Classifications

• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • 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
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

• the present invention relates to a method for producing a cyclic olefin-based copolymer comprising ethylene and / or a C 3-20 monoolefin and a cyclic olefinic compound. More specifically, the present invention relates to a method for efficiently producing a cyclic olefin-based copolymer using a complex metal catalyst system that is easy to synthesize and has high polymerization activity and high copolymerizability.
• a copolymer of ethylene and / or ⁇ -olefin having 3 to 20 carbon atoms and a cyclic olefin compound is excellent in transparency, chemical resistance, water resistance, etc., and in recent years, the cyclic olefin content is increased.
• Industrial applications are actively carried out as optical materials with controlled heat resistance.
• various production methods have been proposed such as G) using coordination polymerization and (i) a combination of ring-opening metathesis and hydrogenation reaction.
• a so-called bridged metamouth catalyst comprising a transition metal complex having a bimolecular cyclopentagenyl skeleton crosslinked with a carbon atom or a carbon atom and an aluminoxane compound is used.
• the method used see, for example, Patent Documents 1 to 4
• a method for obtaining a copolymer with an olefinic compound has been proposed.
• the polymerization activity and the amount of cyclic olefin compound incorporated in the copolymer (copolymerizability) are not sufficient.
• Patent Document 7 a polymerization method using a non-metacene synthetic compound (for example, see Patent Document 7) has also been proposed.
• This is a complex metal catalyst system consisting of a transition metal compound having one molecule of an anilide group having two or more substituents and one molecule of an aryloxy group having two or more substituents. It is a ring-opening metathesis reaction and is not a method capable of copolymerizing ethylene and / or a 1-year-old olefin having 3 to 20 carbon atoms and a cyclic olefin compound. Therefore, development of a method for producing a cyclic olefin copolymer that is easy to synthesize and satisfies both high polymerization activity and high copolymerizability is desired.
• Patent Document 1 JP-A-3-45612
• Patent Document 2 JP-A-6-271626
• Patent Document 3 JP-A-6-271627
• Patent Document 4 Japanese Unexamined Patent Publication No. 2000-26518
• Patent Literature 5 Japanese Patent Publication No. 11-504973
• Patent Document 6 Japanese Unexamined Patent Publication No. 2000-302811
• Patent Document 7 JP 2002-53647 A
• Non-patent literature l Macromolecules, 36, 3797 (2003)
• the present invention can be synthesized more easily industrially, and can be synthesized with ethylene and Z or a carbon number of 3 to 20 using a complex metal catalyst system having high polymerization activity and high copolymerizability.
• the object is to find a method for producing a cyclic olefin-based copolymer comprising an olefin and a cyclic olefin compound. Means for solving the problem
• one easy-to-synthesize ligand molecule containing a cyclopentadienyl skeleton and one anionic ligand molecule having at least one specific skeleton are grouped into metals of Group 4 of the periodic table.
• a complex metal catalyst system composed of a coordinated transition metal compound and an activator has high polymerization activity for copolymerization of ethylene and / or ⁇ -olefin having 3 to 20 carbon atoms and a cyclic olefin compound, and This is based on the surprising fact that it has excellent copolymerizability.
• the present invention is a method for producing a cyclic olefin-based copolymer according to the following [1] to [9].
• a polymerization catalyst comprising a transition metal compound ( ⁇ ) represented by the following general formula (1) and one or more activators ( ⁇ ) selected from organoaluminum compounds or organoboron compounds
• ⁇ transition metal compound represented by the following general formula (1)
• activators selected from organoaluminum compounds or organoboron compounds
• a process for producing a cyclic olefin-based copolymer comprising copolymerizing ethylene and / or a monoolefin having 3 to 20 carbon atoms and at least one cyclic olefin compound.
• ⁇ represents a transition metal of Group 4 of the periodic table.
• L represents a monovalent anionic ligand in which a group 15 element of the periodic table is a coordination atom.
