WO2004020413A1 - Composes metalliques de transition, catalyseurs de polymerisation pour dienes conjugues, procede de production de polymeres de dienes conjugues, polyisoprene et produits de cyclisation de ce dernier, et procede de production correspondant - Google Patents

Composes metalliques de transition, catalyseurs de polymerisation pour dienes conjugues, procede de production de polymeres de dienes conjugues, polyisoprene et produits de cyclisation de ce dernier, et procede de production correspondant Download PDF

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WO2004020413A1
WO2004020413A1 PCT/JP2003/010863 JP0310863W WO2004020413A1 WO 2004020413 A1 WO2004020413 A1 WO 2004020413A1 JP 0310863 W JP0310863 W JP 0310863W WO 2004020413 A1 WO2004020413 A1 WO 2004020413A1
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atom
group
polyisoprene
transition metal
pyridine
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PCT/JP2003/010863
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Japanese (ja)
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Shintaro Ikeda
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Zeon Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and 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
    • C08F36/04—Homopolymers and 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

Definitions

  • Transition metal compound catalyst for conjugated diene polymerization, method for producing conjugated diene polymer, polyisoprene and cyclized product thereof, and methods for producing them
  • the present invention relates to a novel transition metal compound in which a heterocyclic compound is coordinated to a transition metal atom of Group 8 of the periodic table, a catalyst for conjugated gen polymerization containing the transition metal compound, and a catalyst for this polymerization. And a method for producing a conjugated gen polymer using the same.
  • the present invention relates to a novel polyisoprene obtained by using a specific transition metal compound as a catalyst, a novel cyclized polyisoprene obtained by cyclizing the polyisoprene, and a method for producing the same.
  • Titanium nonadium, cobalt, nickel, etc.
  • ethylene which is composed of iron or coparte having bisiminopyridine as a ligand, and methylaluminoxane ⁇ g ⁇ raw ⁇ 200 0 0-5 16 9 See report 5.
  • ⁇ Moth is a polymerization activity against the crepe! 3 ⁇ 4S Extremely low
  • the isoprene is polymerized by using the azimuth advance composed of ⁇ K terpyridine 3 ⁇ 4rSSf standing cubes and methylaluminoxane, the amount of polyisoprene power is also severely reduced.
  • this ( ⁇ butadiene was polymerized using a butterfly: ⁇ is a few thousand hectares (f ⁇ amount of polybutadiene.
  • an object of the present invention is to be useful as a pirate who can polymerize various kinds of * -gen such as butadiene and isoprene with high activity.
  • * -gen such as butadiene and isoprene with high activity.
  • Compounds and window-shadow compounds ⁇ ⁇
  • the method of using the horned butterflies and the horned butterflies is to use the compound butterfly.
  • the present inventors have found that a new polyisoprene having an unusual ⁇ ⁇ t and an intense ⁇ t can be obtained by the present inventors. It has been found that when used as a butterfly, it is possible to polymerize gens such as butadiene and isoprene extremely rawly. Based on this finding, the present invention has been achieved.
  • the general formula (1) the general formula (1)
  • ⁇ a represents (a) a hydrogen atom or a halogen atom, (b) a free atom, a chromium atom, a boron atom, a sulfur atom, a phosphorus atom, a phosphorus atom, a ke atom, a geno ⁇ .
  • a transition metal compound (A) comprising a heterocyclic compound represented by the formula (1) coordinated to a transition metal of Group 8 of the periodic table is provided.
  • conjugated diene polymerization catalyst comprising the above transition metal compound (A).
  • (A) is used for polymerization of gen such as butadiene and isoprene. You can get more books.
  • conjugated-gen polymerization catalyst at least one selected from the group consisting of an organometallic reducing agent (B-1) and a compound (B-2) which reacts with the transition metal compound (A) to form an ion pair is used. It is preferable to further contain. By containing these compounds, the polymerization activity can be further enhanced.
  • the complex cyclic compound in which R 1 in the above general formula (1) is an aryl group substituted with a halogen atom is selected from Group 8 of the periodic table. It is preferable that the compound be coordinated with a transition metal.
  • the halogen atom is preferably a fluorine atom.
  • conjugated gen polymer wherein conjugated gen is polymerized in the presence of the conjugated gen polymerization catalyst. According to this method, conjugated diene polymers having various structures can be obtained.
  • the heterocyclic compound in which R 1 in the above general formula (1) is a halogen atom, preferably an aryl group substituted with a fluorine atom is a transition metal belonging to Group 8 of the periodic table.
