WO2008004514A1 - Composé de silicium contenant une chaîne polyoléfine et polymère d'oléfine - Google Patents

Composé de silicium contenant une chaîne polyoléfine et polymère d'oléfine Download PDF

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Publication number
WO2008004514A1
WO2008004514A1 PCT/JP2007/063221 JP2007063221W WO2008004514A1 WO 2008004514 A1 WO2008004514 A1 WO 2008004514A1 JP 2007063221 W JP2007063221 W JP 2007063221W WO 2008004514 A1 WO2008004514 A1 WO 2008004514A1
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group
atom
olefin
carbon atoms
polymer
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PCT/JP2007/063221
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English (en)
Japanese (ja)
Inventor
Nobuo Kawahara
Norio Kashiwa
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Mitsui Chemicals, Inc.
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Priority to JP2008523671A priority Critical patent/JPWO2008004514A1/ja
Publication of WO2008004514A1 publication Critical patent/WO2008004514A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups

Definitions

  • the present invention relates to a novel key compound having a polyolefin chain in the molecule, and an olefin polymer.
  • Polyolefins have excellent processability, chemical resistance, electrical properties, mechanical properties, etc., and are therefore processed into extruded products, injection molded products, hollow molded products, films, sheets, and the like. It is used for various purposes.
  • polyolefin is a non-polar resin that does not have a polar group in its molecule, it adheres to polar substances that have poor affinity with metals and various polar substances. Also, blending with polar resins was difficult.
  • a polar group has been introduced into polyolefin.
  • a method of reacting polyolefin and polar olefin in the presence of a radical initiator is generally performed.
  • the polar group-containing olefin polymer obtained by such a method often contains a homopolymer of radically polymerizable polar olefin or unreacted polyolefin, and the introduction positions are non-uniform. In some cases, it may be accompanied by a cross-linking / decomposition reaction, which may impair the physical properties of the polymer.
  • Japanese Patent Application Laid-Open No. 2002-145944 disclose that a polar group-containing olefin polymer is used in the production of an olefin polymer. Is disclosed. However, these methods have problems such as poor introduction efficiency of reactive groups into olefin polymers.
  • Japanese Patent Application Laid-Open No. 7-196728 discloses an amino group-containing polymer, but there is a problem that the amino group concentration in the polymer is low.
  • Japanese Laid-Open Patent Publication No. 9-59317 discloses a method for producing a silicon-containing polyolefin. However, liquid oligomer is used as the polyolefin, and sufficient mechanical strength cannot be expected.
  • the smaller the diameter of the dispersed phase the more the polyolefins having different properties. It is said that the advantages of both are compatible.
  • polyolefin blends having different properties it is difficult to make the dispersed phase fine because of the problem of poor compatibility, and it is difficult to achieve the performance expected by the blend. For this reason, attempts have been made to reduce the diameter of the dispersed phase by blending polyolefins with different properties together with compatibilizers such as elastomers, but the method is limited to living polymerization, etc. It was difficult to make the diameter of the dispersed phase as fine as 1 ⁇ m or less.
  • the long-chain branched polymer having a specific structure is generally disclosed, for example, in JP-A-2002-308933 as a polymer having a structure excellent in both moldability and mechanical strength. Only a polymer material with a limited structure is known.
  • Patent Document 1 Japanese Patent Laid-Open No. 2002-155109
  • Patent Document 2 JP 2002-145944
  • Patent Document 3 Japanese Patent Laid-Open No. 7-196728
  • Patent Document 4 JP-A-9-59317
  • Patent Document 5 Special Table 2005-509701
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2004-131620
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-204058
  • Patent Document 8 Japanese Patent Laid-Open No. 2002-308933
  • Patent Document 9 WO2002Z022713
  • the present invention is intended to solve an enormous problem, and does not impair mechanical properties and the like.
  • the reactive key compound containing a polyolefin chain and the efficiency of the key compound are high. It is to provide a manufacturing method.
  • the present invention provides an olefin-based polymer excellent in chemical stability, in which material design can be freely performed and the mechanical properties and the like are not impaired.
  • polyolefin chain-containing key compound of the present invention is a polyolefin chain-containing key compound represented by the following formula (I). [0015] [Chemical 1]
  • PO is a group consisting of olefin polymers having a repeating unit derived from at least one olefin selected from 2 to 20 carbon atoms as a main structural unit, and R and R Is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and an acid.
  • a group comprising an atomic atom and a Z or key atom, force is a monovalent group selected, R
  • R may be the same or different from each other.
  • R contains a key atom
  • Is a divalent group consisting of Si is a key atom, and H is a hydrogen atom.
  • n is an integer of 1 or more.
  • the silicon residue in the formula (I) (the following formula ( ⁇ )) is present in the PO group and at the Z or terminal. ]
  • PO is an olefin polymer force mainly composed of repeating units derived from at least one olefin selected from olefin linkers having 2 to 20 carbon atoms.
  • R, R, R and R are monovalent groups selected from a hydrogen atom, a hydrocarbon group having 30 carbon atoms, and a group comprising an oxygen atom and Z or a key atom. , R, R, R, and R may be the same or different.
  • O is acid
  • PO is an olefin polymer group having a repeating unit derived from at least one olefin selected from 2 to 20 carbon atoms as a main structural unit
  • R, R , R 1, and R 2 are a hydrogen atom, a carbon atom number] a hydrocarbon group of '30, an oxygen atom, a group comprising Z or a key atom, and an olefin linker having 2 to 20 carbon atoms.
  • the olefin polymer power group (PO ") force selected from the above olefin-derived repeating units as the main structural unit is a monovalent group, and at least one of R, R, R and R is: PO ".
  • O is an oxygen atom
  • Si is a key atom
  • H is a hydrogen atom
  • p is 0 or an integer greater than or equal to 1
  • q is an integer greater than or equal to 1
  • the key residue in the formula (m) (the following formula ( ⁇ ')) is present inside the ⁇ group and at the ⁇ or terminal. ]
  • the olefin-based polymer of the present invention is an olefin-based polymer represented by the following formula (IV).
  • ⁇ and PO ′ are selected from an olefin polymer comprising a repeating unit derived from at least one type of olefin as the main structural unit. ⁇ and PO ′ may be the same or different from each other.
  • R 4 is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom and Z or a silicon atom, and a monovalent group selected from
  • Q 2 is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and a Z or silicon atom, and a divalent group selected from S i is a key atom.
  • Y is an oxygen atom, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including an atom selected from an oxygen atom, a silicon atom, and a halogen atom.
  • m is 0 or an integer of 1 or more, and n is an integer of 1 or more.
  • the segment containing a residue in the formula (IV) (the following formula (IV ′)) is present inside the PO group and at the Z or terminal. ] [0029]
  • the olefin-based polymer of the present invention is an olefin-based polymer represented by the following formula (V).
  • PO and PO ′ are groups consisting of an olefin polymer comprising a repeating unit derived from at least one olefin having at least one carbon atom having 2 to 20 carbon atoms as a main structural unit. Yes, PO and PO ′ may be the same or different from each other.
  • R 5 and R 8 are each a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom and a group comprising Z or a key atom, and an olefin force having 2 to 20 carbon atoms.
  • Olefin polymer consisting mainly of repeating units derived from olefins of more than one species.
  • Group (PO ") force as a main component unit.
  • One is PO ".
  • PO can be the same or different from PO or PO '.
  • R 5 , And R 8 may be the same as or different from each other.
  • Q and Q 2 is a divalent group selected hydrocarbon group, and a hydrocarbon group having 1 to 30 carbon atoms comprising an oxygen atom and Z or Kei atom having 1 to 30 carbon atoms from Si is a key atom.
