JPWO2008004514A1 - Polyolefin chain-containing silicon compound and olefin polymer - Google Patents

Abstract

The polyolefin chain-containing silicon compound of the present invention is characterized by having a specific polyolefin group and silicon residue. The olefin polymer of the present invention is characterized in that it has a specific polyolefin group and a specific silicon-containing group as a bonding part. According to the present invention, a novel polyolefin chain-containing silicon compound can be obtained efficiently without impairing mechanical properties. Further, according to the present invention, an olefin polymer having excellent chemical stability without impairing mechanical properties can be produced while freely designing materials.

Description

  The present invention relates to a novel silicon compound having a polyolefin chain in the molecule, and an olefin polymer.

  Polyolefins have excellent processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc. for various applications. It is used.

  However, since polyolefin is a so-called nonpolar resin that does not have a polar group in the molecule, it has poor affinity with various polar substances including metals, and adhesion with polar substances or blending with polar resins is difficult. It was.

  In order to solve these problems, introduction of polar groups into polyolefin has been performed. When introducing a polar compound (polar olefin), a method of reacting a polyolefin and a polar olefin in the presence of a radical initiator is generally performed. However, the polar group-containing olefin polymer obtained by such a method often contains a homopolymer of a radically polymerizable polar olefin or an unreacted polyolefin, and the introduction positions are not uniform. In some cases, there is a cross-linking / decomposition reaction, which may impair polymer properties. In order to solve these problems, JP 2002-155109 A, JP 2002-145944 A, and the like disclose a method for obtaining a polar group-containing olefin polymer by using a polar group-containing olefin compound for the production of an olefin polymer. It is disclosed. However, these methods have problems such as poor introduction efficiency of reactive groups into the olefin polymer. 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. JP-A-9-59317 discloses a method for producing a silicon-containing polyolefin, but a liquid oligomer is used as the polyolefin, and sufficient mechanical strength cannot be expected. Moreover, it is difficult to specify the structure, and the structure cannot be sufficiently controlled because gelation proceeds. Therefore, when the obtained silicon-containing polyolefin is further used as a raw material for various reactions, it is difficult to sufficiently control the reaction. In JP 2005-509701 A, a copolymer of olefin and vinyl silane is known, but there are problems such as poor introduction efficiency of silicon-containing groups or poor reactivity of silicon-containing groups.

  Development of an olefin polymer having a polar group which has improved such problems is desired.

  In recent years, physical property requirements for polyolefins have been diversified and compounded. For example, in Japanese Patent Application Laid-Open No. 2004-131620, development of an olefin-based polymer material having segments having different properties is in progress. Further, for example, as described in JP-A No. 2004-204058, different properties such as blending a crystalline polyolefin excellent in heat resistance and an amorphous polyolefin excellent in impact resistance having a soft feel. It is also necessary to blend and use polyolefins. When polyolefins having different properties are blended as described above, usually, a sea-island structure in which the dispersed phase is dispersed in the matrix phase is obtained. Generally, the smaller the diameter of the dispersed phase, the better the advantages of the polyolefins having different properties. Has been. However, in a blend of polyolefins having different properties, it is difficult to make the dispersed phase fine because of the problem of poor compatibility, and it is difficult to exhibit the performance expected by the blend. For this reason, attempts have been made to reduce the diameter of the dispersed phase by blending polyolefins having different properties together with a compatibilizing agent such as an elastomer, but this method is a limited method such as living polymerization. It was difficult to make the diameter as fine as 1 μm or less.

  Further, the long-chain branched polymer having a specific structure is generally disclosed in, for example, JP 2002-308933 A as a polymer having a structure excellent in both moldability and mechanical strength, but has a limited structure. Only polymer materials are known.

  In order to solve these problems, for example, in WO2002 / 022713, a block type olefin polymer having a specific structure has been developed, but it has a chemically reversible binding site, and the chemistry of the binding site. There is a problem with mechanical stability. Therefore, it is industrially valuable if a more chemically stable material can be developed.

  In terms of chemical stability, a block-type olefin polymer having a relatively stable crosslinked structure, such as a silicon-carbon bond or silicon-oxygen bond, is reported in, for example, JP-A-9-59317. However, the polymer tends to have a gelled structure, the structure is difficult to control, and the processability of the polymer is also problematic.

Therefore, it has been desired to develop a block-type olefin polymer that can be freely designed and manufactured and has excellent chemical stability.
JP 2002-155109 A JP 2002-145944 A JP-A-7-196728 JP-A-9-59317 JP 2005-509701 A JP 2004-131620 A JP 2004-204058 A JP 2002-308933 A WO2002 / 022713

  The present invention is intended to solve such problems, and provides a reactive silicon compound containing a polyolefin chain that does not impair mechanical properties and the like, and an efficient method for producing the silicon compound. is there. The present invention also provides an olefin polymer having excellent chemical stability that can be freely designed and that does not impair mechanical properties.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel silicon compound containing a polyolefin chain and an efficient production method thereof.

  In addition, as a result of intensive studies to solve the above problems, the inventors have found a polymer that can be freely designed and has excellent chemical stability that does not impair mechanical properties.

  That is, the polyolefin chain-containing silicon compound of the present invention is a polyolefin chain-containing silicon compound represented by the following formula (I).

[In the formula (I), PO is a group consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, and R ₁ and R ₂ is a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group comprising an oxygen atom and / or a silicon atom, and R ₁ and R ₂ are the same as each other. It may or may not be. R ₃ is a divalent group containing a silicon atom. Si is a silicon 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 (I ′)) is present inside and / or at the end of the PO group. ]

  Among the polyolefin chain-containing silicon compounds, a compound represented by the following formula (II) is preferable.

[In the formula (II), PO is a group consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, R ₄ , R ₅ , R ₆ , and R ₇ are monovalent groups selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group containing an oxygen atom and / or a silicon atom, R ₄ , R ₅ , R ₆ , and R ₇ may be the same as or different from each other. O is an oxygen atom, Si is a silicon atom, and H is a hydrogen atom. m is 0 or an integer of 1 or more, and l is an integer of 1 or more. The silicon residue in the formula (II) (the following formula (II ′)) is present inside and / or at the end of the PO group. ]

  Among the polyolefin chain-containing silicon compounds, a compound represented by the following formula (III) is preferable.

[In the formula (III), PO is a group consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, R ₈ , R ₉ , R ₁₀ and R ₁₁ are at least one selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom and / or a silicon atom, and an olefin having 2 to 20 carbon atoms. A monovalent group selected from a group (PO ″) composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one kind of olefin, and at least one of R ₈ , R ₉ , R ₁₀ , and R ₁₁ One is PO ". R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same as or different from each other. O is an oxygen atom, Si is a silicon atom, and H is a hydrogen atom. p is 0 or an integer of 1 or more, and q is an integer of 1 or more. The silicon residue in the formula (III) (the following formula (III ′)) is present inside and / or at the end of the PO group. ]

  The olefin polymer of the present invention is an olefin polymer represented by the following formula (IV).

[In the formula (IV), PO and PO ′ are groups composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, PO and PO ′ may be the same as or different from each other. R ¹ , R ² , R ³ , and R ⁴ are monovalent groups selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group comprising an oxygen atom and / or a silicon atom. R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other. Q ¹ and Q ² are divalent groups selected from a hydrocarbon group having 1 to 30 carbon atoms and a hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and / or a silicon atom. And Si is a silicon 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 silicon residue-containing segment (formula (IV ′) below) in formula (IV) is present inside and / or at the end of the PO group. ]

  The olefin polymer of the present invention is an olefin polymer represented by the following formula (V).

[In the formula (V), PO and PO ′ are groups composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms; , And PO ′ may be the same as or different from each other. R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom and / or a silicon atom, and an olefin having 2 to 20 carbon atoms. A monovalent group selected from a group (PO ″) composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from R ⁵ , R ⁵ , R ⁶ , R ⁷ , and At least one of R ⁸ is PO ″. PO ″ may be the same as or different from PO or PO ′. R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same as or different from each other. Q ¹ And Q ² is a divalent group selected from a hydrocarbon group having 1 to 30 carbon atoms and a hydrocarbon group having 1 to 30 carbon atoms comprising an oxygen atom and / or a silicon atom, Si is a silicon atom, Y is an oxygen atom, a hydrocarbon group having 1 to 50 carbon atoms, or a carbon atom having 1 to 50 carbon atoms including an atom selected from an oxygen atom, a silicon atom, and a halogen atom. A hydrogen group, m is 0 or an integer of 1 or more, and n is an integer of 1 or more The silicon residue-containing segment in the formula (V) (the following formula (V ′)) is the interior of the PO group. And / or present at the end.]

  The polyolefin chain-containing silicon compound in the present invention is a polyolefin having a silicon moiety that is a polar group, and since the polar moiety has a highly reactive structure, it has both the characteristics of a polyolefin and the characteristics of a reactive polar moiety. The present invention is extremely useful industrially.

  Further, 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. Useful.