  • a method for producing polyisoprene which comprises polymerizing isoprene in the presence of a catalyst for conjugated diene polymerization comprising a coordinated transition metal compound (A). According to this method, it is possible to obtain a polyisoprene having a novel specific structure and a cyclized product thereof as described later.
  • the weight measured by gel permeation chromatography A polyisoprene having a weight average molecular weight of 5,000 to 2,000,000 in terms of polystyrene, wherein the polyisoprene is composed of cis 1,4 bonds, and the cis 1,4 bonds are Polyisoprene is provided that contains at least 25% of monomer units ( ⁇ ) in which the 4-position carbon atom is linked to a monomer unit composed of 3,4-bonds in all monomer units .
  • a method for producing a cyclized polyisoprene which comprises cyclizing the polyisoprene in the presence of an acid catalyst.
  • a cyclized product of a polymer having a peak derived from methine carbon at 58 to 61 ppm in a 13 C-NMR spectrum measured by using chloroform as a solvent is provided.
  • the difficulties of the present invention are as follows: 1) ⁇ compound, 2) J-shaped angle butterfly, 3) ⁇ ⁇ -ge ⁇ book ⁇ method, 4) $ S ⁇ of polyisoprene, 5) polyisoprene, 6) polyisoprene Ring method, and 7) Polyisoprene ring! ⁇ Page XI.
  • (A) is a child of the 8th family of pregnancy, which is represented by the (i) »i formula ⁇ / (hereinafter sometimes referred to as ⁇ ⁇ ⁇ minopyridines).
  • ⁇ 1 to! ⁇ 6 each independently contain (a) a hydrogen atom or a halogen atom, (b) an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a phosphorus atom, a silicon atom, a germanium atom or a tin atom Or (c) a halogen atom or a hydrocarbon group which may be substituted with the functional group.
  • halogen atom examples include F, Cl, Br and .1 atoms.
  • Specific examples of the functional group containing an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a phosphorus atom, a silicon atom, a germanium atom or a tin atom include an alkoxy group, an aryloxy group, a carboxyl group, and a carbonyl group.
  • Etro nitroso, amide, amino, amino, cyano, pyridyl and pyrimidyl, and other nitrogen-containing heterocyclic groups, alkylthio, arylthio, sulfonyl, phosphino, silyl, and silyl groups.
  • Examples include a group in which a silicon atom is substituted with a germanium atom or a tin atom.
  • hydrocarbon group examples include methyl group, ethyl group, isopropyl group, sec-butyl group, tert-butylinole group, n-butyl group, n-pentynole group, neopentyl group, t-pentyl group, and n-hexyl Alkyl group having 1 to 20 carbon atoms, such as a group, isohexyl group, etc .; cycloa, rekyl group having 3 to 20 carbon atoms, such as a pentyl group, a hexyl group, an adamantyl group, etc .; a benzyl group, 1_ C7-C20 aralkyl groups such as phenylethyl group, 11- ( ⁇ -naphthyl) ethyl group, and 11-(] 3-naphthyl) ethyl group; vinylinole groups, propyl groups,
  • Formula groups are preferred phenyl groups 2 _ methylphenyl 4 1-methylphenyl 2, 6-diethylphenyl 2, 6-diisopropylphenyl mesityl Naphthyl and other aryl groups; 2-aminophenyl groups 4 2-aminophen-2-ole 4-hydroxyphen-2-ene mouth phenyl 4-nitrophenyl 2-acetoxyphenole 4-aryloxy group, such as acetoxyphenole group; 2 —Black mouth 7 2
  • R 2 is preferably an alkyl group having 1 to 20 carbon atoms and an aryl group having a prime number of 6 to 20 among the prime groups.
