a protecting group include compounds having an unsaturated bond and a protected amine in the molecule.
- Such compounds are not particularly limited, but are, for example, 4,4'-binylidenebis [N, N-bis (trimethylsilyl) aniline], 4,4'-binilidenbis [N, N-bis (triethylsilyl)).
- examples of the protected amine compound in which active hydrogen is substituted with a protecting group include compounds having alkoxysilane and a protected amine in the molecule.
- Such compounds are not particularly limited, but are, for example, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl).
- Aminopropyltriethoxysilane N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (triethylsilyl) aminopropylmethyldiethoxysilane, 3- (4-trimethylsilyl-1-piperazino) propyltriethoxysilane, 3- (3-triethylsilyl-1-imidazolidinyl) propylmethyldiethoxysilane, 3- (3-trimethylsilyl-1-hexahydropyrimidinyl) propyltrimethoxysilane, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy -1- (3-Triethoxy
- R 12 , R 13 , R 14 , and R 15 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- R 16 Indicates an alkylene group having 1 to 10 carbon atoms
- R 17 indicates an alkylene group having 1 to 20 carbon atoms
- q indicates an integer of 1 or 2
- r indicates an integer of 2 or 3.
- the sum of q and r is an integer greater than or equal to 4.
- R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms.
- R 24 , R 25 , and R 26 each independently represent an alkylene group having 1 to 20 carbon atoms, and s, t, and u each independently represent an integer of 1 to 3. Shown, the sum of s, t, and u is an integer of 4 or more.
- A is a hydrocarbon group having 1 to 20 carbon atoms, or at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom.
- R 27 , R 28 , and R 29 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms, indicating an organic group having and having no active hydrogen
- R 30 , R 31 , R 32 , R 33 , and R 35 each independently represent an alkyl group having 1 to 20 carbon atoms
- R 34 and R 37 each independently represent an alkylene group having 1 to 20 carbon atoms.
- i indicates an integer of 0 to 6
- j indicates an integer of 0 to 6
- k indicates an integer of 0 to 6
- the sum of i, j, and k is an integer of 4 to 10. Is.
- R 36 represents an alkylene group having 1 to 20 carbon atoms
- R 37 , R 39 , and R 40 are independently alkyl groups having 1 to 20 carbon atoms or carbon atoms. It represents an aryl group of 6 to 20, R 38 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and z represents an integer of 1 to 3.
- the coupling modifier represented by the formula (A) is not particularly limited, but for example, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2 , 2-Diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-sila Cyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza- 2-Silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-tri
- q is 2 and r is 3 in the formula (A) from the viewpoint of enhancing the reactivity and interaction between the conjugated diene polymer and the inorganic filler such as silica, and from the viewpoint of enhancing the processability.
- reaction temperature and reaction time in the coupling step using the coupling modifier represented by the formula (A) are not particularly limited, but are preferably 0 ° C. or higher and 120 ° C. or lower, preferably 30 seconds or longer. Let me.
- the amount of the coupling modifier added by the formula (A) is such that the total number of moles of the alkoxy groups bonded to the silyl group in the compound represented by the formula (A) is 0, which is the number of moles of the polymerization initiator added.
- the range is preferably 5 times or more and 3.0 times or less, more preferably 0.6 times or more and 2.5 times or less, and 0.8 times or more and 2.0 times or less. Is more preferable. From the viewpoint of further setting the modification rate, molecular weight, and branched structure of the obtained modified conjugated diene polymer in a more preferable range, it is preferably 0.5 times or more. Further, from the viewpoint of suppressing a decrease in workability due to an excessive increase in the degree of branching, it is preferably 3.0 times or less.
- the number of moles of the polymerization initiator is preferably 3.0 times or more, more preferably 4.0 times or more, the number of moles of the coupling modifier represented by the formula (A).
- the amount of the polymerization initiator and the coupling modifier represented by the formula (A) may be adjusted so as to be.
- the coupling modifier represented by the formula (B) is not particularly limited, and is, for example, tris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine, and tris (3-triethoxy). Cyrilpropyl) amines, tris (3-methyldiethoxysilylpropyl) amines, tris (trimethoxysilylmethyl) amines, tris (2-trimethoxysilylethyl) amines, and tris (4-trimethoxysilylbutyl) amines. Be done.
- n, m, and l in the formula (B) are all 3 from the viewpoint of enhancing the reactivity and interaction between the conjugated diene polymer and the inorganic filler such as silica, and from the viewpoint of enhancing the processability. Is preferable. Specific examples thereof include tris (3-trimethoxysilylpropyl) amine and tris (3-triethoxysilylpropyl) amine.
- reaction temperature and reaction time in the coupling step using the coupling modifier represented by the formula (B) are not particularly limited, but are preferably 0 ° C. or higher and 120 ° C. or lower, preferably 30 seconds or longer. Let me.
- the amount of the coupling modifier added by the formula (B) is such that the total number of moles of the alkoxy groups bonded to the silyl group in the compound represented by the formula (B) is 0, which is the number of moles of the polymerization initiator added.
- the range is preferably 5 times or more and 3.0 times or less, more preferably 0.6 times or more and 2.5 times or less, and 0.8 times or more and 2.0 times or less. Is more preferable. From the viewpoint of further setting the modification rate, molecular weight, and branched structure of the obtained modified conjugated diene polymer in a more preferable range, it is preferably 0.5 times or more. Further, from the viewpoint of suppressing a decrease in workability due to an excessive increase in the degree of branching, it is preferably 3.0 times or less.
- the number of moles of the polymerization initiator is preferably 4.0 times or more, more preferably 5.0 times or more, the number of moles of the coupling modifier represented by the formula (B).
- the amount of the polymerization initiator and the coupling modifier represented by the formula (B) may be adjusted so as to be.
- A is preferably represented by any of the following formulas (iii) to (vi).
- B 1 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. B 1 in the case of a plurality of carbon atoms is each. being independent.
- B 2 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms
- B 3 represents an alkyl group having 1 to 20 carbon atoms
- a represents 1 to 10 carbon atoms. Indicates an integer of. B 2 and B 3 are independent when there are a plurality of them.
- B 4 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. B 4 in the case of a plurality of carbon atoms is each. being independent.)
- B 5 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. B 5 in the case of a plurality of carbon atoms is each. being independent.)
- the coupling modifier when A is represented by the formula (iii) is not particularly limited, and is, for example, tris (3-trimethoxysilylpropyl) amine and bis (3-trimethoxysilyl).
- the coupling modifier when A is represented by the formula (iv) is not particularly limited, but for example, tris (3-trimethoxysilylpropyl) -methyl-1,3-propanediamine.
- the coupling modifier when A is represented by the formula (v) is not particularly limited, but for example, tetrax [3- (2,2-dimethoxy-1-aza-2-sila). Cyclopentane) propyl] silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) silane, tris [3- (2,2-2) Dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl) -Bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, (3-trimethoxysilyl)-[3- (1-methoxy-2-trimethylsilyl)-
- the coupling modifier when A is represented by the formula (vi) is not particularly limited, but is, for example, 3-tris [2- (2,2-dimethoxy-1-aza-2). -Silacyclopentane) ethoxy] Cyril-1- (2,2-dimethoxy-1-aza-2-silacyclopentane) propane, and 3-tris [2- (2,2-dimethoxy-1-aza-2-) Silacyclopentane) ethoxy] silyl-1-trimethoxysilylpropane.
- A is more preferably represented by the formula (iii) or the formula (iv), and k is 0.
- Conjugated diene-based polymers obtained by using such a coupling modifier tend to be more excellent in wear resistance and low hysteresis loss when used as a vulcanized product.
- Such a coupling modifier is not particularly limited, but is, for example, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine.
- A is more preferably represented by the formula (iii) or the formula (iv), k is 0, and in the formula (iii) or the formula (iv), a is 2 to 10. It is an integer. Conjugated diene-based polymers obtained by using such a coupling modifier tend to be more excellent in wear resistance and low hysteresis loss when used as a vulcanized product.
- Such coupling modifiers are not particularly limited, but are, for example, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis ( 3-Trimethoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, and N 1- (3- (bis (3- (trimethoxysilyl)) ) propyl) amino) propyl) -N 1 - methyl -N 3 - (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl) -N 3 - (3- (trimethoxysilyl) propyl) - Examples thereof include 1,3-propanediamine.
- the amount of the coupling modifier added represented by the formula (C) can be determined based on the ratio of the number of moles of the polymerization initiator added to the number of moles of the coupling modifier represented by the formula (C). preferable. By doing so, the conjugated diene-based polymer and the modifier can be adjusted to react at a desired stoichiometric ratio, and as a result, the conjugated diene-based polymer having a desired star-shaped polymer structure can be adjusted. There is a tendency to obtain a polymer.
- the number of moles of the polymerization initiator is preferably 5.0 times or more, more preferably 6.0 times or more, the number of moles of the coupling modifier represented by the formula (C). Therefore, the amount of the polymerization initiator and the coupling modifier represented by the formula (C) may be adjusted.
- the number of functional groups of the denaturant for example, i and j are 2 or more and there are a plurality of w and x and w and x are equal to each other
- ⁇ j + k is preferably an integer of 5 to 10, and more preferably an integer of 6 to 10.
- the coupling modifier represented by the formula (D) is not particularly limited, and is, for example, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine, N- ( 1,3-Dimethylbutylidene) -3- (trimethoxysilyl) -1-propaneamine, N- (1,3-dimethylbutylidene) -3-methyl (dimethoxysilyl) -1-propaneamine, N- ( 1,3-Dimethylbutylidene) -3-methyl (diethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propaneamine, N- (1-) Methylethylidene) -3- (trimethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3-methyl (dimethoxysilyl
- reaction temperature and reaction time in the coupling step using the coupling modifier represented by the formula (D) are not particularly limited, but are preferably 0 ° C. or higher and 120 ° C. or lower, preferably 30 seconds or longer. Let me.
- the addition amount of the coupling modifier represented by the formula (D) is such that the total number of moles of the alkoxy groups (OR 40 ) bonded to the silyl group in the compound represented by the formula (D) is the addition of the polymerization initiator.
- the range is preferably 0.2 times or more and 2.0 times or less of the number of moles, and more preferably 0.3 times or more and 1.5 times or less. From the viewpoint of further setting the modification rate and the molecular weight of the obtained conjugated diene polymer in a more preferable range, it is preferably 0.2 times or more. Further, from the viewpoint of suppressing a decrease in workability due to an excessive increase in the degree of bifurcation, it is preferably 2.0 times or less.
- the number of moles of the polymerization initiator is preferably 0.5 times or more, more preferably 1.0 times or more, the number of moles of the coupling modifier represented by the formula (D). be.
- the amount of the polymerization initiator and the coupling modifier represented by the formula (D) may be adjusted so as to be.
- the production method of the present embodiment may have a condensation reaction step of causing a condensation reaction by adding a condensation accelerator after the coupling step and / or before the coupling step.
- the production method of the present embodiment may include a modification step using a modifier other than the coupling modifier, instead of the coupling step.
- the production method of the present embodiment may include a hydrogenation step of hydrogenating the conjugated diene portion in the modified conjugated diene polymer or the conjugated diene polymer.
- the method for hydrogenating the conjugated diene portion of the modified conjugated diene polymer or the conjugated diene polymer is not particularly limited, and a known method can be used.
- a preferred hydrogenation step is a method of hydrogenating the conjugated diene portion of the modified conjugated diene polymer or the conjugated diene polymer by blowing gaseous hydrogen into the polymer solution in the presence of a catalyst.
- the catalyst to be used is not particularly limited, but for example, a heterogeneous catalyst such as a catalyst in which a noble metal is supported on a porous inorganic substance; and a catalyst in which salts such as nickel and cobalt are solubilized and reacted with organic aluminum and the like.
- a homogeneous catalyst such as a catalyst using a metallocene such as titanosen.
- the titanocene catalyst is preferable from the viewpoint that milder hydrogenation conditions can be selected.
