WO2008032417A1 - Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué - Google Patents

Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué Download PDF

Info

Publication number
WO2008032417A1
WO2008032417A1 PCT/JP2006/318797 JP2006318797W WO2008032417A1 WO 2008032417 A1 WO2008032417 A1 WO 2008032417A1 JP 2006318797 W JP2006318797 W JP 2006318797W WO 2008032417 A1 WO2008032417 A1 WO 2008032417A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
hydrocarbon
carbon atoms
conjugation
Prior art date
Application number
PCT/JP2006/318797
Other languages
English (en)
Japanese (ja)
Inventor
Mayumi Oshima
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to PCT/JP2006/318797 priority Critical patent/WO2008032417A1/fr
Priority to CNA2006800558435A priority patent/CN101511884A/zh
Priority to DE112006004023.5T priority patent/DE112006004023B4/de
Publication of WO2008032417A1 publication Critical patent/WO2008032417A1/fr

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a conjugation-based polymer, a method for producing a conjugation-based polymer, a conjugation-based polymer composition, and a method for producing a conjugation-based polymer composition.
  • polymer compositions used for automobile tires are also required to have excellent fuel economy.
  • polymer compositions for automobile tires include polymer compositions containing a conjugate polymer such as polybutadiene or butadiene-styrene copolymer, and a filler such as carbon black.
  • a polymer composition using a polymer obtained by modifying a polymer obtained by copolymerizing butadiene and styrene using alkyllithium as a polymerization initiator with a tin halide compound as a conjugation-based polymer is known. (For example, JP-A-60-255838, USP4, 742, 124).
  • a conjugated gen-based polymer a polymer obtained by polymerizing butadiene or alkylating butadiene and styrene using alkyllithium as a polymerization initiator, Having alkoxysilane A polymer composition using a polymer modified with the above (for example, JP-A-63-186748, USP4, 957, 976, JP-A-2005-290355, US2 005/0203251 A1) It has been proposed as a polymer composition having good properties.
  • the polymer composition using the conventional conjugation-based polymer is not sufficiently satisfactory in terms of fuel saving when silica is used as the filler.
  • the problem to be solved by the present invention is that a conjugated gen-based polymer and a conjugated polymer that can obtain a polymer composition excellent in fuel efficiency when a filler is blended, particularly when silica is blended.
  • the present invention provides a method for producing a gen-based polymer, a polymer composition obtained by blending a conjugated gen-based polymer and a silicic force, and a method for producing the polymer composition. .
  • the present invention is a conjugated gen-based polymer having a monomer unit based on a conjugated gen and a group represented by the formula (I), wherein the total area of the molecular weight distribution curve obtained by gel permeation chromatography measurement is calculated.
  • a conjugation polymer having a peak area of 50% or more of the molecular weight peak at the lowest molecular weight side at 100%.
  • R 1 and R 2 are each independently a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group.
  • M represents an integer of 0 to 10
  • a 1 represents a polar functional group having no active hydrogen.
  • the present invention provides a process for producing a conjugated gen-based polymer having steps 1 and 2.
  • Step 1 In the presence of an alkali metal catalyst, in a hydrocarbon solvent, polymerize a monomer containing conjugation to obtain a conjugation-based polymer having an alkali metal derived from the catalyst at the end, and
  • Step 2 A key compound represented by the formula (IV) is added to a hydrocarbon solution of the conjugation polymer at a time to modify the conjugation polymer with the key compound.
  • R 6 , R 7 and R 8 each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R 6 , R 7 And at least one of R 8 is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A 2 represents a polar functional group having no active hydrogen.
  • the present invention also provides a conjugated diene polymer composition comprising the above conjugated diene polymer and silica. '
  • the present invention provides a process for producing a conjugated gen-based polymer composition having steps 1, 2, and 3.
  • Step 1 In the presence of an alkali metal catalyst, a monomer containing conjugation is polymerized in a hydrocarbon solvent to obtain a conjugation-based polymer having an alkali metal terminal from the catalyst.
  • Step 2 Add a gate compound represented by the formula (IV) to the hydrocarbon solution of the conjugated gen 3 ⁇ 4 polymer at a time to modify the conjugated gen-based polymer with the key compound.
  • Step 3 The conjugation polymer obtained in Step 2 and silica are blended.
  • R 6 , R 7 and R 8 each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R 6 , R 7 And at least one of R 8 is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A 2 represents a polar functional group having no active hydrogen.
  • FIG. 1 shows an example of a molecular weight distribution curve of a polymer.
  • Figure 2 shows an example of the boundary line between the lowest molecular weight peak and the adjacent peak.
  • Figure 3 shows an example of the area of the molecular weight peak on the lowest molecular weight side.
  • the conjugation-based polymer of the present invention is a conjugation-based polymer having a monomer unit based on conjugation and a group represented by the formula (I), This is a polymer in which the peak area of the molecular weight peak on the lowest molecular weight side is 50% or more, assuming that the total area of the molecular weight distribution curve obtained by one chromatography chromatography is 100%.
