WO2018164161A1 - Polymère à base de propylène et corps élastique - Google Patents

Polymère à base de propylène et corps élastique Download PDF

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Publication number
WO2018164161A1
WO2018164161A1 PCT/JP2018/008686 JP2018008686W WO2018164161A1 WO 2018164161 A1 WO2018164161 A1 WO 2018164161A1 JP 2018008686 W JP2018008686 W JP 2018008686W WO 2018164161 A1 WO2018164161 A1 WO 2018164161A1
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group
propylene
dimethylsilylene
bis
mol
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PCT/JP2018/008686
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English (en)
Japanese (ja)
Inventor
望 藤井
智明 武部
金丸　正実
岡本　卓治
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出光興産株式会社
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Priority to JP2019504624A priority Critical patent/JPWO2018164161A1/ja
Publication of WO2018164161A1 publication Critical patent/WO2018164161A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a propylene polymer and an elastic body comprising the propylene polymer.
  • Patent Documents 1 to 3 disclose propylene polymers having a mesopentad fraction [mmmm] of 20 to 60 mol%.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a propylene-based polymer having a high elastic recovery rate and an elastic body made of the propylene-based polymer.
  • Intrinsic viscosity [ ⁇ ] measured in a tetralin solvent at 135 ° C. is 0.3 to 5.0 dL / g
  • DSC differential scanning calorimeter
  • Heat quantity ( ⁇ HD) is 3-30J / g
  • DSC differential scanning calorimeter
  • One or more melting points (Tm-D) defined as the top are in the range of 20 to 65 ° C. (4) Using a differential scanning calorimeter (DSC), hold the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min.
  • the melting endotherm ( ⁇ HD) in the range is 30% or more with respect to the melting endotherm ( ⁇ HD) of (2).
  • the melting point (Tm-D) is one or more in the range of 20 to 65 ° C.
  • the melting endotherm ( ⁇ HD) in the range of 20 to 65 ° C. is 3 to 30 J / g. 1].
  • Tm-D melting point
  • ⁇ HD melting endotherm
  • the term “A to B” relating to the description of numerical values means “A to B or less” (when A ⁇ B) or “A or less to B or more” (when A> B). .
  • the combination of a preferable aspect is a more preferable aspect.
  • the propylene polymer of the present invention is characterized by satisfying the following (1) to (4).
  • Intrinsic viscosity [ ⁇ ] measured in a tetralin solvent at 135 ° C. is 0.3 to 5.0 dL / g
  • DSC differential scanning calorimeter
  • Heat quantity ( ⁇ HD) is 3-30J / g
  • DSC differential scanning calorimeter
  • One or more melting points (Tm-D) defined as the top are in the range of 20 to 65 ° C. (4) Using a differential scanning calorimeter (DSC), hold the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min.
  • the melting endotherm ( ⁇ HD) in the range is 30% or more with respect to the melting endotherm ( ⁇ HD) of (2).
  • the propylene-based polymer of the present invention becomes an elastic body (elastomer) having an excellent elastic recovery rate.
  • the mechanism is not clear, but can be considered as follows.
  • An isotactic propylene-based polymer forms a lamellar structure in a form in which 3/1 helical chains are packed, and generally forms a lamellar structure having a different melting point depending on stereoregularity.
  • a tufted micelle structure formed by self-assembly of the 3/1 helical chain like a smectic phase may be formed.
  • This tufted micelle structure does not have a long-range order like a lamellar structure, and has a low stereoregularity and a low crystallinity, the amorphous part 3/1 helix that did not become a lamellar structure. Since the chain is formed by gathering together, unlike a lamellar structure, it has a melting point in a specific temperature range without depending on stereoregularity.
  • the lamella structure is a regular packing in which each 3/1 spiral chain forms a crystal lattice, and the structure to be formed has a long-range order and is a strong structure, so that external strain On the other hand, the structure is destroyed because the energy cannot be dispersed.
  • the polymer chain is restrained without being able to move freely by incorporating a part of it, and is low in stereoregularity and low in crystallinity.
  • the polymer apparently forms a state like a three-dimensional network structure in which the tufted micelle structure functions as a physical cross-linking point.
  • the entire mesh absorbs energy against strain from the outside, the strain is not applied, and a force to restore the original structure works. That is, it is considered that a propylene-based polymer having a high elastic recovery property can be obtained by forming a tufted micelle structure and reducing the amount of the lamellar structure that causes permanent deformation.
  • the crystallinity is thereby lowered, and the tufted micelle structure is formed in such an amount that the elastic recovery is good.
  • the amount of tufted micelle structures formed is reduced. In that case, the amount of the tufted micelle structure that acts as a physical cross-linking point of the three-dimensional network structure is insufficient, and the entanglement of the polymer chain with respect to external strain is unraveled, so that the elastic recovery property is deteriorated. It is done.
  • the isotactic chain is shortened, whereby the 3/1 helical chain is shortened, so that the melting point of the lamellar structure is lowered and the tufted micelle structure is formed, thereby improving the elastic recovery.
  • good elastic recovery can be achieved by appropriately adjusting the amount of the comonomer to be copolymerized so that a tufted micelle structure is formed.
  • the propylene polymer of the present invention has an intrinsic viscosity [ ⁇ ] measured in a tetralin solvent at 135 ° C. of 0.3 to 5.0 dL / g, preferably 0.33 to 5.0 dL / g, more preferably Is 0.35 to 2.0 dL / g.
  • the intrinsic viscosity [ ⁇ ] is less than 0.3 dL / g, the frequency of molecular entanglement decreases without depending on stereoregularity, and elastic recovery is not caused.
  • the intrinsic viscosity [ ⁇ ] is calculated by measuring the reduced viscosity ( ⁇ SP / c) in tetralin at 135 ° C. with an Ubbelohde viscometer and using the following equation (Haggins equation).
  • the propylene polymer of the present invention has a melting endotherm ( ⁇ HD) of 3 to 30 J / g, preferably 5 to 27 J / g, more preferably 7 to 25 J / g. If the melting endotherm ( ⁇ H ⁇ D) is less than 3 J / g, the crystallinity of the propylene polymer is too low, so that the physical crosslinking points necessary for elastic recovery are not formed, and the elastic recovery rate is low. On the other hand, if the melting endotherm ( ⁇ HD) exceeds 30 J / g, the crystallinity of the propylene-based polymer is too high, so that the lamellar structure causing permanent distortion increases and the elastic recovery rate decreases.
  • ⁇ HD melting endotherm
  • the melting endotherm ( ⁇ H ⁇ D) is the highest temperature in the melting endotherm curve obtained by DSC measurement, with the line connecting the point on the low temperature side where there is no change in heat quantity and the point on the high temperature side where there is no change in heat quantity as the baseline. It is calculated by calculating the area surrounded by the line portion including the peak observed on the side and the base line. Note that the melting endotherm ( ⁇ HD) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.