  • Y is an oxygen atom, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms comprising an atom selected from an oxygen atom, a silicon atom, and a halogen atomic energy.
  • n is an integer of 1 or more.
  • a segment containing a silicon residue in formula (V) (following formula (V ') ) Is present inside the po group and at the Z or terminus. ]
  • the polyolefin chain-containing key compound in the present invention is a polyolefin having a key moiety that is a polar group, and the polar part has a highly reactive structure.
  • the present invention is extremely useful from an industrial point of view.
  • the olefin polymer in the present invention is an olefin polymer having a chemically stable silicon-containing site, and is a material having a specific structure advantageous for manifesting various physical properties. Is extremely useful industrially.
  • PO in the above formulas (I), (II), and ( ⁇ ) is an olefin polymer-strength group mainly composed of repeating units derived from at least one olefin selected from olefin linkers having 2 to 20 carbon atoms. That is, it is a polymer segment having an olefin fin chain force.
  • olefins having 2 to 20 carbon atoms include linear or branched ⁇ -olefins, cyclic olefins, aromatic vinyl compounds, conjugated genes, non-conjugated polyenes, and functionalized vinyl compounds. Is mentioned.
  • Linear ⁇ -olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexade.
  • Examples thereof include linear ⁇ -olefins having 2 to 20 carbon atoms such as sen, 1-octadecene, and 1 eicosene.
  • linear olefins having 2 to L0 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene are preferable.
  • Examples of branched ⁇ -olefin include 3-methyl-1-butene, 4-methyl-1 pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4 dimethyl-1-pentene, 4-methyl-1
  • Examples thereof include branched ⁇ -olefins having 5 to 20, preferably 5 to 10 carbon atoms, such as —hexene, 4,4 dimethyl-1-hexene, 4-ethyl 1-hexene, 3 ethyl-1 hexene. .
  • Cyclic olefins include cyclopentene, cycloheptene, norbornene, and 5-methyl.
  • Cyclic olefins having 3 to 20 carbon atoms, preferably 5 to 15 carbon atoms, such as norbornene, tetracyclododecene, and bullcyclohexane.
  • aromatic bur compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylenostyrene, 4-methinostyrene, 2,4 dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, And alkyl styrene such as 4-ethyl styrene.
  • Examples of conjugation include 1,3 butadiene, isoprene, black-opened plane, 1,3 pentagene, 2,3 dimethylbutadiene, 4-methyl-1,3 pentagen, 1,3 pentagene, and 1,3 Examples thereof include conjugation atoms having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms such as xagene and 1,3-octagen.
  • Non-conjugated polyenes include 1,4 pentagen, 1,4 monohexagen, 1,5 hexagen, 1,4-octagen, 1,5-octagen, 1,6-octagen, 1,7 octatagene 2-methyl-1,5-hexagen, 6-methyl-1,5-hexabutadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7 nonagen, 4,8 dimethyl-1,4,8 decatrylene (DMDT ), Dicyclopentagen, cyclohexagen, cyclooctagen, 5 burnorbornene, 5 ethylidene 2 norbornene, 5-methyl-2-norbornene, 5-isopropylidene-2-norbornene, 6 chloromethyl-5 isopropyl 2 Norbornene, 2, 3 Diisopropylidene 5— Non-conjugated polyenes having 5 to 20 carbon atoms such as norbornene,
  • Examples of the functionalized bur compound include hydroxyl group-containing olefins, halogenated olefins, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated amines, unsaturated epoxy compounds, and the like. It is done.
  • Examples of the unsaturated carboxylic acid include acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-otatenic acid, 8-nonenoic acid, and 9-decene. An acid etc. are mentioned.
  • Examples of the unsaturated carboxylic acid anhydride include (2, 7-octagel) succinic acid anhydride, pentapropyl succinic acid anhydride, and anhydride of the unsaturated carboxylic acid.
  • Examples of the unsaturated carboxylic acid halide include compounds obtained by replacing the carboxyl group of the unsaturated carboxylic acid with a carboxynolide group.
  • Examples of the unsaturated amine include arylamine, 5-hexeneamine, and 6-heptamine.
  • the unsaturated epoxy compounds include 4 epoxy 1-butene, 5 epoxy-1 pentene, 6 epoxy 1 1 hexene, 7 epoxy 1 heptene, 8 epoxy 1-otaten, 9 epoxy 1-nonene, 10 epoxy 1-decene, 11-epoxy 1undecene, etc.
  • the hydroxyl group-containing olefin is not particularly limited as long as it is a hydroxyl group-containing olefin-based compound, and examples thereof include a terminal hydroxyl-olefin compound.
  • Examples of the terminal hydroxy-olefin compound include terminal hydroxylated linear ex-olefin and terminal hydroxylated branched ⁇ -olefin.
  • the terminal hydroxylated linear ⁇ -olefin includes butyl alcohol, aryl alcohol, 3 butene 1 ol, 4 pentene 1 ol, 5 hexene 1 ol, 7 — otaten 1 ol, 9-decene 1 ol, 1 1-dedecene 1-ol, 13-tetradecene 1-ol, 15-hexadecene 1-ol, 17-octadecene-1-ol, 19-eicosen-1-ol, etc. Can be mentioned.
  • carbon atoms such as butyl alcohol, allylic alcohol, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 7-octene-1-ol, 9-decene-1-ol, etc.
  • a terminal aquatic linear ⁇ -year-old refin of 2-10 is preferred.
  • terminal hydroxylated ⁇ -olefin 2-methyl-3 butene-1 ol, 2-methyl-4 pentene 1 ol, 3-methyl-4 pentene 1 ol, 3 ethyl 4 pentene 1 ol, 2, 2 dimethyl 4 Number of carbon atoms such as pentene 1-ol, 3-methyl-5-hexene 1-ol, 3, 3 dimethyl-5-hexene 1-ol, 3 ethyl 5-hexene 1-ol, 4 ethyl 5-hexene 1-ol Examples thereof include 5 to 20, preferably 5 to 10, terminal hydroxylated branched ⁇ -olefins.
  • halogenated olefin examples include halogenated linear ⁇ - olefin having a group 17 atom of the periodic table of chlorine, bromine and iodine, and halogenated branched olefin.
  • the halogenated linear ⁇ -olefin includes halogenated bulu, halogenated 1-butene, halogen 1-pentene, halogen 1-hexene, neurogen 1 octene, halogenated 1 -Decene, halogenated 1-dedecene, halogenated 1-tetradecene, halogenated 1 monohexadecene, halogenated 1-octadecene, halogen 1-eicosene and other halogenated linear ⁇ -olefins with 2 to 20 carbon atoms Can be mentioned.
  • halogenated butyl halogenated 1-butene
  • neurogen 1 pentene halogen 1 hexene
  • halogen 1-octene halogenated linear ⁇ -olefins having 2 to 10 carbon atoms such as halogenated 1 decene are preferred.
  • the halogenated branched ⁇ -olefins include halogenated 3-methyl-1-butene, halogenated 4-methyl 1-pentene, halogenated 3-methyl 1-pentene, halogenated-3 ethyl-1 —Pentene, Halogenated— 4,4 Dimethyl 1—Pentene, Halogenated 4-Methyl 1 Monohexene, Halogenated 4, 4 Dimethyl 1 Monohexene, Halogen 4-Echinenole 1 Hexene, Halogen 3-Ethenole (1) Halogenated branched ⁇ -olefins having 5 to 20, preferably 5 to 10 carbon atoms such as monohexene.
  • the heel part is a polymer segment having an olefin chain strength mainly composed of repeating units derived from at least one olefin selected from these olefins.
