WO2016039381A1 - 共役ジエン重合体及び共役ジエン重合体組成物 - Google Patents
共役ジエン重合体及び共役ジエン重合体組成物 Download PDFInfo
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
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- 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
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- 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
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- 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
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- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Definitions
- the present invention relates to a conjugated diene polymer capable of giving a conjugated diene polymer composition having excellent durability, and a conjugated diene polymer composition containing the conjugated diene polymer.
- the characteristics required for automobile tires include fuel efficiency, durability, and grip.
- conjugated diene polymer compositions containing conjugated diene polymers such as polybutadiene and styrene-butadiene copolymers and reinforcing agents have been proposed as polymer compositions used for automobile tires. .
- Patent Document 1 n-butyllithium is used as a polymerization initiator in a hydrocarbon solvent, butadiene is homopolymerized, or a polymer obtained by copolymerizing butadiene and styrene is used as a reinforcing agent.
- a polymer composition containing silica has been proposed.
- Patent Document 2 discloses a polymer obtained by blending silica and carbon black as a reinforcing agent with a polymer obtained by copolymerizing butadiene and styrene using n-butyllithium as a polymerization initiator in a hydrocarbon solvent. Compositions have been proposed.
- the problem to be solved by the present invention is a conjugated diene polymer capable of providing a conjugated diene polymer composition having excellent durability, and a conjugated diene polymer composition containing the conjugated diene polymer. To provide things.
- One aspect of the present invention relates to a conjugated diene polymer containing a conjugated diene as a monomer unit.
- the conjugated diene polymer is a polymerization reaction in a polymerization solution containing a conjugated diene, at least one compound selected from the group consisting of limonene, terpinene and terpinolene, and an organic alkali metal compound as a polymerization initiator. Obtained by.
- the Z-average molecular weight of the conjugated diene polymer is Mz
- the number-average molecular weight of the conjugated diene polymer is Mn
- the Z-average molecular weight and the number-average molecular weight are (standard) polystyrene-converted values obtained by gel permeation chromatography.
- Mz / Mn is 1.7 or more and 4.0 or less.
- the conjugated diene polymer is a hydrocarbon solution containing at least one compound selected from the group consisting of limonene, terpinene and terpinolene, Using an organic alkali metal compound as a polymerization initiator, A polymer obtained by polymerizing a conjugated diene or copolymerizing a conjugated diene and a comonomer may be used.
- Another aspect of the present invention includes the conjugated diene polymer and a reinforcing agent, and the content of the reinforcing agent is 10 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the conjugated diene polymer.
- the following relates to a conjugated diene polymer composition.
- a conjugated diene polymer capable of giving a conjugated diene polymer composition having excellent durability and a conjugated diene polymer composition containing the conjugated diene polymer can be obtained.
- the conjugated diene polymer includes a monomer unit derived from a conjugated diene, and may further include a monomer unit derived from a comonomer other than the conjugated diene.
- the conjugated diene constituting the conjugated diene polymer is selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, for example. It may contain at least one kind.
- the conjugated diene may comprise 1,3-butadiene and / or isoprene.
- the comonomer constituting the conjugated diene polymer is at least one selected from the group consisting of aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. May be included.
- the comonomer may contain styrene.
- the conjugated diene polymer includes, for example, a conjugated diene, at least one compound selected from the group consisting of limonene, terpinene, and terpinolene, an organic alkali metal compound as a polymerization initiator, and a carbonization as a solvent. It can be obtained by a polymerization reaction in a polymerization solution (hydrocarbon solution) containing hydrogen.
- the conjugated diene polymer obtained by a polymerization reaction in a polymerization solution containing at least one compound selected from the group consisting of limonene, terpinene and terpinolene, and an organic alkali metal compound is A conjugated diene polymer composition having superior durability compared to a conjugated diene polymer obtained by a polymerization reaction in a polymerization solution not containing at least one compound selected from the group consisting of limonene, terpinene and terpinolene Can give things.
- Limonene can be selected from isomers such as ⁇ -limonene and ⁇ -limonene, and may be D-form, L-form or racemic form.
- Terpinene can be selected from isomers such as ⁇ -terpinene, ⁇ -terpinene, and ⁇ -terpinene.
- Terpinolene can be selected from isomers such as ⁇ -terpinolene. When simply referred to as “limonene”, “terpinene”, or “terpinolene”, it usually means the ⁇ form.
- the total content of limonene, terpinene and terpinolene in the polymerization solution (or hydrocarbon solution) is 0.5 mol or more and 40 mol or less, 0.6 mol or more and 37 mol or less, per mol of alkali metal of the organic alkali metal compound, It may be 0.8 mol or more and 35 mol or less, or 1 mol or more and 30 mol or less.
- the upper limit value and lower limit value of these numerical ranges can be arbitrarily combined.
- Conjugated diene polymers according to some embodiments may include monomer units derived from limonene, terpinene or terpinolene.