  • the propylene-based polymer of the present invention is a melting endotherm obtained by using a differential scanning calorimeter (DSC) and holding the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min.
  • the melting endotherm ( ⁇ H ⁇ D) in the range of 20 to 65 ° C. of the curve is 10 ° C./min after holding the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC). It is 30% or more, preferably 50 to 100%, more preferably 75 to 100% with respect to the melting endotherm ( ⁇ HD) obtained from the melting endotherm curve obtained by raising the temperature. If it is less than 30%, the number of tufted micelle structures that act as physical cross-linking points necessary for elastic recovery is small, and the number of lamellar structures that cause permanent deformation increases, so the elastic recovery rate is low.
  • the propylene-based polymer of the present invention has one or more melting points (Tm-D) in the range of 20 to 65 ° C., preferably 25 to 60 ° C., more preferably 30 to 60 ° C. D) One or more. If one or more melting points (Tm-D) are not higher than 20 ° C., the physical recovery point will be lower than the standard room temperature, and a physical cross-linking point necessary for elastic recovery will not be formed, and the elastic recovery rate will be low. If the melting point (Tm-D) is not more than one at 65 ° C. or lower, the crystal component does not follow the deformation and becomes a factor of permanent strain, so the elastic recovery rate is lowered.
  • Tm-D melting points
  • a differential scanning calorimeter manufactured by Perkin Elmer, “DSC-7”
  • 10 mg of a sample is held at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min.
  • Tm-D melting point
  • each peak top is defined as the melting point (Tm-D) of the propylene-based polymer.
  • the melting point can be controlled by appropriately adjusting the monomer concentration and reaction pressure.
  • the propylene-based polymer of the present invention has one or more melting points (Tm-D) in the range of 20 to 65 ° C., and the melting endotherm ( ⁇ HD) at 20 to 65 ° C. is preferably Is 3 to 30 J / g, more preferably 5 to 27 J / g, still more preferably 7 to 25 J / g. If the melting endotherm ( ⁇ HD) is within the above range, the propylene-based polymer has an appropriate degree of crystallinity, and more sufficient physical cross-linking points necessary for elastic recovery are formed. There are not too many lamella structures, and the elastic recovery rate is higher.
  • the propylene-based polymer of the present invention may further have a melting point (Tm-D) in the range of more than 65 ° C. and 180 ° C. or less, and the melting endotherm ( ⁇ H ⁇ D) is preferably 1 to 20 J / g, more preferably 2 to 15 J / g, still more preferably 3 to 10 J / g. If the melting endotherm ( ⁇ H ⁇ D) is within the above range, the degree of crystallinity of the propylene-based polymer is appropriate, the physical cross-linking points necessary for elastic recovery are sufficiently formed, and the cause of permanent distortion There are not too many lamella structures, and the elastic recovery rate is higher.
  • Tm-D melting point in the range of more than 65 ° C. and 180 ° C. or less
  • the melting endotherm ( ⁇ H ⁇ D) is preferably 1 to 20 J / g, more preferably 2 to 15 J / g, still more preferably 3 to 10 J / g. If the melting endotherm (
  • the mesotriad fraction [mm] is preferably 40 to 60 mol%, more preferably 42 to 59 mol%, still more preferably 44 to 58 mol%. is there.
  • the mesotriad fraction [mm] is a stereoregularity index indicating isotacticity. If the mesotriad fraction [mm] is within the above range, the crystallinity is lowered and the elastic recovery property is improved. A suitable amount of physical cross-linking points.
  • the propylene polymer is a copolymer of propylene with one or more structural units selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 30 carbon atoms
  • the propylene, ethylene, and carbon number are From the viewpoint of polymerizability of 4 to 30 ⁇ -olefin, the mesotriad fraction [mm] is preferably 50 to 95 mol%, more preferably 52 to 85 mol%, still more preferably 54 to 80 mol%.
  • the mesopentad fraction [mmmm] of the propylene-based polymer of the present invention is preferably 22 to 44 mol%, more preferably 25 to 43 mol%, still more preferably 28 to 42 mol, from the viewpoint of obtaining a higher elastic recovery rate. %.
  • the mesopentad fraction [mmmm] is an index representing the stereoregularity of the propylene-based polymer, and the stereoregularity increases as the mesopentad fraction [mmmm] increases.
  • the mesopentad fraction [mmmm] can be controlled by selecting the type of catalyst and adjusting the polymerization conditions.
  • mesotriad fraction [mm], the mesopentad fraction [mmmm], and the racemic pentad fraction [rrrr], which will be described later, are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al.
  • the meso fraction of triad units in the polypropylene molecular chain and the meso fraction and racemic fraction of pentad units measured by the signal of the methyl group in the 13 C-NMR spectrum, in accordance with the method proposed in . [Rr] and [mr] described later are also calculated by the above method.
  • the molecular weight distribution (Mw / Mn) of the propylene-based polymer of the present invention is preferably 3. from the viewpoint of the balance between the amount of low molecular weight components causing stickiness and bleeding and the amount of high molecular weight components preventing crystallization. It is 0 or less, more preferably 2.8 or less, and still more preferably 2.6 or less.
  • the molecular weight distribution (Mw / Mn) is a value calculated from the polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC).
  • the propylene polymer of the present invention preferably further satisfies at least one of the following (5) and (6).
  • [rrrr] / (100- [mmmm]) The value of [rrrr] / (100- [mmmm]) is obtained from the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] and is an index indicating the uniformity of the regularity distribution of polypropylene. If the value of [rrrr] / (100- [mmmm]) is small, the ratio of the mixture of highly stereoregular polypropylene and atactic polypropylene is low, and stickiness of the polypropylene molded product after molding is suppressed.
  • the unit of [rrrr] and [mmmm] in the above is mol%.
  • the value of [rrrr] / (100- [mmmm]) in the propylene-based polymer is preferably 0.1 or less, more preferably 0.025 to 0.075, still more preferably from the viewpoint of suppressing stickiness. 0.035 to 0.05.
  • the propylene polymer of the present invention preferably satisfies the following (7) and (8) from the viewpoint of thermal stability.
  • (7) 2,1-bond fraction is less than 1.0 mol%
  • 1,3-bond fraction is less than 0.5 mol%
  • the 2,1-bond fraction of the propylene-based polymer is preferably It is less than 1.0 mol%, more preferably 0.7 mol% or less, still more preferably 0.5 mol% or less.
  • the 1,3-bond fraction of the propylene-based polymer is preferably less than 0.5 mol%, more preferably 0.4 mol% or less, still more preferably 0.3 mol% or less.
  • the propylene-based polymer of the present invention is not particularly limited as long as the above conditions (1) to (4) are satisfied.
  • a propylene-based polymer selected from propylene- ⁇ -olefin graft copolymers and the like is preferable.
  • Propylene homopolymer propylene-ethylene random copolymer, propylene-butene random copolymer, propylene- ⁇ -olefin Random copolymer, propylene-ethylene- More preferably a propylene-based polymer selected from the ten ternary random copolymer, more preferably a propylene homopolymer.
