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
  • 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
  • C08F4/645—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
• • 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
  • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• the present invention relates to a process for performing solution polymerization of an olefin, wherein the polymerization is carried out in the presence of a catalyst containing a metallocene compound with a specific structure in a temperature range from 120 to 300° C.
• a process using a Ziegler-type titanium-based catalyst composed of a titanium compound and an organo-aluminum compound is widely known. More recently, since the publication of a process of olefin polymerization in the presence of a metallocene-based catalyst which is composed of a transition metal compound such as zirconocene and an organo-aluminum oxy-compound (hereinafter which may also be referred to as “aluminoxane” described below) as a catalyst capable of producing olefin polymers with high polymerization activity [for example, Adv. Organomet. Chem.
• the present invention was completed in order to solve the problems described above, and an object of the invention is to provide a process for producing a polymer having a high molecular weight with high polymerization activity that was so far unattainable, and when the polymer is a copolymer, it is to provide a process for producing a high molecular weight olefin polymer having a large comonomer content, a narrow composition distribution, and a narrow molecular weight distribution.
• the present invention is a process for producing an olefin polymer characterized by carrying out solution polymerization of ethylene and one or more kinds of monomers selected from ⁇ -olefins at the temperature ranging from 120 to 300° C., in the presence of a catalyst for olefin polymerization composed of:
• R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , and R 12 are each selected from hydrogen atom, hydrocarbon group, and silicon-containing group, and may be identical or different, or neighboring groups may be combined to form a ring structure;
• R 6 and R 11 are each identical atoms or identical groups selected from hydrogen, hydrocarbon group, and silicon-containing group, and may be combined to form a ring structure;
• R 7 and R 10 are each identical atoms or identical groups selected from hydrogen, hydrocarbon group, and silicon-containing group, and may be combined to form a ring structure;
• R 6 and R 7 may be combined to form a ring structure;
• R 10 and R 11 may be combined to form a ring structure;
• R 6 , R 7 , R 10 and R 11 are not simultaneously hydrogen atoms;
• R 13 and R 14 are each aryl group, and may be identical or different;
• M represents Ti, Zr or Hf, and is preferably Zr or
• the present invention provides a process, in the presence of a catalyst for olefin polymerization composed of:
• a bridged metallocene compound of the present invention an olefin polymerization catalyst containing the bridged metallocene compound, a method for carrying out high temperature solution polymerization in the presence of the olefin polymerization catalyst, and characteristics of a polymer obtained by the high temperature solution polymerization will be explained successively in terms of the best mode of carrying out the invention.
• one ligand is cyclopentadienyl group, and the other ligand is fluorenyl group having substituents (hereinafter which may also be referred to as “substituted fluorenyl group”).
• the two ligands are linked by a covalent-bond bridge which contains a carbon atom or a silicon atom having an aryl group (hereinafter which may also be referred to as “aryl group-containing covalent-bond bridge”).
• the transition metal (M) that composes the metallocene compound is titanium, zirconium, or hafnium.
• Cyclopentadienyl group may or may not be substituted.
• Cyclopentadienyl group which may not be substituted refers to the cyclopentadienyl group in which R 1 , R 2 , R 3 , and R 4 that belong to the cyclopentadienyl group part of the general formula [I] mentioned above are all hydrogen atoms; or the cyclopentadienyl group of which one or more among R 1 , R 2 , R 3 , and R 4 is substituted with hydrocarbon group (f1), preferably hydrocarbon group having the total number of carbon atoms of 1 to 20 (f1′), or with silicon-containing group (f2), or preferably silicon-containing group having the total number of carbon atoms of 1 to 20 (f2′).
• R 1 , R 2 , R 3 , and R 4 substituents may be each identical or different.
• the hydrocarbon groups having the total number of carbon atoms of 1 to 20 refer to alkyl, alkenyl, alkynyl, and aryl groups that are composed of carbon and hydrogen only. Among them, those in which neighboring hydrogen atoms are both substituted to form alicyclic group or aromatic group are included.