- organic alkali metal compound examples include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2- Butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-cyclopentyllithium, dimethylaminopropyllithium, diethylaminopropyllithium, tert-butyldimethylsiloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide, lithium pyrrolidide Lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, 1,4-dilithio-2-butene, sodium naphthaleni , Sodium biphenylide, potassium naphthalenide,
- the organic alkali metal compound as the polymerization initiator may be supplied to the polymerization reactor (polymerization solution) at the start of the polymerization, or may be supplied in a divided or continuous manner during the polymerization reaction.
- the molecular weight distribution can be adjusted by supplying the organic alkali metal compound separately or continuously.
- “divide and supply the organic alkali metal compound” means that the total amount of the organic alkali metal compound used in the polymerization reaction is divided and supplied twice or more.
- “Supplying the organic alkali metal compound continuously” means that the organic alkali metal compound used in the polymerization reaction is continuously supplied at a predetermined supply rate while the polymerization reaction proceeds.
- an organic alkali metal compound may be supplied to the polymerization solution over 10 minutes to 5 hours while the polymerization reaction is proceeding.
- the organic alkali metal compound may be supplied to the polymerization solution in the state of a solution dissolved in a solvent such as hydrocarbon.
- the total amount of the organic alkali metal compound used in the polymerization reaction may be 0.5 mmol or more, 0.67 mmol or more, or 0.77 mmol or more, and 0.46 mol or less, relative to 1 kg of the conjugated diene. Or 0.23 mol or less may be sufficient.
- the solvent contained in the polymerization solution may be a solvent that does not substantially deactivate the organic alkali metal compound used as the polymerization initiator.
- the solvent include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, and hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and alicyclic rings such as cyclopentane and cyclohexane.
- Group hydrocarbons can be mentioned. Two or more kinds of solvents selected from these may be used in combination.
- the polymerization solution (hydrocarbon solution) is an agent that adjusts the vinyl bond amount of the monomer unit derived from the conjugated diene, and an agent that adjusts the distribution of the monomer unit derived from the conjugated diene in the conjugated diene polymer ( Hereinafter, it may be collectively referred to as “regulator”).
- Examples of the adjusting agent include ether compounds, tertiary amines, phosphine compounds, alkali metal alkoxides, and alkali metal phenoxides.
- Examples of ether compounds include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; Aliphatic monoethers such as diethyl ether and dibutyl ether; Aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; Examples include aliphatic triethers such as diethylene glycol diethyl ether and diethylene glycol dibutyl ether; and aromatic ethers such as diphenyl ether and anisole.
- Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, 1,1,2,2-tetramethylethylenediamine, N, N-diethylaniline, pyridine, and quinoline.
- Examples of the phosphine compound include trimethylphosphine, triethylphosphine, and triphenylphosphine.
- Examples of the alkali metal alkoxide include sodium-tert-butoxide, potassium-tert-butoxide, sodium-tert-pentoxide, and potassium-tert-pentoxide.
- Examples of the alkali metal phenoxide include sodium phenoxide and potassium phenoxide. Two or more kinds of regulators selected from these may be used in combination.
- the content of the monomer component in the polymerization solution may be 1% by mass to 50% by mass and 5% by mass to 30% by mass. However, the total amount of the polymerization solution is 100% by mass.
- the content of the monomer component in the hydrocarbon solution is the content of the conjugated diene.
- the content of the monomer component in the polymerization solution is the total content of the conjugated diene and the comonomer.
- Limonene, terpinene and terpinolene can be copolymerized with conjugated dienes, but these amounts are not included in the monomer component content.
- the polymerization temperature (temperature of the polymerization solution) may be 25 ° C. or more and 100 ° C. or less, 35 ° C. or more and 90 ° C. or less, or 50 ° C. or more and 80 ° C. or less.
- the polymerization time may be 10 minutes or more and 5 hours or less.
- the polymerization active terminal of the conjugated diene polymer is reacted with at least one compound selected from the group consisting of an alkoxysilane compound, a halogen-containing silicon compound, a ketone compound, and a tin compound, to give a conjugated diene polymer. May be modified.
- a conjugated diene copolymer having a modifying group derived from an alkoxysilane compound, a halogen-containing silicon compound, a ketone compound or a tin compound bonded to the end of the molecular chain is obtained.
- alkoxysilane compounds include [3- (dimethylamino) propyl] triethoxysilane, [3- (dimethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [3- (diethylamino) [(Propyl] trimethoxysilane, [3- (dimethylamino) propyl] methyldiethoxysilane, [2- (dimethylamino) ethyl] triethoxysilane, [2- (dimethylamino) ethyl] trimethoxysilane, [( Dialkylamino) alkyl] alkoxysilane compounds; (1-hexamethyleneiminomethyl) trimethoxysilane, [3- (1-hexamethyleneimino) propyl] triethoxysilane, N- (3-triethoxysilylpropy
- halogen-containing silicon compounds include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane. , Tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.