  • the content of one or more structural units selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 30 carbon atoms exceeds 0 mol% and is 20 mol%. It is more preferable to include the following.
  • the constituent unit of the olefin having 2 carbon atoms is preferably 0 mol%. More than 20 mol%, more preferably more than 0 mol% and 18 mol% or less, still more preferably more than 0 mol% and 16 mol% or less, still more preferably more than 0 mol% and 14 mol% or less.
  • the content of the ⁇ -olefin having 4 or more carbon atoms is preferably more than 0 mol% and 30 mol% or less, more preferably 0 More than mol% and 25 mol% or less, more preferably more than 0 mol% and 20 mol% or less.
  • the propylene-based polymer of the present invention can have a tensile modulus of preferably 5 to 65 MPa, more preferably 7 to 60 MPa, and still more preferably 10 to 55 MPa.
  • the propylene polymer of the present invention can have an elastic recovery rate of preferably 80% or more, more preferably 84% or more, and still more preferably 88% or more.
  • a tensile elasticity modulus and an elastic recovery rate can be measured by the method as described in an Example.
  • a polymerization catalyst for example, a metallocene catalyst or a Ziegler catalyst
  • a metallocene catalyst or a Ziegler catalyst containing a transition metal compound and a promoter component
  • the molded body made of the propylene-based polymer has a poor heat stability, nozzle clogging, and generation of fish eyes during film formation. May occur.
  • reduction of catalyst residues has not been sufficient.
  • the ash content derived from the catalyst and the cocatalyst can be preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less.
  • the ash content refers to the amount of non-combustible mineral remaining after the organic matter has been ashed.
  • the approximate amount of catalyst residue contained in the propylene polymer can be known from the ash.
  • the catalyst residue contained in the propylene polymer can be reduced, and when the molded body made of the propylene polymer is a film or sheet, The generation of fish eyes can be suppressed, and nozzle clogging can be suppressed in the case of spinning fibers or nonwoven fabrics.
  • the said ash content can be measured by the method as described in an Example.
  • the method for producing the propylene-based polymer of the present invention is not particularly limited.
  • a bi-bridged metallocene complex (component (A)) and boron that can react with the bi-bridged metallocene complex to form an ionic complex A method of polymerizing propylene in the presence of a polymerization catalyst containing a compound (component (B)) can be mentioned.
  • the bibridged metallocene complex is not particularly limited, but a transition metal compound of Group 3 to 10 of the periodic table represented by the following general formula (I) or a lanthanoid series is preferable.
  • a combination of a transition metal compound having a structure represented by the following general formula (I) and the above specific boron compound has a high catalytic activity and is more steric.
  • a propylene polymer having a low regularity and a high elastic recovery rate can be synthesized.
  • the catalyst residue contained in the obtained propylene polymer can be reduced.
  • a double bridged group 3 to 10 or lanthanoid series transition metal compound having a structure represented by the following general formula (I) is preferably used.
  • a 1 and A 2 each independently represent a bridging group consisting of Group 14 (C, Si, Ge, Sn), and they may be the same or different from each other.
  • X is ⁇ -bonding or ⁇ Represents a binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, Y represents a Lewis base, and when there are a plurality of Y, a plurality of Y may be the same or different Y may be cross-linked with other Y or X.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group, wherein R 3 to R 10 are R 3 combinations all ⁇ R 10 is a hydrogen atom, R 4, R 5, R 8 and R 9 is substituted if Is a straight-chain or branched alkyl group unsubstituted 1-8 carbon atoms, and combinations R 3, R 6, R 7 and R 10 are hydrogen atoms, or R 4, R 5, R 8 and R 9 is a hydrogen atom, and R 3, R 6, R 7 and R 10 are combined a linear or branched alkyl group having 1 to 8 carbon atoms substituted or unsubstituted.
  • R 4 and R 5 and R 8 and R 9 may be bonded to each other to form a substituted or unsubstituted cyclic structure having 5 to 8 carbon atoms, where M is a group 3-10 of the periodic table or a lanthanoid series metal Element.
  • a 1 and A 2 each represent a bridging group consisting of Group 14 (C, Si, Ge, Sn), which may be the same or different.
  • Examples of A 1 and A 2 include a crosslinking group represented by the following general formula (II).
  • E represents C, Si, Ge, Sn, and R 11 and R 12 are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. And they may be the same or different from each other, and may be bonded to each other to form a ring.
  • E represents an integer of 1 to 4.
  • halogen atom in the general formula (II) examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
  • hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group, a vinyl group, a propenyl group, and a cyclo group.
  • Alkenyl groups such as hexenyl group; arylalkyl groups such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group And aryl groups such as a methylnaphthyl group, anthracenyl group, and phenanthryl group.
  • alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.
  • halogenated hydrocarbon group having 1 to 20 carbon atoms examples include a halogenated hydrocarbon group in which a halogen atom is substituted on the hydrocarbon group.
  • halogenated alkyl groups such as a trifluoromethyl group and a trichloromethyl group are preferred.
  • bridging group consisting of carbon atoms in the general formula (II) include alkylidene groups such as methylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group; 1,1-cyclohexylene group, vinylidene group Is mentioned.
  • Specific examples of the bridging group comprising a silicon atom include alkylsilylene groups such as methylsilylene group, dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, di (i-propyl) silylene group, and di (cyclohexyl) silylene.
  • Silylene groups alkylarylsilylene groups such as methylphenylsilylene groups and ethylphenylsilylene groups; arylsilylene groups such as diphenylsilylene groups, di (p-tolyl) silylene groups, and di (p-chlorophenyl) silylene groups.
  • Specific examples of the bridging group comprising a germanium atom include a germanylene group in which the silicon atom of the bridging group comprising the silicon atom is replaced with a germanium atom.
  • the bridging group comprising a tin atom include a stannylene group in which the silicon atom of the bridging group comprising the silicon atom is substituted with a tin atom.
  • a 1 and A 2 a bridging group consisting of carbon atoms or a bridging group consisting of silicon atoms is preferable.
  • X is a ⁇ bond or ⁇ bond ligand, and when there are a plurality of X, the plurality of X may be the same or different.
  • ⁇ bondable ligands include halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and amide groups having 1 to 20 carbon atoms.
  • a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferred. Specific examples of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are the same as described above.
  • alkoxy group having 1 to 20 carbon atoms examples include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, phenylmethoxy group, phenylethoxy group and the like.
  • aryloxy group having 6 to 20 carbon atoms examples include phenoxy group, methylphenoxy group, and dimethylphenoxy group.
  • amide group having 1 to 20 carbon atoms include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, methylethylamide group, and other alkylamide groups, divinylamide group, and dipropenylamide group.
  • Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
  • Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group Examples thereof include substituted silyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl group and phenyldimethylsilylethyl group; silicon-substit
  • Examples of the phosphide group having 1 to 20 carbon atoms include alkyl phosphide groups such as dimethyl phosphide group, diethyl phosphide group, dipropyl phosphide group, dibutyl phosphide group, dihexyl phosphide group, dicyclohexyl phosphide group, and dioctyl phosphide group.
  • alkenyl phosphide group such as divinyl phosphide group, dipropenyl phosphide group, dicyclohexenyl phosphide group; arylalkyl phosphide such as dibenzyl phosphide group, phenylethyl phosphide group, phenylpropyl phosphide group Group: diphenylphosphide group, ditolylphosphide group, bis (dimethylphenyl) phosphide group, bis (trimethylphenyl) phosphide group, bis (ethylphenyl) phosphide group, bis (propylphenyl) phosphide group, bis (bif Yl) phosphide group, dinaphthyl sulfo Sufi de group, bis (methylnaphthyl) phosphide group, Jian tiger Se sulfonyl
  • Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group, vinyl sulfide group, and propenyl.
  • alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group, vinyl sulfide group, and propenyl.
  • Alkenyl sulfide groups such as sulfide groups and cyclohexenyl sulfide groups; arylalkyl sulfide groups such as benzyl sulfide groups, phenylethyl sulfide groups and phenylpropyl sulfide groups; phenyl sulfide groups, tolyl sulfide groups, dimethylphenyl sulfide groups, trimethylphenyl sulfide groups Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide De group, anthracenyl Nils sulfide group, an aryl sulfide groups such phenanthryl sulfide group.
  • arylalkyl sulfide groups such as benz
  • Examples of the sulfoxide group having 1 to 20 carbon atoms include methyl sulfoxide group, ethyl sulfoxide group, propyl sulfoxide group, butyl sulfoxide group, hexyl sulfoxide group, cyclohexyl sulfoxide group, octyl sulfoxide group and the like, vinyl sulfoxide group, propenyl Alkenyl sulfoxide groups such as sulfoxide group, cyclohexenyl sulfoxide group; arylalkyl sulfoxide groups such as benzyl sulfoxide group, phenylethyl sulfoxide group, phenylpropyl sulfoxide group; phenyl sulfoxide group, tolyl sulfoxide group, dimethylphenyl sulfoxide group, trimethylphenyl sulfoxide group , Ethylphenyl
  • acyl group having 1 to 20 carbon atoms examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, stearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.
  • the ⁇ -bonding ligand include compounds having a conjugated diene bond having 4 to 20 carbon atoms and compounds having a non-conjugated diene bond having 5 to 20 carbon atoms.
  • the compound having a conjugated diene bond having 4 to 20 carbon atoms include 1,3-butadiene, isoprene, chloroprene, 1,3-heptadiene, 1,3-hexadiene, 1,3,5-hexatriene, 1,3,5 Examples thereof include 6-heptatriene and diphenylbutadiene.
  • the compound having a non-conjugated diene bond having 5 to 20 carbon atoms include 1,4-pentadiene and 1,5-hexadiene.
  • Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different. Y may be cross-linked with other Y or X. In some cases, Y may be bridged with the cyclopentadienyl ring of the general formula (I). Examples of Y include amine, ether, phosphine, thioether and the like.
  • amines having 1 to 20 carbon atoms examples include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and dicyclohexylamine.
  • Alkylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine, etc .; arylalkylamines such as phenylethylamine, phenylpropylamine; phenylamine, diphenylamine, dinaphthylamine, etc. Of the arylamine.
  • ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl -Aliphatic mixed ether compounds such as n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl vinyl ether Aliphatic unsaturated ether compounds such as methyl allyl ether, ethyl vinyl ether and e
  • phosphine examples include phosphine having 1 to 20 carbon atoms.
  • monohydrocarbon substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkylphosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine,
  • Q is an integer of 1 to 5 and represents [(M valence) -2], and r is an integer of 0 to 3.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group.
  • the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
  • hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an octyl group.
  • alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an octyl group.
  • aryl groups such as phenyl and naphthyl groups
  • arylalkyl groups such as benzyl, phenylethyl and phenylpropyl
  • Examples of the substituent that the hydrocarbon group having 1 to 20 carbon atoms may have include a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the silicon-containing group include a silicon-containing group having 1 to 20 carbon atoms, and specific examples include a trimethylsilyl group, a trimethylsilylmethyl group, and a triphenylsilyl group.
  • Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups, and specifically include nitrogen-containing groups such as dimethylamino group, diethylamino group, and diphenylamino group, phenylsulfide group, and methylsulfide group.
  • Sulfur-containing groups such as: phosphorus-containing groups such as dimethylphosphino group and diphenylphosphino group; oxygen-containing groups such as methoxy group, ethoxy group and phenoxy group.
  • a group containing a heteroatom such as halogen, oxygen, or silicon is preferable because of high polymerization activity.
  • R 3 to R 10 are combinations in which all of R 3 to R 10 are hydrogen atoms, and R 4 , R 5 , R 8 and R 9 are substituted or unsubstituted linear or branched alkyl having 1 to 8 carbon atoms. Or a combination in which R 3 , R 6 , R 7 and R 10 are hydrogen atoms, or R 4 , R 5 , R 8 and R 9 are hydrogen atoms and R 3 , R 6 , R 7 And R 10 is a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms.
  • R 3 to R 10 may be R 4 , R 5 , R 8 and R 9 are substituted or unsubstituted linear alkyl groups having 1 to 8 carbon atoms. More preferred. R 4 and R 5 , and R 8 and R 9 may be bonded to each other to form a substituted or unsubstituted cyclic structure having 5 to 8 carbon atoms.
  • Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t- Examples include butyl group, t-pentyl group, hexyl group, cyclohexyl group, isooctyl group, t-octyl group, 2-ethylhexyl and the like.
  • Examples of the substituent that the linear or branched alkyl group having 1 to 8 carbon atoms may have include a methyl group, an ethyl group, and a butyl group.
  • R 4 , R 5 , R 8 and R 9 are each independently a substituted or unsubstituted straight chain having 1 to 8 carbon atoms from the viewpoint of increasing catalytic activity and decreasing regularity. Or, it is preferably a branched alkyl group, more preferably a substituted or unsubstituted linear alkyl group having 1 to 8 carbon atoms, and a substituted or unsubstituted linear alkyl group having 1 to 4 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. Moreover, it is preferable from a viewpoint of improving a catalyst activity that at least one of R ⁇ 4 >, R ⁇ 5 >, R ⁇ 8 > and R ⁇ 9 > is a methyl group.
  • R 4 and R 5 and / or R 8 and R 9 are preferably the same group from the viewpoint of uniformly controlling regularity.
  • the transition metal compound in which R 4 , R 5 , R 8 , and R 9 are methyl groups, and R 3 , R 6 , R 7 , and R 10 are hydrogen atoms is When used in combination with a cocatalyst, a propylene polymer having high catalytic activity and lower stereoregularity can be synthesized, which is preferable.