  • the above-mentioned segment is an ethylene homopolymer segment, a propylene homopolymer segment, a copolymer of ethylene and at least one type of olefin selected from 3 to 20 carbon atoms.
  • a polymer segment and a copolymer segment obtained from at least one olefin selected from propylene and olefin having 4 to 20 carbon atoms are preferred.
  • the molecular weight of the above-mentioned heel is in the range of 1,000,000 to 10,000,000 in terms of weight average molecular weight (Mw) measured by gel-permeation chromatography in terms of polystyrene. It is in the range of 2,000 to 5,000,000, more preferably ⁇ is in the range of 3,000 to 2,000,000.
  • the polyolefin chain-containing key compound of the present invention represented by the above formula (I) is characterized in that it is composed of the above PO group and a specific key residue represented by the following formula ( ⁇ ).
  • R and R are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms,
  • R and R can be used without limitation as long as they satisfy the above requirements.
  • the viewpoint power of chemical stability is preferably a monovalent group that can also be a hydrocarbon group having 1 to 30 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group and dodecyl group.
  • Linear alkyl group such as isopropyl group, isobutyl group, tert-butyl group, etc .
  • cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group
  • aromatic ring-containing hydrocarbon groups such as benzyl group, naphthyl group, and anthracenyl group.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a benzyl group, and a naphthyl group are preferable, and a methyl group, an ethyl group, and a propyl group are more preferable.
  • Group, cyclohexyl group, and phenyl group are more preferable.
  • Examples of the group containing an oxygen atom include a hydroxyl group, a carboxyl group, a group having an ether bond, a group having an ester bond, and a ketone group.
  • Examples of the group containing a silicon atom include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, and tricyclohexylsilyl group; pentamethyldisilyl group, pentaethyldiethyl group Alkylsilyl groups such as silyl group, heptamethyltrisilyl group, heptaethyltrisilyl group; aromatic ring-containing silyl groups such as triphenylsilyl group, diphenylmethylsilyl group, tribenzylsilyl group, dibenzylmethylsilyl group , Etc.
  • trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, and tricyclohexylsilyl group
  • Examples of the group containing oxygen and a silicon atom include trimethylsiloxy group, triethylsiloxy group, triphenylsiloxy group, pentamethyldisiloxy group, pentaethyldisiloxy group, pentaphenyldisiloxy group, heptamethyltrioxy group.
  • R is a divalent group containing a key atom.
  • R is a group that satisfies the above requirements.
  • X is a halogen atom, and is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • r is 0 or an integer from 1 to 4.
  • the silicon residue represented by the above formula (I ′) is present inside the PO group segment and at the Z or terminal of the olefin chain-containing silicon compound represented by the formula (I).
  • a key residue represented by the following formula ( ⁇ ) is preferable. That is, in the present invention, a polyolefin chain-containing key compound represented by the following formula (II), which is composed of the above PO group and a key residue of the following formula (II,) is preferable.
  • a polyolefin chain-containing key compound represented by the following formula (II) which is composed of the above PO group and a key residue of the following formula (II,) is preferable.
  • the polyolefin chain-containing key compound of the present invention is a compound represented by the formula ( ⁇ )
  • a highly reactive site is firmly bonded to the PO group, and the structure is stable.
  • ⁇ is a group having the above-described polymer force, and R, R, R, and
  • R are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom and
  • a group comprising ⁇ or a key atom, force is a monovalent group chosen, R, R, R, and
  • R may be the same as or different from each other.
  • m is 0 or an integer greater than or equal to 1
  • , 1 is an integer greater than or equal to 1.
  • the silicon residue represented by the above formula ( ⁇ ) is present inside the po group segment and at the Z or terminal of the olefin chain-containing silicon compound represented by the formula (II).
  • a key residue represented by the following formula ( ⁇ ) is preferable. That is, in the present invention, a polyolefin chain-containing key compound represented by the following formula ( ⁇ ), which is composed of the above PO group and a key residue of the following formula ( ⁇ ,) is preferable.
  • the polyolefin chain-containing key compound of the present invention is a compound represented by the formula (I II)
  • the structure is stable because the highly reactive site is firmly bonded to the PO group, Because it has multiple PO groups, it has an excellent balance of molding processability and mechanical properties.
  • PO is a group that also has the above-described polymer force, and R, R, R,
  • Group (PO ") force consisting of an olefin polymer whose main structural unit is the derived repeating unit is a monovalent group selected from R, R, R and R
  • At least one of 8 9 10 11 is a group (PO ") composed of an olefin polymer having as a main structural unit a repeating unit derived from at least one type of olefin selected from 2 to 20 carbon atoms.
  • R, R, R and R may be the same or different from each other.
  • p is 0 or an integer of 1 or more
  • q is an integer of 1 or more.
  • Polyolefin part which is the raw material of the PO part, can be obtained by polymerizing the above-mentioned olefin with an olefin polymerization catalyst.
  • the olefin polymerization catalyst used in the production of the polyolefin will be described.
  • the olefin polymerization catalyst used in the production of polyolefin include magnesium-supported titanium-based catalysts, meta-catacene-based catalysts, and other conventionally known catalysts.
  • the catalysts described in International Patent Publications WO01Z53369 or WO01Z27124 are preferred. Used.
  • a magnesium-supported titanium-based catalyst containing a solid titanium catalyst component (a) or a prepolymerized catalyst thereof, an organometallic compound catalyst component (b), and an electron donor (ED) as constituent components is used.
  • the solid titanium catalyst component (a) or its prepolymerized catalyst Is usually used in an amount of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol in terms of titanium atom per liter of polymerization volume, and the organometallic compound catalyst component (b) is used as the catalyst.
  • the metal atom in component (b) is usually used in an amount of 1 to 2000 mol, preferably 2 to 1000 mol, per 1 mol of titanium atom in the solid titanium catalyst component (a) in the polymerization system.
  • the donor (ED) is generally used in an amount of 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, relative to 1 mol of the metal atom of the organometallic compound catalyst component (b).
  • the hydrogen concentration is usually from 0 to 0.01 monolayer, preferably from 0 to 0.005 monolayer per monomer.
  • the amount is preferably 0 to 0.001 mol.
  • the polymerization temperature is usually 70 ° C or higher, preferably 80 to 150 ° C, more preferably 85 to 140 ° C, particularly preferably. Is in the range of 90 to 130 ° C., and the polymerization pressure is usually set to normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
  • the meta-mouth compound (c) in the case of using a meta-mouth catalyst containing a meta-mouth compound (c) and an organoaluminum compound (d) as constituent components, the meta-mouth compound ( The concentration of c) is usually used in an amount of from 0.0005 to 0.1 millimonore, preferably from 0.0001 to 0.05 millimoles per liter of polymerization volume, and the organoaluminum oxide compound (d)
  • the molar ratio (A1ZM) of the aluminum atom (A1) to the transition metal atom (M) in the metaguchisen compound (c) is usually 5-1000, preferably 10-400. Use.
  • organoaluminum compound (e) other than an organoaluminum compound when used, it is usually about 1 to 300 mol per 1 mol of a transition metal atom in the metallocene compound (c). Preferably it is used in an amount of about 2 to 200 mol.
  • the metalocene catalyst may be used as a solution in a solvent in which the metalocene catalyst is soluble, or may be supported on an inorganic compound or a resin composition and used as a supported catalyst. Good.
  • the polymerization temperature is usually in the range of -20 to 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C.
  • the polymerization pressure is in the range of more than 0 to 8 MPa, preferably more than 0 to 5 MPa.
  • the polyolefin is a liquid phase polymerization such as solution polymerization or suspension polymerization, or gas phase polymerization. It can be manufactured by any of the methods.