- a method of hydrogenating the aromatic group of the modified conjugated diene polymer or the conjugated diene polymer a method using a supported catalyst of a noble metal can be mentioned.
- the hydrogenation catalyst is not particularly limited, but for example, (1) a supported non-uniform system in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, or Keisou soil.
- a hydrogenation catalyst (2) a so-called Cheegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, or Cr or a transition metal salt such as an acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti. , Ru, Rh, or so-called organometallic complexes such as organometallic compounds such as Zr.
- the other hydrogenation catalyst is not particularly limited, but for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Square Root Guide No. 1-377970, and Japanese Patent Publication No. 43-6636.
- Examples thereof include known hydrogenation catalysts described in JP-A-1-53851, JP-A-2-9041 and JP-A-8-109219.
- Preferred hydrogenation catalysts include reaction mixtures of titanocene compounds and reducing organometallic compounds.
- a deactivating agent and / or a neutralizing agent or the like may be added to the polymer solution, if necessary.
- the deactivating agent is not particularly limited, and examples thereof include water and alcohols such as methanol, ethanol, and isopropanol.
- the neutralizing agent is not particularly limited, but is, for example, branched, containing stearic acid, oleic acid, and versatic acid (mainly composed of those having 9 to 11 carbon atoms and 10 carbon atoms).
- Examples thereof include carboxylic acids such as (mixtures of carboxylic acids having a large amount of water), aqueous solutions of inorganic acids, and carbon dioxide gas.
- the production method of the present embodiment may include a step of obtaining the obtained conjugated diene-based polymer from the polymer solution.
- a known method can be used, but for example, the following method may be used.
- the conjugated diene polymer composition of the present embodiment contains 100 parts by mass of the conjugated diene polymer and 1.0 part by mass or more and 60 parts by mass or less of the softener for rubber.
- a softening agent for rubber added to the conjugated diene-based polymer of the present embodiment, it is possible to obtain a composition having further improved processability when a filler or the like is blended.
- the softening agent for rubber is not particularly limited, and examples thereof include spreading oil, liquid rubber, and resin.
- the spreading oil examples include aroma oil, naphthenic oil, paraffin oil and the like.
- an aroma substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less according to the IP346 method is preferable from the viewpoint of environmental safety, prevention of oil bleeding, and improvement of wet grip.
- the aroma substitute oil is not particularly limited, and is, for example, TDAE (Treated Distyllate Aromatic Extracts), MES (Mild Plastic Extract), MES (Mild ExtractRation), and MES (Mild ExtractRation) shown in Kautschuk Kunststoffe 52 (12) 799 (1999). Can be mentioned.
- the liquid rubber is not particularly limited, and examples thereof include liquid polybutadiene and liquid styrene-butazine rubber.
- the glass transition temperature of the conjugated diene polymer composition can be further lowered, so that the vulcanized product has abrasion resistance and low hysteresis loss. Properties and low temperature characteristics tend to be further improved.
- the resin is not particularly limited, and is, for example, aromatic petroleum resin, Kumaron-inden resin, terpene resin, rosin derivative (including tung oil resin), tall oil, tall oil derivative, rosin ester resin, natural and synthetic.
- Terpen resin aliphatic hydrocarbon resin, aromatic hydrocarbon resin, mixed aliphatic-aromatic hydrocarbon resin, coumarin-inden resin, phenol resin, p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene- Formaldehyde resin, monoolefin oligomer, diolefin oligomer, aromatic hydrocarbon resin, aromatic petroleum resin, hydride aromatic hydrocarbon resin, cyclic aliphatic hydrocarbon resin, hydride hydrocarbon resin, hydrocarbon resin , Hydrocarboned tung oil resin, hydrocarbon oil resin, and esters of hydrocarbon oil resin with monofunctional or polyfunctional alcohol.
- One type of these resins may be used alone, or two or more types may be used
- the breaking strength of the vulcanized product of the conjugated diene-based polymer composition tends to be further improved.
- the amount of the softening agent for rubber added is not particularly limited as long as it is 1.0 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the conjugated diene polymer of the present embodiment, but is preferably 3.0 parts by mass or more. It is 50 parts by mass or less, more preferably 5.0 parts by mass or more and 40 parts by mass or less, and further preferably 10 parts by mass or more and 35 parts by mass or less.
- a softening agent for rubber is added within the above range, the processability when a filler or the like is added tends to be further improved, and the fracture strength and wear resistance of the vulcanized product tend to be further improved.
- the method of adding the softening agent for rubber to the conjugated diene-based polymer is not particularly limited.
- the softening agent for rubber is added to the conjugated diene-based polymer solution, mixed, and then the polymer solution is desolvated. There is a way to do it.
- the conjugated diene polymer composition of the present embodiment may further contain a stabilizer for rubber from the viewpoint of suppressing gel formation and improving stability during processing.
- the stabilizer for rubber is not particularly limited, and known ones can be used.
- BHT 2,6-di-tert-butyl-4-hydroxytoluene
- Antioxidants such as -octadecyl-3- (4'-hydroxy-3', 5'-di-tert-butylphenol) propinate and 2-methyl-4,6-bis [(octylthio) methyl] phenol can be mentioned. ..
- the rubber composition of the present embodiment contains a rubber component and a filler of 5.0 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the rubber component, and the rubber component is a total amount of 100 parts by mass of the rubber component. 10 parts by mass or more of the conjugated diene-based polymer or the conjugated diene-based polymer composition of the present embodiment is contained in a portion.
- the processability at the time of vulcanization is further excellent, and the vulcanized product has low hysteresis loss property, fracture characteristics, and abrasion resistance. Can be obtained with a more excellent rubber composition.
- the rubber component contains the conjugated diene-based polymer or the conjugated diene-based polymer composition of the present embodiment in a predetermined ratio, fuel saving performance, workability, and abrasion resistance are further improved.
- the filler is not particularly limited, and examples thereof include silica-based inorganic fillers, carbon black, metal oxides, and metal hydroxides. Among these, silica-based inorganic fillers are preferable.
- silica-based inorganic fillers are preferable.
- a silica-based inorganic filler may be used alone or in combination of two or more.
- the silica-based inorganic filler is not particularly limited, but may be a known, solid particles preferably comprise SiO 2 or Si 3 Al as a constituent unit, the main structural units of SiO 2 or Si 3 Al Solid particles contained as a component are more preferable.
- the main component means a component contained in the silica-based inorganic filler in an amount of more than 50% by mass, preferably 70% by mass or more, and more preferably 80% by mass or more.
- the silica-based inorganic filler include, but are not limited to, inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. Further, a silica-based inorganic filler having a hydrophobic surface and a mixture of the silica-based inorganic filler and a non-silica-based inorganic filler may be used. Among these, silica or glass fiber is preferable, and silica is more preferable, from the viewpoint of further improving the strength and abrasion resistance of the rubber composition.
- the silica is not particularly limited, and examples thereof include dry silica, wet silica, and synthetic silicate silica. Among these silicas, wet silica is preferable from the viewpoint of further improving the breaking strength of the rubber composition.
- the nitrogen adsorption specific surface area required by the BET adsorption method of a silica-based inorganic filler is 100 m 2 / g or more and 300 m 2 / g. It is preferably 170 m 2 / g or more, and more preferably 250 m 2 / g or less. If necessary, a silica-based inorganic filler having a relatively small specific surface area (for example, a specific surface area of 200 m 2 / g or less) and a silica-based inorganic filler having a relatively large specific surface area (for example, 200 m 2 / g or more) are filled.
- the conjugated diene-based polymer or the conjugated diene-based polymer composition may be used in combination with an agent.
- the conjugated diene-based polymer or the conjugated diene-based polymer composition has a dispersibility of silica. Further improve. As a result, the obtained rubber composition tends to have more excellent wear resistance, fracture strength and low hysteresis loss.
- the carbon black is not particularly limited, and examples thereof include carbon blacks of each class such as SRF, FEF, HAF, ISAF, and SAF.
- DBP dibutyl phthalate
- the metal oxide is a solid particle whose main component is the chemical formula M x O y (M represents a metal atom, and x and y each independently represent an integer of 1 to 6). Examples thereof include, but are not limited to, alumina, titanium oxide, magnesium oxide, and zinc oxide.
- the metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and zirconium hydride.
- the content of the filler in the rubber composition of the present embodiment is 5.0 parts by mass or more and 150 parts by mass, preferably 20 parts by mass or more and 100 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the rubber component. More than 90 parts by mass is more preferable.
- the filler is within the above range, the rubber composition tends to be more excellent in processability at the time of vulcanization, and the vulcanized product tends to be further excellent in low hysteresis loss property, fracture property, and wear resistance. be.
- carbon black is added to 100 parts by mass of the rubber component containing the conjugated diene polymer from the viewpoint of surely imparting the performance required for applications such as tires such as dry grip performance and conductivity. On the other hand, it is preferably contained in an amount of 0.5 parts by mass or more and 100 parts by mass or less. From the same viewpoint, in the rubber composition, carbon black is more preferably 3.0 parts by mass or more and 100 parts by mass or less, still more preferably 5.0, with respect to 100 parts by mass of the rubber component containing the conjugated diene polymer. It is included in an amount of 5 parts by mass or more and 50 parts by mass or less.
- the rubber composition of the present embodiment may further contain a silane coupling agent.
- a silane coupling agent is not particularly limited, but for example, a compound having a sulfur-bonded moiety and an alkoxysilyl group or silanol group moiety in one molecule is preferable.
- Such compounds are not particularly limited, but are, for example, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, and bis-. [2- (Triethoxysilyl) -ethyl] -tetrasulfide can be mentioned.
- the content of the silane coupling agent is preferably 0.1 part by mass or more and 30 parts by mass or less, and 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the filler. Is more preferable, and 1.0 part by mass or more and 15 parts by mass or less is further preferable.
- the content of the silane coupling agent is in the above range, the interaction between the rubber component and the filler tends to be further improved.
- the rubber composition of the present embodiment may contain a rubber-like polymer other than the conjugated diene-based polymer of the present embodiment (hereinafter, simply referred to as "rubber-like polymer”) as a rubber component.
- rubber-like polymer other than the conjugated diene-based polymer of the present embodiment
- the rubber-like polymer is not particularly limited, but for example, a conjugated diene-based polymer and its hydrogen additive, a random copolymer of a conjugated diene compound and a vinyl aromatic compound and its hydrogen additive, a conjugated diene compound and vinyl.
- a conjugated diene-based polymer and its hydrogen additive a random copolymer of a conjugated diene compound and a vinyl aromatic compound and its hydrogen additive
- a conjugated diene compound and vinyl examples thereof include block copolymers with aromatic compounds and their hydrogenated products, non-diene polymers, and natural rubbers.
- the specific rubber-like polymer is not particularly limited, but for example, butadiene rubber and its hydrogen additive, isoprene rubber and its hydrogen additive, styrene-butadiene rubber and its hydrogen additive, and styrene-butadiene block copolymer. And its hydrogenated products, styrene-based elastomers such as styrene-isoprene block copolymers and their hydrogenated products, and acrylonitrile-butadiene rubber and its hydrogenated products.
- the non-diene polymer is not particularly limited, and examples thereof include olefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber.
- olefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber.
- the natural rubber is not particularly limited, and examples thereof include smoked sheets RSS3 to 5, SMR, and epoxidized natural rubber.
- the rubber-like polymer may be a modified rubber to which a functional group having polarity such as a hydroxyl group or an amino group is added.
- the rubber-like polymer is one or more selected from the group consisting of butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber, and butyl rubber. preferable.
- the weight average molecular weight of the rubber-like polymer is preferably 2000 or more and 20000 or less, preferably 5000 or more and 1500,000 or less, from the viewpoint of the balance between wear resistance, breaking strength, low hysteresis loss and processability of the rubber composition. Is more preferable.
- a rubber-like polymer having a low molecular weight so-called liquid rubber, can also be used. These rubber-like polymers may be used alone or in combination of two or more.