  • R 1 and R 2 each independently represents a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group, m represents an integer of 0 to 10 and A 1 represents a polar functional group having no active hydrogen.
  • Table group The Conjugation can include 1,3-butadiene, isoprene, 1,3-pentagene, 2,3-dimethyl_1,3-butadiene, 1,3-hexagen, etc. It may be a seed, or two or more. From the viewpoint of availability in production, 1,3-butadiene and isoprene are preferred.
  • R 1 and R 2 each independently represents a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group.
  • hydrocarbon group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.
  • the hydrocarbon group may be a group composed of a polymer chain such as a polymer chain having a monomer unit based on a conjugated diene. As these hydrocarbon groups, a methyl group and an ethyl group are preferable.
  • hydrocarbonoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group.
  • hydrocarbonoxy groups a methoxy group and a ethoxy group are preferable.
  • R 1 and R 2 are preferably a hydrocarbon oxy group, more preferably a methoxy group or an ethoxy group, from the viewpoint of improving fuel economy.
  • m represents an integer of 0 to 10; From the viewpoint of improving fuel economy, it is preferably 3 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less.
  • a 1 represents a polar functional group having no active hydrogen, a group represented by the formula (II), a formula (III ) And the like. ;
  • R 3 and R 4 each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom, and R 3 and R 4 represent It may be bonded to form a ring structure.
  • X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom
  • R 5 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. . ]
  • R 3 and R 4 each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom.
  • Hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, neopentyl, isopentyl, and n- Xyl, cyclohexyl, phenyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, trimethylsilyl Group, t-butyl dimethylsilyl group and the like.
  • R 3 and R 4 may be bonded, and examples of the group to which R 3 and R 4 are bonded include trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group.
  • Xylene group such as xylene group, oxydipropylene group, etc .; group represented by one CH 2 CH 2 _NH—CH 2 —, group represented by —CH 2 CH 2 —N ⁇ CH—, etc. And the like.
  • R 3 and R 4 are preferably a methyl group, an ethyl group, an n-propyl group, or a trimethylsilyl group.
  • the group to which R 3 and R 4 are bonded is preferably a group represented by 1 CH 2 CH 2 —NH—CH 2 —, a group represented by —CH 2 CH 2 —N ⁇ CH—. . ''.
  • X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom.
  • hydrocarbon group examples include ethylene group, propylene group, butylene group, 1-oxyethylene group, 1-oxytrimethylene group, 1-oxytetramethylene group and the like.
  • X is preferably a 1-oxytrimethylene group.
  • R 5 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.
  • Hydrocarbon groups include methyl, ethyl, n-propyl, i'sopropyl, n-butyl, sec-butyl, t_butyl, n-pentyl, neopentyl, isopentyl, n —Hexyl group, cyclohexyl group, phenyl group and the like can be mentioned.
  • R 5 is preferably hydrogen or a methyl group.
  • Examples of the group represented by the formula (II) include an acyclic amino group and a cyclic amino group.
  • Examples of acyclic amino groups include dimethylamino groups, jetylamino groups, and ethylmethyl.
  • Ruamino group, di (methoxymethyl) amino group, di (methoxychetyl) amino group, di (ethoxymethyl) amino group, di (ethoxyethyl) amino group, di ((propyldimethylsilyl) amino) group, [di (Trimethylsilyl) amino group and the like can be mentioned.
  • Cyclic amino groups include: 1-pyrrolidinyl group, piperidino group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino group 1-polymethyleneimino group such as 1-tetradecamethylimino group and 1-year-old kutadecamethyleneimino group.
  • examples of the cyclic amino group include 1-imidazolyl group, 4,5-dihydro-1-1imidazolyl group, 1_imidazolidinyl group, 1-piperazinyl group, morpholino group and the like.
  • Examples of the group represented by the formula (I I I) include a 3-glycidoxychetyl group and a 3-glycidoxypropyl group.
  • a 1 is preferably a group represented by the formula (II) in view of economy and availability, and more preferably an acyclic amino group.
  • the conjugation-based polymer of the present invention has monomer units based on other monomers in addition to monomer units based on conjugation (conjugation units) and groups represented by formula (I). You may do it.
  • Examples of other monomers include aromatic vinyl, vinyl nitrile, and unsaturated carboxylic acid ester.
  • the conjugation-based polymer of the present invention preferably has a monomer unit (aromatic vinyl unit) based on aromatic vinyl from the viewpoint of increasing strength, and the content of the aromatic vinyl unit is as follows.
  • the total amount of conjugation units and aromatic vinyl units is 100% by weight, preferably 10% by weight or more (conjugation unit content is 90% by weight or less), more preferably 1%.
  • the conjugated gen-based polymer of the present invention is the conjugated gen-based polymer on the lowest molecular weight side, assuming that the total area of the molecular weight distribution curve obtained by gel permeation chromatography measurement is 100%. It is preferable that the molecular weight peak has a peak area of 50% or more. The peak area is