• X is hydrogen , Halogen or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an aryloxy group, or an aralkyl group, L or X may be the same or different from each other; Represents an integer of 1 to 3.!
• ⁇ ⁇ May be the same or different, each of hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, or an aryloxy group.
• Y represents a group 15 element of the periodic table
• Z represents one element selected from group 14 or 15 or 16 of the periodic table.
• R represents hydrogen, carbon number 1 to 20]
• Each represents an alkyl group, an alkoxy group, an amide group, an arylene group, an aralkyl group, a silyl group, an alkynoleamide group, an alkylsilyl group, an arylamide group, a silylamide group, a phosphinoamide group, or a phosphide group, each independently represented by R 1.
• n may represent an integer of 1 to 3 depending on the valence of Z.
• R may be bonded to each other to form a ring. It may be bonded to the pentagenyl group.
• the cyclic olefin compound is a compound in which a bond angle between a carbon atom forming a double bond and an adjacent carbon atom is smaller than 120 ° or larger than 120 °.
• R 6 to 7 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with halogen, a substituent containing oxygen, or A substituent containing a nitrogen atom, R 14 to R 17 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; R 14 and R 15 may form an alkylidene group.
• n represents an integer of 0-2.
• M represents a transition metal of Group 4 of the periodic table.
• L represents a monovalent anionic ligand in which a group 15 element in the periodic table is a coordination atom.
• X represents hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an aryloxy group or an aralkyl group. L or X may be the same or different from each other.
• m represents an integer of:! ⁇ 3. !
• ⁇ ⁇ May be the same or different from each other, and may be hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, or an aryloxy group, and any two or three may be condensed to form a ring. May be.
• the ring has aromaticity with a conjugated double bond Including things.
• L is a monovalent anionic ligand represented by the general formula (2).
• Y represents a group 15 atom in the periodic table
• Z represents a group 14 or group 15 atom in the periodic table.
• R may independently be the same or different hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an anolenoquinole group. It represents an amide group, an alkylsilyl group, a arylenoamide group, a silinoreamide group, a phosphinoamide group, or a phosphide group.
• n is an integer of 1 to 3 depending on the valence of Z.
• R may be bonded to each other to form a ring, or R may be bonded to a cyclopentagenyl group.
• alkyl group, alkoxy group, aryleno group, aryloxy group, aralkyl group, alkylamide group, alkylsilyl group, alkyl of arylamide group, aryl, and aryloxy moieties include methinole, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec butyl, n pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2 —Methylpentyl, 3-methylpentyl, 1,1 dimethylbutyl, 2,2 dimethylbutyl, 3,3 dimethylbutyl, 1,2 dimethylbutyl, 1,3-dimethylbutyl, 1,1 ethyl
• R constituting the anionic ligand L a t-butyl group is particularly preferable among alkyl groups.
• a high molecular weight cyclic olefin-based copolymer with high catalytic activity can be synthesized.
• C1 is particularly preferred. These may be used alone or in combination.
• Cp represents a cyclopentadenyl group
• Cp * represents a 7] 5 -pentamethylcyclopentadienyl group
• the organoaluminum oxy compounds that can be used in the present invention include the organoaluminum oxy compounds represented by the following general formulas (4), (5), (6) and (7). Of these, at least one compound is listed.
• R 1 to! ⁇ May be the same or different from each other.
• the hydrocarbon group has! To 8 carbon atoms, and n represents an integer from 1 to 50.
• R 1 to R 4 may be the same or different from each other:! -8 hydrocarbon group, n represents an integer of 1-50]
• R represents a hydrocarbon group having 1 to 8 carbon atoms, and ⁇ represents an integer of 1 to 50.
• organoaluminum compounds include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutyraluminoxane and the like.
• methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane can be suitably used. Two or more of these may be used in combination.
• organoaluminum compounds may contain organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.
• the organoboron compound that can be used in the present invention includes at least one of the organoboron compounds represented by the following general formula (8) or (9).
• R y to R d may be the same or different from each other.