  • M represents a metal element of Group 3 to 10 of the periodic table or a lanthanoid series. Specific examples include titanium, zirconium, hafnium, vanadium, chromium, manganese, nickel, cobalt, palladium, and a lanthanoid metal. It is done. As M, a metal element belonging to Group 4 of the periodic table is preferable because of its high activity.
  • a 1 and A 2 each represent a bridging group composed of a carbon atom or a silicon atom, May be the same as or different from each other.
  • X represents a ⁇ bond or ⁇ bond ligand, and when there are a plurality of X, the plurality of X may be the same or different.
  • Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different.
  • Y may be cross-linked with other Y or X.
  • q is an integer of 1 to 5 and represents [(valence of M) -2]
  • r is an integer of 0 to 3.
  • R 1 and R 2 each represent a group containing a hetero atom such as halogen, oxygen, or silicon.
  • R 3 to R 10 are combinations in which all of R 3 to R 10 are hydrogen atoms, and R 4 , R 5 , R 8 and R 9 are substituted or unsubstituted linear or branched alkyl having 1 to 8 carbon atoms. Or a combination in which R 3 , R 6 , R 7 and R 10 are hydrogen atoms, or R 4 , R 5 , R 8 and R 9 are hydrogen atoms and R 3 , R 6 , R 7 And R 10 is a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms.
  • R 4 and R 5 , and R 8 and R 9 may be bonded to each other to form a substituted or unsubstituted cyclic structure having 5 to 8 carbon atoms.
  • M is a transition metal compound which is a metal element of Group 4 of the periodic table.
  • transition metal compound represented by the general formula (I) an example of Group 4 of the periodic table is shown as (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4 , 7-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethyl-4,7-dimethylindenyl) zirconium dichloride, (1,2 '-Dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilyl) Methyl-5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilyl) (2,1'-
  • Examples of the boron compound that can react with the aforementioned transition metal compound to form an ionic complex include coordination complex compounds composed of an anion and a cation in which a plurality of groups are bonded to boron.
  • a compound represented by the general formula (III) or (IV) can be preferably used.
  • L 2 is M 1 , R 13 R 14 M 2 or R 15 3 C described later, L 1 is a Lewis base, M 1 is Group 1 of the periodic table and 8 Metal selected from Group 12 to Group 12, M 2 is a metal selected from Group 8 to Group 10 of the Periodic Table, Z 1 to Z 4 are each a hydrogen atom, dialkylamino group, alkoxy group, aryloxy group, carbon number 1 Represents an alkyl group having ⁇ 20, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group, or a halogen atom.
  • R 13 and R 14 each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R 15 represents an alkyl group.
  • s is an integer of 1 to 7 in terms of the ionic valence of L 1 -H and L 2
  • t is an integer of 1 or more
  • l t ⁇ s ]
  • M 1 is a metal selected from groups 1 and 8 to 12 of the periodic table, specific examples are Ag, Cu, Na, Li and other atoms, and M 2 is selected from groups 8 to 10 of the periodic table Specific examples of metals that can be used include atoms such as Fe, Co, and Ni.
  • Z 1 to Z 4 include, for example, a dimethylamino group as a dialkylamino group, a diethylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group, a phenoxy group as an aryloxy group, 2, 6 -As a C1-C20 alkyl group such as dimethylphenoxy group and naphthyloxy group, carbon such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group and 2-ethylhexyl group A phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tertiary-butyl as an aryl group, alkylaryl group or arylalkyl group of formula 6-20
  • substituted cyclopentadienyl group represented by each of R 13 and R 14 include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.
  • anions in which a plurality of groups are bonded to boron include B (C 6 F 5 ) 4 ⁇ , B (C 6 HF 4 ) 4 ⁇ , and B (C 6 H 2 F 3 ). 4 ⁇ , B (C 6 H 3 F 2 ) 4 ⁇ , B (C 6 H 4 F) 4 ⁇ , B (C 6 CF 3 F 4 ) 4 ⁇ , B (C 6 H 5 ) 4 ⁇ , BF 4 -And the like.
  • the metal cation Cp 2 Fe +, (MeCp ) 2 Fe +, (tBuCp) 2 Fe +, (Me 2 Cp) 2 Fe +, (Me 3 Cp) 2 Fe +, (Me 4 Cp) 2 Fe + , (Me 5 Cp) 2 Fe + , Ag + , Na + , Li + and the like can be mentioned, and other cations include pyridinium, 2,4-dinitro-N, N-diethylanilinium, diphenylammonium.
  • Nitrogen-containing compounds such as p-nitroanilinium, 2,5-dichloroanilinium, p-nitro-N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, N, N-diethylanilinium,
  • triphenylcarbenium tri (4-methylphenyl) carbenium, tri (4-methoxyphenyl) carbenium Rubeniumu compound, CH 3 PH 3 +, C 2 H 5 PH 3 +, C 3 H 7 PH 3 +, (CH 3) 2 PH 2 +, (C 2 H 5) 2 PH 2 +, (C 3 H 7 ) 2 PH 2 +, (CH 3) 3 PH +, (C 2 H 5) 3 PH +, (C 3 H 7) 3 PH +, (CF 3) 3 PH +, (CH 3) 4 P +, Alkylphosphonium ions such as (C 2 H 5 ) 4 P + , (C 3 H 7 ) 4 P + , and C
  • Examples of the compound of the general formula (III) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, Examples include
  • examples of the compound of the general formula (IV) include, for example, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, decamethylferrous tetrakis (pentafluorophenyl) borate.
  • a preferred coordination complex compound is composed of a non-coordinating anion and a substituted triarylcarbenium, and the non-coordinating anion includes, for example, the general formula (V) (BZ 1 Z 2 Z 3 Z 4) - ⁇ (V) [Wherein Z 1 to Z 4 are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group) , An alkylaryl group, an arylalkyl group, a substituted alkyl group and an organic metalloid group or a halogen atom. ] The compound represented by these can be mentioned.
  • examples of the substituted triarylcarbenium include, for example, the general formula (VI) [CR 16 R 17 R 18 ] + ... (VI)
  • R 16 , R 17 and R 18 in the general formula (VI) are each an aryl group such as a phenyl group, a substituted phenyl group, a naphthyl group and an anthracenyl group, and they may be the same or different from each other. However, at least one of them is a substituted phenyl group, a naphthyl group or an anthracenyl group.
  • the substituted phenyl group is, for example, represented by the general formula (VII) C 6 H 5-k R 19 k (VII) It can be expressed as R 19 in the general formula (VII) represents a hydrocarbyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an amino group, an amide group, a carboxyl group, and a halogen atom, and k is It is an integer from 1 to 5. When k is 2 or more, the plurality of R 19 may be the same or different.
  • non-coordinating anion represented by the general formula (V) include tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, Tetrakis (pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate And tridecahydride-7,8-dicarboundeborate.