  • Examples include: methylethyl isopropynole cyclohexyl, 1-phenylethyl 1-naphthylethyl 1-tert-butylethyl, tert-butyl, and other alkyl groups that do not have: hydroxymethyl group 2-hydroxyshethyl 3-hydroxypropynole 2- An alkyl group having, such as chloroethynole 3-funoleo mouth propinole 2-aminoethyl 3-aminopropyl 2-aceti / reethylaminoethyl ethoxyethyl ethoxyacetinole methoxycanoleponylethyl ethoxycarbonylethyl group;
  • -iW (1) is preferably represented by 2— (1 2- [1- (2-methylphenyl) / pyridine] 2- [1- (3-methylphenylamino) ethyl] pyridine, 2- [1- (3-methylphenylamino) ethyl] pyridine, 2- [1- (4-methylphenyl) Limino) ethyl] pyridine, 2- [1- (2-phenylmethylphenylimino) ethyl] pyridine, 2- [1- (2,6-dimethylphenylimino) ethyl] pyridine, 2- [1- (2,6-diisopropylphenylimino) ethyl] pyridine, 2- [1- (2-tert-butylphenyl-imino) ethyl] pyridine, 2- (1-methycyliminoethyl) pyridine, 2- (1-methycyliminoethyl) pyridine
  • Minopyridine pyridi ⁇ Pyrazine ⁇ Minopyrazine; substituted iminopyridine pyridine substituted pyridazine substituted iminopyridazine; m ⁇ i minopyridine pyridine substituted triazine « ⁇ minotriazine; above ⁇ f minopyridine pyridine is substituted for quinoline ⁇ f minoquinoline; JtlHfii ⁇ pyridine of minopyridine is replaced by quinazoline quinazoline; pyridine of ⁇ iminopyridine above
  • the above substituted iminopyridines can be synthesized by the method described in Naturforsch, 1981, 36b, pp. 823-832. More specifically, the substituted iminopyridines are synthesized by a condensation reaction of an acetylpyridine derivative with a primary amamine. be able to.
  • the group 8 fibers used in the present invention include iron, nickel, osmium and the like.
  • a X ⁇ A 4 S i , j, k, 1 and ⁇ is an ⁇ (1) ⁇ .
  • m is from 1 to 3 («3 ⁇ 43 ⁇ 4, m is 2 Ji ( ⁇ is a queer girl! ⁇ ⁇ )» At least two of them may be 3 ⁇ 4 ⁇ .
  • X is any anion translation ⁇ (represents a lattice, ⁇ is Fe ( ⁇ Satisfies ⁇ .
  • n is 2 or more: ⁇ may be the same or different for a plurality of groups represented by X, A plurality of groups represented by X may form each other.
  • the fiber (X) is a medium 'L ⁇ S (Fe) force bow I.
  • the negative 3 ⁇ 4 is a ligand;
  • the anion free ligand (X) include: fluorine, chlorine, halogen atoms belonging to a difficult group; hydrogen atoms; diketonate groups such as acetyl acetonate; Alkyl alkyl alkylaryl alkoxyaryl which may have a cyclopentagenenyl group; ⁇ alkoxycarboninole carboxylalkylsnorrefonate arylarylsulfonate alkylthioalkenyl arylinoalkylsulfonyl alkyls / Refiel 3 ⁇ 45S. Of these, halogen atoms are preferred.
  • Specific examples of the compound represented by the general formula (2) include ⁇ 2- [1-1 (2,6-diisopropylphenylimino) ethyl] pyridine ⁇ iron (II) dichloride, [2-1 (11 Phueliminoethyl) pyridine] iron (II) dichloride, ⁇ 2— [1 I (2,6-dimethylphenyliminoethyl) pyridine] iron (II) dichloride, [2- (1-mesityliminoethyl) pyridine] iron (II) dichloride, etc., where m is 1 and R 1 is Compounds that are aryl groups; ⁇ 2_ [1- (pentafluorophenylimino) ethyl] pyridine ⁇ iron (II) dichloride, ⁇ 2— [1— (2-fluorophenylimino) ethyl] pyridine ⁇ iron (II) dichloride, ⁇ 2— [1— (3-F
  • the method for producing the transition metal compound (A) of the present invention is not particularly limited.
  • the compound can be synthesized by bringing the above substituted iminopyridines into contact with a Group 8 transition metal compound having an anionic ligand.
  • Specific examples of the Group 8 transition metal compound having an auronic ligand include iron chloride (1 1), salt yidani (1 1 1), iron bromide (1 1), and bromide.
  • the method is not particularly kneeling.
  • ⁇ minopyridin which has been converted or ⁇ into organic fibers and anion which has been dissolved or dispersed in a tree-like manner has an anion of 8th; .
  • the organic venom used is not particularly limited as long as it does not denote or denote the 8 ⁇ 3 ⁇ 4 3 ⁇ 4 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . ⁇ .
  • organic males examples include ingredients such as benzene, toluene, and xylene; halogen-based fats such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; Halogen ife ⁇ ifek element such as lipstick, dichlorobenzene, etc .; nitromethane, Fatty oils such as tetrahydrofuran ft3 ⁇ 4 ⁇ -ter type; Anisole, phenetole, etc.-Teral type Nada; Fatty acids such as pentane, hexane, heptane ( ⁇ ( ⁇ ); The joy of the moon, such as Bisik heptane, Tricyclodecane, Shik mouth otatan, etc.
