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  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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  • 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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  • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
  • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
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  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

• the present invention relates to a method for producing an organic transition metal complex compound, a metathesis catalyst produced by the method, a ring-opening metathesis polymer obtained by polymerization using the metathesis catalyst, and a method for producing the polymer .
• an organic transition metal complex compound is easily affected by oxygen, water, and a compound having a proton donating property.
• a compound having a proton donating property when it comes into contact with oxygen, water, or a compound having a proton-donating property, it decomposes by oxidative decomposition, hydrolysis or elimination decomposition.
• an organic transition metal complex compound having a strong electron donating atomic group such as cyclopentagel, alkoxy, carboxyl, etc.
• a compound having a proton donating property has no proton donating property. It is often converted to an alkyl alkali metal salt and used as a reaction reagent for atomic groups with a stronger electron donating property.
• the organic transition metal complex compound when an organic transition metal complex compound is produced by this method, due to the strong cationic nature of the alkali metal, the organic transition metal complex compound can be decomposed without reacting with the desired site of the organic transition metal complex compound, or a side reaction can occur. Or the desired organic transition metal complex compound may not be obtained! / ⁇ .
• the reactivity of ligand exchange differs depending on the type of alkali metal ion and counter-on atom group, which limits the organic transition metal complex compounds that can be produced. For these reasons, decomposition reactions and side reactions do not occur. Improvement of the manufacturing method of an organic transition metal complex compound is desired.
• organic transition metal metallocene complex compounds having hydrocarbon ligands such as cyclopentagel are used in a conventional manner by Jordan et al.
• organometallic compounds such as butyllithium and alkali metal hydrides.
• a method of synthesizing an organic transition metal meta-octene complex compound without using an alkali metal salt by contacting a specific proton-donating cyclopentagen and a transition metal dimethylamide compound without performing a reaction has been reported. .
• Non-patent Documents 2, 3 and 4 are organic electron transition metal alkylidene complex compounds that have stronger electron donating properties such as alkoxy and atomic groups, and compounds that have proton donating properties such as alcohol and sodium, lithium, force lithium or An organic transition metal complex having an alkylalkali metal salt obtained by contact with such a metal hydride compound or an organic metal compound such as butyl lithium as an electron-attracting atomic group halogen or triflate as a ligand.
• an excess of an alkyl alkali metal salt that is a reaction reagent remains in the produced metathesis catalyst, and when a metathesis reaction is performed using a metathesis catalyst in which these by-products or reaction reagents remain. Due to the strong ionic nature of by-products and reaction reagents, the by-products and reaction reagents act as polymerization initiators for anion polymerization to polymerize the reaction substrate, or cause ligand exchange reactions with active species in the metathesis reaction. Metathesis catalyst may be altered or decomposed. In addition, if metal remains in a product produced by a metathesis reaction, the physical properties and color of the product may be adversely affected.
• the unsaturated bond formed in the main chain after polymerization is generally converted to a saturated bond by a hydrogenation reaction.
• the product contains an alkali metal salt derived from a metathesis catalyst synthesis reaction, that is, a by-product or a reaction reagent
• the by-product or the reaction reagent reacts with the hydrogenation reaction catalyst to cause alteration or decomposition. May interfere with normal hydrogenation reaction.
• the conventional methods for synthesizing metathesis catalysts have high ionicity and various problems due to the use of alkali metals, and development of methods for producing metathesis catalysts without using alkali metals is desired. .
• Patent Document 1 International Publication No. 95Z32979 Pamphlet
• Patent Document 2 US Pat. No. 5,597,935
• Non-Patent Document 1 Gary M. Diamond and 1 other, "Synthesis of Group 4 Metal rac- (EBI) M (NR 2) 2 Complexes by Amine Elimination. Scope and Limitations", Organometallics, 15, 4030-4037 (1996)
• Non-Patent Document 2 Richard R. Schrock, “Living Ring-Opening Metathesis Polymerization Catalyzed by Well-Characterized Transition-Metal Alkylidene Complexes”, Acc. Chem. Res., 23, 158 (1990)
• Non-Patent Document 3 R.R.Schrock and 13 others, ⁇ Further Studies of Imido Alkylidene Complex es of Tungsten, Well-Characterized Olefin Metathesis Catalysts with ControllableJ, Organometallics ⁇ 9, 2262 (1990)
• Non-Patent Document 4 Richard R. Schrock et al., "Synthesis of Molybdenum Imido Alkyiden e Complexes and Some Reactions Involving Acyclic 01efins", J. Am. And hem. Soc., 112, 3875 (1990)
• the present invention provides an industrially or economically advantageous organic transition metal complex compound having an electron-donating atomic group in the presence of a basic compound in which a compound having proton-donating properties is not converted to a metal salt.
• a production method for synthesis, a metathesis catalyst produced by the method, a ring-opening metathesis polymer obtained by polymerization using the metathesis catalyst, and a method for producing the polymer are provided.
• the present inventor arbitrarily selected an organic transition metal complex compound having an arbitrary electron-withdrawing atomic group in the presence of an arbitrary basic compound.
• the electron-withdrawing atomic group in the organic transition metal complex compound having an arbitrary electron-withdrawing atomic group is derived from the compound having an arbitrary proton-donating property.
• Electron-withdrawing atoms with strong electron donating properties A method for producing a novel organic transition metal complex compound to be converted into a group, a metathesis catalyst having a reduced alkali metal content obtained by the method, and further polymerizing cyclic olefins using the metathesis catalyst.
• the present inventors have found a ring-opening metathesis polymer and a method for producing the polymer, thereby completing the present invention.
• the present invention provides:
• a metathesis catalyst represented by the following general formula (1) obtained by synthesis by the method for producing an organic transition metal complex compound according to any one of the above;
• R 1 is selected from alkyl, aryl, substituted aryl force.
• R 2 and R 3 are each independently hydrogen, alkyl, aryl, substituted aryl, alkylsilyl, alkyl- Luka is also selected and may be the same or different
• R 4 is selected from alkyl, halogenated alkyl, aryl, substituted aryl force, N is a nitrogen atom, Q is an oxygen or sulfur atom.
• E is a coordination molecule and is selected from ether, alkylphosphine, aryl phosphine, alkoxyphosphine, pyridine, alkylamine, and alkylideneamine.
• M is a transition metal atom selected from Groups 3 to 12 of the periodic table.
• m is an integer of 1 to 3, and when m is 2 or 3, R 4 may be bonded to each other.
• N is an integer from 0 to 2.
• the transition metal atom M selected from Group 3 to Group 12 of the periodic table is tantalum, vanadium, molybdenum, tandastene, rhenium, ruthenium and One kind of group power consisting of osmium
• M is 1 or 2, and n is 0 or 1,
• a metathesis catalyst represented by the following general formula (1) and having an alkali metal content of 10 ppm or less;
• R 1 is selected from alkyl, aryl, substituted aryl force.
• R 2 and R 3 are each independently hydrogen, alkyl, aryl, substituted aryl, alkylsilyl.
• Alkelluka are also selected, which may be the same or different R 4 is alkyl, alkyl halide, aryl, substituted aryl force N is a nitrogen atom, Q is oxygen or sulfur
• E is a coordination molecule, selected from ether, alkylphosphine, allylphosphine, alkoxyphosphine, pyridine, alkylamine, alkylideneamine M is selected from groups 3 to 12 of the periodic table M is an integer from 1 to 3, and when m is 2 or 3, R 4 is bonded to each other Also good.
