WO2017154710A1 - 重合触媒、共重合体、重合体組成物及び架橋重合体 - Google Patents
重合触媒、共重合体、重合体組成物及び架橋重合体 Download PDFInfo
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- 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
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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
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- 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
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- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/622—Component covered by group C08F4/62 with an organo-aluminium compound
- C08F4/6228—Component covered by group C08F4/62 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
Definitions
- the present disclosure relates to a polymerization catalyst, a copolymer, a polymer composition, and a cross-linked polymer, and more particularly to a polymerization catalyst suitable for producing a copolymer of a conjugated diene compound and an ⁇ -olefin.
- Patent Document 1 discloses that an alternating copolymer of butadiene and propylene is obtained by polymerizing butadiene and propylene in the presence of an organometallic catalyst composed of an oxyvanadium compound and a trialkylaluminum.
- Patent Document 2 discloses a copolymer of a conjugated diene compound and an acyclic nonconjugated olefin, wherein the polystyrene-equivalent weight average molecular weight exceeds 25,000, and the content of the nonconjugated olefin is within a predetermined range.
- a copolymer in which the cis-1,4 bond content of the conjugated diene compound portion is 50% or more is disclosed.
- a polymerization catalyst a copolymer is obtained by polymerization using a polymerization catalyst composition containing a metallocene complex, a polymerization catalyst composition containing a rare earth element compound, or a polymerization catalyst composition containing a metallocene composite catalyst. It is described to obtain.
- the copolymerization of a conjugated diene compound and an ⁇ -olefin can yield a high molecular weight compound only at extremely low temperatures of ⁇ 50 ° C. and ⁇ 30 ° C.
- a low molecular weight substance for example, a polymer having a number average molecular weight smaller than 10,000
- the conventional polymerization catalyst comprising an oxyvanadium compound and a trialkylaluminum
- only an alternating copolymer of a conjugated diene compound and an ⁇ -olefin can be obtained, and the composition ratio of monomers cannot be changed.
- the polymerization catalyst described in Patent Document 2 can be used for copolymerization of butadiene and ethylene, but there is no example using ⁇ -olefin such as propylene. Accordingly, a polymerization catalyst useful for obtaining a copolymer of a conjugated diene compound and an ⁇ -olefin is desired.
- the present disclosure has been made in view of the above problems, a polymerization catalyst capable of performing copolymerization of a conjugated diene compound and an ⁇ -olefin under a mild temperature condition, and a conjugated diene compound / ⁇ -obtained using the polymerization catalyst.
- One object is to provide an olefin copolymer.
- the following polymerization catalyst, copolymer and production method thereof, production method of the polymerization catalyst, polymer composition and crosslinked polymer are provided.
- a metal complex obtained by mixing at least one ketimine derivative selected from the group consisting of ⁇ -ketoimine compounds and tautomers thereof and a compound containing at least one selected from group 4 and group 5 transition metals, A polymerization catalyst comprising an organoaluminum compound and a halogen compound.
- At least one ketimine derivative selected from the group consisting of ⁇ -ketoimine compounds and tautomers thereof, compounds containing at least one selected from group 4 and group 5 transition metals, organoaluminum compounds, halogens A method for producing a polymerization catalyst, comprising mixing a compound with a compound.
- It has a structural unit MA derived from a conjugated diene compound and a structural unit MB derived from an ⁇ -olefin having 3 to 8 carbon atoms, and has a melting point in the range of ⁇ 15 ° C. to 140 ° C.
- a polymer composition comprising the copolymer obtained by the production method of [2] or the copolymer of [4], and a crosslinking agent.
- a conjugated diene compound / ⁇ -olefin copolymer having a number average molecular weight Mn of 10,000 or more can be obtained under moderate temperature conditions, which is industrially advantageous. Also, a novel copolymer is obtained in which the content ratio of the structural unit derived from the conjugated diene compound is larger than the structural unit derived from the ⁇ -olefin, and the content ratio of each structural unit can be changed to a desired ratio. be able to.
- the polymerization catalyst of the present disclosure includes a compound containing at least one ketoimine derivative selected from the group consisting of ⁇ -ketoimine compounds and tautomers thereof, and at least one selected from group 4 and group 5 transition metals (hereinafter simply referred to as “a ketoimine compound”).
- a ketoimine compound A metal complex formed by mixing “transition metal compound”) is included as a catalyst component.
- polymerization catalyst means a single system composed of components independently exhibiting a catalytic action, and a multi-component system composed of a combination of a component exhibiting a single catalytic action and a cocatalyst (composite catalyst). ).
- the ketoimine derivative is not particularly limited as long as it is a ⁇ -ketoimine compound or a tautomer thereof.
- tautomers of ⁇ -ketoimine compounds include enols and enamines.
- Preferable specific examples of the ⁇ -ketoimine compound include compounds represented by the following formula (1). (In Formula (1), R 1 to R 4 are each independently a hydrocarbyl group optionally substituted with a halogen atom.)
- R 1 to R 4 are each independently a branched or straight chain alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or may be substituted with a halogen atom. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom.