  • halogen-based fats such as dichloromethane, chloroform, 1,2-dichloroethane, and the like
  • Halogen ife ⁇ ifek element such as lipstick, dichlorobenz
  • Minopyridin ⁇ ⁇ ⁇ ⁇ ⁇ ' « « «8 8 8 8 3 ⁇ 4 i3 ⁇ 4 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ .
  • Minopyridi the iig of Ken who feeds, and the 8th with the spontaneous ligand; ⁇ ⁇ ⁇ ) 3 ⁇ 4r ⁇ ti ⁇ ⁇ r ⁇ ti ⁇ .
  • the mixing ratio of the eighth amino acid having an anion 'ligand of m-minopyridyl is preferably 1 to 10 times, more preferably 1 to 8 times, and more preferably 1 to 5 times. Too small a proportion of the 8 ⁇ 1 formation ⁇ 3 ⁇ 4 with anion's spontaneous ligand of ⁇ And the '-on' the 8th; ⁇ M-formation with a sphere co-ordinate 'is likely to be an iiff. On the other hand, if too much, the minopyridine of the There is a possibility that it will decline.
  • m ⁇ i ⁇ (A) ⁇ S3 ⁇ 4 is not particularly kneel, but usually between 100 ° C and 120 ° C. C, preferably from 180 ° C to + 180 ° C, more preferably from 170 ° C to + 170 ° C. If it breaks down, it will slow down. If it is too high, it may cause side effects; Is not particularly kneel, but usually 1 ⁇ 1! ⁇ Between one week.
  • the target transition metal compound (A) can be isolated, for example, by a method in which a reaction solution is added to an insoluble organic solvent to cause precipitation. Further, the residue or the reaction solution obtained by distilling the solvent used for the reaction can be used as it is for the preparation of the polymerization catalyst.
  • the structure of (A) can be identified by crystal clarity, ⁇ - and 13 C-NMR spectrum measurements, ⁇ loaves, and the like.
  • the catalyst for conjugated gen polymerization of the present invention contains the above transition metal compound ( ⁇ ).
  • the transition metal compound ( ⁇ ) shows polymerization activity even when used alone, but a compound which forms an ion pair by reacting with the organometallic reducing agent ( ⁇ -1) and the transition metal compound represented by the general formula (1). ( ⁇ -2: hereinafter referred to as an ion pair-forming compound.) It is preferable to combine with at least one compound selected from the power because the polymerization activity is increased.
  • ⁇ m (B-D is, for example, the first, second, first, second, third, third, and fourth group of Circular Fibers having a carbon group of izu Among these, organolithium compounds ⁇ !, organomagnesium compounds ⁇ , organic aluminum compounds, ⁇ -organotinated compounds are preferred, and organolithium compounds ⁇ organoaluminium compounds are preferred. ⁇ , organic tin ⁇ is particularly preferred.
  • Organic lithiation includes ⁇ -butyllithium, methyllithium, phenyllithium, The ability to name neopentyl lithium, neofil lithium, etc.
  • the morphogenization is as follows: butylethyl / magnesium, butyloctino W gnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, arino gnesium bromide, neopentino gnesium chloride, neooffino W Guneshmud mouth lids and the like can be mentioned.
  • Examples of the efficacious mouth include dimethyl-rich mouth and getyl diphenyl mouth.
  • organoaluminum compounds examples include: 1, limetinol 7-remium, triethylaluminum, triisobutylaluminum, ethinorea / reminimum chloride, ethine / rare / reminimum Examples thereof include alkyl anolemminium or alkyl anolemminium halide such as tinoreanolimine dichloride. Further, mention may be made of aluminoxane at the mouth obtained by the above-mentioned organic aluminum and water.
  • organic compound examples include tetramethyltin, tetra (n-butyl) tin, tetraphenyltin and the like.
  • the amount of excitation of (B-1) varies depending on the use of the compound, but the molar ratio of ⁇ M atom in the ⁇ compound represented by-(1): ⁇ S atom in the ⁇ Si ⁇ 0.
  • the compound forming (B-2) is not particularly knee-bonded, but can include organic boron compounds (heteropoly conjugates and so-poly compounds ⁇ ). Among them, organic boron compounds are preferred. .
  • B G + (BQQ 5 Q 6 Q 7 ) Boron compound represented by the following formula (however, ( ⁇ ⁇ is that? ⁇ G + is a fiber or an organic cation.), Borane or rubobarane, or salts or anions of their anions.
  • organoboronated compounds ⁇ include trimethylboron, triethylboron, tri-n-butylboron, trifenylboron, tris (perfluorophenyl) boron, N, N— Dimethylaniline tetrakis (Perfnoreo mouth Feninore) port, Tritino! ⁇ Thrakis (perfluorophenyl) borate and the like can be mentioned.