- Examples of the ketone compound include N, N-dihydrocarbylacetamide such as N, N-dimethylacetamide, N, N-diethylacetamide, and N-methyl-N-ethylacetamide; N, N-dihydrocarbyl acrylamides such as N-dimethylacrylamide, N, N-diethylacrylamide, and N-methyl-N-ethylacrylamide; N, N-dihydrocarbyl methacrylamide such as N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, and N-methyl-N-ethylmethacrylamide; 4- (N, N-dihydrocarbylamino) such as 4- (N, N-dimethylamino) acetophenone, 4- (N-methyl-N-ethylamino) acetophenone, and 4- (N, N-diethylamino) acetophenone) Acetophenone; 4-cyclic amino
- tin compounds include tin tetrachloride, methyltrichlorotin, and dimethyldichlorotin.
- the polymerization active terminal of the conjugated diene polymer may be treated with an alcohol such as methanol, isopropyl alcohol, and 1-butanol.
- an alcohol such as methanol, isopropyl alcohol, and 1-butanol.
- the molecular weight distribution of the conjugated diene polymer can be adjusted by treating the polymerization active terminal of the conjugated diene polymer with alcohol and inactivating a part of the polymerization active terminal of the conjugated diene polymer.
- the conjugated diene polymer can be recovered from the solution in which the conjugated diene polymer is dissolved by a known method.
- methods for recovering the conjugated diene polymer include (a) a method of adding a coagulant to a solution containing the conjugated diene polymer, and (b) a method of blowing steam into the solution containing the conjugated diene polymer. be able to.
- the recovered conjugated diene polymer may be dried with a known dryer such as a band dryer or an extrusion dryer.
- the conjugated diene polymer is a polymer obtained by copolymerizing a conjugated diene and a comonomer
- the content of monomer units derived from the comonomer in the conjugated diene polymer is a single amount derived from the conjugated diene.
- the total amount of monomers derived from the body and the comonomer may be 5% by mass or 10% by mass or more based on 100% by mass.
- the content of the monomer unit derived from the comonomer in the conjugated diene polymer may be 50% by mass or less, or 45% by mass or less.
- the Mooney viscosity (ML 1 + 4 ) of the conjugated diene polymer may be 10 or more, or 20 or more in order to increase the tensile strength at break. In order to improve processability, the Mooney viscosity of the conjugated diene polymer may be 200 or less, or 150 or less.
- the Mooney viscosity (ML 1 + 4 ) is measured at 100 ° C. according to JIS K6300 (1994). The sign of (ML 1 + 4 ) has the following meaning.
- L Large rotor used 1 + 4: Measured value when the sample was heated for 1 minute and then the rotor was rotated at 2 rpm for 4 minutes
- the (standard) polystyrene equivalent weight average molecular weight (Mw) of the conjugated diene polymer by gel permeation chromatography may be 10,000 or more, 50000 or more, or 100,000 or more in order to increase the tensile strength at break. In order to improve processability, the weight molecular weight may be 200000 or less, 1500000 or less, or 1300000 or less.
- the ratio (Mz / Mn, molecular weight distribution) of (average) polystyrene-equivalent Z average molecular weight (Mz) and number average molecular weight (Mn) by gel permeation chromatography of the conjugated diene polymer is to increase the tensile strength at break. 1.7 or more. From the same viewpoint, Mz / Mn may be 1.8 or more, or 1.9 or more. In order to increase the tensile elongation at break, Mz / Mn is 4.0 or less. From the same viewpoint, Mz / Mn may be 3.8 or less, or 3.5 or less. The upper limit value and lower limit value of these numerical ranges can be arbitrarily combined.
- Mz / Mn is, for example, supplying an organic alkali metal compound to a polymerization reactor (polymerization solution) in a divided or continuous manner, supplying alcohol to the polymerization reactor during polymerization, and / or during or after polymerization. It can be adjusted by at least one method selected from modifying the polymerization active terminal of the conjugated diene polymer. For example, when the organic alkali metal compound is divided or continuously supplied to the polymerization solution, the supply rate of the organic alkali metal compound (for example, the amount supplied per unit time) is set so that the Mz / Mn of the conjugated diene polymer to be generated is 1. It can be determined so as to be 7 or more and 4.0 or less.
- the vinyl bond content in the conjugated diene polymer may be 80 mol% or less, or 70 mol% or less, where the content of monomer units derived from the conjugated diene is 100 mol%.
- the amount of vinyl bonds may be 10 mol% or more, 15 mol% or more, 20 mol% or more, or 30 mol% or more.
- the vinyl bond amount is determined based on the absorption intensity around 910 cm ⁇ 1, which is the absorption peak of vinyl group, by infrared spectroscopy.
- the conjugated diene polymer is blended with other polymer components and additives, and vulcanized as necessary to contain the conjugated diene polymer, and other polymer components and / or additives.
- a conjugated diene polymer composition that may be included may be prepared.
- the conjugated diene polymer composition may contain two or more conjugated diene polymers according to the above-described embodiment.
- polymer components include butyl rubber, natural rubber, ethylene-propylene copolymer, and ethylene-octene copolymer. Two or more kinds selected from these polymer components may be used in combination.
- the content of the conjugated diene polymer in the conjugated diene polymer composition is tensile.
- the total content of the conjugated diene polymer and other polymer components is 100% by mass, and is 10% by mass to 99.9% by mass, or 20% by mass to 90% by mass. Also good.