- R 1 to R 4 are alkyl groups, examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. It may be branched. Further, when R 1 ⁇ R 4 is a halogenated alkyl group, for example, at least one of the hydrogen atoms of the fluorine atoms of the alkyl groups exemplified above, such group substituted with a chlorine atom. When R 1 to R 4 are alkyl groups, the carbon number is preferably 1 to 10, and more preferably 1 to 3.
- R 1 and R 3 are preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
- R 2 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.
- R 4 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or at least one of the groups exemplified above.
- a group in which a hydrogen atom is substituted with a fluorine atom or a chlorine atom is preferable.
- a branched alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group is preferable in that the polymerization can be performed under mild temperature conditions. Particularly preferred.
- a ketoimine derivative may be used individually by 1 type, and may be used in combination of 2 or more type.
- the transition metal compound only needs to have at least one selected from Group 4 and Group 5 transition metals.
- the above metal complex can be obtained according to a method usually used in the synthesis of a metal complex of a ⁇ -ketoimine compound.
- it can be synthesized by reacting a ketoimine derivative and a transition metal compound in a suitable organic solvent (for example, toluene).
- a suitable organic solvent for example, toluene.
- the ratio of the ketimine derivative and the transition metal compound used in the reaction is not particularly limited, but for example, the transition metal compound may be 0.1 to 1.0 mol per mol of the ketimine derivative.
- the amount is preferably 0.2 to 0.7 mol.
- the reaction temperature and reaction time can be appropriately set. For example, the reaction temperature is 0 to 100 ° C., and the reaction time is several hours to several tens of hours.
- the obtained reaction solution may be used for polymerization as it is, or a metal complex contained in the reaction solution may be isolated and purified as necessary to be used for polymerization.
- the polymerization catalyst of the present disclosure is a multi-component system containing a halogen compound and an organoaluminum compound as a cocatalyst together with the metal complex. Thereby, the catalyst performance of the said metal complex can fully be expressed.
- the polymerization catalyst of the present disclosure includes other components other than the metal complex, the halogen compound, and the organoaluminum compound (for example, a promoter other than the halogen compound and the organoaluminum compound) within a range that does not impair the effects of the present disclosure. May be included.
- the halogen compound is preferably a chlorine-containing compound, and more preferably a compound having a structure in which tertiary carbon or tertiary silicon and chlorine are bonded.
- “Tertiary carbon” means a carbon atom having 3 hydrocarbon atoms bonded thereto
- “tertiary silicon” means a silicon atom having 3 hydrocarbon atoms bonded.
- the three hydrocarbon groups bonded to the carbon atom and the silicon atom may all be monovalent hydrocarbon groups, and two of the three hydrocarbon groups bonded to the carbon atom and the silicon atom. They may be bonded to each other to form a ring structure containing carbon atoms and silicon atoms.
- a chlorine-containing compound represented by the following formula (2) can be preferably used.
- (R 6 ) 3 —Y 1 —Cl (2) (In Formula (2), Y 1 is a carbon atom or a silicon atom, and a plurality of R 6 are each independently a hydrocarbyl group, and two R 6 are bonded to each other, and together with the carbon atom to which they are bonded, carbon (A ring of the number 3 to 20 may be formed.)
- Examples of the hydrocarbyl group of R 6 to R 8 include groups exemplified for R 4 in the above formula (1). Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms.
- Specific examples of the halogen compound include compounds having a partial structure in which chlorine is bonded to a tertiary carbon, such as 2-chloro-2-methylpropane, 2-chloro-2-methylbutane, 2-chloro-2,3.
- the proportion of the halogen compound used is preferably 1 to 50 mol, and more preferably 5 to 25 mol, relative to 1 mol of the metal atom of the metal complex.
- a halogen compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- the organoaluminum compound is not particularly limited as long as it has a function as a promoter, but an aluminoxane compound can be preferably used.
- an aluminoxane compound can be preferably used.
- Specific examples thereof include, for example, methylaluminoxane (MAO), ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, hexylaluminoxane, isohexylaluminoxane, polymethylaluminoxane (PMAO), modified Examples thereof include methylaluminoxane (MMAO) and cyclic aluminoxane.
- MAO methylaluminoxane
- MMAO methylaluminoxane
- cyclic aluminoxane cyclic aluminoxane.
- the compounding ratio of the organoaluminum compound is preferably 10 to 1000 mol, more preferably 75 to 250 mol, relative to 1 mol of the metal atom of the metal complex.
- an organoaluminum compound can be used individually by 1 type or in combination of 2 or more types.
- the polymerization catalyst of the present disclosure can be produced by a method including a step of mixing the ketoimine derivative, the transition metal compound, the organometallic aluminum compound, and the halogen compound.
- a polymerization catalyst may be prepared by previously mixing a halogen compound and an organoaluminum compound together with the ketoimine derivative and the transition metal compound, and the mixture may be added to the polymerization system.
- the polymerization catalyst may be prepared by mixing the ketoimine derivative and the transition metal compound in advance to prepare a metal catalyst, and then adding the metal catalyst and the cocatalyst to the polymerization system. The latter is preferred.
- the explanation for obtaining the metal complex is applied to the conditions for mixing the ketoimine derivative and the transition metal compound.
- the method for producing a copolymer of the present disclosure includes a step of polymerizing a conjugated diene compound and an ⁇ -olefin having 3 to 8 carbon atoms using the polymerization catalyst of the present disclosure described above.