• N is an integer from 0 to 2.
• a method for producing a ring-opening metathesis polymer comprising a step of superimposing a cyclic olefin in the presence of the metathesis catalyst according to any one of [4] to [7].
• the organic transition metal complex compound can be produced industrially and economically efficiently.
• the ring-opening metathesis polymer polymerized using the catalyst is: The hydrogenation reaction can be performed without removing the alkali metal beforehand.
• the ring-opening metathesis polymer or the hydrogenated product thereof can be suitably used for applications such as electronic materials having severe restrictions on the alkali metal content, and is extremely valuable industrially.
• FIG. 1 is a diagram showing a 1 H-NMR spectrum of an organic transition metal complex compound obtained in an example.
• the method for producing an organic transition metal complex compound according to the present invention comprises:
• each component used in the present invention will be described using specific examples, but the present invention is not limited to the following exemplified compounds.
• an exemplary compound may be used independently and may be used in multiple combination.
• Me represents a methyl group
• 3 ⁇ 4 ⁇ represents a tert-butyl group
• Ph represents a phenyl group
• Ad represents an adamantyl group.
• PMe represents trimethylphosphine
• P (OMe) represents trimethoxyphosphine.
• 1,2-dimethoxyethane 1,2-dimethoxyethane, thf represents tetrahydrofuran.
• the basic compound is a molecule or proton acceptor having a coordinated unshared electron pair, for example, a basic organic compound.
• the basic compound does not contain an alkali metal!
• organic basic compound examples include primary amines such as ammonia and methylamine; secondary amines such as diphenylamine;
• Tertiary amines such as triethylamine, ethyldiisopropylamine.
• 1,4-diazabicyclo [2, 2, 2] nitrogen-containing heterocycles such as octane, pyridine and lutidine; nitrogen-containing basic organic compounds such as;
• Examples thereof include phosphorus-containing basic organic compounds such as phosphine.
• triethylamine, ethyldiisopropylamine, pyridine, lutidine, and 1,4-diazabicyclo [2,2,2] octane are particularly preferable. Further, two or more of these basic compounds may be used in an arbitrary ratio.
• the electron withdrawing property means strong electronegativity.
• electron-withdrawing atomic groups Is a strong electronegative group, halogen, halogen-containing alkyl or aryl sulfonate, alkyl or aryl sulfonate, halogen-containing phosphate, halogen-containing alkyl or aryl carboxylate, and Examples include alkyl or aryl carboxylate. More specific examples of electron-withdrawing atomic groups include fluorine, chlorine, bromine, iodine, trifluoromethanesulfonate, ie triflate, toluenesulfonate, hexafluorophosphate, and trifluoroacetate. Of these, chlorine, trifluoromethanesulfonate, and toluenesulfonate are particularly preferable. Two or more of these may be used in combination.
• the organic transition metal complex compound having an electron-withdrawing atomic group has (A) an electron-withdrawing atomic group in the organic transition metal complex compound having an electron-withdrawing atomic group.
• an organic transition metal complex compound having an electron-withdrawing atomic group can be a single atom or many atoms that may have any ligand in addition to the electron-withdrawing atomic group. Examples include ligands containing atomic groups that are neutral, cationic, or anionic.
• the organic transition metal complex compound having an electron-withdrawing atomic group is preferably an organic transition metal complex compound having metal alkylidene or metal alkylidine or a precursor thereof.
• An organic transition metal complex compound having a metal alkylidene or a metal alkylidin is an organic transition metal complex compound having an electron-attracting atomic group between a transition center metal atom and a carbon at the ⁇ -position.
• a precursor of an organic transition metal complex-containing compound having a metal alkylidene or a metal alkylidene is itself a divalent or 3-valent compound between the transition center metal atom and the ⁇ -position carbon.
• the metal alkylidene is subjected to a treatment such as alkyl ⁇ as a catalyst, followed by heating or contact with an organometallic reagent.
• N is an organometallic complex compound capable of forming metal alkylidyne.
• the compound (B) having a proton donating property may be any compound that can donate a proton, but (A) an organic transition metal complex having an electron-withdrawing atomic group.
• a compound that can be substituted with an atomic group having a stronger electron donating property derived from a compound having a proton donating property is (B) A compound that can be substituted with an atomic group having a stronger electron donating property derived from a compound having a proton donating property.
• (B) the electron-donating property of the electron-withdrawing atomic group derived from the compound having a proton-donating property is as follows: It is stronger than the electron donating property of the electron-withdrawing atomic group in the organic transition metal compound having a group.
• (B) the compound having a proton donating property may be the same compound as the basic compound or may be a different compound.
• (B) Specific examples of compounds having a proton donating property include tert butyl alcohol (2-methylolene 2-prono-norole), 1, 1, 1, 3, 3, 3 Propanol, perfluoro-tert butyl alcohol, phenol, 2,6 diisopropyl phenol, 2,6 diclonal phenol, 2, 2 'biphenol, 3, 3' di tert-butyl-5,5 ', 6,6'-tetramethyl-2 2 'dihydroxybiphenyl, etc.
• Primary amines such as dimethylamine, and the like.
• the compound having a proton donating property is at least one selected from alcohol and thiol power.
• the alcohol may contain an alcoholic hydroxyl group or a phenolic hydroxyl group.
• the compound having proton-donating property is at least one or more selected from alcohol and thiol force
• (A) the organic transition metal complex compound having an electron-withdrawing atomic group is combined.
• An organic transition metal complex-containing compound having metal alkylidene or metal alkylidine may be used.
• the compound having a proton donating property may be one proton or a polyfunctional compound having two or more protons, and these compounds may contain both halogen, cyanide, cyan ether, ester and the like. You may contain. These compounds may be used alone or in combination of two or more.
• the (C) organic transition metal complex compound in the present invention is a periodic table (long-period type) Group 3?
• an organic transition metal complex compound having a transition metal atom up to Group 12 as a central metal preferably an organic transition metal complex compound consisting of a transition metal atom from Group 4 to Group 9.
• transition metal atoms include titanium, vanadium, niobium, tantalum, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, and the like, and preferably tantalum, vanadium, molybdenum, tungsten, Rhenium, ruthenium and osmium are preferred, and molybdenum or tandastene is more preferred.
• organic transition metal complex compound for example, an alkylidene complex compound, an alkylidine complex compound, a Fischer-type carbene complex compound, a meta-cene complex compound, and a post-meta complex
• alkylidene complex compound for example, an alkylidene complex compound, an alkylidine complex compound, a Fischer-type carbene complex compound, a meta-cene complex compound, and a post-meta complex
• examples include cene complex compounds.
• the organic transition metal complex compound having an electron-withdrawing atomic group is an organic transition metal complex compound having metal alkylidene or metal alkylidin
• (C) organic The transition metal complex compound can be suitably used as a catalyst or a precursor of a catalyst such as metathesis polymerization, ring-opening metathesis reaction, ring-closing metathesis reaction or cross-metathesis reaction.
• each component when (B) a compound having proton donating property is brought into contact with (A) an organic transition metal complex compound having an electron-withdrawing atomic group For example, the amount is as follows.