  • the amount of Io ⁇ f formed “ ⁇ (B-2) varies depending on the used” formed " ⁇ /, but the molar ratio of 61 compound (A): yeo / 3 ⁇ 4 ⁇ conjugated compound is 1 : 1: to: LO force, 1: 1 to 5 is more preferable.
  • the organometallic reducing agent (B-1) and the ion pair-forming compound (B-2) are each used alone or in combination of two or more, and both may be used in combination.
  • the preparation of a catalyst comprising a combination of the transition metal compound (A) and at least one selected from the group consisting of an organometallic reducing agent (B_l) and an ion pair-forming compound (B-2) is usually carried out in an organic solvent as described above. This is performed by mixing the components.
  • the organic solvent to be used is not particularly limited as long as it can dissolve or disperse each component and is not affected by the reaction.
  • the same solvents as those used in the production of the transition metal compound (A) described above can be used.
  • the prepared catalyst solution or dispersion can be directly used for the polymerization reaction.
  • the $ ⁇ method of the present invention consists of IS f of a * ge * book by polymerizing a * gen to the above-mentioned polymerization angle.
  • the gen include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyi / l-1,3-butadiene, 2-methinole 1,3-pentadiene, 3-methinole 1,3-pentadiene, 4 -Methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene or other chain or conjugated gens of TO; cyclopentene, methinolenk pentagen, 1,3-cyclohexene, 1,3 Examples include 3-cyclotatagene.
  • the amount of the polymerization catalyst used in the present invention is not particularly limited. However, when expressed by the molar ratio of ⁇ (A)): gen), it is usually 1 unit. : 100 to 1: 2,000, 000, preferably 1: 500 to 1,000,000, more preferably 1: 1,000 to 1: 500, OOO ⁇ f. Too much jiang makes it difficult So, if you don't have too much trouble, there's + ⁇ &&
  • the polymerization method in the present invention is not particularly limited, and may be a liquid phase polymerization method such as solution polymerization or polymerization or a gas phase polymerization method! /, F3 ⁇ 4X can also be seen.
  • Polymerization ⁇ is obtained by shipping a monomer and a polymer.
  • the polymerization key is not particularly limited, but is usually ⁇ 50 ° C. to + 200 ° C., preferably 0. C to + 170 ° C.
  • the weight is not particularly limited, but is usually from 1 minute to 1 hour.
  • the pressure in the polymerization is not particularly limited, but is usually from normal pressure to 1 OMPa, preferably from normal pressure to 5 MPa.
  • the present invention in order to control the amount of heavy ⁇ :, it is possible to add tr to the ij.
  • the Rentanada ij the one that is used in the polymerization of gen from the very beginning!
  • the specific examples thereof include ares such as 1,2-butadiene, and rings such as cyclooctadene: ⁇ ge ⁇ and hydrogen.
  • Polymerization St & ⁇ i is usually carried out by forcing a polymerization agent into the polymerization system when the vehicle reaches a certain level.
  • the deterrent agents include 7]; alcohols such as methanol, ethanol, propanol, butanol, and isobutanol; quenches such as males; In addition, these deterrents may be interchanged as a mixture of two difficulties ⁇ ).
  • the polymer after polymerization can be recovered according to a conventional method. In other words, it is sufficient to recover the s-isomer produced by eye polymerization as it is, and to use ⁇ night-phase polymerization in the steam stripping method, and to use a male that precipitates heavy in a poor sea. Can be.
  • the kitchen biomass ratio can be measured by — and 13 C—NMR.
  • the polyisoprene of the present invention is obtained by removing the polyisoprene according to the method of the present invention, wherein R 1 in the wiping cloth (1) is an aryl group represented by a halogen atom as a square butterfly for the combination of the two.
  • ⁇ -formation (A) in the chemical formula, in the formula ⁇ / represented by venom (2), m is 1 and R 1 is substituted with a halogen atom.
  • a compound which is an aryl group, in which m is 2, and R 1 is an aryl group woven with a halogen atom can also be preferably used.
  • the binding is not particularly limited, and it is not necessary to use any of the methods and methods described in $ S ⁇ of 2) Jae Return and 3) Jae ⁇ Can be.
  • the polyisoprene of the present invention is a polyisoprene having a weight average molecular weight of 5,000 to 2,000,000 in terms of polystyrene as measured by gel permeation chromatography, and cis 1,1 is contained in the polyisoprene.
