WO2014021244A1 - Modified cis-1, 4-polybutadiene and method for producing same - Google Patents
Modified cis-1, 4-polybutadiene and method for producing same Download PDFInfo
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- WO2014021244A1 WO2014021244A1 PCT/JP2013/070430 JP2013070430W WO2014021244A1 WO 2014021244 A1 WO2014021244 A1 WO 2014021244A1 JP 2013070430 W JP2013070430 W JP 2013070430W WO 2014021244 A1 WO2014021244 A1 WO 2014021244A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—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
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
Definitions
- the present invention relates to a modified cis-1,4-polybutadiene which is useful as a rubber material and has excellent processability and low loss and a method for producing the same.
- Patent Document 1 discloses a method for producing high cis-1,4-polybutadiene in which 1,3-butadiene is polymerized using a catalyst comprising a cobalt compound, an acidic metal halide, an alkylaluminum compound, and water. .
- Patent Document 2 discloses a method of polymerizing 1,3-butadiene in a solvent composed of a linear or branched aliphatic hydrocarbon using a catalyst composed of diethylaluminum chloride, water, and cobalt octoate. Has been.
- the polymer chain having a small degree of branching that is, linear type high cis-1,4-polybutadiene has excellent characteristics such as heat resistance and rebound resilience.
- branch type high cis-1,4-polybutadiene having a high degree of branching processability is reduced when producing a compound obtained by compounding carbon black or the like with rubber. A method was sought.
- Patent Document 3 discloses a method of treating a polybutadiene polymerization solution with an organoaluminum compound and an alkyl halide compound.
- Patent Document 4 describes a method in which a rubber having an unsaturated bond is dissolved in a solvent and an organic acid halide is reacted in the presence of a Lewis acid to modify the rubber.
- any of these methods requires a step of modifying the polymer after the polymerization step, and the development of a method that saves complicated operations is desired.
- silica As a measure for improving the heat build-up of the rubber composition, in recent years, an increasing number of cases are using silica instead of carbon black as a reinforcing material. However, since there is a polar silanol group on the surface of silica, silica has low affinity with hydrocarbon structures such as polybutadiene, which makes it easier for silica particles to aggregate and disperse in the rubber compounded with silica. There was a problem that the sex became worse.
- Patent Document 5 discloses a method for improving cold flow properties by polymerizing polybutadiene rubber with a cobalt compound and further reacting with an acid halide, a halogen-containing sulfur compound, a mercapto group-containing alkoxysilane compound, etc., if necessary. Are listed.
- polybutadiene rubber is polymerized with a cobalt compound and then modified with a predetermined amount of an organic halogen compound (Patent Documents 6 and 7).
- Patent Documents 6 and 7 polybutadiene rubber is polymerized with a cobalt compound and then modified with a predetermined amount of an organic halogen compound.
- Japanese Patent Publication No. 38-1243 Japanese Examined Patent Publication No. 61-54808 JP 51-63891 JP-A-61-225202 JP 2001-114817 A Japanese Patent Laid-Open No. 2004-211048 JP 2011-79954 A
- An object of the present invention is to provide a modified cis-1,4-polybutadiene excellent in processability and low loss and a method for producing the same.
- the present inventors have made a modification obtained by reacting cis-1,4-polybutadiene with a specific aromatic compound in the presence of a Lewis acid and an organic halogen compound.
- the present inventors have found that cis-1,4-polybutadiene is excellent in processability and low loss, and completed the present invention. That is, in the first embodiment of the present invention, cis-1,4-polybutadiene is reacted with a 1-3 substituted aromatic compound represented by the following general formula (1) in the presence of a Lewis acid and an organic halogen compound.
- a modified cis-1,4-polybutadiene characterized by being obtained in the above.
- Y represents hydrogen, a hydroxyl group, an alkenyl group or an alkoxy group having 1 to 10 carbon atoms
- Z 1 and Z 2 each represent hydrogen, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms.
- the 1 to 3 substituted aromatic compound is a phenol derivative, a catechol derivative, a resorcin derivative, a hydroquinone derivative, or a 2 to 3 substituted aromatic system. It is preferably at least one selected from the group consisting of alkenyl compounds, and particularly preferably a catechol derivative or a resorcin derivative.
- the Lewis acid is preferably an organoaluminum compound, and the organohalogen compound is preferably a tertiary alkyl halide having 4 to 12 carbon atoms.
- 1,3-butadiene is polymerized using a polymerization catalyst containing a transition metal compound and an organoaluminum compound to produce cis-1,4-polybutadiene, and then this polymerization is performed.
- An organic halogen compound and a 1- to 3-substituted aromatic compound represented by the following general formula (1) are added to the system, and the cis-1,4-polybutadiene is added in the presence of Lewis acid and the organic halogen compound.
- a process for producing a modified cis-1,4-polybutadiene characterized by reacting with a 1 to 3 substituted aromatic compound represented by the following general formula (1).
- Y represents hydrogen, a hydroxyl group, an alkenyl group or an alkoxy group having 1 to 10 carbon atoms
- Z 1 and Z 2 each represent hydrogen, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms.
- the transition metal compound is preferably at least one selected from the group consisting of a cobalt compound, a nickel compound and a titanium compound.
- the 1 to 3 substituted aromatic compound may be at least one selected from the group consisting of phenol derivatives, catechol derivatives, resorcin derivatives, hydroquinone derivatives, and 2 to 3 substituted aromatic alkenyl compounds. preferable.
- the modified cis-1,4-polybutadiene according to the first aspect of the present invention has a polar functional group that interacts with silica particles in the molecule, the rubber composition using this has suppressed silica aggregation. It has excellent low loss properties and can be suitably used for tires. Further, the method for producing a modified cis-1,4-polybutadiene according to the second aspect of the present invention does not require separation after the production of cis-1,4-polybutadiene, and is simple and complicated. It is an excellent manufacturing method that is not required.
- Cis-1,4-polybutadiene is produced by polymerizing 1,3-butadiene in the presence of a polymerization catalyst containing a transition metal compound and an organoaluminum compound. Can do.
- transition metal compound used for the polymerization catalyst examples include a cobalt compound, a nickel compound and a titanium compound, and a cobalt compound is preferably used.
- organoaluminum compound examples include halogen-containing alkylaluminum compounds and alkylaluminum compounds, which can be used alone or in combination.
- a catalyst system using a cobalt compound (hereinafter sometimes referred to as a cobalt-based catalyst composition)
- a catalyst system comprising a cobalt compound, a halogen-containing alkylaluminum compound and water, or a cobalt compound, a halogen-containing alkylaluminum compound
- a catalyst system comprising water and an alkylaluminum compound can be preferably used.
- cobalt compound in the cobalt-based catalyst composition a salt or complex of cobalt is preferably used, and particularly preferable are cobalt chloride, cobalt bromide, cobalt nitrate, cobalt 2-ethylhexanoate (cobalt octoate), and naphthenic acid.
- Cobalt salts such as cobalt, cobalt octenoate, cobalt acetate, cobalt malonate, cobalt bisacetylacetonate, trisacetylacetonate, ethyl acetoacetate cobalt, cobalt halide triarylphosphine complex, trialkylphosphine Examples thereof include organic base complexes such as complexes, pyridine complexes and picoline complexes, and cobalt complexes such as ethyl alcohol complexes.
- the halogen-containing alkylaluminum compound in the cobalt-based catalyst composition includes R 1 3-n AlX n (wherein R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen, and n represents 1 to It is a number represented by 2).
- R 1 represents a hydrocarbon group having 1 to 10 carbon atoms
- X represents a halogen
- n represents 1 to It is a number represented by 2
- Examples include dialkylaluminum halides such as dialkylaluminum chloride and dialkylaluminum bromide; alkylaluminum sesquihalides such as alkylaluminum sesquichloride and alkylaluminum sesquibromide; alkylaluminum dihalides such as alkylaluminum dichloride and alkylaluminum dibromide.
- the compound examples include diethylaluminum monochloride, diethylaluminum monobromide, dibutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, dicyclohexylaluminum monochloride, and diphenylaluminum monochloride. Ride and diisobutylaluminum monochloride are preferred.
- the alkylaluminum compound in the cobalt-based catalyst composition is preferably a compound represented by R 2 3 Al (wherein R 2 represents a hydrocarbon group having 1 to 10 carbon atoms).
- R 2 represents a hydrocarbon group having 1 to 10 carbon atoms.
- a trialkylaluminum compound more specifically, triethylaluminum, trimethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like can be mentioned.
- Aluminoxane may also be used.
- the aluminoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and has a general formula (—Al (R ′) O—) n (wherein R ′ is a carbon atom having 1 to 10 carbon atoms).
- R ′ is a carbon atom having 1 to 10 carbon atoms.
- R ′ includes a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group and an ethyl group are particularly preferable.
- organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.
- Polymerization of 1,3-butadiene For example, the polymerization of 1,3-butadiene is performed as follows. First, 1,3-butadiene and a solvent are charged into a pressure-resistant container whose interior is purged with nitrogen, and then water, a molecular weight regulator and an organoaluminum compound are charged and stirred. After bringing the pressure vessel to a predetermined temperature, a transition metal polymerization catalyst is charged and polymerization is started. The polymerization is carried out under normal pressure or a pressure up to about 10 atm (gauge pressure).