• the amount of the (B) proton-donating compound used relative to 1 mol of the organic transition metal complex compound having an electron-withdrawing atomic group is, for example, 0.1 mol or more, preferably 0.2 mol or more. To do.
• the amount of the (B) proton-donating compound used per 1 mol of the (A) organic transition metal complex compound having an electron-withdrawing atomic group is, for example, 100 mol or less, preferably 10 mol or less. To do.
• the amount of the basic compound used relative to 1 mol of the compound (B) having a proton donating property is, for example, 0.1 mol or more, preferably 0.2 mol or more.
• the amount of the basic compound used per 1 mol of the compound (B) having a proton donating property is, for example, 100 mol or less, preferably 10 mol or less. However, this does not apply when the basic compound also serves as a solvent.
• the contact form of (A) the organic transition metal complex compound having an electron-withdrawing atomic group and (B) the compound having a proton donating property Suspension contact, homogeneous solution contact in these media, contact in the gas phase, etc. may be used.
• hydrocarbons such as pentane, hexane, toluene, and xylene
• Ethers such as jetyl ether, tetrahydrofuran, dixan, dimethoxyethane; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, chlorobenzene; and
• Examples thereof include basic compounds such as pyridine and piperidine. These can be used alone or in combination of two or more.
• the temperature at which these are brought into contact is, for example, 100 ° C or higher, preferably 80 ° C or higher.
• the contact temperature is, for example, 200 ° C or lower, preferably 100 ° C or lower.
• the contact may be performed in an atmosphere of an inert gas such as nitrogen or argon.
• the pressure for contact is, for example, normal pressure or higher.
• the contact pressure is, for example, lOMPa or less
• the contact time is, for example, 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer.
• the contact time is, for example, 1 month or less, preferably 200 hours or less, more preferably 50 hours or less.
• the (C) organic transition metal complex compound obtained by the production method of the present invention may be isolated or separated and purified as necessary. This purification involves general distillation, extraction and separation.
• 10-6 ⁇ is about LOMPa, it is possible to select conditions suitable for each method.
• the production method of the present invention is suitably used, for example, as a method for producing a metathesis catalyst represented by the following general formula (1).
• a metathesis catalyst represented by the following general formula (1) In the present invention, (C) an organic transition metal complex compound force metathesis catalyst may be used.
• R is selected from alkyl, aryl, and substituted aryl power, and particularly, alkyl, aryl, and substituted aryl having 4 to 30 carbon atoms, and further having 4 to 20 carbon atoms. preferable.
• alkyl, aryl, and substituted aryl having 4 to 30 carbon atoms, and further having 4 to 20 carbon atoms.
• tert-butyl, phenol, 4-tert-butylphenyl, 2,6 dimethylphenyl, 2,6 diisopropylmethyl, 1 naphthyl, 2,6 —diclonal phenyl, 4 fluoro-2,6 dimethylphenol -L, adamantyl, etc. are preferable examples.
• hydrogen, alkyl, aryl, substituted aryl, alkylsilyl, and alklucar are also selected as R 2 and R 3 , and these are the same.
• hydrogen, alkyl having 4 to 20 carbon atoms, aryl, substituted aryl, alkylsilyl, and alkyl are preferred, specifically hydrogen, methyl, ethyl, isopropyl.
• R 4 is also selected from alkyl, halogenated alkyl, aryl, and substituted aryl force, and in particular, an alkyl or halogenated carbon having 4 to 20 carbon atoms.
• alkyl, aryl, and substituted aryl are preferred: isopropyl, perfluorinated propyl, tert butyl, perfluoro-n-butyl, 1, 1, 1 trifluoro-2-methylinol-2-propinole, 1, 1, 1, 3, 3, 3 Hexa-fanolate 2-propylene, perfluoro-tert-butyl, phenyl, 1-naphthyl, 2,6 diisopropylphenol, 2,6 dimethylphenol, 2,6 dichlorophenol, 2 , 2'-bi-fell etc. are preferred examples.
• N is a nitrogen atom
• Q is an oxygen or sulfur atom. is there.
• E is a coordination molecule in which ether, alkylphosphine, arylphosphine, alkoxyphosphine, pyridine, alkylamine, and alkylideneamine forces are also selected.
• Specific examples of E include dimethyl ether, tetrahydrofuran, trimethylphosphine, triphenylphosphine, trimethoxyphosphine, pyridine, lutidine, triethylamine, propylidamine, and the like.
• M is a transition metal atom selected from the periodic table (long-period type) Group 3 force from Group 12 and preferably, Group 4 force to Group 9 Transition metal atom.
• the transition metal atom include titanium, vanadium, niobium, tantalum, molybdenum, tungsten, ruthenium, osmium, and rhodium.
• Preferred are tantalum, vanadium, molybdenum, tungsten, rhenium, norte Sulfur and osmium, more preferably molybdenum and tungsten.
• M force is one selected from the group force including tantalum, vanadium, molybdenum, tungsten, rhenium, ruthenium and osmium muc, m may be 1 or 2, and n may be 0 or 1.
• m is an integer of 1 or more and 3 or less, preferably 1 or 2.
• R 4 may be bonded to each other.
• 3, 3'-di-tert-butyl-1,5,5 ', 6,6'-tetramethyl-1,2,2'-biphenyl and the like are exemplified.
• N is an integer of 0 or more and 2 or less, preferably 0 or 1.
• the metathesis catalyst of the general formula (1) is not limited as long as it is a catalyst capable of performing a metathesis reaction and polymerization.
• R 7 is 3 ⁇ 4 ⁇ , CMe
• R 8 is 3 ⁇ 4 ⁇ ⁇ CMe CF, CMe (CF), C (CF), CH, 2 ⁇ Bu
• Alkyl groups such as C H, 2 ⁇ 4, 5—Me C H, 2, 6—CI C H, halides
• Rukil group, aryl group, R 9 is 3 ⁇ 4 ⁇ ⁇ CMe CF, CMe (CF), C (CF), Ph, 2 ⁇ Bu
• R 1Q is an alkyl group such as 3 ⁇ 4 ⁇ and adamantyl
• R 11 is an alkyl group such as H and Me, an alkoxy group such as OMe, or an aryl group such as Ph
• Py is a pyridine such as pyridine and lutidine.
• Derivatives or amine derivatives such as triethylamine and propylidamine, Me is a methyl group, 'Pr is an isopropyl group, 3 ⁇ 4 ⁇ is a tert butyl group, OMe is a methoxy group, and Ph is a phenol group.
• R 8 is 3 ⁇ 4 ⁇ , CMe CF, CM
• R 9 is ⁇ ⁇ CMe CF, CMe (CF), C (CF), Ph, 2- l BuC H, 2— ⁇ 4
• R 9 may be bonded to each other.
• R 1Q is 3 ⁇ 411, an alkyl group such as adamantyl
• R 11 is an alkyl group such as H or Me
• an alkoxy group such as OMe
• an aryl group such as Ph
• Py is a pyridine derivative such as pyridine or lutidine or triethylamine.
• amine derivatives such as propylidamine, Me represents a methyl group, 'Pr represents an isopropyl group, 3 ⁇ 4 ⁇ represents a tert-butyl group, OMe represents a methoxy group, and Ph represents a phenyl group.