- the content ratio (mass ratio) of the conjugated diene polymer to the rubber-like polymer is (conjugated diene polymer / rubber).
- the state polymer) is preferably 10/90 or more and 100/0 or less, more preferably 20/80 or more and 90/10 or less, and further preferably 30/70 or more and 80/20 or less. That is, the rubber component contains, preferably 10 parts by mass or more and 100 parts by mass or less, and more preferably 20 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the total amount of the rubber component.
- the vulcanized product of the rubber composition tends to be more excellent in wear resistance and low hysteresis loss property.
- a softening agent for rubber may be added in addition to the rubber component.
- the softener for rubber the same ones exemplified as those contained in the conjugated diene-based polymer composition can be used, but mineral oil or a liquid or low molecular weight synthetic softener is preferable.
- the mineral oil-based rubber softener called process oil or extender oil used to soften, increase the volume, and improve workability of rubber is a mixture of aromatic ring, naphthen ring, and paraffin chain. .. Among them, those having a carbon number of 50% or more in the total carbon number belonging to the paraffin chain are called paraffin type, and those having a carbon number belonging to the naphthen ring of 30% or more and 45% or less in the total carbon number are naphthen type. The carbon number belonging to the aromatic carbon number exceeds 30% of the total carbon number is called an aromatic system.
- the rubber composition of the present embodiment preferably contains a softening agent for rubber having an appropriate aromatic content. By including such a softening agent for rubber, the compatibility with the conjugated diene polymer is further improved.
- the content of the softening agent for rubber in the rubber composition is the amount of the softening agent for rubber previously added to the conjugated diene polymer composition or the rubber-like polymer, and the amount of the softening agent for rubber added when making the rubber composition. It is represented by the total amount of softener.
- the content of the softening agent for rubber is preferably 0 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the rubber component. More preferably, it is 30 parts by mass or more and 90 parts by mass or less.
- the content of the softening agent for rubber is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, bleed-out can be suppressed and stickiness on the surface of the rubber composition can be further suppressed.
- the method for mixing the conjugated diene-based polymer, the conjugated diene-based polymer composition, the rubber-like polymer, the filler, the silane coupling agent, the softening agent for rubber and the like is not particularly limited, but for example, open roll and the like.
- a melt-kneading method using a general mixer such as a rubbery mixer, kneader, single-screw extruder, twin-screw extruder, or multi-screw screw extruder, and after melting and mixing each component, the solvent is removed by heating. The method can be mentioned.
- a melt-kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferable from the viewpoint of productivity and good kneading.
- the rubber component and the filler, the silane coupling agent, and the additive may be kneaded at one time, or may be mixed in a plurality of times.
- the rubber composition of the present embodiment may be a vulcanized product that has been vulcanized with a vulcanizing agent.
- the sulfide is not particularly limited, and examples thereof include radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, and sulfur compounds.
- Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, high molecular weight polysulfur compounds and the like.
- the content of the vulcanizing agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.1 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the rubber component. More preferred.
- the vulcanization method a conventionally known method can be used.
- the vulcanization temperature is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 140 ° C. or higher and 180 ° C. or lower.
- a vulcanization accelerator and / or a vulcanization aid may be used if necessary.
- Conventionally known materials can be used as the vulcanization accelerator, and the vulcanization accelerator is not particularly limited. Examples include system-based and dithiocarbamate-based vulcanization accelerators.
- the vulcanization aid is not particularly limited, and examples thereof include zinc oxide and stearic acid.
- the contents of the vulcanization accelerator and the vulcanization aid are preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.1 parts by mass or more and 15 parts by mass or less, respectively, with respect to 100 parts by mass of the rubber component. preferable.
- the rubber composition of the present embodiment contains softeners and fillers other than those described above, heat-resistant stabilizers, antistatic agents, weather-resistant stabilizers, anti-aging agents, and colorants, as long as the effects of the present embodiment are not impaired. , And various additives such as lubricants may be used.
- the softener a known softener can be used.
- Specific examples of the filler include, but are not limited to, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
- Known materials can be used as the heat-resistant stabilizer, antistatic agent, weather-resistant stabilizer, anti-aging agent, colorant, and lubricant.
- the rubber composition of this embodiment is suitably used as a rubber composition for tires.
- the rubber composition of the present embodiment is not particularly limited, but for example, various tires such as fuel-efficient tires, all-season tires, high-performance tires, and studless tires; tires such as treads, carcasses, sidewalls, and bead portions. It can be suitably used for a site.
- the degree of branching (Bn) of the conjugated diene polymer or the modified conjugated diene polymer was measured as follows by the GPC-light scattering method with a viscosity detector.
- a GPC measuring device (trade name "GPCmax VE-2001” manufactured by Malvern) in which a conjugated diene polymer or a modified conjugated diene polymer is used as a sample and three columns using a polystyrene gel as a filler are connected.
- a detector (trade name "TDA305” manufactured by Polymer Co., Ltd.) in which a light scattering detector, an RI detector, and a viscosity detector are connected in this order was used.
- the absolute molecular weight was determined from the results of the light scattering detector and the RI detector, and the intrinsic viscosity was determined from the results of the RI detector and the viscosity detector.
- a 5 mmol / L triethylamine-tetrahydrofuran solution was used as the eluent.
- trade names "TSKgel G4000HXL”, “TSKgel G5000HXL”, and “TSKgel G6000HXL” manufactured by Tosoh Corporation were connected in this order and used.
- the ratio of the calculated intrinsic viscosity [ ⁇ 0 ] ([ ⁇ ] / [ ⁇ 0 ]) was taken as the contraction factor (g').
- the modification rate of the modified conjugated diene polymer was measured by the column adsorption GPC method as follows.
- the column adsorption GPC method utilizes the property that the modified basic polymer component in the modified conjugated diene polymer is easily adsorbed on the GPC column using a silica gel as a filler, and the modification rate of the modified polymer. Is a method of finding.
- the sample and the sample solution containing the low molecular weight internal standard polystyrene were measured with a polystyrene column.
- the same sample solution was measured with a silica-based column.
- the amount of the modified conjugated diene polymer adsorbed on the silica column was measured by obtaining the difference between the chromatogram obtained by the measurement using the polystyrene column and the chromatogram obtained by the measurement using the silica column. , The modification rate was determined.
- a sample solution was prepared by dissolving 10 mg of a sample and 5 mg of standard polystyrene in 20 mL of THF.
- the modification rate of the modified conjugated diene polymer was measured under the following measurement conditions. (GPC measurement conditions using polystyrene column) GPC measurement was performed using the trade name "HLC-8320GPC” manufactured by Tosoh Corporation and the RI detector (trade name "HLC8020” manufactured by Tosoh Corporation).
- GPC measurement was performed using the trade name "HLC-8320GPC” manufactured by Tosoh Corporation and the RI detector (trade name "HLC8020” manufactured by Tosoh Corporation).
- RI detector trade name "HLC8020” manufactured by Tosoh Corporation
- a conjugated diene polymer or a modified conjugated diene polymer was used as a sample, and 100 mg of the sample was dissolved in 100 mL of chloroform to prepare a measurement sample. Each sample was measured with a spectrophotometer (trade name "UV-2450" manufactured by Shimadzu Corporation) to obtain an absorption spectrum. The amount of bound styrene (% by mass) with respect to 100% by mass of the conjugated diene polymer or the modified conjugated diene polymer was calculated from the absorption amount of ultraviolet rays (around 254 nm) derived from the phenyl group of styrene.
- a solution prepared by mixing 5 mL of triethylamine with 1 L of tetrahydrofuran was used.
- a column: Tosoh's product name "TSKgel G6000HHR”, “TSKgel G5000HHR”, and “TSKgel G4000HHR” were connected in this order. .. 10 mg of the sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 200 ⁇ L of the measurement solution was injected into a GPC measuring device to measure under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.
- Modified conjugated diene polymer (A1) It has an internal volume of 10 L, an internal height (L) to diameter (D) ratio (L / D) of 4.0, an inlet at the bottom and an outlet at the top, for a stirrer and temperature control.
- Two tank-type pressure vessels having a jacket were connected as a polymerization branch reactor. The bottom of the first reactor while mixing pre-hydrated 1,3-butadiene, styrene, and n-hexane under the conditions of 16.6 g / min, 14.5 g / min, and 113.2 g / min, respectively. was continuously supplied to.
- n-butyllithium for inactivating residual impurities is continuously mixed with a static mixer under the condition of 0.114 mmol / min. Was added to.
- 2,2-bis (2-oxolanyl) propane as a polar compound
- n-butyllithium as a polymerization initiator
- additional 1,3-butadiene was added under the condition of 5.5 g / min from a supply port arranged at a height of 7/8 L from the bottom of the first reactor. The temperature inside the first reactor was maintained at 77 ° C.
- the conjugated diene-based polymer solution produced by the polymerization reaction occurring in the first reactor was continuously withdrawn from the top of the first reactor and continuously supplied to the bottom of the second reactor.
- the polymerization of the solution continuously extracted from the top of the first reactor was sufficiently stable.
- 0.027 mmol of trimethoxy (4-vinylphenyl)silane (hereinafter, also referred to as “BS-1”) as a branching agent. It was supplied under the condition of / minute.
- the temperature inside the second reactor was maintained at 82 ° C.
- a small amount of the conjugated diene polymer solution is withdrawn from the outlet of the second reactor, and after adding the antioxidant (BHT) so that the amount of the antioxidant (BHT) is 0.2 g per 100 g of the conjugated diene polymer, the solvent is used.
- the solvent is used.
- Various average molecular weights (physical characteristics 1) and Mooney viscosity (physical characteristics 2) of the obtained conjugated diene-based polymer were measured. The measurement results are shown in Table 1.
- the conjugated diene polymer solution having a branched structure generated by the branching reaction in the second reactor is continuously extracted from the top of the second reactor and continuously to the bottom of the second reactor.
- 0.029 mmol of tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine (referred to as "a" in Table 1) as a coupling modifier to the polymer solution continuously flowing in the static mixer.
- a conjugated diamine-based polymer having a branched structure was coupled by continuous addition under the condition of / min.
- the modified conjugated diene polymer (A1) has a four-branched structure derived from a branching agent, which is a compound represented by the following formula (1), in a part of the main chain, and a three-branched star derived from a coupling modifier. Shape It has a polymer structure.
- Table 1 shows the physical characteristics of the modified conjugated diene polymer (A1).
- the structure of the modified conjugated diene polymer is measured by GPC measurement for the polymer before the addition of the branching agent, the polymer after the addition of the branching agent, and the polymer after the addition of the coupling modifier. This was performed by comparing the average molecular weight and the degree of branching measured by the GPC-light scattering method with a viscosity detector.
- the structure of each sample was identified in the same manner.
- R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.
- 2 and R 3 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof, and X 1 is each.
- the halogen atom is indicated
- m indicates an integer of 0 to 2
- n indicates an integer of 0 to 3
- l indicates an integer of 0 to 3
- the sum of m, n, and l is. 3.
- Example 2 Modified conjugated diene polymer (A2) 19.2 g / min for 1,3-butadiene, 9.5 g / min for styrene, 115.4 g / min for n-hexane, 0.094 mmol / min for n-butyllithium for treatment of residual impurities, as a polymerization initiator
- N-Butyllithium was 0.208 mmol / min
- additional 1,3-butadiene was 6.4 g / min
- BS-1 as a branching agent was 0.028 mmol / min
- tetrakis as a coupling modifier (tetrakis).
- a modified conjugated diene polymer (A2) was obtained in the same manner as in Example 1 except that 3-trimethoxysilylpropyl) -1,3-propanediamine was supplied under the condition of 0.028 mmol / min.
- the physical characteristics of A2 are shown in Table 1.
- Example 3 Modified conjugated diene polymer (A3) 20.9 g / min for 1,3-butadiene, 10.4 g / min for styrene, 108.2 g / min for n-hexane, 0.062 mmol / min for n-butyllithium for treatment of residual impurities, as a polar compound. Branching of 2,2-bis (2-oxolanyl) propane at 0.067 mmol / min, n-butyllithium as a polymerization initiator at 0.151 mmol / min, and additional 1,3-butadiene at 6.9 g / min.