• hydrocarbon groups represented by the general formulas (8) and (9) include phenyl, benzyl, p-trinole, m-trinole, xylinole, mesitylinole, 2,6 dimethinolephenol, 2, 4, 6-trimethylphenyl, 2, 6 dimethoxyphenyl, 2, 4, 6 trimethoxyphenyl, 2, 6 disopropyl phenyl, 2, 4, 6 triisopropyl phenyl, naphthyl, o isopropoxy phenyl, pentafluorophenyl, pentafluorobenzyl, Examples thereof include tetrafluorophenyl and tetrafluorotolyl.
• organoboron compounds include trimethylammonium tetrakis (pentafluorophenylolate) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and triphenylphosphonium tetrakis (pentafluoro).
• Pheninole) borate triphenylcarbtetrakis (pentafluorophenyl) borate and the like. Two or more of these may be used in combination. Most preferred is triphenylcarbium tetrakis (pentafluorophenyl) borate.
• the catalyst suitable for use in the present invention is one or more activities selected from (A) transition metal compounds and (B) alkylaluminoxy compounds or organoboron compounds. Produced by combining the agents in any order and in any suitable manner
• the catalyst may be prepared in advance by mixing it in a suitable solvent under an inert gas atmosphere such as nitrogen or argon, or (A) and (B) each of the components separately coexisting with monomers. It may be prepared in the reactor by driving into the reactor.
• Suitable solvents for the catalyst preparation include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as tololeene, benzene, and ethylbenzene. In addition, it is preferable to remove moisture and the like from these solvents in the pretreatment.
• the optimum catalyst preparation temperature is 20 ° C to 150 ° C.
• the copolymerization method of the present invention is carried out by any method of Balta, solution, and slurry under the conditions of reduced pressure, atmospheric pressure, and increased pressure in the presence of monomers and a complex metal catalyst system. Is possible.
• the temperature range suitable for carrying out copolymerization is -30 ° C to 260 ° C, preferably 0 ° C to 200 ° C.
• the copolymerization may be carried out in an inert gas atmosphere such as nitrogen or argon, or may be carried out in an ethylene atmosphere, or ethylene and / or an ⁇ - having 3 to 20 carbon atoms. It does not work even in a mixed atmosphere of olefins and the above inert gas.
• the catalyst component may be used by being supported on a suitable carrier such as alumina, magnesium chloride, or silica.
• a solvent can be used in the copolymerization. Suitable solvents for copolymerization include hydrocarbon solvents such as hexane, cyclohexane, and other hydrocarbons, and aromatic solvents such as tolenene, benzene, and ethylbenzene.
• Suitable amount of catalyst for copolymerization is [(Polymer weight) kg] / [Catalyst ( ⁇ ) component lmol]
• a polar solvent which is a poor solvent such as alcohol mixed with acetone or an acid or an alkali is added to the copolymer solution, and the copolymer is precipitated and recovered.
• a method for example, a polar solvent which is a poor solvent such as alcohol mixed with acetone or an acid or an alkali is added to the copolymer solution, and the copolymer is precipitated and recovered.
• examples thereof include a method, a method in which the reaction solution is stirred into hot water and then distilled and collected together with the solvent, or a method in which the solvent is distilled off by directly heating the reaction solution.
• the metal atom which is the coordination center of the transition metal compound (A) is cationized by an organoaluminum compound or an organoboron compound, and coordinated with a single olefin molecule or a cyclic olefin molecule molecular force. Further, another monoolefin molecule or cyclic olefin molecule approaches the metal force thione, and sequentially bonds between the previously coordinated monoolefin molecule or cyclic olefin molecule and the metal cation to form a polymer chain.
• the copolymer of a-olefin and cyclic olefin is composed of a copolymer (alternate copolymer) in which cyclic olefin molecules and ⁇ - olefin molecules are alternately and regularly bonded, and a It can be considered to be a copolymer (random copolymer) in which one or more consecutive olefin molecules or cyclic olefin molecules have a molecular force. Comparing the two, the transparency of the polymer is suitable for optical materials such as plastic lenses and CDs (compact discs), where the random copolymer is higher.