• Molybdenum-based alkylidene catalysts such as
• CH CMePh
• CH CPh, Ph, SiMe and other alkyl groups, aryl groups, and key residues
• R 8 is 3 ⁇ 4 ⁇ ⁇ CMe CF, CMe (CF), C (CF), CH, 2- l BuC H, 2— ⁇ —— 4
• alkyl group, halogenated alkyl group, aryl group, R 1Q is an alkyl group such as 3 ⁇ 4 ⁇ and adamantyl
• R 11 is an alkyl group such as H and Me
• an alkoxy group such as OMe
• Ph Py is a pyridine derivative such as pyridine or lutidine, or an amine derivative such as triethylamine or propylidamine
• Me is a methyl group
• ⁇ ⁇ : is an iso-propyl group
• 3 ⁇ 4 ⁇ is tert-butyl Group
• OMe represents a methoxy group
• Ph represents a phenol group.
• Vanadium alkylidene catalysts such as
• R 5 and R 6 are alkyl groups such as H, 'Pr, Me, etc.
• Alkyl groups such as Me CH, halogenated alkyl groups, aryl groups, R 9 is 3 ⁇ 4 ⁇ , CMe C
• Alkyl group such as alkyl group, halogenated alkyl group, aryl group, R 1Q is alkyl group such as 3 ⁇ 4 ⁇ and adamantyl
• R 11 is alkyl group such as H and Me
• alkoxy group such as OMe, or aryl group such as Ph
• Py Is a pyridine derivative such as pyridine or lutidine
• an amine derivative such as triethylamine or propylidamine
• Me is a methyl group
• ⁇ ⁇ : is an iso-propyl group
• 3 ⁇ 411 is a tert-butyl group
• OMe is a methoxy group
• Ph is Indicates a phenol group.
• Osmium-based alkylidene catalysts such as
• Examples of the (C) organic transition metal complex compound include a metathesis catalyst comprising a combination of an organic transition metal complex as a precursor of a metathesis catalyst and a Lewis acid as a promoter.
• a metathesis catalyst comprising a combination of an organic transition metal complex as a precursor of a metathesis catalyst and a Lewis acid as a promoter.
• ⁇ ⁇ represents an isopropyl group
• 3 ⁇ 4 ⁇ represents a tert-butyl group
• R represents an alkyl group
• X represents a halogen
• thf represents tetrahydrofuran.
• these ring-opening metathesis polymerization catalysts may be used alone or in combination of two or more.
• an organic transition metal complex compound (C) of the present invention a basic compound and (B) a compound having a proton donating property are used.
• the electron-withdrawing atomic group of the organic transition metal complex compound having a neutral atomic group can be converted into an atomic group having a stronger electron-donating property.
• (C) an organic transition metal complex compound can be obtained without using a compound containing an alkali metal. For this reason, the concentration of alkali metal in the (C) organic transition metal complex compound can be reduced.
• the alkali metal content may be, for example, 10 ppm or less, preferably 5 ppm or less, and more preferably 2 ppm or less.
• the content of the alkali metal in the metathesis catalyst is, for example, Oppm or more. Further, the content of the alkali metal may be included in a range that does not impair the object of the present invention, which is preferably less, from the viewpoint of more reliably suppressing the occurrence of side reactions due to the influence of the alkali metal. For example, about 0.001 ppm may be contained.
• the alkali metal in the metathesis catalyst is contained as an alkali metal salt, if the content of the alkali metal is too large, As described above, side reactions with the reaction substrate occur during the metathesis polymerization reaction, resulting in The possibility of affecting the physical properties of the resulting polymer is increased.
• the alkali metal salt remaining in the polymer reacts with the hydrogenation catalyst to be altered or decomposed to correct. The possibility of inhibiting the normal hydrogenation reaction is increased.
• the alkali metal means lithium, sodium and potassium, and the content of alkali metal is the total amount of the alkali metal in the metathesis catalyst.
• the metathesis catalyst represented by the general formula (1) can be obtained without using a compound containing an alkali metal, the alkali metal is substantially excluded except for the unavoidable inclusion in the metathesis catalyst. It is also possible not to be included.
• the alkali metal concentration in the metathesis catalyst can be set below the detection limit in inductively coupled plasma mass spectrometry (ICP-MS), more specifically below lOppb. As a result, it is possible to more reliably prevent deterioration of the product quality during the metathesis polymerization reaction and subsequent hydrogenation.
• the ring-opening metathesis polymer is obtained by polymerizing cyclic olefins in the presence of the metathesis catalyst represented by the general formula (1).
• the method for producing a ring-opening metathesis polymer in the present invention includes a step of polymerizing cyclic olefin in the presence of the metathesis catalyst represented by the general formula (1).
• the cyclic olefin represented by the following general formula (2) or the following general formula (3) is polymerized using the metathesis catalyst represented by the above general formula (1), and then opened.
• a ring metathesis polymer can be obtained.
• R ′′ to R 15 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, A halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, A group force consisting of an aryloxycarbonyl group having 6 to 20 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, an acid anhydride, a cyano group, and a silicon-containing group force.
• R 12 to R 15 may be bonded to each other to form a ring structure
• X 1 is —O—, —S—, —NR 16 —, —PR 16 —, and —CR 16 From — (R 16 represents hydrogen, an alkyl group having 1 to 20 carbon atoms)
• p represents 0 or an integer of 1 to 3.
• R 1 R 1S independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, carbon, Halogenated alkyl group having 1 to 20 atoms, alkoxy group having 1 to 20 carbon atoms, alkoxyalkyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon An aryloxycarbonyl group having 6 to 20 atoms A droxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, an acid anhydride, a cyano group, and a silicon-containing basic group are selected groups, and R 17 to R 18 are bonded to each other to form a ring structure May be formed.
• X 2 is selected from O, 1 S, 1 NR 19 —, —PR 19 —, and —CR 19 — (R 19 represents hydrogen, an alkyl group having 1 to 20 carbon atoms)
• q represents 0 or an integer of 1 to 3.
• cyclic olefin represented by the general formula (2) or the general formula (3) to be polymerized using a metathesis catalyst bicycloheptene in which p or q is 0.
• tetracyclododecene in which p or q is 1 derivatives of hexacycloheptadecene in which p or q is 2
• R 12 to R 15 in the general formula (2) is like et be the following.
• R 12 to R 15 examples include hydrogen.
• alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, tert butyl, cyclohexyl, menthyl and the like.
• aryl groups having 6 to 20 carbon atoms include alkyl-substituted aryls such as phenyl, naphthyl, and methyl.
• halogen examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
• halogenoalkyl group having 1 to 20 carbon atoms include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl and the like.
• examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, menthoxy and the like.
• alkoxyalkyl group having 2 to 20 carbon atoms examples include alkoxy sugars such as methoxymethyl, methoxyethyl, tert-butoxymethyl, tert-butoxystil, methoxymenthol, and methylglucose.
• alkoxycarbonyl group having 2 to 20 carbon atoms methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycanoleboninole, n-butoxycarbonyl, tert-butoxycarbonyl, 1-methylcyclopentyloxycarboninole, 1- Ethenorecyclopentinoreoxycanoleboninole, 1-etinolenenoreboninoreoxycanole, 1-ethyladamantyloxycarbole, cyclohexyloxycarbonyl, tetrahydropyran 2-yloxycarbonyl, tetrahydrofuran 2-yloxycarbonyl, 1 ethoxyethoxycarbonyl, 1 butoxyethoxycarbonyl, and the like.