<Polyolefin chain-containing silicon compound>
Hereinafter, the polyolefin chain-containing silicon compound of the present invention will be described in detail.

[PO Department]
PO in the above formulas (I), (II) and (III) is composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms. It is a polymer segment consisting of groups, ie olefin chains.

  Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, and functionalized vinyl compounds.

  Examples of the linear α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, -C2-C20 linear alpha olefins, such as eicosene. Among these, linear α-olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene are preferable.

  Examples of the branched α-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-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like having 5 to 20, preferably 5 to 10 carbon atoms Examples include α-olefins.

  Examples of the cyclic olefin include cyclic olefins having 3 to 20, preferably 5 to 15 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethyl. Examples thereof include alkyl styrene such as styrene.

  Conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene, Examples thereof include conjugated dienes having 4 to 20, preferably 4 to 10, carbon atoms such as 1,3-octadiene.

  Non-conjugated polyenes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2- Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1, 4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methyl-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-nor Runen, 5-2-ethylidene-3-isopropylidene-norbornene, such as a non-conjugated polyene having 5 to 20 carbon atoms, such as 2-propenyl-2,2-norbornadiene and the like. Among these, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl- 1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, Non-conjugated polyenes having 5 to 10 carbon atoms such as 5-methyl-2-norbornene, 5-isopropylidene-2-norbornene, 2-propenyl-2,2-norbornadiene are preferred.

  Examples of the functionalized vinyl compound include a hydroxyl group-containing olefin, a halogenated olefin, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, an unsaturated carboxylic acid halide, an unsaturated amine, and an unsaturated epoxy compound.

  Examples of the unsaturated carboxylic acid include acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid. Can be mentioned.

  Examples of the unsaturated carboxylic acid anhydride include (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride, and anhydride of the unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid halide include compounds in which the carboxyl group of the unsaturated carboxylic acid is replaced with a carboxy halide group.

  Examples of the unsaturated amine include allylamine, 5-hexeneamine, and 6-hepteneamine.

  Examples of the unsaturated epoxy compound include 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9- Epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene and the like can be mentioned.

  The hydroxyl group-containing olefin is not particularly limited as long as it is a hydroxyl group-containing olefin compound, and examples thereof include terminal hydroxylated olefin compounds.

  Examples of the terminal hydroxylated olefin compound include a terminal hydroxylated linear α-olefin and a terminal hydroxylated branched α-olefin.

  As the terminal hydroxylated linear α-olefin, vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 7-octen-1-ol, 2-20 carbon atoms, such as 9-decene-1-ol, 11 dodecene-1-ol, 13 tetradecene-1-ol, 15 hexadecene-1-ol, 17 octadecene-1-ol, 19 eicosen-1-ol And terminal aquatic linear α-olefins. Among these compounds, vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 7-octen-1-ol, 9-decene-1-ol A terminal aquatic linear α-olefin having 2 to 10 carbon atoms such as is preferred.

  Examples of the terminal hydroxylated branched α-olefin include 2-methyl-3-buten-1-ol, 2-methyl-4-penten-1-ol, 3-methyl-4-penten-1-ol, and 3-ethyl. -4-penten-1-ol, 2,2-dimethyl-4-penten-1-ol, 3-methyl-5-hexen-1-ol, 3,3-dimethyl-5-hexen-1-ol, 3 Examples thereof include terminal hydroxylated branched α-olefins having 5 to 20, preferably 5 to 10, carbon atoms such as -ethyl-5-hexen-1-ol and 4-ethyl-5-hexen-1-ol.

  Examples of the halogenated olefin include a halogenated linear α-olefin having a group 17 atom of the periodic table of chlorine, bromine, iodine, and a halogenated branched α-olefin.

  Examples of the halogenated linear α-olefin include vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, and halogenated-1-decene. Halogenated linear α having 2 to 20 carbon atoms, such as halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1-eicocene -Olefin and the like. Among these compounds, the number of carbon atoms is 2 to 2, such as vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, and halogenated-1-decene. Ten halogenated linear α-olefins are preferred.

  Examples of the halogenated branched α-olefin include halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogenated-3-methyl-1-pentene, and halogenated-3-ethyl. -1-pentene, halogenated-4,4-dimethyl-1-pentene, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1 Examples thereof include halogenated branched α-olefins having 5 to 20, preferably 5 to 10, carbon atoms such as hexene and halogenated-3-ethyl-1-hexene.

  The PO part is a polymer segment composed of an olefin chain whose main constituent unit is a repeating unit derived from at least one olefin selected from these olefins. From the viewpoint of mechanical properties such as rigidity, the segment is an ethylene homopolymer segment, a propylene homopolymer segment, a copolymer of ethylene and at least one olefin selected from olefins having 3 to 20 carbon atoms. A coalescent segment and a copolymer segment obtained from at least one olefin selected from propylene and an olefin having 4 to 20 carbon atoms are preferred.

  The molecular weight of the PO part is in the range of 1,000 to 10,000,000, preferably 2,000 to 5, preferably in terms of weight average molecular weight (Mw) measured by gel permeation chromatography in terms of polystyrene. It is in the range of 3,000,000, more preferably in the range of 3,000 to 2,000,000.

[Silicon residue]
The polyolefin chain-containing silicon compound according to the present invention represented by the above formula (I) is characterized in that it is composed of the above PO group and a specific silicon residue represented by the following formula (I ′).

In the above formula (I ′), R ₁ and R ₂ are monovalent groups selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group comprising an oxygen atom and / or a silicon atom. It is. R ₁ and R ₂ can be used without limitation as long as they satisfy the above requirements. From the viewpoint of chemical stability, R ₁ and R ₂ are preferably monovalents composed of a hydrocarbon group having 1 to 30 carbon atoms. It is the basis of.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include linear groups 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, tert-butyl group; cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group; phenyl group, benzyl group, naphthyl group, anthracenyl group An aromatic ring-containing hydrocarbon group such as Among these, Preferably, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a benzyl group, a naphthyl group is mentioned, More preferably, a methyl group, an ethyl group, a propyl group is mentioned. Cyclohexyl group and phenyl group.

  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, pentaethyldisilyl group, hepta Examples thereof include alkylsilyl groups such as methyltrisilyl group and heptaethyltrisilyl group; aromatic ring-containing silyl groups such as triphenylsilyl group, diphenylmethylsilyl group, tribenzylsilyl group and dibenzylmethylsilyl group.

  Groups comprising oxygen and silicon atoms include trimethylsiloxy, triethylsiloxy, triphenylsiloxy, pentamethyldisiloxy, pentaethyldisiloxy, pentaphenyldisiloxy, heptamethyltrisiloxy, hepta Siloxy groups such as phenyltrisiloxy group, dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexaphenyltrisiloxy group, etc. Can be mentioned.

R ₁ and R ₂ in the above formula (I ′) may be the same as or different from each other.

R ₃ is a divalent group containing a silicon atom. R ₃ is not particularly limited as long as it satisfies the above requirements, and examples thereof include a divalent group having the following structure.

[Wherein, X is a halogen atom, and R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. r is 0 or an integer of 1 to 4. ]
The silicon residue represented by the above formula (I ′) is present inside and / or at the end of the PO group segment of the olefin chain-containing silicon compound represented by the formula (I).

  In the polyolefin chain-containing silicon compound of the present invention, among the silicon residues (I ′), a silicon residue represented by the following formula (II ′) is preferable. That is, in the present invention, a polyolefin chain-containing silicon compound represented by the following formula (II) composed of the PO group and a silicon residue represented by the following formula (II ′) is preferable. When the polyolefin chain-containing silicon compound of the present invention is a compound represented by the formula (II), a highly reactive site is firmly bonded to the PO group, and the structure is stable.

In the above formulas (II ′) and (II), PO is a group composed of the aforementioned polymer, and R ₄ , R ₅ , R ₆ , and R ₇ are a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. And a monovalent group selected from a group comprising an oxygen atom and / or a silicon atom, and R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different from each other. good. m is 0 or an integer of 1 or more, and l is an integer of 1 or more.

  The silicon residue represented by the above formula (II ′) is present inside and / or at the end of the PO group segment of the olefin chain-containing silicon compound represented by the formula (II).

  In the polyolefin chain-containing silicon compound of the present invention, among the silicon residues (I ′), a silicon residue represented by the following formula (III ′) is preferable. That is, in the present invention, a polyolefin chain-containing silicon compound represented by the following formula (III) composed of the PO group and a silicon residue represented by the following formula (III ′) is preferable. When the polyolefin chain-containing silicon compound of the present invention is a compound represented by the formula (III), the reactive site is firmly bonded to the PO group, so the structure is stable, Since it has a PO group, it has an excellent balance of molding processability and mechanical properties.

