WO2015199222A1 - 水素化重合体の製造方法 - Google Patents
水素化重合体の製造方法 Download PDFInfo
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- WO2015199222A1 WO2015199222A1 PCT/JP2015/068513 JP2015068513W WO2015199222A1 WO 2015199222 A1 WO2015199222 A1 WO 2015199222A1 JP 2015068513 W JP2015068513 W JP 2015068513W WO 2015199222 A1 WO2015199222 A1 WO 2015199222A1
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- 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
- C08F4/60—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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/60—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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
Definitions
- the present invention relates to a method for producing a hydrogenated polymer. Specifically, the present invention relates to a conjugate of a polymer in which at least a part of a living polymer obtained by polymerizing a monomer containing an organic alkali metal compound as a polymerization initiator and containing one or more conjugated dienes is terminated with a hydrogen molecule. The present invention relates to a method for producing a hydrogenated polymer by hydrogenating a carbon-carbon double bond based on a diene constituent unit.
- a conjugated diene polymer obtained by copolymerizing one or more conjugated dienes, or one or more conjugated dienes and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator has heat resistance and oxidation resistance.
- Weather resistance, ozone resistance, etc. can be improved by hydrogenating a carbon-carbon double bond based on the conjugated diene constituent unit of the polymer, and the hydride of such a conjugated diene polymer is an elastic body or a thermoplastic elastomer. It is known that it is useful industrially.
- a Ziegler-type catalyst such as nickel or cobalt has been suitably used.
- the catalyst residue derived from the Ziegler-type catalyst is extracted from the hydrogenation reaction solution. It was necessary to remove by means such as washing.
- titanocene-based compounds a solution obtained by reacting bis (cyclopentadienyl) titanium dichloride with 2 equivalents of trimethylaluminum in a toluene solvent is called a Tebbe reagent and is mainly present in ⁇ -chloro- ⁇ -methylene- Bis ( ⁇ 5 -cyclopentadiel) titanium dimethylaluminum (Cp 2 TiCH 2 AlClMe 2 ) is known as the Teve complex. Further, the Teve complex can be isolated from the Teve reagent by recrystallization (see Non-Patent Documents 1 to 3).
- Tebbe type metallacycle compound represented by a Tebbe complex is useful as a catalyst for hydrogenating a carbon-carbon double bond based on a conjugated diene constituent unit of a conjugated diene polymer (patent) References 2-3 and 6-8).
- At least one conjugated diene is polymerized or copolymerized using an organic alkali metal compound as a polymerization initiator in the presence of a solvent, and then reacted with hydrogen.
- a method of selectively hydrogenating unsaturated double bonds in a conjugated diene constituent unit by stopping and reacting the obtained conjugated diene polymer with hydrogen in the presence of an accelerator which is an organic alkali metal compound and a Tebbe complex In order to achieve a hydrogenation rate of 95% or more, the alkali metal atom / titanium atomic ratio is at least 2 or more, preferably 5 to 15.
- the conjugated diene polymer solution has a high viscosity (the conjugated diene polymer has a high molecular weight)
- an alkali metal hydride is prepared in the system by adding an organoalkali metal compound to the system before and after the polymerization termination reaction and then reacting with hydrogen dispersed by a spargers. It is disclosed that it can be done.
- Patent Documents 4 and 5 disclose a hydrogenation reaction in which lithium hydride coexists using a titanocene compound that is different from the Tebbe type metallacycle compound.
- a living polymer is produced by homopolymerizing or copolymerizing at least one conjugated diene using an organolithium compound as an initiator, and (2) the same living polymer is formed. After the end treatment with an equivalent amount of the end-modifying substance, (3) a specific monocyclopentadienyl titanium compound, an organic lithium compound and lithium hydride produced from hydrogen are individually added to the end-treated polymer.
- a method for selectively hydrogenating a polymer containing a conjugated diene by mixing externally is disclosed.
- Patent Document 5 (a) a step of polymerizing or copolymerizing at least one conjugated diene with an organic alkali metal polymerization initiator in a hydrocarbon solvent to form a living polymer, and (b) the living polymer.
- the active terminal is deactivated by adding one or more terminal modifiers selected from the group consisting of amines, alcohols, esters, ketones, and halogens to form a conjugated diene polymer.
- Non-Patent Document 4 discloses a nanometer-sized sodium hydride (specific surface area 90 m 2 / g) prepared in a hydrogenation reaction of a terminal alkene such as 1-hexene with a titanocene compound using sodium hydride as a cocatalyst. Although it showed high hydrogenation activity, it has been reported that the hydrogenation reaction does not proceed at all when commercially available sodium hydride (specific surface area of 1.4 m 2 / g) is used.
- Patent Document 6 discloses a conjugated diene polymer obtained by polymerizing an organic alkali metal compound (M is the molar amount of the alkali metal compound contained) as a polymerization initiator, and a deactivator (molar amount of the deactivator).
- An organic titanium compound (organic compound) that is a Tbbe-type metallacycle compound when hydrogenating a double bond of a conjugated diene unit by bringing it into contact with hydrogen in an inert hydrocarbon solvent.
- the conjugated diene polymer is used in the range of ⁇ 6 ⁇ (MZ + Al—Ti) / Ti ⁇ + 2 in the presence of Ti.
- the molar amount of the titanium compound is Ti.
- the molar amount of the organoaluminum compound is Al.
- a hydrogenation method is disclosed.
- Ti corresponds to the total molar amount of the unreacted organotitanium compound as a raw material for synthesizing the Tebbe type metallacycle compound, the Tebbe type metallacycle compound and other organic titanium compounds by-produced
- Al represents the Tebbe type metallacycle compound.
- This corresponds to the total molar amount of the unreacted organoaluminum compound as a raw material for the synthesis of the cycle compound, aluminum present in the Tebbe type metallacycle compound and aluminum in other organotitanium compounds by-produced.
- a conjugated diene polymer obtained by polymerizing an organic alkali metal compound as a polymerization initiator is hydrogenated using a metallocene hydrogenation catalyst to obtain a conjugated diene polymer having a hydrogenation rate of 98% or more.
- the conjugated diene polymer is characterized in that the hydrogenation catalyst is divided into two or more times, preferably at a time when the hydrogenation rate is 60% to 95%, the hydrogenation catalyst is added once or more and the hydrogenation proceeds.
- a hydrogenation method is disclosed. It is also disclosed that the addition timing of the hydrogenation catalyst is determined by measuring the hydrogen absorption rate (see Patent Document 8).
- the metallocene hydrogenation catalyst a Tebbe type metallacycle compound is mentioned.
- Patent Document 9 discloses a catalyst composition comprising at least one kind of oxygen-containing organic compound or nitrogen-containing organic compound having 2 or more carbon atoms and a salt thereof and a Tebbe-type metallacycle compound.
- the catalyst composition is used to hydrogenate an olefinic compound, particularly an olefinically unsaturated double bond of a conjugated diene polymer, it is used at a level that does not require decalcification without using a co-catalyst alkyl alkali metal compound. It is disclosed that the catalyst has sufficient hydrogenation catalytic activity in an amount and is excellent in heat resistance of the catalyst. It is also disclosed that long-term storage stability can be improved and active stability can be maintained over a long period by further combining certain other organometallic compounds as appropriate.
- Patent Documents 10 and 11 disclose that a titanocene compound, a specific silylhydride compound, and an alkali metal hydride, an alkali metal alkoxide, an organoaluminum compound, an organomagnesium compound, an organic compound as a third component, which are different from the Teve type metallacycle compound.
- a hydrogenation reaction of a conjugated diene polymer having high hydrogenation activity and excellent catalyst stability (heat resistance and storage stability) in which a zinc compound, an organic titanium compound other than a titanocene compound, etc. coexist is disclosed.
- the hydrogenation catalytic activity of the titanocene compound depends on the specific surface area of the sodium hydride to be added.
- it is effective to produce an alkali metal hydride as a cocatalyst (reducing agent) in the system, preferably by a specific method, from the viewpoint of enhancing the hydrogenation reaction catalytic activity of the titanocene compound.
- gaseous hydrogen supplied through a high-speed injection nozzle to act with alkyllithium.
- Patent Document 6 does not require an alkali metal compound as a co-catalyst and defines a range of “ ⁇ 6 ⁇ (M ⁇ Z + Al—Ti) / Ti ⁇ + 2”.
- the agent (Z) there is a problem that the titanium concentration in an actual hydrogenation reaction system is several tens of ppm.
- the total addition amount of the metallocene catalyst by divided addition increases from 25 ppm to 70 ppm in order to achieve a high hydrogenation rate.
- the oxygen-containing organic compound or nitrogen-containing organic compound having 2 or more carbon atoms used together with the Tube-type metallacycle compound in the method of Patent Document 9 may lead to a decrease in hydrogenation catalytic activity depending on the amount of use. This is pointed out in Patent Document 6.
- R 1 to R 10 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a trialkylsilyl group having an alkyl group having 1 to 12 carbon atoms, wherein R 1 to R Any two adjacent groups out of 5 may form a ring, and any two adjacent groups out of R 6 to R 10 may form a ring, and one of R 1 to R 5 And one of R 6 to R 10 may be bridged to each other directly or via a divalent organic group.
- organometallic compound (I) organometallic compound
- a silane compound having at least one silyl hydride bond (hereinafter sometimes referred to as silane compound (II)) is a silyl hydride compound represented by the following general formula (II-1): 2) at least one selected from a silylhydride polymer compound represented by 2), a
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently a hydrogen atom, a halogen atom, Represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group or a carboxyl group, n represents a positive number of 0 or more, and m represents an integer of 2 to 5 To express.); [3] Silane compound (II) is methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, pentyldichlorosilane, hexyldichlorosilane, heptyldichlorosilane
- the conjugated diene block B of the living polymer contains at least one of butadiene or isoprene and the vinyl aromatic compound block S contains at least styrene, and at least a part of the living polymer is terminated with hydrogen molecules.
- the polymer has a standard polystyrene equivalent weight average molecular weight measured by gel permeation chromatography of 50,000 to 500,000 and a molecular weight distribution of 1.00 to 1.25, and the content of structural units derived from conjugated dienes in the polymer is
- the amount of the organometallic compound (I) used per 1 mol of the carbon-carbon double bond based on the conjugated diene structural unit contained in the polymer is 1.0 ⁇ as titanium atoms of the organometallic compound (I). Titanium possessed by the organometallic compound (I) is in the range of 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 1 mmol, and the amount of the silane compound (II) used is the number of moles of silicon atoms constituting the silylhydride bond.
- the amount of the organometallic compound (I) used per 1 mol of the carbon-carbon double bond based on the conjugated diene structural unit contained in the polymer is 1.0 ⁇ as titanium atoms of the organometallic compound (I).
- the range of 10 ⁇ 3 to 1.0 ⁇ 10 ⁇ 2 mmol and the amount of the silane compound (II) used is the titanium of the organometallic compound (I) as the number of moles of silicon atoms constituting the silylhydride bond.
- the method for producing a hydrogenated polymer according to [7] which is in the range of 1 to 500 moles per mole of atoms; [9]
- organometallic compound (I) by reacting trititanium aluminum in an organic solvent with titanocene dichloride (hereinafter referred to as titanocene dichloride (III)) represented by formula (1), and using such organometallic compound (I)
- titanocene dichloride (III) A process for producing a hydrogenated polymer according to any one of [1] to [8];
- Titanocene dichloride (III) is bis (cyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (tert-cyclopentadienyl) titanium dichloride, bis (pentamethylcyclopenta).
- the method for producing a hydrogenated polymer according to [9] which is at least one of dienyl) titanium dichloride, dichlorobis (fluorenyl) titanium, and dichlorobis (indenyl) titanium.
- a hydrogenated polymer is produced by selectively hydrogenating a carbon-carbon double bond based on a conjugated diene constituent unit of a conjugated diene polymer using a Tebbe type metallacycle compound as a hydrogenation catalyst.
- a hydrogenated polymer can be produced industrially advantageously.
- the hydrogenation catalyst system used in the production method of the present invention is very highly active.
- the polymer to which the production method of the present invention can be applied is a polymer in which at least a part of a living polymer obtained by polymerizing a monomer containing one or more conjugated dienes using an organic alkali metal compound as a polymerization initiator is terminated with hydrogen molecules. It is a coalescence.
- a hydrogenated polymer is obtained by selectively hydrogenating a carbon-carbon double bond based on a conjugated diene constituent unit contained in such a polymer.