• Examples of the aryloxycarbonyl group having 6 to 20 carbon atoms include phenoxycarbonyl.
• hydroxyalkyl group having 1 to 20 carbon atoms examples include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, menthol, and hydroxyalkyl groups containing sugars such as glucose.
• Examples of the acid anhydride include carboxylic anhydride.
• cyan group examples include a cyan group having 1 to 20 carbon atoms, such as nitrile, cyanomethyl or cyanoethyl.
• the C-containing group has 3 or more carbon atoms such as trimethylsilyl, triethylsilyl, triprovirsilyl, triisopropylpropylsilyl, tributylsilyl, triisobutylsilyl, tri-tert-butylsilyl, tripentylsilyl, trihexylsilyl, etc. 20 The following trialkylsilyl groups;
• R 12 to R 15 may be bonded to each other to form a ring structure.
• a cyclic alkyl structure capable of forming a cyclohexyl ring, a rataton ring examples include a cyclic ester structure that can be formed, a cyclic imide structure that can form a phenylmaleimide ring, and an acid anhydride structure that can form a carboxylic anhydride.
• X 1 is further selected as 1 O, 1 S, 1 NR 16 —, 1 PR 16 —, and CR 16 — force.
• R 16 is hydrogen or an alkyl having 1 to 20 carbon atoms.
• p is 0 or an integer of 1 or more and 3 or less, preferably 0 or 1.
• X 1 may be the same or different.
• NR 16 —, -PR 16 and CR 16 — R 16 is hydrogen, methyl having 1 to 20 carbon atoms, ethyl
• alkyl groups such as n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, or menthyl.
• R 12 to R 15 an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, carbon Halogenated alkyl group having 1 to 20 atoms, alkoxy group having 1 to 20 carbon atoms, alkoxyalkyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon An aryloxycarbonyl group having 6 to 20 atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, an acid anhydride or a cyano group, a cyclic olefin having a selected substituent, X 1 is — 0—, — S—, -NR 1 From 6 —, —PR 16 —, and —CR 16 — (R 16 is hydrogen, an alkyl having 1 to 20 carbon atoms.
• a methylene group (one CH—) of the bicycloheptenes is a methylene group (one CH—) of the bicycloheptenes.
• 7-phosphabicycloheptenes 7-methyl 7-phosphabicycloheptenes and the like can be exemplified in place of tilphospha (1P (methyl) 1).
• R 12 to R 15 may be bonded to each other to form a ring structure.
• a cyclic anolenoquine structure that forms a cyclohexenole ring 1, 4, 4a, 5, 6, 7, 8, 8a- old Kutahi draw 1, 4, etc. meth no naphthalene and the like
• an annular ester le structure capable of forming a Rataton ring for example, 4-Okisa one tricyclo [5.2.2 1.0 2 ' 6 ] —8 Decene-3-one or 4,10 Dioxatritricyclo [5. 2. 1.
• phenylmaleimide ring is a cyclic imide structure
• tetracyclododecenes, hexacycloheptadecenes, or octacyclodokocenes can be substituted with, for example, methylene of these X 1 methylmethylene ((one CH (methyl) one)
• methyltetracyclododecenes, methylhexacyclopentacenes, or methyloctacyclodocosenes methylene instead of oxa (-0-), oxatetracyclododecenes, oxahexacyclo Putadecenes, or oxaoctacyclodocosenes, thiatetracyclododecenes, thiahexacycloheptadecenes, or thiaoctacyclodocosenes, replacing methylene with thia (1 S-)
• R 17 to R 18 in the general formula (3) include the following.
• R 17 to R 18 examples include hydrogen.
• alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, menthyl and the like.
• aryl groups having 6 to 20 carbon atoms include phenyl, naphthyl, and alkyl-substituted aryls such as methyl.
• halogen examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
• halogenoalkyl group having 1 to 20 carbon atoms include fluoromethylenole, chloromethylenole, bromomethinole, difunoleolomethylenore, dichloromethinole, dibu-mochimochinole, trifluoromethyl, trichloromethyl, tribromomethyl and the like.
• examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, and menthoxy.
• alkoxyalkyl group having 2 to 20 carbon atoms examples include alkoxy sugars such as methoxymethyl, methoxyethyl, tert-butoxymethyl, tert-butoxytyl, methoxymenthol, and methylglucose.
• alkoxycarbonyl group having 2 to 20 carbon atoms examples include, for example, methoxycarboninole, ethoxycanoleboninole, n-propoxynoleboninole, isopropoxycanoleboninole, n-butoxycarbonyl, tert-butoxycarbonyl, 1-methylcyclopentyl Oxycanoreboninole, 1-etinorecyclopentinorexoxynoreboninole, 1-etinorenoreboninoleo Xyloxycarbonyl, 1-ethyladamantyloxycarbonyl, cyclohexyloxycarbonyl, tetrahydropyran 2-yloxycarbonyl, tetrahydrofuran 2-yloxycarbonyl, 1 ethoxyethoxycarbonyl, 1 butoxyethoxycarbonyl Etc.
• Examples of the aryloxycarbonyl group having 6 to 20 carbon atoms include phenoxycarbol.
• hydroxyalkyl group having 1 to 20 carbon atoms examples include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, menthol and the like, and hydroxyalkyl groups containing sugars such as glucose.
• examples of the acid anhydride include carboxylic anhydride.
• cyan group examples include a cyan group having 1 to 20 carbon atoms, such as nitrile, cyanomethyl, or cyanoethyl.
• group containing a silicon for example, 3 carbon atoms such as trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylpropylsilyl, tributylsilyl, triisobutylsilyl, tri-tert-butylsilyl, tripentylsilyl, trihexylsilyl, etc. More than 20 trialkylsilyl groups;
• R 17 to R 18 may be bonded to each other to form a ring structure.
• a cyclic alkyl structure capable of forming a cyclohexyl ring or a cyclic ester structure capable of forming a rataton ring.
• a cyclic imide structure capable of forming a phenylmaleimide ring and an acid anhydride structure capable of forming a carboxylic anhydride.
• X 2 is further selected from 1 O, 1 S, 1 NR 19 , 1 PR 19 , and CR 19 —force.
• R 19 is hydrogen, an alkyl having 1 to 20 carbon atoms.
• q is 0 or an integer from 1 to 3, preferably 0 or 1, and when q is an integer from 1 to 3, X 2 may be the same or different.
• NR 19 —, -PR 19 one, or — CR 19 — R 19 is, for example, hydrogen or a methyl group having 1 to 20 carbon atoms.
• alkyl groups such as ru, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl.
• X 2 is preferably —O—, —S or —CH 1.
• R 17 to R 18 hydrogen, carbon atom number of 1 to 20 alkyl group, 20 following Ariru group having 6 or more carbon atoms, halogen, A halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, C 6 to 20 carbon atom arylcarbonyl group, hydroxy group, hydroxyalkyl group having 1 to 20 carbon atoms, acid anhydride or cyano group Cyclic olefin having a selected substituent Yes, from X 2 — O—, — S—, — NR 19 —, —PR 19 —, and — CR 19 — (R 19 is hydrogen, 1 to 20 carbon atoms
• phospha (1PH) and methylphospha (1P (methyl) 1) 2 can be exemplified by 7-phosphacyclocyclobutadienes, 7-methyl-7-phosphacyclocyclobutadienes, and the like.