  • Shirazou can be identified by and 13 C-NMR measurements.
  • the harmfulness of the polymer in the polymer can be determined from 13 C-NMR measurements.
  • the harmful U of the simple substance f-zen position ( ⁇ ) is 25% or more, preferably 30% or more, and more preferably 35% or more in the heavy-to-one unit amount. ⁇
  • the weight average molecular weight of the polysoprene of the present invention is determined by gel permeation chromatography, and is preferably 5,000 to 2,000,000 by polystyrene calculation, preferably 10,000 to 1,500,000, more preferably It has 20,000 to 1,000,000 chapters. This (7 marriage becomes ⁇ of the key ring.
  • the iS ⁇ method of polyisoprene of the present invention is not particularly ⁇ 3 ⁇ 4.
  • ⁇ : 3t * ⁇ of the polyisoprene of the present invention, that is, * ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . 1 is an aryl group woven with a halogen atom.
  • the compound (A) can be used to polymerize isoprene using a rice cake having the compound (A).
  • the $ S ⁇ method of the polysoprene ring of the present invention is based on the fact that the polysoprene of the present invention is cyclized under a craft butterfly.
  • the ring is usually performed in Sekiiku Fiber.
  • the acid catalyst may be one usually used in a cyclization reaction, for example, sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, and sulfur.
  • Organic sulfonic acid compounds such as organic sulfonic acids such as rat toluene sulfonic acid and their anhydrides or alkyl esters; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, Metal halides such as aluminum chloride, getyl aluminum monochloride, ethyl ammonium chloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, and iron chloride; and the like.
  • These acid catalysts may be used alone or in combination of two or more. Among them, an organic sulfonic acid conjugate is preferable, and p-toluenesulfonic acid is more preferable.
  • the amount of the acid catalyst to be used is generally 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, per 100 parts by weight of the polyisoprene of the present invention. Parts by weight.
  • the hydrocarbon solvent used in the reaction is not particularly limited as long as it does not inhibit the cyclization reaction.
  • Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; n-pentane, n-hexane And aliphatic hydrocarbons such as n-heptane and n-octane; alicyclic hydrocarbons such as pentane and hexahexane; and those having a boiling point of 70 ° C or more. Is preferred.
  • the solvent used for the polymerization reaction of the co-polymer may be used as it is. In this case, an acid catalyst is added to the polymerization reaction solution after the polymerization.
  • the amount of the solvent used is usually 1 to 60% by weight of the solid concentration of the polyisoprene of the present invention. /. It is preferably in the range of 2 to 40% by weight.
  • the cyclization reaction can be carried out under any pressure, reduced pressure or atmospheric pressure.It is desirable to carry out the cyclization reaction under atmospheric pressure from the viewpoint of simplicity of operation, especially under dry air flow, especially dry nitrogen or dry nitrogen. When performed in an atmosphere of anoregon, side reactions due to moisture can be suppressed.
  • the reaction temperature and reaction time may be in accordance with a conventional method, and the reaction temperature is usually 20 to 200 ° C, preferably 50 to 150 ° C, and the reaction time is usually 1 to 2 ° C. 0 hours, preferably 3 to 10 hours.
  • the cyclized polyisoprene of the present invention obtained as described above is usually prepared by inactivating a cyclization catalyst, removing a residue of the cyclization catalyst, and removing an inert solvent by a conventional method. However, it can be obtained as a solid.
  • the polyisoprene ring of the present invention has a 13 C-NMR spectrum measured using heavy-mouthed form as difficult. It is a polyisoprene cyclized product having a peak at 58-6 lppm derived from methine.
  • a conventionally known polyisoprene cyclized product has no peak at 58-61 pm in 13 C-NMR spectrum measurement.
  • the cyclized polyisoprene of the present invention has a peak at 58-61 ppm derived from methine carbon. This is presumed to be because the conventional polyisoprene cyclized product has a 6-membered ring structure, whereas the ring structure is a 5-membered ring.
  • the cyclized polyisoprene of the present invention having such a structure can be obtained by cyclizing the polyisoprene of the present invention.
  • the specific production method is as described in the above 6) Production method of cyclized polyisoprene.
  • the weight average molecular weight (Mw) of the polyisoprene cyclized product of the present invention is a value measured by gel permeation chromatography (converted to standard polystyrene), and is usually 3,000 to 2,000,000, preferably 5,000 to 2,000. It is in the range of 1,500,000, more preferably 8,000 to 1,000,000.
  • the polyisoprene cyclized product of the present invention can be subjected to a hydrogenation reaction or a modification reaction with a polar group-containing compound, if necessary.