- conjugated diene compounds examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, Examples include 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene and the like. Among these, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene are preferable, and 1,3-butadiene is more preferable. In addition, 1 type may be sufficient as the conjugated diene compound used for superposition
- the ⁇ -olefin used in the polymerization is not particularly limited as long as it is an alkene having 3 to 8 carbon atoms and having a carbon-carbon double bond in the ⁇ -position.
- propylene, 1-butene, 1-pentene examples include 1-hexene, 1-heptene, 1-octene and the like. Among these, propylene and 1-butene are preferable, and propylene is more preferable.
- the ⁇ -olefin used for the polymerization may be one kind or two or more kinds.
- the use ratio of the conjugated diene compound and the ⁇ -olefin is preferably 5/95 to 99/1 in terms of molar ratio (conjugated diene compound / ⁇ -olefin).
- the use ratio of the conjugated diene compound and the ⁇ -olefin is more preferably 20/80 to 99/1, and in terms of processability, More preferably, the ratio is 30/70 to 90/10.
- other monomers other than the conjugated diene compound and the ⁇ -olefin may be used.
- Other monomers include ethylene; aromatic vinyl compounds such as styrene and methylstyrene; (meth) acrylic compounds such as acrylonitrile, methyl (meth) acrylate and ethyl (meth) acrylate; and cyclics such as dicyclopentadiene Examples thereof include olefin compounds.
- the proportion of other monomers used may be appropriately determined according to the purpose of using the polymer. For example, it is preferably 10% by mass or less, and preferably 5% by mass or less with respect to the total amount of monomers. More preferably, it is more preferably 1% by mass or less.
- the polymerization method may be any of solution polymerization method, gas phase polymerization method and bulk polymerization method, but solution polymerization method is preferred.
- the polymerization method either a batch type or a continuous type may be used.
- examples of the organic solvent used for the polymerization include hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane. Among them, it is preferable to use toluene.
- an organic solvent can use the said thing individually by 1 type or in combination of 2 or more types.
- the amount of the organic solvent used is preferably 200 to 3,000 parts by mass with respect to a total of 100 parts by mass of the monomers used for the polymerization, from the viewpoint of maintaining a balance between productivity and ease of polymerization control. .
- the proportion of the polymerization catalyst used is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of monomers used for the polymerization.
- the polymerization temperature can be in the range of ⁇ 100 ° C. to 50 ° C., preferably ⁇ 80 ° C. to 50 ° C., more preferably in the range of ⁇ 50 ° C. to 50 ° C.
- the number average molecular weight Mn is 10,000 even when the polymerization temperature is in the range of ⁇ 20 ° C. to 40 ° C., and further in the range of ⁇ 10 ° C. to 20 ° C.
- the above conjugated diene compound / ⁇ -olefin copolymer is preferred in that it can be obtained.
- the number average molecular weight Mn is a polystyrene conversion value measured by gel permeation chromatography (GPC).
- the polymerization reaction is preferably carried out under a pressure sufficient to keep the monomer in a substantially liquid phase. Such a pressure can be obtained by a method such as pressurizing the inside of the reactor with a gas inert to the polymerization reaction.
- a conjugated diene compound / ⁇ -olefin copolymer having a structural unit derived from a conjugated diene compound and a structural unit derived from an ⁇ -olefin having 3 to 8 carbon atoms can be obtained.
- the polystyrene-equivalent weight average molecular weight Mw measured by GPC of the resulting conjugated diene compound / ⁇ -olefin copolymer is preferably 1.5 ⁇ 10 3 to 1.5 ⁇ 10 from the viewpoint of mechanical strength and workability. 6 , more preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 6 .
- the number average molecular weight Mn is preferably 1.5 ⁇ 10 3 ⁇ 1.5 ⁇ 10 6, more preferably from 2.0 ⁇ 10 3 ⁇ 1.0 ⁇ 10 6, more preferably, It is 5.0 ⁇ 10 3 to 5.0 ⁇ 10 5 , and particularly preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 .
- the molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight Mw and the average molecular weight Mn is preferably 5.0 or less, and more preferably 3.0 or less.
- a conjugated diene compound / ⁇ -olefin copolymer having a melting point in the range of ⁇ 15 ° C. to 140 ° C. can be obtained.
- the melting point of the copolymer is too low, the crystallinity of the resulting copolymer is lowered, and the mechanical strength of the crosslinked polymer obtained by crosslinking the copolymer tends to be reduced.
- the conjugated diene compound / ⁇ -olefin copolymer preferably has a melting point in the range of ⁇ 10 ° C. to 140 ° C., more preferably in the range of 0 to 100 ° C.
- the melting point of the copolymer is a value indicated as the temperature at which the endothermic amount due to crystal melting shows a peak in the melting curve obtained using a differential scanning calorimeter (DSC).
- the conjugated diene compound / ⁇ -olefin copolymer obtained by the above polymerization is obtained by changing the ratio of the structural unit MA derived from the conjugated diene compound possessed by the copolymer and the structural unit MB derived from the ⁇ -olefin.
- the melting point can be adjusted.
- Such a copolymer is preferable because of its high design freedom.
- the structural unit MA derived from the conjugated diene compound is larger than the structural unit MB derived from the ⁇ -olefin.