- BS-1 as an agent is supplied under the condition of 0.017 mmol / min, and N-benzidiene-3 is used as a coupling modifier instead of tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine.
- -(Triethoxysilyl) propane-1-amine (referred to as "b" in Table 1) was used, and the same procedure as in Example 1 was applied except that the supply condition of the coupling modifier was 0.086 mmol / min.
- a modified conjugated diene polymer (A3) was obtained. The physical characteristics of A3 are shown in Table 1.
- Example 4 Modified conjugated diene polymer (A4) 20.3 g / min for 1,3-butadiene, 5.9 g / min for styrene, 115.4 g / min for n-hexane, 0.104 mmol / min for n-butyllithium for treatment of residual impurities, as a polar compound. Branching of 2,2-bis (2-oxolanyl) propane at 0.041 mmol / min, n-butyllithium as a polymerization initiator at 0.208 mmol / min, and additional 1,3-butadiene at 6.8 g / min.
- a modified conjugated diene-based polymer (A4) was obtained in the same manner as in Example 1 except that the RAE oil was supplied under the condition that the amount of S-RAE oil was 5.0 g with respect to 100 g of the polymer.
- the physical characteristics of A4 are shown in Table 1.
- Example 6 Modified conjugated diene polymer (A6) A modified conjugated diene system similar to Example 4 except that styrene was supplied at 13.1 g / min and 2,2-bis (2-oxolanyl) propane as a polar compound was supplied at 0.058 mmol / min. A polymer (A6) was obtained. The physical characteristics of A6 are shown in Table 1.
- Example 7 Modified conjugated diene polymer (A7) 13.1 g / min of styrene, 0.035 mmol / min of 2,2-bis (2-oxolanyl) propane as a polar compound, 0.224 mmol / min of n-butyllithium as a polymerization initiator, as a branching agent BS-1 was supplied at 0.011 mmol / min, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine as a coupling modifier was supplied at 0.032 mmol / min, and the first reaction was carried out.
- a modified conjugated diene polymer (A7) was obtained in the same manner as in Example 4 except that the temperature inside the vessel was set to 83 ° C and the temperature inside the second reactor was set to 88 ° C.
- the physical characteristics of A7 are shown in Table 1.
- Modified conjugated diene polymer (A8) As a coupling modifier, instead of tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (referred to as "d” in Table 1). ) was used, and a modified conjugated diamine-based polymer (A8) was obtained in the same manner as in Example 4 except that the supply condition of the coupling modifier was 0.059 mmol / min. The physical characteristics of A8 are shown in Table 1.
- Example 9 Modified conjugated diene polymer (A9) Modified conjugated diene-based weight in the same manner as in Example 4 except that tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine as a coupling modifier was supplied under the condition of 0.014 mmol / min. A coalescence (A9) was obtained. The physical characteristics of A9 are shown in Table 1.
- Conjugated diene polymer (A10) 0.255 mmol / min for n-butyllithium as a polymerization initiator, 0.056 mmol / min for 2,2-bis (2-oxolanyl) propane as a polar compound, and 0.045 mmol / min for BS-1 as a branching agent.
- a conjugated diene polymer (A10) was obtained in the same manner as in Example 4 except that the coupling modifier was not added. The physical characteristics of A10 are shown in Table 1.
- Example 11 Modified conjugated diene polymer (A11) 15.9 g / min for 1,3-butadiene, 17.4 g / min for styrene, 0.063 mmol / min for 2,2-bis (2-oxolanyl) propane as a polar compound, n-butyl as a polymerization initiator 0.312 mmol / min for lithium, 5.3 g / min for additional 1,3-butadiene, 0.014 mmol / min for BS-1 as a branching agent, tetrakis (3-trimethoxysilyl) as a coupling modifier.
- Butadiene) -1,3-propanediene was supplied under the condition of 0.040 mmol / min, the temperature inside the first reactor was set to 83 ° C, the temperature inside the second reactor was set to 88 ° C, and the softener for rubber was used.
- a modified conjugated diene-based polymer (A11) was obtained in the same manner as in Example 4 except that S-RAE oil was not added. The physical characteristics of A11 are shown in Table 1.
- Example 12 Modified conjugated diene polymer (A12) 2,2-Bis (2-oxolanyl) propane as a polar compound at 0.052 mmol / min, n-butyllithium as a polymerization initiator at 0.167 mmol / min, and BS-1 as a branching agent at 0.008 mmol / min. / Min, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediene as a coupling modifier was supplied under the condition of 0.019 mmol / min, and the temperature inside the first reactor was set to 82 ° C. 2 Examples except that the temperature inside the reactor was set to 86 ° C.
- a modified conjugated diene-based polymer (A12) was obtained in the same manner as in 11. The physical characteristics of A12 are shown in Table 1.
- Example 13 Modified conjugated diene polymer (A13) 19.8 g / min of styrene, 0.081 mmol / min of 2,2-bis (2-oxolanyl) propane as a polar compound, 0.172 mmol / min of n-butyllithium as a polymerization initiator, as a branching agent
- a modified conjugated diene-based polymer (A13) was obtained in the same manner as in Example 12 except that BS-1 was supplied under the condition of 0.009 mmol / min.
- the physical characteristics of A13 are shown in Table 2.
- Example 15 Modified conjugated diene polymer
- A15 Modified conjugated diene-based weight in the same manner as in Example 1 except that tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine as a coupling modifier was supplied under the condition of 0.020 mmol / min. A coalescence (A15) was obtained. The physical characteristics of A15 are shown in Table 2.
- Example 16 Modified conjugated diene polymer
- A16 Modified conjugated diene-based weight in the same manner as in Example 2 except that tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine as a coupling modifier was supplied under the condition of 0.019 mmol / min. A coalescence (A16) was obtained. The physical characteristics of A16 are shown in Table 2.
- Example 17 Modified conjugated diene polymer (A17) Except that BS-1 as a branching agent was supplied at 0.015 mmol / min and tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine as a coupling modifier was supplied at 0.013 mmol / min. Obtained a modified conjugated diene-based polymer (A17) in the same manner as in Example 13. Table 2 shows the physical characteristics of A17.
- Example 18 Modified conjugated diene polymer (A18) Using n-butyllithium and piperidinolithium as the polymerization initiator, n-butyllithium was 0.062 mmol / min, piperidinolithium was 0.187 mmol / min, and n-butyllithium for treatment of residual impurities was used.
- a modified conjugated diene-based polymer (A18) was obtained in the same manner as in Example 5 except that the mixture was supplied under the condition of 0.104 mmol / min. The physical characteristics of A18 are shown in Table 2.
- Example 19 Modified conjugated diene polymer (A19) A modified conjugated diene polymer (A19) was obtained in the same manner as in Example 2 except that 2,2-bis (2-oxolanyl) propane as a polar compound was supplied under the condition of 0.136 mmol / min. .. Table 2 shows the physical characteristics of A19.
- Modified conjugated diene polymer (B1) It has an internal volume of 10 L, an internal height (L) to diameter (D) ratio (L / D) of 4.0, an inlet at the bottom and an outlet at the top, for a stirrer and temperature control.
- Two tank-type pressure vessels having a jacket were connected as a polymerization branch reactor. The bottom of the first reactor while mixing pre-hydrated 1,3-butadiene, styrene, and n-hexane under the conditions of 20.3 g / min, 5.9 g / min, and 115.4 g / min, respectively. was continuously supplied to.
- n-butyllithium for inactivating residual impurities is continuously mixed with a static mixer under the condition of 0.104 mmol / min. Was added to. Further, at the same time as supplying 1,3-butadiene, styrene, n-hexane, and n-butyllithium, 2,2-bis (2-oxolanyl) propane as a polar compound and n-butyllithium as a polymerization initiator are supplied. The reaction solution was supplied to the bottom of the first reactor while vigorously stirring with a stirrer under the conditions of 0.041 mmol / min and 0.208 mmol / min, respectively. Further, additional 1,3-butadiene was added under the condition of 6.8 g / min from the supply port arranged at a height of 7/8 L from the bottom of the first reactor. The temperature inside the first reactor was maintained at 77 ° C.
- the conjugated diene-based polymer solution produced by the polymerization reaction occurring in the first reactor was continuously withdrawn from the top of the first reactor and continuously supplied to the bottom of the second reactor.
- the temperature inside the second reactor was maintained at 82 ° C.
- a small amount of the conjugated diene polymer solution is withdrawn from the outlet of the second reactor, and after adding the antioxidant (BHT) so that the amount of the antioxidant (BHT) is 0.2 g per 100 g of the conjugated diene polymer, the solvent is used.
- BHT antioxidant
- Various average molecular weights (physical characteristics 1) of the obtained conjugated diene-based polymer and Mooney viscosity (physical characteristics 2) at 110 ° C. were measured. The physical characteristics are shown in Table 2.
- the conjugated diene polymer solution produced in the second reactor was continuously withdrawn from the top of the second reactor and continuously supplied to the bottom of the second reactor.
- tetrakis (3-trimethoxysilylpropyl) -1,3 propanediamine as a coupling modifier to the polymer solution continuously flowing in the static mixer under the condition of 0.030 mmol / min.
- the conjugated diene polymer was coupled.
- the time until the coupling modifier was added to the polymer solution flowing out from the outlet of the second reactor was 4.8 minutes, and the temperature of the polymer solution when the coupling modifier was added was It was 68 ° C.
- the difference between the temperature of the polymer solution at the outlet of the second reactor and the temperature of the polymer solution when the coupling modifier was added was 2 ° C.
- a small amount of the modified conjugated diene polymer solution after coupling was withdrawn, an antioxidant (BHT) was added so that the amount of the antioxidant (BHT) was 0.2 g per 100 g of the polymer, and then the solvent was removed.
- the amount of bound styrene (physical property 5) of the obtained modified conjugated diene polymer and the amount of 1,2-vinyl bond in bonded butadiene (physical property 6) were measured. The measurement results are shown in Table 2.
- Table 2 shows the physical characteristics of the modified conjugated diene polymer (B1).
- the structure of the modified conjugated diene polymer is identified by the average molecular weight measured by GPC measurement and the GPC-light scattering method with a viscosity detector for the polymer before and after the addition of the coupling modifier. This was done by comparing the degree of branching.
- the structure of each sample was identified in the same manner.
- B3 was supplied in the same manner as in Example 5 except that the amount of S-RAE oil was 25.0 g with respect to 100 g of the polymer to obtain a modified conjugated diene-based polymer (B3).
- the physical characteristics of B3 are shown in Table 2.
- Modified conjugated diene polymer or conjugated diene polymer (either A1 to A19 or B1 to B5): 100 parts by mass (without oil) Silica (trade name “Ultrasil 7000GR” manufactured by Ebonic Degusa) Nitrogen adsorption ratio surface area 170 m 2 / g): 75.0 parts by mass Carbon black (trade name "Seast KH (N339)” manufactured by Tokai Carbon Co., Ltd.): 5.0 Parts by mass silane coupling agent (trade name "Si75” manufactured by Ebonic Degusa, bis (triethoxysilylpropyl) disulfide): 6.0 parts by mass S-RAE oil (trade name "Process” manufactured by JX Nikko Nisseki Energy Co., Ltd.
- a modified conjugated diene polymer or conjugated diene is used as the first stage kneading using a closed kneader equipped with a temperature control device under the conditions of a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm.
- the system polymer any of A1 to A19 or B1 to B5
- filler silicon, carbon black
- silane coupling agent silane coupling agent
- S-RAE oil silane coupling agent
- zinc oxide zinc oxide
- stearic acid stearic acid
- the formulation obtained above was cooled to room temperature, an antiaging agent was added, and the mixture was kneaded again under the same conditions as the first stage kneading to improve the dispersion of silica.
- the temperature of the mixer was controlled so that the discharge temperature of the compound was adjusted to 155 to 160 ° C.