- organic alkali metal compound used for the polymerization initiator examples include methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, butyl lithium, sec-butyl lithium, tert-butyl lithium, isobutyl lithium, pentyl lithium, hexyl lithium, butadieni Ryl lithium, cyclohexyl lithium, phenyl lithium, benzyl lithium, p-toluyl lithium, styryl lithium, trimethylsilyl lithium, 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1 , 1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilich
- n-butyllithium and sec-butyllithium are preferable.
- An organic alkali metal compound may be used individually by 1 type, or may use 2 or more types together.
- the usage-amount of an organic alkali metal compound can be suitably set according to the weight average molecular weight of a desired living polymer, or the living polymer concentration in a living polymer solution.
- conjugated diene examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1, 3-hexadiene, 4,5-diethyl-1,3-butadiene, phenyl-1,3-butadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3- Cyclohexadiene, 1,3,7-octatriene, myrcene (7-methyl-3-methyleneocta-1,6-diene), farnesene (3,7,11-trimethyl-1,3,6,10-dodecatetra)
- conjugated dienes having 4 to 15 carbon atoms are mentioned, but not limited thereto. These conjugated dienes may be used alone or in combination of two or more. It preferably contains buta
- the polymer applicable to the present invention is not particularly limited as long as it has a structural unit composed of one or more conjugated dienes. That is, it may be a homopolymer of one type of conjugated diene or a copolymer of two or more types of conjugated dienes, and other monomers that can be polymerized using one or more types of conjugated dienes and an organic alkali metal compound as a polymerization initiator. And a copolymer.
- the bonding mode is not particularly limited, and any of a random copolymer, a block copolymer, a block copolymer having a tapered structure, a star copolymer and the like may be used.
- Examples of other monomers that can be polymerized using an organic alkali metal compound as a polymerization initiator include vinyl aromatic compounds.
- vinyl aromatic compounds include styrene, ⁇ -methylstyrene, ⁇ -methyl-4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5- Dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene, 4-tert-butylstyrene 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (4-pheny
- a polymer in which at least a part of a living polymer polymerized using an organic lithium compound as an organic alkali metal compound is terminated with hydrogen molecules.
- the living polymer has a conjugated diene block B composed of one or more conjugated dienes and a vinyl aromatic compound block S composed of one or more vinyl aromatic compounds.
- the conjugated diene block B more preferably contains at least one butadiene or isoprene as a structural unit, and more preferably is composed of butadiene, isoprene or a mixture thereof.
- the vinyl aromatic compound block S more preferably contains at least styrene as a structural unit, and more preferably is composed of styrene.
- conjugated diene block B means that the constitutional unit based on conjugated diene is 50% by mass or more
- vinyl aromatic compound block S means constitution based on vinyl aromatic compound. It means that the unit is 50% by mass. That is, the conjugated diene block B may contain a structural unit based on a monomer other than the conjugated diene, and the structural unit based on another monomer other than the vinyl aromatic compound in the vinyl aromatic compound block S. There are no particular restrictions on the bonding mode of the structural units in each block.
- a polymer in which at least a part of a living polymer obtained by polymerizing a monomer containing one or more conjugated dienes using an organic alkali metal compound as a polymerization initiator was stopped with hydrogen molecules was measured by gel permeation chromatography.
- the standard polystyrene equivalent weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 50,000 to 500,000.
- the molecular weight distribution is preferably 1.00 to 3.00, and more preferably 1.00 to 1.25.
- the content of the structural unit derived from the conjugated diene in the polymer is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass.
- a Lewis base can coexist in the polymerization in order to control the bond units).
- Lewis bases include acyclic monoesters such as dimethyl ether, methyl ethyl ether, diethyl ether, ethyl propyl ether, dipropyl ether, butyl methyl ether, tert-butyl methyl ether, dibutyl ether, dioctyl ether, ethyl phenyl ether, and diphenyl ether.
- Lewis bases may be used alone or in combination of two or more. There is no restriction
- the method for producing the polymer used in the present invention is not particularly limited, and may be any of batch, semi-batch and continuous. There is no particular limitation on the type of the reactor, and a complete mixing tank reactor, a tubular reactor, or the like can be used, and two or more of them may be connected in series or in parallel.
- the production of the polymer is preferably performed in the presence of a solvent.
- a solvent water that deactivates the polymerization initiator, hydroxy compounds such as alcohol, hydrocarbons from which ketones have been removed are preferable.
- hydroxy compounds such as alcohol, hydrocarbons from which ketones have been removed are preferable.
- hydroxy compounds such as alcohol, hydrocarbons from which ketones have been removed are preferable.
- hydroxy compounds such as alcohol, hydrocarbons from which ketones have been removed
- a solvent may be used individually by 1 type, or may use 2 or more types together. There is no restriction
- the polymer is preferably produced in an inert gas atmosphere such as nitrogen, argon or helium.
- an inert gas atmosphere such as nitrogen, argon or helium.
- a hydrocarbon solvent and an organic alkali metal compound are charged into a reactor substituted with an inert gas, and the temperature is raised to a predetermined temperature.
- a conjugated diene, another monomer (preferably vinyl aromatic) A living polymer is produced by appropriately adding a compound) and conducting a polymerization reaction.
- the living homopolymer of the conjugated diene is added.
- two or more conjugated dienes are mixed and added, the living of the two or more conjugated dienes is added.
- a random block is added to the living block copolymer of the two or more kinds of conjugated dienes, conjugated dienes and other monomers.
- the living random copolymer of the conjugated diene and vinyl aromatic compound is converted to conjugated diene and other monomer (preferably vinyl aromatic compound).
- the Lewis base for controlling the bonding mode of the conjugated diene may be added simultaneously with the addition of the conjugated diene and other monomers (preferably vinyl aromatic compounds), or charged in the reactor in advance. You can leave it.
- the concentration of the living polymer formed from the conjugated diene and another monomer is not particularly limited, but is usually preferably in the range of 1 to 50% by mass.
- the polymerization temperature in the polymerization reaction can usually be selected from the range of ⁇ 20 to 250 ° C., preferably above the solvent freezing point and below the thermal decomposition temperature of the polymer, and preferably within the range of 30 to 150 ° C.
- the polymer used in the present invention is obtained by stopping at least a part of the living polymer obtained as described above with hydrogen molecules.
- a polymer After acting a polymerization terminator which may have a function as a terminal modifier described below, which is less than equivalent to the active living terminal of the living polymer, a polymer can be obtained by acting a hydrogen molecule.
- a polymer may be obtained by allowing a large excess of hydrogen molecules to act on the active living end of the living polymer.
- Hydrogen gas can be used as the hydrogen molecule.
- the pressure of the hydrogen gas is not particularly limited, and usually the gauge pressure can be selected from the range of 0 (normal pressure) to 20 MPaG, and the range of 0.5 to 10 MPaG is preferable.
- the operation of stopping at least a part of the living polymer with hydrogen molecules is preferably performed by supplying hydrogen gas to the same reactor following the production of the living polymer.
- it can be performed by supplying hydrogen gas into a storage tank storing the solution, and the solution is transferred to a hydrogenation reactor.
- the hydrogen gas can be supplied at the same time, or the hydrogen gas can be supplied after the solution is charged into the hydrogenation reactor.
- a suitable temperature for stopping with hydrogen molecules is the same as the range for producing the living polymer.
- the operation time for stopping at least a part of the living polymer with hydrogen molecules can be selected from the range of 5 minutes to 10 days, and preferably in the range of 15 minutes to 2 hours.
- Examples of the polymerization terminator that may have a function as a terminal modifier of the living polymer include water; methanol, ethanol, propanol, isopropanol, butanol, heptanol, cyclohexanol, phenol, benzyl alcohol, o- Alcohols such as cresol, m-cresol, p-cresol, ethylene glycol, propylene glycol, butanediol, glycerin, catechol; methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, butyl chloride , Butyl bromide, butyl iodide, benzyl chloride, benzyl bromide, benzyl iodide, trimethylsilyl fluoride, trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl i
- the polymer described above when the polymer described above is hydrogenated using a hydrogen molecule and an organometallic compound (I), less organometallic compound (I) is used by coexisting the silane compound (II). Even if it is an amount, the hydrogenation reaction can be pursued, and a hydrogenated polymer having a very small content of catalyst residues can be obtained.
- the organometallic compound (I) used in the production method of the present invention is a TB type metallacycle compound represented by the following general formula (I).
- trimethylaluminum can be produced by reacting them in the presence of an organic solvent.
- Examples of the hydrocarbon group that R 1 to R 10 in the organometallic compound (I) and titanocene dichloride (III) each independently represent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- Examples thereof include an alkyl group which may have a hetero atom such as a butoxy group.
- Examples of the trialkylsilyl group having an alkyl group having 1 to 12 carbon atoms include a trimethylsilyl group and a triethylsilyl group.
- Examples of the ring that any two adjacent groups out of R 1 to R 5 may form and the ring that any two adjacent groups out of R 6 to R 10 may form include, for example, an indenyl group and a fluorenyl group Etc.
- Examples of the structure in which one of R 1 to R 5 and one of R 6 to R 10 are bridged to each other directly or via a divalent organic group include a methylene group, an ethylidene group, 1- Examples thereof include a methyl ethylidene group, an ethylene group, a dimethylsilylene group, and a diethylsilylene group.
- titanocene (III) dichloride for example, bis (cyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (tert-cyclopentadienyl) titanium dichloride, bis Preferred examples include (pentamethylcyclopentadienyl) titanium dichloride, dichlorobis (fluorenyl) titanium, dichlorobis (indenyl) titanium, and the like.
- bis (cyclopentadienyl) titanium dichloride is more preferable from the viewpoint of economy, and ⁇ -chloro- ⁇ -methylene-bis (cyclopentadiel) titanium dimethyl as an organometallic compound (I) is reacted with trimethylaluminum.
- Aluminum (Tube complex) is obtained and is preferably used for the hydrogenation reaction in the production method of the present invention.
- the organic solvent used when reacting titanocene (III) dichloride with trimethylaluminum is not particularly limited as long as it is inert to the reaction.
- titanocene (III) dichloride with trimethylaluminum
- Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene, p-xylene; dimethyl ether, methyl ethyl ether, diethyl ether, ethyl-n-propyl ether , Acyclic monoethers such as di-n-propyl ether, n-butyl methyl ether, tert-butyl methyl
- Acyclic diether such as tetrahydrofuran, tetrahydropyran, 1 Cyclic ethers such as 4-dioxane and 2-methyltetrahydrofuran; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutylene glycol diethyl ether, triethylene glycol dimethyl ether, tripropylene glycol Dimethyl ether, Tributylene glycol dimethyl ether, Triethylene glycol diethyl ether, Tripropylene glycol diethyl ether, Tributylene glycol diethyl ether, Tetraethylene glycol dimethyl ether, Tetrapropylene glycol dimethyl ether, Tetrabutylene glycol dimethyl ether And acyclic polyethers such as tetraethylene glycol diethyl ether, tetrapropylene glycol
- an organic solvent may be used individually by 1 type, or may use 2 or more types together.
- An organic solvent may be used individually by 1 type, or may use 2 or more types together.
- titanocene (III) dichloride may be in a uniform solution, suspension, or solid state, and trimethylaluminum may be diluted with the organic solvent described above.
- the reaction method is not particularly limited, for example, a method in which trimethylaluminum is supplied to a suspension of titanocene (III) dichloride, or a suspension of titanocene (III) dichloride in a solution obtained by diluting trimethylaluminum with an organic solvent. The method of making it react is mentioned.
- titanocene dichloride (III) When reacting titanocene dichloride (III) with trimethylaluminum, it is extremely preferable to carry out the reaction in an inert gas atmosphere such as nitrogen, helium, or argon. From the viewpoint of the stability of the resulting organometallic compound (I), the reaction is carried out. It is very preferable to remove water, alcohol, ketone, oxygen and the like from the raw material and solvent to be used in advance.
- the amount of trimethylaluminum used may be 1 mol or more per 1 mol of titanium atom of titanocene (III) dichloride, preferably 1 to 100 mol times, more preferably 2 to 5 mol times.
- the reaction temperature is not particularly limited, but is usually preferably in the range of 0 to 125 ° C, more preferably in the range of 10 to 50 ° C.
- the reaction time is not particularly limited, but is usually preferably in the range of 1 to 200 hours, more preferably in the range of 24 to 100 hours.