In the above formulas (III ′) and (III), PO is a group comprising the above-mentioned polymer, and R ₈ , R ₉ , R ₁₀ , and R ₁₁ are a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. A group comprising an olefin polymer comprising, as a main constituent unit, a group comprising a group, an oxygen atom and / or a silicon atom, and a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms (PO ″) is a monovalent group, and at least one of R ₈ , R ₉ , R ₁₀ , and R ₁₁ is at least one olefin selected from olefins having 2 to 20 carbon atoms. This is a group (PO ″) composed of an olefin polymer whose main constituent unit is a derived repeating unit. R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same as or different from each other. p is 0 or an integer of 1 or more, and q is an integer of 1 or more.

  Furthermore, the silicon residue represented by the formula (III ') is present in the interior and / or terminal of the PO group segment of the olefin chain-containing silicon compound represented by the formula (III).

[Production of PO department]
Next, the manufacturing method of PO part (polyolefin part) used as a part of polyolefin chain containing silicon compound concerning this invention is demonstrated. The polyolefin that is the raw material of the PO part is obtained by polymerizing the olefin described above using an olefin polymerization catalyst.

  First, the olefin polymerization catalyst used for the production of the polyolefin will be described. Examples of the olefin polymerization catalyst used for the production of polyolefin include magnesium-supported titanium-based catalysts, metallocene-based catalysts, and other conventionally known catalysts. For example, the catalysts described in International Patent Publications WO01 / 53369 or WO01 / 27124 are preferable. Used for.

  For example, when 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 The 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, The organometallic compound catalyst component (b) is usually 1 to 2000 mol, preferably 1 to 2000 mol of metal atoms in the catalyst component (b) with respect to 1 mol of titanium atoms in the solid titanium catalyst component (a) in the polymerization system. Is used in an amount of 2 to 1000 mol, and the electron donor (ED) is usually 0.001 mol to 10 mol, preferably 0, relative to 1 mol of the metal atom of the organometallic compound catalyst component (b). 01 mol to 5 used in an amount of mol.

  In the case of polymerization using the magnesium-supported titanium-based catalyst, the hydrogen concentration is usually from 0 to 0.01 mol, preferably from 0 to 0.005 mol, more preferably from 0 to 0.00 mol per mol of the monomer. The amount is 001 mol.

  In the case of polymerization using the magnesium-supported titanium catalyst, the polymerization temperature is usually 70 ° C. or higher, preferably 80 to 150 ° C., more preferably 85 to 140 ° C., and particularly preferably 90 to 130 ° C. The polymerization pressure is usually set to normal pressure to 10 MPa, preferably normal pressure to 5 MPa.

  For example, when a metallocene catalyst containing a metallocene compound (c) and an organoaluminum oxy compound (d) as constituent components is used, the concentration of the metallocene compound (c) is usually 0.00005 per liter of polymerization volume. The organoaluminum oxy compound (d) is used in an amount of ˜0.1 mmol, preferably 0.0001 to 0.05 mmol, and the organoaluminum oxycompound (d) is used as the aluminum atom (Al) relative to the transition metal atom (M) in the metallocene compound (c). The molar ratio (Al / M) is usually 5 to 1000, preferably 10 to 400. Furthermore, when an organoaluminum compound (e) other than the organoaluminum oxy compound is used, it is usually about 1 to 300 mol, preferably about 2 to 1 mol of the transition metal atom in the metallocene compound (c). The amount used is 200 mol.

  The metallocene catalyst may be used as a solution in a solvent in which the metallocene catalyst is soluble, or may be supported on an inorganic compound, a resin composition or the like and used as a supported catalyst.

  When the metallocene catalyst is used, the polymerization temperature is usually in the range of −20 to 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and the polymerization pressure exceeds 0 to 8 MPa. , Preferably in the range of more than 0 and 5 MPa.

  The polyolefin can be produced by either liquid phase polymerization such as solution polymerization or suspension polymerization, or gas phase polymerization. The polyolefin can be produced by any of batch, semi-continuous and continuous systems.

  Further, the polymerization can be carried out in two or more stages. When carrying out by dividing into two or more steps, the reaction conditions may be the same or different. In the above polymerization, the above-mentioned olefin homopolymer may be produced, or a random copolymer or block copolymer may be produced from two or more kinds of olefins selected from the above-mentioned olefins.

  It is desirable that the polyolefin used as the base material of the PO part has an unsaturated group. This unsaturated group may be an unsaturated group generated by chain transfer during the above polymerization, and a thermal degradation method (for example, Japanese Patent Laid-Open No. Hei 3- (1993)) which is a known method from the olefin polymer obtained as described above. It may be an unsaturated group generated in the polyolefin portion by the method described in Japanese Patent No. 62804. Moreover, when the said polyolefin is a polymer containing the structural unit derived from a conjugated diene and a nonconjugated polyene, the unsaturated group derived from the conjugated diene and a nonconjugated polyene may be sufficient. Examples of the unsaturated group include a vinyl group, a vinylidene group, a linear cis- and / or trans-2 substituted vinyl group, a cyclic disubstituted vinyl group, and a trisubstituted vinyl group. Among these groups, from the viewpoint of ease of production of the polyolefin chain-containing silicon compound described later, a vinyl 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.

[Production of polyolefin chain-containing silicon compound]
Next, the manufacturing method of the polyolefin chain containing silicon compound which concerns on this invention is demonstrated.

  The polyolefin chain-containing silicon compound according to the present invention is a silicon compound having a specific structure having the above-mentioned PO part, and by reacting the polyolefin which is the base of the PO part having the specific structure described above with a silicon compound having a specific structure. Can be manufactured.

  As described above, it is desirable that the polyolefin that is the base of the PO part used when producing the polyolefin chain-containing silicon compound has an unsaturated group. When the polyolefin has an unsaturated bond as described above, the polyolefin chain-containing silicon compound of the present invention can be produced by treating the polyolefin with a silicon compound having a specific structure described later.

  Any silicon compound having a specific structure can be used without particular limitation as long as it is a compound in which the aforementioned silicon residue (I ′) is formed by the reaction with the polyolefin that is the raw material of the aforementioned PO moiety.

  When a polyolefin having an unsaturated group is used as the polyolefin serving as the raw material of the PO portion, the silicon compound having a specific structure preferably has 2 Si—H bonds (Si represents silicon and H represents hydrogen). The alkyl group-containing silicon compound or the aromatic ring-containing silicon compound containing two or more Si—H bonds.

Among these compounds, tetrasiloxanes such as tetramethyldisiloxane, tetraethyldisiloxane, tetrapropyldisiloxane, tetraphenyldisiloxane, dimethyldiphenyldisiloxane, hexamethyltrisiloxane, hexaethyltrisiloxane, hexaphenyltrisiloxane, trimethyl More preferred are trisiloxanes such as triphenyltrisiloxane, dimethyldiethyldiphenyltrisiloxane, and tetramethyldiphenyltrisiloxane, and tetrasiloxanes such as octamethyltetrasiloxane and octaphenyltetrasiloxane. Further, siloxanes having the following structure are more preferable.

  By using such a compound, the reaction with the polyolefin as a raw material proceeds efficiently, and the polyolefin chain-containing silicon compound of the present invention can be easily produced.

  The polyolefin chain-containing silicon compound of the present invention can be produced by reacting a silicon compound containing two or more Si-H bonds with a polyolefin having an unsaturated group. Specifically, for example, using a silicon compound containing two or more Si—H bonds as a solvent, dissolving or suspending a polyolefin having an unsaturated group as a base of the PO part, and reacting the silicon compound with the polyolefin Manufactured by. This solution method and suspension method are suitable from the viewpoint of producing a polyolefin chain-containing silicon compound having a controlled structure.

  At this time, a solvent may be further used as necessary. Although it can use without a restriction | limiting in particular as a solvent, Aromatic hydrocarbon solvents, such as aliphatic hydrocarbon solvents, such as hexane, heptane, a decane, toluene, xylene, etc. are used suitably.

  The above production is usually performed in a temperature range of 0 ° C to 400 ° C, preferably 20 ° C to 250 ° C, more preferably 50 ° C to 220 ° C.

  The reaction time between the silicon compound and the polyolefin is usually 1 minute to 24 hours, preferably 5 minutes to 10 hours. In order to promote the reaction, an acid catalyst, a noble metal-containing catalyst, and other known catalysts may be used. Among these catalysts, a platinum-containing catalyst that is a noble metal-containing catalyst is preferably used from the viewpoint of reactivity and versatility. Furthermore, radical initiators such as peroxides 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, a multi-screw kneader of two or more axes, a kneading extruder, a stirrer, or the like. For example, with a high-speed stirrer or the like, after uniformly mixing a polyolefin that is the raw material of the PO part and a silicon compound containing two or more Si-H bonds, with a single-screw or multi-screw extruder having sufficient kneading ability, By melting and kneading the obtained mixture, the polyolefin chain-containing silicon compound of the present invention can be produced. 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 kneading 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. Moreover, you may add organic solvents, such as toluene and xylene, for viscosity adjustment and reaction efficiency improvement at the time of melt-kneading. The melt kneading can be performed in the range of 0.01 mmHg to atmospheric pressure. Melting and kneading under reduced pressure is effective for removing a 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 silicon 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 silicon compound of the present invention can be produced, it can be produced by other known methods. May be.