  • Peak L when the high molecular weight curve does not drop to the baseline ( Figure 1), that is, when peak L overlaps with an adjacent peak. From the minimum point of the curve between the peak top of L and the peak top of the adjacent peak, a boundary line is set perpendicular to the baseline ( Figure 2), and the low molecular weight region from the boundary line is the area of peak L (Fig.
  • the Mooney viscosity (ML 1 + 4 ) of the conjugated gen-based polymer of the present invention is preferably 10 or more, more preferably 20 or more, from the viewpoint of increasing mechanical strength. Further, from the viewpoint of improving workability, it is preferably 200 or less, more preferably 'is 150 or less. The Mooney viscosity ML 1 + 4 ) is measured at 100 ° C according to JIS K6300 (1994).
  • the vinyl bond content of the conjugation-based polymer of the present invention is preferably 70 mol% or less, and more preferably from the viewpoint of improving fuel economy by setting the content of the conjugation unit to 1 G 0 mol%. 60 mol% or less. Further, from the viewpoint of improving the grip performance of the tire, it is preferably at least 10 mol%, more preferably at least 15 mol%.
  • the amount of vinyl bonds is the absorption peak of the vinyl group by infrared spectroscopy.
  • An example of the method for producing a conjugation-based polymer of the present invention is a method having the following steps 1 and 2.
  • Step 1 In the presence of an alkali metal catalyst, a monomer containing conjugation is polymerized in a hydrocarbon solvent to obtain a conjugation-based polymer having an alkali metal terminal of the catalyst.
  • Step 2 The cationization represented by the formula (IV) is added to the hydrocarbon solution of the conjugate polymer. Occasionally added, the conjugate polymer is modified with the key compound,
  • R 6 , R 7 and R 8 each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R 6 , R 7 And at least one of R 8 is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10 and A 2 represents a polar functional group having no active hydrogen.
  • the alkali metal catalyst used in Step 1 include alkali metals, organic alkali metal compounds, complexes of alkali metals and polar compounds, and oligomers having alkali metals. '
  • alkali metal examples include lithium, sodium, potassium, rubidium, and cesium.
  • Organic alkali metal compounds include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, t-year-old cutyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium 2-butyl-phenyllithium, 4-monophenyl-butyllithium, cyclohexyllithium, 4-cyclopentylpentyllithium, dimethylaminopropyllithium, jetylaminopropyllithium, t-butyldimethylsiloxypro Pyrlithium, N-morpholinopropyllithium, Lithium hexamethylene imide, Lithium pyrrolidide, Lithium piperidide, Lithium hepramethylene imide, Lithium dodecamethylene imide, 1,4-
  • Examples of the oligomer having an alkali metal include 0: -methylstyrene tetramer sodium salt.
  • the hydrocarbon solvent used in step 1 is a solvent that does not deactivate the alkali metal catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.
  • Aliphatic hydrocarbons include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-one 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and the like.
  • aromatic hydrocarbons examples include benzene, toluene, xylene, and ethylbenzene.
  • alicyclic hydrocarbons examples include cyclopentane and cyclohexane.
  • Step 1 a monomer containing a conjugated gen is polymerized to produce a conjugated gen-based polymer having an alkali metal derived from the above-mentioned alkali metal catalyst at its terminal.
  • Conjugation generators include 1,3-butadiene, isoprene, and 1,3-pen evening. 2,3-dimethyl-1,3-butadiene, 1,3-hexagen, and these may be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred from the viewpoint of availability.
  • step 1 polymerization may be carried out with the conjugate conjugate alone, or polymerization may be carried out by combining the conjugate conjugate with another monomer.
  • aromatic vinyl examples include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene.
  • aromatic pinyl examples include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene.
  • Examples of benzonitrile include acrylonitrile.
  • Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Among these, styrene is preferable from the viewpoint of availability. '
  • Polymerization in step 1 is an agent that adjusts the vinyl bond content of the conjugation unit.
  • Conjugation system The distribution of monomer units based on conjugation units and monomers other than conjugation units in the polymer chain is adjusted. Do this in the presence of agents (hereinafter collectively referred to as “regulators”).
  • Examples of the adjusting agent include ether compounds, tertiary amines, and phosphine compounds.
  • ether compounds include tetrahydrofuran, tetrahydropyran, and 1,4-dioxane, cyclic ethers; aliphatic monoethers such as jetyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol jetyl ether, and ethylene glycol.
  • Dibutyl ether, diethylene glycol examples include aliphatic ethers such as rugetyl ether and diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole.
  • Tertiary amines include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylethylenediamine, N, N-jetylaniline, pyridine, quinoline, etc. it can.
  • Examples of the phosphine compound include trimethylphosphine, triethylphosphine, and triphenylphosphine.
  • the polymerization temperature in step 1 is usually from 30 to 100 ° C., preferably from 35 to 65, and the polymerization time is usually from 10 minutes to 5 hours.