- the solution containing the organometallic compound (I) obtained by reacting titanocene (III) dichloride and trimethylaluminum can be used as it is in the hydrogenation reaction in the production method of the present invention, and is unreacted by distillation. It may be used after removing trimethylaluminum, by-product dimethylaluminum chloride and the like. Or, after isolating and purifying the organometallic compound (I) once by applying the usual separation / purification method in the field of organometallic chemistry, it is dissolved in the same type of solvent as that used in the hydrogenation reaction, and the hydrogenation reaction You may use for. For example, after adding hexane etc. to the solution containing organometallic compound (I) and depositing and isolating organometallic compound (I), it can use for the manufacturing method of this invention.
- Examples of the silane compound having at least one silyl hydride bond used in the production method of the present invention include a silyl hydride compound represented by the following general formula (II-1) and a silyl hydride polymer represented by the following general formula (II-2). It is preferably at least one selected from a compound, a cyclic silylhydride compound represented by the following general formula (II-3), and a silazane compound represented by the following general formula (II-4).
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently a hydrogen atom, a halogen atom, Represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group or a carboxyl group, n represents a positive number of 0 or more, and m represents an integer of 2 to 5 To express.)
- Examples of the silylhydride compound represented by the general formula (II-1) include methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, pentyldichlorosilane, hexyldichlorosilane, heptyldichlorosilane, octyldichlorosilane, and nonyl.
- n is preferably 0 to 100, polymethylhydrosiloxane, polyethylhydrosiloxane, polypropylhydrosiloxane, polybutylhydrosiloxane, Polypentylhydrosiloxane, polyhexylhydrosiloxane, polyheptylhydrosiloxane, polyoctylhydrosiloxane, polynonylhydrosiloxane, polydecylhydrosiloxane, polyphenylhydrosiloxane, 1,1,3,3-tetramethyldisiloxane, etc. It is done.
- Examples of the cyclic silylhydride compound represented by the general formula (II-3) include methylhydrocyclosiloxane, ethylhydrocyclosiloxane, propylhydrocyclosiloxane, butylhydrocyclosiloxane, and phenylhydrocyclosiloxane.
- silazane compound represented by the general formula (II-4) examples include 1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane, 1,1,3,3-tetra Examples thereof include propyldisilazane, 1,1,3,3-tetrabutyldisilazane, 1,1,3,3-tetraphenyldisilazane and the like.
- silylhydride polymer compound represented by the general formula (II-2) is preferable, and polymethylhydrosiloxane is more preferable.
- Silane compound (II) may be used individually by 1 type, or may use 2 or more types together.
- the production method of the present invention is very preferably carried out in the presence of a solvent.
- a solvent is not particularly limited as long as it is inert to the hydrogenation reaction.
- a solvent is not particularly limited as long as it is inert to the hydrogenation reaction.
- a solvent is not particularly limited as long as it is inert to the hydrogenation reaction.
- the solvent used for the production of the polymer can be used as a polymer solution as it is in the hydrogenation reaction, which is the production method of the present invention, and is preferable from the viewpoint of recovering and reusing the solvent.
- the polymer solution can be stored in an atmosphere of an inert gas such as nitrogen, argon or helium, or hydrogen gas, preferably in the range of normal pressure to 5 MPaG and 0 to 50 ° C.
- the organometallic compound (I) can be supplied to the hydrogenation reaction system as a solid, but it is preferable to use it by dissolving it in the same type of solvent as that used in the hydrogenation reaction. From the viewpoint that the ease of use and the amount used can be easily and precisely controlled.
- the concentration is not particularly limited.
- a solution in which the organometallic compound (I) is dissolved in a solvent can be stored in an atmosphere of an inert gas such as nitrogen, argon or helium, preferably at normal pressure to 0.5 MPaG and 0 to 50 ° C.
- an inert gas such as nitrogen, argon or helium
- There is no particular limitation on the storage container and for example, a stainless steel container, a glass-lined container, or the like can be used.
- the amount of the organometallic compound (I) used is not strictly limited, but the organometallic compound (I) has one mole of the carbon-carbon double bond based on the conjugated diene constituent unit of the polymer.
- the titanium atom is preferably in the range of 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 1 mmol, and more preferably in the range of 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 ⁇ 2 mmol. Within this range, a sufficiently practical reaction rate and hydrogenation rate can be achieved industrially, and in particular, when it is 1.0 ⁇ 10 ⁇ 2 mmol or less, the organometallic compound (I) is contained after the hydrogenation reaction is completed.
- the amount of aluminum atom relative to the titanium atom of the organometallic compound (I) depends on the production conditions of the organometallic compound (I) and the purification conditions such as whether it is used after recrystallization or not.
- the amount of aluminum atom relative to 1 mol of titanium atom can range from 0.5 to 100 mol, and from the viewpoint of enhancing the hydrogenation reaction activity per titanium atom, More preferably, the amount of aluminum atoms per mole is in the range of 0.8 to 5 moles.
- the silane compound (II) can be used as it is or dissolved in a solvent, but it is preferable to use it by dissolving it in the same kind of solvent as that used in the hydrogenation reaction. From the viewpoint that the amount used can be easily and precisely controlled.
- the concentration is not particularly limited.
- a solution in which the silane compound (II) is dissolved in a solvent can be stored in an atmosphere of an inert gas such as nitrogen, argon or helium, preferably at normal pressure to 0.5 MPaG and 0 to 50 ° C.
- the storage container there is no particular limitation on the storage container, and for example, a stainless steel container, a glass-lined container, or the like can be used.
- the amount of the silane compound (II) used is not strictly limited, but the number of silicon atoms having a silyl hydride bond per 1 mol of titanium atom is usually preferably in the range of 1 to 500 mol.
- the production method of the present invention can be carried out by any of batch, semi-batch and continuous methods.
- a complete mixing tank reactor, a tubular reactor, or two or more of these may be connected in series or in parallel.
- a polymer solution is first charged under a hydrogen atmosphere, and then (A) a solution of organometallic compound (I) and a solution of silane compound (II) are mixed in advance.
- a method of introducing the solution (B) a method of introducing the solution of the silane compound (II) after introducing the solution of the organometallic compound (I), (C) an organic metal after introducing the solution of the silane compound (II)
- Examples thereof include a method of introducing a solution of compound (I).
- the method B and the method C are preferable in that an apparatus for previously mixing the solution of the organometallic compound (I) and the solution of the silane compound (II) is not necessary.
- the method C is more preferable in that it is utilized.
- the reaction temperature in the production method of the present invention is usually selected from the range of ⁇ 20 to 250 ° C., preferably higher than the solvent freezing point and lower than the thermal decomposition temperature of the polymer, and the range of 30 to 150 ° C. is the hydrogenation reaction activity. From the viewpoint that the hydrogenated polymer can be produced sufficiently and industrially advantageously, and from the viewpoint that the amount of the organometallic compound (I) and the silane compound (II) used as the catalyst component can be reduced, 60 to 90 ° C. The range of is more preferable.
- hydrogen gas can be used as the hydrogen molecule.
- a gauge pressure in the range of 0 (normal pressure) to 20 MPaG can sufficiently develop the hydrogenation reaction activity and industrially produce a hydrogenated polymer. From the viewpoint, the range of 0.5 to 10 MPaG is more preferable from the viewpoint of reducing the amount of the organometallic compound (I) and the silane compound (II) used as the catalyst component.
- the time required for the hydrogenation reaction varies depending on the reaction conditions such as the amount of the organometallic compound (I) and silane compound (II) used as the catalyst component, reaction temperature, hydrogen gas pressure, etc., but the organometallic compound as the catalyst component
- the time when the supply of (I) into the reaction system is completed is defined as 0 minutes from the start of the reaction, and is usually preferably in the range of 10 minutes to 24 hours.
- the reaction solution After completion of the hydrogenation reaction, the reaction solution is further diluted with a solvent or concentrated as necessary, and then washed with a basic aqueous solution or an acidic aqueous solution to obtain an organometallic compound (I) and silane as catalyst components. Compound (II) and the like can be removed.
- the reaction solution may be concentrated without washing and supplied to an extruder as necessary to isolate the hydrogenated polymer.
- the hydrogenated polymer may be isolated by removing the solvent by contacting with steam without washing, or the hydrogenated polymer by removing the solvent by contacting the reaction solution with a heated inert gas. May be isolated.
- organometallic compound (I) used in Examples and Comparative Examples will be described in detail.
- the production of the organometallic compound (I) was carried out at room temperature, normal pressure, and argon atmosphere unless otherwise specified.
- toluene and hexane used in advance were distilled in an argon atmosphere using sodium hydride as a desiccant.
- the titanium atom molar concentration in the catalyst solution containing the organometallic compound (I) was quantified by analyzing these wet decomposition products with a polarized Zeeman atomic absorption spectrophotometer (model Z-2000 manufactured by Hitachi, Ltd.).
- the total molar amount of titanium atoms in the obtained catalyst solution was calculated from the titanium atom molar concentration in the catalyst solution obtained from the catalyst solution mass and atomic absorption analysis. That is, the ratio of the total molar amount of titanium atoms in the obtained catalyst liquid to the molar amount of titanium atoms charged when the catalyst liquid was produced was defined as the yield (%), and was calculated by the following formula 1. Each amount in the formula is (mol).
- the titanium compound present in the catalyst solution obtained in the reference example can take the structures of the following general formulas IV-1 to IV-6.
- 1 H-NMR is obtained from the molar amount of titanium contained in 1 g of catalyst solution based on atomic absorption analysis.
- the molar amount of titanium compounds IV-1 to IV-5 calculated from the analysis was subtracted to obtain the molar amount of titanium compound IV-6.
- the Al / Ti ratio as the aluminum atomic ratio with respect to one titanium atom was calculated.
- the ratio of the molar amount of titanium atoms having an IV-4 structure as the organometallic compound (I) to the total molar amount of titanium atoms in the catalyst solution was defined as purity (%), and was calculated by the following mathematical formula 2. Each amount in the formula is (mol).
- Reference example 1 25.0 g of bis (cyclopentadienyl) titanium dichloride (Cp 2 TiCl 2 , manufactured by Wako Pure Chemical Industries, Ltd.) was added to a 200 mL three-necked flask equipped with a thermometer and a rotor and dried under reduced pressure and then purged with argon. .40 mmol) and 30 g of toluene were added, and the mixture was stirred at 25 ⁇ 2 ° C. for 30 minutes. The reaction was performed at 25 ⁇ 3 ° C. for 60 hours. The obtained reaction solution was concentrated at 10 mmHg (1.33 kPa) and 30 ° C.
- catalyst solution A and Called a catalyst solution
- the total required time from the start of the reaction to the end of the preparation of the catalyst solution A was about 64 hours.
- the catalyst solution A contained 2.57% by mass of titanium atoms (concentration: 0.537 mmol / g), and the total mass of the catalyst solution A was 54.5 g.
- the yield based on was 29.1%.
- the peak attributable to the methylene group of IV-4 is ⁇ 8.49 ppm (2H, s), the peak attributable to the cyclopentadienyl ring is ⁇ 5.85 ppm (10 H, s), and the peak attributable to the dimethylaluminum group is ⁇ -0. .11 ppm (6H, s), and the concentration was 0.496 mmol / g.
- the peak attributable to the methylene group of IV-5 is ⁇ 7.88 ppm (2H, s), the peak attributable to the cyclopentadienyl ring is ⁇ 5.85 ppm (10H, s), and the peak attributable to the dimethylaluminum group is ⁇ -0.
- Reference example 2 A bis (cyclopentadienyl) titanium dichloride (Cp 2 TiCl 2 , manufactured by Wako Pure Chemical Industries, Ltd.) 7.9 g (31) was added to a 100 mL three-necked flask equipped with a thermometer and a rotor and dried under reduced pressure and then purged with argon. 7 mmol) and 21.5 g of toluene were added, and the mixture was stirred at 25 ⁇ 2 ° C. for 30 minutes, and then 35.0 mL of a toluene solution of trimethylaluminum (manufactured by Tokyo Chemical Industry Co., Ltd., 63.5 mmol as trimethylaluminum) was added over 10 minutes.
- Cp 2 TiCl 2 manufactured by Wako Pure Chemical Industries, Ltd.
- catalyst solution B a catalyst solution was obtained by reacting at 25 ⁇ 3 ° C. for 60 hours (hereinafter referred to as catalyst solution B). The total time required from the start to the end of the reaction was about 60 hours.
- the catalyst solution B contained 2.60% by mass of titanium atoms (concentration: 0.543 mmol / g), and the total mass of the catalyst solution B was 57.2 g. The yield based on was 98.0%.