- the molar ratio (MA / MB) of the structural unit MA derived from the conjugated diene compound and the structural unit MB derived from the ⁇ -olefin is preferably 51/49 to 99/1, more preferably Is 55/45 to 99/1, more preferably 55/45 to 95/5, and particularly preferably 60/40 to 90/10.
- the content of trans-1,4-bonds in the entire structural unit derived from butadiene develops the melting point.
- the amount is preferably more than 50%. More preferably, it is 60% or more, further preferably 80% or more, and particularly preferably 90% or more.
- trans-1,4-bond content can be measured by, for example, FT-IR and 13 C-NMR.
- the conjugated diene compound / ⁇ -olefin copolymer has a melting point in the range of ⁇ 15 ° C. to 140 ° C., and has a number average molecular weight Mn in terms of polystyrene measured by GPC. Having a molar ratio (MA / MB) of the structural unit MA derived from the conjugated diene compound and the structural unit MB derived from the ⁇ -olefin of 55/45 to 99/1 Can be obtained.
- Such a conjugated diene compound / ⁇ -olefin copolymer can be produced under mild temperature conditions by using the polymerization catalyst of the present disclosure, and is industrially advantageous.
- the melting point can be adjusted by adjusting the composition ratio of the monomers, the degree of freedom in design is high, and it can be applied to various applications.
- the above explanation is applied to the preferable ranges of the melting point, the number average molecular weight Mn, and the molar ratio (MA / MB).
- the polymer composition of the present disclosure includes the conjugated diene compound / ⁇ -olefin copolymer of the present disclosure described above as a polymer component.
- the content ratio of the copolymer in the polymer composition is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass with respect to the total amount of the polymer composition. It is still more preferable that it is above.
- the upper limit of the said content rate can be 99 mass% or less with respect to the whole quantity of a polymer composition, for example.
- the polymer composition may contain a polymer other than the copolymer as a polymer component.
- a polymer other than the copolymer examples include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene- ⁇ -olefin copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, halogenated butyl rubber, styrene- Examples include known polymers such as isoprene copolymer rubber and butadiene-isoprene copolymer rubber, and mixtures thereof.
- the blending ratio of the other polymer is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass with respect to the total amount of the polymer components contained in the polymer composition. More preferably, it is as follows.
- the polymer composition contains a crosslinking agent (vulcanizing agent).
- the crosslinking agent include sulfur, sulfur halides, organic peroxides, quinonedioximes, organic polyvalent amine compounds, and alkylphenol resins having a methylol group.
- Sulfur is usually used as the cross-linking agent.
- the mixing ratio of sulfur is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polymer components contained in the polymer composition.
- the polymer composition may contain various additives usually used in the rubber industry in addition to the above-described components within a range not impairing the effects of the present disclosure.
- additives include anti-aging agents, zinc white, stearic acid, extender oil, softeners, sulfur, vulcanization accelerators, antioxidants, ultraviolet absorbers, colorants, pigments, light stabilizers, and thermal polymerization prohibition.
- the polymer composition in addition to the polymer component and the crosslinking agent, components to be blended as necessary are mixed into an open kneader (for example, a roll), a closed kneader (for example, a Banbury mixer) or the like. It can manufacture by kneading
- the polymer composition can be applied to various rubber molded articles as a crosslinked polymer by crosslinking (vulcanizing) after molding.
- seals such as packings, gaskets, weather strips, O-rings, etc .; interior and exterior skin materials for various vehicles such as automobiles, ships, aircrafts, railways, etc .; building materials; protection for industrial machinery and equipment Vibration rubbers; Diaphragms, rolls, radiator hoses, air hoses and other hoses and hose covers; belts such as power transmission belts; tire treads and sidewalls; linings; dust boots; Materials for general goods such as daily goods and sports goods; heat-resistant packing, heat-resistant gaskets, heat-resistant O-rings, heat-resistant sealing materials, heat-resistant vibration-proof rubber for engine mounts, heat-resistant hoses and hose covers, heat-resistant belts, Heat resistant lining such as heat resistant lining, heat resistant dust boots, medical equipment materials that are subjected to heat treatment such as heat disinfection It can be used as materials.
- polystyrene conversion was determined using gel permeation chromatography (trade name “HLC-8320GPC EcoSEC”, manufactured by Tosoh Corporation) under the following conditions.
- butadiene content and propylene content [mol%] The content ratio [mol%] of the butadiene structural unit to the total structural unit of the polymer and the content ratio [mol%] of the propylene structural unit were determined as follows from a 400 MHz 1 H-NMR spectrum measured using deuterated chloroform as a solvent. Asked. In the following, among the butadiene structural units, the cis-1,4-bond component is the structural unit (Ubc14), the trans-1,4-bond component is the structural unit (Ubt14), and the 1,2-bond component is the structural unit. (Ub12) and the propylene structural unit is represented as a structural unit (Upp).
- A Total content of structural unit (Ubc14) and structural unit (Ubt14): ⁇ 5.36
- B Content of structural unit (Ub12): ⁇ 4.95
- C Content of structural unit (Upp): ⁇ 0.84
- a 1 represents the integrated value of the peak at ⁇ 5.36
- a 2 represents the integrated value of the peak at ⁇ 4.95
- a 3 represents the integrated value of the peak at ⁇ 0.84.