  • the polyolefin can be produced by any of batch, semi-continuous and continuous methods.
  • the polymerization can be carried out in two or more stages.
  • the reaction conditions may be the same or different.
  • two or more kinds of olefin-in-random copolymers or block copolymers selected from the above-mentioned olefins may be produced, or the above-mentioned olefin homopolymer may be produced.
  • the polyolefin used as the base of the above-described PO part has an unsaturated group.
  • the unsaturated group may be an unsaturated group generated by chain transfer during the polymerization.
  • the olefin polymer force obtained as described above is a thermal degradation method (for example, JP-A-3-62804). It may be an unsaturated group generated in the polyolefin portion by the method described in Japanese Patent Publication.
  • the polyolefin is a polymer containing a structural unit derived from conjugated gen or non-conjugated polyene, it may be an unsaturated group derived from the conjugated gen or non-conjugated polyene.
  • Examples of the unsaturated group include a bur group, a bilidene group, a linear cis- and Z- or trans-2-substituted bur group, a cyclic disubstituted vinyl group, and a trisubstituted vinyl group.
  • these groups from the viewpoint of ease of production of the polyolefin chain-containing silicon compound described later, preferably a bur group, a vinylidene group, a cyclic disubstituted bur group, and a trisubstituted bur group, and more preferably a vinyl group.
  • the polyolefin chain-containing key compound according to the present invention is a key compound having a specific structure having the above-described PO part, and a polyolefin having a specific structure and a key element of the PO part having the specific structure described above. It can be produced by reacting with a compound.
  • the polyolefin used as the base of the PO portion used in the production of the polyolefin chain-containing key compound has an unsaturated group.
  • the polyolefin chain-containing key compound of the present invention can be produced by treating the polyolefin with a key compound having a specific structure described later.
  • the key compound having a specific structure any compound can be used without particular limitation as long as it is a compound in which the above-mentioned key residue ( ⁇ ) is formed by the reaction with the polyolefin as the base of the above-mentioned PO part. be able to.
  • the silicon compound having a specific structure is preferably a Si-H bond (Si is a silicon, H is a An alkyl group-containing silicon compound containing 2 or more hydrogen atoms) or an aromatic ring-containing silicon compound containing 2 or more Si—H bonds.
  • disiloxanes such as tetramethyldisiloxane, tetraethyldisiloxane, tetrapropyldisiloxane, tetraphenyldisiloxane, dimethyldiphenyldisiloxane, hexamethyltrisiloxane, hexetheryltri Trisiloxanes such as siloxane, hexenyltrisiloxane, trimethyltriphenyltrisiloxane, dimethyljetyldiphenyltrisiloxane, tetramethyldiphenyltrisiloxane, and tetrasiloxanes such as otamethyltetrasiloxane and octaphenyltetrasiloxane Siloxanes are more preferred. Further, siloxanes having the following structure are more preferable.
  • the polyolefin chain-containing silicon compound of the present invention can be produced by reacting the above-described silicon compound containing two or more Si-H bonds with a polyolefin having an unsaturated group. Specifically, for example, by using a key compound containing two or more Si—H bonds as a solvent, the polyolefin having an unsaturated group as a base of the PO part is dissolved or suspended, and the key compound and the polyolefin are reacted. It is manufactured by doing.
  • This solution method and suspension method are suitable from the viewpoint of producing a polyolefin chain-containing silicon compound having a controlled structure.
  • a solvent may be further used.
  • the solvent can be used without any particular limitation, but aliphatic hydrocarbon solvents such as hexane, heptane and decane, and aromatic hydrocarbon solvents such as toluene and xylene are preferably used.
  • the above production is usually performed in a temperature range of 0 ° C to 400 ° C, preferably 20 ° C to 250 ° C. C, more preferably in the temperature range of 50 ° C to 220 ° C.
  • the reaction time of the key compound and polyolefin is usually 1 minute to 24 hours, preferably 5 minutes to 10 hours.
  • an acid catalyst a noble metal-containing catalyst, and
  • other known catalysts may be used.
  • a platinum-containing catalyst that is a noble metal-containing catalyst is preferably used from the viewpoint of reactivity and versatility.
  • radical initiators such as peroxy compounds and azo compounds may be added as reaction aids.
  • the polyolefin chain-containing silicon compound of the present invention can also be produced by a melt kneading method.
  • the melt kneading method is performed using a lab plast mill, a single-screw kneader or a multi-screw kneader of two or more axes, a kneading extruder, a stirrer, or the like.
  • a high-speed stirrer or the like uniformly mixes polyolefin, which is the raw material of the PO part, with a key compound containing two or more Si-H bonds, and then a single-screw or multi-screw extruder with sufficient mixing ability. Then, the polyolefin chain-containing silicon compound of the present invention can be produced by melt-kneading the obtained mixture.
  • the kneading temperature is not particularly limited and may be room temperature, but is usually in the range of about 50 ° C to 400 ° C, preferably in the range of about 100 ° C to 350 ° C.
  • the chaos time is usually in the range of about 0.1 second to 5 hours, preferably in the range of about 1 second to 1 hour.
  • an organic solvent such as toluene or xylene may be added to adjust viscosity and improve reaction efficiency during melt kneading.
  • the melt kneading can be performed in the range of 0. OlmmHg to atmospheric pressure. Melting and kneading under reduced pressure is effective in removing the silicon compound containing two or more unreacted Si—H bonds and the added organic solvent.
  • Examples of the method for producing the polyolefin chain-containing key compound of the present invention include a solution method, a suspension method, and a melt kneading method.
  • a solution method a suspension method
  • a melt kneading method a melt kneading method
  • the total amount [SiH] (mol) of the Si-H groups in the silicon compound containing two or more Si-H bonds and the raw material of the PO part is strongly satisfying the relationship of the following equation (Eq— 1) and satisfying the relationship of the following equation (Eq— 2): It is even more preferable to satisfy the relationship of the following equation (Eq—3), which is more preferable!
  • the amount of the silicon compound containing two or more Si—H bonds exceeds the above upper limit, it is not preferable because it is necessary to remove unreacted substances in production.
  • a single PO moiety is cyclized via a key compound containing two or more Si-H bonds.
  • a compound is formed, or a compound in which a plurality of PO parts are bonded through a key compound containing two or more Si—H bonds may be generated.
  • the polyolefin chain-containing key compound of the present invention may be used as a mixture containing these by-products.
  • the polyolefin chain-containing key compound of the present invention comprises various polyolefins, elastomers, pigments, dyes, reinforcing materials such as glass fibers, metal fibers and carbon fibers, and fillers such as talc and calcium carbonate, depending on the purpose.
  • Antioxidants, UV absorbers, lubricants, flame retardants, etc. can be added. Further, it is possible to enhance the antistatic effect by adding conductive carbon or the like.
  • the polyolefin chain-containing key compound according to the present invention is a key compound having a PO group having an olefin chain force and a key group-containing group having a specific structure.
  • the polyolefin chain-containing silicon compound according to the present invention is a polymer having both physical properties derived from an olefin polymer and physical properties derived from a Si—H part that is a polar group.
  • the polyolefin chain-containing key compound according to the present invention can be used for various applications without any particular limitation.
  • adhesives for example, adhesives, building materials ⁇ ⁇ wood materials, automotive interior and exterior materials, gasoline tanks, electrical and electronic parts, antistatic agents, medical and hygiene materials, sundries, film 'sheets, magnetic recording materials, modifiers, structures It can be suitably used for control materials.
  • the polyolefin chain-containing key compound of the present invention is an additive such as a softening agent, a stabilizer, a filler, an antioxidant, a crystal nucleating agent, etc., as necessary, as long as the object of the present invention is not impaired. Can be used in combination.