In the production of the polyolefin chain-containing silicon compound of the present invention, the total amount of Si—H groups [SiH] (mol) in the silicon compound containing two or more Si—H bonds and the polyolefin that is the raw material of the PO part. The total amount of saturated bonds [PV] (mol) preferably satisfies the relationship of the following formula (Eq-1), more preferably satisfies the relationship of the following formula (Eq-2), and the following formula (Eq− It is more preferable to satisfy the relationship 3).
1000 × [P−V] ≧ [SiH] ≧ 1 × [P−V] − (Eq−1)
500 × [P−V] ≧ [SiH] ≧ 5 × [P−V] − (Eq-2)
100 × [PV] ≧ [SiH] ≧ 10 × [PV] − (Eq-3)
When the amount of the silicon compound containing two or more Si—H bonds is greater than or equal to the above lower limit relative to the polyolefin that is the raw material of the PO part, the gel fraction is effectively reduced. If the amount of the silicon compound containing two or more Si—H bonds exceeds the upper limit, it is not preferable because it is necessary to remove unreacted substances in production.

  In the production of the polyolefin chain-containing silicon compound of the present invention, as a by-product, a compound in which a single PO moiety is cyclized via a silicon compound containing two or more Si-H bonds may be produced. In some cases, a compound in which a plurality of PO parts are bonded via a silicon compound containing two or more Si—H bonds may be generated. In addition, you may use the polyolefin chain containing silicon compound of this invention as a mixture containing these by-products.

  The polyolefin chain-containing silicon compound of the present invention includes various polyolefins, elastomers, pigments, dyes, glass fibers, metal fibers, reinforcing materials such as carbon fibers, fillers such as talc and calcium carbonate, antioxidants, An ultraviolet absorber, a lubricant, a flame retardant, etc. can be added. Further, it is possible to enhance the antistatic effect by adding conductive carbon or the like.

[Use]
The polyolefin chain-containing silicon compound according to the present invention is a silicon compound having a PO group composed of an olefin chain and a silicon-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 portion that is a polar group. The polyolefin chain-containing silicon compound according to the present invention can be used for various applications without any particular limitation. For example, adhesives, building materials and civil engineering materials, automotive interior and exterior materials, gasoline tanks, electrical and electronic parts, antistatic agents, medical and sanitary materials, sundries, films and sheets, magnetic recording materials, modifiers, structure control It can be suitably used for materials and the like.

  The polyolefin chain-containing silicon compound of the present invention is blended with additives such as a softening agent, a stabilizer, a filler, an antioxidant, a crystal nucleating agent, etc., as necessary, as long as the purpose of the present invention is not impaired. Can be used.

  When the PO chain of the polyolefin chain-containing silicon compound of the present invention is a polyolefin having a characteristic of excellent tackiness, heat-resistant creep properties and fluidity, for example, as an adhesive such as a hot melt adhesive It can be suitably used.

  When the polyolefin chain-containing silicon compound of the present invention is used as an adhesive, it may further contain a tackifying resin. The tackifier resin is blended, for example, in order to improve the hot tack property and the wet property in order to adjust the melt viscosity of the adhesive. The tackifier resin is not particularly limited as long as it is generally blended with the olefin copolymer.

  Tackifying resins include alicyclic hydrogenated tackifiers, rosins, modified rosins and esterified products thereof, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic components and aromatics. Group-component copolymer petroleum resins, low molecular weight styrene resins, isoprene resins, alkylphenol resins, terpene resins, coumarone-indene resins, and the like. These tackifying resins can be used singly or in combination of two or more.

  When the polyolefin chain-containing silicon compound of the present invention is used as a hot melt adhesive, it preferably contains the polyolefin chain-containing silicon compound and a tackifying resin. When used as a hot-melt adhesive, the polyolefin chain-containing silicon compound is usually 10 to 90 parts by weight, preferably 20 to 100 parts by weight with respect to 100 parts by weight of the total amount of the polyolefin chain-containing silicon compound and the tackifying resin. It contains 85 parts by weight, more preferably 30 to 80 parts by weight, and 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.

  Moreover, when using as said adhesive agents, such as a hot-melt-adhesive, you may add and use an inorganic filler further as needed. The added amount of the inorganic filler is usually 5 to 50 parts by weight, preferably 5 to 20 parts by weight, and the inorganic filler is usually 5 parts by weight with respect to 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 adhesive such as a hot melt adhesive is prepared by supplying the polyolefin chain-containing silicon compound, tackifying resin, and, if necessary, the additive to a mixer such as Brabender, and heating and melting and mixing. Thereafter, it can be prepared by forming it into a desired shape, for example, granular, flakes, rods and the like.

  When the polyolefin chain-containing silicon compound of the present invention is the above-described polyolefin chain-containing silicon compound having an excellent balance of physical properties such as strength and transparency, the polymer may be further blended with other thermoplastic resins as necessary. A composition can be produced, and a molded product can be produced from the composition. The obtained molded product 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.

  When these polyolefin chain-containing silicon compounds are used in molded articles, one kind may be used alone, or a plurality of kinds may be mixed and used. Furthermore, an inorganic filler such as magnesium hydroxide and a crosslinking agent such as vinyltrimethoxysilane may be used in combination.

  The blending amount of the thermoplastic resin is not particularly limited, but the polyolefin chain-containing silicon compound is usually 0.01 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and optionally 0.01 to 150 parts by weight of filler. 300 parts by weight, preferably 0.1 to 20 parts by weight of polyolefin chain-containing silicon compound, 0.1 to 40 parts by weight of filler, more preferably 0.5 to 10 parts by weight of polyolefin chain-containing silicon compound, filler Is preferably used in an amount of 0.5 to 20 parts by weight.

  In addition, an excellent magnetic recording material can be obtained by kneading the polyolefin chain-containing silicon compound and magnetic powder. In this case, the blending ratio of the polyolefin chain-containing silicon compound and the magnetic powder (polyolefin chain-containing silicon compound / magnetic powder: weight ratio) is preferably 99/1 to 10/90.

  Moreover, this magnetic powder mixture can be preferably used as a plastic magnet for a stationery or the like.

The polyolefin chain-containing silicon compound of the present invention produces a polymer composition as described above,
A molded body such as a sheet, a film, or a hollow molded body can be produced from the composition by calendar molding, extrusion molding, injection molding, blow molding, press molding, stamping molding, and the like, and can be used as a medical / sanitary material. Moreover, a filament can be produced from the said composition, a nonwoven fabric or a woven fabric can be produced from the filament, and it can use as a medical and sanitary material. The filament can be produced, for example, by extruding a molten composition through a spinneret. Furthermore, a nonwoven fabric laminated body can be manufactured using the obtained film and sheet, and this laminated body 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 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 is formed from the polyolefin chain-containing silicon compound of the present invention. Among these, 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 above-described olefin polymer according to the present invention. A film or sheet excellent in mechanical strength characteristics is preferably used.

  The film or sheet having at least one layer formed from the polyolefin chain-containing silicon compound of the present invention is particularly excellent in transparency, heat resistance, and cloud resistance, and is therefore preferable for agriculture and wrapping.

  Examples of the method 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, and foam molding.

  The polyolefin chain-containing silicon compound of the present invention can also be used as a modifier, including resin, rubber, wax, and lubricant modifiers, pigment dispersion modifiers such as cement and ink / paint, and denture materials, sealing It is used suitably for modifiers, such as an agent.

  The modifying agent may be a composition containing the polyolefin chain-containing silicon compound of the present invention and a resin, rubber, a base material for lubricating oil, wax, cement, ink / paint, or the like.

  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 silicon compound of the present invention has an effect of suppressing electrification. For example, the polyolefin chain-containing silicon compound and resin, rubber, base material for lubricating oil, wax, or ink / paint In the composition containing, the effect is exhibited suitably.

  According to the present invention, a novel polyolefin chain-containing silicon compound that does not impair mechanical properties and the like can be obtained efficiently, and is extremely valuable industrially.

<Olefin polymer>
Hereinafter, the olefin polymer of the present invention will be described in detail.

[PO department, PO 'department, PO "department]
In the above formulas (IV) and (V), 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 consisting of a group consisting of a polymer, that is, an olefin chain.

  The olefin used in the olefin polymer to be the PO, PO ′, and PO ″ groups is the same as the olefin used in the PO portion of the polyolefin chain-containing silicon compound described above.

  The molecular weights of the PO, PO ′, and PO ″ parts are in the range of 1,000 to 10,000,000 in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography. , Preferably in the range of 2,000 to 5,000,000, more preferably in the range of 3,000 to 2,000,000.

  The PO part, PO ′ part, and PO ″ part in the olefin polymer according to the present invention are a saturated hydrocarbon group, an aromatic ring-containing group, a halogen atom-containing group, a phosphorus atom-containing group, an oxygen atom-containing group, nitrogen An atom-containing group or a silicon atom-containing group may be introduced into the whole amount or a part of the unsaturated group.