- the order of addition of the catalyst components it is preferable to add water in an inert solvent and mix uniformly, add an organoaluminum compound, add a cobalt compound, and start polymerization. After adding the organoaluminum compound, it is preferable to age for a predetermined time and add the cobalt compound.
- the aging time is preferably 0.1 to 24 hours, and the aging temperature is preferably 0 to 80 ° C.
- a cobalt compound when using a halogen-containing alkyl aluminum compound and cobalt catalyst composition consisting of water, for cobalt compound, 1 relative to 1,3 mole butadiene ⁇ 10 -7 ⁇ 1 ⁇ 10 - A range of 3 moles is preferred.
- the halogen-containing alkylaluminum compound is preferably in the range of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 1 mol with respect to 1 mol of 1,3-butadiene.
- the water is preferably in the range of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 1 mol per 1 mol of 1,3-butadiene.
- the addition amount of the halogen-containing alkylaluminum compound used in the cobalt-based catalyst composition is preferably 0.9 to 3.0 times, more preferably 1.0 to 2.0 times the amount of water to be added. . If it is larger than this range, the desired physical properties cannot be obtained, and if it is smaller than this range, the workability tends to deteriorate.
- the addition amount of the halogen-containing alkylaluminum compound and the ratio of water to be added are particularly important in controlling the linearity of polybutadiene.
- Polymerization solvents include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as butane, pentane, hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, 1-butene, cis- Examples include olefinic hydrocarbons such as C4 fraction such as 2-butene and trans-2-butene, hydrocarbon solvents such as mineral spirit, solvent naphtha, and kerosene, and halogenated hydrocarbon solvents such as methylene chloride. . Further, 1,3-butadiene itself may be used as a polymerization solvent.
- benzene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is preferably used.
- non-conjugated dienes such as cyclooctadiene and allene, or ⁇ -olefins such as ethylene, propylene and 1-butene
- cyclooctadiene preferably 0.5 to 40 mmol, more preferably 1 to 10 mmol, particularly preferably 1 to 7 mmol per mole of 1,3-butadiene. If an amount outside this range is used, the processability of the polymer tends to deteriorate.
- the polymerization temperature is preferably in the range of ⁇ 30 to 100 ° C., particularly preferably in the range of 30 to 80 ° C.
- the polymerization time is preferably in the range of 5 minutes to 12 hours, more preferably 10 minutes to 6 hours, and particularly preferably 15 minutes to 1 hour.
- the Mooney viscosity of the cis-1,4-polybutadiene used in the present invention is 10 to 120, preferably 15 to 100, more preferably 20 to 70. If the Mooney viscosity is greater than the above range, processing is difficult, and if it is less than the above range, wear resistance and low loss tend to be reduced.
- the ratio (Tcp / ML 1 + 4 ) of the solution viscosity (Tcp) and Mooney viscosity (ML 1 + 4 ) of a 5 wt% toluene solution is preferably from 1.0 to 6.0. Further, Mw / Mn is preferably 1.2 to 5.0, particularly preferably 1.5 to 4.5.
- the modified cis-1,4-polybutadiene according to an embodiment of the present invention includes a cis-1,4-polybutadiene and a modifier in the presence of a Lewis acid and an organic halogen compound. It can be produced by reacting with a 1 to 3 substituted aromatic compound represented by the following general formula (1).
- Y represents hydrogen, a hydroxyl group, an alkenyl group or an alkoxy group having 1 to 10 carbon atoms
- Z 1 and Z 2 each represent hydrogen, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms.
- modifying agent represented by the general formula (1) include anisole, phenetole, n-propoxybenzene, isopropoxybenzene, n-butoxybenzene, isobutoxybenzene, sec-butoxybenzene, n- Pentyloxybenzene, isopentyloxybenzene, neopentyloxybenzene, n-hexyloxybenzene, (2-ethylbutyloxy) benzene, n-octyloxybenzene, n-decyloxybenzene, veratrol, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,2-diethoxybenzene, 1,3-diethoxybenzene, 1,4-diethoxybenzene, 1,2-di-n-propoxybenzene, 1,3-di-n- Propoxybenzene, 1,4-di-n-propoxybenzene, 1 2-d
- modifiers selected from the group consisting of phenol derivatives, catechol derivatives, resorcin derivatives, hydroquinone derivatives, and 2- to 3-substituted aromatic alkenyl compounds, and phenol derivatives and catechol derivatives.
- Resorcin derivatives are preferred, and anisole, phenetole, anethole, veratrol, 1,3-dimethoxybenzene, 1,3-diethoxybenzene, 1,2-methylenedioxybenzene, safrole, isosafrole, and methylisoeugenol are particularly preferred.
- Lewis acid As the Lewis acid used for the modification reaction, a generally known Lewis acid can be used. Typical examples are metal or metalloid halides such as Be, B, Al, Si, P, S, Ti, V, Fe, Zn, Ga, Ge, As, Se, Zr, Nb, Mo, An element such as Cd, Sn, Sb, Te, Hf, Ta, W, Hg, Bi, U, or a halide or organic halide of an oxygen-element conjugate such as PO, SeO, SO, SO 2 , or VO; or These complexes are exemplified.
- metal or metalloid halides such as Be, B, Al, Si, P, S, Ti, V, Fe, Zn, Ga, Ge, As, Se, Zr, Nb, Mo, An element such as Cd, Sn, Sb, Te, Hf, Ta, W, Hg, Bi, U, or a halide or organic halide of an oxygen-element conjugate such as PO, SeO, SO,
- an organoaluminum compound can be used as the Lewis acid in the modification reaction. Therefore, the organoaluminum compound used in the polymerization of 1,3-butadiene can be continuously used as a Lewis acid.
- the use of the organoaluminum compound used in the polymerization of 1,3-butadiene as the Lewis acid is preferred because it is not necessary to add a new Lewis acid during the modification reaction.
- the organoaluminum compound can also be added separately as a Lewis acid during the modification reaction.
- Organic halogen compounds used for the modification reaction is not particularly limited as long as it reacts with a Lewis acid to generate a carbocation.
- an alkyl halide represented by the following general formula (2) can be used. .
- R 3 and R 4 are hydrogen, chloro, bromo or an alkyl group having 1 to 12 carbon atoms, an aryl group, a chloro-substituted alkyl group, an alkoxy group, etc.
- R 5 is chloro, bromo or carbon number. 1 to 6 alkyl groups, aryl groups, chloro-substituted alkyl groups, alkoxy groups, and the like
- X is a halogen such as chloro and bromo.
- R 5 is preferably an aryl group.
- the above alkyl group may be saturated or unsaturated, and may be linear, branched or cyclic.
- the compound include chlorides, bromides, and iodides such as methyl, ethyl, isopropyl, isobutyl, t-butyl, phenyl, benzyl, benzoyl, and benzylidene. Further, methyl chloroformate, bromoformate, chlorodiphenylmethane, chlorotriphenylmethane, and the like can be given.
- a tertiary alkyl halide particularly a tertiary alkyl halide having 4 to 12 carbon atoms, is preferred in view of the stability of the carbocation to be produced. Specifically, t-butyl chloride and t-Butyl bromide is preferred.
- an acyl halide compound represented by the following general formula (3) can be used as the organic halogen compound used in the modification reaction.
- R 6 is hydrogen, chloro, bromo or an alkyl group having 1 to 12 carbon atoms, an aryl group, a chloro-substituted alkyl group, an alkoxy group, and the like, and X is a halogen such as chloro and bromo.
- the modification reaction may be carried out after the termination of the polymerization of 1,3-butadiene, after the polymerization, or after removing the solvent and unreacted monomers remaining in the reaction product.
- the polymer may be dried by a steam stripping method or a vacuum drying method and then dissolved again in a solvent such as cyclohexane.
- a solvent such as cyclohexane.
- the polymerization system contains a Lewis acid component such as a halogen-containing aluminum compound, it is preferable to carry out a modification reaction subsequent to the polymerization of 1,3-butadiene.
- a modifier is added after the polymerization, and then an organic halogen compound is added at a predetermined temperature, followed by stirring and mixing for a predetermined time.
- a Lewis acid may be added as necessary.
- the temperature at which the modifier is reacted with polybutadiene is preferably 20 to 100 ° C, more preferably 40 to 100 ° C, and still more preferably 50 to 90 ° C. If it is higher than this temperature range, gelation is promoted, which is not preferable. On the other hand, when the temperature is lower than this temperature range, the modification reaction hardly occurs effectively.
- the reaction time is preferably 1 to 600 minutes. More preferably, it is desirable to stir and mix for 10 to 90 minutes.
- the amount of the modifier is preferably 1 ⁇ 10 ⁇ 3 to 100 mol, particularly 1 ⁇ 10 ⁇ 2 to 10 mol, per 1 mol of 1,3-butadiene unit in cis-1,4-polybutadiene. preferable.