  • the polyolefin chain-containing key compound of the present invention when the PO part is a polyolefin having excellent characteristics of tackiness, heat resistance taperability, and fluidity, for example, a hot melt adhesive is used. It can be suitably used as such an adhesive.
  • a hot melt adhesive is used. It can be suitably used as such an adhesive.
  • the polyolefin chain-containing silicon compound of the present invention when used as an adhesive, it may further contain a tackifier resin.
  • the tackifier resin is blended in order to improve hot tackiness and wettability.
  • the tackifying resin is not particularly limited as long as it is generally blended with an olefin copolymer.
  • tackifying resin examples include alicyclic hydrogenated tackifiers, rosins, modified rosins and their esters, aliphatic petroleum resins, alicyclic petroleum resins, and aromatic resins. Petroleum resin, copolymerization of aliphatic and aromatic components, low molecular weight styrene resin, isoprene resin, alkylphenol resin, terpene resin, coumarone indene resin and the like. These tackifiers can be used singly or in combination of two or more.
  • the polyolefin chain-containing key compound of the present invention is used as a hot-melt adhesive, it is preferable that the polyolefin chain-containing key compound and the tackifying resin are included.
  • the polyolefin chain-containing key compound is usually 10 to 90 parts by weight with respect to 100 parts by weight of the total amount of the polyolefin chain-containing key compound and the tackifying resin.
  • the tackifier resin is usually 90 to 10 parts by weight, preferably 80 to 15 parts by weight, more preferably 70 to 20 parts by weight. Contains.
  • an inorganic filler When used as the above-mentioned adhesive such as a hot melt adhesive, an inorganic filler may be further added as necessary.
  • the amount of inorganic filler added is usually 5 to 50 parts by weight, preferably 5 to 20 parts by weight of the above-mentioned polyolefin chain-containing silicon compound, based on 100 parts by weight of the total weight of the adhesive. Is 10 to 60 parts by weight, preferably 20 to 40 parts by weight.
  • the above-mentioned adhesive such as a hot-melt adhesive supplies the polyolefin chain-containing key compound, tackifier resin, and, if necessary, the above additive to a blender such as Brabender. After heating, melting and mixing, it can be prepared by forming it into a desired shape, for example, granular, flake, rod or the like.
  • the polyolefin chain-containing silicon compound of the present invention has a balance of physical properties such as strength and transparency.
  • a polymer composition can be produced by further blending with other thermoplastic resin if necessary, and a molded article can be produced from this composition.
  • the obtained molded body can be suitably used for applications such as building materials / civil engineering materials, automotive interior / exterior materials, gasoline tanks, electric / electronic parts, medical materials, and miscellaneous goods.
  • polyolefin chain-containing silicon compounds When these polyolefin chain-containing silicon compounds are used in molded articles, they may be used singly or in combination.
  • an inorganic filler such as magnesium hydroxide and a crosslinking agent such as vinyltrimethoxysilane may be used in combination.
  • the amount of the thermoplastic resin blended is not particularly limited, but the polyolefin chain-containing key compound is usually 0.01 to 150 parts by weight per 100 parts by weight of the thermoplastic resin, and a filler as necessary. 0.01 to 300 parts by weight, preferably 0.1 to 20 parts by weight of polyolefin chain-containing key compound, 0.1 to 40 parts by weight of filler, more preferably 0.5 to 10 parts by weight of polyolefin chain-containing key compound It is preferable to use the agent in an amount of 0.5 to 20 parts by weight.
  • An excellent magnetic recording material can be obtained by kneading the polyolefin chain-containing silicon compound and magnetic powder.
  • the blending ratio of the polyolefin chain-containing key compound and the magnetic powder is 9 9/1 to 10Z90! /.
  • the magnetic powder mixture can be preferably used as a plastic magnet in a stationery or the like.
  • the polyolefin chain-containing silicon compound of the present invention is produced by producing a polymer composition as described above.
  • a molded body such as a sheet, a film, or a hollow molded body can be produced by calender molding, extrusion molding, injection molding, blow molding, press molding, stamping molding, etc., and used as a medical / sanitary material.
  • the composition force can also be used as a medical / sanitary material by producing a filament and producing a nonwoven fabric or woven fabric from the filament.
  • the filament can be produced, for example, by extruding a molten composition through a spinneret.
  • a nonwoven fabric laminate is produced, This laminate can be used as a medical / sanitary material.
  • the polyolefin chain-containing silicon compound of the present invention can be molded and used as a film or a sheet.
  • the film or sheet may be a single-layer film or sheet, or a multilayer film or sheet in which at least one layer of the polyolefin chain-containing silicon compound of the present invention is formed.
  • a film or sheet having a multilayer structure composed of two or more layers having different compositions, and at least one of these layers is a layer composed of the olefin-based polymer according to the present invention, and has an appearance.
  • a film or sheet excellent in mechanical strength characteristics is preferably used.
  • Polyolefin chain-containing silicon compound strength of the present invention A film or sheet on which at least one layer is formed is particularly excellent in transparency, heat resistance, and cloud resistance, and is therefore preferred for agriculture and wrapping.
  • Examples of methods for forming the film and sheet include extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, and the like. It is done.
  • the polyolefin chain-containing silicon compound of the present invention can also be used as a modifier, such as a resin, rubber, wax, and lubricant modifier, a pigment dispersion modifier such as cement and ink 'paint, and It is suitably used for denture materials, modifiers such as sealants.
  • a modifier such as a resin, rubber, wax, and lubricant modifier, a pigment dispersion modifier such as cement and ink 'paint, and It is suitably used for denture materials, modifiers such as sealants.
  • the modifier may be a composition containing the polyolefin chain-containing key compound of the present invention and a resin, a rubber, a base material for lubricating oil, a wax, a cement, or an ink 'paint.
  • the polyolefin chain-containing silicon compound of the present invention can be used as a structure control material by utilizing its hydrophilicity.
  • Suitable structure control materials include semiconductor encapsulants, ceramic binders, aqueous emulsions, aluminum nitride blended films, and the like.
  • the material comprising the polyolefin chain-containing key compound of the present invention has an effect of suppressing electrification.
  • the polyolefin chain-containing key compound and resin, rubber, base material for lubricating oil, wax In the composition containing the ink or paint the effect is suitably exhibited.
  • PO, PO ′, and PO ′′ are olefins mainly composed of repeating units derived from at least one olefin selected from olefins having 2 to 20 carbon atoms. It is a polymer segment having a polymer force, that is, an olefin chain force.
  • the olefins used in the olefin polymer as the PO, PO ', and PO "groups are the same as the olefin used in the PO part of the polyolefin chain-containing silicon compound described above.
  • the molecular weights of the above PO part, PO, part, and PO "part are 1,000 to 10,000,000 in terms of polystyrene-converted weight average molecular weight (Mw) measured by gel 'permeation' chromatography. , 000 in the range ⁇ 2,000, 5,000, 000, 000 in the range ⁇ 000, 000, 000 in the range 3,000 to 2,000, 000.
  • the ⁇ part, PO 'part, and ⁇ "part in the olefin-based polymer according to the present invention include a saturated hydrocarbon group, an aromatic ring-containing group, a halogen atom-containing group, a phosphorus atom-containing group, and an oxygen atom-containing group.
  • a group, a nitrogen atom-containing group or a silicon atom-containing group may be introduced into the whole or a part of the unsaturated group.
  • the olefin-based polymer according to the present invention has a structure in which polyolefin segments such as a heel portion and a PO ′ portion, which are represented by the following formula (IV), are bonded to each other by a kalein-containing group.