  • step 2 the carbonyl compound polymer represented by formula (IV) is added to the hydrocarbon solution of the conjugated gen polymer having the alkali metal terminal obtained in step 1, and the conjugated gen polymer is gained. Denature with elemental compounds.
  • R 6 , R 7 and R 8 each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms, R 6 , R 7 and at least R 8
  • One is a hydrocarbon oxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 10, and A 2 represents a polar functional group having no active hydrogen.
  • R 6 , R 7 and R 8 each independently represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon oxy group having 1 to 4 carbon atoms. At least one of R 6 , R 7 and R 8 is charcoal It is preferably a hydrocarbon oxy group having 1 to 4 elemental atoms, and R 6 , R 7 and R 8 are all hydrocarbon oxy groups having 1 to 4 carbon atoms.
  • the hydrocarbon groups having 1 to 4 carbon atoms of R 6 , R 7 and R 8 include methyl group, ethyl group, ⁇ -propyl group, isopropyl group, ⁇ -butyl group, sec-butyl group, t One butyl group can be mentioned. As these hydrocarbon groups, a methyl group or an ethyl group is preferable.
  • hydrocarbonoxy group having 1 to 4 carbon atoms of RR 2 and R 3 a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group , T-butoxy group.
  • hydrocarbon hydrocarbon oxy groups are preferably methoxy groups or ethoxy groups.
  • n represents an integer of 0 to 10; From the viewpoint of improving fuel economy, it is preferably 3 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less.
  • a 2 represents a polar functional group having no active hydrogen, and examples thereof include a group represented by formula (II) and a group represented by 'formula' (III). ,
  • R 3 and R 4 each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a nitrogen atom, an oxygen atom or a key atom, and R 3 and R 4 represent It may be bonded to form a ring structure.
  • X represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom
  • R 5 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. . ]
  • X are each represented by formula (II) in A 1 a group represented by the group represented by formula (III), are the same as exemplified for R 3, RR 5 and X, a group represented by the formula ([pi), a group represented by the formula (III), R 3 , R 4 , R ′ 5 and X are preferably groups represented by the formula (II) in A 1 , a group represented by the formula (III), R 3 , R 4 , R 5 and The same as the preferable group of X.
  • the preferred group for A 2 is the same as the preferred group for A 1 .
  • the key compounds in which A 2 is an acyclic amino group represented by the formula (II) are [3- (Jetylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl. Triethoxysilane is preferred.
  • [3-(jetylamino) propyl] methyldimethoxysilane is preferable from the viewpoint of achieving both the fuel saving cost and the availability of the compound and the long-term storage stability.
  • Examples of the silicon compound represented by the formula (IV) include 3-morpholinopropyltrimethoxysilane, 3-morpholinopropyltriethoxysilane, and the like, wherein A 2 is a cyclic amino group represented by the formula (II). , 3-morpholinopropylmethyldimethyl dioxy
  • 5-imidazole 3-hexamethyleneiminopropyltrimethoxysilane, 3-hexamethyleneiminopropyltriethoxysilane, 3-hexamethyleneimi Nopropylmethyldimethoxysilane, 3-hexamethyleneiminopropylethyl dimethoxysilane, 3-hexamethyleneiminopropylmethyljetoxysilane.
  • N- (3-trimethoxysilylpropyl) —4,5-dihydroimidazole N is a key compound in which A 2 is a cyclic amino group represented by the formula (II). -(3-triethoxysilylpropyl) —4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) _ 4,5-imidazole, N- (3-triethoxysilylpropyl) -4,5 —Imidazole is preferred.
  • Examples of the key compound represented by the formula (IV) include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxy as a key compound in which A 2 is a group represented by the formula (III).
  • Examples thereof include propyltriethoxysilane, 3-dalysidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, and 3-glycitoxysilane.
  • the key compound in which A 2 is a group represented by the formula (III) is as follows: From the viewpoint of improving the fuel efficiency, the availability of the compound, and the long-term storage stability, (Doxypropyl) Trimethoxysilane is preferred.
  • the addition of the silicon compound represented by formula (IV) in Step 2 is performed at a time while the hydrocarbon solution is stirred.
  • the addition rate of the key compound is preferably 6 mmol Zsec per unit volume and unit time of the hydrocarbon solvent from the viewpoint of improving fuel economy (from the viewpoint of increasing the peak L area of the conjugated gen-based polymer).
  • the supplementary acceleration is preferably 100 million mmol / sec or less Zm 3 .
  • the addition amount of the silicon compound is the same as that of the alkali metal catalyst used in step 1. From the viewpoint of improving fuel economy per mole (from the viewpoint of increasing the peak L area of the conjugated gen-based polymer), it is preferably at least 0.5 mole, more preferably at least 0.8 mole. In addition, from the viewpoint of improving economics during production, the amount is preferably 10 mol or less, more preferably 2 mol or less.
  • the silicon compound may be added to the hydrocarbon solution as a solution in a solvent that does not deactivate the alkali metal catalyst such as tetrahydrofuran or hexane.