  • the hydrogenation reaction method is not particularly limited as long as hydrogen is added to the cyclized polyisoprene of the present invention, and can be carried out by a known method. That is, the cyclized polyisoprene of the present invention may be brought into contact with hydrogen in the presence of a normal hydrogenation catalyst.
  • the hydrogenation catalyst can be used as long as it is generally used for hydrogenation of an olefin compound.
  • a heterogeneous catalyst nickel, palladium, platinum or a metal such as carbon, silica
  • a solid catalyst supported on a carrier such as diatomaceous earth, alumina, and titanium oxide can be used.
  • a catalyst containing a metal belonging to Group 8 of the periodic table can be used.
  • the hydrogenation reaction can be carried out under a hydrogen pressure of 0.01 to 1 OMPa, usually in a range of 0 to 200 ° C, preferably 20 to 150 ° C, depending on the type of the catalyst. it can.
  • the polar group-containing compound used in the modification reaction is not particularly limited as long as the compound can introduce a polar group into the cyclized polyisoprene of the present invention.
  • Examples include ethylenically unsaturated compounds having a polar group such as an acid anhydride group, a hydroxyl group, a hydroxyl group, a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyano group, a silyl group, and a halogen. .
  • the method for introducing the polar group-containing compound into the polyisoprene cyclized product of the present invention is not particularly limited.However, when an ethylenically unsaturated compound is added, a known reaction generally called an ene addition reaction or a graft polymerization reaction is used. .
  • This addition reaction is carried out by reacting the cyclized polyisoprene of the present invention with a polar group-containing compound in the presence of a radical generator as required.
  • the addition reaction may be carried out in a solid phase or in a solution, but is preferably carried out in a solution because of easy control of the reaction.
  • the solvent to be used for example, those similar to the hydrocarbon solvents in the cyclization reaction described above can be mentioned.
  • the reaction temperature and the reaction time may be in accordance with a conventional method.
  • the reaction temperature is usually 30 to 250 ° C, and the reaction time is usually 0.5 to 5 hours.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a polystyrene conversion value.
  • the copolymerization ratio and the different I 1 biometric ratio of the heavy polymer were determined by 1 H-NMR and 13 C-NMR (measured in a room while using a fi-form mouth).
  • the amount of 2-acetylpyridine was 120 parts, the amount of paratoluenesulfo ⁇ 9 was 2 parts, and instead of 500 parts of aniline, 298 parts of 2,3,4,5,6-pentafluoroa-phosphorus was used.
  • the Mw of the obtained heavy books was 2,090,000, Mn was 1,090,000, and 1,2—! ⁇
  • the ratio of / 1, 4 is 67 to 33.
  • Example 9 Polymerization was carried out as in Example 9 to obtain 164 parts of heavy “ ⁇ book”, except that ⁇ j3 ⁇ 4 of 115 parts of isoprene and 49 parts of butadiene was used instead of 123 parts of isoprene.
  • Is 1,180,000, Mn is 845,000, and the 3 ⁇ 4S combined ratio is 60/40 in the ratio of isoprene single ptadene units, and the ratio of 3,4- ⁇ / 1,41 in isoprene units is 46Z54, the ratio of 1,2 —! ⁇ 1,4_ to butadiene units is 78/22.
  • the Mw of the obtained heavy ⁇ is 757,000, Mn is 538,000, and the ratio of isoprene single butadiene units is 25/75. Also, 3, 4- ⁇ ⁇ / ⁇ , 4 i! The ratio of ⁇ is 43/57, and the total ratio of 1,2 — ⁇ / 1,4 to butadiene units is 78/22.
  • the transition metal compound (A) of the present invention is useful as a polymerization catalyst for conjugated diene polymers having various structures.
  • a polymerization catalyst having stereoselectivity can be obtained, and a conjugated diene polymer corresponding to the required characteristics can be obtained by a relatively inexpensive and simple method. be able to.
  • the polyisoprene and the cyclized product thereof of the present invention can have different properties from the conventional ones because they have a novel and unique structure.
  • the polyisoprene cyclized product of the present invention is useful in that it does not easily form a polycyclic structure, and is useful for paints, adhesives, electric and electronic materials, vehicles for printing ink, optical materials, resists, dry film resists, and the like. It is applied to a wide variety of uses.