• the cyclic olefins are sterically bulky molecules such as norbornene.
• norbornene since the previously coordinated norbornene molecule becomes an obstacle and the new norbornene molecule cannot approach the metal cation, an alternating copolymer of norbornene molecule and ⁇ -olefin molecule can be obtained, but the content of norbornene is high. It was difficult to synthesize a random copolymer.
• the content of cyclic olefin in the copolymer is determined by the steric and electronic environment around the metal cation based on the type of ligand L constituting the transition metal compound ( ⁇ ).
• Examples of monoolefin having 3 to 20 carbon atoms that can be used in the present invention include propylene, 1-butene, 1-hexene, 4_methyl_1_pentene, 1_heptene, 1-octene, 1 -I can give decene.
• examples of the cyclic olefin compounds that can be used in the present invention include compounds represented by the following general formula (3), cyclopentene, cyclohexene, cycloheptene, and cyclootaten.
• R 6 to R 17 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with halogen, or a substituent containing oxygen, which may be the same or different from each other. Or a substituent containing a nitrogen atom, R 14 to R 17 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond R 14 and R 15 may form an alkylidene group, and n represents an integer of 0 to 2.
• halogen atom of the general formula (3) and the hydrocarbon group which may be substituted with halogen include, for example, halogen groups such as fluorine, chlorine, bromine and iodine, chloromethylol group, bromomethyl group, chloromethyl group, and chloromethyl group.
• halogen groups such as fluorine, chlorine, bromine and iodine
• chloromethylol group bromomethyl group
• chloromethyl group chloromethyl group
• chloromethyl group chloromethyl group
• chloromethyl group chloromethyl group
• chloromethyl group bromomethyl group
• chloromethyl group chloromethyl group
• the oxygen-containing substituent of the general formula (3) specifically includes an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a methoxycarbon group.
• an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a methoxycarbon group.
• C 1 -C 20 alkoxy carbonyl group such as ethoxycarbonyl group.
• substituent containing a nitrogen atom of the general formula (3) include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a jetylamino group, and a cyano group. be able to.
• cyclic olefin compound represented by the general formula (3) include bicyclo [2.2. 1] hept-2-ene (hereinafter referred to as norbornene), 5_methylnorbornene, 5-ethylnorbornene, 5_propylnorbornene, 5, 6-dimethylnorbornene, 1-methylnorenolevonolenene, 7_ Methylnorbornene, 5, 5, 6_trimethylnorbornene, 5_phenylnorbornene, 5_benzylnorbornene, 5-ethylidenenorbornene, 5-vininorenorebonorenene, 5_black-norbornene, 5_cyanorbornene 5_Fluoronorbornene, 5,5-Dichloronorbornene, 5,5,6_Trifluoronorbornene, 5-Methoxynorbornene, 5-Dimethylaminonorbornene, 5,
• the cyclic olefin compound used in the present invention is preferably a compound having a certain degree of double bond reactivity.
• the carbon atoms at both ends of the double bond form sp 2 hybrid orbitals at the ⁇ bond and ⁇ bond, so the atoms bonded to this exist on the same plane and are adjacent to the carbon atom forming the double bond.
• Bond angle with carbon atom (hereinafter simply referred to as bond angle) is 120 °.
• the bond angle is about 120 °, which matches the sp 2 hybrid orbital, so the ring is not distorted.
• the bond angle is less than 120 °
• the bond angle is greater than 120 °, resulting in a distorted ring.
• a 6-membered ring (norbornene unit) containing a double bond is greatly strained due to the crosslinked structure, and the bond angle is greatly deviated from 120 °. .
• cyclohexene having no ring distortion can be used as the cyclic olefin compound, but since cyclohexene has a low double bond reactivity, a high content copolymer is synthesized. It is difficult.