  • the concentration of the conjugated gen-based polymer in the hydrocarbon solution before adding the silicon compound is from the viewpoint of improving fuel efficiency (from the viewpoint of increasing the peak L area of the conjugated gen-based polymer). It is preferably 30% by weight or less, more preferably 20% by weight or less. From the viewpoint of increasing productivity, it is preferably 5% by weight or more, and more preferably 10% by weight or more.
  • the stirring speed of the hydrocarbon solution when adding the silicon compound is preferably 30 rpm or more, more preferably 50 rpm or more, and even more preferably 7 O rpm. Further, from the viewpoint of improving economy, it is preferably 40 O r pm or less, more preferably 3 0 0 r pm, and further preferably 2 0 0 r pm or less. Further, the temperature of the hydrocarbon solution when adding the silicon compound is usually 35 to 65 T :.
  • the hydrocarbon solution of the conjugated diene polymer having an alkali metal terminal obtained in step 1 is added to the following formula:
  • the indicated coupling agent may be added.
  • R 9 represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group
  • M represents a silicon atom or a tin atom
  • L represents a halogen atom
  • a is an integer of 0 to 2
  • Examples of the coupling agent represented by the above formula include silicon tetrachloride, methyl trichloro.rosilan, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyl trichlorotin, dimethyldichlorotin, trimethylchlorotin, and the like. .
  • the addition amount of the coupling agent is preferably 0.03 mol or more, more preferably 0.0 mol or more, from the viewpoint of improving the kneading processability of the conjugate polymer based on 1 mol of the alkali metal of the alkali metal catalyst. 5 moles or more. Further, from the viewpoint of improving fuel economy, it is preferably 0.4 mol or less, more preferably 0.3 mol or less. ''
  • Conjugated polymers can be obtained by a known recovery method, for example, (1) a method of adding a coagulant to a hydrocarbon solution of a conjugated diene polymer, (2) By the method of adding a team, it can be recovered from the hydrocarbon solution of the conjugate conjugate polymer after the treatment in Step 2.
  • the recovered conjugation polymer may be dried with a known dryer such as a band dryer or an extrusion dryer.
  • the conjugated gen-based polymer of the present invention can be used as a conjugated gen-based polymer composition by blending other polymer components and additives.
  • Examples of other polymer components include conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and butyl rubber. be able to.
  • natural rubber, ethylene-propylene copolymer, ethylene-octene copolymer and the like can also be mentioned. Two or more of these polymer components may be used in combination.
  • additives can be used, such as sulfur vulcanizing agents; vulcanization accelerators such as thiazol vulcanization accelerators, thiuram vulcanization accelerators, and sulfenamide vulcanization accelerators.
  • Vulcanization activators such as stearic acid and zinc oxide; organic peroxides; fillers such as silica, carbon black, calcium carbonate and talc; silane coupling agents; extension oils; processing aids; Agents: Lubricants can be exemplified.
  • silica As the filler.
  • the amount of silica is usually 10 to 150 parts by weight.
  • the blending amount is preferably 20 parts by weight or more, more preferably 30 parts by weight, from the viewpoint of improving fuel efficiency, with the blending amount of the conjugate conjugate polymer of the present invention being 100 parts by weight. Or more. Further, from the viewpoint of enhancing the reinforcing property, it is preferably 120 parts by weight or less, more preferably 100 parts by weight or less.
  • the blending amount of the conjugate polymer of the present invention is 10% from the viewpoint of improving fuel economy.
  • it is preferably 10 parts by weight or more, more preferably 20 parts by weight or more.
  • the blending amount of the other filler is preferably 50 parts by weight or less, more preferably 30 parts by weight, from the viewpoint of improving fuel economy, with the total blending amount of the filler being 100 parts by weight. It is as follows. In addition, from the viewpoint of enhancing reinforcement, the amount is preferably 1 part by weight or more, more preferably 3 parts by weight or more.
  • An example of a method for producing a composition comprising the conjugation polymer of the present invention and silica is a production method having the following step 3 in addition to the above step 1 and step 2.
  • Step 3 The conjugation polymer obtained in Step 2 and silica are blended. 'In step 3, other polymer components and other additives may be blended.
  • a blending method in Step 3 a known method, for example, a method of kneading each component with a known mixer such as a roll or a Banbury machine can be used.
  • the kneading temperature is usually 50 to 200 ° C., preferably 80 to 19.
  • the kneading time is usually 30 seconds to 30 minutes, preferably 1 minute to 30 minutes.
  • the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C.
  • a composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization.
  • the vulcanization temperature is usually
  • step 3 the compounding amount of the conjugation polymer obtained in step 2, the compounding amount of silica, the compounding amount of the other polymer components, and the compounding amount of the filler other than silica are as described above. An amount is preferred.
  • the conjugate conjugate polymer and conjugate conjugate polymer composition of the present invention are excellent in fuel efficiency. It also has good processability, grip, wear resistance, and strength.