- the amount of the organic halogen compound is 0.05 to 50 times, preferably 1 to 20 times that of the organoaluminum compound in the polymerization reaction. If the amount is less than this amount, the modification reaction does not proceed sufficiently and the desired polymer may not be obtained. Moreover, when there are too many, gelation by reaction of polybutadiene molecules will be accelerated
- the degree of modification of the modified cis-1,4-polybutadiene of this embodiment is calculated by a technique using gel permeation chromatography (GPC) measurement. This will be described in detail with reference to FIG.
- the vertical axis indicates the ratio of the peak area value UV obtained from the UV absorbance of the polymer obtained by GPC measurement and the peak area value RI obtained from the differential refractive index (RI), the value of UV / RI.
- Li-BR (unmodified) is a plot of the UV / RI value of a polymer obtained by polymerizing 1,3-butadiene by anionic polymerization using a Li-based catalyst for five different types of polymers having a number average molecular weight Mn. It can be approximated as a straight line.
- Li-BR (modified) is polymerized by anionic polymerization using a Li-based catalyst, and then the UV / RI value of the polymer modified by reacting the polymerization terminal with 3,5-dimethoxybenzyl bromide is changed into five different types. This is plotted for a polymer having a number average molecular weight Mn and can be approximated as a straight line.
- the modified cis-1,4-polybutadiene of this embodiment having a certain number average molecular weight (Mn1) and the unmodified cis-1,4 obtained by the same method as used for modification
- Mn1 the number average molecular weight
- the modification degree of the modified cis-1,4-polybutadiene of this embodiment can be expressed by the following equation.
- the degree of modification of the cis-1,4-polybutadiene of the present embodiment determined as described above is not particularly limited, but is preferably more than 0.1 and more preferably more than 0.5. . Further, the degree of modification preferably does not exceed 20, and more preferably does not exceed 15. If the degree of modification is 0.1 or less, the effect of modification may not be sufficient, and if the degree of modification is 20 or more, the characteristics of the original cis-1,4-polybutadiene may be impaired.
- a rubber composition obtained by adding a filler (filler) such as carbon black or silica, a silane coupling agent, a vulcanizing agent, a vulcanization accelerator, and other ordinary compounding agents and vulcanizing.
- a filler such as carbon black or silica, a silane coupling agent, a vulcanizing agent, a vulcanization accelerator, and other ordinary compounding agents and vulcanizing.
- a vulcanizable rubber As the other synthetic rubber contained in the rubber composition, a vulcanizable rubber is preferable. Specifically, ethylene propylene diene rubber (EPDM), nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), Examples thereof include polyisoprene, high cis polybutadiene rubber, low cis polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and acrylonitrile-butadiene rubber. Among these, SBR is preferable. Further, among SBR, solution-polymerized styrene butadiene copolymer rubber (S-SBR) is particularly preferable. These rubbers may be used alone or in combination of two or more.
- EPDM ethylene propylene diene rubber
- NBR nitrile rubber
- IIR butyl rubber
- the microstructure of the solution polymerized styrene butadiene copolymer rubber has a styrene content of 15 to 35% by weight, preferably 17 to 30% by weight, and a vinyl bond content of the butadiene portion of 30 to 75%, preferably 32-72%.
- S-SBR solution polymerized styrene butadiene copolymer rubber
- silane coupling agent used in the rubber composition is an organosilicon compound represented by the general formula R 7 n SiR 8 4-n , where R 7 is a vinyl group, acyl group, allyl group, allyloxy group, amino group.
- R 8 Is a hydrolyzable group selected from a chloro group, an alkoxy group, an acetoxy group, an isopropenoxy group, an amino group and the like, and n represents an integer of 1 to 3.
- R 7 components of the silane coupling agent those containing a vinyl group and / or a chloro group are preferable.
- silane coupling agents include, for example, the following, but are not limited to these.
- the addition amount of the silane coupling agent is preferably 0.2 to 20% and particularly preferably 5 to 15% with respect to the filler amount. If it is less than the above range, it is not preferable because it causes scorch. Moreover, since it will become the cause of a deterioration of a tensile characteristic and elongation when it exceeds more than said range, it is unpreferable.
- the modified cis-1,4-polybutadiene of this embodiment is used as a modifier for plastics, for example, impact-resistant polystyrene.
- a modified impact-resistant polystyrene resin composition can also be produced.
- styrene resin composition As a method for producing the above rubber-modified impact-resistant polystyrene resin composition, a method of polymerizing a styrene monomer in the presence of the modified cis-1,4-polybutadiene of the present embodiment is adopted. Bulk suspension polymerization is an economically advantageous method.
- the styrene monomer for example, styrene, alkyl-substituted styrene such as ⁇ -methyl styrene and p-methyl styrene, and halogen-substituted styrene such as chlorostyrene are conventionally known for producing rubber-modified impact-resistant polystyrene resin compositions. One kind or a mixture of two or more kinds of styrenic monomers are used. Of these, styrene is preferred.
- the modified cis-1,4-polybutadiene In addition to the above-mentioned modified cis-1,4-polybutadiene at the time of production, the modified cis-1,4-polybutadiene, styrene-butadiene copolymer, ethylene-propylene polymer, ethylene-vinyl acetate polymer, acrylic rubber, etc. It can be used in combination within 50% by weight based on 4-polybutadiene. Moreover, you may blend the resin manufactured by these methods. Furthermore, you may manufacture by mixing the polystyrene-type resin which does not contain resin manufactured by these methods.
- a modified cis-1,4-polybutadiene (1 to 25% by weight) is dissolved in a styrene monomer (99 to 75% by weight). Then, a polymerization initiator or the like is added to convert into particles in which the modified cis-1,4-polybutadiene is dispersed to a styrene monomer conversion rate of 10 to 40%. Until the rubber particles are produced, the rubber phase forms a continuous phase.
- the polymerization is continued until the conversion into a dispersed phase as a rubber particle (particle formation process), and the polymerization is carried out to a conversion rate of 50 to 99% to produce a rubber-modified impact-resistant polystyrene resin composition.
- the dispersed particles (rubber particles) of modified cis-1,4-polybutadiene are particles dispersed in a resin, and are composed of modified cis-1,4-polybutadiene and a polystyrene resin.
- the polystyrene resin is a modified cis-1,4-polybutadiene. It is occluded with 4-polybutadiene grafted or not grafted.
- the modified cis-1,4-polybutadiene having a dispersed particle diameter in the range of 0.5 to 7.0 ⁇ m, preferably in the range of 1.0 to 3.0 ⁇ m, can be suitably produced.
- a graft ratio in the range of 150 to 350 can be preferably produced. It may be a batch type or a continuous production method and is not particularly limited.
- the raw material solution mainly composed of the styrene monomer and the modified cis-1,4-polybutadiene is polymerized in a complete mixing type reactor.
- the complete mixing type reactor the raw material solution is uniformly mixed in the reactor.
- a stirring blade of types such as a helical ribbon, a double helical ribbon, an anchor, is mentioned. It is preferable that a draft tube is attached to the helical ribbon type stirring blade to further enhance the vertical circulation in the reactor.
- the rubber-modified impact-resistant polystyrene-based resin composition includes a stabilizer such as an antioxidant and an ultraviolet absorber, a release agent, a lubricant, a colorant, various fillers, and various fillers as necessary at the time of production and after production.
- a stabilizer such as an antioxidant and an ultraviolet absorber
- release agent such as an antioxidant and an ultraviolet absorber
- lubricant such as an antioxidant and an ultraviolet absorber
- a colorant such as a lubricant, a colorant, various fillers, and various fillers
- various fillers such as plasticizers, higher fatty acids, organic polysiloxanes, silicone oils, flame retardants, antistatic agents and foaming agents may be added.
- the rubber composition obtained from the modified cis-1,4-polybutadiene of this embodiment includes industrial articles such as tires, vibration-insulating rubbers, belts, hoses, seismic isolation rubbers, footwear such as men's shoes, women's shoes, and sports shoes. Used for various rubber applications.
- the rubber component is preferably blended so as to contain at least 10% by weight of the modified cis-1,4-polybutadiene of the present embodiment.
- the rubber-modified impact-resistant polystyrene resin composition can be used in various known molded products, but has excellent flame retardancy, impact strength, and tensile strength, so that it can be used in electrical and industrial applications, packaging materials, and housing.
- it can be used in a wide range of applications such as housings for televisions, personal computers, air conditioners, exterior materials for office equipment such as copiers and printers, and food containers for frozen foods, lactic acid beverages, and ice creams.
- the Mooney viscosity, toluene solution viscosity, number average molecular weight, processability, rebound resilience of the vulcanized product, tan ⁇ of the vulcanized product, and permanent set in the examples were measured by the following methods.
- Mooney viscosity (ML 1 + 4 , 100 ° C.): In accordance with JIS-K6300, pre-heated at 100 ° C. for 1 minute using a Mooney viscometer (SMV-300) manufactured by Shimadzu Corporation, and measured for 4 minutes. Expressed as Mooney viscosity (ML 1 + 4 , 100 ° C.).
- Number average molecular weight Calculated using a calibration curve obtained from a molecular weight distribution curve obtained by GPC (manufactured by Shimadzu Corporation) using polystyrene as a standard substance and tetrahydrofuran as a solvent at a temperature of 40 ° C. Asked.
- A is the difference between the UV / RI value of Li-BR (modified) and the UV / RI value of Li-BR (unmodified) at the same number average molecular weight as the target example.