• the cyclic olefin compounds other than cyclohexene described above have double bond reactivity because the bond angle is larger than 120 ° or smaller than 120 ° due to the presence of strain in the ring.
• a copolymer having a high cyclic olefin content can be synthesized efficiently.
• the repeating unit derived from the olefin-based monomer and the repeating unit derived from the cyclic olefin-based monomer may each be composed of two or more kinds of component forces. Ternary or quaternary copolymers can also be produced.
• an aromatic vinyl compound such as styrene can be copolymerized as a copolymerized monomer, if necessary, in addition to the above monomer.
• the composition in the cyclic olefin-based copolymer is cyclic with respect to ethylene and Z or 1 to 99 mol% of olefins having 3 to 20 carbon atoms.
• Olefins can be copolymerized in the range of 99 to lmol%.
• the amount of cyclic olefins is 90 to 25 mol% with respect to / o .
• the present invention will be specifically described below with reference to Examples and Test Examples, but the present invention is not limited thereto.
• the complex metal catalyst was prepared with reference to J. Am. Chem. Soc., 122, 5499 (2000) and Macromolecules, 31, 7588 (1998).
• the polymerization activity was determined from the amount of polymer obtained after completion of the polymerization.
• the norbornene content in the polymer is Macromolecules, 33, 8931 (2000)
• the cyclopentene content is Macromolecules, 35, 9999 (2002)
• the cyclohexene content is J. Am. Chem. Soc., 127, 4582. (2005) according to 13 C-NMR spectrum. NMR measurement is d-benzene
• the glass transition temperature (Tg) of the polymer was measured using a differential scanning calorimeter (DSC) at a heating rate of 20 ° C / min in a nitrogen atmosphere.
• the molecular weight of the polymer (Mn, Mw, and Mw / Mn) was detected by RI using o-dichlorobenzene as a measurement solvent at 140 ° C by the GPC method, and calculated by polystyrene conversion.
• the resulting reaction solution was slowly warmed to room temperature with stirring and stirred overnight.
• the reaction solution was filtered, concentrated, and then recrystallized from hexane at 30 ° C to obtain the target complex in a yield of 60%.
• Examples 5 to 8 were added in a predetermined amount to synthesize an ethylene norbornene copolymer, which was designated as Examples 5 to 8, respectively.
• the synthesis of the ethylene norbornene copolymer was carried out in the same manner as in Examples 1 and 2 except that 50 ml of toluene solution (concentration: 0.2 mmolZml or 1. OmmolZml) of norbornene subjected to dehydration and deoxygenation treatment was used.
• Examples 5 to 8 were prepared by adding a predetermined amount of InTi (2,6 1 ipr PhO) Cl (hereinafter referred to as metal complex-4) synthesized in the same manner as in Reference Example 2 except that a denenyl group was used.
• metal complex-4 InTi (2,6 1 ipr PhO) Cl
• a len-norbornene copolymer was synthesized as Comparative Examples 2 to 5, respectively.
• Examples 4 to 7 were performed by adding a predetermined amount of Si (Me Cp) (t-BuN) TiCl (hereinafter referred to as metal complex_6).
• the ethylene-norbornene copolymer was synthesized in the same manner as in Comparative Examples 6 to 9, respectively.
• catalyst activity, polymer The molecular weight and the norbornene content in the polymer were determined and are shown in Table 1 together with the amount of catalyst added and the norbornene concentration.
• Example 6 showed about twice the activity of Example 5 in which the norbornene concentration was 0.2 mmol / ml.
• ethylene and / or by using a complex metal catalyst system having high polymerization activity and copolymerizability that does not depend on the concentration of cyclic olefin ethylene and / or by using a complex metal catalyst system having high polymerization activity and copolymerizability that does not depend on the concentration of cyclic olefin.
• a new cyclic olefin-based copolymer with a high content of cyclic olefin compounds and excellent heat stability is produced from ⁇ -olefins with 3 to 20 carbon atoms and at least one cyclic olefin compound. Efficient manufacturing.

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