  • R 4 are selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group or force comprising an oxygen atom and a Z or key atom 1 Is a valent group. And R 4 can be used without limitation as long as it satisfies the above requirements.
  • hydrocarbon group having 1 to 30 carbon atoms examples include methyl group, ethyl group, propyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group and dodecyl group.
  • Linear alkyl group such as isopropyl group, isobutyl group, tert-butyl group, etc .
  • cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclyl group
  • aromatic ring-containing hydrocarbon groups such as benzyl group, naphthyl group and anthracyl group.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a benzyl group, and a naphthyl group are mentioned, More preferably, a methyl group and an ethyl group are mentioned.
  • a propyl group, a cyclohexyl group, and a phenol group are mentioned.
  • Examples of the group containing an oxygen atom include a hydroxyl group, a carboxyl group, a group having an ether bond, a group having an ester bond, and a ketone group.
  • Examples of the group containing a cation atom include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, tricyclohexylsilyl group; pentamethyldisilyl group, pentaethyldi Alkylsilyl groups such as silyl group, heptamethyltrisilyl group, heptaethyltrisilyl group; aromatic ring-containing silyl groups such as triphenylsilyl group, diphenylmethylsilyl group, tribenzylsilyl group, dibenzylmethylsilyl group , Etc.
  • trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, tricyclohexylsilyl group
  • the groups comprising oxygen and silicon atoms include trimethylsiloxy group, triethylsiloxy group, triphenylsiloxy group, pentamethyldisiloxy group, pentaethyldisiloxy group, pentaphenyldisiloxy group, heptamethyltrioxy group.
  • R 2 , And R 4 may be the same as or different from each other.
  • Q 1 and Q 2 are each a hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom, Z or Is a hydrocarbon group having 1 to 30 carbon atoms containing a silicon atom, and a divalent group selected by force.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopropylene group, a cyclobutylene group, and a cyclohexylene group.
  • An aromatic ring-containing hydrocarbon residue such as a phenylene group, a benzylene group, a naphthylene group, or an anthracene group.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms including the oxygen atom include those having the above-mentioned alkyl residue such as a tetrahydrofuran residue or an aromatic ring-containing hydrocarbon residue containing an oxygen atom.
  • a group having an ether bond, a group having an ester bond, a ketone group and the like can be mentioned.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms including the above-described silicon atom include those in which the above alkyl residue or aromatic ring-containing hydrocarbon residue has a carbon atom-containing substituent.
  • Other dialkylsilyl groups such as dimethylsilyl group, jetylsilyl group, dibutylsilyl group, methylethylsilyl group, dicyclohexylsilyl group; tetramethyldisilyl group, tetraethyldisilyl group, hexamethyltrisilyl group, hexae
  • Examples include alkylsilyl groups such as a tiltrisilyl group; aromatic ring-containing silyl groups such as a diphenylsilyl group, a phenylmethylsilyl group, a dibenzylsilyl group, and a benzylmethylsilyl group.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and a silicon atom include a dimethylsiloxy group, a jetylsiloxy group, a diphenylsiloxy group, a tetramethyldisiloxy group, a tetraethyldisiloxy group, Tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexaphenyretrisiloxy group, dimethylenoresyloxy group, jetinoresi-oxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, Examples thereof include a siloxy group such as a hexamethyltrisiloxy group and a hexaphenyl trisyloxy group.
  • Y is an oxygen atom, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including atoms selected from oxygen atoms, silicon atoms, and halogen atomic energy. is there.
  • a hydrocarbon group having 1 to 50 carbon atoms and comprising an oxygen atom and a silicon atom are preferred.
  • hydrocarbon group having 1 to 50 carbon atoms examples include methyl group, ethyl group, propyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group and dodecyl group.
  • Linear alkyl groups such as docosyl group, dotriacontyl group and hexatetracontyl group; branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group; cyclopropyl group, cyclobutyl group, cyclohexyl group, Cyclooctyl group, hexade force Hydropyrenyl group, 5-alpha-cholestyl group, cyclic alkyl group such as cyclodotriacontyl group; phenol group, benzyl group, naphthyl group, anthracyl group, coronal group, An aromatic ring-containing hydrocarbon group such as a rubrenyl group).
  • hydrocarbon groups having 1 to 30 carbon atoms are preferable.
  • hydrocarbon group having 1 to 30 carbon atoms include straight chain such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group and dodecyl group.
  • Alkyl group branched alkyl group such as isopropyl group, isobutyl group and tert-butyl group; cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group and cyclooctyl group; phenyl group, benzyl group, Aromatic ring-containing hydrocarbon groups such as a naphthyl group and an anthracene group can be mentioned.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a benzyl group, and a naphthyl group are more preferable, and a methyl group is more preferable.
  • a methyl group is more preferable.
  • ethyl group, propyl group, cyclohexyl group, and phenyl group are more preferable, and a methyl group is more preferable.
  • Examples of the hydrocarbon group having 1 to 50 carbon atoms and containing the oxygen atom include those having the above alkyl residue such as a tetrahydrofuran residue and aromatic ring-containing hydrocarbon residues containing an oxygen atom.
  • a group having an ether bond, a group having an ester bond, a ketone group and the like can be mentioned.
  • a hydrocarbon group having 1 to 30 carbon atoms and containing an oxygen atom is preferable.
  • Examples of the hydrocarbon group having 1 to 50 carbon atoms including the above-mentioned silicon atom include those in which the above alkyl residue or aromatic ring-containing hydrocarbon residue has a carbon atom-containing substituent.
  • a dialkylsilyl group such as a dimethylsilyl group, a jetylsilyl group, a dibutylsilyl group, a methylethylsilyl group, a dicyclohexylsilyl group, a didocosylsilyl group; a tetramethyldisilyl group, a tetraethyldisilyl group, a hexamethyltrisilyl group, Examples thereof include alkylsilyl groups such as oxacetylsilyl group; aromatic ring-containing silyl groups such as diphenylsilyl group, phenylmethylsilyl group, dibenzylsilyl group, benzylmethylsilyl group, and dina
  • a hydrocarbon group having 1 to 30 carbon atoms and containing a key atom is preferable.
  • the hydrocarbon group having 1 to 30 carbon atoms comprising a key atom include an alkyl residue having 1 to 30 carbon atoms and an aromatic ring-containing hydrocarbon residue having 1 to 30 carbon atoms.
  • dialkylsilyl groups such as dimethylsilyl group, jetylsilyl group, dibutylsilyl group, methylethylsilyl group, dicyclohexylsilyl group; tetramethyldisilyl group, tetraethyldisilyl group, Alkylsilyl groups such as oxamethyltrisilyl group and hexamethyltrisilyl group; aromatic ring-containing silyl groups such as diphenylsilyl group, fullmethylsilyl group, dibenzylsilyl group, benzylmethylsilyl group, etc. It is done.
  • Examples of the hydrocarbon group having 1 to 50 carbon atoms including an oxygen atom and a silicon atom include a dimethylsiloxy group, a dimethylsiloxy group, a diphenylsiloxy group, a tetramethyldisiloxy group, a tetraethyldisiloxy group, Tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexaphenyretrisiloxy group, dimethylenoresyloxy group, jetinoresi-oxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, Examples include a siloxy group such as a hexamethyltrisiloxy group, a hexaphenyltrisiloxy group, and a octafeltetracyloxy group.
  • Examples of the hydrocarbon group having 1 to 50 carbon atoms and containing a halogen atom include a perfluorinated ethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluoro group.
  • a perfluoroalkyl group such as a mouth hexyl group is exemplified.
  • a hydrocarbon group having 1 to 30 carbon atoms and containing an oxygen atom and a silicon atom is preferable.