- a known additive can be used.
- vulcanizing agents such as sulfur
- Vulcanization accelerators such as thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, and guanidine vulcanization accelerators
- Vulcanization activators such as stearic acid and zinc oxide
- Organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide
- Reinforcing agents such as silica and carbon black
- Fillers such as calcium carbonate, talc, alumina, clay, aluminum hydroxide, and mica
- Examples include silane coupling agents; extension oils; processing aids; anti-aging agents; and lubricants.
- the vulcanizing agent may be sulfur.
- sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
- the amount of sulfur is 0.1 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the conjugated diene polymer.
- it may be 0.3 parts by mass or more and 10 parts by mass or less, or 0.5 parts by mass or more and 5 parts by mass or less.
- vulcanization accelerators include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; Thiuram vulcanization accelerators such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N-oxymethylene-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfen Amido and sulfenamide vulcanization accelerators such as N, N′-diisopropyl-2-benzothiazole sulfenamide; and guanidine vulcanization accelerators such as diphenylguanidine, diortolylguan
- the blending amount of the vulcanization accelerator is based on 100 parts by mass of the conjugated diene polymer. It may be 0.1 to 5 parts by mass, or 0.2 to 3 parts by mass.
- the reinforcing agent may be at least one selected from the group consisting of silica, calcium silicate, aluminum silicate, and carbon black, for example.
- silica examples include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, and precipitated silica. One type or two or more types of silica selected from these can be used.
- the BET specific surface area of the silica may be 50 m 2 / g or more and 250 m 2 / g or less.
- the BET specific surface area is measured according to ASTM D1993-03.
- trade names such as Degussa's trade name Ultrasil VN3-G, Tosoh Silica's trade names VN3, AQ, ER, RS-150, Rhodia's trade names Zeosil 1115MP, 1165MP, etc. can be used. .
- carbon black examples include furnace black, acetylene black, thermal black, channel black, and graphite.
- Carbon blacks include channel carbon blacks such as EPC, MPC and CC; Furnace carbon blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; Illustrative are thermal carbon blacks such as FT and MT; and acetylene carbon black. Two or more types of carbon black selected from these may be used in combination.
- the nitrogen adsorption specific surface area (N 2 SA) of carbon black may be 5 m 2 / g or more and 200 m 2 / g or less.
- Carbon black may have a dibutyl phthalate (DBP) absorption of 5 ml / 100 g or more and 300 ml / 100 g or less.
- the nitrogen adsorption specific surface area is measured according to ASTM D4820-93.
- the DBP absorption is measured according to ASTM D2414-93.
- As a commercial product of carbon black trade name Diamond Black N339 manufactured by Mitsubishi Chemical Corporation, trade name Seast 6, Seast 7HM, Seast KH, trade name CK 3, Special Black 4A manufactured by Degussa, etc. can be used. .
- the content of the reinforcing agent in the conjugated diene polymer composition is 100 parts by mass of the conjugated diene polymer. In order to increase the tensile strength at break, it may be 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more. In order to increase the tensile elongation at break, the content of the reinforcing agent may be 150 parts by mass or less, 120 parts by mass or less, or 100 parts by mass or less.
- silane coupling agent examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -amino Propyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, bis (3- (triethoxysily
- the amount of the silane coupling agent is 100 parts by mass of silica. 1 mass part or more and 20 mass parts or less, 2 mass parts or more and 15 mass parts or less, or 5 mass parts or more and 10 mass parts or less may be sufficient.
- extender oils examples include aromatic mineral oils (viscosity specific gravity constant (VGC value) 0.900 to 1.049) and naphthenic mineral oils (VGC value 0.850 to 0). 899), and paraffinic mineral oil (VGC value 0.790 to 0.849).
- the content of the polycyclic aromatic in the extending oil may be less than 3% by mass or less than 1% by mass with respect to 100% by mass of the extending oil.
- the polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method. 20 mass% or more may be sufficient as content (CA) of the aromatic compound of extending oil.
- One or more extending oils selected from these can be used.
- Examples of a method for producing a conjugated diene polymer composition by blending other polymer components and additives with a conjugated diene polymer include, for example, a method of kneading each component with a known mixer such as a roll and a Banbury. Can be used.
- the kneading temperature is usually 50 ° C. or higher and 200 ° C. or lower, and may be 80 ° C. or higher and 190 ° C. or lower, and the kneading time is usually 30 seconds. It is 30 minutes or less and may be 1 minute or more and 30 minutes or less.
- the kneading temperature is usually 100 ° C. or lower, and may be room temperature or higher and 80 ° C. or lower.
- the conjugated diene polymer composition containing a vulcanizing agent and a vulcanization accelerator is usually subjected to vulcanization treatment such as press vulcanization.
- the vulcanization temperature is usually 120 ° C. or higher and 200 ° C. or lower, and may be 140 ° C. or higher and 180 ° C. or lower.
- the conjugated diene polymer composition of the present embodiment has excellent durability and good workability, and is suitably used for tires.