  • the conjugation-based polymer and the conjugation-based polymer composition of the present invention are used for tires, shoe sole flooring materials, vibration-proofing materials and the like, and are particularly preferably used for tires.
  • the physical properties were measured by the following method.
  • the measurement was performed under the following conditions (1) to (8) using a gel permeation chromatograph (GPC) method.
  • GPC gel permeation chromatograph
  • a stainless steel polymerization reactor with an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen.
  • Hexane (specific gravity 68gZcm 3 ) 10.2kg, 1,3-butadiene 608g, styrene 192g, tetrahydrofuran 6 lml, ethylene glycol jetyl ether 5.0ml was added.
  • n-butyl lithium 13.8 mmo 1 was added as an n-hexane solution, the temperature in the polymerization reactor was adjusted to 65, and 1,3-butadiene and styrene were fed to the polymerization reactor. Polymerization was performed for 3 hours to obtain a polymer solution.
  • 1,3-butadiene was supplied in 912 g, and styrene was supplied in 288 g.
  • the obtained polymer solution was stirred at a stirring speed of 130 rpm, and [3- (Jetylamino) propyl] trimethoxysilane 11.3 mm o 1 was added to the polymer solution in 1 second.
  • silica made by Degussa, trade name: Ultrasil VN3-G
  • silane coupling agent made by Degussa, trade name: Si 69
  • extension oil manufactured by Kyodo Oil Co., Ltd., trade name: X-140
  • anti-aging agent manufactured by Sumitomo Chemical, trade name: Antigen 3C
  • n-Butyllithium 20. 7 mmo 1 was added as an n-hexane solution to initiate polymerization, and [3- (Jetylamino) propyl] trimethoxysilane 18.2 mm o 1 was added to 50 ml of hexane. The same procedure as in Example 1 was performed except that the solution was added to the polymer solution over 10 minutes. Table 1 shows the results of measuring the physical properties of the polymer and the fuel efficiency evaluation results of the vulcanized sheet. table 1
  • a stainless steel polymerization reactor with an internal volume of 20 liters was washed, dried and replaced with dry nitrogen, then hexane (specific gravity 68 g // cm 3 ) 10.2 kg, 1,3-butagen 608 g, styrene 192 g, tetrahydrofuran (6 lml), and ethylenedalchol jetyl ether (5.0 ml) were added.
  • n-butyllithium 16.7 mmo 1 was added as an n-hexane solution, the temperature in the polymerization reactor was adjusted to 65, and 1,3-butadiene and styrene were fed to the polymerization reactor. Polymerization was performed for 3 hours to obtain a polymer solution.
  • 1,3-butadiene was supplied in 912 g, and styrene was supplied in 288 g.
  • the resulting polymer solution was stirred at a stirring speed of 130 rpm, and 3-glycidoxyl pyrtrimethoxysilane 14.3 mm o 1 was added to the polymer solution in 1 second, and the polymer solution was stirred for 60 minutes.
  • 10 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
  • VN3-G 78. 4 parts by weight, silane coupling agent (Degussa, product name: Si 69) 6.4 parts by weight, carbon 6.4 parts by weight, extension oil (manufactured by Kyodo Oil Co., Ltd., product) Name: X—140) 47. 6 parts by weight, anti-aging agent (trade name: Antigen 3C, manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator
  • Vulcanization was performed by heating at 160 ° C for 45 minutes, and the fuel efficiency of the vulcanized sheet was evaluated. Table 2 shows the evaluation results. Comparative Example 2.
  • Example 2 The same procedure as in Example 2 was conducted, except that 3-glycidoxypropyltrimethoxysilane was added to the polymer solution as a 50 ml tetrahydrofuran solution over 10 minutes.
  • Table 2 shows the physical property measurement results of the obtained polymer and the fuel efficiency evaluation results of the vulcanized sheet.
  • a filler when blended, particularly when silica is blended, a conjugation-based polymer capable of obtaining a polymer composition excellent in fuel-saving properties, a method for producing a conjugated-gen polymer,
  • a polymer composition comprising a polymer based on silica and a method for producing the polymer composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un polymère de diène conjugué, un procédé de fabrication du polymère de diène conjugué, une composition de polymère de diène conjugué et un procédé de fabrication de la composition de polymère de diène conjugué. Le polymère de diène conjugué est un polymère de diène conjugué ayant une unité monomère à base de diène conjugué et un groupe représenté par la formule (I), dans lequel, en considérant que l'aire totale de la courbe de distribution de masse moléculaire obtenue par chromatographie par perméabilité de gel représente 100 %, l'aire de pic du pic de masse moléculaire à la masse moléculaire la plus basse est de 50 % ou plus. [Dans la formule, R1 et R2 représentent chacun indépendamment un groupe hydrocarboné, un groupe hydrocarbonéoxy ou un groupe hydroxyle, m représente un entier de 0 à 10, et A1 représente un groupe fonctionnel polaire exempt d'un atome d'hydrogène actif.]
PCT/JP2006/318797 2006-09-15 2006-09-15 Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué WO2008032417A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/JP2006/318797 WO2008032417A1 (fr) 2006-09-15 2006-09-15 Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué
CNA2006800558435A CN101511884A (zh) 2006-09-15 2006-09-15 共轭二烯类聚合物、共轭二烯类聚合物的制造方法、共轭二烯类聚合物组合物以及共轭二烯类聚合物组合物的制造方法
DE112006004023.5T DE112006004023B4 (de) 2006-09-15 2006-09-15 Konjugiertes-Dien-Polymer, Verfahren zur Herstellung eines Konjugiertes-Dien-Polymers, Konjugiertes-Dien-Polymerzusammensetzung und Verfahren zur Herstellung einer Konjugiertes-Dien-Polymerzusammmensetzung