(Joining part)
The olefin polymer according to the present invention has a structure in which polyolefin segments such as PO part and PO ′ part represented by the following formula (IV) are bonded by a silicon-containing group.

In the above formula (IV), R ¹ , R ² , R ³ , and R ⁴ are each a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group comprising an oxygen atom and / or a silicon atom. It is a monovalent group selected. R ¹ , R ² , R ³ , and R ⁴ can be used without limitation as long as they satisfy the above requirements.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include linear groups 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, tert-butyl group; cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group; phenyl group, benzyl group, naphthyl group, anthracenyl group An aromatic ring-containing hydrocarbon group such as Among these, Preferably, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a benzyl group, a naphthyl group is mentioned, More preferably, a methyl group, an ethyl group, a propyl group is mentioned. Cyclohexyl group and phenyl group.

  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, pentaethyldisilyl group, hepta Examples thereof include alkylsilyl groups such as methyltrisilyl group and heptaethyltrisilyl group; aromatic ring-containing silyl groups such as triphenylsilyl group, diphenylmethylsilyl group, tribenzylsilyl group and dibenzylmethylsilyl group.

  Groups comprising oxygen and silicon atoms include trimethylsiloxy, triethylsiloxy, triphenylsiloxy, pentamethyldisiloxy, pentaethyldisiloxy, pentaphenyldisiloxy, heptamethyltrisiloxy, hepta Siloxy groups such as phenyltrisiloxy group, dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexaphenyltrisiloxy group, etc. Can be mentioned.

R ¹ , R ² , R ³ , and R ⁴ in the above formula (IV) may be the same as or different from each other.

Q ¹ and Q ² are divalent groups selected from a hydrocarbon group having 1 to 30 carbon atoms and a hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and / or a silicon atom. .

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclopropylene group, cyclobutylene group, cyclohexylene group and other alkyl residues; And aromatic ring-containing hydrocarbon residues such as benzylene, naphthylene, and anthracenylene.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms containing the oxygen atom include an ether bond in addition to the above-described alkyl residue such as a tetrahydrofuran residue and the aromatic ring-containing hydrocarbon residue containing an oxygen atom. , A group having an ester bond, a ketone group, and the like.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms including the silicon atom include a dimethylsilyl group, in addition to the alkyl residue and aromatic ring-containing hydrocarbon residue having a silicon atom-containing substituent. Dialkylsilyl groups such as diethylsilyl group, dibutylsilyl group, methylethylsilyl group, dicyclohexylsilyl group; alkylsilyl groups such as tetramethyldisilyl group, tetraethyldisilyl group, hexamethyltrisilyl group, hexaethyltrisilyl group An aromatic ring-containing silyl group 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 dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group Group, hexamethyltrisiloxy group, hexaphenyltrisiloxy group, dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexamethyl group Examples include a siloxy group such as a phenyltrisiloxy 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 an atom selected from an oxygen atom, a silicon atom, and a halogen atom. Among these Y, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including an oxygen atom, a hydrocarbon group having 1 to 50 carbon atoms including a silicon atom, A hydrocarbon group having 1 to 50 carbon atoms and containing an oxygen atom and a silicon atom is preferred.

  Examples of the hydrocarbon group having 1 to 50 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptylki, octyl, decyl, undecyl, dodecyl, docosyl, dotriacontyl Straight chain alkyl groups such as hexatetracontyl group; branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group; cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group, hexadecahydropyre Nyl group, 5-alpha-cholestyl group, cyclic alkyl group such as cyclodotriacontyl group; aromatic ring-containing hydrocarbon group such as phenyl group, benzyl group, naphthyl group, anthracenyl group, coronenyl group, rubrenyl group) Can be mentioned.

  Among these, a hydrocarbon group having 1 to 30 carbon atoms is preferable. Examples of the hydrocarbon group having 1 to 30 carbon atoms include linear groups 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, tert-butyl group; cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group; phenyl group, benzyl group, naphthyl group, anthracenyl group An aromatic ring-containing hydrocarbon group such as Among these, more preferred are 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, and more preferred are a methyl group, an ethyl group, and a propyl group. Group, cyclohexyl group and phenyl group.

  Examples of the hydrocarbon group having 1 to 50 carbon atoms containing the oxygen atom include an ether bond in addition to the alkyl residue such as a tetrahydrofuran residue and the aromatic ring-containing hydrocarbon residue containing an oxygen atom. , A group having an ester bond, a ketone group, and the like.

  Among the above groups, 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 silicon atom include a dimethylsilyl group, in addition to the alkyl residue and aromatic ring-containing hydrocarbon residue having a silicon atom-containing substituent, Dialkylsilyl groups such as diethylsilyl group, dibutylsilyl group, methylethylsilyl group, dicyclohexylsilyl group, didocosylsilyl group; alkyls such as tetramethyldisilyl group, tetraethyldisilyl group, hexamethyltrisilyl group, hexaethyltrisilyl group Silyl group; aromatic phenyl-containing silyl groups such as diphenylsilyl group, phenylmethylsilyl group, dibenzylsilyl group, benzylmethylsilyl group, dinaphthacenylsilyl group, and the like.

  Among the above groups, a hydrocarbon group having 1 to 30 carbon atoms including a silicon atom is preferable. Examples of the hydrocarbon group having 1 to 30 carbon atoms comprising a silicon atom include an alkyl residue having 1 to 30 carbon atoms and an aromatic ring-containing hydrocarbon residue having 1 to 30 carbon atoms, In addition to those having a group, dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group, dibutylsilyl group, methylethylsilyl group, dicyclohexylsilyl group; tetramethyldisilyl group, tetraethyldisilyl group, hexamethyltrisilyl group And alkylsilyl groups such as hexaethyltrisilyl group; aromatic ring-containing silyl groups such as diphenylsilyl group, phenylmethylsilyl group, dibenzylsilyl group, and benzylmethylsilyl group.

  Examples of the hydrocarbon group having 1 to 50 carbon atoms including an oxygen atom and a silicon atom include dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group Group, hexamethyltrisiloxy group, hexaphenyltrisiloxy group, dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexamethyl group Examples include a siloxy group such as a phenyltrisiloxy group and an octaphenyltetrasiloxy group.

  Examples of the C1-C50 hydrocarbon group containing a halogen atom include perfluoroalkyl groups such as a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Can be mentioned.

  Among the above groups, a hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and a silicon atom is preferable. Examples of the hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and a silicon atom include a dimethylsiloxy group, a diethylsiloxy group, a diphenylsiloxy group, a tetramethyldisiloxy group, a tetraethyldisiloxy group, and a tetraphenyldisiloxy group. , Hexamethyltrisiloxy group, hexaphenyltrisiloxy group, dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, tetramethyldisiloxy group, tetraethyldisiloxy group, tetraphenyldisiloxy group, hexamethyltrisiloxy group, hexaphenyl Examples include a siloxy group such as a trisiloxy group.

  Moreover, it is also one aspect that the olefin polymer of the present invention has a silicon-containing group which is a bonding part represented by the following formula (V).

In the above formula (V), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom and / or a silicon atom, and carbon A monovalent group selected from a group (PO ″) consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 atoms, R ⁵ , At least one of R ⁶ , R ⁷ , and R ⁸ is PO ″. PO ″ may be the same as or different from PO or PO ′. R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same as or different from each other. Q ¹ , Q ² , and Y are the same as those in the above formula (IV), and m and n are the same as those in the above formula (IV).

The above-mentioned hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom, a group comprising a silicon atom, and a group comprising an oxygen atom and a silicon atom are represented by the above formula (IV). The same as R ¹ , R ² , R ³ and R ⁴ .

Q ¹ , Q ² and Y are the same as those described above. R ⁵ , R ⁶ , R ⁷ , R ⁸ , Q ¹ , Q ² , and Y can be used without limitation as long as they satisfy the above requirements, and the structures mentioned in the above description are preferably used.

R ⁵ , R ⁶ , R ⁷ and R ⁸ can be used without limitation as long as the structure satisfies the above requirements. ^{R 5, R 6, R 7} , R 8 are hydrogen atom and a monovalent group selected from the group comprising a hydrocarbon group having 1 to 30 carbon atoms, and an oxygen atom and / or silicon atom For the above, the structures referred to for R ¹ , R ² , R ³ and R ⁴ are preferably used.

[Olefin polymer]
The olefin polymer according to the present invention has a structure in which different / or the same kind of polyolefin parts are bonded via a specific silicon-containing group, and the segment comprising the polyolefin is linear or branched. It has a structure connected in a shape.

  In the olefin polymer according to the present invention, the polymer segment PO part, PO ′ part, and PO ″ part may be crystalline or amorphous, but the PO part is crystalline. When 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.

  Further, it is preferable that at least one of PO ′ part and PO ″ part is crystalline. Thus, when at least one of PO ′ part and PO ″ part is crystalline, the olefin polymer according to the present invention. The rigidity and heat resistance of the olefin polymer can be improved, and the compatibility of the olefin polymer can be expected to be improved.