- the physical properties were evaluated by the following method. 1. Mooney viscosity (ML 1 + 4 ) According to JIS K6300 (1994), the Mooney viscosity of the polymer was measured at 100 ° C.
- Vinyl bond amount (unit: mol%) The amount of vinyl bonds in the monomer derived from 1,3-butadiene in the polymer was determined by infrared spectroscopy based on the absorption intensity in the vicinity of 910 cm ⁇ 1, which is the absorption peak of the vinyl group.
- Tensile breaking strength (unit: MPa) and tensile breaking elongation (unit:%)
- a No. 3 dumbbell test piece was used, and the tensile rate was set to 500 mm / min, and the stress (tensile rupture strength) and elongation rate (tensile rupture elongation) when the test piece broke were measured.
- Example 1 (Preparation of polymer) A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas inside the polymerization reactor was replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m 3 ), 517 g of 1,3-butadiene, 163 g of styrene, 38 g of limonene, 6.1 ml of tetrahydrofuran, and 4.6 ml of ethylene glycol diethyl ether were placed in the polymerization reactor. I put it in. Next, a small amount of n-butyllithium hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.
- n-hexane solution of n-butyllithium (a content of n-butyllithium of 12.2 mmol) was started to be charged into the polymerization reactor.
- the n-hexane solution was charged into the polymerization reactor over 1 hour.
- Polymerization reaction was performed for 3 hours. During the polymerization reaction, the temperature in the polymerization reactor was adjusted to 65 ° C., and the solution in the polymerization reactor was stirred at a stirring speed of 130 rpm. During the polymerization reaction, 775 g of 1,3-butadiene and 245 g of styrene were continuously fed into the polymerization reactor.
- the obtained polymerization solution was stirred in the polymerization reactor at a stirring speed of 130 rpm to polymerize 12.9 mmol of [3- (diethylamino) propyl] trimethoxysilane. Added to the solution and stirred for 15 minutes. 20 ml of hexane solution containing 0.8 ml of methanol was put into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
- Example 2 (Preparation of polymer) A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas inside the polymerization reactor was replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m 3 ), 517 g of 1,3-butadiene, 163 g of styrene, 38 g of limonene, 6.1 ml of tetrahydrofuran, and 4.6 ml of ethylene glycol diethyl ether were placed in the polymerization reactor. I put it in. Next, a small amount of n-butyllithium hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.
- industrial hexane density 680 kg / m 3
- n-butyllithium solution in n-butyllithium (content of n-butyllithium 12.2 mmol) was charged into the polymerization reactor to initiate the polymerization reaction.
- Polymerization reaction was performed for 3 hours. During the polymerization reaction, the temperature in the polymerization reactor is adjusted to 65 ° C., and the solution in the polymerization reactor is stirred at a stirring speed of 130 rpm. In the polymerization reactor, 1,775 butadiene and 245 g of styrene are continuously added. Supplied.
- the obtained polymerization solution was stirred in the polymerization reactor at a stirring speed of 130 rpm, 0.39 mmol of silicon tetrachloride was added to the polymerization solution, and the mixture was stirred for 15 minutes. .
- 10.6 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymerization solution and stirred for 15 minutes.
- 20 ml of hexane solution containing 0.8 ml of methanol was put into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
- n-butyllithium n-hexane solution (n-butyllithium content 11.4 mmol) was charged into the polymerization reactor to initiate the polymerization reaction.
- Polymerization reaction was performed for 3 hours. During the polymerization reaction, the temperature in the polymerization reactor is adjusted to 65 ° C., and the solution in the polymerization reactor is stirred at a stirring speed of 130 rpm. In the polymerization reactor, 1,775 butadiene and 245 g of styrene are continuously added. Supplied.
- the obtained polymerization solution was stirred in the polymerization reactor at a stirring speed of 130 rpm, and 11.4 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymerization solution. And stirred for 15 minutes. 20 ml of hexane solution containing 0.8 ml of methanol was put into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
- Example 3 In Example 1, a corresponding polymer and a polymer composition containing the polymer are obtained by carrying out in the same manner as in Example 1 except that terpinene is used instead of limonene.
- Example 4 In Example 1, a corresponding polymer and a polymer composition containing the polymer are obtained by carrying out in the same manner as in Example 1 except that terpinolene is used in place of limonene.