  • substituted triarylcarbenium represented by the general formula (VI) include tri (toluyl) carbenium, tri (methoxyphenyl) carbenium, tri (chlorophenyl) carbenium, tri (fluorophenyl) carbenium, tri ( Xylyl) carbenium, [di (toluyl), phenyl] carbenium, [di (methoxyphenyl), phenyl] carbenium, [di (chlorophenyl), phenyl] carbenium, [toluyl, di (phenyl)] carbenium, [methoxyphenyl, di (Phenyl)] carbenium, [chlorophenyl, di (phenyl)] carbenium and the like.
  • the use ratio (molar ratio) of the component (A) / component (B) is preferably 1/100 to 1/1, more preferably 1/10 to 1/1.
  • the method for preparing the polymerization catalyst is not particularly limited, and a conventionally known method can be used.
  • the component (A) and the component (B) may be added to the polymerization solvent at the same time and mixed, or after the component (A) is added to the polymerization solvent, the component (B) is added and mixed. May be.
  • the polymerization catalyst may be prepared by adding each component in a polymerization reaction vessel, or preparing a catalyst solution by mixing each component in another vessel in advance, and polymerizing the obtained catalyst solution. A polymerization reaction may be performed in addition to the reaction vessel.
  • the polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, decalin, and tetralin, pentane, hexane, and heptane. And aliphatic hydrocarbons such as octane, halogenated hydrocarbons such as chloroform and dichloromethane, etc., and toluene, xylene and decalin are preferred. These solvents may be used alone or in combination of two or more.
  • the method for polymerizing propylene is not particularly limited, and any polymerization method such as a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, or a suspension polymerization method can be employed.
  • the polymerization temperature is usually ⁇ 100 to 250 ° C., preferably ⁇ 50 to 200 ° C., more preferably 0 to 130 ° C.
  • the polymerization pressure is preferably from normal pressure to 20 MPa (gauge), more preferably from normal pressure to 10 MPa (gauge).
  • the polymerization time is preferably 5 minutes to 15 hours.
  • examples of the method for adjusting the molecular weight of the propylene polymer include selection of the type of each component, the amount used and the polymerization temperature, and further polymerization in the presence of hydrogen.
  • the concentration of the component (A) is preferably 0.001 to 500 ⁇ mol / L. Good activity is obtained by being in this range. From this viewpoint, the concentration of the component (A) is more preferably 0.005 to 250 ⁇ mol / L, and further preferably 0.01 to 100 ⁇ mol / L.
  • concentration of (A) component here means the density
  • prepolymerization using the above-mentioned polymerization catalyst or in the process of preparing the catalyst.
  • This prepolymerization can be carried out by bringing a small amount of olefin into contact with the catalyst or the catalyst being prepared, but the method is not particularly limited, and a known method can be used.
  • the olefin used for the prepolymerization is not particularly limited, and examples thereof include ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, or a mixture thereof.
  • the reaction temperature for the prepolymerization is preferably ⁇ 20 to 100 ° C., more preferably ⁇ 10 to 70 ° C., and further preferably 0 to 50 ° C.
  • a solvent selected from the polymerization solvents is preferably used, and an aliphatic hydrocarbon or an aromatic hydrocarbon is more preferable.
  • This prepolymerization can also be carried out without a solvent.
  • the amount of the prepolymerized product per millimole of the transition metal component in the catalyst is preferably 1 to 10000 g, and more preferably the conditions are adjusted to 10 to 1000 g.
  • the elastic body of the present invention is composed of the above-mentioned propylene-based polymer, it has an excellent elastic recovery rate and is suitably used for applications such as molded articles such as films, sheets, fibers, and nonwoven fabrics, and hot melt adhesives. .
  • the melting endotherm ( ⁇ HD) is a differential scanning calorimeter (manufactured by Perkin Elmer Co., Ltd.) with a line connecting the point on the low temperature side where there is no change in calorie and the point on the high temperature side where there is no change in calorie as the baseline. , “DSC-7”), and calculating the area surrounded by the line portion including the peak of the melting endothermic curve obtained by DSC measurement and the base line.
  • the melting endotherm ( ⁇ HD) at 20 to 65 ° C. is 20 ° C. and 65 ° C. obtained by DSC measurement. It is calculated by determining the area surrounded by the line portion including the peak of the melting endothermic curve between ° C and the baseline between 20 ° C and 65 ° C.
  • ⁇ GPC measurement device Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation Detector: RI detection for liquid chromatogram "WATERS 150C” manufactured by Waters Corporation ⁇ Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL Injection volume: 160 ⁇ l Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver.1.0)
  • 1,3-bond fraction (D / 2) / (A + B + C + D) ⁇ 100 (mol%)
  • 2,1-bond fraction [(A + B) / 2] / (A + B + C + D) ⁇ 100 (mol%)
  • the ash content is measured according to ISO3451-1 (1997). That is, 200 g of the sample was heated at 600 ° C. for 1 hour in a muffle furnace and then weighed.
  • a mixed solution of 48.50 g (278 mmol) of 1,2,3,5-tetrahydro-s-indacene, 11.6 mL of water and 275 mL of DMSO was prepared in a 1 L three-necked flask.
  • the mixed solution was cooled in an ice bath, and 49.5 g (278 mmol) of N-bromosuccinimide was slowly added so that the temperature of the reaction system was 15 ° C. or lower.
  • the obtained dark brown solution was returned to room temperature (25 ° C.) and stirred for 10 hours.
  • the mixture was cooled again to 0 ° C. and quenched with 750 mL of water.
  • a dropping funnel and a Dimroth condenser were installed in a 300 mL three-necked flask, and 9.3 g (384 mmol) of magnesium pieces were suspended in 100 mL of tetrahydrofuran (THF) on the flask side.
  • THF tetrahydrofuran
  • a small amount of 1,2-dibromoethane (0.1 mL) was added to a magnesium suspension in THF, stirred for 15 minutes, and then 35.60 g (151.6- (6) -bromo-1,2,3,5-tetrahydro-s-indacene). 4 mmol) in THF (150 mL) was added dropwise from a dropping funnel.
  • Dimethylbis (1,5,6,7-tetrahydro-s-indasen-2-yl) silane (27.35 g, 74.20 mmol) is dissolved in 300 mL of diethyl ether, and n-butyllithium (2. 65M, 67.3 mL, 178.4 mmol) was added dropwise. After completion of dropping, the mixture was stirred overnight at room temperature (25 ° C.). The supernatant was removed and the residue was washed with 100 mL of hexane. The resulting white powder was dried under reduced pressure.
  • This lithium salt was dissolved in 200 mL of THF, cooled using an ice bath, and 7.40 mL (61.9 mmol) of dichlorodimethylsilane was added dropwise. After the reaction mixture was stirred for 2 hours at room temperature (25 ° C.), a Dimroth condenser was attached to the reaction vessel, and the reaction mixture was stirred at 50 ° C. for 4 hours. The reaction mixture was cooled to room temperature (25 ° C.) and filtered.
  • dilithium salt (6.50 g, yield 83%).