- the UV / RI value of the example was set as B, and was calculated from the following formula.
- Processability Evaluated by Mooney viscosity of unvulcanized product.
- the prototype 2 or 3 was displayed as an index, and the value was converted so that the larger the index, the better.
- Rebound resilience of the vulcanizate According to BS903, the rebound resilience was measured at room temperature using a Dunlop trypometer, and the prototype 2 or 3 was displayed as an index. The larger the index, the better the low loss property.
- G ′ Storage elastic modulus
- Vulcanized tan ⁇ Measured under conditions of temperature 50 ° C., frequency 10 Hz, dynamic strain 0.3% using EBO LEXOR 100N manufactured by GABO, and the index is shown with prototype 2 or 3 as 100, the index being large It converted so that it might become so favorable.
- Heat generation amount / permanent strain Measured according to the measurement method stipulated in JIS K6265, displayed as an index with prototype 2 or 3 as 100, and converted so that the larger the index, the better.
- Example 1 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 600 mL of a cyclohexane-C4 fraction mixed solution containing 32.4% by weight of 1,3-butadiene (26.4% by weight of cyclohexane, cis-2) -39.2% by weight of C4 fraction containing butene as the main component), and then stirred by adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride, and adding 5.1 mmol of cyclooctadiene did.
- Example 2 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -C4 fraction containing butene as the main component (containing 31.2% by weight)), and then stirred by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, and adding 7.3 mmol of cyclooctadiene did.
- Example 3 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did.
- Example 4 The reaction was conducted in the same manner as in Example 3 except that 1,3-diethoxybenzene (DEOB) was used as the modifier.
- DEOB 1,3-diethoxybenzene
- Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
- Example 5 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -C4 fraction containing butene as the main component (containing 31.2% by weight)), and then stirred by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, and adding 7.3 mmol of cyclooctadiene did.
- Example 6 The reaction was conducted in the same manner as in Example 3 except that 1,2-methylenedioxybenzene (MDB) was used as the modifier. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
- Example 7 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did.
- Example 8 The reaction was performed in the same manner as in Example 7 except that the denaturant was phenetole. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
- Example 9 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did.
- Example 10 The reaction was performed in the same manner as in Example 3 except that the modifier was safrole. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
- Example 11 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did.
- Example 12 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution, 600 mL of a cyclohexane-C4 fraction mixed solution containing 30.6% by weight of 1,3-butadiene (36.8% by weight of cyclohexane, cis-2) -Containing 31.1% by weight of C4 fraction containing butene as the main component), then adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stirring, and adding 4.5 mmol of cyclooctadiene did.
- Example 13 In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution, 600 mL of a cyclohexane-C4 fraction mixed solution containing 30.6% by weight of 1,3-butadiene (36.8% by weight of cyclohexane, cis-2) -Containing 31.1% by weight of C4 fraction containing butene as the main component), then adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stirring, and adding 4.5 mmol of cyclooctadiene did.
- Table 3 shows the evaluation results of the obtained blend. Each evaluation item of prototype 2 was defined as 100 and compared with prototype 1. For each item, the larger the value, the better the characteristics.
- Table 5 shows the evaluation results of the obtained blend.
- Each evaluation item of prototype 3 was defined as 100 and compared with prototypes 4 and 5. For each item, the larger the value, the better the characteristics.
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Abstract
Description
すなわち本発明の第1の態様は、ルイス酸および有機ハロゲン化合物の存在下、シス-1,4-ポリブタジエンと下記一般式(1)で表される1~3置換の芳香族化合物とを反応させて得られたことを特徴とする変性シス-1,4-ポリブタジエンを提供する。 As a result of intensive investigations to solve the above-mentioned problems, the present inventors have made a modification obtained by reacting cis-1,4-polybutadiene with a specific aromatic compound in the presence of a Lewis acid and an organic halogen compound. The present inventors have found that cis-1,4-polybutadiene is excellent in processability and low loss, and completed the present invention.
That is, in the first embodiment of the present invention, cis-1,4-polybutadiene is reacted with a 1-3 substituted aromatic compound represented by the following general formula (1) in the presence of a Lewis acid and an organic halogen compound. There is provided a modified cis-1,4-polybutadiene characterized by being obtained in the above.
シス-1,4-ポリブタジエンは、遷移金属化合物および有機アルミニウム化合物を含有する重合触媒の存在下、1,3-ブタジエンを重合することにより製造することができる。 (1) Production of cis-1,4-polybutadiene Cis-1,4-polybutadiene is produced by polymerizing 1,3-butadiene in the presence of a polymerization catalyst containing a transition metal compound and an organoaluminum compound. Can do.
重合触媒に用いられる遷移金属化合物としては、コバルト化合物、ニッケル化合物およびチタン化合物などを挙げることができるが、コバルト化合物が好適に用いられる。また、有機アルミニウム化合物としては、ハロゲン含有アルキルアルミニウム化合物及びアルキルアルミニウム化合物などを挙げることができ、これらは単独でも併用して用いることもできる。例えば、コバルト化合物を用いた触媒系(以下、コバルト系触媒組成物という場合がある。)としては、コバルト化合物、ハロゲン含有アルキルアルミニウム化合物および水からなる触媒系またはコバルト化合物、ハロゲン含有アルキルアルミニウム化合物、水およびアルキルアルミニウム化合物からなる触媒系を好ましく用いることができる。 (Polymerization catalyst)
Examples of the transition metal compound used for the polymerization catalyst include a cobalt compound, a nickel compound and a titanium compound, and a cobalt compound is preferably used. Examples of the organoaluminum compound include halogen-containing alkylaluminum compounds and alkylaluminum compounds, which can be used alone or in combination. For example, as a catalyst system using a cobalt compound (hereinafter sometimes referred to as a cobalt-based catalyst composition), a catalyst system comprising a cobalt compound, a halogen-containing alkylaluminum compound and water, or a cobalt compound, a halogen-containing alkylaluminum compound, A catalyst system comprising water and an alkylaluminum compound can be preferably used.
1,3-ブタジエンの重合は、例えば、次のように行う。まず、内部を窒素置換した耐圧容器に1,3-ブタジエンと溶媒を仕込み、次いで、水、分子量調節剤及び有機アルミニウム化合物を仕込んで攪拌する。耐圧容器を所定の温度にした後、遷移金属重合触媒を仕込み、重合を開始する。重合は、常圧または10気圧(ゲ-ジ圧)程度までの加圧下に行われる。 (Polymerization of 1,3-butadiene)
For example, the polymerization of 1,3-butadiene is performed as follows. First, 1,3-butadiene and a solvent are charged into a pressure-resistant container whose interior is purged with nitrogen, and then water, a molecular weight regulator and an organoaluminum compound are charged and stirred. After bringing the pressure vessel to a predetermined temperature, a transition metal polymerization catalyst is charged and polymerization is started. The polymerization is carried out under normal pressure or a pressure up to about 10 atm (gauge pressure).
本発明で用いるシス-1,4-ポリブタジエンのムーニー粘度は10~120、好ましくは15~100、より好ましくは、20~70である。ムーニー粘度が上記範囲より大きいと加工が困難であり、上記範囲より小さいと耐摩耗性や低ロス性が低下する傾向がある。 (Properties of cis-1,4-polybutadiene)
The Mooney viscosity of the cis-1,4-polybutadiene used in the present invention is 10 to 120, preferably 15 to 100, more preferably 20 to 70. If the Mooney viscosity is greater than the above range, processing is difficult, and if it is less than the above range, wear resistance and low loss tend to be reduced.
本発明の一実施形態に係る変性シス-1,4-ポリブタジエンは、ルイス酸および有機ハロゲン化合物の存在下、シス-1,4-ポリブタジエンと変性剤である下記一般式(1)で表される1~3置換の芳香族化合物とを反応させることにより製造することができる。 (2) Modification of cis-1,4-polybutadiene The modified cis-1,4-polybutadiene according to an embodiment of the present invention includes a cis-1,4-polybutadiene and a modifier in the presence of a Lewis acid and an organic halogen compound. It can be produced by reacting with a 1 to 3 substituted aromatic compound represented by the following general formula (1).
