JP5074013B2 - Block copolymer or thermoplastic resin composition containing the copolymer and method for producing them - Google Patents

Description

  The present invention relates to a combination of a terminal unsaturated polyolefin and a terminal saturated polyolefin by reacting a metallized polyolefin obtained by metallizing the terminal unsaturated polyolefin with an anionic polymerizable monomer, and then reacting the terminal unsaturated polyolefin with an anion. Production method of block copolymer forming polymerizable monomer chain or thermoplastic resin composition containing the copolymer, copolymer obtained by the production method, or thermoplastic resin containing the copolymer Relates to the composition.

Conventionally, an olefin polymer obtained by graft-modifying a polyolefin such as polyethylene or polypropylene with an unsaturated carboxylic acid or an acid anhydride thereof has been used as a modifier for various resins, an adhesiveness imparting agent, or the like.
These modifiers are expected to further improve performances such as adhesion and compatibility by improving the graft modification amount and enhancing the controllability of the graft structure.
On the other hand, low-order polyolefin obtained using a metallocene-based catalyst is low-ordered, so it is excellent in flexibility and miscibility with olefin-based resins. Applications are expected to be combined with other resins.

It has been generally carried out in the field of organometallic synthesis that hydrocarbons are metallized in the presence of alkyllithium alone or in the presence of ethers or amines and used for reactions with various nucleophilic reagents.
There are examples in which this technique is applied to polymer modification and graft polymerization.
In order to form a reaction site to be metallized, a method is known in which α-olefin and 1-alkenyl monomer are copolymerized and 1-alkenyl monomer residue is metallized to produce a graft copolymer (for example, ) (See Patent Document 1), which involves a copolymerization process.
In addition, a method for introducing an ethylenically unsaturated functional group into the first benzyl carbon atom in an alkylstyrene polymer is known (for example, see Patent Document 2), and after metallization with an alkali metal alkoxide and an alkyllithium compound, Alkenylsilane can be added to introduce a functional group, but the production process is complicated because a graft reaction point is ensured by copolymerization.
Furthermore, in the graft polymerization reaction of ethylene-propylene-diene terpolymer (EPDM), a method of graft-polymerizing an anionic polymerizable monomer by lithiating an allyl moiety of a carbon-carbon unsaturated bond present in the main chain of EPDM Is known (see, for example, Patent Documents 3 to 5).
As described above, in the prior art, as a site to be metallized, a carbon-silicon bond site of a polymer side chain, a carbon-carbon unsaturated bond site of a copolymerization monomer, a methyl group of a paramethylstyrene residue, etc. The main chain is a carbon-carbon unsaturated bond site derived from diolephin.
Therefore, there is no known method for metallizing terminal unsaturated groups to produce block copolymers.

Japanese National Patent Publication No. 10-512916 JP-T-2001-506111 U.S. Pat. No. 4,761,546 U.S. Pat. No. 4,786,689 U.S. Pat. No. 4,794,145

  The present invention has been made in view of the above circumstances, and is a polyolefin-based block copolymer useful as a polyolefin modifier, a dispersibility improver between different materials, a compatibilizing agent, or the like, or a thermoplastic resin containing the copolymer It is an object to provide compositions and methods for producing them effectively.