- a peak attributable to the methyl group of IV-3 can be observed at ⁇ 3.26 ppm (6H, s), a peak attributable to the cyclopentadienyl ring at ⁇ 5.85 ppm (10 H, s), and the concentration is 0.012 mmol / g. there were.
- the peak attributable to the methylene group of IV-4 is ⁇ 8.49 ppm (2H, s)
- the peak attributable to the cyclopentadienyl ring is ⁇ 5.85 ppm (10 H, s)
- the peak attributable to the dimethylaluminum group is ⁇ -0. .11 ppm (6H, s), and the concentration was 0.304 mmol / g.
- the concentration of IV-6 obtained from the results of 1 H-NMR analysis and atomic absorption analysis was 0.163 mmol / g. From the concentration of the titanium compounds IV-1 to IV-6, the purity was 56.0%. Further, the Al / Ti ratio was 2.00 from the amount of the chemical solution charged.
- R 1 to R 10 in IV-1 to IV-6 all represent hydrogen atoms.
- MPaG as a pressure notation means a gauge pressure.
- the chemicals used are as follows. The production of the polymer in the production examples was carried out in a nitrogen gas atmosphere unless otherwise specified.
- Cyclohexane Dehydrated with molecular sieves 3A and further nitrogen gas bubbled.
- sec-Butyllithium 1.32 mmol / g cyclohexane solution was used.
- N, N, N ′, N′-tetramethylethylenediamine dehydrated with neutral activated alumina, further bubbled with nitrogen gas, and diluted with cyclohexane used for polymerization.
- Tetrahydrofuran Dehydrated with neutral activated alumina, further bubbled with nitrogen gas, diluted with cyclohexane used for polymerization.
- butadiene, isoprene, a mixture of butadiene and isoprene water and polymerization inhibitor were removed with molecular sieves 3A and neutral activated alumina, and the mixture was used under a nitrogen atmosphere.
- Styrene Water and polymerization inhibitor were removed with neutral activated alumina, and nitrogen gas was bubbled.
- Organometallic compound (I) The catalyst solution A produced in Reference Example 1 is transferred to a light-shielded container, and the time when the preparation of the catalyst solution A is completed is stored as 0 days, and the reaction is performed at 8 ⁇ 2 ° C. for 5 to 30 days in a nitrogen atmosphere. Using. Transfer the catalyst solution B produced in Reference Example 2 to a light-shielded container, and use the catalyst solution B that has been stored for 2 days at 8 ⁇ 2 ° C. in a nitrogen atmosphere, with the completion of preparation of the catalyst solution B as 0 days. It was.
- polymer solution A containing polymer A is obtained by reducing the nitrogen gas pressure to the reaction mixture to 0.1 MPaG, then increasing the pressure to 1.0 MPaG with hydrogen gas and treating at a liquid temperature of 53 ⁇ 3 ° C. for 1 hour. 3 g was obtained (hereinafter referred to as polymer solution A).
- the polymer A concentration in the polymer solution A is 9.98% by mass because the polymer A is 587.5 g, and the lithium atom concentration is 0.5256 mmol / kg from the amount of sec-butyllithium used.
- the content of butadiene units was 66.3% by mass based on the amounts of butadiene and styrene used.
- the weight average molecular weight Mw and molecular weight distribution Mw / Mn in terms of standard polystyrene are determined by gel permeation chromatography (hereinafter referred to as GPC) measurement of the polymer A, and the conjugated diene bonding mode (1,2 in butadiene units) is determined by 1 H-NMR analysis.
- GPC gel permeation chromatography
- 2-bond unit, 1,4-bond unit; in the production examples described later, the content ratio of 1,2-bond unit, 3,4-bond unit, 1,4-bond unit in the isoprene unit was further determined in some cases. .
- Each measurement condition is as follows.
- Example 1 The inside of a 3 L SUS316 autoclave equipped with a thermometer, electric heater, electromagnetic induction stirrer, hydrogen supply port, polymer solution A supply port, glass 10 mL pressure bottle and sampling port was replaced with hydrogen gas. After 750 g of the combined solution A (containing 73.866 g of polymer A) was pumped using hydrogen gas, the temperature was raised to 75 ° C. with stirring at 500 rpm for about 20 minutes. To this, 15.684 g (1.164 mmol as silicon atoms) of polymethylhydrosiloxane 1 diluted with cyclohexane to 0.0742 mmol / g as a silicon atom content was added, and the pressure was increased to 0.8 MPaG with hydrogen gas.
- the carbon-carbon double bond based on the butadiene unit is 890.0 mmol
- the lithium atom is 0.420 mmol
- the titanium atom is 4.61. ⁇ 10 ⁇ 3 mmol, 4.47 ⁇ 10 ⁇ 3 mmol of aluminum atoms, and 1.164 mmol of silicon atoms were present.
- the amount of titanium atom used per mole of carbon-carbon double bond based on butadiene units was 5.18 ⁇ 10 ⁇ 3 mmol
- the amount of titanium atom used relative to polymer A was 3.0 ppm
- the lithium atom ratio relative to 1 atom of titanium (Hereinafter referred to as the Li / Ti ratio) was 91.1
- the Al / Ti ratio was 0.97
- the silicon atomic ratio to one titanium atom (hereinafter referred to as the Si / Ti ratio) was 252.5.
- the progress of the hydrogenation reaction was analyzed as follows. That is, when the supply of the catalyst solution A into the reaction system is completed, the reaction start time is 0 hour, and 15 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 7 hours, and 9 hours have passed. Then, 5 g of the reaction solution was sampled, 5 g of acetone and appropriate methanol were added to precipitate and recover the polymer A during the hydrogenation reaction, and a 1 H-NMR spectrum of a solution in which 50 mg was dissolved in 1 g of deuterated chloroform was obtained.
- Example 2 In Example 1, the amount of catalyst solution A used as a titanium atom diluted with cyclohexane to 2.89 ⁇ 10 ⁇ 4 mmol / g (hereinafter referred to as “diluted solution of catalyst solution A”) was used from 15.950 g. 5.137 g (1.48 ⁇ 10 ⁇ 3 mmol as titanium atom) and polymethylhydrosiloxane diluted with cyclohexane to 0.0742 mmol / g as silicon atom content (hereinafter referred to as “Silane Compound Diluent 1”) The same operation as in Example 1 was performed except that the amount used was changed from 15.684 g to 5.051 g (0.375 mmol as a silicon atom).
- the carbon-carbon double bond based on the butadiene unit is 890.0 mmol
- the lithium atom is 0.420 mmol
- the titanium atom is 1.48 ⁇ 10 6. ⁇ 3 mmol
- aluminum atoms were 1.43 ⁇ 10 ⁇ 3 mmol
- silicon atoms were 0.375 mmol. That is, the amount of titanium atoms used per mole of carbon-carbon double bonds based on butadiene units was 1.67 ⁇ 10 ⁇ 3 mmol, and the amount of titanium atoms used per polymer A was 1.0 ppm.
- Table 1 shows the Li / Ti ratio, Al / Ti ratio, Si / Ti ratio, and hydrogenation rate.
- Example 3 In Example 1, the usage amount of the diluted solution of the catalyst solution A was changed from 15.950 g to 39.878 g (1.15 ⁇ 10 ⁇ 2 mmol as titanium atom), and the usage amount of the silane compound diluted solution 1 was changed from 15.684 g. The same operation as in Example 1 was carried out except that the amount was changed to 39.210 g (2.909 mmol as a silicon atom). 73.866 g of polymer A is present in the reaction system immediately after the start of the hydrogenation reaction, the carbon-carbon double bond based on butadiene units is 890.0 mmol, the lithium atom is 0.420 mmol, and the titanium atom is 1.15 ⁇ 10 6.
- Example 4 In Example 3, the same operation as in Example 3 was performed except that the addition of the silane compound diluent 1 was not performed before the supply of the diluted solution of the catalyst solution A but after 2 hours from the start of the reaction. That is, no silicon atom was present in the reaction system in the range of reaction from 0 to 2 hours, and 2.909 mmol of silicon atom was present after 2 hours of reaction.
- Table 1 shows the Li / Ti ratio, Al / Ti ratio, Si / Ti ratio, and hydrogenation rate.
- Comparative Example 1 In Example 3, the same operation as in Example 3 was performed except that the silane compound diluent 1 was not added. Table 1 shows the Li / Ti ratio, Al / Ti ratio, Si / Ti ratio, and hydrogenation rate. Comparative Example 2 In Example 1, the amount of the diluent used for the catalyst solution A was changed from 15.950 g to 79.986 g (2.31 ⁇ 10 ⁇ 2 mmol as titanium atoms), and the silane compound diluent 1 was not added. The same operation as in Example 1 was performed. Table 1 shows the Li / Ti ratio, Al / Ti ratio, Si / Ti ratio, and hydrogenation rate.
- Example 3 the usage amount of the diluted solution of the catalyst solution A was changed from 15.950 g to 39.878 g (1.15 ⁇ 10 ⁇ 2 mmol as titanium atom), and diluted 2 hours after the reaction started. The same operation as in Example 1 was carried out except that 39.878 g of the liquid (1.15 ⁇ 10 ⁇ 2 mmol as titanium atoms) was additionally supplied to the reaction system and the silane compound diluent 1 was not added. Table 1 shows the Li / Ti ratio, Al / Ti ratio, Si / Ti ratio, and hydrogenation rate.
- Comparative Example 2 Although the titanium concentration was 15 times that of Example 2, the progress of the hydrogenation reaction reached its peak, and the hydrogenation rate in the reaction of 4 hours was only 89.3%.
- Comparative Example 3 the hydrogenation reaction was performed by adding the organometallic compound (I) after 2 hours of reaction, but the hydrogenation rate hardly improved.
- Example 4 when the silane compound (II) was added after 2 hours of the reaction, the hydrogenation rate improved by 2.7% during the reaction 2 to 4 hours compared to Comparative Example 1, and the silane compound was hydrogenated. It can be seen that the chemical reaction is promoted.
- Example 5 In Example 1, instead of the diluted solution of catalyst solution A 15.95 g (4.62 ⁇ 10 ⁇ 3 mmol as titanium atom), catalyst solution B was 2.89 ⁇ 10 ⁇ 4 mmol / g as cyclohexane and titanium atom. The same operation as in Example 1 was carried out except that 15.95 g of the diluted solution (4.61 ⁇ 10 ⁇ 3 mmol as titanium atoms) was used. The Al / Ti ratio was 2.00. The hydrogenation rate is shown in Table 2.
- Production Example 2 In Production Example 1, after reducing the nitrogen gas pressure to the reaction mixture containing the living polymer to 0.1 MPaG, 7.748 g (1.682 mmol as ethanol) of a cyclohexane solution containing 1% by mass of ethanol was added. Thereafter, the pressure was increased to 1.0 MPaG with hydrogen gas, and the mixture was treated at a liquid temperature of 53 ⁇ 3 ° C. for 1 hour to obtain 5886.3 g of a solution containing polymer B (hereinafter referred to as polymer solution B).
- the molar ratio of lithium atoms derived from sec-butyllithium (3.364 mmol) used in the polymerization to ethanol (1.682 mmol) was 0.50.
- Example 6 In Example 1, the same operation as in Example 1 was performed except that 750 g of polymer solution B (containing 73.866 g of polymer B) was used instead of 750 g of polymer solution A (containing 73.866 g of polymer A). It was.
- the hydrogenation rate is shown in Table 2.
- Example 7 In Example 1, instead of 15.684 g (1.164 mmol as a silicon atom) of the silane compound diluent 1, a solution obtained by diluting polymethylhydrosiloxane 2 with cyclohexane to 0.0742 mmol / g as a silicon atom content was 15 .684 g (1.164 mmol as a silicon atom) was used, and the same operation as in Example 1 was performed. The Si / Ti ratio is 252.4. The hydrogenation rate is shown in Table 2.
- Example 8 In Example 1, the same operation as Example 1 was performed except having changed the usage-amount of the silane compound diluent 1 from 15.684 g to 7.960 g (0.591 mmol as a silicon atom). The Si / Ti ratio is 128.1. The hydrogenation rate is shown in Table 2.
- Example 9 In Example 1, the same operation as Example 1 was performed except having changed the usage-amount of the silane compound diluent 1 from 15.684 g to 31.368 g (2.328 mmol as a silicon atom). The Si / Ti ratio is 504.9. The hydrogenation rate is shown in Table 2.
- Example 10 In Example 1, the same operation as in Example 1 was performed except that the hydrogenation reaction was performed while supplying hydrogen so that the internal pressure of the autoclave was maintained at 3.0 MPaG.