  Here, “having crystallinity” means that the melting point is observed by differential scanning calorimetry (temperature rising condition: 10 ° C./min). 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.

  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. Examples include a segment, a hexene polymer segment, and a methylpentene polymer segment.

[Manufacture of polyolefin part]
Next, a method for producing a PO part, a PO ′ part, and a PO ″ part (hereinafter collectively referred to as a polyolefin part) that are part of the polyolefin polymer according to the present invention will be described. , PO ′ part, and PO ″ part are obtained as a raw material by polymerizing the above-mentioned olefin using an olefin polymerization catalyst.

  The olefin polymerization catalyst used for the production of the polyolefin is the same as the catalyst used for the production of the polyolefin that is the raw material of the PO part of the polyolefin chain-containing silicon compound according to the present invention, a magnesium-supported titanium catalyst, a metallocene catalyst, Other conventionally known catalysts may be mentioned. For example, the catalysts described in International Patent Publication WO01 / 53369 or WO01 / 27124 are preferably used.

  Regarding the polymerization of the polyolefin, 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 the raw materials of the PO part of the polyolefin chain-containing silicon compound according to the present invention. It is the same as that of the manufacture of polyolefin which becomes.

  It is desirable that the polyolefin serving as the base of the polyolefin portion described above has an unsaturated group. This unsaturated group may be an unsaturated group generated by chain transfer during the above polymerization, and a thermal degradation method (for example, Japanese Patent Laid-Open No. Hei 3- (1993)) which is a known method from the olefin polymer obtained as described above. It may be an unsaturated group generated in the polyolefin portion by the method described in Japanese Patent No. 62804. Moreover, when the said polyolefin is a polymer containing the structural unit derived from a conjugated diene and a nonconjugated polyene, the unsaturated group derived from the conjugated diene and a nonconjugated polyene may be sufficient. Examples of the unsaturated group include a vinyl group, a vinylidene group, a linear cis- and / or trans-2 substituted vinyl group, a cyclic disubstituted vinyl group, and a trisubstituted vinyl group. Among these groups, a vinyl group, a vinylidene group, a cyclic 2-substituted vinyl group, and a 3-substituted vinyl group are preferable from the viewpoint of easy production of an olefin polymer, and a vinyl group and a vinylidene group are more preferable. More preferably, it is a vinyl group.

[Production of olefin polymers]
Next, the manufacturing method of the olefin polymer which concerns on this invention is demonstrated.

  The olefin polymer according to the present invention may be produced by any method as long as the requirements are not impaired. Preferably, it can be produced by reacting a polyolefin containing an unsaturated group, which is the base of the PO moiety having the specific structure described above, with a silicon-containing compound having the specific structure.

  Any silicon compound having a specific structure can be used without particular limitation as long as it is a compound in which the aforementioned silicon residue (I ′) is formed by the reaction with the polyolefin that is the raw material of the aforementioned PO moiety.

  When a polyolefin having an unsaturated group is used as the polyolefin serving as the raw material of the polyolefin part, the silicon compound preferably has two or more Si-H bonds (Si represents silicon and H represents hydrogen). An alkyl group-containing silicon compound or an aromatic ring-containing silicon compound containing two or more Si—H bonds.

Among these compounds, tetrasiloxanes such as tetramethyldisiloxane, tetraethyldisiloxane, tetrapropyldisiloxane, tetraphenyldisiloxane, dimethyldiphenyldisiloxane, hexamethyltrisiloxane, hexaethyltrisiloxane, hexaphenyltrisiloxane, trimethyl More preferred are trisiloxanes such as triphenyltrisiloxane, dimethyldiethyldiphenyltrisiloxane, and tetramethyldiphenyltrisiloxane, and tetrasiloxanes such as octamethyltetrasiloxane and octaphenyltetrasiloxane. Further, siloxanes having the following structure are more preferable.

  By using such a compound, the reaction with the polyolefin as a raw material proceeds efficiently, and the polyolefin polymer of the present invention can be easily produced.

  The olefin polymer according to the present invention can be produced by reacting the silicon compound containing two or more Si-H bonds with a polyolefin having an unsaturated group. Moreover, the olefin polymer which concerns on this invention can be manufactured also by reacting the polyolefin which has Si-H bond, and the polyolefin which has an unsaturated group. Specifically, for example, using a silicon compound containing two or more Si—H bonds as a solvent, a polyolefin part having an unsaturated group as a base of a polyolefin part is dissolved or suspended, and the silicon compound and the polyolefin are reacted. It is manufactured by. This solution method and suspension method are suitable from the viewpoint of producing a polyolefin chain-containing silicon compound having a controlled structure.

  At this time, a solvent may be further used as necessary. 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 performed 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 between the silicon compound and the polyolefin is usually 1 minute to 24 hours, preferably 5 minutes to 10 hours. In order to promote the reaction, an acid catalyst, a noble metal-containing catalyst, and other known catalysts may be used. Among these catalysts, a platinum-containing catalyst that is a noble metal-containing catalyst is preferably used from the viewpoint of reactivity and versatility. Furthermore, radical initiators such as peroxides 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, a multi-screw kneader of two or more axes, a kneading extruder, a stirrer, or the like. For example, with a high-speed stirrer or the like, after uniformly mixing a polyolefin that is the raw material of the polyolefin part and a silicon compound containing two or more Si-H bonds, a single-screw or multi-screw extruder having sufficient kneading ability, By melting and kneading the obtained mixture, the polyolefin chain-containing silicon compound of the present invention can be produced. 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 kneading 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. Moreover, you may add organic solvents, such as toluene and xylene, for viscosity adjustment and reaction efficiency improvement at the time of melt-kneading. The melt kneading can be performed in the range of 0.01 mmHg to atmospheric pressure. Melting and kneading under reduced pressure is effective for removing a 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 silicon 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 silicon compound of the present invention can be produced, it can be produced by other known methods. May be.

In the production of the olefin polymer of the present invention, the total amount [SiH] (mol) of Si—H groups in the silicon compound containing two or more Si—H bonds and the unsaturation of the polyolefin that is the raw material of the polyolefin part. The total amount of bonds [PV] (mol) preferably satisfies the relationship of the following formula (Eq-1), more preferably satisfies the relationship of the following formula (Eq-2), and the following formula (Eq-3) It is more preferable to satisfy the relationship of
1000 × [P−V] ≧ [SiH] ≧ 1 × [P−V] − (Eq−1)
500 × [P−V] ≧ [SiH] ≧ 5 × [P−V] − (Eq-2)
100 × [PV] ≧ [SiH] ≧ 10 × [PV] − (Eq-3)
When the amount of the silicon compound containing two or more Si-H bonds is greater than or equal to the above lower limit relative to the polyolefin that is the base material of the polyolefin portion, the gel fraction is effectively reduced. If the amount of the silicon compound containing two or more Si—H bonds exceeds the upper limit, it is not preferable because it is necessary to remove unreacted substances in production.

  As a more preferable method for producing the olefin polymer according to the present invention, the silicon compound containing two or more Si-H bonds and one or more kinds of polyolefins having an unsaturated group are reacted in a solvent, After the polyolefin chain-containing silicon compound of the present invention is produced, separated and recovered, the polyolefin chain-containing silicon compound is further reacted with one or more types of polyolefin having an unsaturated group in a solvent, and one or more The method of manufacturing the olefin polymer which has a seed | species polyolefin segment is mentioned.

  The properties and structure of the produced olefin polymer can usually be analyzed by generally known analysis methods. For example, specific parts 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, intrinsic viscosity, etc. The molecular weight can be measured by measurement, and the thermal characteristics can be confirmed by thermal analysis. Morphology can also be confirmed by morphological observation with a transmission electron microscope, a scanning electron microscope, an atomic force microscope, or the like.

  The olefin polymer of the present invention can be suitably produced by the above-described methods, but when produced by these methods, depending on the production conditions, a mixture of olefin polymers represented by the above formulas (IV) and (V). It may be obtained as

  A mixture of these polymers can be separated into each polymer by a column or the like, but in the present invention, the obtained olefin polymer may be used as it is depending on its use.

  Moreover, according to the said manufacturing method, it may be obtained as a mixture of the polyolefin chain containing silicon compound and olefin polymer of this invention. 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 the olefin polymer are used as they are in accordance with the application. Also good.

  The olefin polymer according to the present invention includes various polyolefins, elastomers, pigments, dyes, glass fibers, metal fibers, reinforcing materials such as carbon fibers, fillers such as talc and calcium carbonate, antioxidants, depending on the purpose. An ultraviolet absorber, a lubricant, a flame retardant, etc. can be added. Further, it is possible to enhance the antistatic effect by adding conductive carbon or the like.

[Use]
The olefin polymer according to the present invention can be used for various applications without particular limitation. For example, it is used as adhesive resin, daily miscellaneous goods, industrial materials, etc., and is suitable for molded products such as fibers, films and sheets, elastic materials, various sealing materials, foaming members, modifiers, structure control materials, lubricants, etc. Can be used for

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

〔Evaluation of the physical properties〕
In the examples, physical properties were measured under the following conditions.