- a sample for measurement was prepared by enclosing 5 mg of a polymer in an aluminum sample pan (model numbers “900786.901” and “900779.901”, manufactured by TA Instruments Japan Co., Ltd.).
- the measurement sample was held at 200 ° C. for 1 minute, then cooled to ⁇ 150 ° C. at a rate of 10 ° C./minute, then held at ⁇ 150 ° C. for 1 minute, and then to 200 ° C. at a rate of 20 ° C./minute.
- the temperature was raised by the method.
- the total endothermic amount resulting from crystal melting in the step of raising the temperature from ⁇ 150 ° C. to 200 ° C. was defined as melting enthalpy ⁇ H, and the temperature at which the endothermic amount reached a peak was defined as melting point Tm.
- Example 2 to 5 Polymerization was carried out in the same manner as in Example 1 except that the amounts of propylene and butadiene used were changed as shown in Table 1 below to obtain copolymers B to E. Table 1 below shows the yield and yield.
- the inside of the polymerization tube was replaced with ethylene gas, and further, a toluene solution of methylaluminoxane as an organometallic aluminum compound (10% by mass, manufactured by Albemarle) 5.8 mL, and a toluene solution of 2-chloro-2-methylpropane as a halogen compound 0.8 mL (1.0 mol / L, manufactured by Wako Pure Chemical Industries, Ltd.) and 1.6 mL of the vanadium catalyst solution obtained in Preparation Example 1 were added, and a polymerization reaction was performed for 3 hours.
- a toluene solution of methylaluminoxane as an organometallic aluminum compound 10% by mass, manufactured by Albemarle
- 2-chloro-2-methylpropane as a halogen compound 0.8 mL (1.0 mol / L, manufactured by Wako Pure Chemical Industries, Ltd.) and 1.6 mL of the vanadium catalyst solution obtained in Preparation Example 1 were added,
- polymer Q a polymer (hereinafter referred to as “polymer Q”).
- the yield of the obtained polymer Q was 0.8 g, and the yield was 50.7%.
- polymer R After the polymerization, 2.0 mL of methanol was added to stop the reaction, and a coagulation reaction was performed with a large amount of methanol, followed by vacuum drying at 60 ° C. to obtain a polymer (hereinafter referred to as “polymer R”).
- the yield of the obtained polymer R was 0.2 g, and the yield was 5.2%.
- FIG. 1 shows DSC curves of the (co) polymers A to E and R obtained in Examples 1 to 5 and Reference Example 2. Further, when the 1,4-bond component of the butadiene structural unit was analyzed by the ATR method for each of the obtained polymers, a butadiene homopolymer (polymer R) and a butadiene-propylene copolymer (polymer A) were obtained. In E), no absorption derived from the cis-1,4-bond was observed, indicating that the 1,4-bond component of the butadiene structural unit was a trans-1,4-bond.
- a high molecular weight conjugated diene compound can be obtained under mild temperature conditions. And an ⁇ -olefin copolymer could be obtained. Further, in the obtained copolymer, the content ratio of the structural unit derived from the conjugated diene compound was changed by changing the composition ratio of the monomers, thereby changing the melting point.
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Abstract