上記一般式(1)で表される変性剤の例として、具体的には、アニソール、フェネトール、n-プロポキシベンゼン、イソプロポキシベンゼン、n-ブトキシベンゼン、イソブトキシベンゼン、sec-ブトキシベンゼン、n-ペンチルオキシベンゼン、イソペンチルオキシベンゼン、ネオペンチルオキシベンゼン、n-ヘキシルオキシベンゼン、(2-エチルブチルオキシ)ベンゼン、n-オクチルオキシベンゼン、n-デシルオキシベンゼン、ベラトロール、1,3-ジメトキシベンゼン、1,4-ジメトキシベンゼン、1,2-ジエトキシベンゼン、1,3-ジエトキシベンゼン、1,4-ジエトキシベンゼン、1,2-ジ-n-プロポキシベンゼン、1,3-ジ-n-プロポキシベンゼン、1,4-ジ-n-プロポキシベンゼン、1,2-ジ-n-ブトキシベンゼン、1,3-ジ-n-ブトキシベンゼン、2-エトキシ-メトキシベンゼン、3-エトキシ-メトキシベンゼン、4-エトキシ-メトキシベンゼン、2-プロポキシ-メトキシベンゼン、3-プロポキシ-メトキシベンゼン、4-プロポキシ-メトキシベンゼン、1,4-ジ-n-ブトキシベンゼン、1,2-メチレンジオキシベンゼン、1,2,3-トリメトキシベンゼン、1,2,4-トリメトキシベンゼン、1,3,5-トリメトキシベンゼン、フェノール、2-メトキシフェノール、3-メトキシフェノール、4-メトキシフェノール、2-エトキシフェノール、3-エトキシフェノール、4-エトキシフェノール、2,6-ジメトキシフェノール、3,4-ジメトキシフェノール、3,5-ジメトキシフェノール、カテコール、3-メトキシカテコール、レゾルシノール、2-メトキシレゾルシノール、5-エトキシレゾルシノール、ヒドロキノン、ヒドロキノンモノメチルエーテル、アネトール、サフロール、イソサフロール、オイゲノール、メチルオイゲノール、イソオイゲノール、メチルイソオイゲノール、ピロガロール、ピロガロールトリメチルエーテル、フロログルシノール、フロログルシノールトリメチルエーテルなどが挙げられる。この中でもフェノール誘導体、カテコール誘導体、レゾルシン誘導体、ヒドロキノン誘導体、および2~3置換の芳香族系アルケニル化合物からなる群より選択された1種以上の変性剤を用いることが好ましく、さらにフェノール誘導体、カテコール誘導体、レゾルシン誘導体が好ましく、特にアニソール、フェネトール、アネトール、ベラトロール、1,3-ジメトキシベンゼン、1,3-ジエトキシベンゼン、1,2-メチレンジオキシベンゼン、サフロール、イソサフロール、メチルイソオイゲノールが好ましい。また、これらのうち2種類以上を組み合わせて使用しても問題ない。 (Modifier)
Specific examples of the modifying agent represented by the general formula (1) include anisole, phenetole, n-propoxybenzene, isopropoxybenzene, n-butoxybenzene, isobutoxybenzene, sec-butoxybenzene, n- Pentyloxybenzene, isopentyloxybenzene, neopentyloxybenzene, n-hexyloxybenzene, (2-ethylbutyloxy) benzene, n-octyloxybenzene, n-decyloxybenzene, veratrol, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,2-diethoxybenzene, 1,3-diethoxybenzene, 1,4-diethoxybenzene, 1,2-di-n-propoxybenzene, 1,3-di-n- Propoxybenzene, 1,4-di-n-propoxybenzene, 1 2-di-n-butoxybenzene, 1,3-di-n-butoxybenzene, 2-ethoxy-methoxybenzene, 3-ethoxy-methoxybenzene, 4-ethoxy-methoxybenzene, 2-propoxy-methoxybenzene, 3- Propoxy-methoxybenzene, 4-propoxy-methoxybenzene, 1,4-di-n-butoxybenzene, 1,2-methylenedioxybenzene, 1,2,3-trimethoxybenzene, 1,2,4-trimethoxy Benzene, 1,3,5-trimethoxybenzene, phenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,6-dimethoxyphenol 3,4-dimethoxyphenol, 3,5-dimethoxy Phenol, catechol, 3-methoxycatechol, resorcinol, 2-methoxyresorcinol, 5-ethoxyresorcinol, hydroquinone, hydroquinone monomethyl ether, anethole, safrole, isosafrole, eugenol, methyleugenol, isoeugenol, methylisoeugenol, pyrogallol, pyrogallol trimethyl Examples include ether, phloroglucinol, and phloroglucinol trimethyl ether. Among these, it is preferable to use one or more modifiers selected from the group consisting of phenol derivatives, catechol derivatives, resorcin derivatives, hydroquinone derivatives, and 2- to 3-substituted aromatic alkenyl compounds, and phenol derivatives and catechol derivatives. Resorcin derivatives are preferred, and anisole, phenetole, anethole, veratrol, 1,3-dimethoxybenzene, 1,3-diethoxybenzene, 1,2-methylenedioxybenzene, safrole, isosafrole, and methylisoeugenol are particularly preferred. Moreover, there is no problem even if two or more of these are used in combination.
変性反応に用いられるルイス酸は、一般に知られているものが使用可能である。その代表例は金属または半金属のハロゲン化物であって、例えばBe、B、Al、Si、P、S、Ti、V、Fe、Zn、Ga、Ge、As、Se、Zr、Nb、Mo、Cd、Sn、Sb、Te、Hf、Ta、W、Hg、Bi、Uなどの元素、またはPO、SeO、SO、SO2、VOなどの酸素-元素結合体のハロゲン化物もしくは有機ハロゲン化物、またはこれらの錯体などが挙げられる。さらに具体的には、BF3、BF3・O(C2H5)2、(CH3)2BF、BCl3、AlCl3、AlBr3、(C2H5)AlCl2、POCl3、TiCl4、VCl4、MoCl6、SnCl4、(CH3)SnCl3、SbCl5、TeCl4、TeBr4、FeCl3、WCl6、Sc(OTf)3、Hf(OTf)3、Sb(OTf)3、Bi(OTf)3、およびGa(OTf)3などが挙げられる。中でも好ましいのはアルミニウムのハロゲン化物またはアルミニウムの有機ハロゲン化物である。
また、本実施形態においては、変性反応におけるルイス酸として、有機アルミニウム化合物を用いることができる。そのため、上記1,3-ブタジエンの重合で用いた有機アルミニウム化合物をルイス酸として引き続き使用することができる。1,3-ブタジエンの重合で用いた有機アルミニウム化合物をルイス酸として引き続き使用することで、変性反応の際に新たなルイス酸を添加する必要がないため好ましい。本実施形態においては、例えば、上記コバルト系触媒組成物に用いられるハロゲン含有アルキルアルミニウム化合物と同じものを用いることが好ましい。なお、有機アルミニウム化合物は、変性反応の際にルイス酸として別途添加することもできる。 (Lewis acid)
As the Lewis acid used for the modification reaction, a generally known Lewis acid can be used. Typical examples are metal or metalloid halides such as Be, B, Al, Si, P, S, Ti, V, Fe, Zn, Ga, Ge, As, Se, Zr, Nb, Mo, An element such as Cd, Sn, Sb, Te, Hf, Ta, W, Hg, Bi, U, or a halide or organic halide of an oxygen-element conjugate such as PO, SeO, SO, SO 2 , or VO; or These complexes are exemplified. More specifically, BF 3 , BF 3 .O (C 2 H 5 ) 2 , (CH 3 ) 2 BF, BCl 3 , AlCl 3 , AlBr 3 , (C 2 H 5 ) AlCl 2 , POCl 3 , TiCl 4 , VCl 4 , MoCl 6 , SnCl 4 , (CH 3 ) SnCl 3 , SbCl 5 , TeCl 4 , TeBr 4 , FeCl 3 , WCl 6 , Sc (OTf) 3 , Hf (OTf) 3 , Sb (OTf) 3 , Sb (OTf) 3 Bi (OTf) 3 , and Ga (OTf) 3 . Among these, aluminum halides or aluminum organic halides are preferable.
In this embodiment, an organoaluminum compound can be used as the Lewis acid in the modification reaction. Therefore, the organoaluminum compound used in the polymerization of 1,3-butadiene can be continuously used as a Lewis acid. The use of the organoaluminum compound used in the polymerization of 1,3-butadiene as the Lewis acid is preferred because it is not necessary to add a new Lewis acid during the modification reaction. In the present embodiment, for example, it is preferable to use the same halogen-containing alkylaluminum compound used for the cobalt-based catalyst composition. The organoaluminum compound can also be added separately as a Lewis acid during the modification reaction.
変性反応に用いられる有機ハロゲン化合物は、ルイス酸と反応してカルボカチオンを生成するものであれば特に制限はなく、例えば、下記一般式(2)で表されるハロゲン化アルキルを用いることができる。 (Organic halogen compounds)
The organic halogen compound used for the modification reaction is not particularly limited as long as it reacts with a Lewis acid to generate a carbocation. For example, an alkyl halide represented by the following general formula (2) can be used. .
変性反応は、1,3-ブタジエンの重合停止後、重合に引き続いて行ってもよく、反応生成物中に残留している溶媒や未反応モノマーを除去した後に行ってもよい。また、スチームストリッピング法や真空乾燥法などで重合体を乾燥させた後、シクロヘキサンなどの溶媒に再度溶解させてから行ってもよい。重合系にハロゲン含有アルミニウム化合物などのルイス酸成分が含まれている場合は、1,3-ブタジエンの重合に引き続き変性反応を行うのが好適である。 (Denaturation reaction)
The modification reaction may be carried out after the termination of the polymerization of 1,3-butadiene, after the polymerization, or after removing the solvent and unreacted monomers remaining in the reaction product. Alternatively, the polymer may be dried by a steam stripping method or a vacuum drying method and then dissolved again in a solvent such as cyclohexane. When the polymerization system contains a Lewis acid component such as a halogen-containing aluminum compound, it is preferable to carry out a modification reaction subsequent to the polymerization of 1,3-butadiene.