  • the hydrocarbon group having 1 to 30 carbon atoms including oxygen atom and silicon atom include dimethylsiloxy group, jetylsiloxy group, diphenylsiloxy group.
  • the olefin-based polymer of the present invention has a silicon-containing group as a bonding portion represented by the following formula (V).
  • R 5 , R 6 , R 7 , and R 8 include a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom, and a Z or silicon atom.
  • a olefinic group having 2 to 20 carbon atoms and an olefinic polymer having a repeating unit derived from at least one type of olefin selected as a main structural unit (PO ") force is a monovalent group selected.
  • R 5 , R 6 , R 7 , and R 8 are PO ". PO "may be the same as PO or P 0, or different.
  • R 5 , And R 8 may be the same as or different from each other.
  • QQ and Y are the same as in the above formula (IV).
  • M and n are the same as in the case of the above-described formula (IV).
  • Y can be used without limitation as long as it satisfies the above requirements, and the structure mentioned in the above description is preferably used.
  • R 5 and R 8 can be used without limitation as long as they satisfy the above requirements.
  • R 5 , R 6 , R 7 , R 8 are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and an oxygen atom. And a basic force comprising Z or a key atom is also selected.
  • the structure referred to as R 4 is preferably used.
  • the olefinic polymer according to the present invention has a structure in which different Z or the same kind of polyolefin moiety is bonded via a specific group containing a group, and the segment comprising the polyolefin is linear or branched. It has a combined structure!
  • the PO segment, PO ′ portion, and PO ′′ portion which are polymer segments, may be crystalline or amorphous, but the PO portion.
  • the PO part is crystalline, the rigidity and heat resistance of the olefin polymer according to the present invention can be improved, and the compatibility of the olefin polymer can be expected.
  • At least one of PO 'and PO " is crystalline.
  • the olefin when at least one of PO' and PO" is crystalline, the olefin The rigidity and heat resistance of the polymer can be improved, and the compatibility of the olefin polymer can be expected.
  • “having crystallinity” means that the melting point is observed by differential scanning calorimetry (temperature rising condition: 10 ° C. Z).
  • the melting point observed by differential scanning calorimetry is usually in the range of 40 ° C to 360 ° C, preferably in the range of 60 ° C to 320 ° C, more preferably in the range of 80 ° C to 280 ° C. is there.
  • Suitable polymer segments to be the PO part, PO 'part, and PO "part are ethylene polymer segment, propylene polymer segment, butene polymer segment, pentene polymer segment. Methylbutene polymer segment, hexene polymer segment, methylpentene polymer segment, and the like.
  • PO part a PO part, a PO ′ part, and a PO ′′ part (hereinafter collectively referred to as a polyolefin part), which are a part of the polyolefin polymer according to the present invention, will be described.
  • PO, part and PO "part are obtained by polymerizing the above-mentioned olefin with an olefin-based polymerization catalyst.
  • the olefin polymerization catalyst used in the production of the above-mentioned polyolefin is a polyolefin according to the present invention. It is the same as the catalyst used for the production of polyolefin which is the raw material of the PO part of the lefin chain-containing key compound, and examples thereof include magnesium-supported titanium catalyst, metalocene catalyst, and other conventionally known catalysts.
  • the catalyst described in Patent WO01Z53369 or WO01Z271 24 is preferably used.
  • suitable polymerization conditions such as the amount of the polymerization catalyst used, the hydrogen concentration, the polymerization temperature, the polymerization pressure, the polymerization mode, and the polymerization method are as follows. This is the same as the production of polyolefin which is the base of the PO part.
  • the polyolefin used as the base of the above-mentioned polyolefin portion has an unsaturated group.
  • This unsaturated group may be an unsaturated group generated by chain transfer during the above polymerization, and the olefin polymer power obtained as described above may be a thermal degradation method (for example, JP-A-3-62804). It may be an unsaturated group generated in the polyolefin portion by the method described in the Japanese Patent Publication.
  • the polyolefin is a polymer containing a structural unit derived from a conjugated gen or non-conjugated polyene, it may be an unsaturated group derived from the conjugated gen or non-conjugated polyethylene.
  • Examples of the unsaturated group include a bur group, a bilidene group, a linear cis- and Z- or trans-2-substituted vinyl group, a cyclic disubstituted vinyl group, and a trisubstituted bur group.
  • a bur group, a vinylidene group, a cyclic disubstituted vinyl group, and a trisubstituted vinyl group are preferable, and a vinyl group and vinylidene are more preferable.
  • Group more preferably a vinyl group.
  • the olefin-based polymer according to the present invention may be produced by any method as long as the requirements are not impaired.
  • it can be produced by reacting a polyolefin containing an unsaturated group as a base of the PO part having a specific structure described above with a key compound containing a specific structure.
  • any compound can be used without particular limitation as long as it is a compound in which the above-mentioned key residue ( ⁇ ) is formed by reaction with the polyolefin as the base of the aforementioned PO moiety. be able to.
  • the above-mentioned key compound is preferably a Si-H bond (Si is a key element, H is a hydrogen atom).
  • Si is a key element, H is a hydrogen atom.
  • disiloxanes such as tetramethyldisiloxane, tetraethyldisiloxane, tetrapropyldisiloxane, tetraphenyldisiloxane, dimethyldiphenyldisiloxane, hexamethyltrisiloxane, and hexetheryltri Trisiloxanes such as siloxane, hexenyltrisiloxane, trimethyltriphenyltrisiloxane, dimethyljetyldiphenyltrisiloxane, tetramethyldiphenyltrisiloxane, and tetrasiloxanes such as otamethyltetrasiloxane and octaphenyltetrasiloxane Siloxanes are more preferred. Further, siloxanes having the following structure are more preferable.
  • the olefin-based polymer according to the present invention can be produced by reacting the above-mentioned cage compound containing two or more Si-H bonds with a polyolefin having an unsaturated group.
  • the olefin polymer according to the present invention can also be produced by reacting a polyolefin having a Si—H bond with a polyolefin having an unsaturated group.
  • a polyolefin part having an unsaturated group as a base of the polyolefin part is dissolved or suspended, and the key compound and the polyolefin are It is manufactured by reacting.
  • This solution method and suspension method are suitable from the viewpoint of producing a polyolefin compound containing a polyolefin chain having a controlled structure.
  • a solvent may be further used.
  • the solvent can be used without any particular limitation, and aliphatic hydrocarbon solvents such as hexane, heptane and decane, and aromatic hydrocarbon solvents such as toluene and xylene are preferably used.
  • the above production is usually carried out in the range of 0 ° C to 400 ° C, preferably 20 ° C to 250 ° C, more preferably 50 ° C to 220 ° C.
  • the reaction time of the key compound and polyolefin is usually 1 minute to 24 hours, preferably 5 minutes to 10 hours.
  • an acid catalyst a noble metal-containing catalyst, and other known catalysts may be used.
  • a platinum-containing catalyst that is a noble metal-containing catalyst is preferably used from the viewpoint of reactivity and versatility.
  • radical initiators such as peroxy compounds and azo compounds may be added as reaction aids.
  • the polyolefin chain-containing silicon compound of the present invention can also be produced by a melt kneading method.
  • the melt kneading method is performed using a lab plast mill, a single-screw kneader or a multi-screw kneader of two or more axes, a kneading extruder, a stirrer, or the like.
  • a high-speed stirrer or the like uniformly mixes polyolefin, which is the raw material of the polyolefin portion, with a key compound containing two or more Si-H bonds, and then a single-screw or multi-screw extruder with sufficient mixing ability.
  • the polyolefin chain-containing silicon compound of the present invention can be produced by melt-kneading the obtained mixture.
  • the kneading temperature is not particularly limited and may be room temperature, but is usually in the range of about 50 ° C to 400 ° C, preferably in the range of about 100 ° C to 350 ° C.
  • the chaos time is usually in the range of about 0.1 second to 5 hours, preferably in the range of about 1 second to 1 hour.
  • an organic solvent such as toluene or xylene may be added to adjust viscosity and improve reaction efficiency during melt mixing.
  • the melting and kneading can be performed in the range of 0. OlmmHg to atmospheric pressure. Melting and kneading under reduced pressure is effective in removing the key compound containing two or more unreacted Si—H bonds and the added organic solvent.
  • Examples of the method for producing the polyolefin chain-containing key compound of the present invention include a solution method, a suspension method, and a melt kneading method. However, as long as the polyolefin chain-containing key compound of the present invention can be produced, other methods are available. You may manufacture by a well-known method.
  • the total amount of Si-H groups in the silicon compound containing two or more Si-H bonds [SiH] (mol) and the base of the polyolefin moiety preferably satisfies the relationship of the following equation (Eq— 1), and more preferably satisfies the relationship of the following equation (Eq— 2): More preferably, the relationship of the following equation (Eq-3) is satisfied.
  • the amount of a key compound containing two or more Si—H bonds is greater than or equal to the above lower limit with respect to the polyolefin that is the base material of the polyolefin portion, there is an effect of reducing the gel fraction. If the amount of the silicon compound containing two or more Si—H bonds exceeds the above upper limit, it is not preferable because it is necessary to remove unreacted substances in production.
  • the Si-H bond is used as a more preferable production method of the olefin-based polymer according to the present invention.
  • a key compound containing two or more compounds and one or a plurality of unsaturated group-containing polyolefins are reacted in a solvent to produce the above-described polyolefin chain-containing key compound of the present invention, which is separated and recovered.
  • a method for producing an olefin-based polymer having one or more kinds of polyolefin segments by reacting the polyolefin chain-containing silicon compound with one or more kinds of polyolefin having an unsaturated group in a solvent. Can be mentioned.
  • the properties and structure of the produced olefin polymer can usually be analyzed by a generally known analysis method. For example, specific sites can be identified by nuclear magnetic resonance analysis, infrared spectroscopic analysis, ultraviolet / visible spectroscopic analysis, X-ray scattering, Raman spectroscopy, etc., and temperature elution fractionation, gel permeation chromatography, and measurement of intrinsic viscosity
  • the molecular weight can be measured, and thermal characteristics can be confirmed by thermal prayer.
  • the morphology can be confirmed by observation with a transmission electron microscope, a scanning electron microscope, an atomic force microscope, or the like.
  • the olefin-based polymer of the present invention can be suitably produced by the above-described methods.
  • the olefin-containing polymers represented by the above formulas (IV) and (V) are produced depending on the production conditions It may be obtained as a mixture of a polymer.
  • a mixture of these polymers can be separated into each polymer by a column or the like.
  • the obtained olefin polymer may be used as it is depending on its use. Good.
  • the above production method it may be obtained as a mixture of the polyolefin chain-containing silicon compound of the present invention and an olefin polymer. These mixtures can be separated into a compound and a polymer by a column or the like. However, in the present invention, the obtained polyolefin chain-containing silicon compound and olefin-based polymer are used as a mixture according to the use. May be.
  • the olefinic polymer according to the present invention is filled with reinforcing materials such as various polyolefins, elastomers, pigments, dyes, glass fibers, metal fibers, carbon fibers, talc, calcium carbonate, etc., depending on the purpose. Agents, antioxidants, UV absorbers, lubricants, flame retardants, etc. can be added. Further, it is possible to enhance the antistatic effect by adding conductive carbon or the like. [0204] [Usage]
  • the olefin-based polymer according to the present invention can be used for various applications without any particular limitation.
  • it is used as adhesive resin, daily miscellaneous goods, industrial materials, etc.
  • molded products such as fibers, film sheets, elastic materials, various sealing materials, foam materials, modifiers, structural control materials, lubricants, etc. It can be suitably used.
  • Measuring apparatus Gel permeation chromatograph Alliance GPC 2000 (Waters) Measurement conditions: Column: TSKgel GMH6-HT X 2+ TSKgel GMH6-HTL X 2 (Tosohichi)
  • Sample treatment 30 mg of sample at 145 ° C was completely dissolved in 20 mL of 1,2-dichlorobenzene and then filtered through a sintered filter with a pore size of 1 ⁇ m.
  • Measuring device JEOL GSX-400 Spectrometer 400MHz (FT mode) Measuring condition: Pulse angle: 45 ° Pulse repetition: 5 seconds
  • Analytical sample was prepared by completely dissolving 50 mg of sample at 120 ° C in 0.5 mL of deuterium 1,2-dichlorobenzene.
  • Measuring device JEOL FT-IR 410 Spectrometer (FT mode)
  • Sample processing A press sheet of the sample was prepared by a heat press at 200 ° C. and used as an analysis sample.
  • the polymer was extracted with refluxing xylene for 3 hours, the mesh residual polymer was regarded as the gel content, and the gel fraction was determined from its dry weight.
  • the one-terminal unsaturation rate is the number average molecular weight value [Mn] of the polymer obtained by the GPC measurement force and the value of the unsaturated group amount in the polymer obtained by ⁇ H-NMR analysis power [V The polymer chain end when it is assumed that the unsaturated group exists only at one end of the polymer chain.
  • the ratio of the terminal unsaturated group is expressed as the single terminal unsaturated ratio.
  • Example 2A 10 parts by weight of the unsaturated group-containing ethylene polymer obtained in Reference Example 2, 1, 1, 3, 3, 5, 5—tetramethyltrisiloxane 3 parts by weight, hexachloroplatinic acid 0.01 parts by weight xylene 200 Mix in parts by weight at 130 ° C for 4 hours. After cooling to room temperature, the reaction product obtained by filtration under a nitrogen atmosphere was recovered. This was washed with 1000 parts by weight of hexane and dried under reduced pressure at 80 ° C. to obtain 10.1 parts by weight of a polyolefin chain-containing silicon compound.
  • FIG. 1 is a transmission electron micrograph of a press sheet in Example 1B.
  • FIG. 2 is a transmission electron micrograph of a press sheet in Comparative Example 1B.

Abstract

L'invention concerne un composé de silicium contenant une chaîne de polyoléfine, caractérisé en ce qu'il comporte un groupement polyoléfine spécifique et un résidu de silicium. L'invention concerne également un polymère d'oléfine, caractérisé en ce qu'il comporte un groupement polyoléfine spécifique et un groupement contenant du silicium spécifique en tant que fonction de liaison. La présente invention permet d'obtenir de manière efficace un nouveau composé de silicium contenant une chaîne polyoléfine, les propriétés mécaniques et analogues n'étant pas détériorées. La présente invention permet en outre de produire un polymère d'oléfine présentant une excellente stabilité chimique, les propriétés mécaniques et analogues n'étant pas détériorées et la conception des matériaux étant libre.
PCT/JP2007/063221 2006-07-04 2007-07-02 Composé de silicium contenant une chaîne polyoléfine et polymère d'oléfine WO2008004514A1 (fr)

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WO2012098865A1 (fr) * 2011-01-21 2012-07-26 三井化学株式会社 Corps moulé
JP2015189088A (ja) * 2014-03-28 2015-11-02 三井化学株式会社 接着体、樹脂組成物、成形体およびガラスランチャンネル
US11814555B2 (en) * 2018-03-19 2023-11-14 Dow Silicones Corporation Hot melt adhesive compositions containing polyolefin-polydiorganosiloxane copolymers and methods for the preparation and use thereof

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