• the hydrocarbon groups having the total number of carbon atoms of 1 to 20 include, in addition to alkyl, alkenyl, alkynyl, and aryl groups that are composed of carbon and hydrogen only, heteroatom-containing hydrocarbon groups in which a part of hydrogen atoms directly bonded to these carbon atoms are substituted with halogen atom, oxygen-containing group, nitrogen-containing group, or silicon-containing group, or groups in which neighboring hydrogen atoms form alicyclic group.
• group (f1′) include straight-chain hydrocarbon groups such as methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like; branched-chain hydrocarbon groups such as isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group and the like; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycl
• the silicon-containing groups (f2) refer, for example, to groups in which the ring-carbon of cyclopentadienyl group is directly bonded with a covalent bond to silicon atom, and specifically to alkylsilyl groups and arylsilyl groups.
• Examples of the silicon-containing groups having the total number of carbon atoms of 1 to 20 (f2′) include trimethylsilyl group, triphenylsilyl group and the like.
• R 6 and R 11 in the general formula [I] mentioned above are each identical atoms or identical groups selected from hydrogen, hydrocarbon group (f1), or silicon-containing group (f2), and may be combined to form a ring;
• R 7 and R 10 are each identical atoms or identical groups selected from hydrogen, hydrocarbon group (f1), or silicon-containing group (f2), and may be combined to form a ring;
• R 6 and R 7 may be combined to form a ring structure;
• R 10 and R 11 may be combined to form a ring structure; and
• R 6 , R 7 , R 10 , and R 11 are not simultaneously hydrogen atoms.
• R 6 and R 11 are hydrogen atoms; it is preferable that none of R 6 , R 7 , R 10 and R 11 are hydrogen atoms; and it is particularly preferable that R 6 and R 11 are identical group selected from hydrocarbon groups and silicon-containing groups, and that R 7 and R 10 are an identical group selected from hydrocarbon groups and silicon-containing group.
• the preferable hydrocarbon groups (f1) are the hydrocarbon groups (f1′) mentioned above, having the total number of carbon atoms of 1 to 20, and the preferable examples of silicon-containing groups (f2) are the silicon-containing groups (f2′), mentioned above, having the total number of carbon atoms of 1 to 20.
• the main chain part of the bond linking cyclopentadienyl group and fluorenyl group is a divalent covalent-bond bridge that contains a carbon atom or a silicon atom.
• the important point of the high temperature polymerization of the present invention is that the bridging atom Y of the covalent-bond bridge part has aryl groups [R 13 and R 14 ] that may be each identical or different. It was found for the first time that, when aryl groups that may be each identical or different are introduced into the bridging atom (Y), a high molecular olefin polymer is produced efficiently in the high temperature polymerization of the present invention, which was not achieved in the conventional solution polymerization.
• aryl groups include phenyl group, naphthyl group, anthracenyl group, and groups in which one or more of the aromatic hydrogen atoms (sp 2 type hydrogen) is substituted with substituents.
• substituents include the hydrocarbon groups having the total number of carbon atoms of 1 to 20 (f1′) mentioned above, the silicon-containing groups having the total number of carbon atoms of 1 to 20 (f2′) mentioned above, and halogen atoms.
• More preferable aryl groups include phenyl group, tolyl group, t-butylphenyl group, dimethylphenyl group, biphenyl group, cyclohexylphenyl group, (trifluoromethyl)phenyl group, bis(trifluoromethyl)phenyl group, and those having halogen atoms introduced in the substituents such as chlorophenyl group, dichlorophenyl group and the like. Substituted phenyl groups having these substituents at meta- and/or para-positions are particularly favorable. Further, in the bridged metallocene compounds of the present invention, those having identical R 13 and R 14 are used preferably because of easy production.
• Y is silicon atom
• component (B) that is a component composing the olefin polymerization catalyst of the present invention (b-1) an organo-aluminum oxy-compound and/or (b-3) an organo-aluminum compound are used, but (b-2) a compound which forms an ion pair by reacting with the bridged metallocene compound (A) mentioned above is not used.