• R 17 to R 18 may be bonded to each other to form a ring structure.
• a cyclic alkyl structure capable of forming a cyclohexyl ring 1, 4, 5, 6, 7 , 8 Hexahydro 1, 4 methanonaphthalene and the like
• cyclic ester structures capable of forming a rataton ring include, for example, 4-oxatritricyclo [5. 2. 1. 0 2 ' 6 ] — 2, 8 decadien 3-one or 4, 10 dioxertricyclo [5. 2. 1.
• tetracyclododecadiene, hexacycloheptadecadiene, or octacyclodocadiene is similar to bicyclobutadiene, for example, these X 2 methylenes are converted to methylmethylene ((1CH (methyl )-) Instead of methyltetracyclododecadiene, methylhexacycloheptadecadiene, or methyloctacyclodococadiene, methylene instead of oxa (1 O), oxatetracyclododecadiene, oxahexa Cycloheptadedecadiene or oxaoctacyclodococadiene, thiatetracyclododecadiene, methylenehexacycloheptadecadiene or thiaoctacyclodococadiene instead of thia (-S-), Instead of aza (one NH) or methylaza
• cycloolefins such as dicyclopentagen, cyclopropene, cyclobutene, cyclopentene, cycloheptene, and cyclotene;
• Cyclohexers such as cyclohexer 1,4-gen, cyclohexer 1,3-gen, cycloocta 1,5-gen, cycloocta 1,4-gen, cycloocta 1,3-gen; Examples include cyclotrienes such as 3,5-trien and cyclochota 1,3,6-trien.
• the ring-opening metathesis polymer includes at least one of the above general formula (2), the above general formula (3), and cyclic olefins such as cycloolefins, cyclogens, and cyclotrienes. It may be one obtained by polymerizing one kind of cyclic olefin, or one obtained by copolymerizing with at least two kinds of cyclic olefins.
• acetylene, a derivative thereof, and a diacetylene derivative may be used alone or copolymerized with cyclic olefin as monomers other than cyclic olefin.
• a metathesis catalyst such as a combination of the above organic transition metal complex as a precursor of a metathesis catalyst and a Lewis acid as a cocatalyst can be used.
• the molar ratio of cyclic olefin to metathesis catalyst is tantalum, vanadium, molybdenum, tungsten, rhenium, ruthenium, and osmium.
• the molar ratio of cyclic olefin is 2 or more, preferably 10 or more, per 1 mol of the catalyst.
• the molar ratio of cyclic olefin to metathesis catalyst is, for example, 30,000 or less, preferably 20,000 or less, with respect to 1 mole of the catalyst.
• the above organic transition metal complex as a precursor of a metathesis catalyst and a promoter
• the molar ratio of cyclic olefins is, for example, 2 or more, preferably 10 or more, with respect to 1 mol of the organic transition metal complex.
• the molar ratio of cyclic olefin to one mole of the organic transition metal complex is, for example, 10,000 or less, and preferably ⁇ is 5,000 or less.
• the organometallic compound as a co-catalyst is, for example, 0.01 or more, preferably 0.1 or more, more preferably 1 or more in a molar ratio with respect to 1 mol of the organic transition metal complex. Further, the organometallic compound as a co-catalyst is 100 or less, preferably 10 or less, more preferably 5 or less with respect to 1 mol of the organic transition metal complex.
• the polymerization of cyclic olefins with a metathesis catalyst may be performed without using a solvent or with a solvent.
• a solvent to be used ethers such as tetrahydrofuran, jetyl ether, dibutyl ether, dimethoxyethane, or dioxane;
• Aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene; aliphatic hydrocarbons such as pentane, hexane or heptane;
• An aliphatic cyclic hydrocarbon such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or decalin;
• halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, and trichlorobenzene, etc. may be mentioned, and two or more of these may be used in combination.
• olefins and genes can be used as chain transfer agents. Polymerization can be carried out in the presence of a kind.
• olefins used as chain transfer agents include a-olefins such as ethylene, propylene, butene-1, pentene 1, hexene 1, and otaten 1, and further include vinyltrimethylsilane, aryltrimethylsilane, Examples include kale-containing olefins such as allyltriethylsilane and aryltriisopropylsilane, and examples of genes include 1,4 pentagene, 1,5 hexagen, and 1,6 non-conjugated gen such as butadiene. It is done. In addition, these olefins or gens can be used alone or in combination of two or more. May be used in combination.
• the amount of olefin or gen used in the present invention is, for example, 0.001 or more, preferably 0.01 or more in a molar ratio with respect to 1 mol of cyclic olefin. Further, the molar ratio is, for example, 1000 or less, preferably 100 or less, per mole of olefin or gen-force cyclic olefin.
• olefin or gen is, for example, 10,000 equivalents or less, preferably 1000 equivalents or less, more preferably 500 equivalents or less with respect to 1 equivalent of the metathesis catalyst.
• the solvent polymerization concentration of cyclic olefins is preferably in the range of about 0.1 to 100 mol ZL, although it depends on the reactivity of cyclic olefins and the solubility in polymer solvents.
• a deactivator such as aldehydes such as butyraldehyde, ketones such as acetone, and alcohols such as methanol.
• a ring-opening metathesis polymer solution can be obtained.
• the repeating unit of the ring-opening metathesis polymer obtained by polymerizing the cyclic olefin represented by the general formula (2) or the general formula (3) is represented by the following general formula (4) or the following general formula (5). expressed.
• R ′′ to R 15 are independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, and the number of carbon atoms. 1 More than 20 halogenoalkyl groups, alkoxy groups having 1 to 20 carbon atoms, alkoxyalkyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, 6 carbon atoms More than 20 aryloxycarbonyl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, acid anhydride, cyano group, and key group containing key group are selected.
• R 12 to R 15 may be bonded to each other to form a ring structure.
• X 1 is one O—, one S—, one NR 16 —, —PR 16 —, and one CR 16 —force, and may be the same or different.
• R 16 is hydrogen and has 1 or more carbon atoms
• the upper 20 or less alkyl groups are represented.
• p represents 0 or an integer of 1 to 3.
• R 17 to R 18 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, A halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, A group force consisting of an aryloxycarbonyl group having 6 to 20 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, an acid anhydride, a cyano group, and a silicon-containing group force.
• R 17 to R 18 may be bonded to each other to form a ring structure
• X 2 represents —0—, —S—, —NR 19 —, —PR 19 —, and —CR 19 from (R 19 represents hydrogen, an alkyl group having 1 to 20 carbon atoms) selected
• q represents 0 or an integer of 1 to 3.
• the polystyrene-equivalent weight average molecular weight (Mw) measured by (Gel Permeation Chromatography: GPC) is, for example, 2,000 or more, preferably 5,000 or more.
• M w is, for example, 1, OOO, 000 or less, preferably 300,000 or less.
• the ring-opening metathesis polymer of the present invention does not contain an alkali metal salt in the metathesis catalyst, the polymerization reaction solution can be directly used in the ring-opening metathesis polymer without performing a process operation for removing the alkali metal.