- the hydrogenation rate is shown in Table 2.
- Example 11 In Example 1, the same operation as in Example 1 was performed except that the hydrogenation reaction was performed so that the liquid temperature was maintained at 85 ⁇ 2 ° C.
- the hydrogenation rate is shown in Table 2.
- Example 12 In Example 1, the same operation as in Example 1 was performed except that the hydrogenation reaction was performed so that the liquid temperature was maintained at 65 ⁇ 2 ° C.
- the hydrogenation rate is shown in Table 2.
- Example 5 From the results of Example 5, it can be seen that even if the organometallic compound (I) is used as a catalyst solution in the production method of the present invention without isolation, the target hydrogenation reaction proceeds without problems. From the results of Example 6, it can be seen that the production method of the present invention can be applied to a polymer in which at least a part of the living polymer is terminated with hydrogen molecules. From the results of Examples 7 to 9, it can be seen that the production method of the present invention can be applied with the kind of silane compound (II) and a wide Si / Ti ratio. From the results of Examples 10 to 12, it can be seen that the production method of the present invention can achieve a high hydrogenation rate in a wide range of hydrogen pressure and reaction temperature.
- the pressure was raised to 0.4 MPaG and the reaction was carried out at a liquid temperature of 53 ⁇ 3 ° C. for 3 hours. Subsequently, 30.5 g (292.89 mmol) of styrene was added all at once, the pressure was increased to 0.5 MPaG with nitrogen gas, and the mixture was reacted at a liquid temperature of 53 ⁇ 3 ° C. for 1.5 hours, thereby causing a reaction mixture containing a living polymer. A liquid was obtained.
- the nitrogen gas pressure to the reaction mixture is reduced to 0.1 MPaG, then the pressure is increased to 1.0 MPaG with hydrogen gas, and the mixture is treated at a liquid temperature of 53 ⁇ 3 ° C. for 1 hour, whereby a solution 1794. 5 g was obtained (hereinafter referred to as polymer solution C).
- the concentration of the polymer C in the polymer solution C is 9.97% by mass because the polymer C is 178.8 g, and the lithium atom concentration is 0.5741 mmol / kg from the amount of sec-butyllithium used.
- the butadiene unit in C was 65.9% by mass based on the amounts of butadiene and styrene used.
- Example 13 In Example 1, operation similar to Example 1 was carried out except that 750 g of polymer solution C (containing 74.775 g of polymer C) was used instead of 750 g of polymer solution A (containing 73.866 g of polymer A). went. Table 3 shows the hydrogenation rates.
- the nitrogen gas pressure to the reaction mixture is reduced to 0.1 MPaG, and then the pressure is increased to 1.0 MPaG with hydrogen gas, followed by treatment at a liquid temperature of 53 ⁇ 3 ° C. for 1 hour, whereby a solution 1793. 1 g was obtained (hereinafter referred to as polymer solution D).
- the concentration of the polymer D in the polymer solution D is 9.94% by mass because the polymer D is 178.2 g, and the lithium atom concentration is 0.5654 mmol / kg from the amount of sec-butyllithium used.
- the butadiene unit in D was 66.1% by mass based on the amount of butadiene and styrene used.
- Example 14 In Example 1, operation similar to Example 1 was carried out except that 750 g of polymer solution D (containing 74.550 g of polymer D) was used instead of 750 g of polymer solution A (containing 73.866 g of polymer A). went. Table 3 shows the hydrogenation rates.
- the nitrogen gas pressure to the reaction mixture is reduced to 0.1 MPaG, then the pressure is increased to 1.0 MPaG with hydrogen gas, and the mixture is treated at a liquid temperature of 53 ⁇ 3 ° C. for 1 hour, whereby a solution 1794. 3 g was obtained (hereinafter referred to as polymer solution E).
- the concentration of the polymer E in the polymer solution E is 9.96% by mass because the polymer E is 178.8 g, and the lithium atom concentration is 2.227 mmol / kg from the amount of sec-butyllithium used.
- the butadiene unit in E was 65.9% by mass based on the amounts of butadiene and styrene used.
- Example 15 In Example 1, operation similar to Example 1 was carried out except that 750 g of polymer solution E (containing 74.700 g of polymer E) was used instead of 750 g of polymer solution A (containing 73.866 g of polymer A). went. Table 3 shows the hydrogenation rates.
- a solution 1818. containing polymer F is obtained by lowering the nitrogen gas pressure to the reaction mixture to 0.1 MPaG, then increasing the pressure to 1.0 MPaG with hydrogen gas and treating at a liquid temperature of 80 ⁇ 3 ° C. for 1 hour. 8 g was obtained (hereinafter referred to as polymer solution F).
- the concentration of the polymer F in the polymer solution F is 10.91% by mass because the polymer F is 182.1 g, and the lithium atom concentration is 0.5372 mmol / kg from the amount of sec-butyllithium used.
- the butadiene unit in F was 40.91% by mass, and the isoprene unit was 24.35% by mass.
- Example 16 In Example 1, 750 g of polymer solution F (containing 75.075 g of polymer F) was used instead of 750 g of polymer solution A (containing 73.866 g of polymer A), and 15.950 g of a diluted solution of catalyst solution A was used.
- the carbon-carbon double bond based on the butadiene and isoprene units is 825.4 mmol
- the lithium atom is 0.424 mmol
- the titanium atom is 0. 0.0139 mmol, 0.0135 mmol of aluminum atoms, and 16.631 mmol of silicon atoms were present.
- the amount of titanium atom used per mole of carbon-carbon double bond based on the conjugated diene unit is 0.1347 mmol
- the amount of titanium atom used for polymer F is 71.8 ppm
- Li / The Ti ratio was 3.82
- the Al / Ti ratio was 0.97
- the Si / Ti ratio was 250.8.
- Table 3 shows the hydrogenation rates.
- a hydrogenated polymer is produced by selectively hydrogenating a carbon-carbon double bond based on a conjugated diene constituent unit of a conjugated diene polymer using a Tebbe type metallacycle compound as a hydrogenation catalyst.
- a hydrogenated polymer can be produced industrially advantageously.
- the hydrogenation catalyst system used in the production method of the present invention is very highly active.
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Abstract
Description
特許文献7~8の方法では、分割添加によるメタロセン系触媒の合計の添加量が高水素化率達成のためには25ppm~70ppmと多くなってしまうという問題点がある。
特許文献9の方法でTebbe型メタラサイクル化合物と共に用いる炭素数が2個以上の含酸素有機化合物または含窒素有機化合物は、その使用量によっては逆に水添触媒活性の低下につながってしまうことが特許文献6に指摘されている。
[1] 有機アルカリ金属化合物を重合開始剤とし、1種以上の共役ジエンを含有する単量体を重合したリビング重合体の少なくとも一部を水素分子で停止した重合体の共役ジエン構成単位に基づく炭素-炭素二重結合を、少なくとも1つのシリルヒドリド結合を有するシラン化合物および下記一般式(I)
で示される有機金属化合物(以下、有機金属化合物(I)と称する)の存在下に、水素分子で水素化することを特徴とする水素化重合体の製造方法;
[2]少なくとも1つのシリルヒドリド結合を有するシラン化合物(以下、シラン化合物(II)と称する場合がある)が、下記一般式(II-1)で示されるシリルヒドリド化合物、下記一般式(II-2)で示されるシリルヒドリド高分子化合物、下記一般式(II-3)で示される環状シリルヒドリド化合物、および下記一般式(II-4)で示されるシラザン化合物から選択される少なくとも1種であることを特徴とする、[1]の水素化重合体の製造方法;
[3]シラン化合物(II)がメチルジクロロシラン、エチルジクロロシラン、プロピルジクロロシラン、ブチルジクロロシラン、ペンチルジクロロシラン、ヘキシルジクロロシラン、ヘプチルジクロロシラン、オクチルジクロロシラン、ノニルジクロロシラン、デシルジクロロシラン、フェニルジクロロシラン、ジメチルクロロシラン、ジエチルクロロシラン、ジプロピルクロロシラン、ジブチルクロロシラン、ジペンチルクロロシラン、ジヘキシルクロロシラン、ジヘプチルクロロシラン、ジオクチルクロロシラン、ジノニルクロロシラン、ジデシルクロロシラン、メチルプロピルクロロシラン、メチルヘキシルクロロシラン、メチルフェニルクロロシラン、ポリメチルヒドロシロキサン、ポリエチルヒドロシロキサン、ポリプロピルヒドロシロキサン、ポリブチルヒドロシロキサン、ポリペンチルヒドロシロキサン、ポリヘキシルヒドロシロキサン、ポリヘプチルヒドロシロキサン、ポリオクチルヒドロシロキサン、ポリノニルヒドロシロキサン、ポリデシルヒドロシロキサン、ポリフェニルヒドロシロキサン、1,1,3,3-テトラメチルジシロキサン、1,1,3,3-テトラメチルジシラザン、1,1,3,3-テトラエチルジシラザン、1,1,3,3-テトラプロピルジシラザン、1,1,3,3-テトラブチルジシラザン、1,1,3,3-テトラフェニルジシラザンから選択される少なくとも1種類を含むことを特徴とする、[2]の水素化重合体の製造方法;
[4]リビング重合体が、1種類以上の共役ジエンから構成される共役ジエンブロックBと1種類以上のビニル芳香族化合物から構成されるビニル芳香族化合物ブロックSを有するS-B-Li、S-B-S-Li、S-B-S-B-Li、B-S-Li、B-S-B-Li、B-S-B-S-Liのいずれかであり、かつ該リビング重合体の少なくとも一部を水素分子で停止したブロック共重合体のゲルパーミエーションクロマトグラフィーで測定した標準ポリスチレン換算重量平均分子量が5000~1000000および分子量分布が1.00~3.00であり、該重合体における共役ジエンに由来する構成単位の含有量が10~90質量%であることを特徴とする、[1]~[3]のいずれかの水素化重合体の製造方法;
[6]共役ジエンブロックBがブタジエンイソプレンまたはこれらの混合物から構成され、ビニル芳香族化合物ブロックSがスチレンから構成されることを特徴とする、[4]または[5]の水素化重合体の製造方法;
[7]重合体に含まれる共役ジエン構成単位に基づく炭素-炭素二重結合1モルに対する有機金属化合物(I)の使用量が、該有機金属化合物(I)が有するチタン原子として1.0×10-4~1.0×10-1ミリモルの範囲であり、シラン化合物(II)の使用量が、シリルヒドリド結合を構成するケイ素原子のモル数として、前記有機金属化合物(I)が有するチタン原子1モルに対して1モル以上である、[1]~[6]のいずれかの水素化重合体の製造方法;
[8]重合体に含まれる共役ジエン構成単位に基づく炭素-炭素二重結合1モルに対する有機金属化合物(I)の使用量が、該有機金属化合物(I)が有するチタン原子として1.0×10-3~1.0×10-2ミリモルの範囲であり、シラン化合物(II)の使用量が、シリルヒドリド結合を構成するケイ素原子のモル数として、前記有機金属化合物(I)が有するチタン原子1モルに対して1~500モルの範囲である、[7]の水素化重合体の製造方法;
[9]下記一般式(III)
で示される二塩化チタノセン(以下、二塩化チタノセン(III)と称する)とトリメチルアルミニウムを有機溶媒中で反応させることによって有機金属化合物(I)を製造し、かかる有機金属化合物(I)を用いることを特徴とする、[1]~[8]のいずれかの水素化重合体の製造方法;
[10]二塩化チタノセン(III)が、ビス(シクロペンタジエニル)チタニウムジクロリド、ビス(エチルシクロペンタジエニル)チタニウムジクロリド、ビス(tert-シクロペンタジエニル)チタニウムジクロリド、ビス(ペンタメチルシクロペンタジエニル)チタニウムジクロリド、ジクロロビス(フルオレニル)チタニウム、ジクロロビス(インデニル)チタニウムの少なくとも1種であることを特徴とする、[9]の水素化重合体の製造方法。
また、前記共役ジエンブロックBは、ブタジエンまたはイソプレンの少なくとも1種を構成単位として含有することがより好ましく、ブタジエン、イソプレンまたはこれらの混合物から構成されることがさらに好ましい。前記ビニル芳香族化合物ブロックSは、スチレンを構成単位として少なくとも含有することがより好ましく、スチレンから構成されることがさらに好ましい。
かかるルイス塩基としては、例えばジメチルエーテル、メチルエチルエーテル、ジエチルエーテル、エチルプロピルエーテル、ジプロピルエーテル、ブチルメチルエーテル、tert-ブチルメチルエーテル、ジブチルエーテル、ジオクチルエーテル、エチルフェニルエーテル、ジフェニルエーテルなどの非環状モノエーテル;1,2-ジメトキシエタン、1,2-ジエトキシエタン、1,2-ジイソプロポキシエタン、1,2-ジブトキシエタン、1,2-ジフェノキシエタン、1,2-ジメトキシプロパン、1,2-ジエトキシプロパン、1,2-ジフェノキシプロパン、1,3-ジメトキシプロパン、1,3-ジエトキシプロパン、1,3-ジイソプロポキシプロパン、1,3-ジブトキシプロパン、1,3-ジフェノキシプロパンなどの非環状ジエーテル;テトラヒドロフラン、テトラヒドロピラン、1,4-ジオキサンなどの環状エーテル;ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジブチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジエチルエーテル、ジブチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、トリプロピレングリコールジメチルエーテル、トリブチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリプロピレングリコールジエチルエーテル、トリブチレングリコールジエチルエーテル、テトラエチレングリコールジメチルエーテル、テトラプロピレングリコールジメチルエーテル、テトラブチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテル、テトラプロピレングリコールジエチルエーテル、テトラブチレングリコールジエチルエーテルなどの非環状ポリエーテル;
水素分子により停止する際の好適な温度は前記リビング重合体を製造する際の範囲と同様である。リビング重合体の少なくとも一部を水素分子で停止する操作時間は5分~10日間の範囲から選択でき、15分~2時間の範囲が好ましい。
かかる有機金属化合物(I)の製造方法に特に制限はないが、好適には、例えば一般式(III)で表される二塩化チタノセン(III)
とトリメチルアルミニウムを有機溶媒存在中で反応させることによって製造できる。
R1~R5のうち隣接する任意の2つが形成していてもよい環、R6~R10のうち隣接する任意の2つが形成していてもよい環としては、例えばインデニル基、フルオレニル基などが挙げられる。R1~R5のうちの1個とR6~R10のうち1個とが直接または2価の有機基を介して互いに橋架けされた構造としては、例えばメチレン基、エチリデン基、1-メチルエチリデン基、エチレン基、ジメチルシリレン基、ジエチルシリレン基などが挙げられる。
トリメチルアルミニウムの使用量は二塩化チタノセン(III)が有するチタン原子1モルに対して1モル以上であればよく、1~100モル倍が好ましく、2~5モル倍がより好ましい。反応温度に特に制限はないが、通常、0~125℃の範囲が好ましく、10~50℃の範囲がより好ましい。反応時間にも特に制限はないが、通常、1~200時間の範囲が好ましく、24~100時間の範囲がより好ましい。
一般式(II-4)で示されるシラザン化合物としては、例えば1,1,3,3-テトラメチルジシラザン、1,1,3,3-テトラエチルジシラザン、1,1,3,3-テトラプロピルジシラザン、1,1,3,3-テトラブチルジシラザン、1,1,3,3-テトラフェニルジシラザンなどが挙げられる。
溶媒の使用量は、水素化反応に付する重合体の濃度として1~50質量%の範囲となることが好ましく、5~25質量%の範囲となるようにすることがより好ましい。なお、重合体の製造に使用する溶媒を、重合体溶液としてそのまま本発明の製造方法たる水素化反応においても溶媒として用いることができ、溶媒を回収再使用する観点から好ましい。この場合、重合体溶液は窒素、アルゴン、ヘリウムなどの不活性ガスまたは水素ガスの雰囲気下で、好ましくは常圧~5MPaG、0~50℃の範囲で保存しておくこともできる。
有機金属化合物(I)を溶媒に溶解させて用いる場合、その濃度に特に制限はない。有機金属化合物(I)を溶媒に溶解させた溶液は、窒素、アルゴン、ヘリウムなどの不活性ガス雰囲気下で、好ましくは常圧~0.5MPaG、0~50℃の範囲で保存できる。保存容器に特に制限はなく、例えばステンレス容器、内部がグラスライニングされている容器などを用いることができる。
なお、有機金属化合物(I)が有するチタン原子に対するアルミニウム原子の量は、有機金属化合物(I)の製造条件や、再結晶を行った後に用いるか精製せずに用いるかなどの精製条件にも依存して変化しうるが、チタン原子1モルに対するアルミニウム原子の量は0.5~100モルの範囲を取り得ることができ、チタン原子当たりの水素化反応活性を高める観点からは、チタン原子1モルに対するアルミニウム原子の量が0.8~5モルの範囲であることがより好ましい。
シラン化合物(II)を溶媒に溶解させた溶液は、窒素、アルゴン、ヘリウムなどの不活性ガスの雰囲気下で、好ましくは常圧~0.5MPaG、0~50℃の範囲で保存できる。保存容器に特に制限はなく、例えばステンレス容器、内部がグラスライニングされている容器などを用いることができる。
シラン化合物(II)の使用量に厳密な意味での制限はないが、チタン原子1モルに対するシリルヒドリド結合を有するケイ素原子の数として、通常、1~500モルの範囲が好ましい。
水素化反応に要する時間は、触媒成分としての有機金属化合物(I)およびシラン化合物(II)の使用量、反応温度、水素ガス圧力などの反応条件によって変動するが、触媒成分としての有機金属化合物(I)を反応系内に供給完了した時点を反応開始0分として、通常、好ましくは10分~24時間の範囲である。
有機金属化合物(I)を含む触媒液中のチタン原子モル濃度は、これらの湿式分解物を偏光ゼーマン原子吸光分光光度計(株式会社日立製作所製 Z-2000型)により分析することで定量した。取得した触媒液中のチタン原子総モル量は、触媒液質量と原子吸光分析から求めた触媒液中のチタン原子モル濃度より算出した。すなわち、触媒液を製造する際のチタン原子仕込みモル量に対する、取得触媒液中のチタン原子総モル量の割合を収率(%)と定義し、下記数式1によって算出した。なお、式中の各量は(モル)である。
脱水した重ベンゼン-d60.3gで触媒液0.3gを希釈した溶液を1H-核磁気共鳴分光法(以下、1H-NMR分析と略称する)で測定し[核磁気共鳴装置:日本電子株式会社製、JNM-ECS400]、ケミカルシフトからチタン化合物IV-1~IV-5の構造帰属を行い、ベンゼンに対する相対ピーク面積値から触媒液1gに含まれるIV-1~IV-5のモル量を算出した。
チタン化合物IV-6は常磁性核種で1H-NMRのピーク面積値からの正確な定量は困難であるため、原子吸光分析に基づく触媒液1gに含まれるチタン原子モル量から、1H-NMR分析から算出されるチタン化合物IV-1~IV-5のモル量を差し引いてチタン化合物IV-6のモル量とした。また、触媒液1gに含まれるチタン化合物IV-1~IV-6のモル量を用いて、チタン1原子に対するアルミニウム原子比としてのAl/Ti比を算出した。
温度計および回転子を備え減圧乾燥後に内部をアルゴンで置換した容量200mLの三つ口フラスコにビス(シクロペンタジエニル)チタニウムジクロリド(Cp2TiCl2、和光純薬工業製)25.0g(100.40mmol)およびトルエン30gを加え、25±2℃で30分攪拌し、次いで、トリメチルアルミニウムのトルエン溶液112.0mL(東京化成株式会社製、トリメチルアルミニウムとして201.6mmol)を10分かけて加え、25±3℃で60時間反応させた。得られた反応液を10mmHg(1.33kPa)、30℃で1時間濃縮し、未反応トリメチルアルミニウム、副生するクロロジメチルアルミニウムおよびトルエンを含有する混合物を約134mL留去した後、アルゴンで常圧に戻して残留液にトルエン約50mLを加え、30℃に加温して30分かけて溶解させた。得られた溶解液を0℃に冷却して1時間撹拌したところ、茶褐色結晶が析出した。上澄み液をデカンテーションで除き、得られた茶褐色結晶8.5gにトルエン46gを加えて30℃に加温し、30分撹拌して溶解することによって触媒液を得た(以後、触媒液Aと称する)。なお、反応開始から触媒液Aの調製終了までの総所要時間は約64時間であった。
原子吸光分析の結果、触媒液Aはチタン原子を2.57質量%(濃度は0.537mmol/g)含有しており、触媒液Aの全質量が54.5gであったことから、数式1に基づく収率は29.1%であった。