• Q is selected in an identical or different combination from halogen; hydrocarbon group having 1 to 10 carbon atoms; neutral, conjugated or non-conjugated diene having 10 or less carbon atoms; anionic ligand; and neutral ligand capable of coordinating with a lone electron pair.
• halogen are fluorine, chlorine, bromine, and iodine
• hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, and the like.
• neutral, conjugated, or non-conjugated diene having 10 or less carbon atoms include s-cis- or s-trans- ⁇ 4 -1,3-butadiene, s-cis- or s-trans- ⁇ 4 -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans- ⁇ 4 -3-methyl-1,3-pentadiene, s-cis- or s-trans- ⁇ 4 -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans- ⁇ 4 -2,4-hexadiene, s-cis- or s-trans- ⁇ 4 -1,3-pentadiene, s-cis- or s-trans- ⁇ 4 -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans- ⁇ 4 -1,4-bis(trimethylsilyl)-1
• anionic ligand examples include alkoxy group such as methoxy, tert-butoxy, phenoxy, and the like; carboxylate group such as acetate, benzoate and the like; and sulfonate group such as mesylate, tosylate and the like.
• neutral ligand capable of coordinating with a lone electron pair include organo-phosphorous compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine and the like; or ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like.
• j is an integer of 1 to 4, and when j is 2 or more, Q may be each identical or different.
• octamethyloctahydrodibenzofluorene refers to compounds having a structure represented by formula [II]
• octamethyltetrahydrodicyclopentafluorene refers to compounds having a structure represented by formula [III]
• dibenzofluorene refers to compounds having a structure represented by formula [IV]
• 1,1′,3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to compounds having a structure represented by formula [V]
• 1,3,3′,6,6′,8-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to compounds having a structure represented by formula [VI].
• the examples are the following: diphenylmethylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride, diphenylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride, diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride, diphenylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconiumdichloride, diphenylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconiumdichloride, diphenylmethylene(cyclopentadienyl)(1,1′,3,6,8,8′-hex
• the bridged metallocene compounds (A) of the present invention can be produced by a method known in the art, and the method of production is not specifically limited.
• Official Gazette WO01/27174 and Official Gazette WO04/029062 by the present applicant can be cited.
• the catalyst components are composed of the bridged metallocene compound (A) represented by the general formula [I] mentioned above, and at least one kind of the compounds (B) selected from (b-1) an organoaluminum oxy-compound, (b-2) a compound capable of forming an ion pair in a reaction with the bridged metallocene compound (A) mentioned above, and (b-3) an organoaluminum compound.
• the components of (B) among the following [c1] to [c4] are used preferably:
• R is hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.
• the organoaluminum oxy-compound with methyl group as R in general formula [VII] or [VIII] may also be referred to as “methylaluminoxane” in the following.
• Methylaluminoxane is an organoaluminum oxy-compound that has been used widely in the polyolefin industry sector due to easy availabilities and high polymerization activity. However, because it is difficult to be dissolved in a saturated hydrocarbon, it had to be used as a solution of aromatic hydrocarbons such as toluene, benzene and the like that cause large environmental impact. Under these circumstances, compounds analogous to methylaluminoxane have been developed. As an example of such analogous compounds, modified methylaluminoxane represented by general formula [IX] described below can be cited.
• the organoaluminum oxy-compound (b-1) in the method of high temperature polymerization of the present invention includes also such modified methylaluminoxane.
• R is hydrocarbon group having 2 to 20 carbon atoms; and m and n are integers of 2 or more.
• the modified methylaluminoxane represented by general formula [IX] mentioned above can be prepared by using trimethylaluminum and alkylaluminum except trimethylaluminum (of which manufacturing methods are disclosed for example in U.S. Pat. No. 4,960,878, U.S. Pat. No. 5,041,584, etc.).
• Modified methylaluminoxane products in which R is isobutyl group prepared by using trimethylaluminum and isobutylaluminum are commercially available with trade names such as MMAO, TMAO from manufacturers such as Tosoh Finechem Corporation (for example, Tosoh Research & Technology Review, Vol. 47, 55 (2003)).
• organoaluminum oxy-compounds that are insoluble in benzene exemplified in Japanese Patent Publication No. H02-78687 can also be employed.
• organoaluminum oxy-compounds used in the present invention organoaluminum oxy-compounds containing boron represented by general formula [X] mentioned below can be cited.
• R c represents hydrocarbon group having 1 to 10 carbon atoms.
• R d may be each identical or different, and represents hydrogen atom, halogen atom, or hydrocarbon group having 1 to carbon atoms.
• organoaluminum oxy-compounds described above (b-1) the presence of a few organoaluminum compounds is not problematic.
• ionic compound As the compounds that form an ion pair in a reaction with the bridged metallocene compound (A) (b-2) (hereinafter which may be referred to as “ionic compound”), Lewis acids, ionic compounds, borane compounds, etc. that are described in, for example, Japanese Patent Publication No. H-01-501950, Japanese Patent Publication No. H-01-502036, Japanese Patent Publication No. H-03-179005, Japanese Patent Publication No. H-03-179006, Japanese Patent Publication No. H-03-207703, Japanese Patent Publication No. H-03-207704, U.S. Pat. No. 5,321,106, etc. can be cited. Further, heteropoly-compounds and isopoly-compounds can also be cited.
• the ionic compounds that are employed preferably in the present invention are the compounds represented by general formula [XI] mentioned below.
• examples of R e+ include H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation containing transition metal element, and the like.
• Groups R f to R i may be each identical or different, and refer to organic group, preferably aryl group.
• Specific examples of the carbenium cation mentioned above include triply substituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, tris(dimethylphenyl)carbenium cation, and the like.
• ammonium cations mentioned above include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, triisobutylammonium cation, and the like; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, N,N-2,4,6-pentamethylanilinium cation, and the like; and dialkylammonium cations such as diisopropylammonium cation, dicyclohexylammonium cation, and the like.
• trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)am
• phosphonium cations examples include triarylphosphonium cations etc. such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, tris(dimethylphenyl)phosphonium cation, and the like.
• carbenium cation, ammonium cation, and the like are preferable as R e+ ; and triphenylcarbenium cation, N,N-dimethylanilinium cation, and N,N-diethylanilinium cation are particularly preferable as R e+ .
• carbenium salts include triphenylcarbeniumtetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, and the like.
• ammonium salts trialkyl-substituted ammonium salt, N,N-dialkylanilinium salt, dialkylammonium, and the like are cited.
• trialkyl-substituted ammonium salts include triethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, trimethylammoniumtetrakis(p-tolyl)borate, trimethylammoniumtetrakis(o-tolyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium
• N,N-dialkylanilinium salts include N,N-dimethylaniliniumtetraphenylborate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylaniliniumtetraphenylborate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-2,4,6-pentamethylaniliniumtetraphenylborate, N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate, and the like.
• dialkylammonium salts include di(1-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetraphenylborate, and the like.
• ionic compounds that have been disclosed by the present applicant (Japanese Patent Publication No. 2004-51676) can also be used without limitation.
• the ionic compounds (b-2) mentioned above can be used in a combination of 2 or more kinds.
• organoaluminum compounds (b-3) that compose the olefin polymerization catalyst for example, organoaluminum compounds represented by general formula [XII] mentioned below, alkyl complex compounds containing Group 1 metal element and aluminum represented by general formula [XIII], and the like are cited.
• R a m Al(OR b ) n H p X q [XII] (In the formula, R a and R b may be each identical or different, and refer to hydrocarbon group having 1 to 15 carbon atoms, preferably having 1 to 4 carbon atoms.
• X refers to halogen atom
• the compounds represented by general formula [XII] refer to organoaluminum compounds.
• Such compounds include tri(n-alkyl)aluminum such as trimethylaluminum, triethylaluminum, tri(n-butyl)aluminum, trihexylaluminum, trioctylaluminum, and the like; tri(branched chain-alkyl)aluminum such as triisopropylaluminum, triisobutylaluminum, tri(sec-butyl)aluminum, tri(tert-butyl)aluminum, tri(2-methylbutyl)aluminum, tri(3-methylexyl)aluminum, tri(2-ethylexyl)aluminum, and the like; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, and the like; triarylaluminum such as triphenylaluminum, tritolylaluminum, and the like; dialkylaluminumhalide
• alkylaluminumalkoxide such as isobutylaluminummethoxide, isobutylaluminumethoxide, and the like; dialkylaluminumalkoxide such as dimethylaluminummethoxide, diethylaluminumethoxide, dibutylaluminumbutoxide, and the like; alkylaluminumsesquialkoxide such as ethylaluminumsesquiethoxide, butylaluminumsesquibutoxide, and the like; partially alkoxylated alkylaluminum having mean compositions represented by general formula R a 2.5 Al(OR b ) 0.5 and the like; alkylaluminumaryloxide such as diethylaluminumphenoxide,
• M 2 AlR a 4 [XIII] (In the formula, N represents Li, Na, or K, and R a represents hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4.)
• the compounds represented by general formula [XIII] refer to complex alkyl compounds containing Group 1 metal element of the periodic table and aluminum. Such compounds are exemplified by LiAl(C 2 H 5 ) 4 , LiAl(C 7 H 15 ) 4 , and the like.
• organoaluminum compounds in which 2 or more aluminum compounds are bonded via nitrogen atom can also be cited.
• organoaluminum compounds in which 2 or more aluminum compounds are bonded via nitrogen atom can be cited.
• Specific examples of such compounds include (C 2 H 5 ) 2 AlN(C 2 H 5 )Al(C 2 H 5 ) 2 , and the like.
• organoaluminum compound (b-3) trimethylaluminum and triisobutylaluminum are used preferably.
• At least 2 of the catalyst components may be in contact with each other in advance.
• component (A) is usually used in the amount of 10 ⁇ 9 to 10 ⁇ 1 mole, preferably 10 ⁇ 8 to 10 ⁇ 2 mole with respect to the reaction volume of 1 liter.
• Component (b-1) is used in the amount at which the molar ratio of component (b-1) to the total transition metal (M) in component (A), that is, [(b-1)/M], is usually in the range between 0.01 and 5,000, preferably between 0.05 and 2,000.
• Component (b-2) is used in the amount at which the molar ratio of aluminum atoms in component (b-2) to the total transition metal (M) in component (A), that is, [(b-2)/M], is usually in the range between 10 and 5,000, preferably in the range between 20 and 2,000.
• Component (b-3) is used in the amount at which the molar ratio of component (b-3) to the transition metal (M) in component (A), that is, [(b-3)/M], is usually in the range between 1 and 10,000, preferably in the range between 1 and 5,000.
• the olefins applicable to the high temperature solution polymerization are one or more kinds of monomers selected from ethylene and ⁇ -olefins.
• the high temperature solution polymerization of the present invention by carrying out (co)polymerization using ethylene as the essential olefin and at least one kind of olefins selected from ⁇ -olefins having 3 to 20 carbon atoms as the optional olefin(s), it is possible to produce efficiently an ethylenic polymer which has a high comonomer content, a narrow composition distribution, and a narrow molecular weight distribution.
• Examples of the ⁇ -olefins having 3 to 20 carbon atoms include straight-chain or branched chain ⁇ -olefins having 3 to 20 carbon atoms, and the following are cited for example: propylene, 1-butene, 2-butenes, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.
• the ⁇ -olefins applicable in the high temperature solution polymerization of the present invention also include olefins containing polar groups.
• olefins containing polar groups include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, and the like, and metal salts thereof such as sodium salts etc.; ⁇ , ⁇ -unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, methyl methacrylate, ethyl methacrylate, and the like; vinyl esters such as vinyl acetate, vinyl propionate, and the like; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and the like.
• the high temperature solution polymerization by co-presence, in the reaction system, of the following compounds: vinylcyclohexane, dienes or polyenes; aromatic vinyl compounds such as styrenes like styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylvenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene, and the like; and 3-phenylpropylene, 4-phenylpropylene, ⁇ -methylstyrene, and the like.
• ⁇ -olefins described above propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are used preferably.
• cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclodecene may also be co-present.
• the “the solution polymerization” of the present invention refers to a general name of the method of carrying out polymerization under the conditions in which a polymer is dissolved in an inert hydrocarbon solvent described below at the temperature higher than the melting point of the polymer.
• the polymerization temperature in the solution polymerization of the present invention is usually in the range between 120- and 300° C., preferably between 130 and 250° C., and more preferably between 130 and 200° C. (As described above, this solution polymerization is called “the high temperature solution polymerization” throughout the present specification.)
• the high temperature solution polymerization of the present invention when the polymerization temperature is below 120° C., the polymerization activity decreases extremely and hence it is not practical from the point of productivity.
• the polymerization temperature is 120° C. or more, as the temperature increases, the viscosity of the solution during polymerization decreases and removing of polymerization heat becomes easy, and thus it is possible to achieve higher polymerization of the obtained olefin polymer.
• the polymerization temperature exceeds 300° C., deterioration of the obtained polymer may occur and hence it is not preferable.
• the ethylenic polymer used favorably in many industrial sectors such as films, etc. can be efficiently produced as described below.
• Polymerization is performed under the polymerization pressure usually in the range between the normal pressure and 10 MPa gauge, and preferably between the normal pressure and 8 MPa gauge.
• the polymerization can be carried out by using any of batch, semi-continuous, and continuous methods. Also, the polymerization can be carried out by dividing the process into two or more steps that are different in the polymerization conditions.
• the molecular weight of the obtained olefin polymer can also be controlled by changing the hydrogen concentration in the polymerization system and the polymerization temperature, within the range of the present invention. Further, the molecular weight can be controlled by the amount of component (B) used. When hydrogen is added, the amount is usually in the range between 0.001 and 5,000 NL per 1 kg the produced olefin polymer.
• Solvents used in the high temperature solution polymerization of the present invention are usually inert hydrocarbon solvents, and are preferably saturated hydrocarbons having boiling points in the range between 50 and 200° C. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene, and the like; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and the like.
• aromatic hydrocarbons such as benzene, toluene, xylenes, and the like
• halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, and the like are also included as “the inert hydrocarbon solvents” of the high temperature solution polymerization of the present invention, and the use thereof is not limited.
• the high temperature solution polymerization of the present invention not only organoaluminum oxy-compounds of the type soluble in aromatic hydrocarbons, that were frequently used, but also modified methylaluminoxanes soluble in aliphatic hydrocarbons and alicyclic hydrocarbons, such as MMAO, can be used.
• modified methylaluminoxanes soluble in aliphatic hydrocarbons and alicyclic hydrocarbons, such as MMAO can be used.
• aliphatic hydrocarbons and alicyclic hydrocarbons are employed as the solvent for the solution polymerization, it has become possible to completely eliminate the possibility that an aromatic hydrocarbon is mixed into the polymerization system or the produced olefin polymer. That is, the method of the high temperature solution polymerization of the present invention has also characteristics of reducing the environmental load and minimizing the health effect to humans.
• properties of the olefin polymer produced in the high temperature solution polymerization of the present invention are not specifically limited.
• the olefin polymer having extremely high industrial usefulness obtained by the high temperature solution polymerization of the present invention is an ethylenic polymer.
• the density of the ethylenic polymer obtained by the high temperature solution polymerization of the present invention is usually in the range between 0.85 and 0.95 g/cm 3 , and preferably between 0.86 and 0.95 g/cm 3 .
• the molecular weight distribution, (Mw/Mn, calculated as converted to polystyrene, where Mw: weight average molecular weight, and Mn: number average molecular weight) of the ethylenic polymer, obtained by the high temperature solution polymerization of the present invention, determined by GPC is in the range between 1.0 and 4.0, preferably between 1.2 and 3.0, and more preferably between 1.5 and 2.5.
• the ethylene content of the ethylenic polymer obtained by the high temperature solution polymerization of the present invention is contained in the range between 100 and 50 mole %, preferably between 99.9 and 65 mole %, and more preferably between 99.7 and 70 mole %.
• the ethylenic polymer satisfying the properties described above can also be produced by a method known in the art which uses a Ziegler-Natta catalyst, or by slurry polymerization and vapor-phase polymerization known in the art which use polymerization catalysts containing certain metallocene compounds.
• the pressed sheet was processed at 120° C. for 1 hour, and after cooling it linearly to room temperature in 1 hour, measurement was performed by using a density gradient tube.
• an ethylene-1-octene copolymer was obtained with a yield of 59.7 g.
• an ethylene-1-octene copolymer was obtained with a yield of 110.7 g.
• an ethylene-1-octene copolymer was obtained with a yield of 88.6 g.
• an ethylene-1-octene copolymer was obtained with a yield of 79.6 g.
• an ethylene-1-octene copolymer was obtained with a yield of 80.3 g.
• an ethylene-1-octene copolymer was obtained with a yield of 35.0 g.
• polymerization was performed in the manner similar to Example 9, except for charging 970 milliliter of hexane, 30 milliliter of 1-octene, and 2000 milliliter of hydrogen.
• Polymerization was performed in the manner similar to Example 1, except for replacing di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride with 0.002 millimole of di(1-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride, changing the amount of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate to 0.02 millimole, and cutting off the charge of hydrogen.
• an ethylene-1-octene copolymer was obtained with a yield of 59.8 g.
• an ethylene-1-octene copolymer was obtained with a yield of 69.8 g.
• an ethylene-1-octene copolymer was obtained with a yield of 50.6 g.
• an ethylene-1-octene copolymer was obtained with a yield of 70.4 g.
• an ethylene-1-octene copolymer was obtained with a yield of 75.9 g.
• an ethylene-1-octene copolymer was obtained with a yield of 44.8 g.
• an ethylene-1-octene copolymer was obtained with a yield of 48.4 g.
• an ethylene-1-octene copolymer was obtained with a yield of 75.9 g.
• an ethylene1-octene copolymer was obtained with a yield of 18.9 g.
• an ethylene-1-octene copolymer was obtained with a yield of 97.5 g.
• an ethylene-1-octene copolymer was obtained with a yield of 11.2 g.
• an ethylene-1-octene copolymer was obtained with a yield of 35.0 g.
• an ethylene-1-octene copolymer was obtained with a yield of 17.7 g.
• an ethylene-1-octene copolymer was obtained with a yield of 27.9 g.
• Example 1 a 0.001 A 0.01 0.3 200 500 150
• Example 2 0.00025 B 0.625 1 200 1500 150
• Example 3 0.001 B 0.25 1 200 1000 180
• Example 4 0.0005 C 0.125 1 200 1500 150
• Example 5 0.00025 D 0.0625 1 200 1500 150
• Example 6 0.001 B 0.25 1 200 700
• Example 7 0.0005 C 0.125 1 400 1500 150
• Example 8 0.0005 C 0.125 1 400 1500 140
• Example 9 0.001 C 0.25 1 50 1000 150
• Example 0.001 C 0.25 1 30 2000 150
• Example b 0.002 A 0.02 0.3 200 — 150 11
• Example 0.001 B 0.125 1 200 — 150 Example 0.0005 B 0.125 1 200 1500 150 13
• Example c 0.0005 B 0.125 1 200 1000 150 14
• Example d 0.0005 B 0.125 1 200 1500 150
• Example e 0.0005 B 0.125 1 200 1500 150
• Example f 0.0005 B 0.125 1 200 1500 150 17
• Example g 0.000
• component (a) the following metallocene compounds were used.
• c diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconiumdichloride
• An olefin polymer having a high comonomer content, a narrow composition distribution, and a narrow molecular weight distribution in a copolymer can be produced efficiently with high polymerization activity under the conditions of high temperature in the range between 120 and 300° C. by the method of high temperature solution polymerization of the present invention.
• the olefin polymer produced is a raw material resin that is useful in the field of various forming materials, and the impact of the method of high temperature solution polymerization of the present invention on the industry is immense.

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