Description
[2] 上記[1]の重合触媒を用いて、共役ジエン化合物と炭素数3~8のα-オレフィンとを重合する、共重合体の製造方法。
[3] β-ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物と、有機アルミニウム化合物と、ハロゲン化合物と、を混合する、重合触媒の製造方法。
[4] 共役ジエン化合物に由来する構造単位MAと、炭素数3~8のα-オレフィンに由来する構造単位MBとを有し、-15℃~140℃の範囲内に融点があり、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量が10,000以上であり、かつ前記構造単位MAと前記構造単位MBとのモル比(MA/MB)が55/45~99/1である、共重合体。
[5] 上記[2]の製造方法により得られた共重合体又は上記[4]の共重合体と、架橋剤とを含む重合体組成物。
[6] 上記[5]の重合体組成物を架橋して得られる架橋重合体。
<重合触媒>
本開示の重合触媒は、β-ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物(以下、単に「遷移金属化合物」とも言う。)とを混合してなる金属錯体を触媒成分として含む。なお、本明細書において「重合触媒」は、単独で触媒作用を示す成分からなる単一系のもの、及び単独で触媒作用を示す成分と助触媒とを組み合わせた多成分系のもの(複合触媒)を含む意味である。
(R6)3-Y1-Cl …(2)
(式(2)中、Y1は炭素原子又はケイ素原子であり、複数のR6はそれぞれ独立にヒドロカルビル基であり、2個のR6が互いに結合して、これらが結合する炭素原子と共に炭素数3~20の環を形成していてもよい。)
本開示の共重合体の製造方法は、上記で説明した本開示の重合触媒を用いて、共役ジエン化合物と炭素数3~8のα-オレフィンとを重合する工程を含む。
上記重合に使用する共役ジエン化合物としては、例えば1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエン、1,3-ヘプタジエン、2-フェニル-1,3-ブタジエン、3-メチル-1,3-ペンタジエン、2-クロロ-1,3-ブタジエン等が挙げられる。これらの中でも、1,3-ブタジエン、イソプレン及び2,3-ジメチル-1,3-ブタジエンが好ましく、1,3-ブタジエンがより好ましい。なお、重合に使用する共役ジエン化合物は、1種であってもよいし2種以上であってもよい。
上記重合に使用するα-オレフィンとしては、炭素数3~8であって炭素-炭素二重結合がα位にあるアルケンであれば特に制限されず、例えばプロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン等が挙げられる。これらの中でも、プロピレン及び1-ブテンが好ましく、プロピレンがより好ましい。なお、重合に使用するα-オレフィンは、1種であってもよいし2種以上であってもよい。
(重合体成分)
本開示の重合体組成物は、重合体成分として、上述した本開示の共役ジエン化合物/α-オレフィン共重合体を含む。重合体組成物中の上記共重合体の含有割合は、重合体組成物の全体量に対して、20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましい。また、当該含有割合の上限は、重合体組成物の全体量に対して、例えば99質量%以下とすることができる。
上記重合体組成物は、架橋剤(加硫剤)を含む。架橋剤としては、硫黄、ハロゲン化硫黄、有機過酸化物、キノンジオキシム類、有機多価アミン化合物、メチロール基を有するアルキルフェノール樹脂などが挙げられる。架橋剤としては通常、硫黄が使用される。硫黄の配合割合は、重合体組成物に含まれる重合体成分の合計量100質量部に対して、好ましくは0.1~5質量部、より好ましくは0.5~3質量部である。
ポリエチレン以外の重合体については、以下の条件で、ゲルパーミエーションクロマトグラフィー(商品名「HLC-8320GPC EcoSEC」、東ソー社製)を使用してポリスチレン換算を求めた。
カラム:商品名「TSK gel Multipore HXL-M」(東ソー社製)
カラム温度:40℃
移動相;テトラヒドロフラン
流速;1.0ml/分
サンプル濃度;10mg/20ml
・ポリエチレンの重量平均分子量Mw及び数平均分子量Mn
ポリエチレンについては、以下の条件で、高温ゲルパーミエーションクロマトグラフィー(商品名「PL-GPC 220」、Agilent社製)を使用してポリスチレン換算を求めた。
カラム:商品名「PLgel Olexis」(Agilent社製)
カラム温度:135℃
移動相;オルトジクロロベンゼン
流速;1.0ml/分
サンプル濃度;4mg/4ml
重合体の全構造単位に対するブタジエン構造単位の含有割合[モル%]、及びプロピレン構造単位の含有割合[モル%]を、重クロロホルムを溶媒として測定した400MHzの1H-NMRスペクトルから次のようにして求めた。なお、以下では、ブタジエン構造単位のうちcis-1,4-結合成分を構造単位(Ubc14)、trans-1,4-結合成分を構造単位(Ubt14)、及び1,2-結合成分を構造単位(Ub12)と表し、プロピレン構造単位を構造単位(Upp)と表す。
<1H-NMR>
以下の(a)~(c)のピークの積分値から、共重合体中における構造単位(Ubc14)及び構造単位(Ubt14)の合計と、構造単位(Ub12)と、構造単位(Upp)との含有比率((Ubc14+Ubt14):Ub12:Upp[モル比])を下記数式(1)により算出し、該算出した含有比率から、共重合体中における各構造単位の含有割合(モル%)を算出した。
(a)構造単位(Ubc14)及び構造単位(Ubt14)の合計の含有量:δ5.36
(b)構造単位(Ub12)の含有量:δ4.95
(c)構造単位(Upp)の含有量:δ0.84
FT-IR(商品名「Frontier」)を用いてATR(Attenuated Total Reflection)法により特性吸収帯(cis-1,4-結合は740cm-1、trans-1,4-結合は967cm-1)から解析した。
・ガラス転移温度Tg[℃]、融点Tm[℃]及び融解エンタルピーΔH[J/g]
DSC(商品名「DSC Q20」、ティー・エイ・インスツルメント・ジャパン社製)を用いて測定を行い、測定により得られた融解曲線から求めた。測定用サンプルは、アルミニウム製サンプルパン(型番「900786.901」と「900779.901」、ティー・エイ・インスツルメント・ジャパン社製)に5mgの重合体を封入して作製した。測定は、測定用サンプルを200℃で1分間保持した後、-150℃まで10℃/分の速度で冷却し、次いで-150℃で1分間保持した後、200℃まで20℃/分の速度で昇温する方法で行った。この-150℃から200℃に昇温する工程における結晶融解に起因する吸熱量の総和を融解エンタルピーΔHとし、吸熱量がピークを示す温度を融点Tmとした。
[調製例1]