(GPC measurement)
Measuring device: Gel permeation chromatograph Alliance GPC 2000 (Waters)
Measurement conditions: Column: TSKgel GMH6-HT x2 + TSKgel GMH6-HTL x2 (Tosoh Corporation)
Column temperature: 140 ° C
Mobile phase: 1,2-dichlorobenzene Detector: Differential refractometer Flow rate: 1 mL / min Sample concentration: 0.15% (W / V)
Injection volume: 500 μL
Sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)
Molecular weight conversion: Polystyrene conversion Sample treatment: An analysis sample was prepared by completely dissolving 30 mg of a sample in 20 mL of 1,2-dichlorobenzene at 145 ° C., and then filtering through a sintered filter having a pore size of 1 μm.

(NMR analysis)
Measuring device: JEOL GSX-400 Spectrometer 400MHz (FT mode)
Measurement conditions: Pulse angle: 45 °
Pulse repetition: 5 seconds
Pulse width: 8000Hz
Temperature: 118 ° C
Number of sampling points: 32000
Sample treatment: An analytical sample was prepared by completely dissolving 50 mg of a sample in 0.5 mL of deuterated 1,2-dichlorobenzene at 120 ° C.

(IR analysis)
Measuring device: JEOL FT-IR 410 spectrometer (FT mode)
Sample processing: A press sheet of the sample was prepared by a heat press treatment at 200 ° C. and used as an analysis sample.

(Gel fraction)
Using SUS 325 mesh, 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.

[Reference Example 1]
A propylene homopolymer (an intrinsic viscosity [η] = 135 dl / g at 135 ° C. in a decalin solvent) was treated at 380 ° C. for 2 hours in a nitrogen atmosphere using a plastomyl. The weight average molecular weight (Mw) of the polymer obtained by the treatment is 17500 g / mol (PP conversion by general-purpose calibration method: Mw = 10500 g / mol) from the molecular weight measurement by gel permeation chromatography (GPC). Met. From the results of IR analysis and ¹ H-NMR analysis, it was confirmed that 1.69 vinylidene groups were present per polymer chain.

[Reference Example 2]
In reference to the method described in Synthesis Example 1 in JP-A-2006-137873, an ethylene polymer having Mw = 3780 (PE conversion by general-purpose calibration method: Mw = 1890 g / mol) and Mw / Mn = 1.68 was synthesized. did. ^{From 1} H-NMR analysis, it was vinyl group / vinylene group / vinylidene group = 83.9 / 13.4 / 2.8 (mol%), and the one-terminal unsaturation rate of the polymer was 78.7 mol%. . Here, the one-terminal unsaturation rate means the value [Mn] of the number average molecular weight of the polymer obtained from GPC measurement and the value [V of the unsaturated group in the polymer obtained from ¹ H-NMR analysis] The ratio of the unsaturated group of the polymer chain when the unsaturated group is assumed to exist only at one end of the polymer chain is expressed as the unsaturation rate at one end.
Unsaturation at one end (%) = [V] × ([Mn] / [M])
[V] (mol%): Unsaturated group amount in polymer chain determined from NMR [Mn] (g / mol): Number average molecular weight after conversion by a general-purpose calibration method of a polymer obtained from GPC measurement [ M] (mol / g): (average) molecular weight of monomers constituting the polymer chain [Reference Example 3]
A propylene homopolymer (an intrinsic viscosity at 135 ° C. [η] = 7.6 dl / g in a decalin solvent) was treated at 360 ° C. for 2 hours in a nitrogen atmosphere using a plastomyl. The weight average molecular weight (Mw) of the polymer obtained by the treatment was 45000 g / mol (PP conversion by general-purpose calibration method: Mw = 27000 g / mol) from GPC molecular weight measurement. From the results of IR analysis and ¹ H-NMR analysis, it was confirmed that 0.92 vinylidene groups were present per polymer chain.

(Examples of polyolefin chain-containing silicon compound)
[Example 1A]
100 parts by weight of the vinylidene group-containing propylene polymer obtained in Reference Example 1, 30 parts by weight of 1,1,3,3,5,5-tetramethyltrisiloxane, 0.01 part by weight of hexachloroplatinic acid, 1300 parts by weight of xylene In part, mix 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 101 parts by weight of a polyolefin chain-containing silicon compound. The weight average molecular weight (Mw) of the obtained polyolefin chain-containing silicon compound was 20000 g / mol (PP conversion by general-purpose calibration method: Mw = 12000 g / mol) from GPC molecular weight measurement. ^From the result of ¹ H-NMR analysis, no signal derived from the vinylidene group (4.7 ppm) in the propylene polymer of Reference Example 1 was observed, but the signal of the methyl group derived from Si—CH ₃ (0.5 ppm). Were newly observed. ^From the integral ratio derived from hydrogen atoms obtained from ¹ H-NMR analysis, 100% of the vinylidene groups in the propylene polymer reacted with 1,1,3,3,5,5-tetramethyltrisiloxane. It was concealed. From the IR analysis, it was confirmed that Si—H bonds (2200 cm ⁻¹ ) were present in the obtained polymer.

[Example 2A]
10 parts by weight of the unsaturated group-containing ethylene polymer obtained in Reference Example 2, 3 parts by weight of 1,1,3,3,5,5-tetramethyltrisiloxane and 0.01 parts by weight of hexachloroplatinic acid were added to 200 parts of xylene. 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 then dried under reduced pressure at 80 ° C. to obtain 10.1 parts by weight of a polyolefin chain-containing silicon compound. The weight average molecular weight (Mw) of the obtained polyolefin chain-containing silicon compound was 3900 g / mol (PE conversion by general-purpose calibration method: Mw = 1950 g / mol) from GPC molecular weight measurement. ^From the result of ¹ H-NMR analysis, signals derived from the vinyl group and vinylidene group in the ethylene polymer of Reference Example 2 were not observed, and a methyl group signal derived from Si—CH ₃ was newly observed. ^From the integral ratio derived from hydrogen atoms obtained from ¹ H-NMR analysis, 90% of vinyl groups and vinylidene groups in the ethylene polymer reacted with 1,1,3,3,5,5-tetramethyltrisiloxane. It was confirmed. From the IR analysis, it was confirmed that Si—H bonds (2200 cm ⁻¹ ) were present in the obtained polymer.

(Examples and comparative examples of olefin polymers)
[Example 1B]
100 parts by weight of the vinylidene group-containing propylene polymer obtained in Reference Example 1, 30 parts by weight of 1,1,3,3,5,5-tetramethyltrisiloxane, 0.01 part by weight of hexachloroplatinic acid, 1300 parts by weight of xylene In part, mix 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 101 parts by weight of a polyolefin chain-containing silicon compound. The resulting polyolefin chain-containing silicon compound had Mw = 20000 g / mol (PP conversion by general-purpose calibration method: Mw = 12000 g / mol). ^From the result of ¹ H-NMR analysis, no signal derived from the vinylidene group (4.7 ppm) in the polypropylene of Reference Example 1 was observed, and the methyl group signal derived from Si—CH ₃ (0.5 ppm) was newly observed. Observed. ^From the integral ratio derived from hydrogen atoms obtained from ¹ H-NMR analysis, it was found that 100% of the vinylidene groups in the polypropylene reacted with 1,1,3,3,5,5-tetramethyltrisiloxane. It was. From the IR analysis, it was confirmed that Si—H bonds (2200 cm ⁻¹ ) were present in the obtained polymer.

10 parts by weight of the polyolefin chain-containing silicon compound obtained above, 2 parts by weight of the unsaturated group-containing ethylene polymer obtained in Reference Example 2, 0.01 part by weight of hexachloroplatinic acid in 150 parts by weight of xylene, Mix at 10 ° C. for 10 hours. After cooling to room temperature, the above mixed solution was poured into 1000 parts by weight of methanol, and the resulting reaction product was recovered. After drying at 80 ° C. for 10 hours under reduced pressure, 11.9 parts by weight of an olefin polymer was recovered. ^From the result of ¹ H-NMR analysis, no signal derived from the vinylidene group (4.7 ppm) vinyl group of the ethylene polymer of Reference Example 1 was observed. The obtained olefin polymer was Mw = 23300 g / mol (PP conversion by general-purpose calibration method: Mw = 14000 g / mol). A press sheet of the obtained olefin polymer was prepared, and the sheet was observed with a transmission electron microscope. The observation results are shown in FIG. The interface between the polypropylene phase and the polyethylene phase is not observed, and the polypropylene phase and the polyethylene phase are dispersed in a nanometer size.

[Example 2B]
100 parts by weight of the vinylidene group-containing propylene polymer obtained in Reference Example 3, 10 parts by weight of 1,1,3,3,5,5-tetramethyltrisiloxane, 0.01 part by weight of hexachloroplatinic acid, and 1300 parts by weight of xylene In a part, it processed at 130 degreeC for 4 hours. After cooling to room temperature, the reaction product was recovered by filtration under a nitrogen atmosphere. This was washed with 1000 parts by weight of hexane and then dried under reduced pressure at 80 ° C. to obtain 101 parts by weight of a polymer.