- sulfur and vulcanization accelerators 1 and 2 were added and kneaded by an open roll set at 70 ° C. Then, it was molded and vulcanized in a vulcanization press at 160 ° C. for 20 minutes.
- the rubber composition before vulcanization and the rubber composition after vulcanization were evaluated. Specifically, it was evaluated by the following method. The results are shown in Tables 3-6.
- V The edge of the sheet is smooth by 50% or less and the workability is very poor
- IV The edge of the sheet is smooth by more than 50% and 60% or less and the workability is poor.
- III The edge of the sheet is smoother than 60% and 80% or less, and the workability is good.
- II The edge of the sheet is smoother than 80% and 90% or less, and has excellent workability.
- I The edge of the sheet is 90% ultra-smooth, and the workability is very excellent.
- Viscoelastic parameters fuel efficiency and wet grip
- the viscoelasticity parameters were measured in the torsion mode using a viscoelasticity tester "ARES" manufactured by Leometrics Scientific. Each measured value was indexed with the result for the rubber composition of Example 9 as 100. Tan ⁇ measured at 50 ° C. at a frequency of 10 Hz and a strain of 3% was used as an index of low hysteresis loss, that is, fuel efficiency. The smaller the index, the better the fuel efficiency. Further, tan ⁇ measured at 0 ° C. at a frequency of 10 Hz and a strain of 1% was used as an index of wet grip property. The larger the index, the better the wet grip.
- the modified conjugated diene-based polymer or conjugated diene-based polymer of Examples 1 to 19 has a vulcanized product as compared with the modified conjugated diene-based polymer of Comparative Examples 1 to 5. It was confirmed that it has excellent low hysteresis loss and excellent wear resistance. It was also confirmed that it has excellent cohesiveness during vulcanization and exhibits good processability.
- the modified conjugated diene polymers A1, A2, A5, A15, A18, B2, or B4 shown in Tables 1 and 2 are used as raw materials, and the rubber compositions are formulated as shown below.
- Got A rubber composition was obtained by the same method as described above except that butadiene rubber was added together with the modified conjugated diene polymer in the first stage kneading. Then, the rubber composition before vulcanization and the rubber composition after vulcanization were evaluated by the same method as described above. The results are shown in Table 7.
- Modified conjugated diene polymer (A1, A2, A5, A15, A18, B2, or B4): 70 parts by mass (without oil) Butadiene rubber (trade name "BR150” manufactured by Ube Kosan): 30 parts by mass Silica (trade name "Ultrasil 7000GR” manufactured by Ebony Degusa) Nitrogen adsorption ratio surface area 170 m 2 / g): 75.0 parts by mass Carbon black (Tokai carbon) Product name "Seast KH (N339)”): 5.0 parts by mass Silane coupling agent (Product name "Si75” manufactured by Ebony Degusa, bis (triethoxysilylpropyl) disulfide): 6.0 parts by mass S-RAE oil (trade name "Process NC140” manufactured by JX Nikko Nisseki Energy Co., Ltd.): 32.0 parts by mass Zinc flower: 2.5 parts by mass Stealic acid: 2.0 parts by mass Anti-aging agent (N- (1) , 3-Dimethyl
- the modified conjugated diene polymer rubber compositions of Examples 20 to 24 have lower hysteresis in the vulcanized product as compared with the modified conjugated diene polymer rubber compositions of Comparative Examples 6 to 7. It was confirmed that it has excellent loss resistance and wear resistance. It was also confirmed that it has excellent cohesiveness during vulcanization and exhibits good processability. From this, the conjugated diene polymer of the present embodiment has the workability of the rubber composition, the low hysteresis loss property of the vulcanized product, and the abrasion resistance even when the ratio to the total rubber component in the rubber composition is small. It has been shown that sex can be improved.
- the conjugated diene-based polymer of the present invention is excellent in processability at the time of vulcanization, and the vulcanized product has abrasion resistance. And because of its excellent low hysteresis loss property, it is suitably used for applications such as tires, resin modifications, automobile interior and exterior parts, anti-vibration rubber, and footwear, and has industrial applicability.
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Abstract
Description
[1]
粘度検出器付きGPC-光散乱法測定法による分岐度が7以上であり、
結合芳香族ビニル量が1質量%以上32質量%以下であり、
結合共役ジエン中のビニル結合量が11mol%以上35mol%以下である、
共役ジエン系重合体。
[2]
前記結合芳香族ビニル量が1質量%以上30質量%以下であり、
前記結合共役ジエン中のビニル結合量が11mol%以上30mol%以下である、[1]に記載の共役ジエン系重合体。
[3]
窒素原子を有する、[1]又は[2]に記載の共役ジエン系重合体。
[4]
珪素原子を有する、[1]~[3]のいずれか1つに記載の共役ジエン系重合体。
[5]
変性基を有する、[1]~[4]のいずれか1つに記載の共役ジエン系重合体。
[6]
前記変性基が窒素原子を有し、
前記共役ジエン系重合体の変性率が70質量%以上である、[5]に記載の共役ジエン系重合体。
[7]
前記結合芳香族ビニル量(質量%)の値が、前記結合共役ジエン中のビニル結合量(mоl%)の値よりも大きい、[1]~[6]のいずれか1つに記載の共役ジエン系重合体。
[8]
3分岐以上の星形高分子構造を有し、
前記星形高分子構造の少なくとも1つの分岐鎖は、アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する部分を少なくとも1つ有し、かつ、該部分において、更に分岐している、[1]~[7]のいずれか1つに記載の共役ジエン系重合体。
[9]
アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、下記式(1)又は(2)で表される化合物に由来する部分である、[8]に記載の共役ジエン系重合体。
R2、及びR3は、各々独立して、炭素数1~20のアルキル基又は炭素数6~20のアリール基を示し、その一部分に分岐構造を有していてもよく、
X1は、各々独立してハロゲン原子を示し、
mは、0~2の整数を示し、nは、0~3の整数を示し、lは、0~3の整数を示し、
m、n、及びlの和は、3である。)
(式(2)中、R2、R3、R4、及びR5は、各々独立して、炭素数1~20のアルキル基又は炭素数6~20のアリール基を示し、その一部分に分岐構造を有していてもよく、
X2、及びX3は、各々独立してハロゲン原子を示し、
mは、0~2の整数を示し、nは、0~3の整数を示し、lは、0~3の整数を示し、
m、n、及びlの和は、3であり、
aは、0~3の整数を示し、bは、0~2の整数を示し、cは、0~3の整数を示し、
a、b、及びcの和は、3である。)
[10]
アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(1)中、R1が水素原子であり、mが0である化合物に由来する部分である、[9]に記載の共役ジエン系重合体。
[11]
アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(2)中、mが0であり、bが0である化合物に由来する部分である、[9]に記載の共役ジエン系重合体。
[12]
アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(1)中、R1が水素原子であり、mが0であり、lが0であり、nが3である化合物に由来する部分である、[9]に記載の共役ジエン系重合体。
[13]
アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(2)中、mが0であり、lが0であり、nが3であり、aが0であり、bが0であり、cが3である化合物に由来する部分である、[9]に記載の共役ジエン系重合体。
[14]
[1]~[13]のいずれか1つに記載の共役ジエン系重合体の製造方法であって、
有機リチウム化合物を重合開始剤として用いて、少なくとも共役ジエン化合物及び芳香族ビニル化合物を重合しながら、分岐化剤を添加することにより、分岐構造を有する共役ジエン系重合体を得る工程を有する、製造方法。
[15]
分岐構造を有する前記共役ジエン系重合体にカップリング変性剤を反応させることにより、変性共役ジエン系重合体を得る工程を更に有する、[14]に記載の共役ジエン系重合体の製造方法。
[16]
[1]~[13]のいずれか1つに記載の共役ジエン系重合体100質量部と、ゴム用軟化剤1.0質量部以上60質量部以下と、を含有する、共役ジエン系重合体組成物。