Abstract
Description
有機アルカリ金属化合物を重合開始剤として用いて、
共役ジエンを重合、又は、共役ジエンとコモノマーとを共重合して得られる重合体であってもよい。
ジエチルエーテル、及びジブチルエーテル等の脂肪族モノエーテル;
エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、及びエチレングリコールジブチルエーテル等の脂肪族ジエーテル;
ジエチレングリコールジエチルエーテル、及びジエチレングリコールジブチルエーテル等の脂肪族トリエーテル;並びに
ジフェニルエーテル、及びアニソール等の芳香族エーテル等を挙げることができる。第三級アミンとしては、トリエチルアミン、トリプロピルアミン、トリブチルアミン、1,1,2,2-テトラメチルエチレンジアミン、N,N-ジエチルアニリン、ピリジン、及びキノリン等を挙げることができる。ホスフィン化合物としては、トリメチルホスフィン、トリエチルホスフィン、及びトリフェニルホスフィン等を挙げることができる。アルカリ金属アルコキシドとしては、ナトリウム-tert-ブトキシド、カリウム-tert-ブトキシド、ナトリウム-tert-ペントキシド、及びカリウム-tert-ペントキシド等を挙げることができる。アルカリ金属フェノキシドとしては、ナトリウムフェノキシド、及びカリウムフェノキシド等を挙げることができる。これらから選ばれる2種類以上の調整剤を併用してもよい。
(1-ヘキサメチレンイミノメチル)トリメトキシシラン、[3-(1-ヘキサメチレンイミノ)プロピル]トリエトキシシラン、N-(3-トリエトキシシリルプロピル)-4,5-ジヒドロイミダゾ-ル、及びN-(3-トリメトキシシリルプロピル)-4,5-イミダゾ-ル等の環状アミノアルキルアルコキシシラン化合物;
{3-[ジ(テトラヒドロフラニル)アミノ]プロピル}トリメトキシシラン、及び{3-[ジ(テトラヒドロフラニル)アミノ]プロピル}トリエトキシシラン等の{[ジ(テトラヒドロフラニル)アミノ]アルキル}アルコキシシラン化合物;並びに
{3-[N,N-ビス(トリメチルシリル)アミノ]プロピル}メチルジメトキシシラン、及び{3-[N,N-ビス(トリメチルシリル)アミノ]プロピル}メチルジエトキシシラン等の[N,N-ビス(トリアルキルシリル)アミノアルキル]アルキルアルコキシシラン化合物等を挙げる事ができる。
N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド、及びN-メチル-N-エチルアクリルアミド等のN,N-ジヒドロカルビルアクリルアミド;
N,N-ジメチルメタクリルアミド、N,N-ジエチルメタクリルアミド、及びN-メチル-N-エチルメタクリルアミド等のN,N-ジヒドロカルビルメタクリルアミド;
4-(N,N-ジメチルアミノ)アセトフェノン、4-(N-メチル-N-エチルアミノ)アセトフェノン、及び4-(N,N-ジエチルアミノ)アセトフェノン等の4-(N,N-ジヒドロカルビルアミノ)アセトフェノン;
4’-(イミダゾール-1-イル)アセトフェノン等の4-環状アミノアセトフェノン化合物;
1,7-ビス(メチルエチルアミノ)-4-ヘプタノン、及び1,3-ビス(ジフェニルアミノ)-2-プロパノン等のビス(ジヒドロカルビルアミノアルキル)ケトン;
4-N,N-ジメチルアミノベンゾフェノン、4-N,N-ジエチルアミノベンゾフェノン、4-N,N-ジ-t-ブチルアミノベンゾフェノン、及び4-N,N-ジフェニルアミノベンゾフェノン等の4-(ジヒドロカルビルアミノ)ベンゾフェノン;並びに
4,4’-ビス(ジメチルアミノ)ベンゾフェノン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、及び4,4’-ビス(ジフェニルアミノ)ベンゾフェノン等の4,4’-ビス(ジヒドロカルビルアミノ)ベンゾフェノン等を挙げることができる。
M:ムーニー粘度
L:ラージローターを使用
1+4:試料を1分加熱した後、ローターを4分間2rpmで回転させた時の測定値
チアゾール系加硫促進剤、チウラム系加硫促進剤、スルフェンアミド系加硫促進剤、及びグアニジン系加硫促進剤等の加硫促進剤;
ステアリン酸、及び酸化亜鉛等の加硫活性化剤;
ジクミルパーオキシド、及びジターシャリブチルパーオキシド等の有機過酸化物;
シリカ、及びカーボンブラック等の補強剤;
炭酸カルシウム、タルク、アルミナ、クレー、水酸化アルミニウム、及びマイカ等の充填剤;
シランカップリング剤;伸展油;加工助剤;老化防止剤;並びに滑剤を例示することができる。
テトラメチルチウラムモノスルフィド、及びテトラメチルチウラムジスルフィド等のチウラム系加硫促進剤;
N-シクロヘキシル-2-ベンゾチアゾールスルフェンアミド、N-tert-ブチル-2-ベンゾチアゾールスルフェンアミド、N-オキシメチレン-2-ベンゾチアゾールスルフェンアミド、N-オキシエチレン-2-ベンゾチアゾールスルフェンアミド、及びN,N’-ジイソプロピル-2-ベンゾチアゾールスルフェンアミド等のスルフェンアミド系加硫促進剤;並びに