本実施形態の変性シス-1,4-ポリブタジエンの変性度は、ゲルパーミエーションクロマトグラフィー(GPC)測定を用いる手法により算出する。これについて、図1に基づいて詳細に説明する。 (Denatured degree)
The degree of modification of the modified cis-1,4-polybutadiene of this embodiment is calculated by a technique using gel permeation chromatography (GPC) measurement. This will be described in detail with reference to FIG.
本実施形態の変性シス-1,4-ポリブタジエンは、単独で、または他の合成ゴム若しくは天然ゴムとブレンドして配合し、必要ならばプロセス油で油展し、次いでカーボンブラックやシリカ等の充填剤(フィラー)、シランカップリング剤、加硫剤、加硫促進剤、その他の通常の配合剤を加えて加硫することでゴム組成物とすることができる。 (3) Production of rubber composition The modified cis-1,4-polybutadiene of this embodiment is blended alone or blended with other synthetic rubber or natural rubber, and if necessary, is oil-extended with process oil, Subsequently, a rubber composition can be obtained by adding a filler (filler) such as carbon black or silica, a silane coupling agent, a vulcanizing agent, a vulcanization accelerator, and other ordinary compounding agents and vulcanizing.
ゴム組成物に含まれる他の合成ゴムとしては、加硫可能なゴムが好ましく、具体的にはエチレンプロピレンジエンゴム(EPDM)、ニトリルゴム(NBR)、ブチルゴム(IIR)、クロロプレンゴム(CR)、ポリイソプレン、ハイシスポリブタジエンゴム、ローシスポリブタジエンゴム(BR)、スチレン-ブタジエンゴム(SBR)、ブチルゴム、塩素化ブチルゴム、臭素化ブチルゴム、アクリロニトリル-ブタジエンゴム等を挙げることができる。これらの中でもSBRが好ましい。さらにSBRの中でも溶液重合スチレンブタジエン共重合体ゴム(S-SBR)が特に好ましい。これらのゴムは単独でも、二種以上組合せて用いても良い。 (Other synthetic rubber)
As the other synthetic rubber contained in the rubber composition, a vulcanizable rubber is preferable. Specifically, ethylene propylene diene rubber (EPDM), nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), Examples thereof include polyisoprene, high cis polybutadiene rubber, low cis polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and acrylonitrile-butadiene rubber. Among these, SBR is preferable. Further, among SBR, solution-polymerized styrene butadiene copolymer rubber (S-SBR) is particularly preferable. These rubbers may be used alone or in combination of two or more.
ゴム組成物に用いられるシランカップリング剤としては、一般式R7 nSiR8 4-nで表される有機珪素化合物で、R7は、ビニル基、アシル基、アリル基、アリルオキシ基、アミノ基、エポキシ基、メルカプト基、クロル基、アルキル基、フェニル基、水素、スチリル基、メタクリル基、アクリル基、ウレイド基などから選ばれる反応基を有する炭素数1~20の有機基であり、R8は、クロル基、アルコキシ基、アセトキシ基、イソプロペノキシ基、アミノ基などから選ばれる加水分解基であり、nは1~3の整数を示す。 (Silane coupling agent)
The silane coupling agent used in the rubber composition is an organosilicon compound represented by the general formula R 7 n SiR 8 4-n , where R 7 is a vinyl group, acyl group, allyl group, allyloxy group, amino group. , an epoxy group, a mercapto group, a chloro group, an alkyl group, a phenyl group, hydrogen, a styryl group, a methacryl group, an acryl group, an organic group having 1 to 20 carbon atoms having a reactive group selected from the ureido group, R 8 Is a hydrolyzable group selected from a chloro group, an alkoxy group, an acetoxy group, an isopropenoxy group, an amino group and the like, and n represents an integer of 1 to 3.
また、本実施形態の変性シス-1,4-ポリブタジエンは、プラスチック、例えば、耐衝撃性ポリスチレンの改質剤として使用する、すなわち、ゴム変性耐衝撃性ポリスチレン系樹脂組成物を製造することもできる。 (4) Production of rubber-modified impact-resistant polystyrene-based resin composition The modified cis-1,4-polybutadiene of this embodiment is used as a modifier for plastics, for example, impact-resistant polystyrene. A modified impact-resistant polystyrene resin composition can also be produced.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらにより何ら制限されるものではない。なお、実施例中のムーニー粘度、トルエン溶液粘度、数平均分子量、加工性、加硫物の反撥弾性、加硫物のtanδ、永久歪の測定は、以下の方法により行った。 (Evaluation methods)
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The Mooney viscosity, toluene solution viscosity, number average molecular weight, processability, rebound resilience of the vulcanized product, tan δ of the vulcanized product, and permanent set in the examples were measured by the following methods.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを32.4重量%含有するシクロヘキサン-C4留分混合溶液600mL(シクロヘキサン26.4重量%、シス-2-ブテンを主成分とするC4留分を39.2重量%含有)を仕込み、次に水1.3mmol、ジエチルアルミニウムモノクロライド1.9mmolを加えて攪拌を行ない、シクロオクタジエン5.1mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.005mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤1,3-ジメトキシベンゼン(DMOB)を430mmol添加し、オートクレーブを昇温した。70℃に内温が到達してから、t-ブチルクロライド3.8mmolを添加して60分反応した。そこに老化防止剤を添加して80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの変性度は0.35であった。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 1)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 600 mL of a cyclohexane-C4 fraction mixed solution containing 32.4% by weight of 1,3-butadiene (26.4% by weight of cyclohexane, cis-2) -39.2% by weight of C4 fraction containing butene as the main component), and then stirred by adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride, and adding 5.1 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.005 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 430 mmol of a modifier 1,3-dimethoxybenzene (DMOB) was added, and the temperature of the autoclave was increased. After the internal temperature reached 70 ° C., 3.8 mmol of t-butyl chloride was added and reacted for 60 minutes. Antiaging agent was added there and it vacuum-dried at 80 degreeC for 3 hours. The degree of modification of the resulting modified cis-1,4-polybutadiene was 0.35. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.3重量%含有するシクロヘキサン-C4留分混合溶液500mL(シクロヘキサン37.3重量%、シス-2-ブテンを主成分とするC4留分を31.2重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン7.3mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤1,3-ジメトキシベンゼン(DMOB)を9.1mmol添加し、オートクレーブを内温70℃まで昇温した。次いで、t-ブチルクロライド15.8mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 2)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -C4 fraction containing butene as the main component (containing 31.2% by weight)), and then stirred by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, and adding 7.3 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.1 mmol of a modifier 1,3-dimethoxybenzene (DMOB) was added, and the autoclave was heated to an internal temperature of 70 ° C. Then, 15.8 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.3重量%含有するシクロヘキサン-C4留分混合溶液500mL(シクロヘキサン37.3重量%、シス-2-ブテンを主成分とするC4留分を31.2重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン4.5mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤1,3-ジメトキシベンゼン(DMOB)を9.0mmol添加し、80℃まで昇温した。次いで、t-ブチルクロライド3.3mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 3)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.0 mmol of a modifier 1,3-dimethoxybenzene (DMOB) was added, and the temperature was raised to 80 ° C. Next, 3.3 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
変性剤を1,3-ジエトキシベンゼン(DEOB)とした他は、実施例3と同様に反応を行った。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 Example 4
The reaction was conducted in the same manner as in Example 3 except that 1,3-diethoxybenzene (DEOB) was used as the modifier. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.3重量%含有するシクロヘキサン-C4留分混合溶液500mL(シクロヘキサン37.3重量%、シス-2-ブテンを主成分とするC4留分を31.2重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン7.3mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤ベラトロールを9.2mmol添加し、70℃まで昇温した。次いで、t-ブチルクロライド31.3mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 5)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -C4 fraction containing butene as the main component (containing 31.2% by weight)), and then stirred by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, and adding 7.3 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.2 mmol of the modifier veratrol was added, and the temperature was raised to 70 ° C. Next, 31.3 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
変性剤を1,2-メチレンジオキシベンゼン(MDB)とした他は、実施例3と同様に反応を行った。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 6)
The reaction was conducted in the same manner as in Example 3 except that 1,2-methylenedioxybenzene (MDB) was used as the modifier. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.3重量%含有するシクロヘキサン-C4留分混合溶液500mL(シクロヘキサン37.3重量%、シス-2-ブテンを主成分とするC4留分を31.2重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン4.5mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤アニソールを9.3mmol添加し、70℃まで昇温した。次いで、t-ブチルクロライド3.3mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 7)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.3 mmol of the modifier anisole was added, and the temperature was raised to 70 ° C. Next, 3.3 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
変性剤をフェネトールとした他は、実施例7と同様に反応を行った。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 8)