  • Dilithium salt (6.50 g, 8.58 mmol) was suspended in 100 mL of hexane and cooled in a dry ice / ethanol bath.
  • Zirconium tetrachloride (2.00 g, 8.58 mmol) was suspended in hexane (50 mL) and added dropwise to the cooled hexane suspension of the ligand dilithium salt using a cannula. After completion of the dropwise addition, the temperature was gradually returned to room temperature (25 ° C.) and stirred overnight at room temperature (25 ° C.).
  • reaction mixture was cooled and then poured into 1000 g of ice water.
  • the reaction mixture was extracted with 500 mL of toluene, washed with saturated aqueous sodium hydrogen carbonate solution, water and brine, and then dried over anhydrous magnesium sulfate. It was then filtered and the solvent was removed under reduced pressure.
  • the obtained crude product was dissolved in 2500 mL of hexane, filtered, and crystallized at 4 ° C. to obtain 14.2 g of 5,6-dimethyl-1-indanone (yield 19%). This operation was repeated three times to obtain 51.3 g of 5,6-dimethyl-1-indanone.
  • Synthesis was performed in the same manner as in Production Example 2 except that zirconium tetraiodide was used instead of zirconium tetrachloride in (2-5) of Production Example 2, and (1,2′-dimethylsilylene) (2,1 '-Dimethylsilylene) bis (3-trimethylsilylmethyl-5,6-dimethylindenyl) zirconium diiodide was obtained as a yellow solid (yield 40%).
  • the white precipitate was filtered off, then the mother liquor was evaporated and 31.5 g of lithium salt was isolated by washing with hexane.
  • the lithium salt was dissolved in 200 mL of THF, and methyltrimethylsilane iodide (16.0 mL, 108 mmol) was added dropwise at 0 ° C. After completion of the addition, the mixture was stirred for 1 hour after raising to 25 ° C. Then, 30 mL of water was added.
  • This lithium salt was suspended in 60 mL of hexane, and 5.9 g (25.0 mmol) of zirconium tetrachloride suspended in 20 mL of hexane was added at ⁇ 20 ° C. After raising to 25 ° C. and stirring overnight, the produced yellow solid was filtered off and washed with 100 mL of hexane. The obtained solid was recrystallized from 100 mL of dichloromethane to give (1,2'-methylphenylsilylene) (2,1'-methylphenylsilylene) bis (3- 7.35 g of trimethylsilylmethylindenyl) zirconium dichloride was obtained (yield 37%).
  • Example 1 To a heat-dried 1 liter autoclave, 400 mL of heptane and 0.4 mmol of triisobutylaluminum were added at room temperature in a nitrogen atmosphere and stirred, and then (1,2'-dimethylsilylene) (2,1'-dimethyl) was used as a catalyst species.
  • Example 2 In Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethyl-5,6-dimethylindenyl) zirconium diiodide [1] is used as a catalyst species. 110 g of a propylene polymer was obtained in the same manner as in Example 1 except that the transition metal compound a3] was changed.
  • Example 3 In Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethyl-5,6-dimethylindenyl) zirconium dichloride [transition] is used as a catalyst species. 128 g of a propylene polymer was obtained in the same manner as in Example 1 except that the metal compound a2] was changed.
  • Example 4 Into a stainless steel reactor with an internal volume of 20 L equipped with a stirrer, n-heptane was 20 L / hr, triisobutylaluminum was 15 mmol / hr, dimethylanilinium tetrakis (pentafluorophenyl) borate, (1,2'-dimethyl) A catalyst component obtained by pre-contacting silylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride and triisobutylaluminum in a mass ratio of 1: 2: 20 in advance with propylene, It was continuously supplied at 6 ⁇ mol / hr in terms of zirconium.
  • a polymerization solution having a desired molecular weight maintaining the total pressure in the reactor at 1.0 MPa ⁇ G, continuously supplying hydrogen and propylene so that the hydrogen / propylene ratio is 0.05, setting the polymerization temperature to 72 ° C. Got.
  • an antioxidant was added so that the content thereof was 1000 ppm by mass, and then n-heptane as a solvent was removed to obtain a propylene polymer.
  • Example 5 In Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-5,6-dimethylindenyl) zirconium dichloride [transition metal] is used as the catalyst species. 74g of a propylene polymer was obtained in the same manner as in Example 1 except that the polymerization temperature was changed to 70 ° C.
  • Example 6 In Example 1, 145 g of a propylene polymer was obtained in the same manner as in Example 1 except that the polymerization temperature was set to 70 ° C.
  • Example 7 In Example 3, 115 g of a propylene polymer was obtained in the same manner as in Example 3 except that the polymerization temperature was set to 70 ° C.
  • Example 8 In Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-cyclopentylmethyl-5,6-dimethylindenyl) zirconium dichloride [transition] is used as a catalyst species. 121 g of a propylene polymer was obtained in the same manner as in Example 1 except that the polymerization temperature was changed to 70 ° C. and the polymerization time was 30 minutes.
  • Example 9 In Example 1, 0.5 ⁇ m of (1,2′-methylphenylsilylene) (2,1′-methylphenylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride [transition metal compound a7] was used as a catalyst species. 154 g of a propylene polymer was obtained in the same manner as in Example 1, except that 2 micromole of dimethylanilinium tetrakis (pentafluorophenyl) borate was used as a promoter, the reaction temperature was 69 ° C., and the reaction time was 13 minutes. It was.
  • Example 10 (Example 10) In Example 3, 76 g of a propylene polymer was obtained in the same manner as in Example 3 except that the reaction temperature was 80 ° C.
  • Example 11 In Example 5, 81 g of a propylene polymer was obtained in the same manner as in Example 5 except that the polymerization temperature was 80 ° C.
  • Example 12 In Example 9, 197 g of a propylene polymer was obtained in the same manner as in Example 9 except that the polymerization temperature was 72 ° C. and the polymerization time was 15 minutes.
  • Example 13 111 g of a propylene polymer was obtained in the same manner as in Example 8 except that the polymerization temperature was 80 ° C.
  • Example 14 In Example 9, the transition metal compound a7 was converted to (1,2′-dimethylsilylene) (2,1′-diphenylsilylene) bis (3-n-butylindenyl) zirconium dichloride [transition metal compound a8] as a catalyst species. 157 g of a propylene polymer was obtained in the same manner as in Example 9, except that the polymerization temperature was 67 ° C. and the polymerization time was 25 minutes.
  • Propylene and hydrogen were continuously supplied at a polymerization temperature of 65 ° C. so that the gas phase hydrogen concentration was 8 mol% and the total pressure in the reactor was maintained at 1.0 MPa ⁇ G.
  • n-heptane which is a solvent of the obtained polymerization solution, a propylene polymer was obtained.
  • Propylene and hydrogen were continuously supplied at a polymerization temperature of 75 ° C. so that the gas phase hydrogen concentration was 1 mol% and the total pressure in the reactor was kept at 1.0 MPa ⁇ G.