ジフェニルグアニジン、ジオルトトリルグアニジン、及びオルトトリルビグアニジン等のグアニジン系加硫促進剤等を挙げることができる。
SAF、ISAF、HAF、MAF、FEF、SRF、GPF、APF、FF、CF、SCF及びECFのようなファーネスカーボンブラック;
FT及びMTのようなサーマルカーボンブラック;並びに
アセチレンカーボンブラックが例示される。これらから選ばれる2種類以上のカーボンブラックを併用してもよい。
1.ムーニー粘度(ML1+4)
JIS K6300(1994)に従って、100℃にて重合体のムーニー粘度を測定した。
ゲルパーミエイションクロマトグラフ(GPC)法を用いて、下記の条件(1)~(8)により重合体の分子量分布を測定した。
(1)装置:東ソー製HLC-8020
(2)分離カラム:東ソー製GMH-XL(2本直列)
(3)測定温度:40℃
(4)キャリア:テトラヒドロフラン
(5)流量:0.6mL/分
(6)注入量:5μL
(7)検出器:示差屈折
(8)分子量標準:標準ポリスチレン
赤外分光分析法により、ビニル基の吸収ピークである910cm-1付近の吸収強度に基づいて、重合体中の1,3-ブタジエンに由来する単量体中のビニル結合量を求めた。
JIS K6383(1995)に従って、屈折率から重合体中のスチレンに由来する単量体単位の含有量(スチレン単位量)を求めた。
JIS K6251に従い、3号形ダンベル試験片を用い、引張速度を500mm/分として、該試験片が破断する時の応力(引張破断強度)と伸び率(引張破断伸び)を測定した。引張破断強度が高いほど、また、引張破断伸びが高いほど、重合体が耐久性に優れる。
(重合体の調製)
内容積20リットルの撹拌装置付きステンレス製重合反応器を、洗浄及び乾燥し、当該重合反応器の内部のガスを乾燥窒素に置換した。次に、工業用ヘキサン(密度680kg/m3)10.2kg、1,3-ブタジエン517g、スチレン163g、リモネン38g、テトラヒドロフラン6.1ml、及びエチレングリコールジエチルエーテル4.6mlを、重合反応器内に投入した。次に、重合開始剤の失活に作用する不純物を予め無毒化させるために、スカベンジャーとして少量のn-ブチルリチウムのヘキサン溶液を重合反応器内に投入した。
メタノール0.8mlを含むヘキサン溶液20mlを重合反応器内に投入し、重合体溶液を5分間撹拌した。
得られた重合体100質量部、シリカ(デグッサ社製、商品名:ウルトラシルVN3-G)78.4質量部、シランカップリング剤(デグッサ社製、商品名:Si69)6.4質量部、カーボンブラック(三菱化学社製、商品名:ダイヤブラックN339)6.4質量部、伸展油(ジャパンエナジー社製、商品名:JOMOプロセスNC-140)47.6質量部、老化防止剤(住友化学社製、商品名:アンチゲン3C)1.5質量部、ワックス(大内新興化学工業社製、商品名:サンノックN)1.5質量部、及びステアリン酸2質量部を、ラボプラストミルにて混練して、重合体組成物を得た。
次に、第二段の混練として、上記重合体組成物に、亜鉛華2質量部、加硫促進剤(住友化学社製、商品名:ソクシノールCZ)1.5質量部、加硫促進剤(住友化学社製、商品名:ソクシノールD)1.5質量部、及び硫黄1.4質量部を添加し、6インチロールで混練し、混錬物(重合体組成物)をシートに成形した。
当該シートを160℃で55分加熱して加硫し、得られたシートの物性を評価した。シートの物性の評価結果を表1に示す。
(重合体の調製)
内容積20リットルの撹拌装置付きステンレス製重合反応器を、洗浄及び乾燥し、当該重合反応器の内部のガスを乾燥窒素に置換した。次に、工業用ヘキサン(密度680kg/m3)10.2kg、1,3-ブタジエン517g、スチレン163g、リモネン38g、テトラヒドロフラン6.1ml、及びエチレングリコールジエチルエーテル4.6mlを、重合反応器内に投入した。次に、重合開始剤の失活に作用する不純物を予め無毒化させるために、スカベンジャーとして少量のn-ブチルリチウムのヘキサン溶液を重合反応器内に投入した。
メタノール0.8mlを含むヘキサン溶液20mlを重合反応器内に投入し、重合体溶液を5分間撹拌した。
得られた重合体100質量部、シリカ(デグッサ社製、商品名:ウルトラシルVN3-G)78.4質量部、シランカップリング剤(デグッサ社製、商品名:Si69)6.4質量部、カーボンブラック(三菱化学社製、商品名:ダイヤブラックN339)6.4質量部、伸展油(ジャパンエナジー社製、商品名:JOMOプロセスNC-140)47.6質量部、老化防止剤(住友化学社製、商品名:アンチゲン3C)1.5質量部、ワックス(大内新興化学工業社製、商品名:サンノックN)1.5質量部、及びステアリン酸2質量部を、ラボプラストミルにて混練して、重合体組成物を得た。
次に、第二段の混練として、上記重合体組成物に、亜鉛華2質量部、加硫促進剤(住友化学社製、商品名:ソクシノールCZ)1.5質量部、加硫促進剤(住友化学社製、商品名:ソクシノールD)1.5質量部、及び硫黄1.4質量部を添加し、6インチロールで混練し、混錬物(重合体組成物)をシートに成形した。