The reaction was performed in the same manner as in Example 7 except that the denaturant was phenetole. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.3重量%含有するシクロヘキサン-C4留分混合溶液500mL(シクロヘキサン37.3重量%、シス-2-ブテンを主成分とするC4留分を31.2重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン4.5mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤アネトールを9.3mmol添加し、70℃まで昇温した。次いで、t-ブチルクロライド7.9mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 Example 9
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.3 mmol of the modifier anethole was added, and the temperature was raised to 70 ° C. Subsequently, 7.9 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
変性剤をサフロールとした他は、実施例3と同様に反応を行った。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 10)
The reaction was performed in the same manner as in Example 3 except that the modifier was safrole. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.3重量%含有するシクロヘキサン-C4留分混合溶液500mL(シクロヘキサン37.3重量%、シス-2-ブテンを主成分とするC4留分を31.2重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン4.5mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤イソサフロールを9.0mmol添加し、70℃まで昇温した。次いで、t-ブチルクロライド3.3mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 11)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 500 mL of cyclohexane-C4 fraction mixed solution containing 30.3% by weight of 1,3-butadiene (37.3% by weight of cyclohexane, cis-2) -31.2% by weight of C4 fraction containing butene as the main component), then add 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stir, and add 4.5 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.0 mmol of a modifier isosafrole was added, and the temperature was raised to 70 ° C. Next, 3.3 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.6重量%含有するシクロヘキサン-C4留分混合溶液600mL(シクロヘキサン36.8重量%、シス-2-ブテンを主成分とするC4留分を31.1重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン4.5mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤1,2-メチレンジオキシベンゼン(MDB)を18mmol添加し、80℃まで昇温した。次いで、t-ブチルクロライド3.3mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 Example 12
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution, 600 mL of a cyclohexane-C4 fraction mixed solution containing 30.6% by weight of 1,3-butadiene (36.8% by weight of cyclohexane, cis-2) -Containing 31.1% by weight of C4 fraction containing butene as the main component), then adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stirring, and adding 4.5 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 18 mmol of a modifier 1,2-methylenedioxybenzene (MDB) was added, and the temperature was raised to 80 ° C. Next, 3.3 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.6重量%含有するシクロヘキサン-C4留分混合溶液600mL(シクロヘキサン36.8重量%、シス-2-ブテンを主成分とするC4留分を31.1重量%含有)を仕込み、次に水1.1mmol、ジエチルアルミニウムモノクロライド1.6mmolを加えて攪拌を行ない、シクロオクタジエン4.5mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.003mmolを加えて、60℃で25分間重合反応を行なった。重合反応後に変性剤イソサフロールを9.0mmol添加し、80℃まで昇温した。次いで、t-ブチルクロライド3.3mmolを添加して15分反応した。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られた変性シス-1,4-ポリブタジエンの物性を表1に示した。 (Example 13)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution, 600 mL of a cyclohexane-C4 fraction mixed solution containing 30.6% by weight of 1,3-butadiene (36.8% by weight of cyclohexane, cis-2) -Containing 31.1% by weight of C4 fraction containing butene as the main component), then adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride, stirring, and adding 4.5 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.003 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After the polymerization reaction, 9.0 mmol of a modifier isosafrole was added, and the temperature was raised to 80 ° C. Next, 3.3 mmol of t-butyl chloride was added and reacted for 15 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. Table 1 shows the physical properties of the resulting modified cis-1,4-polybutadiene.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを32.4重量%含有するシクロヘキサン-C4留分混合溶液600mL(シクロヘキサン26.4重量%、シス-2-ブテンを主成分とするC4留分を39.2重量%含有)を仕込み、次に水1.3mmol、ジエチルアルミニウムモノクロライド1.9mmolを加えて攪拌を行ない、シクロオクタジエン5.3mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.005mmolを加えて、60℃で25分間重合反応を行なった。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られたシス-1,4-ポリブタジエンの物性を表1に示した。 (Comparative Example 1)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution inside, 600 mL of a cyclohexane-C4 fraction mixed solution containing 32.4% by weight of 1,3-butadiene (26.4% by weight of cyclohexane, cis-2) -Containing 39.2% by weight of C4 fraction containing butene as the main component), then adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride, stirring, and adding 5.3 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.005 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. The physical properties of the resulting cis-1,4-polybutadiene are shown in Table 1.
内部を充分窒素置換した1.5リットル容量のステンレス製のオートクレーブに、1,3-ブタジエンを30.6重量%含有するシクロヘキサン-C4留分混合溶液600mL(シクロヘキサン36.8重量%、シス-2-ブテンを主成分とするC4留分を31.1重量%含有)を仕込み、次に水1.3mmol、ジエチルアルミニウムモノクロライド1.9mmolを加えて攪拌を行ない、シクロオクタジエン5.3mmolを添加した。オートクレーブを昇温し、60℃に内温が到達してから、コバルトオクトエート0.005mmolを加えて、60℃で25分間重合反応を行なった。老化防止剤を添加後、重合体をエタノールで析出させ、80℃で3時間真空乾燥した。得られたシス-1,4-ポリブタジエンの物性を表1に示した。 (Comparative Example 2)
In a 1.5 liter stainless steel autoclave with sufficient nitrogen substitution, 600 mL of a cyclohexane-C4 fraction mixed solution containing 30.6% by weight of 1,3-butadiene (36.8% by weight of cyclohexane, cis-2) -Containing 31.1% by weight of C4 fraction containing butene as the main component), then adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride, stirring, and adding 5.3 mmol of cyclooctadiene did. After the temperature of the autoclave was raised and the internal temperature reached 60 ° C., 0.005 mmol of cobalt octoate was added, and a polymerization reaction was performed at 60 ° C. for 25 minutes. After adding the anti-aging agent, the polymer was precipitated with ethanol and vacuum dried at 80 ° C. for 3 hours. The physical properties of the resulting cis-1,4-polybutadiene are shown in Table 1.
実施例1で得られた変性シス-1,4-ポリブタジエンを用い、表2に示す配合処方に従って250ccのラボプラストミルによりSBR及びシリカ等と混練した後、加硫剤及び加硫助剤をオープンロールで混合した。次いで、温度160℃でプレス加硫し、得られた加硫試験片の物性評価を行った。その結果を表3に示した。 (Prototype 1)
Using the modified cis-1,4-polybutadiene obtained in Example 1 and kneading with SBR, silica, etc. by a 250 cc lab plast mill according to the formulation shown in Table 2, the vulcanizing agent and vulcanizing aid are opened. Mixed by roll. Subsequently, press vulcanization was performed at a temperature of 160 ° C., and physical properties of the obtained vulcanized test piece were evaluated. The results are shown in Table 3.
比較例1で得られたシス-1,4-ポリブタジエンを用いた他は、試作品1と同様に配合加工し、物性評価を行った。その結果を表3に示した。 (Prototype 2)
Except for using the cis-1,4-polybutadiene obtained in Comparative Example 1, the compounding and processing were performed in the same manner as in Prototype 1, and the physical properties were evaluated. The results are shown in Table 3.
SBR:スチレン含量が23%、ML1+4(100℃)70
シリカ:東ソー・シリカ(株)製、商品名 ニップシールAQ
シランカップリング剤:エボニック製、商品名 Si69
オイル:サン石油(SUNOCO)製、サンセンオイル4240
酸化亜鉛:堺化学工業 Sazex 1号
ステアリン酸:花王ステアリン酸
老化防止剤:住友化学 アンチゲン6C
硫黄:細井化学工業(株)製
加硫促進剤1:大内新興化学工業(株)製 ノクセラーCZ
加硫促進剤2:大内新興化学工業(株)製 ノクセラーD Details of the compounds used in the blending are as follows.
SBR: 23% styrene content, ML 1 + 4 (100 ° C.) 70
Silica: Tosoh Silica Co., Ltd., trade name: Nip seal AQ
Silane coupling agent: Evonik, product name Si69
Oil: San Petroleum (SUNOCO), Sansen Oil 4240
Zinc oxide: Sakai Chemical Industry Sazex No. 1 stearic acid: Kao stearate anti-aging agent: Sumitomo Chemical Antigen 6C
Sulfur: Vulcanization accelerator manufactured by Hosoi Chemical Industry Co., Ltd. 1: Noxeller CZ manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator 2: NOCELLER D manufactured by Ouchi Shinsei Chemical Co., Ltd.
比較例2で得られたシス-1,4-ポリブタジエンを用い、表4に示す配合処方に従って250ccのラボプラストミルによりSBR及びシリカ等と混練した後、加硫剤及び加硫助剤をオープンロールで混合した。次いで、温度160℃でプレス加硫し、得られた加硫試験片の物性評価を行った。その結果を表5に示した。 (Prototype 3)
The cis-1,4-polybutadiene obtained in Comparative Example 2 was used and kneaded with SBR, silica, etc. by a 250 cc lab plast mill according to the formulation shown in Table 4, and then the vulcanizing agent and vulcanizing aid were opened rolls. Mixed with. Subsequently, press vulcanization was performed at a temperature of 160 ° C., and physical properties of the obtained vulcanized test piece were evaluated. The results are shown in Table 5.
実施例12で得られた変性シス-1,4-ポリブタジエンを用いた他は、試作品3と同様に配合加工し、物性評価を行った。その結果を表3に示した。 (Prototype 4)
Except that the modified cis-1,4-polybutadiene obtained in Example 12 was used, the compounding and processing were performed in the same manner as in prototype 3, and the physical properties were evaluated. The results are shown in Table 3.