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/318797 WO2008032417A1 (fr) 2006-09-15 2006-09-15 Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué

Publications (1)

Publication Number Publication Date
WO2008032417A1 true WO2008032417A1 (fr) 2008-03-20

Family

ID=39183488

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/318797 WO2008032417A1 (fr) 2006-09-15 2006-09-15 Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué

Country Status (3)

Country Link
CN (1) CN101511884A (fr)
DE (1) DE112006004023B4 (fr)
WO (1) WO2008032417A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015086039A1 (fr) 2013-12-09 2015-06-18 Trinseo Europe Gmbh Polymères élastomères modifiés par un silane
CN111032744A (zh) * 2017-08-18 2020-04-17 Jsr株式会社 橡胶组合物的制造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112019005573A2 (pt) * 2016-09-23 2019-06-04 Japan Elastomer Co Ltd polímero de dieno conjugado modificado, composição de polímero de dieno conjugado modificado, pneu e método para produção de polímero de dieno conjugado modificado
JP7089850B2 (ja) * 2017-03-31 2022-06-23 住友化学株式会社 共役ジエン系重合体及び共役ジエン系重合体の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186748A (ja) * 1987-01-28 1988-08-02 Sumitomo Chem Co Ltd 変性ゴム組成物
JPH0987426A (ja) * 1995-09-20 1997-03-31 Bridgestone Corp ゴム組成物の製造方法
JP2001158834A (ja) * 1999-12-02 2001-06-12 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2005290355A (ja) * 2004-03-11 2005-10-20 Sumitomo Chemical Co Ltd 変性ジエン系重合体ゴム及びその製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60255838A (ja) 1984-06-01 1985-12-17 Japan Synthetic Rubber Co Ltd タイヤ用ゴム組成物
DE3789203T2 (de) 1986-12-01 1994-06-01 Sumitomo Chemical Co Verfahren zur Herstellung von modifizierten Kautschuk-Dienpolymeren.
JP2540901B2 (ja) 1988-02-25 1996-10-09 住友化学工業株式会社 変性ゴム組成物
US5189109A (en) 1988-02-25 1993-02-23 Sumitomo Chemical Company, Limited Modified diene polymer rubbers
CA1338805C (fr) * 1988-05-02 1996-12-17 Akio Imai Caoutchoucs de polymeres dieniques modifies
FR2722503A1 (fr) * 1994-07-15 1996-01-19 Michelin & Cie Polymeres dieniques fonctionnels, leur procede de preparation et leur utilisation dans des compositions elastomeres chargees a la silice utilisables pour des enveloppes de pneumatiques
JP4159993B2 (ja) * 2001-12-03 2008-10-01 株式会社ブリヂストン 変性重合体の製造方法、その方法で得られた変性重合体及びゴム組成物
US20050203251A1 (en) * 2004-03-11 2005-09-15 Sumitomo Chemical Company, Limited Process for producing modified diene polymer rubber