なお本参考例1でIV-1~IV-6におけるR1~R10はすべて水素原子を表す。
温度計および回転子を備え減圧乾燥後に内部をアルゴンで置換した容量100mLの三つ口フラスコにビス(シクロペンタジエニル)チタニウムジクロリド(Cp2TiCl2、和光純薬工業製)7.9g(31.7mmol)およびトルエン21.5gを加え、25±2℃で30分攪拌し、次いで、トリメチルアルミニウムのトルエン溶液35.0mL(東京化成株式会社製、トリメチルアルミニウムとして63.5mmol)を10分かけて加え、25±3℃で60時間反応させて触媒液を得た(以後、触媒液Bと称する)。反応開始から終了までの総所要時間は約60時間であった。
原子吸光分析の結果、触媒液Bはチタン原子を2.60質量%(濃度は0.543mmol/g)含有しており、触媒液Bの全質量が57.2gであったことから、数式1に基づく収率は98.0%であった。
なお本参考例2でIV-1~IV-6におけるR1~R10はすべて水素原子を表す。
sec-ブチルリチウム:1.32mmol/gのシクロヘキサン溶液を使用した。
N,N,N’,N’-テトラメチルエチレンジアミン:中性活性アルミナで脱水し、さらに窒素ガスバブリングし、これを重合に用いるシクロヘキサンで希釈して使用した。
テトラヒドロフラン:中性活性アルミナで脱水し、さらに窒素ガスバブリングし、重合に用いるシクロヘキサンによって希釈して使用した。
ブタジエン、イソプレン、ブタジエンとイソプレンの混合物:モレュラーシーブス3Aおよび中性活性アルミナで水分と重合禁止剤を除去し、窒素雰囲気下で使用した。
スチレン:中性活性アルミナで水分および重合禁止剤を除去し、さらに窒素ガスバブリングしたものを使用した。
シラン化合物(II):
ポリメチルヒドロシロキサン1(シグマ-アルドリッチ社製、数平均分子量1700~3200)
ポリメチルヒドロシロキサン2(シグマ-アルドリッチ社製、数平均分子量390)
は、いずれも窒素ガスバブリングし、重合に用いるシクロヘキサンによって希釈して使用した。
有機金属化合物(I):
参考例1で製造した触媒液Aは遮光した容器に移し、触媒液Aの調製完了の時点を保存0日とし、窒素雰囲気下、8±2℃で保存日数5~30日のものを反応に用いた。
参考例2で製造した触媒液Bは遮光した容器に移し、触媒液Bの調製完了の時点を保存0日として、窒素雰囲気下、8±2℃で保存日数2日以内のものを反応に用いた。
温度計、電気ヒーター、電磁誘導攪拌装置およびサンプリング口を備えた容量10Lのハステロイ(登録商標)製オートクレーブの内部を窒素ガスで置換した後、シクロヘキサン5291.0gおよびsec-ブチルリチウムの1.33mmol/gシクロヘキサン溶液2.529g(sec-ブチルリチウムとして3.364mmol)を加え500rpmで攪拌しながら30分かけて50℃に昇温した。次いで、スチレン99.1g(951.33mmol)をオートクレーブ内に一括添加し、窒素ガスで0.3MPaGに昇圧して液温53±3℃で1時間反応させた。続いてN,N,N’,N’-テトラメチルエチレンジアミンの0.29mmol/gシクロヘキサン溶液5.248g(N,N,N’,N’-テトラメチルエチレンジアミンとして1.535mmol)をオートクレーブ内に加え、さらにブタジエン389.4g(7198.1mmol)を10分かけてオートクレーブ内に添加し、窒素ガスで0.4MPaGに昇圧して液温53±3℃で3時間反応させた。続いてスチレン99.1g(951.33mmol)を一括添加し、窒素ガスで0.5MPaGに昇圧し、液温53±3℃で1.5時間反応させることにより、リビング重合体を含有する反応混合液を得た。
該反応混合液への窒素ガス圧力を0.1MPaGに低下させてから水素ガスで1.0MPaGに昇圧して液温53±3℃で1時間処理することで、重合体Aを含む溶液5886.3gを得た(以下、重合体溶液Aと称する)。重合体溶液A中の重合体A濃度は重合体Aが587.5gであることから9.98質量%、リチウム原子濃度はsec-ブチルリチウムの使用量より0.5256mmol/kg、重合体A中のブタジエン単位含有量はブタジエンおよびスチレンの使用量から66.3質量%であった。
装置:東ソー株式会社製、HLC-8320GPC EcoSECシステム
試料:重合体5mgをテトラヒドロフラン10mLに溶解させた溶液
試料注入量:1μL
カラム:東ソー株式会社製TSKgel SuperHZ4000
(内径4.6mm×長さ150mm)
カラム温度:40℃
溶離液:テトラヒドロフラン
溶離液流量:1.0mL/分
検出器:UV検出器(検出波長254nm)
検量線:標準ポリスチレンにより作成
GPC分析より、重量平均分子量Mwは303100、分子量分布Mw/Mnは1.06であった。
装置:ブルカー・バイオスピン株式会社製、AVANCEIII 600USPlus
試料:重合体50mgを重クロロホルム1.0gに溶解させた溶液
基準物質:テトラメチルシラン
測定温度:32℃(305K)
積算回数:256回
重合体に含まれる共役ジエンの総モル量に対する、分岐状結合単位(1,2-結合単位、3,4-結合単位)の割合[ビニル化度(%)]を下記数式3によって算出した。
温度計、電気ヒーター、電磁誘導攪拌装置、水素供給口、重合体溶液Aの供給口、ガラス製10mL耐圧瓶およびサンプリング口を備えた容量3LのSUS316製オートクレーブの内部を水素ガスで置換し、重合体溶液A750g(重合体Aを73.866g含有)を水素ガスを用いて圧送した後、攪拌500rpm、約20分で75℃に昇温した。ここに、ポリメチルヒドロシロキサン1をシクロヘキサンでケイ素原子含有量として0.0742mmol/gに希釈した溶液15.684g(ケイ素原子として1.164mmol)を加えて水素ガスで0.8MPaGに昇圧し、続いてガラス製10mL耐圧瓶から、触媒液Aをシクロヘキサンでチタン原子として2.89×10-4mmol/gに希釈した溶液15.950g(チタン原子として4.61×10-3mmol)を水素ガスで圧送(1.0MPaG)して供給し、オートクレーブ内圧が1.0MPaGを維持するように水素を供給しながら、液温を75±2℃の範囲に制御して水素化反応を行った。
なお、スチレンの芳香環に結合した水素原子に帰属できるδ6.2~7.5ppmのピーク積分値の変化も同時に観察したが、変化は見られなかった。
実施例1において、触媒液Aをシクロヘキサンでチタン原子として2.89×10-4mmol/gに希釈した溶液(以下、「触媒液Aの希釈液」と称する)の使用量を15.950gから5.137g(チタン原子として1.48×10-3mmol)に、ポリメチルヒドロシロキサンをシクロヘキサンでケイ素原子含有量として0.0742mmol/gに希釈した溶液(以下、「シラン化合物希釈液1」と称する)の使用量を15.684gから5.051g(ケイ素原子として0.375mmol)に変更した以外は、実施例1と同様の操作を行った。
水素化反応開始直後の反応系には重合体Aは73.866g存在し、ブタジエン単位に基づく炭素-炭素二重結合は890.0mmol、リチウム原子は0.420mmol、チタン原子は1.48×10-3mmol、アルミニウム原子は1.43×10-3mmol、ケイ素原子は0.375mmol存在した。すなわち、ブタジエン単位に基づく炭素-炭素二重結合1モルに対するチタン原子使用量は1.67×10-3mmol、重合体Aに対するチタン原子使用量は1.0ppmであった。Li/Ti比、Al/Ti比、Si/Ti比、水素化率を表1に示す。
実施例1において、触媒液Aの希釈液の使用量を15.950gから39.878g(チタン原子として1.15×10-2mmol)に、シラン化合物希釈液1の使用量を15.684gから39.210g(ケイ素原子として2.909mmol)に変更した以外は、実施例1と同様の操作を行った。
水素化反応開始直後の反応系には重合体Aは73.866g存在し、ブタジエン単位に基づく炭素-炭素二重結合は890.0mmol、リチウム原子は0.420mmol、チタン原子は1.15×10-2mmol、アルミニウム原子は1.11×10-2mmol、ケイ素原子は2.909mmol存在した。すなわち、ブタジエン単位に基づく炭素-炭素二重結合1モルに対するチタン原子使用量は1.29×10-2mmol、重合体Aに対するチタン原子使用量は7.5ppmであった。Li/Ti比、Al/Ti比、Si/Ti比、水素化率を表1に示す。
実施例3において、シラン化合物希釈液1の添加を触媒液Aの希釈液の供給前ではなく、反応開始2時間経過後に添加した以外は実施例3と同様の操作を行った。すなわち、反応0~2時間の範囲では反応系にケイ素原子は存在せず、反応2時間以降にケイ素原子は2.909mmol存在した。Li/Ti比、Al/Ti比、Si/Ti比、水素化率を表1に示す。
実施例3において、シラン化合物希釈液1を添加しなかった以外は実施例3と同様の操作を行った。Li/Ti比、Al/Ti比、Si/Ti比、水素化率を表1に示す。
比較例2
実施例1において、触媒液Aの希釈液の使用量を15.950gから79.986g(チタン原子として2.31×10-2mmol)に変更し、シラン化合物希釈液1を添加しなかった以外は、実施例1と同様の操作を行った。Li/Ti比、Al/Ti比、Si/Ti比、水素化率を表1に示す。
比較例3
実施例1において、触媒液Aの希釈液の使用量を15.950gから39.878g(チタン原子として1.15×10-2mmol)に変更しかつ反応開始2時間経過後に触媒液Aの希釈液39.878g(チタン原子として1.15×10-2mmol)をさらに反応系に追加供給し、シラン化合物希釈液1を添加しなかった以外は、実施例1と同様の操作を行った。Li/Ti比、Al/Ti比、Si/Ti比、水素化率を表1に示す。
これに対し、シラン化合物(II)を共存させなかった比較例では水素化反応活性に劣る上、反応を追い込めない。比較例1では反応開始2時間以降水素化反応の進行は頭打ちとなり、水素化率も反応4時間で89.5%にとどまる。比較例2ではチタン濃度は実施例2の15倍であるにもかかわらず水素化反応の進行は頭打ちであり、反応4時間での水素化率は89.3%にとどまる。比較例3では反応2時間後に有機金属化合物(I)を追加して水素化反応を行ったが、水素化率は殆ど向上しない。
実施例4では反応2時間後にシラン化合物(II)を添加した場合に、比較例1に対して反応2~4時間の間に水素化率が2.7%も向上し、該シラン化合物が水素化反応を促進することがわかる。
実施例1において、触媒液Aの希釈液15.95g(チタン原子として4.62×10-3mmol)の代わりに、触媒液Bをシクロヘキサンでチタン原子として2.89×10-4mmol/gに希釈した溶液を15.95g(チタン原子として4.61×10-3mmol)使用した以外は実施例1と同様の操作を行った。Al/Ti比は2.00であった。水素化率を表2に示す。
製造例1において、リビング重合体を含有する反応混合液への窒素ガス圧力を0.1MPaGに低下させてから、エタノールを1質量%含有するシクロヘキサン溶液7.748g(エタノールとして1.682mmol)を加え、その後水素ガスで1.0MPaGに昇圧して液温53±3℃で1時間処理することで、重合体Bを含む溶液5886.3gを得た(以下、重合体溶液Bと称する)。なお、重合に用いたsec-ブチルリチウム(3.364mmol)に由来するリチウム原子とエタノール(1.682mmol)のモル比は0.50であった。
実施例1において、重合体溶液A750g(重合体Aを73.866g含有)の代わりに重合体溶液B750g(重合体Bを73.866g含有)を使用した以外は実施例1と同様の操作を行った。水素化率を表2に示す。
実施例1において、シラン化合物希釈液1を15.684g(ケイ素原子として1.164mmol)の代わりに、ポリメチルヒドロシロキサン2をシクロヘキサンでケイ素原子含有量として0.0742mmol/gに希釈した溶液を15.684g(ケイ素原子として1.164mmol)使用した以外は実施例1と同様の操作を行った。Si/Ti比は252.4である。水素化率を表2に示す。
実施例1において、シラン化合物希釈液1の使用量を15.684gから7.960g(ケイ素原子として0.591mmol)に変更した以外は、実施例1と同様の操作を行った。Si/Ti比は128.1である。水素化率を表2に示す。
実施例1において、シラン化合物希釈液1の使用量を15.684gから31.368g(ケイ素原子として2.328mmol)に変更した以外は、実施例1と同様の操作を行った。Si/Ti比は504.9である。水素化率を表2に示す。
実施例1において、オートクレーブ内圧が3.0MPaGを維持するように水素を供給しながら水素化反応した以外は実施例1と同様の操作を行った。水素化率を表2に示す。
実施例1において、液温が85±2℃を維持するように水素化反応を行った以外は実施例1と同様の操作を行った。水素化率を表2に示す。
実施例1において、液温が65±2℃を維持するように水素化反応を行った以外は実施例1と同様の操作を行った。水素化率を表2に示す。
実施例6の結果より、本発明の製造方法はリビング重合体の少なくとも一部を水素分子で停止した重合体にも適用できることがわかる。
実施例7~9の結果より、本発明の製造方法はシラン化合物(II)の種類および幅広いSi/Ti比で適用できることがわかる。
実施例10~12の結果より、本発明の製造方法は幅広い水素圧力範囲および反応温度範囲で高い水素化率を達成できることがわかる。
温度計、電気ヒーター、電磁誘導攪拌装置およびサンプリング口を備えた容量3LのSUS316製オートクレーブの内部を窒素ガスで置換した後、シクロヘキサン2070.0gおよびsec-ブチルリチウムの1.33mmol/gシクロヘキサン溶液0.774g(sec-ブチルリチウムとして1.030mmol)を加え、500rpmで攪拌しながら30分かけて50℃に昇温した。次いで、スチレン30.5g(292.89mmol)をオートクレーブ内に一括添加し、窒素ガスで0.3MPaGに昇圧して液温53±3℃で1時間反応させた。続いてテトラヒドロフランの13.87mmol/gシクロヘキサン溶液2.375g(テトラヒドロフランとして32.936mmol)をオートクレーブ内に加え、さらにブタジエン117.8g(2177.8mmol)を10分かけてオートクレーブ内に添加し、窒素ガスで0.4MPaGに昇圧して液温53±3℃で3時間反応させた。続いてスチレン30.5g(292.89mmol)を一括添加し、窒素ガスで0.5MPaGに昇圧し、液温53±3℃で1.5時間反応させることにより、リビング重合体を含有する反応混合液を得た。