実施例13で得られた変性シス-1,4-ポリブタジエンを用いた他は、試作品3と同様に配合加工し、物性評価を行った。その結果を表5に示した。 (Prototype 5)
Except for using the modified cis-1,4-polybutadiene obtained in Example 13, the compounding and processing were performed in the same manner as in Prototype 3, and the physical properties were evaluated. The results are shown in Table 5.
SBR:スチレン含量が23%、ML1+4(100℃)70
シリカ:エボニック製、商品名 Ultrasil 7000GR
シランカップリング剤:エボニック・デグサ製、商品名 Si75
オイル:代替アロマオイル
酸化亜鉛:堺化学工業 Sazex 1号
ステアリン酸:花王ステアリン酸
老化防止剤:住友化学 アンチゲン6C
硫黄:細井化学工業(株)製
加硫促進剤1:大内新興化学工業(株)製 ノクセラーCZ
加硫促進剤2:大内新興化学工業(株)製 ノクセラーD Details of the compounds used in the blending are as follows.
SBR: 23% styrene content, ML 1 + 4 (100 ° C.) 70
Silica: Product name made by Evonik, Ultrasil 7000GR
Silane coupling agent: Evonik Degussa, trade name Si75
Oil: Alternative aroma oil Zinc oxide: Sakai Chemical Industry Sazex No. 1 Stearic acid: Kao Stearic acid anti-aging agent: Sumitomo Chemical Antigen 6C
Sulfur: Vulcanization accelerator manufactured by Hosoi Chemical Industry Co., Ltd. 1: Noxeller CZ manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator 2: NOCELLER D manufactured by Ouchi Shinsei Chemical Co., Ltd.
Claims (7)
- ルイス酸および有機ハロゲン化合物の存在下、シス-1,4-ポリブタジエンと下記一般式(1)で表される1~3置換の芳香族化合物とを反応させて得られたことを特徴とする変性シス-1,4-ポリブタジエン。
- 1~3置換の芳香族化合物が、フェノール誘導体、カテコール誘導体、レゾルシン誘導体、ヒドロキノン誘導体、および2~3置換の芳香族系アルケニル化合物からなる群より選択された1種以上であることを特徴とする請求項1に記載の変性シス-1,4-ポリブタジエン。 The 1 to 3 substituted aromatic compound is at least one selected from the group consisting of phenol derivatives, catechol derivatives, resorcin derivatives, hydroquinone derivatives, and 2 to 3 substituted aromatic alkenyl compounds. The modified cis-1,4-polybutadiene according to claim 1.
- ルイス酸が有機アルミニウム化合物であることを特徴とする請求項1または2に記載の変性シス-1,4-ポリブタジエン。 3. The modified cis-1,4-polybutadiene according to claim 1, wherein the Lewis acid is an organoaluminum compound.
- 有機ハロゲン化合物が炭素数4~12の第3級ハロゲン化アルキルであることを特徴とする請求項1乃至3のいずれかに記載の変性シス-1,4-ポリブタジエン。 The modified cis-1,4-polybutadiene according to any one of claims 1 to 3, wherein the organic halogen compound is a tertiary alkyl halide having 4 to 12 carbon atoms.
- 遷移金属化合物および有機アルミニウム化合物を含有する重合触媒を用いて1,3-ブタジエンを重合してシス-1,4-ポリブタジエンを製造し、次いで、この重合系内に有機ハロゲン化合物および下記一般式(1)で表される1~3置換の芳香族化合物を添加して、ルイス酸および前記有機ハロゲン化合物の存在下、前記シス-1,4-ポリブタジエンと下記一般式(1)で表される1~3置換の芳香族化合物とを反応させることを特徴とする変性シス-1,4-ポリブタジエンの製造方法。
- 遷移金属化合物がコバルト化合物、ニッケル化合物およびチタン化合物からなる群より選択された1種以上であることを特徴とする請求項5に記載の変性シス-1,4-ポリブタジエンの製造方法。 6. The method for producing a modified cis-1,4-polybutadiene according to claim 5, wherein the transition metal compound is at least one selected from the group consisting of a cobalt compound, a nickel compound and a titanium compound.
- 1~3置換の芳香族化合物が、フェノール誘導体、カテコール誘導体、レゾルシン誘導体、ヒドロキノン誘導体、および2~3置換の芳香族系アルケニル化合物からなる群より選択された1種以上であることを特徴とする請求項6に記載の変性シス-1,4-ポリブタジエンの製造方法。 The 1 to 3 substituted aromatic compound is at least one selected from the group consisting of phenol derivatives, catechol derivatives, resorcin derivatives, hydroquinone derivatives, and 2 to 3 substituted aromatic alkenyl compounds. A process for producing the modified cis-1,4-polybutadiene according to claim 6.
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WO2019093512A1 (en) * | 2017-11-13 | 2019-05-16 | 横浜ゴム株式会社 | Polymer, method for producing polymer, and rubber composition |
CN114805641A (en) * | 2021-01-21 | 2022-07-29 | 中国科学院大连化学物理研究所 | Polybutadiene low-temperature-resistant rubber base rubber and preparation method thereof |
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KR102251267B1 (en) | 2018-05-17 | 2021-05-12 | 주식회사 엘지화학 | Rubber composition |
CN113234261B (en) * | 2021-06-01 | 2022-07-12 | 泰凯英(青岛)专用轮胎技术研究开发有限公司 | Mining engineering tire tread rubber containing 4-ethoxyphenol and preparation method thereof |
CN114085300B (en) * | 2021-12-24 | 2023-09-15 | 南亚新材料科技股份有限公司 | Modified polybutadiene resin and preparation method and application thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5819305A (en) * | 1981-07-29 | 1983-02-04 | Ube Ind Ltd | Modification of butadiene rubber |
JPH0987426A (en) * | 1995-09-20 | 1997-03-31 | Bridgestone Corp | Production of rubber composition |
JPH10330418A (en) * | 1997-05-22 | 1998-12-15 | Goodyear Tire & Rubber Co:The | Means for controlling particle size and removing fouling in synthesizing syndiotactic 1,2-polybutadiene |
JP2000256507A (en) * | 1999-03-04 | 2000-09-19 | Ube Ind Ltd | Polybutadiene rubber and its production |
JP2004211048A (en) * | 2002-11-11 | 2004-07-29 | Ube Ind Ltd | Production method and composition of cis-1,4-polybutadiene |
JP2004217876A (en) * | 2003-01-17 | 2004-08-05 | Ube Ind Ltd | Rubber composition |
JP2011079954A (en) * | 2009-10-07 | 2011-04-21 | Ube Industries Ltd | Method for producing cis-1,4-polybutadiene and composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1030698B (en) | 1974-10-09 | 1979-04-10 | Snam Progetti | PROCEDURE FOR IMPROVING THE CHARACTERISTICS OF POLYIDIENIC ELASTOMERS AND MODULATED ELASTOMERS THUS OBTAINED |
DE2731067C3 (en) | 1977-07-09 | 1981-11-26 | Bunawerke Hüls GmbH, 4370 Marl | Process for the preparation of polybutadiene with a high content of monomer units in a cis-1,4 structure |
JPS61225202A (en) | 1985-03-29 | 1986-10-07 | Nippon Zeon Co Ltd | Modification of rubber |
FR2713229B1 (en) * | 1993-11-30 | 1996-01-19 | Atochem Elf Sa | Composition comprising a vinyl aromatic polymer and a rubber and its production process. |
US5453471B1 (en) * | 1994-08-02 | 1999-02-09 | Carbide Chemicals & Plastics T | Gas phase polymerization process |
JP2001114817A (en) | 1999-10-19 | 2001-04-24 | Jsr Corp | Method for producing (modified) conjugated diene-based polymer |
-
2013
- 2013-07-29 MY MYPI2014704029A patent/MY169946A/en unknown
- 2013-07-29 WO PCT/JP2013/070430 patent/WO2014021244A1/en active Application Filing
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5819305A (en) * | 1981-07-29 | 1983-02-04 | Ube Ind Ltd | Modification of butadiene rubber |
JPH0987426A (en) * | 1995-09-20 | 1997-03-31 | Bridgestone Corp | Production of rubber composition |
JPH10330418A (en) * | 1997-05-22 | 1998-12-15 | Goodyear Tire & Rubber Co:The | Means for controlling particle size and removing fouling in synthesizing syndiotactic 1,2-polybutadiene |
JP2000256507A (en) * | 1999-03-04 | 2000-09-19 | Ube Ind Ltd | Polybutadiene rubber and its production |
JP2004211048A (en) * | 2002-11-11 | 2004-07-29 | Ube Ind Ltd | Production method and composition of cis-1,4-polybutadiene |
JP2004217876A (en) * | 2003-01-17 | 2004-08-05 | Ube Ind Ltd | Rubber composition |
JP2011079954A (en) * | 2009-10-07 | 2011-04-21 | Ube Industries Ltd | Method for producing cis-1,4-polybutadiene and composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019093512A1 (en) * | 2017-11-13 | 2019-05-16 | 横浜ゴム株式会社 | Polymer, method for producing polymer, and rubber composition |
CN114805641A (en) * | 2021-01-21 | 2022-07-29 | 中国科学院大连化学物理研究所 | Polybutadiene low-temperature-resistant rubber base rubber and preparation method thereof |
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