• Hydrogenation to the main chain double bond is possible.
• the hydrogenation rate (percentage of the ratio of the number of double bonds contained in the polymer to the number of hydrogenated double bonds) is preferably 50% or more and 100% or less. Hydrogen is preferably added at a rate of 80% to 100%.
• the light transmittance of the hydrogenated product with respect to the wavelength in the ultraviolet region can be controlled by adding the main chain double bond of the ring-opening metathesis polymer with hydrogen to form a saturated bond at an arbitrary ratio.
• hydrogenation increases stability against acid and salt, and by reducing these double-chain double bonds depending on the application, weather resistance and thermal stability are improved, and ring-opening metathesis polymers are practically used. Can be used more neatly.
• R "to R lb are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, A halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, An aryloxycarbonyl group having 6 to 20 carbon atoms, A droxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, an acid anhydride, a cyano group, and a silicon-containing basic group are selected groups, and R 12 to R 15 are bonded to each other to form a ring structure May be formed.
• X 1 is selected from one O—, one S—, one NR 16 —, —PR 16 —, and one CR 16 (wherein R 16 represents hydrogen, an alkyl group having 1 to 20 carbon
• p represents 0 or an integer of 1 to 3.
• R 1 R 1S independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, halogen, carbon.
• Halogenated alkyl group having 1 to 20 atoms, alkoxy group having 1 to 20 carbon atoms, alkoxyalkyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon Alkyloxycarbonyl group, hydroxyl group having 6 to 20 atoms, hydroxyalkyl group having 1 to 20 carbon atoms, acid anhydride, cyano group, and key group containing key group group selected R 17 to R 18 may be bonded to each other to form a ring structure
• X 2 represents one 0—, one S—, one NR 19 —, —PR 19 —, and one CR 19 (R 19 represents hydrogen, an alkyl group having 1 to 20 carbon atoms)
• q represents 0 or an integer of 1 to 3.
• the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the hydrogenated ring-opening metathesis polymer in the present invention is preferably 2,000 or more. Preferably it is 5,000 or more.
• the above Mw is preferably
• the weight average molecular weight (Mw) and number average molecular weight of the hydrogenated ring-opening metathesis polymer The molecular weight distribution (MwZMn), which is a ratio to (Mn), is preferably 1.0 or more. Further, (MwZMn) is preferably 5.0 or less.
• a heterogeneous catalyst is a metal such as radium, platinum, nickel, rhodium, ruthenium, carbon, silica, alumina. And supported metal catalysts supported on a carrier such as titanium, magnesia, diatomaceous earth, and synthetic zeolite.
• nickel naphthenate / triethylaluminum nickel acetylacetonate / triisobutylaluminum, cobalt oxalate Zn-butyllithium, titanocene dichloride Z-deethylaluminum chloride, rhodium acetate, dichlorobis (triphenyl) -Luphosphine) paradium, chlorotris (triphenylphosphine) rhodium, dihydridotetrakis (triphenylphosphine) ruthenium, and the like.
• homogeneous catalysts include dichlorobis (triphenylphosphine) nickel, dichlorobis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) platinum, chlorotris (triphenylphosphine) rhodium, dichloromethane.
• these homogeneous catalysts and amine compounds may be used in combination.
• amine compounds include primary amine compounds such as methylamine, ethylamine, ⁇ -line, ethylenediamine, 1,3-diaminocyclobutane;
• Secondary amine compounds such as dimethylamine, methylisopropylamine, and N-methylamine
• tertiary amine compounds such as trimethylamine, triethylamine, triphenylamine, N, N-dimethylaniline, pyridine, and ⁇ -picoline Examples include compounds. Of these, tertiary amine compounds are preferably used, and particularly when triethylamine is used, the hydrogenation rate is remarkably improved. Two or more of these homogeneous catalysts or amine compounds can be used in combination at any ratio.
• the amount of the ring-opening metathesis polymer and the hydrogenation catalyst used is the same as that of the known hydrogenation catalyst.
• the known hydrogenation catalyst is, for example, 50, OOOppm or less, preferably 1, OOOppm or less, relative to the ring-opening metathesis polymer.
• the homogeneous catalyst is, for example, 5 ppm or more, preferably 10 ppm or more, particularly preferably 50 ppm, relative to the ring-opening metathesis polymer. That's it.
• the homogeneous catalyst is, for example, 50, OOOppm or less, preferably 10, OOOppm or less, particularly preferably 1, OOOppm or less, relative to the ring-opening metathesis polymer.
• the amine compound is, for example, not less than 0.1 equivalent, preferably not less than 0.5 equivalent, particularly preferably not less than 1 equivalent, relative to 1 equivalent of the homogeneous catalyst used. Further, the amine compound is, for example, 1,000 equivalents or less, preferably 500 equivalents or less, particularly preferably 100 equivalents or less, with respect to 1 equivalent of the homogeneous catalyst used.
• the hydrogenation catalyst having a homogeneous catalyst and an amine compound it is possible to use a catalyst obtained by previously contacting a homogeneous catalyst and an amine compound. Each may be added directly to the reaction system without prior contact treatment.
• the solvent used in the hydrogenation reaction of the ring-opening metathesis polymer may be any solvent as long as it dissolves the ring-opening metathesis polymer and the solvent itself is not hydrogenated.
• Etherols such as til ether, dibutyl ether, dimethoxyethane;
• Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene;
• Aliphatic hydrocarbons such as pentane, hexane, heptane;
• Aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, decalin;
• halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chronobenzene, trichlorobenzene, etc. These should be used in combination of two or more.
• the hydrogen pressure is usually normal pressure or higher, preferably 0.5 MPa or higher, particularly preferably 2 MPa or higher.
• the hydrogen pressure is usually 30 MPa or less, preferably 20 MPa or less, particularly preferably 15 MPa or less.
• the reaction temperature of the hydrogenation reaction is usually 0 ° C or higher, room temperature or higher, particularly preferably 50 ° C or higher.
• the reaction temperature is usually 300 ° C or lower, preferably 250 ° C or lower, particularly preferably 200 ° C or lower.
• these conditions and reaction time can be set according to the desired hydrogenation rate.
• the ring-opening metathesis catalyst or hydrogenation catalyst remaining in the polymer can be removed by a known method.
• the ring-opening metathesis polymer hydrogenated product solution strength The method for recovering the polymer hydrogenated product is not particularly limited, and a known method can be used.
• the reaction solution is discharged into a poor solvent under stirring, the polymer hydrogenated product is solidified, and collected by filtration, centrifugation, decantation, or the like, or the polymer is obtained by blowing steam into the reaction solution.
• a steam stripping method for precipitating the hydrogenated product and a method for directly removing the solvent from the reaction solution by heating, etc. I can get lost.
• the metathesis catalyst of the present invention is used as a reaction catalyst for organic synthesis reactions such as ring-closing metathesis reactions and cross-metathesis reactions of organic compounds having alkyne polymerization of acetylenes, double bonds or triple bonds in addition to the polymerization of cyclic olefins.
• the metathesis reaction can be performed without causing a side reaction as in the polymerization reaction.
• These metathesis reactions may be suspension polymerization or solution polymerization in a solvent-free or organic solvent, and the reaction conditions such as temperature, pressure, time and concentration are not particularly limited.