[17]
ゴム成分と、該ゴム成分100質量部に対して5.0質量部以上150質量部以下の充填剤と、を含み、
前記ゴム成分は、該ゴム成分の総量100質量部に対して、[1]~[13]のいずれか1つに記載の共役ジエン系重合体、又は[16]に記載の共役ジエン系重合体組成物を10質量部以上含む、
ゴム組成物。
なお、以下の本実施形態は、本発明を説明するための例示であり、本発明は以下の実施形態に限定されるものではない。本発明は、その要旨の範囲内で適宜に変形して実施することができる。
本実施形態の共役ジエン系重合体は、粘度検出器付きGPC-光散乱法測定法による分岐度(Bn)が7以上であり、結合芳香族ビニル量が1質量%以上32質量%以下であり、結合共役ジエン中のビニル結合量が11mol%以上35mol%以下である。
本実施形態の共役ジエン系重合体は、少なくとも1つの共役ジエン化合物と少なくとも1つの芳香族ビニル化合物との共重合体である。共役ジエン系重合体のミクロ構造中、結合芳香族ビニル量の下限値は、共役ジエン系重合体全体に対して、1質量%であり、好ましくは2質量%であり、より好ましくは3質量%であり、更に好ましくは5質量%である。上記下限値は7質量%であってもよい。結合芳香族ビニル量の上限値は32質量%であり、好ましくは31質量%であり、より好ましくは30質量%である。結合芳香族ビニル量の上限値は、29質量%、28質量%、27質量%、又は26質量%であってもよい。結合芳香族ビニル量が上記の範囲内にあると、共役ジエン系重合体の加硫物は耐摩耗性及び低ヒステリシスロス性に一層優れるようになる。結合芳香族ビニル量は、上記の上限値及び下限値を任意に組み合わせた範囲内としてもよく、例えば1質量%以上30質量%以下であってもよい。なお、本明細書において、「結合芳香族ビニル量」とは、共役ジエン系重合体全体に対する芳香族ビニル化合物に由来する部分の含有量を意味する。
結合共役ジエン中のビニル結合量は、共役ジエン系重合体を得る重合反応において、反応温度、及び後述する極性化合物の添加量等を適宜調整することにより制御することができる。具体的には、共役ジエン系重合体を得る重合反応における反応温度を高くすると、ビニル結合量を小さくすることができる傾向にある。また、後述する極性化合物の添加量を小さくすると、ビニル結合量を小さくすることができる傾向にある。より詳細には、後述する製造方法を用いることにより、上記範囲のビニル結合量を有する共役ジエン系重合体を容易に得ることができる。
本実施形態の共役ジエン系重合体のガラス転移温度(Tg)は、好ましくは-85℃以上であり、より好ましくは-80℃以上であり、更に好ましくは-75℃以上である。ガラス転移温度が上記の範囲内にあると、加硫する際の加工性に一層優れる。また、上記ガラス転移温度は好ましくは-35℃以下であり、より好ましくは-38℃以下である。ガラス転移温度は、-40℃以下、又は-45℃以下であってもよい。ガラス転移温度が上記の範囲内にあると、共役ジエン系重合体の加硫物の耐摩耗性及び低ヒステリシスロス性が一層優れるものとなる。ガラス転移温度は、上記の上限値及び下限値を任意に組み合わせた範囲内としてもよい。共役ジエン系重合体及び共役ジエン系重合体のガラス転移温度は、ISO 22768:2017に従って測定される。より詳細には、所定の温度範囲で昇温しながら示差走査熱量(DSC)測定をすることでDSC曲線を記録し、DSC微分曲線のピークトップ(Inflection point)をガラス転移温度とする。具体的には、後述する実施例に記載の方法により測定すればよい。
本実施形態の共役ジエン系重合体は、加工性、耐摩耗性、及び破壊強度を向上させる観点から、粘度検出器付きGPC-光散乱法測定法による分岐度(Bn)(以下、単に「分岐度(Bn)」、「分岐度」又は「Bn」ともいう。)が7以上である。
本明細書中では、固有粘度として、実施例に記載の方法により測定した値を用いた。
本実施形態の共役ジエン系重合体は、少なくとも1つの共役ジエン化合物と少なくとも1つの芳香族ビニル化合物との共重合体である。したがって、共役ジエン系重合体は、1又は複数の共役ジエン化合物と、1又は複数の芳香族ビニル化合物との共重合体であってもよい。
本実施形態の共役ジエン系重合体は、好ましくは変性基を有する。「変性基」とは、充填剤に親和性又は結合反応性を有する特定官能基を意味する。共役ジエン系重合体は、このような変性基を有することにより、充填剤との相互作用が一層向上するため、共役ジエン系重合体と充填剤とを含む共役ジエン系重合体組成物としたときに、該組成物の機械強度が一層向上する。同様の観点から、本実施形態の共役ジエン系重合体は、より好ましくは、炭素原子及び水素原子以外の原子を有する変性基を有し、更に好ましくは珪素原子又は窒素原子を有する変性基を有し、更により好ましくは窒素原子を有する変性基を有する。
本明細書中、特に断りがある場合、又は「共役ジエン系重合体又は変性共役ジエン系重合体」というように並列に記載されているなどの明確に区別されている場合を除き、「共役ジエン系重合体」は、変性されていない共役ジエン系重合体及び変性共役ジエン系重合体を包含するものである。なお、「共役ジエン系重合体又は変性共役ジエン系重合体」というように並列に記載されている場合において、「共役ジエン系重合体」とは、変性されていない共役ジエン系重合体を意味する。
本実施形態の共役ジエン系重合体は、好ましくは3分岐以上の星形高分子構造を有している。そのような共役ジエン系重合体は、分岐度が高い傾向にある。同様の観点から、共役ジエン系重合体は、より好ましくは4分岐以上、更に好ましくは6分岐以上、特に好ましくは7分岐以上の星形高分子構造を有する。
分岐化剤を添加することにより生じる分岐点は、窒素原子又は珪素原子を含むことが好ましい。すなわち、本実施形態の共役ジエン系重合体は、好ましくは窒素原子又は珪素原子を有し、窒素原子又は珪素原子を有する部分において分岐が生じている。
また、式(2)中、R2、R3、R4、及びR5は、各々独立して、炭素数1~20のアルキル基又は炭素数6~20のアリール基を示し、その一部分に分岐構造を有していてもよく、X2、及びX3は、各々独立してハロゲン原子を示し、mは、0~2の整数を示し、nは、0~3の整数を示し、lは、0~3の整数を示し、m、n、及びlの和は、3であり、aは、0~3の整数を示し、bは、0~2の整数を示し、cは、0~3の整数を示し、a、b、及びcの和は、3である。
式(1)又は(2)で表される化合物の例示は後述する。
本実施形態の共役ジエン系重合体のGPC測定法により測定される重量平均分子量は、好ましくは30×104以上であり、より好ましくは40×104以上であり、更に好ましくは45×104以上であり、特に好ましくは60×104以上である。GPC測定法により測定される重量平均分子量が上記の範囲内にあると、加硫する際の加工性に一層優れ、その加硫物が低ヒステリシスロス性に一層優れる。また、上記重量平均分子量は、好ましくは300×104以下であり、より好ましくは250×104以下であり、更に好ましくは180×104以下であり、更により好ましくは150×104以下である。上記重量平均分子量が上記の範囲内にあると、その加硫物において充填剤の分散性に一層優れ、実用上十分な破壊特性が得られる傾向にある。上記の重量平均分子量は、上記の上限値及び下限値を任意に組み合わせた範囲内としてもよい。変性共役ジエン系重合体及び後述する共役ジエン系重合体のGPC測定法により測定される重量平均分子量は、詳細には、後述する実施例に記載の方法により測定される。
本実施形態の共役ジエン系重合体の、100℃で測定されるムーニー粘度は、好ましくは50以上180以下であり、より好ましくは70以上160以下である。上記のムーニー粘度が上記の範囲内にあることにより、加硫する際の加工性と、その加硫物の耐摩耗性が一層向上する傾向にある。変性共役ジエン系重合体及び後述する共役ジエン系重合体のムーニー粘度は、後述する実施例に記載の方法により測定することができる。
本実施形態の効果を有効かつ確実に奏する観点から、本実施形態の共役ジエン系重合体は、好ましくは窒素原子又は珪素原子を有する。その中でも、下記式(i)又は下記式(A)~(D)のいずれかで表される化合物に由来する構造を含むことがより好ましい。共役ジエン系重合体は、更に好ましくは、下記式(i)又は下記式(A)~(D)のいずれかで表される化合物をカップリング変性剤として用いて変性されたものである。下記式(i)又は下記式(A)~(D)のいずれかで表される化合物の例示は後述する。
また、R9が1価の炭化水素基の場合、R8と互いに結合した環状構造であってもよい。ただし、R9に結合しているNとR8とが直接結合している場合にのみ、R9は水素原子であってもよい。
上述した共役ジエン系重合体は、上述した構成を有する重合体が得られる方法であれば、いかなる方法によっても製造することができるが、以下に詳述する、本実施形態の共役ジエン系重合体の製造方法を用いることにより、確実かつ簡便に上述した共役ジエン系重合体を得ることができる。
上記重合分岐工程は、後述する有機リチウム化合物を重合開始剤とし、少なくとも共役ジエン化合物及び芳香族ビニル化合物を重合しながら、分岐化剤を添加することにより、分岐構造を有する共役ジエン系重合体を得る工程である。したがって、重合分岐工程において、分岐化剤を添加する前は、少なくとも共役ジエン化合物及び芳香族ビニル化合物の重合反応が主反応であり、分岐化剤を添加した後に、分岐反応が開始する。
そのため、重量平均分子量40×104以上、45×104以上、又は60×104以上の比較的高分子量の重合体において、変性率を高く設定したい場合、重合開始末端側ではなく、重量終了末端側に窒素原子を反応させることが好ましい。すなわち、比較的高分子量であって、かつ、両末端に窒素原子を含む重合体は製造しにくい傾向にある。重量平均分子量やカップリング剤及び変性剤の構造にもよるが、終了末端側のみに窒素原子を有する場合、重合体の窒素含有量は3質量ppm~500質量ppmが一般的である。
また、式(2)中、R2、R3、R4、及びR5は、各々独立して、炭素数1~20のアルキル基又は炭素数6~20のアリール基を示し、その一部分に分岐構造を有していてもよく、X2、及びX3は、各々独立してハロゲン原子を示し、mは、0~2の整数を示し、nは、0~3の整数を示し、lは、0~3の整数を示し、m、n、及びlの和は、3であり、aは、0~3の整数を示し、bは、0~2の整数を示し、cは、0~3の整数を示し、a、b、及びcの和は、3である。
本実施形態の製造方法は、好ましくは、上記の重合分岐工程により得られた分岐構造を有する共役ジエン系重合体を、カップリング変性剤と反応させることにより、変性共役ジエン系重合体を得るカップリング工程を有する。このようなカップリング工程を有すると、重合分岐工程により得られた分岐構造を有する共役ジエン系重合体を、充填剤に親和性又は結合反応性を有する特定官能基により変性させることができる。また、複数の共役ジエン系重合体をカップリングさせることができるため、分岐度(Bn)の高い共役ジエン系重合体を確実かつ簡便に得ることができる。したがって、このようなカップリング工程を有する製造方法は、一層確実かつ簡便に上述した本実施形態の共役ジエン系重合体を得ることができる。
また、R9が1価の炭化水素基の場合、R8と互いに結合した環状構造であってもよい。ただし、R9に結合しているNとR8とが直接結合している場合のみ、R9は水素原子であってもよい。
本実施形態の共役ジエン系重合体組成物は、共役ジエン系重合体100質量部と、ゴム用軟化剤1.0質量部以上60質量部以下とを、含有する。本実施形態の共役ジエン系重合体に、ゴム用軟化剤を添加することにより、充填剤等を配合した場合の加工性が一層向上した組成物を得ることができる。
本実施形態のゴム組成物は、ゴム成分と、該ゴム成分100質量部に対して5.0質量部以上150質量部以下の充填剤とを含み、ゴム成分は、該ゴム成分の総量100質量部に対して、本実施形態の共役ジエン系重合体又は共役ジエン系重合体組成物を10質量部以上含む。本実施形態の共役ジエン系重合体を含むゴム成分に充填剤を分散させることにより、加硫する際の加工性に一層優れ、その加硫物の低ヒステリシスロス性、破壊特性、及び耐摩耗性が一層優れるゴム組成物を得ることができる。また、ゴム成分が本実施形態の共役ジエン系重合体又は共役ジエン系重合体組成物を所定の割合で含むことにより、省燃費性能、加工性、及び耐摩耗性が一層向上する。
共役ジエン系重合体又は変性共役ジエン系重合体を試料として、ポリスチレン系ゲルを充填剤としたカラムを3本連結したGPC測定装置(東ソー社製の商品名「HLC-8320GPC」)、及び屈折率(RI)検出器(東ソー社製の商品名「HLC8020」)を用いてGPC測定を行った。標準ポリスチレンを用いて得られる検量線に基づいて、重量平均分子量(Mw)、数平均分子量(Mn)、及び分子量分布(Mw/Mn)を求めた。
溶離液は5mmol/Lのトリエチルアミン-THF(テトラヒドロフラン)溶液を用いた。カラムは、東ソー社製の商品名「TSKgel SuperMultiporeHZ-H」を3本接続し、その前段にガードカラムとして東ソー社製の商品名「TSKguardcolumn SuperMP(HZ)-H」を接続して用いた。
測定用の試料10mgを10mLのTHFに溶解して測定溶液とし、測定溶液10μLをGPC測定装置に注入して、オーブン温度40℃、THF流量0.35mL/分の条件で測定した。
測定した結果を当該試料の各平均分子量とした。
共役ジエン系重合体又は変性共役ジエン系重合体を試料として、ムーニー粘度計(上島製作所社製の商品名「VR1132」)を用い、ISO 289に準拠して、L形ローターを用いてムーニー粘度を測定した。
測定温度は、共役ジエン系重合体を試料とする場合には110℃とし、変性共役ジエン系重合体を試料とする場合には100℃とした。
試料を1分間試験温度で予熱した後、ローターを2rpmで回転させ、4分後のトルクを測定することで、ムーニー粘度(ML(1+4))を測定した。
共役ジエン系重合体又は変性共役ジエン系重合体の分岐度(Bn)は、粘度検出器付きGPC-光散乱法測定法によって以下のとおり測定した。共役ジエン系重合体又は変性共役ジエン系重合体を試料として用い、ポリスチレン系ゲルを充填剤としたカラムを3本連結したGPC測定装置(Malvern社製の商品名「GPCmax VE-2001」)と、光散乱検出器、RI検出器、及び粘度検出器がこの順番に接続されている検出器(Malvern社製の商品名「TDA305」)とを用いた。標準ポリスチレンに基づいて、光散乱検出器及びRI検出器の結果から絶対分子量を求め、RI検出器及び粘度検出器の結果から固有粘度を求めた。