窒素置換した内容積1Lのガラス製容器に、脱水トルエン700ml、ケトイミン誘導体として下記式(1-A)で表される化合物7.5g、及び遷移金属化合物としてバナジウムオキシトリイソプロポキシド5.2gを加えて、20時間還流させた。次に、反応液を室温に戻した後、真空下で溶媒を留去することで黒色固体を得た。この黒色固体から70℃の脱水アセトニトリルを用いて抽出を行い、窒素雰囲気下で抽出溶液を空冷したところ、黒色結晶が析出した。次に、上澄みを取り除き、真空下でアセトニトリルを留去することで黒色結晶状のバナジウム化合物6.0gを得た。このバナジウム化合物1.1gとテトラヒドロフラン(THF)0.38gを脱水トルエン53mlに溶解させたものを、バナジウム触媒溶液として重合に用いた。
[実施例1]
窒素置換した500mLのガラス製重合管中に、室温でトルエンを29mL添加してから、その重合管を-55℃の低温槽に沈積した。次に、重合管中にモノマーとしてプロピレン0.9g及びブタジエン5.8gを加え、さらに有機金属アルミニウム化合物としてメチルアルミノキサンのトルエン溶液(10質量%、アルベマール社製)1.8mLと、ハロゲン化合物として2-クロロ-2-メチルプロパンのトルエン溶液(1.0mol/L、和光純薬社製)0.3mLを加え、重合管を0℃に昇温した。次に、実施例1で調製したバナジウム触媒溶液0.5mLを加えて、3時間重合反応を行った。重合後、メタノール2.0mLを加えて反応を停止させ、更に大量のメタノールで凝固反応を行い、60℃で真空乾燥して重合体(これを「共重合体A」とする。)を得た。得られた共重合体Aの収量は0.5gであった。
[実施例2~5]
使用するプロピレン及びブタジエンの量をそれぞれ下記表1に記載の通りに変更した以外は実施例1と同様にして重合を行い、共重合体B~Eを得た。下記表1に収量及び収率を併せて示した。
窒素置換した500mLのガラス製重合管中に、室温でトルエンを6.9mL添加してから、その重合管を0℃の低温槽に沈積した。次に、重合管内をエチレンガスで置換し、さらに有機金属アルミニウム化合物としてメチルアルミノキサンのトルエン溶液(10質量%、アルベマール社製)5.8mL、ハロゲン化合物として2-クロロ-2-メチルプロパンのトルエン溶液(1.0mol/L、和光純薬社製)0.8mL、及び調製例1で得たバナジウム触媒溶液1.6mLを加えて、3時間重合反応を行った。重合後、メタノール2.0mLを加えて反応を停止させ、更に大量のメタノールで凝固反応を行い、60℃で真空乾燥して重合体(これを「重合体Q」とする。)を得た。得られた重合体Qの収量は0.8g、収率は50.7%であった。
[参考例2]
窒素置換した500mLのガラス製重合管中に、室温でトルエンを29mL添加してから、その重合管を0℃の低温槽に沈積した。次に、ブタジエン3.5gを加え、さらに有機金属アルミニウム化合物としてメチルアルミノキサンのトルエン溶液(10質量%、アルベマール社製)1.8mL、ハロゲン化合物として2-クロロ-2-メチルプロパンのトルエン溶液(1.0mol/L、和光純薬社製)0.3mL、及び実施例1で調製したバナジウム触媒溶液0.5mLを加えて、3時間重合反応を行った。重合後、メタノール2.0mLを加えて反応を停止させ、更に大量のメタノールで凝固反応を行い、60℃で真空乾燥して重合体(これを「重合体R」とする。)を得た。得られた重合体Rの収量は0.2g、収率は5.2%であった。
Claims (11)
- β-ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物とを混合してなる金属錯体、
有機アルミニウム化合物、及び、
ハロゲン化合物
を含む、重合触媒。 - 前記遷移金属が5族の元素である、請求項1に記載の重合触媒。
- 前記ハロゲン化合物は、3級炭素又は3級ケイ素と、塩素とが結合した構造を有する化合物である、請求項2に記載の重合触媒。
- 前記有機アルミニウム化合物がアルミノキサン化合物である、請求項1~3のいずれか一項に記載の重合触媒。
- 請求項1~5のいずれか一項に記載の重合触媒を用いて、共役ジエン化合物と炭素数3~8のα-オレフィンとを重合する、共重合体の製造方法。
- 重合温度が-50℃~50℃の範囲内である、請求項6に記載の共重合体の製造方法。
- β-ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物と、有機アルミニウム化合物と、ハロゲン化合物と、を混合する、重合触媒の製造方法。
- 共役ジエン化合物に由来する構造単位MAと、炭素数3~8のα-オレフィンに由来する構造単位MBとを有し、-15℃~140℃の範囲内に融点があり、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量が10,000以上であり、かつ前記構造単位MAと前記構造単位MBとのモル比(MA/MB)が55/45~99/1である、共重合体。
- 請求項6若しくは7に記載の製造方法により得られた共重合体又は請求項9に記載の共重合体と、架橋剤とを含む重合体組成物。
- 請求項10に記載の重合体組成物を架橋して得られる架橋重合体。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1321692A (zh) * | 2000-04-30 | 2001-11-14 | 中国石油化工集团公司 | 双齿配体、过渡金属配合物、烯烃聚合催化体系以及该催化体系在烯烃聚合中的应用 |
JP2004277721A (ja) * | 2003-02-24 | 2004-10-07 | Ube Ind Ltd | 結晶性ポリマー |
CN1737020A (zh) * | 2005-07-22 | 2006-02-22 | 中国科学院上海有机化学研究所 | 含卤素取代基的酮亚胺类前过渡金属钛配合物、合成方法和用途 |
WO2014097167A1 (en) * | 2012-12-20 | 2014-06-26 | Versalis S.P.A. | Oxo-nitrogenated complex of cobalt, catalytic system comprising said oxo-nitrogenated complex and process for the (co) polymerization of conjugated dienes |
JP2014166967A (ja) * | 2013-02-28 | 2014-09-11 | Ube Ind Ltd | 新規なイットリウム化合物、共役ジエン重合用触媒、並びにそれを用いた共役ジエン重合体の製造方法 |
WO2015068095A1 (en) * | 2013-11-05 | 2015-05-14 | Versalis S.P.A. | Stereoregular diblock polybutadienes having a 1,4-cis/syndiotactic 1,2 structure from stereospecific polymerization |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1327664A (en) | 1970-05-14 | 1973-08-22 | Bridgestone Tire Co Ltd | Method for manufacturing butadiene-propylene copolymers |