• the organic transition metal complex compound can be produced industrially and economically efficiently.
• the organic transition metal complex compound in the present invention can be used as, for example, an alkylidene complex compound, an alkylidine complex compound, a Fischer-type carbene complex compound, a metaguchisen complex compound, and a post-metallocene complex compound. It can also be used as a catalyst for organic synthesis reactions.
• the metathesis catalyst obtained by synthesis by the method for producing an organic transition metal complex compound of the present invention can reduce the content of alkali metal, for example, the content of alkali metal is set to lOppm or less.
• the ring-opening metathesis polymer such as cyclic olefins polymerized using the catalyst can be subjected to a hydrogenation reaction without removing the alkali metal in advance, and the ring-opening metathesis polymer or hydrogenated product.
• it can be suitably used for electronic material applications that are severely limited in alkali metal content and are extremely valuable industrially.
• the alkali metal content was determined by inductively coupled plasma mass spectrometry (ICP-MS).
• the detection limit for alkali metals is lOppb.
• the molecular weight of the polymer or polymer hydrogenated product is detected by dissolving the ring-opening metathesis polymer obtained by polymerization and the hydrogenated powder in tetrahydrofuran using gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the instrument was 830-RI manufactured by JASCO Corporation, and Shodexk-804, 803, 802.5 was used as the column, and the molecular weight was calibrated with polystyrene standards.
• the glass transition temperature (Tg) of the polymer was measured using DSC-50 manufactured by Shimadzu Corporation at a temperature increase rate of 10 ° C. Z under nitrogen.
• Example 1 Purified perfluoro-tert-butoxylithium (0.64 g) synthesized from perfluoro-tert-butyl alcohol (5.0 g) and n-butyllithium (1.6 M hexane solution 13.2 ml) under nitrogen in Example 1
• triethylenoamine (0.27 g) and perfluoro-tert-butyl alcohol (0.63 g) were used.
• the resulting solid was darkened, and the starting molybdenum complex and decomposition products were mixed.
• 230 ppm of lithium was detected from the obtained solid. Further, even after the obtained solid was washed twice with 5 ml of pentane cooled to ⁇ 30 ° C., lithium was detected in an amount of lOOppm or more.
• Example 2 The same procedure as in Example 1 was performed except that triethylamine was used in Example 1.
• the resulting solid was decomposed to eliminate the starting molybdenum complex and alkylidene. It was a mixture of products. Also, the obtained solid force was strong enough to detect no alkali metal.
• Example 2 1, 1, 1, 1, 3, 3, 3-hexafluoro-2-methyl-2-propanol (5. Og) and n-butyllithium (1. 6M hexane solution 18.9 ml) force synthesis under nitrogen And purified 1,1,1,1,3,3,3-hexafluoro-2-methylpropoxylithium (0.5 Og) with triethylamine (0.27 g) and 1,1,1,1,3,3,3— Except that it was used in place of hexafluoro-2-methyl-2-propanol (0.48 g), the same procedure as in Example 2 was performed to obtain 0.74 g of a yellow solid.
• Example 3 2-Methyl-2-propanethiol (5. Og) and hydrogenation power under nitrogen in Example 3 Synthesized and purified 2-methyl-2 potassium potassium (0.34 g) was used instead of triethylamine (0.27 g) and 2-methyl-2 propanethiol (0.24 g). The procedure was similar to that of Example 3 except for the above. The obtained solid was a mixture of the starting molybdenum complex and decomposition products. In addition, 300 ppm of potassium was detected from the solid powder obtained.
• Ad represents an adamantyl group.
• Triethylamine (0.30 g) was added. Then, the mixture was cooled to 30 ° C, and 3,3'-di-tert-butyl 5, 5 ', 6, 6'-tetramethyl-1,2,2'-dihydroxybiphenyl (0.51 g) was stirred. It was dripped while stirring. After 3 hours, the solvent was removed, extracted with pentane, filtered, and dried under reduced pressure to obtain 1.OOg as a yellow solid. From the NMR spectrum of this solid, formation of a compound represented by the following chemical formula (8) was confirmed. Also, no alkali metal was detected from the obtained solid.
• the ring-opening metathesis polymer had a weight average molecular weight (Mw) of 23,300 and a molecular weight distribution (MwZMn) of 1.70 as measured by GPC.
• Example 13 instead of the reaction solution synthesized in Example 12, the reaction solution synthesized in Comparative Example 5 was used, except that the reaction solution was used.
• the ring-opening metathesis polymer hydrogen additive solution is added to methanol to precipitate the ring-opening metathesis polymer hydrogenate, and it is separated by filtration and vacuum-dried.
• Example 2 The same procedure as in Example 1 was carried out except that pyridine (0.22 g) was used instead of triethylamine (0.27 g) in Example 1, to obtain 1.07 g of a yellow solid.
• pyridine (0.22 g) was used instead of triethylamine (0.27 g) in Example 1, to obtain 1.07 g of a yellow solid.
• the obtained solid force was not detected by alkali metal.
• the ring-opening metathesis polymer had a weight average molecular weight (Mw) measured by GPC of 14500, a molecular weight distribution (Mw / Mn) of 1.68, and a Tg of 155 ° C.
• Luamine (lmg) was added and hydrogenation reaction was carried out for 7 hours at a hydrogen pressure of 10 MPa and 125 ° C. Then, the temperature was returned to room temperature, and then hydrogen gas was released.
• This ring-opening metathesis polymer hydrogenated product solution is added to methanol to precipitate the ring-opening metathesis polymer hydrogenated product, followed by filtration and separation, followed by vacuum drying, whereby powdered ring-opening metathesis polymer hydrogenated product 12 Obtained 0g.
• the hydrogenation rate calculated from 1 H-NMR of the obtained hydrogenated ring-opening metathesis polymer showed no peak attributed to the proton of the main chain olefin, and its hydrogenation The rate was 100%, the weight average molecular weight (Mw) measured by GPC was 20200, the molecular weight distribution (Mw / Mn) was 1.75, and Tg was 125 ° C.
• Example 20 After 50.0 g of the reaction solution synthesized in Example 20 was subjected to hydrogenation reaction with palladium carbon at 160 ° C. and hydrogen pressure lOMPa, the temperature was returned to room temperature, and then hydrogen gas was released. This ring-opening metathesis polymer hydrogenated solution was added to methanol to obtain a powdered ring-opening metathesis polymer hydrogenated product.
• the obtained polymer had a hydrogenation rate of 100%, a weight average molecular weight (Mw) of 53,000, a molecular weight distribution (MwZMn) of 2.64, and a Tg of 107. C.
• the reaction solution 50 Og synthesized in Example 23 was hydrogenated with palladium carbon at 130 ° C. and a hydrogen pressure of 9.5 MPa, the temperature was returned to room temperature, and then hydrogen gas was released.
• This ring-opening metathesis polymer hydrogenated solution was added to methanol to obtain a powdered ring-opening metathesis polymer hydrogenated product.
• the resulting polymer is hydrogenated in both the main chain double bond and the ring internal double bond, the hydrogenation rate is 100%, the weight average molecular weight (Mw) is 190000, the molecular weight distribution (MwZMn) is 1.21, Tg Was 38 ° C.

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