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186748A (ja) * 1987-01-28 1988-08-02 Sumitomo Chem Co Ltd 変性ゴム組成物
JPH0987426A (ja) * 1995-09-20 1997-03-31 Bridgestone Corp ゴム組成物の製造方法
JP2001158834A (ja) * 1999-12-02 2001-06-12 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2005290355A (ja) * 2004-03-11 2005-10-20 Sumitomo Chemical Co Ltd 変性ジエン系重合体ゴム及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015086039A1 (fr) 2013-12-09 2015-06-18 Trinseo Europe Gmbh Polymères élastomères modifiés par un silane
CN111032744A (zh) * 2017-08-18 2020-04-17 Jsr株式会社 橡胶组合物的制造方法

Also Published As

Publication number Publication date
DE112006004023B4 (de) 2020-08-27
DE112006004023T5 (de) 2009-07-23
CN101511884A (zh) 2009-08-19

Similar Documents

Publication Publication Date Title
JP5682599B2 (ja) 共役ジエン系重合体および共役ジエン系重合体組成物
JP5391557B2 (ja) 共役ジエン系重合体、共役ジエン系重合体の製造方法及び共役ジエン系重合体組成物
JP5287605B2 (ja) 共役ジエン系重合体、共役ジエン系重合体組成物及び共役ジエン系重合体の製造方法
JP5287606B2 (ja) 共役ジエン系重合体、共役ジエン系重合体組成物及び共役ジエン系重合体の製造方法
JP5727895B2 (ja) ゴム組成物及び空気入りタイヤ
JP5623925B2 (ja) ゴム組成物及び空気入りタイヤ
JP5623926B2 (ja) ゴム組成物及び空気入りタイヤ
JP5623986B2 (ja) ゴム組成物及び空気入りタイヤ
JP4846250B2 (ja) ゴム組成物及びそれを用いた空気入りタイヤ
JP2012131890A (ja) ゴム組成物及びスタッドレスタイヤ
JP2012131893A (ja) ゴム組成物及びスタッドレスタイヤ
JP2012229286A (ja) ゴム組成物及び空気入りタイヤ
JP2012131891A (ja) ゴム組成物及びスタッドレスタイヤ
WO2012147912A1 (fr) Composition de caoutchouc et bandage pneumatique
US8633281B2 (en) Conjugated diene polymer, process for producing conjugated diene polymer, conjugated diene polymer composition and process for producing conjugated diene polymer composition
JP5628750B2 (ja) ゴム組成物及び空気入りタイヤ
JP2012131892A (ja) ゴム組成物及びスタッドレスタイヤ
JP2012229285A (ja) ゴム組成物及び空気入りタイヤ
JP2013014733A (ja) ゴム組成物及び空気入りタイヤ
WO2008032417A1 (fr) Polymère de diène conjugué, procédé de fabrication d'un polymère de diène conjugué, composition de polymère de diène conjugué et procédé de fabrication d'une composition de polymère de diène conjugué
JP2012229385A (ja) ゴム組成物及び空気入りタイヤ
JP5140974B2 (ja) 共役ジエン系重合体及び共役ジエン系重合体組成物
JPWO2018025998A1 (ja) 変性共役ジエン系重合体の製造方法及び重合体組成物の製造方法
JP2013124328A (ja) ベーストレッド用ゴム組成物及び空気入りタイヤ
JP2012255076A (ja) ゴム組成物及び空気入りタイヤ

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680055843.5

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06798236

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1120060040235

Country of ref document: DE

WWE Wipo information: entry into national phase

Ref document number: 12440254

Country of ref document: US

RET De translation (de og part 6b)

Ref document number: 112006004023

Country of ref document: DE

Date of ref document: 20090723

Kind code of ref document: P

122 Ep: pct application non-entry in european phase

Ref document number: 06798236

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP