US20020156207A1 - Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof - Google Patents

Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof Download PDF

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US20020156207A1
US20020156207A1 US09/947,460 US94746001A US2002156207A1 US 20020156207 A1 US20020156207 A1 US 20020156207A1 US 94746001 A US94746001 A US 94746001A US 2002156207 A1 US2002156207 A1 US 2002156207A1
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group
carbon atoms
atom
hydrocarbon group
same
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Inventor
Junichi Imuta
Nori Kashiwa
Seiji Ota
Satoru Moriya
Tadahito Nobori
Kazumi Mizutani
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority claimed from JP2000345815A external-priority patent/JP2002145948A/ja
Priority claimed from JP2000345737A external-priority patent/JP4409078B2/ja
Priority claimed from JP2000345814A external-priority patent/JP2002145947A/ja
Priority claimed from JP2000345816A external-priority patent/JP2002145949A/ja
Priority claimed from JP2000345736A external-priority patent/JP2002145944A/ja
Priority claimed from JP2000345738A external-priority patent/JP2002145946A/ja
Priority claimed from JP2000362632A external-priority patent/JP4343420B2/ja
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Assigned to MITSUI CHEMICALS, INC. reassignment MITSUI CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMUTA, JUNICHI, KASHIWA, NORIO, MIZUTANI, KAZUMI, MORIYA, SATORU, NOBORI, TADAHITO, OTA, SEIJI
Publication of US20020156207A1 publication Critical patent/US20020156207A1/en
Priority to US10/713,278 priority Critical patent/US7393907B2/en
Priority to US12/153,003 priority patent/US7714087B2/en
Abandoned legal-status Critical Current

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    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
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    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to a polar group-containing olefin copolymer, a process for preparing the copolymer, a thermoplastic resin composition containing the copolymer and uses thereof. More particularly, the invention relates to a polar group-containing olefin copolymer having excellent adhesion properties to metals or polar resins and excellent flexibility, a process for preparing the copolymer, a thermoplastic resin composition containing the copolymer and uses thereof.
  • Polyolefins generally have advantages such as excellent moldability, heat resistance, mechanical properties, hygienic qualities, water vapor permeation resistance and appearance of molded articles thereof, and hence they are broadly used for extrusion molded articles, blow molded articles and injection molded articles.
  • the polyolefins contain no polar group in the molecule, so that they have low compatibility with polar resins such as nylon and EVOH and low adhesion properties to polar resins and metals. Therefore, it is difficult to use the polyolefins by blending or laminating them with these materials.
  • molded products of the polyolefins have problems of poor surface hydrophilic properties and poor antistatic properties.
  • Engineering plastics such as nylon have excellent heat resistance and strength, and hence they are used for electronic/electric parts.
  • the engineering plastics such as nylon generally have low impact resistance, so that they are sometimes blended with olefin copolymers to improve the impact resistance.
  • the polyolefins however, contain no polar group in the molecule and show low compatibility with polar resins, and therefore a method of grafting polar monomers on the polyolefins to improve compatibility with the polar resins has been heretofore widely used.
  • orientation of the polar groups toward the interface between the copolymer and the polar material may be unsatisfactory, and adhesion properties to the polar materials and compatibility therewith may be insufficient.
  • effects in adhesion properties and compatibility are not exhibited unless a graft copolymer is added in a large amount.
  • the present inventors have studied in the light of the above problems. As a result, they have found that a copolymer having a specific molecular structure and a composition containing the copolymer are excellent in compatibility with polar resins and adhesion properties to polar resins and metals, and they have also found that the copolymer and the composition have excellent surface hydrophilic properties and antistatic properties. Moreover, the present inventors have found the copolymer and the composition can be favorably applied to various uses.
  • an olefin polymer such as an ethylene homopolymer, an ethylene/ ⁇ -olefin copolymer, a propylene homopolymer or a propylene/ ⁇ -olefin copolymer
  • a process comprising polymerizing an olefin in the presence of a titanium catalyst comprising a solid titanium catalyst component containing magnesium, halogen and an electron donor, and an organoaluminum compound, or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound has been heretofore known.
  • an olefin is polymerized in the presence of a metallocene catalyst comprising a transition metal compound such as zirconocene and an organoaluminum oxy-compound (aluminoxane). It is also known that if the metallocene catalyst is used, an olefin polymer having a high molecular weight is obtained with high activity and the resulting olefin polymer has narrow molecular weight distribution and narrow composition distribution.
  • a metallocene catalyst comprising a transition metal compound such as zirconocene and an organoaluminum oxy-compound (aluminoxane).
  • a process using a metallocene catalyst is also known.
  • polymerization of an OH group-containing olefin is conducted using a metallocene compound having a ligand of non-crosslinked cyclopentadienyl group, crosslinked or non-crosslinked bisindenyl group, or ethylene crosslinked unsubstituted indenyl group/fluorenyl group, as described in Macromolecules, 28, 5351 (1995), Macromolecules, 29, 5255 (1966), and Polymer Preprints, Japan, 49(2), 215 (2000).
  • polymerization of an olefin having NR 2 (R: alkyl group) as a polar group is conducted using a metallocene compound having a ligand of non-crosslinked cyclopentadienyl group, crosslinked or non-crosslinked bisindenyl group, or crosslinked unsubstituted indenyl group/cyclopentadienyl group, as described in Macromolecules, 31, 2019 (1998) and Macromolecules, 32, 14(1999).
  • a process using an organometallic compound other than the metallocene compound is publicly known, as described in Science, 287, 460 (2000), OCOP2000 at Oslo, and Books of Abstracts (C. W. Chien). These processes, however, have a disadvantage of extremely low polymerization activity.
  • an olefin polymer containing a polar group can be prepared with high polymerization activity by copolymerizing an olefin and a polar group-containing monomer in the presence of a transition metal catalyst into which a cyclopentadienyl group or other special ligands have been introduced, without using radical polymerization or a Ziegler polymerization catalyst. Based on the finding, the present invention has been accomplished.
  • a method of selectively introducing the polar group at only one end of the polymer chain or inside of the main chain and at one end of the main chain has been heretofore unknown. Then, the present inventors have found a method of selectively introducing the polar group at only one end of the polymer chain or inside of the main chain and at one end of the main chain, and accomplished the present invention.
  • the first embodiment of the polar group-containing olefin copolymer according to the present invention comprises a constituent unit represented by the following formula (1), a constituent unit represented by the following formula (2) and a constituent unit represented by the following formula (3), has a molecular weight distribution (Mw/Mn) of not more than 3, and has an intensity ratio of T ⁇ to T ⁇ +T ⁇ (T ⁇ /(T ⁇ +T ⁇ ) as determined from a 13 C-NMR spectrum of said copolymer, of not more than 1.0:
  • R 1 and R 2 may be the same or different and are each a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group of 1 to 18 carbon atoms;
  • R 3 is a hydrocarbon group;
  • R 4 is a hetero atom or a group containing a hetero atom;
  • r is 0 or 1;
  • X is a polar group selected from an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic ester group, an acid anhydride group, arl amino group, an amide group, an epoxy group and a mercapto group;
  • p is an integer of 1 to 3; and when p is 2 or 3, each X may be the same or different, and in this case, if r is 0, X may be bonded to the same or different atom of R 3 , and if r is 1, X may be bonded to the same or different atom of R 4 .
  • R 3 in the constituent unit represented by the formula (3) is preferably a hydrocarbon group of 11 or more carbon atoms.
  • X in the constituent unit represented by the formula (3) is preferably a polar group selected from a phenolic hydroxyl group, a carboxylic ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercapto group
  • R 1 in the constituent unit represented by the formula (1) and R 2 in the constituent unit represented by the formula (2) are each a hydrocarbon group of 2 or more carbon atoms, preferably 2 to 18 carbon atoms, and the crystallinity of said copolymer, as determined by X-ray diffractometry, is not less than 10%.
  • R 1 in the constituent unit represented by the formula (1) and R 2 in the constituent unit represented by the formula (2) are each a hydrocarbon group of 2 or more carbon atoms, preferably 2 to 18 carbon atoms, and the crystallinity of said copolymer, as determined by X-ray diffractometry, is preferably less than 10%.
  • the second embodiment of the polar group-containing olefin copolymer according to the present invention is a branched type copolymer comprising a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (4), and optionally a constituent unit represented by the following formula (5), having a molecular weight distribution (Mw/Mn) of not more than 3, and having an intensity ratio of T ⁇ to T ⁇ +T ⁇ (T ⁇ /(T ⁇ +T ⁇ )), as determined from a 13 C-NMR spectrum of said copolymer, of not more than 1.0:
  • R 1 is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group of 1 to 18 carbon atoms
  • R 5 is a hydrocarbon group
  • R 6 is a hetero atom or a group containing a hetero atom
  • r is 0 or 1
  • Z is a polymer segment obtained by any one of anionic polymerization, ring-opening polymerization and polycondensation
  • W is a hydroxyl group or an epoxy group
  • p is an integer of 1 to 3
  • q is 0, 1 or 2, and p+q ⁇ 3; when p is 2 or 3, each —O—Z may be the same or different, and in this case, if r is 0, —O—Z may be bonded to the same or different atom of R 5 , and if r is 1, —O—Z may be bonded to the same or different atom of R 6 ; when q is 2, each W may be the same or different, and in this case, if r is 0,
  • r is 0 and Z is a polymer segment obtained by anionic polymerization.
  • Z is a polymer segment obtained by ring-opening polymerization or polycondensation.
  • the third embodiment of the polar group-containing olefin copolymer according to the present invention comprises a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (6), and optionally a constituent unit represented by the following formula (3), has a molecular weight distribution (Mw/Mn) of not more than 3, and has an intensity ratio of T ⁇ to T ⁇ +T ⁇ (T ⁇ /(T ⁇ +T ⁇ )), as determined from a 13 C-NMR spectrum of said copolymer, of not more than 1.0:
  • R 1 is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group of 1 to 18 carbon atoms
  • R 3 is a hydrocarbon group
  • R 4 is a hetero atom or a group containing a hetero atom
  • R 7 is a direct bond or an aliphatic hydrocarbon group of 1 or more carbon atoms
  • R 8 is a hydrogen atom, a direct bond or an aliphatic hydrocarbon group of 1 or more carbon atoms
  • Y is a polar group containing O and/or N
  • m and n are each an integer of 0 to 2, and m+n is not 0
  • s is 0 or 1
  • r is 0 or 1
  • X is a polar group selected from an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercap
  • the first embodiment of the process for preparing a polar group containing olefin copolymer according to the present invention comprises copolymerizing at least one ⁇ -olefin selected from ⁇ -olefins of 2 to 20 carbon atoms and at least one polar group-containing monomer selected from a polar group-containing monomer represented by the following formula (7) and a polar group-containing monomer represented by the following formula (8) in the presence of a catalyst comprising:
  • (B-2) a compound which reacts with the compound (A) to form an ion pair
  • R 3 is a hydrocarbon group
  • R 4 is a hetero atom or a group containing a hetero atom
  • r is 0 or 1
  • X is a polar group selected from an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercapto group
  • p is an integer of 1 to 3; when p is 2 or 3, each X may be the same or different, and in this case, if r is 0, X may be bonded to the same or different atom of R 3 , and if r is 1, X may be bonded to the same or different atom of R 4 ;
  • R 7 is a direct bond or an aliphatic hydrocarbon group of 1 or more carbon atoms
  • R 8 is a hydrogen atom, a direct bond or an aliphatic hydrocarbon group of 1 or more carbon atoms
  • Y is a polar group containing O and/or N
  • m and n are each an integer of 0 to 2, and m+n is not 0
  • s is 0 or 1.
  • the transition metal compound (A) is represented by any one of the following formulas (11), (12), (13), (14), (15) and (16) and the polar group-containing monomer is a polar group-containing monomer of the formula (7) wherein X is —OH or an amino group;
  • M 1 is a transition metal atom of Group 4 of the periodic table
  • R 25 , R 26 , R 27 and R 28 may be the same or different and are each a hydrogen atom, a nitrogen-containing group, a phosphorus-containing group, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a halogen atom; of the groups indicated by R 25 , R 26 , R 27 and R 28 , a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded;
  • X 1 and X 2 may be the same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom
  • M 1 is a transition metal atom selected from Group 4 of the periodic table;
  • Cp is a cyclopentadienyl group or its derivative that is n-bonded to M 1 ;
  • Z 1 is a ligand containing an oxygen atom, a sulfur atom, a boron atom or an element of Group 14 of the periodic table;
  • Y 1 is a ligand containing an atom selected from a nitrogen atom, a phosphorus atom, an oxygen atom and a sulfur atom;
  • each Xl may be the same or different and is a hydrogen atom, a halogen atom, a hydrocarbon group which has 20 or less carbon atoms and may contain 1 or more double bonds, a silyl group containing 20 or less silicon atoms, a germyl group containing 20 or less germanium atoms or a boronyl group containing 20 or less boron atoms;
  • M 1 is a transition metal atom selected from Group 4 of the periodic table
  • R 11 to R 14 , R 17 to R 20 , and R 41 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom; of the groups indicated by R 11 , R 12 , R 13 , R 14 , R 17 , R 18 , R 19 , R 20 and R 41 , a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded (except a case where all of R 11 , R 12 , R 13 , R 14 , R 17 , R 18 , R 19 , R 20 and R 41 are hydrogen atoms and a case where R 12 or R 13 is a tert-buty
  • M 1 is a transition metal atom selected from Group 4 of the periodic table
  • R 11 , R 12 , R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom
  • of the groups indicated by R 11 , R 12 , R 41 and R 42 a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded
  • X 1 and X 2 may be the same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom
  • Y 1 is a transition metal
  • M 1 is a transition metal atom selected from Group 4 of the periodic table
  • R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom; of the groups indicated by R 41 and R 42 , a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded;
  • X 1 and X 2 may be the same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atomns, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom; and
  • Y 1 is a divalent hydrocarbon group of 1 to 20 carbon atoms,
  • M 1 is a transition metal atom selected from Group 4 of the periodic table
  • R 11 , R 12 , R 15 to R 20 , and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom; of the groups indicated by R 11 , R 12 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 42 , a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded;
  • X 1 and X 2 may be the same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a
  • the transition metal compound (A) is represented by any one of the above formulas (11), (12), (13), (14), (15) and (16) and the polar group-containing monomer is a polar group-containing monomer of the above formula (7) wherein X is —NR′R′′ (R′ and R′′ may be the same or different and are each a hydrogen atom or an alkyl group).
  • the second embodiment of the process for preparing a polar group-containing olefin copolymer according to the present invention comprises copolymerizing at least one ⁇ -olefin selected from ⁇ -olefins of 2 to 20 carbon atoms and at least one polar group-containing monomer selected from a polar group-containing monomer represented by the following formula (7), a polar group-containing monomer represented by the following formula (8) and a macromonomer represented by the following formula (9) in the presence of a catalyst comprising:
  • (B-2) a compound which reacts with the compound (A) to form an ion pair
  • R 5 is a hydrocarbon group
  • R 6 is a hetero atom or a group containing a hetero atom
  • r is 0 or 1
  • Z is a polymer segment obtained by any one of anionic polymerization, ring-opening polymerization and polycondensation
  • W is a hydroxyl group or an epoxy group
  • p is an integer of 1 to 3
  • q is 0, 1 or 2, and p+q ⁇ 3
  • each —O—Z may be the same or different, and in this case, if r is 0, —O—Z may be bonded to the same or different atom of R 5 , and if r is 1, —O—Z may be bonded to the same or different atom of R 6 ; when q is 2, each W may be the same or different, and in this case, if r is 0, W may be bonded to the same or different atom of R 5 , and if r is 1, W may be bonded to the same or different atom of
  • the third embodiment of the process for preparing a branched type polar group-containing olefin copolymer according to the present invention comprises copolymerizing at least one olefin selected from ⁇ -olefins of 2 to 20 carbon atoms, a polar group-containing monomer represented by the following formula (10), and optionally, a polar group-containing monomer represented by the above formula (8) in the presence of a catalyst comprising:
  • (B-2) a compound which reacts with the compound (A) to form an ion pair
  • R 5 is a hydrocarbon group
  • R 6 is a hetero atom or a group containing a hetero atom
  • m is 0 or 1
  • W is a hydroxyl group or an epoxy group
  • n is an integer of 1 to 3; and when n is 2 or 3, each W may be the same or different, and in this case, if m is 0, W may be bonded to the same or different atom of R 5 , and if m is 1, W may be bonded to the same or different atom of R 6 ;
  • a Z portion is formed by anionic polymerization, ring-opening polymerization or polycondensation;
  • the W portion of the copolymerized polar group-containing monomer is allowed to react with a terminal functional group of a polymer obtained by anionic polymerization, ring-opening polymerization and polycondensation.
  • thermoplastic resin composition according to the present invention contains the polar group-containing olefin copolymer.
  • the adhesive resin according to the present invention comprises the polar group-containing olefin copolymer or the thermoplastic resin composition.
  • the compatibilizing agent according to the present invention comprises the polar group-containing olefin copolymer or the thermoplastic resin composition.
  • the resin modifier according to the present invention comprises the polar group-containing olefin copolymer or the thermoplastic resin composition.
  • the filler dispersant according to the present invention comprises the polar group-containing olefin copolymer or the thermoplastic resin composition.
  • the dispersant according to the present invention comprises the polar group-containing olefin copolymer or the thermoplastic resin composition.
  • the film or the sheet according to the invention comprises the polar group-containing olefin copolymer or the thermoplastic resin composition.
  • the first embodiment of the polar group-containing olefin copolymer of the invention comprises a constituent unit represented by the following formula (1) (also referred to as a “constituent unit (1)” hereinafter), a constituent unit represented by the following formula (2) (also referred to as a “constituent unit (2)” hereinafter) and a constituent unit represented by the following formula (3) (also referred to as a “constituent unit (3)” hereinafter).
  • formula (1) also referred to as a “constituent unit (1)” hereinafter
  • a constituent unit represented by the following formula (2) also referred to as a “constituent unit (2)” hereinafter
  • a constituent unit represented by the following formula (3) also referred to as a “constituent unit (3)” hereinafter
  • R 1 and R 2 may be the same or different and are each a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group of 1 to 18 carbon atoms.
  • Examples of the straight-chain or branched aliphatic hydrocarbon groups of 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, pentyl, neopentyl, n-hexyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 2-ethylhexyl, octyl, decY 1 and dodecyl.
  • hydrocarbon groups of 1 to 10 carbon atoms particularly 1 to 6 carbon atoms.
  • R 3 is a hydrocarbon group, such as a saturated or unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
  • the saturated or unsaturated hydrocarbon group is, for example, a straight-chain or branched hydrocarbon group of 1 to 20 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, methylethylene, tetramethylene, methyltrimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene and eicosamethylene.
  • the alicyclic hydrocarbon group is preferably a group having an alicyclic structure as a part of its structure and having 3 to 20 carbon atoms, and examples thereof include cyclopropylene, cyclopentylene, cyclohexylene and cyclooctylene.
  • the aromatic hydrocarbon group is preferably a group having an aromatic ring as a part of its structure and having 6 to 20 carbon atoms, and examples thereof include —Ph—, —Ph—CH 2 —, —Ph—(CH 2 ) 2 —, —Ph—(CH 2 ) 3 —, —Ph—(CH 2 ) 6 —, —Ph—(CH 2 ) 10 —, —Ph—(CH 2 ) 11 —, —Ph—(CH 2 ) 12 — and —Ph—(CH 2 ) 14 —.
  • R 4 is a hetero atom or a group containing a hetero atom.
  • the hetero atom is, for example, an oxygen atom, a nitrogen atom or a sulfur atom, preferably an oxygen atom or a nitrogen atom.
  • the group containing a hetero atom is, for example, a group containing an oxygen atom, a nitrogen atom or a sulfur atom, and examples thereof include —O—, —C( ⁇ O)—, —C( ⁇ O)O—, —OC( ⁇ O)O—, —C( ⁇ O)NH—, —NH—, (tertiary amine), —S—, and aliphatic, alicyclic or aromatic hydrocarbon groups containing these groups.
  • the hetero atom in R 4 or the carbon atom to which the hetero atom is bonded is preferably bonded to R 3 , and examples of such structures include —R 3 —O—R—X, —R 3 —C( ⁇ O)—R—X, —R 3 —C( ⁇ O)O—R—X, —R 3 —OC( ⁇ O)O—R—X, —R 3 —C( ⁇ O)NH—R—X and —R 3 —S—R—X (R is methylene, phenylene or cyclohexylene).
  • R 4 contains a carbon atom
  • the number of carbon atoms to form R 4 is in the range of preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.
  • r is 0 or 1. When r is 0, X is bonded to any one of carbon atoms for forming R 3 . When r is 1, X is bonded to any one of carbon atoms for forming R 4 .
  • X is a polar group selected from an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic ester group, an acid anhydride group, an amino group (primary, secondary and tertiary), an amide group, an epoxy group and a mercapto group.
  • the polar group-containing olefin copolymer is excellent in coating properties, surface hydrophilic properties (anti-fogging properties), antistatic properties, adhesion properties to polar resins (urethane resin, epoxy resin, etc.), filler dispersibility, moisture absorption properties, gas barrier properties (in case of high content), water absorption properties (in case of high content of alcoholic hydroxyl group), dispersibility in water and oil resistance (in case of high content of alcoholic hydroxyl group).
  • the polar group-containing olefin copolymer is excellent in adhesion properties to polar resins (aromatic polymer, phenolic resin, etc.) and compatibility with polar resins (aromatic polymer, phenolic resin, etc.).
  • the polar group-containing olefin copolymer is excellent in adhesion properties to metals, dispersibility in water (particularly in case of metallic salt), pigment dispersibility, filler dispersibility and oil resistance (in case of high content of carboxyl group).
  • the polar group-containing olefin copolymer is excellent in adhesion properties to polar resins (nylon, EVOH, etc.), compatibility with polar resins (nylon, EVOH, etc.) and surface hydrophilic properties.
  • the polar group-containing olefin copolymer is excellent in adhesion properties to metals, adhesion properties to polar resins (polyester, epoxy resin, nylon, EVOH, urea resin, etc.), compatibility with polar resins (polyester, epoxy resin, nylon, EVOH, urea resin, etc.), pigment dispersibility and coating properties.
  • the polar group-containing olefin copolymer is excellent in adhesion properties to metals, adhesion properties to polar resins (nylon, EVOH, polyester, etc.), compatibility with polar resins (nylon, EVOH, polyester, etc.), pigment dispersibility, filler dispersibility and dispersibility in water (particularly in case of metallic salt).
  • the polar group-containing olefin copolymer is excellent in adhesion properties to polar resins (epoxy resin, polyketone, polyurethane, etc.), coating properties, antifungal properties (in case of ammonium salt), ion exchange properties (in case of ammonium salt), surface hydrophilic properties (particularly in case of ammonium salt), antistatic properties (particularly in case of ammonium salt), pigment dispersibility and filler dispersibility (particularly in case of ammonium salt).
  • polar resins epoxy resin, polyketone, polyurethane, etc.
  • coating properties antifungal properties (in case of ammonium salt), ion exchange properties (in case of ammonium salt), surface hydrophilic properties (particularly in case of ammonium salt), antistatic properties (particularly in case of ammonium salt), pigment dispersibility and filler dispersibility (particularly in case of ammonium salt).
  • the polar group-containing olefin copolymer is excellent in adhesion properties to polyamide and compatibility with polyamide.
  • the polar group-containing olefin copolymer is excellent in adhesion properties to rear periodic transition metals such as Fe, Cu, Co, Ni, Cd and Zn, compatibility with polyamide and polyester, and adhesion properties to polyamide and polyester.
  • p is an integer of 1 to 3, and when p is 2 or 3, each X may be the same or different. When p is 2 or 3 and r is 0, X may be bonded to the same or different atom of R 3 , and when p is 2 or 3 and r is 1, X may be bonded to the same or different atom of R 4 .
  • the constituent unit (1), the constituent unit (2) and the constituent unit (3) are bonded usually at random.
  • the molar ratio ((1)+(2):(3)) between the total of the constituent unit (1) and the constituent unit (2), and the constituent unit (3) is in the range of usually 99.99:0.01 to 0.01:99.99, preferably 99.95:0.05 to 10:90, more preferably 99.9:0.1 to 30:70.
  • the molar ratio ((1):(2)) between the constituent unit (1) and the constituent unit (2) is in the range of usually 99.99:0.01 to 0.01:99.99, preferably 99:1 to 1:99, more preferably 90:10 to 10:90.
  • the polar group-containing olefin copolymer of the invention may contain two or more kinds of the constituent units (1), may contain two or more kinds of the constituent units (2), and may contain two or more kinds of the constituent units (3).
  • the polar group-containing olefin copolymer of the invention may contain constituent units other than the constituent unit (1), the constituent unit (2) and the constituent unit (3), within limits not detrimental to the objects of the present invention.
  • constituent units which may be contained include constituent units derived from cyclic olefins other than the polar group-containing monomer represented by the formula (8), non-conjugated polyenes, hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinY 1 ester compounds, and vinY 1 chloride.
  • the amount thereof is not more than 30 mol %, preferably not more than 20 mol %, more preferably not more than 10 mol %, based on all constituent units to constitute the polar group-containing olefin copolymer.
  • the weight-average molecular weight (Mw) of the polar group-containing olefin copolymer of the invention is in the range of usually 500 to 2,000,000, preferably 800 to 1,500,000, more preferably 1,000 to 1,300,000, and the molecular weight distribution (Mw/Mn) thereof is usually not more than 3, preferably not more than 2.8, more preferably not more than 2.7.
  • the polar group-containing olefin copolymer is excellent in orientation of the polar groups toward the interface between said copolymer and a polar material and has excellent adhesion properties to a polar material and excellent compatibility with a polar material.
  • Mw and Mw/Mn were determined from data obtained by the measurement at 140° C. in an orthodichlorobenzene solvent using GPC (gel permeation chromatography).
  • the intensity ratio (T ⁇ /(T ⁇ +T ⁇ )) of T ⁇ to T ⁇ +T ⁇ in the 13 C-NMR spectrum of the polar group-containing olefin copolymer is not more than 1.0, preferably not more than 0.8, more preferably not more than 0.5.
  • the intensity ratio (T ⁇ /(T ⁇ +T ⁇ )) is not more than 1.0, the polar group-containing olefin copolymer is excellent in orientation of the polar groups toward the interface between said copolymer and a polar material.
  • T ⁇ and T ⁇ in the 13 C-NMR spectrum are each a peak intensity of CH 2 present in the constituent unit derived from an ⁇ -olefin of 4 or more carbon atoms, and as shown below, they mean two kinds of CH 2 different in the position to the tertiary carbon.
  • the T ⁇ /(T ⁇ +T ⁇ ) intensity ratio can be determined in the following manner.
  • a 13 C-NMR spectrum of the polar group-containing olefin copolymer is measured by the use of, for example, a Japan Electron Optics Laboratory JEOL-GX270 NMR measuring device. The measurement is made using a mixed solution of hexachlorobutadiene/d6-benzene (2/1, by volume) having a sample concentration of 5 weight % under the conditions of 67.8 MHz, 25° C. and d6-benzene aas a standard (128 ppm). The 13 C-NMR spectrum measured is analyzed in accordance with the proposals by Lindemann Adams (Analysis Chemistry 43, p. 1245 (1971)) and J. C. Randall (Review Macromolecular Chemistry Physics, C29, 201 (1989)) to determine the T ⁇ /(T ⁇ +T ⁇ ) intensity ratio.
  • Examples of the polar group-containing olefin copolymer according to the first embodiment of the invention include the following polar group-containing olefin copolymers (I) to (VI).
  • R 1 in the formula (1) and R 2 in the formula (2) are each a hydrogen atom or a methyl group and R 1 and R 2 are the same as each other.
  • a preferred combination of the constituent unit (1), the constituent unit (2) and the constituent unit (3) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) shown in Table 1 and a constituent unit selected from examples of the constituent units (3) shown in Table 1.
  • Specific examples of such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L and 2-M.
  • the polar group-containing olefin copolymer (I) according to the invention is excellent in adhesion properties to polar materials such as metals and polar resins, compatibility and flexibility.
  • R 1 in the formula (1) and R 2 in the formula (2) are different from each other.
  • a preferred combination of the constituent unit (1), the constituent unit (2) and the constituent unit (3) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) and the constituent units (2) shown in Table 2 and a constituent unit selected from examples of the constituent units (3) shown in Table 2.
  • Such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L, 2-M, 3-A, 3-B, 3-C, 3-D, 3-E, 3-F, 3-G, 3-H, 3-I, 3-J, 3-K, 3-L, 3-M, 4-A, 4-B, 4-C, 4-D, 4-E, 4-F, 4-G, 4-H, 4-I, 4-J, 4-K, 4-L, 4-M, 5-A, 5-B, 5-C, 5-D, 5-E, 5-F, 5-G, 5-H, 5-I, 5-J, 5-K, 5-L, 5-M, 6-A, 6-B, 6-C, 6-D, 6-E, 6-F, 6-G, 6-H, 6-I, 6-J, 6-K, 6-L, 6-M, 7-A, 7-B, 7-C, 7
  • the polar group-containing olefin copolymer (II) contains no other copolymerizable components previously mentioned and is formed from only the constituent unit (1), the constituent unit (2) and the constituent unit (3).
  • X is an alcoholic hydroxyl group, a phenolic hydroxyl group or an amino group
  • the polar group-containing olefin copolymer is particularly preferably formed from only the constituent unit (1), the constituent unit (2) and the constituent unit (3).
  • the polar group-containing olefin copolymer (II) according to the invention is excellent in adhesion properties to polar materials such as metals and polar resins, compatibility and flexibility.
  • R 3 in the formula (3) is a hydrocarbon group of 11 or more carbon atoms.
  • a preferred combination of the constituent unit (1), the constituent unit (2) and the constituent unit (3) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) and (2) shown in Table 3 and a constituent unit selected from examples of the constituent units (3) shown in Table 3.
  • Such combinations include combinations of 1-A, 1-B, 1-C, 2-A, 2-B, 2-C, 3-A, 3-B, 3-C, 4-A, 4-B, 4-C, 5-A, 5-B, 5-C, 6-A, 6-B, 6-C, 7-A, 7-B, 7-C, 8-A, 8-B, 8-C, 9-A, 9-B, 9-C, 10-A, 10-B and 10-C.
  • the polar group-containing olefin copolymer (III) contains no other copolymerizable components previously mentioned and is formed from only the constituent unit (1), the constituent unit (2) and the constituent unit (3).
  • X is an alcoholic hydroxyl group, a phenolic hydroxyl group or an amino group
  • the polar group-containing olefin copolymer is particularly preferably formed from only the constituent unit (1), the constituent unit (2) and the constituent unit (3).
  • the polar group-containing olefin copolymer (III) according to the invention is excellent in adhesion properties to polar materials such as metals and polar resins and compatibility.
  • X in the formula (3) is a polar group selected from a phenolic hydroxyl group, a carboxylic ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercapto group.
  • a preferred combination of the constituent unit (1), the constituent unit (2) and the constituent unit (3) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) shown in Table 4 and a constituent unit selected from examples of the constituent units (3) shown in Table 4.
  • Such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 2-A, 2-B, 2-C, 2-D, 3-A, 3-B, 3-C, 3-D, 4-A, 4-B, 4-C, 4-D, 5-A, 5-B, 5-C, 5-D, 6-A, 6-B, 6-C, 6-D, 7-A, 7-B, 7-C, 7-D, 8-A, 8-B, 8-C, 8-D, 9-A, 9-B, 9-C, 9-D, 10-A, 10-B, 10-C and 10-D.
  • the polar group-containing olefin copolymer (IV) according to the invention is excellent in adhesion properties to polar materials such as metals and polar resins and compatibility.
  • R 1 in the formula (1) and R 2 in the formula (2) are each a hydrocarbon group of 2 or more carbon atoms, preferably 2 to 18 carbon atoms, and the crystallinity of the copolymer, as determined by X-ray diffractometry, is not less than 10%, preferably 15 to 80%, more preferably 20 to 70%.
  • the crystallinity can be measured by X-ray diffractometry (in accordance with S. L. AGGARWAL, J. Polymer Sci., 18, 17 (1955)) or the like.
  • the stereoregularity (isotacticity) of the polar group-containing olefin copolymer (V) is usually not less than 20%, preferably 30 to 100%, more preferably 40 to 100%.
  • a preferred combination of the constituent unit (1), the constituent unit (2) and the constituent unit (3) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) shown in Table 5 and a constituent unit selected from examples of the constituent units (3) shown in Table 5.
  • Specific examples of such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L and 2-M.
  • the polar group-containing olefin copolymer (V) according to the invention is excellent in adhesion properties to polar materials such as metals and polar resins, compatibility and rigidity.
  • R 1 in the formula (1) and R 2 in the formula (2) are each a hydrocarbon group of 2 or more carbon atoms, preferably 2 to 18 carbon atoms, and the crystallinity of the copolymer, as determined by X-ray diffractometry, is less than 10%, preferably not more than 5%, more preferably not more than 2%.
  • the polar group-containing olefin copolymer (VI) contains no other copolymerizable components previously mentioned and is formed from only the constituent unit (1), the constituent unit (2) and the constituent unit (3).
  • X is an alcoholic hydroxyl group, a phenolic hydroxyl group or an amino group
  • the polar group-containing olefin copolymer is particularly preferably formed from only the constituent unit (1), the constituent unit (2) and the constituent unit (3).
  • a preferred combination of the constituent unit (1), the constituent unit (2) and the constituent unit (3) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) shown in Table 6 and a constituent unit selected from examples of the constituent units (3) shown in Table 6.
  • Specific examples of such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L and 2-M.
  • the polar group-containing olefin copolymer (VI) according to the invention is excellent in adhesion properties to polar materials such as metals and polar resins, compatibility, tackiness and flexibility.
  • the second embodiment of the polar group-containing olefin copolymer of the invention is a branched type polar group-containing olefin copolymer comprising a constituent unit represented by the in following formula (1) and a constituent unit represented by the following formula (4) (also referred to as a “constituent unit (4)), and optionally a constituent unit represented by the following formula (5) (also referred to as a “constituent unit (5)).
  • the constituent unit represented by the formula (1) is identical with the aforesaid constituent unit (1).
  • R 5 is a hydrocarbon group, such as a saturated or unsaturated hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and examples of such hydrocarbon groups include the same groups as previously described with respect to R 3 in the formula (3).
  • R 5 in the formula (4) and R 5 in the formula (5) may be the same or different, they preferably are the same as each other.
  • R 6 is a hetero atom or a group containing a hetero atom, and examples the hetero atoms and the groups containing the hetero atom include the same atoms and groups as previously described with respect to R 4 in the formula (3).
  • the hetero atom in R 6 or the carbon atom to which the hetero atom is bonded is preferably bonded to R 5 , and examples of such structures include —R 5 —O—R—O—Z, —R 5 —C( ⁇ O)—R—O—Z, —R 5 —C( ⁇ O)O—R—O—Z, —R 5 —OC( ⁇ O)O—R—O—Z, —R 5 —C( ⁇ O)NH—R—O—Z and —R 5 —S—R—O—Z (R is methylene, phenylene or cyclohexylene).
  • the above examples are those wherein p is 1 and q is 0 in the formula (4), and the same shall apply to other cases.
  • the hetero atom in R 6 or the carbon atom to which the hetero atom is bonded is preferably bonded to R 5 , and examples of such structures include —R 5 —O—R—W, —R 5 —C( ⁇ O)—R—W, —R 5 —C( ⁇ Q)O—R—W, —R 5 —OC( ⁇ O)O—R—X, —R 5 —C( ⁇ O)NH—R—W and —R 5 —S—R—W (R is methylene, phenylene or cyclohexylene).
  • R is methylene, phenylene or cyclohexylene.
  • R 6 contains a carbon atom in the formulas (4) and (5)
  • the number of carbon atoms to form R 6 is in the range of preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.
  • R 6 in the formula (4) and R 6 in the formula (5) may be the same or different, they preferably are the same as each other.
  • r is 0 or 1. When r is 0, —O—Z is bonded to any one of carbon atoms for forming R 5 . When r is 1, —O—Z is bonded to any one of carbon atoms for forming R 6 .
  • m is 0 or 1.
  • W is bonded to any one of carbon atoms for forming R 5 .
  • W is bonded to any one of carbon atoms for forming R 6 .
  • Z is a polymer segment obtained by anionic polymerization, ring-opening polymerization or polycondensation.
  • polymer segments include segments obtained by anionic polymerization of one or more monomers selected from methyl methacrylate, ethyl methacrylate, butyl acrylate, acrylonitrile and acrylamide, segments obtained by ring-opening polymerization of lactone, lactide, siloxane, lactam, cyclic ether, oxazoline, ethylene oxide, propylene oxide, etc., and segments obtained by polycondensation of monomers, such as polycarboxylic acid and polyhydric alcohol, polycarboxylic acid and polyamine, or hydroxycarboxylic acid.
  • monomers such as polycarboxylic acid and polyhydric alcohol, polycarboxylic acid and polyamine, or hydroxycarboxylic acid.
  • Examples of polar monomers employed in formation of the polymer segment include:
  • (meth)acrylic acid esters such as monoesters of monovalent alcohols and acrylic acid or methacrylic acid, specifically,
  • monoesters of divalent alcohols with a terminal protected by an ether linkage and acrylic acid or methacrylic acid such as 2-methoxyethylacrylate, 2-ethoxyethylmethacrylate, 2-phenoxyethylacrylate, 2-dicyclopentenyloxyethylacrylate, 1-methoxy-2-propylmethacrylate, 3-methoxypropylacrylate, 4-ethoxybutylmethacrylate, 6-methoxyhexamethylacrylate, methoxydiethyleneglycolacrylate, phenoxydipropyleneglycolmethacrylete, ethoxytripropyleneglycolmethacrylate, ethoxypolyethyleneglycolacrylate and methoxypolypropyleneglycolmethacrylate;
  • polyvalent esters of a divalent or more alcohol and acrylic acid or methacrylic acid such as ethyleneglycoldiacrylate, ethyleneglycoldimethacrylate, propyleneglycoldiacrylate, propyleneglycoldimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, diethyleneglycol diacrylate, dipropyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, tripropyleneglycol diacrylate, polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, polypropyleneglycol dimethacrylate, glycerintriacrylate, glycerintrimethacrylate, pentaerythritol
  • esters of alcohols having an ester linkage and acrylic or methacrylic acid such as 2-benzoyloxyethyl acrylate, 2-benzoyloxyethyl methacrylate, 2-acetyloxy acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl methacrylate and 2,2,6,6-tetramethyl-4-oxy-5-oxa-heptane-1,7-diyl-diacrylate;
  • esters of alcohols having a cyclic acetal linkage and acrylic acid or methacrylic acid such as 2-tertial-butyl-1,3-dioxycyclopentane-2′-ylmethacrylate and 2-tertial-butyl-5-ethyl-5-vinylcarbonyloxymethyl-1,3-dioxycyclohexane-2′ (2)-ylacrylate;
  • esters of oxysuccinimide and acrylic or methacrylic acid such as N-oxysuccinimido acrylate and N-oxysuccinimido methacrylate;
  • esters of an alcohol having a secondary amino group and acrylic acid or methacrylic acid such as 2-dimethylaminoethyl acrylate and 2-ethylpropylaminoethyl methacrylate;
  • esters of an alcohol having a cyano group and acrylic acid or methacrylic acid such as 2-cyanoethyl acrylate and 2-cyanopropylmethacrylate.
  • Examples of (meth)acrylonitriles include acrylonitrile and methacrylonitrile.
  • Acrylamides include acrylamide, N-monosubstituted or N,N-disubstituted acrylamides, for example, acrylamide;
  • N-monosubstituted acrylamides such as N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-octylacrylamide, N-phenylacrylamide, N-glycidylacrylamide and N,N′-ethylenebisacrylamide;
  • N,N-disubstituted monoacrylamides such as N,N-dimethylacrylamide, N-ethyl-N-methylacrylamide, N,N-diethylacrylamide, N,N-di-n-propylacrylamide, N,N-dioctylacrylamide, N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide, N,N-diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide, N-methyl-N-(5-glycidyloxypentyl)acrylamide, N-methyl-N-d(6-glycidyloxyhexyl)acrylamide , N-acryloylpyrrolidine, N-acryloyl-L-prolinemethylester, N-acryloylpiperidine, N-acryloyl morpholine and 1-acryloylimidazole; and
  • N,N′-disubstituted bisacrylamides such as N,N′-diethyl-N-N′-ethylenebisacrylamide, N,N′-dimethyl-N,N′-hexamethylenebisacrylamide and di(N,N′-ethylene)bisacrylamide.
  • vinylpyridines include vinyl- or isopropenyl-substituted pyridines, such as 2-vinylpyridine, 2-isopropenylpyridine and 4-vinylpyridine.
  • N-substituted maleimide examples include:
  • N-aliphatic-substituted maleimides such as N-methylmaleimide and N-ethylmaleimide
  • N-aromatic-substituted maleimides such as N-phenylmaleimide and N-(4-methylphenyl)maleimide.
  • vinyl ketones include: methyl vinyl ketone, isopropenyl methyl ketone, ethyl vinyl ketone, ethyl isopropenyl ketone, butyl vinyl ketone and phenyl vinyl ketone.
  • styrene derivatives include: p-methoxycarbonyl styrene, p-tertiary-butoxycarbonyl styrene and p-cyano styrene.
  • Examples of the polar monomer include alkylene oxide compounds, for example, epoxy compounds, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methylglycidylether, allylglycidylether and phenylglycidylether.
  • alkylene oxide compounds for example, epoxy compounds, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methylglycidylether, allylglycidylether and phenylglycidylether.
  • epoxy compounds such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide,
  • polymer segments obtained by anionic polymerization of (meth)acrylic esters and polymer segments obtained by ring-opening polymerization of ethylene oxide or propylene oxide.
  • the weight-average molecular weight of the polymer segment is in the range of 200 to 1,000,000, preferably 500 to 100,000.
  • the polar group-containing olefin copolymer is excellent in coating properties, surface hydrophilic properties (anti-fogging properties), antistatic properties, adhesion properties to polar resins (urethane resin, epoxy resin, etc.), compatibility with the polar resins, moisture absorption properties, water absorption properties (in case of high content of Z), dispersibility in water and oil resistance (in case of high content of Z).
  • the polar group-containing olefin copolymer is excellent in surface hardness, adhesion properties to metals, pigment dispersibility, filler dispersibility, oil resistance (in case of high content of Z), adhesion properties to polar resins (acrylic resin, nylon, EVOH, etc.) and compatibility with the polar resins.
  • the polar group-containing olefin copolymer is ark. ⁇ . excellent in surface hardness, surface hydrophilic properties (anti-fogging properties), antistatic properties, coating properties, adhesion properties to metals, adhesion properties to polar resins (polyacrylonitrile, polyacrylamide, polyamide, polyester, etc.), compatibility with the polar resins, dispersibility in water, biocompatibility, stimulation response, moisture absorption properties and water absorption properties.
  • the polar group-containing olefin copolymer is excellent in adhesion properties to metals, adhesion properties to polar resins (acrylic resin, nylon, EVOH, etc.), compatibility with the polar resins and oil resistance.
  • the polar group-containing olefin copolymer is excellent in adhesion properties to polar resins (polyamide, etc.), compatibility with the polar resins, gas barrier properties and oil resistance.
  • the polar group-containing olefin copolymer is excellent in adhesion properties to polar resins (polyester, etc.), compatibility with the polar resins and gas barrier properties.
  • p is an integer of 1 to 3, and when p is 2 or 3, each —O—Z may be the same or different. When p is 2 or 3 and r is 0, —O—Z may be bonded to the same or different atom of R 5 . When p is 2 or 3 and r is 1, —O—Z may be bonded to the same or different atom of R 6 .
  • W is a hydroxyl group or an epoxy group.
  • W in the formula (4) and W in the formula (5) may be the same or different, they are preferably the same as each other.
  • each W may be the same or different.
  • W may be bonded to the same or different atom of R 5 .
  • W may be bonded to the same or different atom of R 6 .
  • n is an integer of 1 to 3, and when n is 2 or 3, each W may be the same or different. When n is 2 or 3 and m is 0, W may be bonded to the same or different atom of R 5 . When n is 2 or 3 and m is 1, W may be bonded to the same or different atom of R 6 .
  • the constituent unit (1), the constituent unit (4), and optionally, the constituent unit (5) are bonded usually at random.
  • the molar ratio ((1):(4)+(5)) between the constituent unit (1) and the total of the constituent unit (4) and the constituent unit (5) is in the range of usually 99.99:0.01 to 0.01:99.99, preferably 99.95:0.05 to 10:90, more preferably 99.9:0.1 to 30:70.
  • the molar ratio ((4):(5)) between the constituent unit (4) and the constituent unit (5) is in the range of usually 100:0 to 0.01:99.99, preferably 100:0 to 1:99, more preferably 100:0 to 10:90.
  • the second embodiment of the polar group-containing olefin copolymer of the invention may contain two or more kinds of the constituent units (1), may contain two or more kinds of the constituent units (4), and may contain two or more kinds of the constituent units (5).
  • a preferred combination of the constituent unit (1), the constituent unit (4) and the constituent unit (5) is, for example, a combination of a constituent unit selected from examples of the constituent units (1) shown in Table 7, a constituent unit selected from examples of the —R 5 —(R 6 ) r —O— portions and examples of the Z portions of constituent units (4) shown in Table 7, and a constituent unit selected from examples of the constituent units (5) shown in Table 7.
  • Such combinations include combinations of: 1-A-Z1-a, 1-A-Z2-a, 1-A-Z3-a, 1-A-Z4-a, 1-A-Z5-a, 1-A-Z6-a, 1-A-Z7-a, 1-B-Z1-b, 1-B-Z2-b, 1-B-Z3-b, 1-B-Z4-b, 1-B-Z5-b, 1-B-Z6-b, 1-B-Z7-b, 1-C-Z1-c, 1-C-Z2-c, 1-C-Z3-c, 1-C-Z4-c, 1-C-Z5-c, 1-C-Z6-c, 1-C-Z7-c, 2-A-Z1-a, 2-A-Z2-a, 2-A-Z3-a, 2-A-Z4-a, 2-A-Z5-a, 2-A-Z6-a, 2-A-Z7-a, 2-B-Z1-b, 2-B-Z2-b, 2-B-Z3-b, 2-B-Z4
  • the branched type polar group-containing olefin copolymer of the invention may contain constituent units other than the constituent unit (1), the constituent unit (4) and the constituent unit (5), within limits not detrimental to the objects of the present invention.
  • constituent units which may be contained include constituent units derived from cyclic olefins other than the polar group-containing monomer represented by the following formula (10), non-conjugated polyenes, hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinyl ester compounds, and vinyl chloride.
  • the amount thereof is not more than 30 mol %, preferably not more than 20 mol %, more preferably not more than 10 mol %, based on all constituent units to constitute the polar group-containing olefin copolymer.
  • the weight-average molecular weight (Mw) of the polar group-containing olefin copolymer of the second embodiment of the invention is in the range of usually 500 to 2,000,000, preferably 1,000 to 1,500,000, more preferably 5,000 to 1,300,000, and the molecular weight distribution (Mw/Mn) thereof is usually not more than 3, preferably not more than 2.8, more preferably not more than 2.5.
  • the polar group-containing olefin copolymer is excellent in orientation of the polar groups toward the interface between said copolymer and a polar material and has excellent adhesion properties to a polar material and excellent compatibility with a polar material.
  • the intensity ratio (T ⁇ /(T ⁇ +T ⁇ )) of T ⁇ to T( ⁇ +T ⁇ in the 13 C-NMR spectrum of the polar group-containing olefin copolymer is not more than 1.0, preferably not more than 0.8, more preferably not more than 0.5.
  • the polar group-containing olefin copolymer is excellent in orientation of the polar groups toward the interface between said copolymer and a polar material.
  • the second embodiment of the polar group-containing olefin copolymer of the invention is excellent in adhesion properties to metals and polar materials such as polar resins, compatibility therewith, surface hydrophilic properties, coating properties, printability, anti-fogging properties, antistatic properties, oil resistance, biocompatibility, dispersibility in water, dispersibility in solvent, pigment dispersibility, filler dispersibility, transparency, mechanical strength and moldability.
  • polar resins such as polar resins, compatibility therewith, surface hydrophilic properties, coating properties, printability, anti-fogging properties, antistatic properties, oil resistance, biocompatibility, dispersibility in water, dispersibility in solvent, pigment dispersibility, filler dispersibility, transparency, mechanical strength and moldability.
  • the third embodiment of the polar group-containing olefin copolymer of the invention comprises a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (6) (also referred to as a “constituent unit (6)), and optionally a constituent unit represented by the following formula (3).
  • the constituent unit represented by the formula (1) is identical with the aforesaid constituent unit (1), and the constituent unit represented by the formula (3) is identical with the aforesaid constituent unit (3).
  • the constituent unit represented by the formula (3) is also preferably a constituent unit represented by the following formula (3′).
  • R 3′ is a hydrocarbon group, preferably a hydrocarbon group of 1 to 20 carbon atoms, more preferably a hydrocarbon group of 3 to 20 carbon atoms.
  • p is an integer of 1 to 3, preferably 1.
  • X′ is a polar group containing O and/or N, preferably —OR, —COOR, —CRO, —NR 2 , an epoxy group,
  • R is hydrogen or hydrocarbon group
  • the constituent unit represented by the formula (3′) is, for example, a constituent unit derived from the polar group-containing monomer represented by the following formula (7′).
  • R 7 is a direct bond or an aliphatic hydrocarbon group of 1 or more carbon atoms, preferably a direct bond or a hydrocarbon group of 1 to 10 carbon atoms.
  • R 8 is a hydrogen atom, a direct bond or an aliphatic hydrocarbon group of 1 or more carbon atoms, preferably a direct bond or a hydrocarbon group of 1 to 10 carbon atoms.
  • Y is a polar group containing O and/or N, and preferred examples of such polar groups include the same groups as previously described with respect to X′.
  • n and n are each an integer of 0 to 2, and m+n is not 0.
  • s is 0 or 1.
  • the constituent unit represented by the formula (6) is, for example, a constituent unit derived from the polar group-containing monomer represented by the following formula (8).
  • the constituent unit (1), the constituent unit (3) and the constituent unit (6) are bonded usually at random.
  • the molar ratio ((1):(3)+(6)) between the constituent unit (1) and the total of the constituent unit (3) and the constituent unit (6) is in the range of usually 99.99:0.01 to 0.01:99.99, preferably 99.95:0.05 to 10:90, more preferably 99.9:0.1 to 30:70.
  • the molar ratio ((3):(6)) between the constituent unit (3) and the constituent unit (6) is in the range of usually 0:100 to 99.99:0.01, preferably 0:100 to 99:1, more preferably 0:100 to 90:10.
  • the third embodiment of the polar group-containing olefin copolymer of the invention may contain two or more kinds of the constituent units (1), may contain two or more kinds of the constituent units (3), and may contain two or more kinds of the constituent units (6).
  • the polar group-containing olefin copolymer of the invention may contain constituent units other than the Constituent unit (1), the constituent unit (3) and the constituent unit (6), within limits not detrimental to the objects of the present invention.
  • constituent units which may be contained include constituent units derived from cyclic olefins other than the polar group-containing monomer represented by the following formula (8) or (7), non-conjugated polyenes, hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinyl ester compounds, and vinyl chloride.
  • the amount thereof is not more than 30 mol %, preferably not more than 20 mol %, more preferably not more than 10 mol %, based on all constituent units to constitute the polar group-containing olefin copolymer.
  • the weight-average molecular weight (Mw) of the third embodiment of the polar group-containing olefin copolymer of the invention is in the range of usually 500 to 2,000,000, preferably 1,000 to 1,500,000, more preferably 5,000 to 1,300,000, and the molecular weight distribution (Mw/Mn) thereof is usually not more than 3, preferably not more than 2.8, more preferably not more than 2.5.
  • the polar group-containing olefin copolymer is excellent in orientation of the polar groups toward the interface between said copolymer and a polar material and has excellent adhesion properties to a polar material and excellent compatibility with a polar material.
  • the intensity ratio (T ⁇ /(T ⁇ +T ⁇ )) of T ⁇ to T ⁇ +T ⁇ in the 13 C-NMR spectrum of the polar group-containing olefin copolymer is not more than 1.0, preferably not more than 0.8, more preferably not more than 0.5.
  • the polar group-containing olefin copolymer is excellent in orientation of the polar groups toward the interface between said copolymer and a polar material.
  • the third embodiment of the polar group-containing olefin copolymer of the invention is excellent in adhesion properties to metals and polar materials such as polar resins, compatibility and flexibility.
  • the first embodiment of the process for preparing a polar-group containing olefin copolymer according to the invention comprises copolymerizing at least one ⁇ -olefin selected from ⁇ -olefins of 2 to 20 carbon atoms and at least one polar group-containing monomer selected from a polar group-containing monomer represented by the following formula (7) and a polar group-containing monomer represented by the following formula (8) in the presence of an olefin polymerization catalyst comprising:
  • (B-2) a compound which reacts with the compound (A) to form an ion pair (sometimes referred to as an “ionizing ionic compound” hereinafter), and
  • the transition metal compound (A) for use in the invention is a compound of a transition metal selected from Group 3 (including lanthanoid and actinoid) to Group 10 of the periodic table.
  • transition metals selected from Group 3 (including lanthanoid and actinoid) to Group 10 of the periodic table include scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, palladium, nickel, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron and ruthenium.
  • scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, palladium, nickel, cobalt and rhodium Particularly preferable are titanium, zirconium and hafnium.
  • transition metal compound (A) not only Ziegler-Natta catalyst and a metallocene catalyst but also a known organometallic complex is employable in the invention.
  • transition metal compounds (A) are any compounds represented by the following formulae (11) to (16).
  • M 1 is a transition metal atom of Group 3 (including lanthanoid and actinoid) to Group 10 of the periodic table, preferably a transition metal atom of Group 4, specifically zirconium, titanium or hafnium, preferably zirconium.
  • R 25 , R 26 , R 27 and R 28 may be the same or different and are each a hydrogen atom, a nitrogen-containing group, a phosphorus-containing group, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a halogen atom.
  • nitrogen-containing groups include amino group; primary amino group; alkylamino groups, such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; and arylamino groups or alkylaryl amino groups, such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino.
  • alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino
  • arylamino groups or alkylaryl amino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino.
  • Examples of the phosphorus-containing groups include phosphino groups, such as dimethylphosphino and diphenylphosphino.
  • Examples of the hydrocarbon groups of 1 to 20 carbon atoms include alkyl groups, cycloalkyl groups, alkenyl groups, arylalkyl groups and aryl groups. More specifically, there can be mentioned alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups, such as vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, nap
  • halogenated hydrocarbon groups of 1 to 20 carbon atoms include groups wherein the above-mentioned hydrocarbon groups of 1 to 20 carbon atoms are substituted with halogens.
  • oxygen-containing groups examples include hydroxyl group; alkoxyl groups, such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups, such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxyl groups, such as phenylmethoxy and phenylethoxy.
  • sulfur-containing groups include groups wherein oxygen is replaced with sulfur in the above-mentioned oxygen-containing groups; sulfonate groups, such as methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; and sulfinate groups, such as methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.
  • sulfonate groups such as methylsulfonate, trifluoromethanesulfonate, phenyls
  • Examples of the silicon-containing groups include monohydrocarbon-substituted silyls, such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls, such as dimethylsilyl and diphenylsilyl; trihydrocarbon-substituted silyls, such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls, such as trimethylsilyl ether; silicon-substituted alkyl groups, such as trimethylsilylmethyl; and silicon-substituted aryl groups, such as trimethylsilylphenyl.
  • halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • R 25 , R 26 , R 27 and R 28 are each shown at two positions, and for example, R 25 and R 25 may be the same groups or different groups. Of the groups indicted by R 25 to R 28 , the groups with the same symbols are a preferred combination of groups which are linked to form a ring.
  • Examples of the rings formed from a part of the neighboring groups out of R 25 , R 26 , R 27 and R 28 together with carbon atoms to which those groups are bonded include condensed rings, such as benzene ring, naphthalene ring, acenaphthene ring and indene ring; and groups wherein hydrogen atoms on these rings are replaced with alkyl groups such as methyl, ethyl, propyl and butyl.
  • a hydrocarbon group of 1 to 20 carbon atoms or a hydrogen atom preferable is a hydrocarbon group of 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl, a benzene ring formed by bonding of a hydrocarbon group, or a group wherein a hydrogen atom on a benzene ring formed by bonding of a hydrocarbon group is replaced with an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
  • X 1 and X 2 may be the same or different and are each the same hydrocarbon group of 1 to 20 carbon atoms, halogenated hydrocarbon group of 1 to 20 carbon atoms, oxygen-containing group, sulfur-containing group, silicon-containing group, hydrogen atom or halogen atom as described above with respect to R 25 , R 26 , R 27 and R 28 . Of these, preferable is a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a sulfonate group.
  • Y 1 is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO 2 —, —Ge—, —Sn—, —NR 21 —, —P(R 21 )—, —P(O)(R 21 )—, —BR 21 — or —AlR 21 — (each R 21 may be the same or different and is a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom or a halogen atom).
  • Examples of the divalent hydrocarbon groups of 1 to 20 carbon atoms include alkylene groups, such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and arylalkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene.
  • Examples of the divalent halogenated hydrocarbon groups of 1 to 20 carbon atoms include groups wherein the above-mentioned divalent hydrocarbon groups of 1 to 20 carbon atoms are halogenated, such as chloromethylene.
  • Examples of the divalent silicon-containing groups include alkylsilylene groups, such as silylene, methylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene, diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene; alkylarylsilylene groups; arylsilylene groups; alkyldisilylene groups, such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene; alkylaryldisilylene groups; and aryldisilylene groups.
  • alkylsilylene groups such as silylene, methylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene, di(i-propy
  • Examples of the divalent germanium-containing groups include groups wherein silicon is replaced with germanium in the above-mentioned divalent silicon-containing groups.
  • divalent tin-containing groups examples include groups wherein silicon is replaced with tin in the above-mentioned divalent silicon-containing groups.
  • R 21 is the same hydrocarbon group of 1 to 20 carbon atoms, halogenated hydrocarbon group of 1 to 20 carbon atoms or halogen atom as described above with respect to R 25 , R 26 , R 27 and R 28 , or a nitrogen compound residue in which one or two hydrocarbon groups of 1 to 20 carbon atoms are bonded to the nitrogen atom.
  • a substituted silylene group such as dimethylsilylene, diphenylsilylene or methylphenylsilylene, is particularly preferable as Y 1 .
  • Examples of the transition metal compounds represented by the formula (11) include
  • the transition metal compound represented by the formula (11) is more specifically a transition metal compound represented by the following formula (11a) or (11b).
  • M 1 is a transition metal atom of Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.
  • Each R 31 may be the same or different and is a hydrocarbon group of 1 to 6 carbon atoms.
  • hydrocarbon groups include alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexY 1 and cyclohexyl; and alkenyl groups, such as vinyl and propenyl.
  • alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexY 1 and cyclohexyl
  • alkenyl groups such as vinyl and propenyl.
  • preferable are alkyl groups whose carbon atoms
  • R 32 , R 34 , R 35 and R 36 may be the same or different and are each a hydrogen atom, a halogen atom or the same hydrocarbon group of 1 to 6 carbon atoms as described above with respect to R 31 .
  • Each R 33 may be the same or different and is a hydrogen atom or an aryl group of 6 to 16 carbon atoms.
  • aryl groups include phenyl, ( ⁇ -naphthyl, ⁇ -naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. Of these, preferable are phenyl, naphthyl, anthryl and phenanthryl.
  • halogen atoms such as fluorine, chlorine, bromine and iodine
  • hydrocarbon groups of 1 to 20 carbon atoms e.g., alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups, such as vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, ⁇ - or ⁇ -naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenap
  • organosilyl groups such as trimethylsilyl, triethylsilyl and triphenylsilyl.
  • X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).
  • atoms and groups preferable is a halogen atom or a hydrocarbon group of 1 to 20 carbon atoms.
  • Y 1 has the same meaning as that of Y 1 in the formula (11).
  • a divalent silicon-containing group a divalent germanium-containing group, a divalent alkylene group or a divalent boron-containing boronyl group
  • more preferable is a divalent silicon-containing group or a divalent alkylene group
  • particularly preferable is alkylsilylene, alkylarylsilylene, arylsilylene, alkylakylene or arylalkylene.
  • transition metal compounds represented by the formula (11a) include
  • a racemic modification of the transition metal compound represented by the formula (11a) is usually used as a catalyst component, but R-form or S-form is also employable.
  • transition metal compound represented by the formula (11a) can be prepared in accordance with the specification and examples of European Patent A No. 0,320,762 described in Journal of Organometallic Chem., 288, pp. 63-67 (1985).
  • M 1 is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium.
  • R 37 and R 38 may be the same or different and are each a hydrogen atom or the same nitrogen-containing group, phosphorus-containing group, hydrocarbon group of 1 to 20 carbon atoms, halogenated hydrocarbon group of 1 to 20 carbon atoms, oxygen-containing group, sulfur-containing group, silicon-containing group or halogen atom as described above with respect to R 25 , R 26 , R 27 and R 28 in the formula (11).
  • R 37 is preferably a hydrocarbon group of 1 to 20 carbon atoms, particularly preferably a hydrocarbon group of 1 to 3 carbon atoms such as methyl, ethyl or propyl.
  • R 38 is preferably a hydrogen atom or a hydrocarbon group of 1 to 20 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms such as methyl, ethyl or propyl.
  • R 39 and R 40 may be the same or different and are each an alkyl group of 1 to 20 carbon atoms.
  • alkyl groups include straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecY 1 and eicosyl; and cycloalkyl groups, such as norbornyl and adamantyl.
  • R 39 is preferably a secondary or tertiary alkyl group.
  • X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).
  • Y 1 has the same meaning as that of Y 1 in the formula (11).
  • Examples of the transition metal compounds represented by the formula (11b) include
  • a racemic modification of the transition metal compound represented by the formula (11b) is usually used as a catalyst component, but R-form or S-form is also employable.
  • the transition metal compound represented by the formula (11b) can be synthesized from an indene derivative by a known process, for example, a process described in Japanese Patent Laid-Open Publication No. 268307/1992.
  • M 1 is a transition metal atom selected from Group 3 to Group 10 of the periodic table, preferably a transition metal atom selected from Group 4 of the periodic table, more preferably zirconium, titanium or hafnium, particularly preferably zirconium.
  • Cp is a cyclopentadienyl group or its derivative that is ⁇ -bonded to M 1 .
  • Z 1 is a ligand containing an oxygen atom, a sulfur atom, a boron atom or an element of Group 14 of the periodic table, for example, —Si(R 22 2 )—, —C(R 22 2 )—, —Si(R 22 2 )Si(R 22 2 )—, —C(R 22 2 )C(R 22 2 )—, —C(R 22 2 )C(R 22 2 )C(R 22 2 )—, —C(R 22 ) ⁇ C(R 22 )—, —C(R 22 2 )Si(R 22 2 )— or —Ge(R 22 2 )—.
  • Y 1 is a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, —N(R 23 )—, —O—, —S— or —P(R 23 )—.
  • Z 1 and Y 1 may together form a condensed ring.
  • R 22 is a hydrogen atom, an alkyl, aryl, silyl, halogenated alkyl or halogenated aryl group having up to 20 of non-hydrogen atoms, or a combination of such groups.
  • R 23 is an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atom or an aralkyl group of 7 to 10 carbon atoms, or may form a condensed ring of up to 30 non-hydrogen atoms together with one or more R 22 .
  • Each X 1 may be the same or different and is a hydrogen atom, a halogen atom, a hydrocarbon group which has 20 or less carbon atoms and may contain 1 or more double bonds, a silyl group containing 20 or less silicon atoms, a germyl group containing 20 or less germanium atoms or a boronyl group containing 20 or less boron atoms.
  • Examples of the transition metal compounds represented by the formula (12) include
  • M 1 is a transition metal atom selected from Group 3 to Group 10 of the periodic table, preferably a transition metal atom selected from Group 4 of the periodic table, more preferably titanium, zirconium or hafnium, particularly preferably zirconium.
  • R 11 to R 14 , R 17 to R 20 , and R 41 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom; of the groups indicated by R 11 , R 12 , R 13 , R 14 , R 17 , R 18 , R 19 , R 20 and R 41 , a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded (except a case where all of R 11 , R 12 , R 13 , R 14 , R 17 , R 18 , R 19 , R 20 and R 41 are hydrogen atoms and a case where R 12 or R 13 is a tert-butyl group and the residual R 11 , R 12 , R 13 , R 14 , R 17
  • hydrocarbons of 1 to 40 carbon atoms are examples of hydrocarbons of 1 to 40 carbon atoms.
  • alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecY 1 and eicosyl;
  • aryl groups of 6 to 20 carbon atoms such as phenyl, ⁇ - or ⁇ -naphthyl, biphenylyl, anthryl and phenanthryl;
  • aryl alkyl groups of 7 to 40 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenanthrylmethyl, phenanthrylethyl and phenanthrylpropyl;
  • aryl alkenyl groups of 8 to 40 carbon atoms such as vinylphenanthryl
  • alkyl aryl groups of 7 to 40 carbon atoms such as methylphenanthryl, ethylphenanthryl and propylphenanthryl;
  • alkenyl groups of 2 to 10 carbon atoms such as vinyl, propenyl and cyclohexenyl.
  • halogenated hydrocarbon groups of 1 to 40 carbon atoms include groups wherein the above-mentioned hydrocarbon groups of 1 to 40 carbon atoms are substituted with halogens.
  • Examples of the oxygen-containing groups, the sulfur-containing groups, the silicon-containing groups and the halogen atoms include the same groups and atoms as previously described with respect to R 25 , R 26 , R 27 and R 28 in the formula (11).
  • X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).
  • Y 1 has the same meaning as that of Y 1 in the formula (11).
  • Examples of the transition metal compounds represented by the formula (13) include
  • M 1 is a transition metal atom selected from Group 3 to Group 10 of the periodic table, preferably a transition metal atom selected from Group 4 of the periodic table, more preferably titanium, zirconium or hafnium, particularly preferably zirconium.
  • R 11 , R 12 , R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.
  • hydrocarbon groups of 1 to 40 carbon atoms include the same groups as previously described with respect to R 11 to R 14 , R 17 to R 20 and R 41 in the formula (13).
  • Examples of the oxygen-containing groups, the sulfur-containing group, the silicon-containing groups and the halogen atoms include the same groups and atoms as previously described with respect to R 25 , R 26 , R 27 and R 28 in the formula (11).
  • a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded.
  • a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded.
  • X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).
  • Y 1 has the same meaning as that of Y 1 in the formula (11), but when all of R 11 , R 12 , R 41 and R 42 are hydrogen atoms, Y 1 is not ethylene.
  • Examples of the transition metal compounds represented by the formula (14) include
  • diphenylsilylene (3-methyl- ⁇ -acenaphto-1-indenyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride
  • M 1 is a transition metal atom selected from Group 3 to Group 10 of the periodic table, preferably a transition metal atom selected from Group 4 of the periodic table, more preferably titanium, zirconium or hafnium, particularly preferably zirconium.
  • R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.
  • hydrocarbon groups of 1 to 40 carbon atoms include the same groups as previously described with respect to R 11 to R 14 , R 17 to R 20 and R 41 in the formula (13).
  • Examples of the oxygen-containing groups, the sulfur-containing group, the silicon-containing groups and the halogen atoms include the same groups and atoms as previously described with respect to R 25 , R 26 , R 27 and R 28 in the formula (11).
  • groups indicated by R 41 and R 42 a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded
  • X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).
  • Y 1 has the same meaning as that of Y 1 in the formula (11).
  • Examples of the transition metal compounds represented by the formula (15) include
  • M 1 is a transition metal atom selected from Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium.
  • R 11 , R 12 , R 15 to R 20 , and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.
  • hydrocarbon groups of 1 to 40 carbon atoms include the same groups as previously described with respect to R 11 to R 14 , R 17 to R 20 and R 41 in the formula (13).
  • Examples of the oxygen-containing groups, the sulfur-containing group, the silicon-containing groups and the halogen atoms include the same groups and atoms as previously described with respect to R 25 , R 26 , R 27 and R 28 in the formula (11).
  • a part of the groups neighboring with each other may be bonded to form a ring together with carbon atoms to which those groups are bonded.
  • X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).
  • Y 1 has the same meaning as that of Y 1 in the formula (11).
  • Examples of the transition metal compounds represented by the formula (16) include the same compounds as previously exemplified with respect to the compounds of the formula (11a) or (11b).
  • transition metal compounds (A) mentioned above can be used singly or in combination of two or more kinds.
  • the organoaluminum oxy-compound (B-1) for use in the invention may be conventional aluminoxane (also referred to as “alumoxane”) or such a benzene-insoluble organoaluminum oxy-compound as exemplified in Japanese Patent Laid-Open Publication No. 78687/1990.
  • the conventional aluminoxane can be prepared by, for example, the following processes, and is generally obtained as a hydrocarbon solvent solution.
  • An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorption water or a salt containing water of crystallization, e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, to allow the organoaluminum compound to react with the adsorption water or the water of crystallization.
  • a compound containing adsorption water or a salt containing water of crystallization e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate
  • organotin oxide such as dimethyltin oxide or dibutyltin oxide is allowed to react with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.
  • the aluminoxane may contain a small amount of an organometallic component. Further, it is possible that the solvent or the unreacted organoaluminum compound is distilled off from the recovered solution of aluminoxane and the remainder is redissolved in a solvent.
  • organoaluminum compounds used for preparing the aluminoxane include trialkylaluminums, such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum;
  • trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctyla
  • tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum
  • dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;
  • dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride
  • dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide
  • dialkylaluminum aryloxides such as diethylaluminum phenoxide.
  • trialkylaluminums and tricycloalkylaluminums are preferable.
  • organoaluminum compounds used for preparing the aluminoxane include isoprenylaluminum represented by the formula (i-C 4 H 9 ) x Al y (C 5 H 10 ) z (wherein x, y and z are each a positive number, and z ⁇ 2x)
  • the organoaluminum compounds are used singly or in combination of two or more kinds.
  • Examples of the solvents used for preparing the aluminoxane include aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions, such as gasoline, kerosine and gas oil; and halogenated products of these aromatic, aliphatic and alicyclic hydrocarbons (e.g., chlorinated or brominated products thereof). Also employable are ethers such as ethyl ether and tetrahydrofuran. Of the solvents, particularly preferable are aromatic hydrocarbons.
  • the organoaluminum oxy-compound for use in the invention is, for example, an organoaluminum oxy-compound containing boron and represented by the following formula (17):
  • R 8 is a hydrocarbon group of 1 to 10 carbon atoms; and each R 9 may be the same or different and is a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 10 carbon atoms.
  • Examples of the compound (B-2) which reacts with the transition metal compound (A) to form an ion pair include Lewis acid, an ionic compound, a borane compound and a carborane compound, which are described in National Publications of International Patents No. 501950/1989 and No. 502036/1989, Japanese Patent Laid-Open Publications No. 179005/1991, No. 179006/1991, No. 207703/1991 and No. 207704/1991, and U.S. Pat. No. 5,321,106.
  • a heteropoly compound and an isopoly compound are also available.
  • the Lewis acid examples include magnesium-containing Lewis acid, aluminum-containing Lewis acid and boron-containing Lewis acid. Of these, boron-containing Lewis acid is preferable.
  • the ionic compound is a salt comprising a cationic compound and an anionic compound. The anion reacts with the transition metal compound to make the transition metal compound cationic and thereby form an ion pair, whereby the transition metal cationic species are stabilized.
  • examples of such anions include organoboron compound anion, organoarsenic compound anion and organoaluminum compound anion. Preferable are those which are relatively bulky and stabilize the transition metal cationic species.
  • Lewis acids containing boron atoms are, for example, compounds represented by the following formula (18);
  • R′, R′′ and R′′′ may be the same or different and are each a fluorine atom or a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group.
  • Examples of compounds represented by the formula (18) include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, tris(3,5-dimethylphenyl)boron and tris[3,5-di(trifluoromethylphenyl)]boron. Of these, preferable is tris(pentafluorophenyl)boron.
  • the ionic compound is a salt comprising a cationic compound and an anionic compound.
  • An anion is reacted with the above transition metal compound to cationize it and form an ion pair which has a function of stabilizing the cation species of the transition metal compound.
  • Examples of such anions include organic boron compound anion, organic arsenic compound anion and organic aluminum compound anion, and preferable are relatively bulky and can stabilize the transition metal cationic species.
  • Cations include metal cation, organic metal cation, carbonium cation, tropylium cation, oxisonium cation, sulfonium cation, phosphonium cation and ammonium cation and, more in detail, triphenylcarbenium cation, tributylammonium cation, N,N-dimethylammonium cation and ferrocenium cation.
  • preferable anions are ionic compounds containing boron compounds as anion.
  • trialkyl-substituted ammonium salts include;
  • tripropylammoniumtetra(phenyl)boron tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron,
  • N,N-dialkylanilinium salts examples include
  • dialkylammonium salts examples include di(n-propyl)ammoniumtetra(pentafluorophenyl)boron and dicyclohexylammoniumtetra(phenyl)boron.
  • triarylphosphonium salts examples include
  • triphenylcarbeniumtetrakis(pentafluorophenyl)borate N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate
  • the ionic compounds having a boron atom are the following compounds. (In the following ionic compounds, the counter ion is tri(n-butyl)ammonium but not restricted.)
  • salts of anions include
  • Examples of salts of borane compounds, carborane compolex compounds and carborane anion include
  • ionic compounds containing a boron atom are following metallic carborane salts and metallic boran anion.
  • the counter ion is tri(n-butyl)ammonium but not restricted.
  • ionic compounds containing a boron atom include following compounds such as
  • the heteropoly compound comprises an atom selected from silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
  • examples of such compounds include phosphovanadic acid, germanovanadic acid, arsenovanadic acid, phosphoniobic acid, germanoniobic acid, silicomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenomolybdic acid, stannomolybdic acid, phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotaungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdon
  • the ionizing ionic compounds may be used singly or in combination of two or more kinds.
  • organoaluminum compounds (B-3) used in the present invention can be represented by the following formula (21):
  • R a is a hydrocarbon group of 1 to 12 carbon atoms
  • X is a halogen atom or a hydrogen atom
  • n is 1 to 3.
  • R a is a hydrocarbon group of 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group. Examples include a methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexY 1 group, octY 1 group, cyclopentyl group, cyclohexY 1 group, phenyl group and tolyl group.
  • organoaluminum compounds examples include
  • trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum;
  • alkenylaluminums such as isoprenylaluminum
  • dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide;
  • alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide,
  • alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;
  • alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.
  • organoaluminum compounds (B-3) can be also represented by the following formula (22):
  • R a is the same as previously described
  • Y is a —OR b group, —OSiR c 3 group, —OAlR d 2 group, —NR e 2 group, —SiR f 3 group or —N(R g )AlR h 2 group
  • n is 1 to 2
  • R b , R c , R d and R h are each a methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group and phenyl group
  • R e is hydrogen, a methyl group, ethyl group, isopropyl group, phenyl group and trimethyl group
  • Rf and Rg are each a methyl group and ethyl group.
  • organoaluminum compounds examples include
  • organoaluminum compounds represented by R a 3 Al, R a n Al(OR b ) 3 ⁇ n , and R a n Al(OAlR d 2 ) 3 ⁇ n .
  • the organoaluminum compounds can be used in combination of two or more kinds.
  • the olefin polymerization catalyst used in the present invention comprises the transition metal compound (A) and at least one compound selected from the group consisting of the organoaluminum-oxy compound (B-1), the ionizing ionic compound (B-2) and the organoaluminum compound (B-3).
  • the catalyst comprises said compound (A) and the organoaluminum-oxy compound (B-1) and/or the ionizing ionic compound (B-2), and optionally the organoaluminum compound (B-3).
  • the olefin polymerization catalyst for use in the invention may be a solid catalyst in which the transition metal compound (A) and at least one component selected from the organoaluminum oxy-compound (B-1), the ionizing ionic compound (B-2) and the organoaluminum compound (B-3) are supported on a particle carrier, or a prepolymerized catalyst comprising a particle carrier, the transition metal compound (A), the organoaluminum oxy-compound (B-1) (or the ionizing ionic compound (B-2)), an olefin polymer produced by prepolymerization, and if necessary, the organoaluminum compound (B-3).
  • An particulate carriers used in the solid catalyst and the prepolymerized catalyst is an inorganic or organic compound in the form of granular or particulate solid having a particle diameter of 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m.
  • the inorganic carrier are porous oxides, inorganic chlorides, clay, clay minerals and ion-exchange layred compounds.
  • Ecamples of porous oxides include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , and mixtures containing these oxides, such as SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 and SiO 2 —TiO 2 —MgO.
  • preferable are compounds containing SiO 2 and/or Al 2 O 3 as the main component.
  • the inorganic oxides may contain small amounts of carbonate, sulfate, nitrate and oxide components, such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 , Na 2 O, K 2 O and Li 2 O.
  • carbonate, sulfate, nitrate and oxide components such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 , Na 2 O, K 2 O and Li 2 O.
  • the particulate carrier preferably has a specific surface area of 50 to 1,000 m 2 /g, preferably 100 to 700 m 2 /g, and a pore volume of 0.3 to 2.5 cm 3 /g. If necessary, the particulate carrier may be calcined at 100 to 1,000° C., preferably 150 to 700° C., prior to use.
  • the particulate carrier is, for example, a granular or particulate solid organic compound having a particle diameter of 10 to 300 ⁇ m.
  • organic compounds include (co)polymers produced using an ⁇ -olefin of 2 to 14 carbon atoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene as a main ingredient and (co)polymers produced using vinylcyclohexane or styrene as a main ingredient.
  • Examples of the inorganic chlorides employable in the invention include MgCl 2 , MgBr 2 , MnCl 2 and MnBr 2 .
  • the inorganic chloride may be used as it is, or may be used after pulverized by, for example, a ball mill or an oscillating mill.
  • the inorganic chloride may also be used as fine particles of a obtained by dissolving the inorganic chloride in a solvent such as alcohol and then precipitating using a precipitant.
  • the clay is generally composed mainly of clay minerals.
  • the ion-exchange layered compounds are compounds having a crystal structure wherein planes formed by ionic bonding or the like are laminated in parallel to one another with a weak bond strength, and the ions contained therein are exchangeable. Most of clay minerals are ion-exchange layered compounds.
  • the clay, the clay minerals and the ion-exchange layered compounds employable in the invention are not limited to natural ones but include synthetic ones.
  • Examples of such clay, clay minerals and ion-exchange layered compounds include clay, clay minerals and ion crystalline compounds having layered crystal structures such as hexagonal closest packing type, antimony type, CdCl 2 type and CdI 2 type.
  • clay and the clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, mica, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, nacrite, dickite and halloysite.
  • ion-exchange layered compounds include crystalline acid salts of polyvalent metals, such as ⁇ -Zr(HAsO 4 ) 2 .H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr (KPO 4 ) 2 .3H 2 O, ⁇ -Ti(HPO 4 ) 2 , ⁇ -Ti(HAsO 4 ) 2 . H 2 O, ⁇ -Sn(HPO 4 ) 2 .H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Ti(HPO 4 ) 2 and ⁇ -Ti(NH 4 PO 4 ) 2 .H 2 O.
  • polyvalent metals such as ⁇ -Zr(HAsO 4 ) 2 .H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr (KPO 4 ) 2 .3H 2 O, ⁇ -Ti(HPO 4 ) 2 , ⁇ -Ti(HAs
  • the clay, the clay minerals and the ion-exchange layered compounds are preferably those having a pore volume, as measured on pores having a radius of not less than 20 ⁇ by a mercury penetration method, of not less than 0.1 cc/g, and are particularly preferably those having a pore volume of 0.3 to 5 cc/g.
  • the pore volume is measured on the pores having a radius of 20 to 3 ⁇ 10 4 ⁇ by a mercury penetration method using a mercury porosimeter.
  • the clay and the clay minerals are subjected to chemical treatments. Any of surface treatments, for example, to remove impurities attached to the surface and to influence on the crystal structure of the clay, are employable.
  • Examples of such chemical treatments include acid treatment, alkali treatment, salt treatment and organic substance treatment.
  • the acid treatment can contribute to not only removing impurities from the surface but also eluting cations such as Al, Fe and Mg present in the crystal structure to increase the surface area.
  • the alkali Ad treatment can destroy crystal structure of clay to bring about change in the structure of the clay.
  • the salt treatment and the organic substance treatment can produce, for example, ionic composites, molecular composites, or organic derivative to change the surface area or the distance between layers.
  • the ion-exchange layered compound may be a layered compound in which the exchangeable ions between layers have been exchanged with other large and bulky ions utilizing ion exchange properties to enlarge the distance between the layers.
  • the bulky ion plays a pillar-like roll to support the layer structure and is generally called a “pillar”. Introduction of other substances between layers of a layered compound is called “intercalation”.
  • Examples of the guest compounds to be intercalated include cationic inorganic compounds, such as TiCl 4 and ZrCl 4 ; metallic alkoxides, such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon group or the like); and metallic hydroxide ions, such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2+ and [Fe 3 O(OCOCH 3 ) 6 ] + .
  • the compounds mentioned above may be used singly or in combination of two or more kinds.
  • the intercalation of the compounds may be carried out in the presence of polymers obtained by hydrolysis of metallic alkoxides such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4 (R is a hydrocarbon group or the like) or in the presence of colloidal inorganic compounds such as SiO 2 .
  • the pillars include oxides produced by intercalation of the above-mentioned metallic hydroxide ions between layers, followed by dehydration under heating.
  • the clay, clay minerals and ion-exchange layered compounds mentioned above may be used as they are, or may be used after they are subjected to a treatment of ball milling, sieving or the like. Moreover, they may be used after they are subjected to water adsorption or dehydration under heating.
  • the clay, clay minerals and ion-exchange layered compounds may be used singly or in combination of two or more kinds.
  • clay and clay minerals are preferable, and particularly preferable are montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica.
  • the olefin polymerization catalyst for use in the invention may contain the following organosilicon compound (C) and/or the following dialkylzinc compound (D).
  • organosilicon compound (C) which is used optionally is represented by the following formula (22):
  • R 1 , R 2 and R 3 may be the same or different and are each a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, an aryl group of 6 to 12 carbon atoms, such as phenyl or tolyl, an alkylaryl group of 7 to 20 carbon atoms, such as ethylphenyl or ethyltolyl, an arylalkyl group of 7 to 20 carbon atoms, such as phenylethyl or benzyl, an alkoxyl group of 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a fluorinated alkyl group of 3 to 6 carbon atoms, such as 3,3,3-trifluoropropyl, a dialkylamino group containing an alkyl group
  • preferable is a hydrogen atom, methyl, ethyl, isopropyl, isobutyl, 3,3,3-trifluoropropyl dimethyamino or a group represented by R 6 3 SiO(SiR 6 2 O) n —.
  • Preferred examples of the organosilicon compounds represented by the formula (22) include phenylsilane, diphenylsilane, phenylmethylsilane, pentamethyldisiloxane, methylsilane and dimethylsilane.
  • organosilicon compounds mentioned above can be used singly or in combination of two or more kinds.
  • dialkylzinc compound (D) which is used optionally is represented by the following formula (23):
  • R 4 and R 5 may be the same or different and are each an alkyl group of 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, nonyl, decyl, dodecY 1 or eicosyl.
  • alkyl group of 1 to 12 carbon atoms preferable is an alkyl group of 1 to 6 carbon atoms.
  • dialkylzinc compounds represented by the formula (23) include diethylzinc, diisobutylzinc an di-n-decylzinc. Of these, diethylzinc is particularly preferable.
  • dialkylzinc compounds (D) mentioned above can be used singly or in combination of two or more kinds.
  • the organosilicon compound (C) and the dialkylzinc compound (D) can be each used as a chain transfer agent in combination with hydrogen.
  • the organosilicon compound (C) is used as a chain transfer agent, an olefin polymer having a silyl group at the end is obtained.
  • Examples of the ⁇ -olefins of 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4, 4-dimethyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Of these, preferable is an ⁇ -olefin selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
  • R 3 , R 4 , r, X and p have the same meanings as those of R 3 , R 4 , r, X and p, respectively, in the formula (3).
  • Examples of the polar group-containing monomers include:
  • ⁇ -alkenylalcohols such as allylalcohol, 4-pentene-1-ol, 5-hexene-1-ol, 6-heptene-1-ol, 7-octene-1-ol, 8-nonene-1-ol, 9-decene-1-ol, 10-undecene-1-ol and 11-dodecene-1-ol;
  • alcohols having a straight-chain hydrocarbon group such as 5-hexene-2-ol, 6-heptene-2-ol, 7-octene-2-ol, 8-nonene-2-ol, 9-decene-2-ol, 10-undecene-2-ol, 6-heptene-3-ol, 7-octene-3-ol, 8-nonene-3-ol, 9-decene-3-ol, 10-undecene-3-ol, 11-dodecene-3-ol, 7-octene-4-ol, 8-nonene-4-ol, 9-decene-4-ol, 10-undecene-4-ol, 8-nonene-5-ol, 9-decene-5-ol and 10-undecene-5-ol;
  • alcohols having a branched hydrocarbon group such as 2-ethyl-5-hexene-1-ol, 3-methyl-6-heptene-1-ol, 3-methyl-7-octene-1-ol, 4-methyl-8-nonene-1-ol, 3-ethyl-9-decene-1-ol, 2-methyl-10-undecene-2-ol, 2,2-dimethyl-7-octene-1-ol, 3-ethyl-2-methyl-8-nonene-1-ol, 2,2,3-trimethyl-9-decene-1-ol and 2,3,3,4-tetramethyl-10-undecene-2-ol;
  • diols such as 9-decene-1,2-diol, 10-undecene-1,2-diol, 11-dodecene-1,2-diol and 11-dodecene-1,2-diol;
  • triols such as 10-undecene-1,2,3-triol
  • ⁇ -alkenylcarboxylic acids such as 3-butenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid and 11-dodecenoic acid;
  • alkenylcarboxylic acids having a straight-chain hydrocarbon group such as 2-methyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2-methyl-10-undecenoic acid, 2-methyl-11-dodecenoic acid, 2-ethyl-5-hexenoic acid, 2-ethyl-6-heptenoic acid, 2-ethyl-7-octenoic acid, 2-ethyl-8-nonenoic acid, 2-ethyl-9-decenoic acid, 2-ethyl-10-undecenoic acid, 2-propyl-5-hexenoic acid, 2-propyl-6-heptenoic acid, 2-propyl-7-octenoic acid, 2-propyl-8-nonenoic acid, 2-propyl-9-decenoic acid, 2-propyl-10-undecenoic acid,
  • alkenylcarboxylic acids having a branched hydrocarbon group such as 2-isopropyl-5-hexenoic acid, 2-isopropyl-6-heptenoic acid, 2-isopropyl-7-octenoic acid, 2-isopropyl-8-nonenoic acid, 2-isopropyl-9-decenoic acid, 2-isopropyl-10-undecenoic acid, 2-isobutyl-5-hexenoic acid, 2-t-butyl-6-heptenoic acid, 2-isopropyl-3-methyl-7-octenoic acid, 2-methyl-3-isopropyl-8-nonenoic acid, 3-isobutyl-3-methyl-9-decenoic acid, 2,2-dimethyl-10-undecenoic acid and 2,3,3-trimethyl-11-dodecenoic acid;
  • ⁇ -alkenylcarboxylic acid esters such as methyl 3-butenoate, methyl 5-hexenoate, methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, methyl 11-dodecenoate, ethyl 5-hexenoate, ethyl 6-heptenoate, ethyl 7-octenoate, ethyl 8-nonenoate, ethyl 9-decenoate, ethyl 10-undecenoate, ethyl 11-dodecenoate, isopropyl 5-hexenoate, isopropyl 6-heptenoate, isopropyl 7-octenoate, isopropyl 8-nonenoate, isopropyl 9-decenoate, isopropyl 5-
  • alkenylcarboxylic acid esters having a straight-chain hydrocarbon group such as methyl 2-methyl-5-hexenoate, methyl 2-methyl-6-heptenoate, ethyl 2-methyl-7-octenoate, methyl 2-methyl-8-nonenoate, butyl 2-methyl-9-decenoate, ethyl 2-methyl-10-undecenoate, butyl 2-ethyl-5-hexenoate, ethyl 2-ethyl-6-heptenoate, isopropyl 2-ethyl-7-octenoate, ethyl 2-ethyl-8-nonenoate, methyl 2-ethyl-9-decenoate, ethyl 2-ethyl-10-undecenoate, methyl 2-propyl-5-hexenoate, methyl 2-propyl-6-heptenoate, ethyl 2-propyl-7-octenoate, such as
  • alkenylcarboxylic acids having a branched hydrocarbon group such as butyl 2-isopropyl-5-hexenoate, ethyl 2-isopropyl-6-heptenoate, methyl 2-isopropyl-7-octenoate, methyl 2-isopropyl-8-nonenoate, butyl 2-isopropyl-9-decenoate, methyl 2-isopropyl-10-undecenoate, methyl 2-isobutyl-5-hexenoate, methyl 2-t-butyl-6-heptenoate, ethyl 2-isopropyl-3-methyl-7-octenoate and propyl 3-isobutyl-3-methyl-9-decenoate;
  • ⁇ -alkenylamines such as allylamine, 5-hexene amine, 6-heptene amine, 7-octene amine, 8-nonene amine, 9-decene amine, 10-undecene amine and 11-dodecene amine;
  • alkenylamines having a straight-chain hydrocarbon group such as 2-methyl-5-hexene amine, 2-methyl-6-heptene amine, 2-methyl-7-octene amine, 2-methyl-8-nonene amine, 2-methyl-9-decene amine, 2-methyl-10-undecene amine, 2-methyl-11-dodecene amine, 2-ethyl-5-hexene amine, 2-ethyl-6-heptene amine, 2-ethyl-7-octene amine, 2-ethyl-8-nonene amine, 2-ethyl-9-decene amine, 2-ethyl-10-undecene amine, 2-propyl-5-hexene amine, 2-propyl-6-heptene amine, 2-propyl-5-hexene amine, 2-propyl-6-heptene amine, 2-propyl-7-octene amine, 2-propyl-5-he
  • alkenylamines having a branched hydrocarbon group such as 2-isopropyl-5-hexene amine, 2-isopropyl-6-heptene amine, 2-isopropyl-7-octene amine, 2-isopropyl-8-nonene amine, 2-isopropyl-9-decene amine, 2-isopropyl-90-undecene amine, 2-isobutyl-5-hexene amine, 2-t-butyl-6-heptene amine, 2-isopropyl-3-methyl-7-octene amine, 2-methyl-3-iso propyl-8-nonene amine, 3-isobutyl-3-methyl-9-decene amine, 2,2-dimethyl-10-undecene amine and 2,3,3-trimethyl-11-dodecene amine;
  • N-alkyl- ⁇ -alkenylamines such as N-methyl-5-hexene amine, N-methyl-6-heptene amine, N-methyl-7-octene amine, N-methyl-8-nonene amine, N-methyl-9-decene amine, N-methyl-10-undecene amine, N-methyl-11-dodecene amine, N-ethyl-5-hexene amine, N-ethyl-6-heptene amine, N-ethyl-7-octene amine, N-ethyl-8-nonene amine, N-ethyl-9-decene amine, N-ethyl-10-undecene amine and N-ethyl-11-dodecene amine;
  • N-alkylalkenylamines having a straight-chain hydrocarbon group such as N-methyl-6-heptene-2-amine, N-ethyl-7-octene-2-amine, N-methyl-8-nonene-2-amine, N-ethyl-9-decene-2-amine, N-methyl-10-undecene-2-amine, N-ethyl-8-nonene-3-amine, N-methyl-9-decene-3-amine, N-ethyl-10-undecene-3-amine, N-ethyl-8-nonene-4-amine, N-methyl-9-decene-4-amine and N-ethyl-10-undecene-4-amine;
  • N-alkylalkenylamines having a branched hydrocarbon group such as N-methyl-2-methyl-5-hexene amine, N-ethyl-2-methyl-6-heptene amine, N-methyl-2-methyl-7-octene amine, N-ethyl-2-methyl-8-nonene amine, N-ethyl-2-methyl-9-decene amine, N-methyl-2-methyl-19-undecene amine, N-methyl-2-ethyl-7-octene amine, N-ethyl-2-ethyl-9-decene amine and N-methyl-2-ethyl-19-undecene amine;
  • N,N-dialkyl-w-alkenylamines such as N,N-dimethyl-5-hexene amine, N,N-dimethyl-6-heptene amine, N,N-dimethyl-7-octene amine, N,N-dimethyl-8-nonene amine, N,N-dimethyl-9-decene amine, N,N-dimethyl-10-undecene amine, N,N-dimethyl-11-dodecene amine, N,N-diethyl-5-hexene amine, N,N-diethyl-6-heptene amine, N,N-diethyl-7-octene amine, N,N-diethyl-8-nonene amine, N,N-diethyl-9-decene amine, N,N-diethyl-10-undecene amine and N,N-diethyl-11-dodecen
  • N,N-dialkylalkenylamines having a straight-chain hydrocarbon group such as N,N-dimethyl-6-heptene-2-amine, N,N-diethyl-7-octene-2-amine, N,N-dimethyl-8-nonene-2-amine, N,N-diethyl-9-decene-2-amine, N,N-dimethyl-10-undecene-2-amine, N,N-diethyl-8-nonene-3-amine, N,N-dimethyl-9-decene-3-amine, N,N-diethyl-10-undecene-3-amine, N,N-diethyl-8-nonene-4-amine, N,N-dimethyl-9-decene-4-amine and N,N-diethyl-10-undecene-4 amine; and
  • N,N-dialkylalkenylamines having a branched hydrocarbon group such as N,N-dimethyl-2-methyl-5-hexene amine, N,N-diethyl-2-methyl-6-heptene amine, N,N-dimethyl-2-methyl-7-octene amine, N,N-diethyl-2-methyl-8-nonene amine, N,N-diethyl-2-methyl-9-decene amine, N,N-dimethyl-2-methyl-10-undecene amine, N,N-dimethyl-2-ethyl-7-octene amine, N,N-diethyl-2-ethyl-9-decene amine and N,N-dimethyl-2-ethyl-10-undecene amine;
  • ⁇ -alkenylamides such as allylamide, 5-hexene amide, 6-heptene amide, 7-octene amide, 8-nonene amide, 9-decene amide, 10-undecene amide and 11-dodecene amide;

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