30 parts by weight of the reaction product obtained above and 70 parts by weight of an ethylene propylene terpolymer (manufactured by Mitsui Chemicals; Mitsui EPT PX-055, decalin solvent, intrinsic viscosity at 135 ° C. [η] = 1.1 dl / g) Then, 0.01 part by weight of hexachloroplatinic acid was treated in 1500 parts by weight of decane at 150 ° C. for 10 hours. After cooling to room temperature, the reaction solution was poured into 1000 parts by weight of acetone to recover the polymer. After drying at 80 ° C. for 10 hours under reduced pressure, 98.9 parts by weight of polymer was recovered. ^From the result of ¹ H-NMR analysis, no signal derived from the vinylidene group (4.7 ppm) in the obtained polymer was observed. The obtained polymer had MFR (230 ° C., 2.16 kg load) = 0.1 g / 10 min. The gel fraction of the obtained polymer was 0.5% by weight or less.

[Example 3B]
100 parts by weight of the vinylidene group-containing propylene polymer obtained in Reference Example 3, 10 parts by weight of 1,1,3,3,5,5-tetramethyltrisiloxane, 0.01 part by weight of hexachloroplatinic acid, and 1300 parts by weight of xylene In a part, it processed at 130 degreeC for 4 hours. After cooling to room temperature, the reaction product was recovered by filtration under a nitrogen atmosphere. This was washed with 1000 parts by weight of hexane and then dried under reduced pressure at 80 ° C. to obtain 101 parts by weight of a reaction product.

30 parts by weight of the reaction product obtained above and 70 parts by weight of ethylene propylene terpolymer (Mitsui Chemicals, Inc .; Mitsui EPT PX-052; decalin solvent, intrinsic viscosity at 135 ° C. [η] = 2.0 dl / g) Then, 0.01 part by weight of hexachloroplatinic acid was treated in 1500 parts by weight of decane at 150 ° C. for 10 hours. After cooling to room temperature, the reaction solution was poured into 1000 parts by weight of acetone to recover the polymer. After drying at 80 ° C. for 10 hours under reduced pressure, 98.9 parts by weight of polymer was recovered. ^From the result of ¹ H-NMR analysis, no signal derived from the vinylidene group (4.7 ppm) in the obtained polymer was observed. The obtained polymer had MFR (230 ° C., 2.16 kg load) = 0.01 g / 10 min. The gel fraction of the obtained polymer was 1.3% by weight or less.

[Comparative Example 1B]
10 parts by weight of the propylene polymer obtained in Reference Example 1 and the ethylene polymer obtained in Reference Example 2 were mixed in 150 parts by weight of xylene to prepare a mixed solution. Treatment in the same manner gave 11.8 parts by weight of polymer mixture. ^From the result of ¹ H-NMR analysis, signals derived from vinylidene groups (4.7 ppm) and vinyl groups in the obtained polymer mixture were recognized. Mw of the whole polymer mixture obtained was 16700 g / mol (PP conversion by general-purpose calibration method: Mw = 10000 g / mol). A press sheet of the obtained polymer was prepared, and the sheet was observed with a transmission electron microscope. The observation results are shown in FIG. It is observed that the boundary between the polypropylene phase and the polyethylene phase is clear and not loose.

[Comparative Example 2B]
30 parts by weight of the propylene polymer obtained in Reference Example 3 and an ethylene propylene terpolymer (manufactured by Mitsui Chemicals; Mitsui EPT PX-055; intrinsic viscosity [135] at 135 ° C. in decalin solvent) = 2.0 dl / g) 70 parts by weight and 0.01 part by weight of hexachloroplatinic acid were treated at 150 ° C. for 10 hours in 1500 parts by weight of decane. After cooling to room temperature, the reaction solution was poured into 1000 parts by weight of acetone to recover the polymer. After drying at 80 ° C. for 10 hours under reduced pressure, 97.8 parts by weight of the polymer was recovered. ^From the result of ¹ H-NMR analysis, a signal derived from the vinylidene group (4.7 ppm) in the obtained polymer was observed, and the obtained polymer had MFR (230 ° C., 2.16 kg load) = 12. It was 4 g / 10 minutes.

It is a transmission electron micrograph of the press sheet in Example 1B. It is a transmission electron micrograph of the press sheet in Comparative Example 1B.

Claims (11)

A polyolefin chain-containing silicon compound represented by the following formula (I):

[In the formula (I), PO is a group consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, and R ₁ and R ₂ is a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group comprising an oxygen atom and / or a silicon atom, and R ₁ and R ₂ are the same as each other. It may or may not be. R ₃ is a divalent group containing a silicon atom. Si is a silicon 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 (I ′)) is present inside and / or at the end of the PO group. ]

The polyolefin chain-containing silicon compound according to claim 1, which is represented by the following formula (II).

[In the formula (II), PO is a group consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, R ₄ , R ₅ , R ₆ , and R ₇ are monovalent groups selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group containing an oxygen atom and / or a silicon atom, R ₄ , R ₅ , R ₆ , and R ₇ may be the same as or different from each other. O is an oxygen atom, Si is a silicon atom, and H is a hydrogen atom. m is 0 or an integer of 1 or more, and l is an integer of 1 or more. The silicon residue in the formula (II) (the following formula (II ′)) is present inside and / or at the end of the PO group. ]

The polyolefin chain-containing silicon compound according to claim 1, which is represented by the following formula (III).

[In the formula (III), PO is a group consisting of an olefin polymer whose main constituent unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, R ₈ , R ₉ , R ₁₀ and R ₁₁ are at least one selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom and / or a silicon atom, and an olefin having 2 to 20 carbon atoms. A monovalent group selected from a group (PO ″) composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one kind of olefin, and at least one of R ₈ , R ₉ , R ₁₀ , and R ₁₁ One is PO ". R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same as or different from each other. O is an oxygen atom, Si is a silicon atom, and H is a hydrogen atom. p is 0 or an integer of 1 or more, and q is an integer of 1 or more. The silicon residue in the formula (III) (the following formula (III ′)) is present inside and / or at the end of the PO group. ]

  The polyolefin chain-containing silicon according to any one of claims 1 to 3, wherein the polyolefin chain-containing silicon is produced by a reaction between a polyolefin containing a carbon-carbon unsaturated bond group and a silicon compound containing two or more Si-H bonds. Compound production method. An olefin polymer represented by the following formula (IV).

[In the formula (IV), PO and PO ′ are groups composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, PO and PO ′ may be the same as or different from each other. R ¹ , R ² , R ³ , and R ⁴ are monovalent groups selected from a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a group comprising an oxygen atom and / or a silicon atom. R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other. Q ¹ and Q ² are divalent groups selected from a hydrocarbon group having 1 to 30 carbon atoms and a hydrocarbon group having 1 to 30 carbon atoms including an oxygen atom and / or a silicon atom. And Si is a silicon 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 silicon residue-containing segment (formula (IV ′) below) in formula (IV) is present inside and / or at the end of the PO group. ]

An olefin polymer represented by the following formula (V).

[In the formula (V), PO and PO ′ are groups composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms; , And PO ′ may be the same as or different from each other. R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group comprising an oxygen atom and / or a silicon atom, and an olefin having 2 to 20 carbon atoms. A monovalent group selected from a group (PO ″) composed of an olefin polymer whose main structural unit is a repeating unit derived from at least one olefin selected from R ⁵ , R ⁵ , R ⁶ , R ⁷ , and At least one of R ⁸ is PO ″. PO ″ may be the same as or different from PO or PO ′. R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same as or different from each other. Q ¹ And Q ² is a divalent group selected from a hydrocarbon group having 1 to 30 carbon atoms and a hydrocarbon group having 1 to 30 carbon atoms comprising an oxygen atom and / or a silicon atom, Si is a silicon atom, Y is an oxygen atom, a hydrocarbon group having 1 to 50 carbon atoms, or a carbon atom having 1 to 50 carbon atoms including an atom selected from an oxygen atom, a silicon atom, and a halogen atom. A hydrogen group, m is 0 or an integer of 1 or more, and n is an integer of 1 or more The silicon residue-containing segment in the formula (V) (the following formula (V ′)) is the interior of the PO group. And / or present at the end.]

  The olefin polymer according to claim 5 or 6, wherein the polymer segment PO is a segment having crystallinity.   The olefin polymer according to any one of claims 5 to 7, wherein the polymer segment PO 'is a segment having crystallinity.   The olefin polymer according to any one of claims 6 to 8, wherein the polymer segment PO "is a segment having crystallinity.   The olefin polymer according to any one of claims 5 to 9, which is produced by a reaction between a polyolefin containing a carbon-carbon unsaturated bond group and a silicon compound containing two or more Si-H bonds. Manufacturing method.   It manufactures by reaction with the polyolefin containing a carbon-carbon unsaturated bond group, and the polyolefin chain containing silicon compound in any one of Claims 1-4. A method for producing an olefin polymer.

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