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Abstract

L'invention concerne des composés métalliques de transition utiles comme catalyseurs hautement actifs permettant la polymérisation de divers diènes conjugués et pouvant être synthétisés à moindres frais au moyen d'un procédé simple. L'invention concerne également des catalyseurs de polymérisation destinés à des diènes conjugués contenant les composés métalliques de transition, un procédé de production de polymères de diènes conjugués, un polyisoprène et des produits de cyclisation de ce dernier, ainsi qu'un procédé de production correspondant. Les composés métalliques de transition sont chacun constitués par un métal de transition du groupe 8 et par un composé hétérocyclique de formule générale (1) se combinant au métal. Dans cette formule, A1 à A4 sont chacun indépendamment un atome de carbone ou d'azote, i, j, k et l valent chacun 1 ou 0 lorsque A1, A2, A3 et A4 sont chacun un atome de carbone ou un atome d'hydrogène, et R1 à R6 sont chacun indépendamment hydrogène, halogéno, un groupe hydrocarbure ou analogue.
PCT/JP2003/010863 2002-08-29 2003-08-27 Composes metalliques de transition, catalyseurs de polymerisation pour dienes conjugues, procede de production de polymeres de dienes conjugues, polyisoprene et produits de cyclisation de ce dernier, et procede de production correspondant WO2004020413A1 (fr)

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US20140011971A1 (en) * 2011-02-08 2014-01-09 President And Fellows Of Harvard College Iron complexes and methods for polymerization
JP2016503088A (ja) * 2012-12-20 2016-02-01 ベルサリス、ソシエタ、ペル、アチオニＶｅｒｓａｌｉｓ Ｓ．Ｐ．Ａ． コバルトオキソ窒化錯体を含む触媒系の存在下での共役ジエン（共）重合体の生成プロセス
IT201800001149A1 (it) * 2018-01-17 2019-07-17 Versalis Spa Procedimento per la preparazione di poliisoprene a struttura prevalentemente alternata cis-1,4-alt-3,4 in presenza di un sistema catalitico comprendente un complesso piridilico di ferro
US10954326B2 (en) * 2016-10-20 2021-03-23 Versalis S.P.A. Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors

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Cited By (14)

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US20140011971A1 (en) * 2011-02-08 2014-01-09 President And Fellows Of Harvard College Iron complexes and methods for polymerization
US9290591B2 (en) * 2011-02-08 2016-03-22 President And Fellows Of Harvard College Iron complexes and methods for polymerization
US20160272742A1 (en) * 2011-02-08 2016-09-22 President And Fellows Of Harvard College Iron complexes and methods for polymerization
JP2016503088A (ja) * 2012-12-20 2016-02-01 ベルサリス、ソシエタ、ペル、アチオニＶｅｒｓａｌｉｓ Ｓ．Ｐ．Ａ． コバルトオキソ窒化錯体を含む触媒系の存在下での共役ジエン（共）重合体の生成プロセス
US10954326B2 (en) * 2016-10-20 2021-03-23 Versalis S.P.A. Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex
CN111587259A (zh) * 2018-01-17 2020-08-25 维尔萨利斯股份公司 用于在包含吡啶基铁络合物的催化体系的存在下制备具有主要为交替的顺式-1,4-交替-3,4结构的聚异戊二烯的方法
WO2019142108A1 (fr) * 2018-01-17 2019-07-25 Versalis S.P.A. Procédé de préparation de polyisoprène présentant une structure cis-1,4-alt-3,4 principalement alternée en présence d'un système catalytique comprenant un complexe pyridyle-fer
IT201800001149A1 (it) * 2018-01-17 2019-07-17 Versalis Spa Procedimento per la preparazione di poliisoprene a struttura prevalentemente alternata cis-1,4-alt-3,4 in presenza di un sistema catalitico comprendente un complesso piridilico di ferro
JP2021511404A (ja) * 2018-01-17 2021-05-06 ベルサリス エッセ．ピー．アー． ピリジル鉄錯体を含む触媒系の存在下にて、主に交互シス−１，４−ａｌｔ−３，４構造を有するポリイソプレンの製造方法
CN111587259B (zh) * 2018-01-17 2023-07-11 维尔萨利斯股份公司 用于制备具有主要为交替的顺式-1,4-交替-3,4结构的聚异戊二烯的方法
JP7317840B2 (ja) 2018-01-17 2023-07-31 ベルサリス エッセ．ピー．アー． ピリジル鉄錯体を含む触媒系の存在下にて、主に交互シス－１，４－ａｌｔ－３，４構造を有するポリイソプレンの製造方法
US11746167B2 (en) 2018-01-17 2023-09-05 Versalis S.P.A. Process for the preparation of polyisoprene with a mainly alternating cis-1,4- alt-3,4 structure in the presence of a catalytic system comprising a pyridyl iron complex
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors

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