US3940378A (en) | 1970-05-14 | 1976-02-24 | Bridgestone Tire Company Limited | Method for manufacturing of butadiene-propylene copolymers |
US3898207A (en) | 1974-03-25 | 1975-08-05 | Firestone Tire & Rubber Co | Process for polymerizing conjugated dienes |
DE3017539A1 (de) | 1980-05-08 | 1981-11-12 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von alternierenden butadien-propylen-copolymeren |
US4575574A (en) | 1984-12-17 | 1986-03-11 | Exxon Research & Engineering Co. | Ethylene polymer useful as a lubricating oil viscosity modifier |
CN100386349C (zh) | 2006-05-25 | 2008-05-07 | 中国科学院长春应用化学研究所 | 一种β-二酮单亚胺钒烯烃聚合催化剂及制备方法和应用 |
CN101575393B (zh) | 2009-06-12 | 2011-08-31 | 中国科学院长春应用化学研究所 | 一类双齿n,o配位的钒系催化剂的用途及用法 |
JP5823674B2 (ja) | 2010-07-30 | 2015-11-25 | 株式会社ブリヂストン | 共役ジエン化合物と非共役オレフィンとの共重合体 |
JP5932224B2 (ja) | 2011-02-04 | 2016-06-08 | 株式会社ブリヂストン | 共重合体、ゴム組成物、架橋ゴム組成物、及びタイヤ |
JP5735886B2 (ja) | 2011-08-08 | 2015-06-17 | 株式会社ブリヂストン | ゴム支承被覆用ゴム組成物及びそれを用いたゴム支承被覆用ゴム |
ES2767308T3 (es) * | 2014-12-23 | 2020-06-17 | Versalis Spa | Complejo de vanadio oxo-nitrogenado, sistema catalítico que comprende dicho complejo de vanadio oxo-nitrogenado y proceso para (co)polimerizar dienos conjugados |
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- 2017-03-01 WO PCT/JP2017/008204 patent/WO2017154710A1/ja active Application Filing
- 2017-03-01 KR KR1020187019143A patent/KR102052439B1/ko active IP Right Grant
- 2017-03-01 US US16/080,152 patent/US10906996B2/en active Active
- 2017-03-01 CN CN201780006335.6A patent/CN108431052B/zh active Active
- 2017-03-01 KR KR1020197007779A patent/KR20190030787A/ko not_active Application Discontinuation
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1321692A (zh) * | 2000-04-30 | 2001-11-14 | 中国石油化工集团公司 | 双齿配体、过渡金属配合物、烯烃聚合催化体系以及该催化体系在烯烃聚合中的应用 |
JP2004277721A (ja) * | 2003-02-24 | 2004-10-07 | Ube Ind Ltd | 結晶性ポリマー |
CN1737020A (zh) * | 2005-07-22 | 2006-02-22 | 中国科学院上海有机化学研究所 | 含卤素取代基的酮亚胺类前过渡金属钛配合物、合成方法和用途 |
WO2014097167A1 (en) * | 2012-12-20 | 2014-06-26 | Versalis S.P.A. | Oxo-nitrogenated complex of cobalt, catalytic system comprising said oxo-nitrogenated complex and process for the (co) polymerization of conjugated dienes |
JP2014166967A (ja) * | 2013-02-28 | 2014-09-11 | Ube Ind Ltd | 新規なイットリウム化合物、共役ジエン重合用触媒、並びにそれを用いた共役ジエン重合体の製造方法 |
WO2015068095A1 (en) * | 2013-11-05 | 2015-05-14 | Versalis S.P.A. | Stereoregular diblock polybutadienes having a 1,4-cis/syndiotactic 1,2 structure from stereospecific polymerization |
Non-Patent Citations (1)
Title |
---|
See also references of EP3428200A4 * |
Also Published As
Publication number | Publication date |
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PL3428200T3 (pl) | 2022-07-18 |
US20190048107A1 (en) | 2019-02-14 |
EP3428200A1 (en) | 2019-01-16 |
KR20190030787A (ko) | 2019-03-22 |
JPWO2017154710A1 (ja) | 2019-01-10 |
US10906996B2 (en) | 2021-02-02 |
JP6819669B2 (ja) | 2021-01-27 |
KR102052439B1 (ko) | 2019-12-05 |
CN108431052A (zh) | 2018-08-21 |
EP3428200A4 (en) | 2019-04-03 |
CN108431052B (zh) | 2021-02-09 |
KR20180089498A (ko) | 2018-08-08 |
EP3428200B1 (en) | 2022-05-04 |
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