溶離液は5mmol/Lのトリエチルアミン-テトラヒドロフラン溶液を用いた。
カラムは、東ソー社製の商品名「TSKgel G4000HXL」、「TSKgel G5000HXL」、及び「TSKgel G6000HXL」をこの順に接続して用いた。
測定用の試料20mgを10mLのTHFに溶解して測定溶液とし、測定溶液100μLをGPC測定装置に注入して、オーブン温度40℃、THF流量1mL/分の条件で測定した。
各試料について、同一の絶対分子量Mを有する直鎖状の重合体の固有粘度[η0]を[η0]=-3.626M0.730の式から算出し、測定された固有粘度[η]と、算出した固有粘度[η0]の比([η]/[η0])を収縮因子(g’)とした。
その後、得られた収縮因子(g’)を用いてg’=6Bn/{(Bn+1)(Bn+2)}の式から分岐度(Bn)を算出した。
変性共役ジエン系重合体における変性率をカラム吸着GPC法で以下のとおり測定した。カラム吸着GPC法とは、シリカ系ゲルを充填剤としたGPCカラムに、変性共役ジエン系重合体中の変性した塩基性重合体成分が吸着しやすい特性を利用して、変性重合体の変性率を求める方法である。
変性共役ジエン系重合体を試料として、試料及び低分子量内部標準ポリスチレンを含む試料溶液をポリスチレン系カラムで測定した。また、同様の試料溶液をシリカ系カラムで測定した。ポリスチレン系カラムを用いた測定により得られるクロマトグラムと、シリカ系カラムを用いた測定により得られるクロマトグラムの差分を求めることにより、変性共役ジエン系重合体のシリカ系カラムへの吸着量を測定し、変性率を求めた。
(ポリスチレン系カラムを用いたGPC測定条件)
東ソー社製の商品名「HLC-8320GPC」、及びRI検出器(東ソー社製の商品名「HLC8020」)を用いてGPC測定を行った。
5mmol/Lのトリエチルアミン-THF溶液を溶離液として用い、試料溶液10μLをGPC装置に注入し、カラムオーブン温度40℃、THF流量0.35mL/分の条件でクロマトグラムを得た。
カラムは、東ソー社製の商品名「TSKgel SuperMultiporeHZ-H」を3本接続し、その前段にガードカラムとして東ソー社製の商品名「TSKguardcolumn SuperMP(HZ)-H」を接続して使用した。
(シリカ系カラムを用いたGPC測定条件)
東ソー社製の商品名「HLC-8320GPC」、及びRI検出器(東ソー社製の商品名「HLC8020」)を用いてGPC測定を行った。
THFを溶離液として用い、試料溶液50μLを装置に注入し、カラムオーブン温度40℃、THF流量0.5ml/分の条件でクロマトグラムを得た。
カラムは、アジレント社製の商品名「Zorbax PSM-1000S」、「PSM-300S」、「PSM-60S」をこの順に接続し、その前段にガードカラムとして商品名「DIOL 4.6×12.5mm 5micron」を接続して用いた。
変性率(質量%)=[1-(P2×P3)/(P1×P4)]×100
(ただし、P1+P2=P3+P4=100)
共役ジエン系重合体又は変性共役ジエン系重合体を試料として、試料100mgをクロロホルム100mLに溶解して測定試料とした。各試料を分光光度計(島津製作所社製の商品名「UV-2450」)により測定し、吸光スペクトルを得た。スチレンのフェニル基に由来する紫外線(254nm付近)の吸光量から、共役ジエン系重合体又は変性共役ジエン系重合体100質量%に対しての結合スチレン量(質量%)を算出した。
共役ジエン系重合体又は変性共役ジエン系重合体を試料として、試料50mgを10mLの二硫化炭素に溶解して測定試料とした。各試料の赤外線スペクトルを600~1000cm-1の範囲で、フーリエ変換赤外分光光度計(日本分光社製の商品名「FT-IR230」)により測定した。ハンプトンの方法(R.R.Hampton,Analytical Chemistry 21,923(1949)に記載の方法)に従い、所定の波数における吸光度から結合ブタジエン中の1,2-ビニル結合量(mol%)を求めた。
共役ジエン系重合体又は変性共役ジエン系重合体を試料として、ポリスチレン系ゲルを充填剤としたカラムを3本連結したGPC-光散乱測定装置(マルバーン社製の商品名「Viscotek TDAmax」)を用いてGPC測定を行い、検出器により測定される溶液粘度及び光散乱に基づいて重量平均分子量を求めた。以下、このようなGPC-光散乱法測定法により測定される重量平均分子量を「絶対分子量」ともいう。
溶離液として、トリエチルアミン5mLをテトラヒドロフラン1Lに混合させた溶液を用いた。
カラムは、ガードカラム:東ソー社製の商品名「TSKguardcolumn HHR-H」、カラム:東ソー社製の商品名「TSKgel G6000HHR」、「TSKgel G5000HHR」、及び「TSKgel G4000HHR」をこの順に接続して用いた。
測定用の試料10mgを20mLのTHFに溶解して測定溶液とし、測定溶液200μLをGPC測定装置に注入して、オーブン温度40℃、THF流量1.0mL/分の条件で測定した。
共役ジエン系重合体又は変性共役ジエン系重合体を試料として、ISO 22768:2006に準拠して、示差走査熱量計(マックサイエンス社製の商品名「DSC3200S」)を用いてDSC測定を行った。ヘリウム50mL/分の流通下、20℃/分で-100℃から昇温しながらDSC曲線を記録し、DSC微分曲線のピークトップ(Inflection point)をガラス転移温度(Tg)とした。
内容積が10Lで、内部の高さ(L)と直径(D)との比(L/D)が4.0であり、底部に入口、頂部に出口を有し、攪拌機及び温度制御用のジャケットを有する槽型圧力容器を重合分岐反応器として2基連結した。
予め水分除去した、1,3-ブタジエン、スチレン、及びn-ヘキサンをそれぞれ、16.6g/分、14.5g/分、及び113.2g/分の条件で混合しながら第1反応器の底部に連続的に供給した。なお、該供給の際、混合溶液が第1反応器に入る直前に、残存不純物を不活性化するためのn-ブチルリチウムを0.114mmol/分の条件で、スタティックミキサーにより混合しながら連続的に添加した。また、1,3-ブタジエン、スチレン、n-ヘキサン、及びn-ブチルリチウムの供給と同時に、極性化合物としての2,2-ビス(2-オキソラニル)プロパン、及び重合開始剤としてのn-ブチルリチウムを、それぞれ0.080mmol/分、及び0.172mmol/分の条件で、反応溶液を攪拌機で激しく撹拌しながら第1反応器の底部へ供給した。更に第1反応器の底部から高さ7/8Lの部位に配置された供給口より、追加の1,3-ブタジエンを5.5g/分の条件で添加した。なお、第1反応器内の温度は77℃に保持した。
1,3-ブタジエンを19.2g/分、スチレンを9.5g/分、n-ヘキサンを115.4g/分、残存不純物処理用のn-ブチルリチウムを0.094mmol/分、重合開始剤としてのn-ブチルリチウムを0.208mmol/分、追加の1,3-ブタジエンを6.4g/分、分岐化剤としてのBS-1を0.028mmol/分、及びカップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.028mmol/分の条件で供給したこと以外は、実施例1と同様にして、変性共役ジエン系重合体(A2)を得た。A2の物性を表1に示す。
1,3-ブタジエンを20.9g/分、スチレンを10.4g/分、n-ヘキサンを108.2g/分、残存不純物処理用のn-ブチルリチウムを0.062mmol/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.067mmol/分、重合開始剤としてのn-ブチルリチウムを0.151mmol/分、追加の1,3-ブタジエンを6.9g/分、分岐化剤としてのBS-1を0.017mmol/分の条件で供給し、かつ、カップリング変性剤としてテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンに代えて、N-ベンジリデン-3-(トリエトキシシリル)プロパン-1-アミン(表1中、「b」という。)を用い、カップリング変性剤の供給条件を0.086mmol/分としたこと以外は、実施例1と同様にして、変性共役ジエン系重合体(A3)を得た。A3の物性を表1に示す。
1,3-ブタジエンを20.3g/分、スチレンを5.9g/分、n-ヘキサンを115.4g/分、残存不純物処理用のn-ブチルリチウムを0.104mmol/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.041mmol/分、重合開始剤としてのn-ブチルリチウムを0.208mmol/分、追加の1,3-ブタジエンを6.8g/分、分岐化剤としてのBS-1を0.010mmol/分、カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.030mmol/分、ゴム用軟化剤としてのS-RAEオイルを重合体100gに対しS-RAEオイルが5.0gとなるような条件で供給したこと以外は、実施例1と同様にして、変性共役ジエン系重合体(A4)を得た。A4の物性を表1に示す。
カップリング変性剤としてテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンに代えて、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタン(表1中、「c」という。)を用い、かつ、カップリング変性剤の供給条件を0.059mmol/分としたこと以外は、実施例4と同様にして、変性共役ジエン系重合体(A5)を得た。A5の物性を表1に示す。
スチレンを13.1g/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.058mmol/分の条件で供給したこと以外は、実施例4と同様にして、変性共役ジエン系重合体(A6)を得た。A6の物性を表1に示す。
スチレンを13.1g/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.035mmol/分、重合開始剤としてのn-ブチルリチウムを0.224mmol/分、分岐化剤としてのBS-1を0.011mmol/分、カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.032mmol/分の条件で供給し、かつ、第1反応器内の温度を83℃とし、第2反応器内の温度を88℃としたこと以外は、実施例4と同様にして、変性共役ジエン系重合体(A7)を得た。A7の物性を表1に示す。
カップリング変性剤としてテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンに代えて、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン(表1中、「d」という。)を用い、かつ、カップリング変性剤の供給条件を0.059mmol/分としたこと以外は、実施例4と同様にして、変性共役ジエン系重合体(A8)を得た。A8の物性を表1に示す。
カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.014mmol/分の条件で供給したこと以外は、実施例4と同様にして、変性共役ジエン系重合体(A9)を得た。A9の物性を表1に示す。
重合開始剤としてのn-ブチルリチウムを0.255mmol/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.056mmol/分、分岐化剤としてのBS-1を0.045mmol/分とし、カップリング変性剤を添加しないこと以外は、実施例4と同様にして、共役ジエン系重合体(A10)を得た。A10の物性を表1に示す。
1,3-ブタジエンを15.9g/分、スチレンを17.4g/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.063mmol/分、重合開始剤としてのn-ブチルリチウムを0.312mmol/分、追加の1,3-ブタジエンを5.3g/分、分岐化剤としてのBS-1を0.014mmol/分、カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.040mmol/分の条件で供給し、第1反応器内の温度を83℃とし、第2反応器内の温度を88℃とし、かつゴム用軟化剤としてのS-RAEオイルを加えなかったこと以外は、実施例4と同様にして、変性共役ジエン系重合体(A11)を得た。A11の物性を表1に示す。
極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.052mmol/分、重合開始剤としてのn-ブチルリチウムを0.167mmol/分、分岐化剤としてのBS-1を0.008mmol/分、カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.019mmol/分の条件で供給し、第1反応器内の温度を82℃とし、第2反応器内の温度を86℃とし、かつゴム用軟化剤としてのS-RAEオイルを重合体100gに対しS-RAEオイルが25.0gとなるような条件で供給したこと以外は、実施例11と同様にして、変性共役ジエン系重合体(A12)を得た。A12の物性を表1に示す。
スチレンを19.8g/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.081mmol/分、重合開始剤としてのn-ブチルリチウムを0.172mmol/分、分岐化剤としてのBS-1を0.009mmol/分の条件で供給したこと以外は、実施例12と同様にして、変性共役ジエン系重合体(A13)を得た。A13の物性を表2に示す。
残存不純物処理用のn-ブチルリチウムを0.104mmol/分、重合開始剤としてのn-ブチルリチウムを0.177mmol/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.086mmol/分、分岐化剤としてのBS-1を0.019mmol/分の条件で供給し、かつ、カップリング変性剤としてテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンに代えて、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサンを用い、カップリング変性剤の供給条件を0.118mmol/分としたこと以外は、実施例3と同様にして、変性共役ジエン系重合体(A14)を得た。A14の物性を表2に示す。
カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.020mmol/分の条件で供給したこと以外は、実施例1と同様にして、変性共役ジエン系重合体(A15)を得た。A15の物性を表2に示す。
カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.019mmol/分の条件で供給したこと以外は、実施例2と同様にして、変性共役ジエン系重合体(A16)を得た。A16の物性を表2に示す。
分岐化剤としてのBS-1を0.015mmol/分、カップリング変性剤としてのテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンを0.013mmol/分の条件で供給したこと以外は、実施例13と同様にして、変性共役ジエン系重合体(A17)を得た。A17の物性を表2に示す。
重合開始剤としてn-ブチルリチウム及びピペリジノリチウムを用い、かつ、n-ブチルリチウムを0.062mmol/分、ピペリジノリチウムを0.187mmol/分、残存不純物処理用のn-ブチルリチウムを0.104mmol/分の条件で供給したこと以外は、実施例5と同様にして、変性共役ジエン系重合体(A18)を得た。A18の物性を表2に示す。
極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.136mmol/分の条件で供給したこと以外は、実施例2と同様にして、変性共役ジエン系重合体(A19)を得た。A19の物性を表2に示す。
内容積が10Lで、内部の高さ(L)と直径(D)との比(L/D)が4.0であり、底部に入口、頂部に出口を有し、攪拌機及び温度制御用のジャケットを有する槽型圧力容器を重合分岐反応器として2基連結した。
予め水分除去した、1,3-ブタジエン、スチレン、及びn-ヘキサンをそれぞれ、20.3g/分、5.9g/分、及び115.4g/分の条件で混合しながら第1反応器の底部に連続的に供給した。なお、該供給の際、混合溶液が第1反応器に入る直前に、残存不純物を不活性化するためのn-ブチルリチウムを0.104mmol/分の条件で、スタティックミキサーにより混合しながら連続的に添加した。また、1,3-ブタジエン、スチレン、n-ヘキサン、及びn-ブチルリチウムの供給と同時に、極性化合物としての2,2-ビス(2-オキソラニル)プロパン、及び重合開始剤としてn-ブチルリチウムを、それぞれ、0.041mmol/分、及び0.208mmol/分の条件で、反応溶液を攪拌機で激しく撹拌しながら第1反応器の底部へ供給した。更に第1反応器の底部から高さ7/8Lの部位に配置された供給口より、追加の1,3-ブタジエンを6.8g/分の条件で添加した。なお、第1反応器内の温度は77℃に保持した。
カップリング変性剤としてテトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミンに代えて、2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンを用い、かつ、カップリング変性剤の供給条件を0.059mmol/分としたこと以外は、比較例1と同様にして、変性共役ジエン系重合体(B2)を得た。B2の物性を表2に示す。
1,3-ブタジエンを15.7g/分、スチレンを22.7g/分、n-ヘキサンを106g/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.271mmol/分、重合開始剤としてのn-ブチルリチウムを0.177mmol/分、追加の1,3-ブタジエンを6.7g/分、分岐化剤としてのBS-1を0.019mmol/分、カップリング変性剤としての2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンを0.054mmol/分の条件で供給し、さらにゴム用軟化剤としてのS-RAEオイルを重合体100gに対しS-RAEオイルが25.0gとなるような条件で供給したこと以外は、実施例5と同様にして、変性共役ジエン系重合体(B3)を得た。B3の物性を表2に示す。
1,3-ブタジエンを19.5g/分、スチレンを12.7g/分、極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.451mmol/分、重合開始剤としてのn-ブチルリチウムを0.364mmol/分、追加の1,3-ブタジエンを4.9g/分、分岐化剤としてのBS-1を7.3mmol/分の条件で供給し、かつ、カップリング変性剤として2,2-ジメトキシ-1-(3-トリメトキシシリルプロピル)-1-アザ-2-シラシクロペンタンに代えて、ジメチルアミノプロピルトリメトキシシラン(表2中、「e」という。)を用い、カップリング変性剤の供給条件を0.18mmol/分とし、さらにゴム用軟化剤としてのS-RAEオイルを重合体100gに対しS-RAEオイルが10.0gとなるような条件で供給したこと以外は、比較例3と同様にして、変性共役ジエン系重合体(B4)を得た。B4の物性を表2に示す。
極性化合物としての2,2-ビス(2-オキソラニル)プロパンを0.206mmol/分の条件で供給したこと以外は、実施例19と同様にして、変性共役ジエン系重合体(B5)を得た。B5の物性を表2に示す。
表1~2に示す変性共役ジエン系重合体又は共役ジエン系重合体A1~A19及びB1~B5を原料として、以下に示す配合で、それぞれゴム組成物を得た。
シリカ(エボニック デグサ社製の商品名「Ultrasil 7000GR」窒素吸着比表面積170m2/g):75.0質量部
カーボンブラック(東海カーボン社製の商品名「シーストKH(N339)」):5.0質量部
シランカップリング剤(エボニック デグサ社製の商品名「Si75」、ビス(トリエトキシシリルプロピル)ジスルフィド):6.0質量部
S-RAEオイル(JX日鉱日石エネルギー社製の商品名「プロセスNC140」):32.0質量部
亜鉛華:2.5質量部
ステアリン酸:2.0質量部
老化防止剤(N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン):2.0質量部
硫黄:1.7質量部
加硫促進剤1(N-シクロヘキシル-2-ベンゾチアジルスルフィンアミド):1.7質量部
加硫促進剤2(ジフェニルグアニジン):2.0質量部
実施例及び比較例に示す方法で製造した未加硫の変性共役ジエン系重合体又は共役ジエン系重合体に関し、加圧ニーダーから排出した直後(混練り1段目における加圧ニーダーによる混練りが終了し、排出された直後)のまとまり(形状)について目視で観察し、以下の基準に基づきパネラー一人当たり5点を満点とし評価した。まとまり性は加硫物の加工性の指標である。
V :シートの端部分が50%以下平滑であり、加工性が非常に悪い
IV :シートの端部分が50%超60%以下平滑であり、加工性が悪い。
III:シートの端部分が60%超80%以下平滑であり、加工性が良い。
II :シートの端部分が80%超90%以下平滑であり、加工性が優れる。
I :シートの端部分が90%超平滑であり、加工性が非常に優れる。
レオメトリックス・サイエンティフィック社製の粘弾性試験機「ARES」を使用し、ねじりモードで粘弾性パラメータを測定した。各々の測定値は、実施例9のゴム組成物に対する結果を100として指数化した。50℃において周波数10Hz、ひずみ3%で測定したtanδを、低ヒステリシスロス性、すなわち省燃費性の指標とした。指数が小さいほど省燃費性が良好であることを示す。また、0℃において周波数10Hz、ひずみ1%で測定したtanδを、ウェットグリップ性の指標とした。指数が大きいほどウェットグリップ性が良好であることを示す。
JIS K6251の引張試験法に準拠し、引張強度及び引張伸びを測定した。各々の測定値は、実施例9の結果を100として標準化した。数値が大きいほど引張強度、引張伸びが良好であることを示す。
アクロン摩耗試験機(安田精機製作所社製)を用い、JIS K6264-2に準拠して、荷重44.4N、1000回転後の摩耗量を測定した。各々の測定値は、実施例9の結果を100として標準化した。数値が大きいほど耐摩耗性が良好であることを示し、かかる数値が90を超えるものを耐摩耗性が優れるものとして評価した。
変性共役ジエン系重合体又は共役ジエン系重合体を、常温・常圧下で1か月間保管した後、保管後のムーニー粘度を測定し、重合直後に測定したムーニー粘度との差異を算出した。表中、「δムーニー粘度」と示す。数値が小さいものほど、経時変化が少なく、品質安定性が優れていることを示す。
ブタジエンゴム(宇部興産製の商品名「BR150」):30質量部
シリカ(エボニック デグサ社製の商品名「Ultrasil 7000GR」窒素吸着比表面積170m2/g):75.0質量部
カーボンブラック(東海カーボン社製の商品名「シーストKH(N339)」):5.0質量部
シランカップリング剤(エボニック デグサ社製の商品名「Si75」、ビス(トリエトキシシリルプロピル)ジスルフィド):6.0質量部
S-RAEオイル(JX日鉱日石エネルギー社製の商品名「プロセスNC140」):32.0質量部
亜鉛華:2.5質量部
ステアリン酸:2.0質量部
老化防止剤(N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン):2.0質量部
硫黄:1.7質量部
加硫促進剤1(N-シクロヘキシル-2-ベンゾチアジルスルフィンアミド):1.7質量部
加硫促進剤2(ジフェニルグアニジン):2.0質量部
Claims (17)
- 粘度検出器付きGPC-光散乱法測定法による分岐度が7以上であり、
結合芳香族ビニル量が1質量%以上32質量%以下であり、
結合共役ジエン中のビニル結合量が11mol%以上35mol%以下である、
共役ジエン系重合体。 - 前記結合芳香族ビニル量が1質量%以上30質量%以下であり、
前記結合共役ジエン中のビニル結合量が11mol%以上30mol%以下である、請求項1に記載の共役ジエン系重合体。 - 窒素原子を有する、請求項1又は2に記載の共役ジエン系重合体。
- 珪素原子を有する、請求項1~3のいずれか一項に記載の共役ジエン系重合体。
- 変性基を有する、請求項1~4のいずれか一項に記載の共役ジエン系重合体。
- 前記変性基が窒素原子を有し、
前記共役ジエン系重合体の変性率が70質量%以上である、請求項5に記載の共役ジエン系重合体。 - 前記結合芳香族ビニル量(質量%)の値が、前記結合共役ジエン中のビニル結合量(mоl%)の値よりも大きい、請求項1~6のいずれか一項に記載の共役ジエン系重合体。
- 3分岐以上の星形高分子構造を有し、
前記星形高分子構造の少なくとも1つの分岐鎖は、アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する部分を少なくとも1つ有し、かつ、該部分において、更に分岐している、請求項1~7のいずれか一項に記載の共役ジエン系重合体。 - アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、下記式(1)又は(2)で表される化合物に由来する部分である、請求項8に記載の共役ジエン系重合体。
R2、及びR3は、各々独立して、炭素数1~20のアルキル基又は炭素数6~20のアリール基を示し、その一部分に分岐構造を有していてもよく、
X1は、各々独立してハロゲン原子を示し、
mは、0~2の整数を示し、nは、0~3の整数を示し、lは、0~3の整数を示し、
m、n、及びlの和は、3である。)
(式(2)中、R2、R3、R4、及びR5は、各々独立して、炭素数1~20のアルキル基又は炭素数6~20のアリール基を示し、その一部分に分岐構造を有していてもよく、
X2、及びX3は、各々独立してハロゲン原子を示し、
mは、0~2の整数を示し、nは、0~3の整数を示し、lは、0~3の整数を示し、
m、n、及びlの和は、3であり、
aは、0~3の整数を示し、bは、0~2の整数を示し、cは、0~3の整数を示し、
a、b、及びcの和は、3である。) - アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(1)中、R1が水素原子であり、mが0である化合物に由来する部分である、請求項9に記載の共役ジエン系重合体。
- アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(2)中、mが0であり、bが0である化合物に由来する部分である、請求項9に記載の共役ジエン系重合体。
- アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(1)中、R1が水素原子であり、mが0であり、lが0であり、nが3である化合物に由来する部分である、請求項9に記載の共役ジエン系重合体。
- アルコキシシリル基又はハロシリル基を含むビニル系単量体に由来する前記部分の少なくとも1つは、前記式(2)中、mが0であり、lが0であり、nが3であり、aが0であり、bが0であり、cが3である化合物に由来する部分である、請求項9に記載の共役ジエン系重合体。
- 請求項1~13のいずれか一項に記載の共役ジエン系重合体の製造方法であって、
有機リチウム化合物を重合開始剤として用いて、少なくとも共役ジエン化合物及び芳香族ビニル化合物を重合しながら、分岐化剤を添加することにより、分岐構造を有する共役ジエン系重合体を得る工程を有する、製造方法。 - 分岐構造を有する前記共役ジエン系重合体にカップリング変性剤を反応させることにより、変性共役ジエン系重合体を得る工程を更に有する、請求項14に記載の共役ジエン系重合体の製造方法。
- 請求項1~13のいずれか一項に記載の共役ジエン系重合体100質量部と、ゴム用軟化剤1.0質量部以上60質量部以下と、を含有する、共役ジエン系重合体組成物。
- ゴム成分と、該ゴム成分100質量部に対して5.0質量部以上150質量部以下の充填剤と、を含み、
前記ゴム成分は、該ゴム成分の総量100質量部に対して、請求項1~13のいずれか一項に記載の共役ジエン系重合体、又は請求項16に記載の共役ジエン系重合体組成物を10質量部以上含む、
ゴム組成物。
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