  • n-heptane which is a solvent of the obtained polymerization solution, a propylene polymer was obtained.
  • Propylene and hydrogen were continuously supplied at a polymerization temperature of 70 ° C. so that the gas phase hydrogen concentration was 15 mol% and the total pressure in the reactor was maintained at 1.0 MPa ⁇ G.
  • n-heptane as a solvent of the obtained polymerization solution, a propylene-based polymer was obtained.
  • Propylene and hydrogen were continuously supplied at a polymerization temperature of 85 ° C. so that the gas phase hydrogen concentration was 15 mol% and the total pressure in the reactor was kept at 1.0 MPa ⁇ G.
  • n-heptane as a solvent of the obtained polymerization solution, a propylene-based polymer was obtained.
  • Example 5 (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-cyclohexylmethyl-5,6-dimethylindenyl) zirconium dichloride [transition metal compound a10] was used as a catalyst species. 1 micromole, 4 micromole of dimethylanilinium tetrakis (pentafluorophenyl) borate as cocatalyst, total pressure 0.68 MPa, hydrogen partial pressure 0.03 MPa, polymerization temperature 83 ° C., polymerization time 90 minutes Except that, 114 g of a propylene polymer was obtained in the same manner as in Example 1.
  • Example 9 (Comparative Example 6) In Example 9, 186 g of a propylene polymer was obtained in the same manner as in Example 9 except that the polymerization temperature was 80 ° C. and the polymerization time was 15 minutes.
  • Comparative Example 7 In Comparative Example 6, 0.5 ⁇ m of (1,2′-methylphenylsilylene) (2,1′-methylphenylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride [transition metal compound a11] was used as a catalyst species. 65 g of a propylene polymer was obtained in the same manner as in Comparative Example 6 except that 500 ⁇ mol of methylaluminoxane and 0.2 mmol of triisobutylaluminum were used as promoters and the polymerization time was 30 minutes.
  • Example 8 In Example 1, the transition metal compound a1 was changed to (1,2′-diphenylsilylene) (2,1′-diphenylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride [transition metal compound a12] as the catalyst species. Then, 128 g of a propylene polymer was obtained in the same manner as in Example 1 except that the total pressure was 0.85 MPa, the polymerization temperature was 40 ° C., and the polymerization time was 19 minutes.
  • the tensile elastic modulus was in the range of 5 to 65 MPa, and the elastic recovery rate was as high as 80% or more. It was.
  • the propylene-based polymer of the present invention becomes an elastic body having an excellent elastic recovery rate, it is suitably used as a raw material for molded articles such as films, sheets, fibers, and nonwoven fabrics, and hot melt adhesives.

Abstract

L'invention concerne un polymère à base de propylène qui satisfait à (1)-(4) ci-dessous : (1) la viscosité intrinsèque [η] mesurée à 135 °C dans un solvant de type tétraline est de 0,3-5,0 dl/g ; (2) l'endotherme de fusion (ΔH-D), qui est obtenu à partir d'une courbe endothermique de fusion acquise à l'aide d'un calorimètre différentiel à balayage (DSC) suite au maintien d'un échantillon à -10 °C pendant 5 minutes dans une atmosphère d'azote puis à l'augmentation de la température de 10 °C/min, est de 3 à 30 J/g ; (3) au moins un point de fusion (Tm-D), dont le sommet de pic est défini comme étant le point maximal de la courbe endothermique de fusion acquise à l'aide du DSC suite au maintien de l'échantillon à -10 °C pendant 5 minutes dans l'atmosphère d'azote puis à l'augmentation de la température de 10 °C/min, est présent dans la plage de 20-65 °C ; et (4) l'endotherme de fusion (ΔH-D) dans la plage de 20 à 65 °C dans la courbe endothermique de fusion acquise à l'aide du DSC suite au maintien de l'échantillon à -10 °C pendant 5 minutes dans l'atmosphère d'azote, puis à l'augmentation de la température de 10 °C/minute, représente au moins 30 % de l'endotherme de fusion (ΔH-D) dans (2).
PCT/JP2018/008686 2017-03-07 2018-03-07 Polymère à base de propylène et corps élastique WO2018164161A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021048030A1 (fr) 2019-09-10 2021-03-18 Sabic Global Technologies B.V. Composés destinés à être utilisés dans des compositions de catalyseur permettant la production de polyoléfines
WO2022024687A1 (fr) * 2020-07-31 2022-02-03 出光興産株式会社 Plastifiant pour résine

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000344833A (ja) * 1999-03-31 2000-12-12 Idemitsu Petrochem Co Ltd プロピレン系樹脂組成物、その製造方法及び成形体
JP2001226498A (ja) * 2000-02-16 2001-08-21 Idemitsu Petrochem Co Ltd ポリプロピレン系フィルム
JP2002327016A (ja) * 1991-07-26 2002-11-15 Idemitsu Kosan Co Ltd オレフィン系共重合体
WO2010018789A1 (fr) * 2008-08-12 2010-02-18 出光興産株式会社 Procédé de fabrication d’une fibre élastique en polypropylène et fibre élastique en polypropylène
JP2010265473A (ja) * 1999-03-24 2010-11-25 Idemitsu Kosan Co Ltd プロピレン系共重合体、及び該共重合体からなる樹脂組成物並びに成形体
WO2016047699A1 (fr) * 2014-09-25 2016-03-31 出光興産株式会社 Polymère à base d'oléfine, et procédé de fabrication de celui-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002327016A (ja) * 1991-07-26 2002-11-15 Idemitsu Kosan Co Ltd オレフィン系共重合体
JP2010265473A (ja) * 1999-03-24 2010-11-25 Idemitsu Kosan Co Ltd プロピレン系共重合体、及び該共重合体からなる樹脂組成物並びに成形体
JP2000344833A (ja) * 1999-03-31 2000-12-12 Idemitsu Petrochem Co Ltd プロピレン系樹脂組成物、その製造方法及び成形体
JP2001226498A (ja) * 2000-02-16 2001-08-21 Idemitsu Petrochem Co Ltd ポリプロピレン系フィルム
WO2010018789A1 (fr) * 2008-08-12 2010-02-18 出光興産株式会社 Procédé de fabrication d’une fibre élastique en polypropylène et fibre élastique en polypropylène
WO2016047699A1 (fr) * 2014-09-25 2016-03-31 出光興産株式会社 Polymère à base d'oléfine, et procédé de fabrication de celui-ci

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021048030A1 (fr) 2019-09-10 2021-03-18 Sabic Global Technologies B.V. Composés destinés à être utilisés dans des compositions de catalyseur permettant la production de polyoléfines
WO2022024687A1 (fr) * 2020-07-31 2022-02-03 出光興産株式会社 Plastifiant pour résine
DE112021003081T5 (de) 2020-07-31 2023-03-23 Idemitsu Kosan Co., Ltd. Weichmacher für Harze

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