重合体CのGPC分析および1H-NMR分析を製造例1と同様にして行ったところ、重量平均分子量は268500、分子量分布は1.059、ブタジエンの1,2-結合単位に帰属できるピークδ4.8~5.1ppm、ブタジエンの1,4-結合単位に帰属できるピークδ5.2~5.5ppmの面積値から、重合体Cのビニル化度は35.2%であった。
実施例1において、重合体溶液A750g(重合体Aを73.866g含有)の代わりに重合体溶液C750g(重合体Cを74.775g含有)を用いた以外は、実施例1と同様の操作を行った。水素化率を表3に示す。
温度計、電気ヒーター、電磁誘導攪拌装置およびサンプリング口を備えた容量3LのSUS316製オートクレーブの内部を窒素ガスで置換した後、シクロヘキサン2070.0gおよびsec-ブチルリチウムの1.33mmol/gシクロヘキサン溶液0.762g(sec-ブチルリチウムとして1.014mmol)を加え、500rpmで攪拌しながら30分かけて50℃に昇温した。次いで、スチレン60.42g(580.16mmol)をオートクレーブ内に一括添加し、窒素ガスで0.3MPaGに昇圧して液温53±3℃で2時間反応させた。続いてN,N,N’,N’-テトラメチルエチレンジアミンの0.29mmol/gシクロヘキサン溶液1.531g(N,N,N’,N’-テトラメチルエチレンジアミンとして0.444mmol)をオートクレーブ内に加え、さらにブタジエン117.8g(2177.8mmol)を10分かけてオートクレーブ内に添加し、窒素ガスで0.4MPaGに昇圧して液温53±3℃で3時間反応させた。窒素ガスで0.5MPaGに昇圧し、液温53±3℃で1.5時間反応させることにより、リビング重合体を含有する反応混合液を得た。
重合体DのGPC分析および1H-NMR分析を製造例1と同様にして行ったところ、重量平均分子量は298300、分子量分布は1.057、ブタジエンの1,2-結合単位に帰属できるピークδ4.8~5.1ppm、ブタジエンの1,4-結合単位に帰属できるピークδ5.2~5.5ppmの面積値から、重合体Dのビニル化度は37.4%であった。
実施例1において、重合体溶液A750g(重合体Aを73.866g含有)の代わりに重合体溶液D750g(重合体Dを74.550g含有)を用いた以外は、実施例1と同様の操作を行った。水素化率を表3に示す。
温度計、電気ヒーター、電磁誘導攪拌装置およびサンプリング口を備えた容量3LのSUS316製オートクレーブの内部を窒素ガスで置換した後、シクロヘキサン2070.0gおよびsec-ブチルリチウムの1.33mmol/gシクロヘキサン溶液3.005g(sec-ブチルリチウムとして3.996mmol)を加え、500rpmで攪拌しながら30分かけて50℃に昇温した。次いで、スチレン30.5g(292.89mmol)をオートクレーブ内に一括添加し、窒素ガスで0.3MPaGに昇圧して液温53±3℃で1時間反応させた。、さらにブタジエン117.8g(2177.8mmol)を10分かけてオートクレーブ内に添加し、窒素ガスで0.4MPaGに昇圧して液温53±3℃で3時間反応させた。続いてスチレン30.5g(292.89mmol)を一括添加し、窒素ガスで0.5MPaGに昇圧し、液温53±3℃で1.5時間反応させることにより、リビング重合体を含有する反応混合液を得た。
重合体EのGPC分析および1H-NMR分析を製造例1と同様にして行ったところ、重量平均分子量は75700、分子量分布は1.027、ブタジエンの1,2-結合単位に帰属できるピークδ4.8~5.1ppm、ブタジエンの1,4-結合単位に帰属できるピークδ5.2~5.5ppmの面積値から、重合体Eのビニル化度は7.7%であった。
実施例1において、重合体溶液A750g(重合体Aを73.866g含有)の代わりに重合体溶液E750g(重合体Eを74.700g含有)を用いた以外は、実施例1と同様の操作を行った。水素化率を表3に示す。
温度計、電気ヒーター、電磁誘導攪拌装置およびサンプリング口を備えた容量3LのSUS316製オートクレーブの内部を窒素ガスで置換した後、シクロヘキサン2070.0gおよびsec-ブチルリチウムの1.33mmol/gシクロヘキサン溶液0.784g(sec-ブチルリチウムとして1.043mmol)を加え、500rpmで攪拌しながら30分かけて50℃に昇温した。次いで、スチレン30.1g(297.53mmol)をオートクレーブ内に一括添加し、窒素ガスで0.3MPaGに昇圧して液温53±3℃で1時間反応させた。その後、10分をかけて液温を80±3℃に昇温し、続いてブタジエン80.7g(1491.6mmol)とイソプレン39.5g(580.0mmol)の混合物を10分かけてオートクレーブ内に添加し、窒素ガスで0.4MPaGに昇圧して、液温80±3℃で2時間反応させた。続いてスチレン31.0g(297.05mmol)を一括添加し、窒素ガスで0.5MPaGに昇圧し、液温80±3℃で1.5時間反応させることにより、リビング重合体を含有する反応混合液を得た。
重合体FのGPC分析および1H-NMR分析を製造例1と同様にして行ったところ、重量平均分子量は338900、分子量分布は1.085、ブタジエンの1,2-結合単位に帰属できるピークδ5.5~5.4ppm、ブタジエンの1,4-結合単位に帰属できるピークδ5.2~5.5ppm、イソプレンの1,2-結合単位に帰属できるピークδ5.7~6.0ppm、イソプレンの3,4-結合単位に帰属できるピークδ4.5~4.8ppm、イソプレンの1,4-結合単位に帰属できるピークδ5.0~5.2ppmの面積値から、重合体Fのビニル化度は8.1%であった。
実施例1において、重合体溶液A750g(重合体Aを73.866g含有)の代わりに重合体溶液Fを750g(重合体Fを75.075g含有)用い、触媒液Aの希釈液15.950gの代わりに、触媒液Aをシクロヘキサンでチタン原子として0.0139mmol/gに希釈した溶液を8.019g(チタン原子として0.1111mmol)用い、シラン化合物希釈液1を15.684gの代わりにポリメチルヒドロシロキサン1をシクロヘキサンでケイ素原子含有量として16.631mmol/gに希釈した溶液を1.676g(ケイ素原子として27.874mmol)用い、温度100±5℃、圧力3.0MPaGに変更した以外は、実施例1と同様の操作を行った。
ここで、触媒液A供給直後の反応系に重合体Fは75.075g存在し、ブタジエンおよびイソプレン単位に基づく炭素-炭素二重結合は825.4mmol、リチウム原子は0.424mmol、チタン原子は0.0139mmol、アルミニウム原子は0.0135mmol、ケイ素原子は16.631mmol存在した。すなわち、共役ジエン単位(ブタジエン単位およびイソプレン単位の合計量)に基づく炭素-炭素二重結合1モルに対するチタン原子使用量は0.1347mmol、重合体Fに対するチタン原子使用量は71.8ppm、Li/Ti比は3.82、Al/Ti比は0.97、Si/Ti比は250.8であった。水素化率を表3に示す。
実施例14~16の結果より、共役ジエン単位を含有する種々の重合体を用いた場合でも高い水素化率を達成できることがわかる。
Claims (10)
- 有機アルカリ金属化合物を重合開始剤とし1種以上の共役ジエンを含有する単量体を重合したリビング重合体の少なくとも一部を水素分子で停止した重合体の共役ジエン構成単位に基づく炭素-炭素二重結合を、少なくとも1つのシリルヒドリド結合を有するシラン化合物および下記一般式(I)
で示される有機金属化合物の存在下に、水素分子で水素化することを特徴とする水素化重合体の製造方法。 - 少なくとも1つのシリルヒドリド結合を有するシラン化合物が、下記一般式(II-1)で示されるシリルヒドリド化合物、下記一般式(II-2)で示されるシリルヒドリド高分子化合物、下記一般式(II-3)で示される環状シリルヒドリド化合物、および下記一般式(II-4)で示されるシラザン化合物から選択される少なくとも1種であることを特徴とする、請求項1に記載の水素化重合体の製造方法。
- 少なくとも1つのシリルヒドリド結合を有するシラン化合物が、メチルジクロロシラン、エチルジクロロシラン、プロピルジクロロシラン、ブチルジクロロシラン、ペンチルジクロロシラン、ヘキシルジクロロシラン、ヘプチルジクロロシラン、オクチルジクロロシラン、ノニルジクロロシラン、デシルジクロロシラン、フェニルジクロロシラン、ジメチルクロロシラン、ジエチルクロロシラン、ジプロピルクロロシラン、ジブチルクロロシラン、ジペンチルクロロシラン、ジヘキシルクロロシラン、ジヘプチルクロロシラン、ジオクチルクロロシラン、ジノニルクロロシラン、ジデシルクロロシラン、メチルプロピルクロロシラン、メチルヘキシルクロロシラン、メチルフェニルクロロシラン、ポリメチルヒドロシロキサン、ポリエチルヒドロシロキサン、ポリプロピルヒドロシロキサン、ポリブチルヒドロシロキサン、ポリペンチルヒドロシロキサン、ポリヘキシルヒドロシロキサン、ポリヘプチルヒドロシロキサン、ポリオクチルヒドロシロキサン、ポリノニルヒドロシロキサン、ポリデシルヒドロシロキサン、ポリフェニルヒドロシロキサン、1,1,3,3-テトラメチルジシロキサン、1,1,3,3-テトラメチルジシラザン、1,1,3,3-テトラエチルジシラザン、1,1,3,3-テトラプロピルジシラザン、1,1,3,3-テトラブチルジシラザン、1,1,3,3-テトラフェニルジシラザンから選択される少なくとも1種類を含むことを特徴とする、請求項2に記載の水素化重合体の製造方法。
- リビング重合体が、1種類以上の共役ジエンから構成される共役ジエンブロックBと1種類以上のビニル芳香族化合物から構成されるビニル芳香族化合物ブロックSを有するS-B-Li、S-B-S-Li、S-B-S-B-Li、B-S-Li、B-S-B-Li、B-S-B-S-Liのいずれかであり、かつ該リビング重合体の少なくとも一部を水素分子で停止したブロック共重合体のゲルパーミエーションクロマトグラフィーで測定した標準ポリスチレン換算重量平均分子量が5000~1000000および分子量分布が1.00~3.00であり、該重合体における共役ジエンに由来する構成単位の含有量が10~90質量%であることを特徴とする、請求項1~3のいずれかに記載の水素化重合体の製造方法。
- リビング重合体の共役ジエンブロックBがブタジエンまたはイソプレンの少なくとも1種を含有しかつビニル芳香族化合物ブロックSがスチレンを少なくとも含有し、該リビング重合体の少なくとも一部を水素分子で停止した重合体のゲルパーミエーションクロマトグラフィーで測定した標準ポリスチレン換算重量平均分子量が50000~500000および分子量分布が1.00~1.25であり、該重合体における共役ジエンに由来する構成単位の含有量が30~70質量%であることを特徴とする、請求項4に記載の水素化重合体の製造方法。
- 共役ジエンブロックBがブタジエン、イソプレンまたはこれらの混合物から構成され、ビニル芳香族化合物ブロックSがスチレンから構成されることを特徴とする、請求項4または5に記載の水素化重合体の製造方法。
- 重合体に含まれる共役ジエン構成単位に基づく炭素-炭素二重結合1モルに対する有機金属化合物(I)の使用量が、該有機金属化合物(I)が有するチタン原子として1.0×10-4~1.0×10-1ミリモルの範囲であり、少なくとも1つのシリルヒドリド結合を有するシラン化合物の使用量が、シリルヒドリド結合を構成するケイ素原子のモル数として、前記有機金属化合物(I)が有するチタン原子1モルに対して1モル以上である、請求項1~6のいずれかに記載の水素化重合体の製造方法。
- 重合体に含まれる共役ジエン構成単位に基づく炭素-炭素二重結合1モルに対する有機金属化合物(I)の使用量が、該有機金属化合物(I)が有するチタン原子として1.0×10-3~1.0×10-2ミリモルの範囲であり、少なくとも1つのシリルヒドリド結合を有するシラン化合物の使用量が、シリルヒドリド結合を構成するケイ素原子のモル数として、前記有機金属化合物(I)が有するチタン原子1モルに対して1~500モルの範囲である、請求項7に記載の水素化重合体の製造方法。
- 下記一般式(III)
で示される有機金属化合物を製造し、かかる有機金属化合物を用いることを特徴とする、請求項1~8のいずれかに記載の水素化重合体の製造方法。 - 二塩化チタノセン(III)が、ビス(シクロペンタジエニル)チタニウムジクロリド、ビス(エチルシクロペンタジエニル)チタニウムジクロリド、ビス(tert-シクロペンタジエニル)チタニウムジクロリド、ビス(ペンタメチルシクロペンタジエニル)チタニウムジクロリド、ジクロロビス(フルオレニル)チタニウム、ジクロロビス(インデニル)チタニウムの少なくとも1種を含むことを特徴とする、請求項9に記載の水素化重合体の製造方法。
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CN110088156A (zh) * | 2016-12-28 | 2019-08-02 | 株式会社可乐丽 | 1,3,7-辛三烯与异戊二烯的共聚物和其氢化物、以及该共聚物的制造方法 |
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CA2953563A1 (en) | 2015-12-30 |
KR102317293B1 (ko) | 2021-10-25 |
JPWO2015199222A1 (ja) | 2017-04-27 |
JP6546890B2 (ja) | 2019-07-17 |
EP3162816A1 (en) | 2017-05-03 |
JP2017039936A (ja) | 2017-02-23 |
JP6010709B2 (ja) | 2016-10-19 |
CN106795231B (zh) | 2019-09-24 |
CA2953563C (en) | 2022-06-07 |
KR20170026365A (ko) | 2017-03-08 |
US20170204214A1 (en) | 2017-07-20 |
EP3162816A4 (en) | 2018-03-07 |
EP3162816B1 (en) | 2019-01-02 |
US10526435B2 (en) | 2020-01-07 |
ES2716377T3 (es) | 2019-06-12 |
CN106795231A (zh) | 2017-05-31 |
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