当該シートを160℃で55分加熱して加硫し、得られたシートの物性を評価した。シートの物性の評価結果を表1に示す。
(重合体の調製)
内容積20リットルの撹拌装置付きステンレス製重合反応器を、洗浄及び乾燥し、当該重合反応器の内部のガスを乾燥窒素に置換した。次に、工業用ヘキサン(密度680kg/m3)10.2kg、1,3-ブタジエン517g、スチレン163g、テトラヒドロフラン6.1ml、及びエチレングリコールジエチルエーテル4.6mlを、重合反応器内に投入した。次に、重合開始剤の失活に作用する不純物を予め無毒化させるために、スカベンジャーとして少量のn-ブチルリチウムのヘキサン溶液を重合反応器内に投入した。
メタノール0.8mlを含むヘキサン溶液20mlを重合反応器内に投入し、重合体溶液を5分間撹拌した。
得られた重合体100質量部、シリカ(デグッサ社製、商品名:ウルトラシルVN3-G)78.4質量部、シランカップリング剤(デグッサ社製、商品名:Si69)6.4質量部、カーボンブラック(三菱化学社製、商品名:ダイヤブラックN339)6.4質量部、伸展油(ジャパンエナジー社製、商品名:JOMOプロセスNC-140)47.6質量部、老化防止剤(住友化学社製、商品名:アンチゲン3C)1.5質量部、ワックス(大内新興化学工業社製、商品名:サンノックN)1.5質量部、及びステアリン酸2質量部を、ラボプラストミルにて混練して、重合体組成物を得た。
次に、第二段の混練として、上記重合体組成物に、亜鉛華2質量部、加硫促進剤(住友化学社製、商品名:ソクシノールCZ)1.5質量部、加硫促進剤(住友化学社製、商品名:ソクシノールD)1.5質量部、及び硫黄1.4質量部を添加し、6インチロールで混練し、混錬物(重合体組成物)をシートに成形した。
当該シートを160℃で55分加熱して加硫し、得られたシートの物性を評価した。シートの物性の評価結果を表1に示す。
実施例1において、リモネンに代えてテルピネンを用いる以外は実施例1と同様に実施することにより、相当する重合体および該重合体を含む重合体組成物が得られる。
実施例1において、リモネンに代えてテルピノレンを用いる以外は実施例1と同様に実施することにより、相当する重合体および該重合体を含む重合体組成物が得られる。
Claims (8)
- 共役ジエンを単量体単位として含む共役ジエン重合体であって、
前記共役ジエンと、リモネン、テルピネン及びテルピノレンからなる群から選ばれる少なくとも1種の化合物と、重合開始剤としての有機アルカリ金属化合物と、を含有する重合溶液中での重合反応によって得られ、
当該共役ジエン重合体のZ平均分子量がMzで、当該共役ジエン重合体の数平均分子量がMnで、前記Z平均分子量及び前記数平均分子量がゲルパーミエーションクロマトグラフィーによるポリスチレン換算の値であるとき、Mz/Mnが1.7以上4.0以下である、共役ジエン重合体。 - 前記重合溶液中のリモネン、テルピネン及びテルピノレンの総含有量が、前記有機アルカリ金属化合物中のアルカリ金属1モルあたり、0.5モル以上40モル以下である、請求項1に記載の共役ジエン重合体。
- 当該共役ジエン重合体の分子鎖の末端に結合した、アルコキシシラン化合物、ハロゲン含有ケイ素化合物、ケトン化合物又はスズ化合物に由来する変性基を有する、請求項1又は2に記載の共役ジエン重合体。
- 請求項1~3のいずれか一項に記載の共役ジエン重合体と、補強剤と、を含有し、
前記補強剤の含有量が、前記共役ジエン重合体100質量部あたり、10質量部以上150質量部以下である、共役ジエン重合体組成物。 - 共役ジエンを単量体単位として含む共役ジエン重合体を製造する方法であって、
前記共役ジエンと、リモネン、テルピネン及びテルピノレンからなる群から選ばれる少なくとも1種の化合物と、重合開始剤としての有機アルカリ金属化合物と、を含有する重合溶液中での重合反応によって、当該共役ジエン重合体を生成させる工程を備え、
当該共役ジエン重合体のZ平均分子量がMzで、当該共役ジエン重合体の数平均分子量がMnで、前記Z平均分子量及び前記数平均分子量がゲルパーミエーションクロマトグラフィーによるポリスチレン換算の値であるとき、Mz/Mnが1.7以上4.0以下である、方法。 - 前記重合溶液中のリモネン、テルピネン及びテルピノレンの総含有量が、前記有機アルカリ金属化合物中のアルカリ金属1モルあたり、0.5モル以上40モル以下である、請求項5に記載の方法。
- 前記重合反応により生成した重合体の末端に、アルコキシシラン化合物、ハロゲン含有ケイ素化合物、ケトン化合物及びスズ化合物からなる群から選ばれる少なくとも1種の化合物に由来する変性基を導入する工程を更に備える、請求項5又は6に記載の方法。
- 前記有機アルカリ金属化合物が、前記重合反応中に、分割又は連続して前記重合溶液に供給される、請求項5~7のいずれか一項に記載の方法。
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