As a result of intensive studies, the present inventors have found that a combination of a terminal unsaturated polyolefin and a terminal saturated polyolefin includes a metallized polyolefin obtained by metallizing the terminal unsaturated polyolefin and an anionic polymerizable monomer. It has been found that the object can be achieved by reacting and forming an anionically polymerizable monomer chain in the terminal unsaturated polyolefin.
The present invention has been completed based on such findings.
That is, the present invention
1. In a combination of 20 to 100% by weight of terminal unsaturated polyolefin and 0 to 80% by weight of terminal saturated polyolefin, a metallized polyolefin obtained by metallizing terminal unsaturated polyolefin and at least one anionic polymerizable monomer A method of producing a block copolymer or a thermoplastic resin composition containing the copolymer, characterized by reacting and forming an anionically polymerizable monomer chain in the terminal unsaturated polyolefin
2. The method for producing a block copolymer according to the above 1, wherein the terminal unsaturated polyolefin satisfies the following (1) to (4) or a thermoplastic resin composition containing the copolymer (1) having 2 to 2 carbon atoms A homopolymer selected from 28 α-olefins or a copolymer of two or more (2) having 0.5 to 1.0 terminal unsaturated groups per molecule;
(3) Molecular weight distribution (Mw / Mn) is 4 or less (4) Intrinsic viscosity [η] measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g
3. The block copolymer according to 1 or 2 above, wherein the anionic polymerizable monomer is selected from an acrylic acid derivative, a methacrylic acid derivative, a styrene derivative, and a diene derivative, or production of a thermoplastic resin composition containing the copolymer Method,
4). The block copolymer according to any one of the above 1 to 3, wherein the terminal unsaturated group is a vinylidene group, or a method for producing a thermoplastic resin composition containing the copolymer,
5. The terminal unsaturated polyolefin is a propylene homopolymer, or a propylene-based copolymer of 90% by mass or more of propylene and one or more types selected from ethylene and α-olefin having 4 to 28 carbon atoms. The block copolymer according to any one of the above 1 to 4 that satisfies (a) to (c), or a method for producing a thermoplastic resin composition containing the copolymer,
(A) Mesopentad fraction [mmmm] of 30 to 80 mol%
(B) Racemic meso racemic meso fraction [rmrm]> 2.5 mol%
(C) The melting point (Tm, unit: ° C.) observed with a differential scanning calorimeter (DSC) and the mesopentad fraction [mmmm] satisfy the following relationship.
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0
6). The terminal unsaturated polyolefin is a butene homopolymer, or a butene copolymer of 90% by mass or more of 1-butene and one or more selected from ethylene, propylene and olefin having 5 to 28 carbon atoms, The block copolymer according to any one of the above 1 to 4, wherein the mesopentad fraction [mmmm] is in the range of 20 to 90 mol%, or a method for producing a thermoplastic resin composition containing the copolymer,
7). A propylene homopolymer, or a propylene-based copolymer of 90% by mass or more of propylene and one or more and 10% by weight or less selected from ethylene and α-olefin having 4 to 28 carbon atoms, and the following (a) and The following propylene polymerization site satisfying (b) is block-bonded to a chain comprising at least one selected from an acrylic acid derivative, a methacrylic acid derivative, a styrene derivative and a diene derivative as an anion polymerizable monomer. A block copolymer satisfying (7).
(A) Mesopentad fraction [mmmm] of 30 to 80 mol%
(B) Racemic meso racemic meso fraction [rmrm]> 2.5 mol%
(5) Block ratio is 2 to 100% by mass
(6) Weight average molecular weight is 2,000 to 500,000
(7) Molecular weight distribution (Mw / Mn) is 1.5-4
8). A butene homopolymer or a butene copolymer of 90% by mass or more of 1-butene and one or more but 10% by mass or less selected from ethylene, propylene, and olefin having 5 to 28 carbon atoms, and a mesopentad fraction [mmmm The butene polymerization site in the range of 20 to 90 mol% is block-bonded to a chain comprising at least one selected from an acrylic acid derivative, a methacrylic acid derivative, a styrene derivative and a diene derivative as an anion polymerizable monomer, A block copolymer satisfying the following (5) to (7).
(5) Block ratio is 2 to 100% by mass
(6) Weight average molecular weight is 2,000 to 500,000
(7) Molecular weight distribution (Mw / Mn) is 1.5-4
9. The block copolymer obtained by the manufacturing method in any one of said 1-6, or the thermoplastic resin composition containing this copolymer is provided.

According to the present invention, by using a terminal unsaturated polyolefin, a block copolymer that does not contain an irregular structure such as a crosslinked structure and that forms an anionic polymerizable monomer chain on the terminal unsaturated polyolefin, or the copolymer Can be produced at low temperature.
Therefore, the copolymer or the thermoplastic resin composition containing the copolymer does not include an irregular structure such as a crosslinked structure, and includes a wide range of anionic polymerizable monomer (for example, polar monomer species) components. Because the monomer content is high, adhesiveness and compatibility are expressed with a small amount of use, and there is a polyolefin chain and an anionically polymerizable monomer chain (for example, a polar monomer chain) in one molecule. Excellent dispersion effect and compatibilization effect between different materials.

The terminal unsaturated polyolefin used in the present invention is one kind of homopolymer or two or more kinds of copolymers selected from α-olefin having 2 to 28 carbon atoms.
Examples of the α-olefin having 2 to 28 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene, 1-decene, 1-undecene and 1-dodecene. 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icocene and the like.
As the terminal unsaturated polyolefin, in detail, one kind of homopolymer or two or more kinds of copolymers selected from ethylene, propylene, 1-butene and α-olefin having 5 to 28 carbon atoms, ethylene 90 to 100 mass. % Ethylene-containing polymer, α-olefin containing 90 to 100% by mass of α-olefin selected from α-olefin having 5 to 28 carbon atoms, propylene homopolymer, or 90% by mass or more of propylene Propylene-based copolymer, butene homopolymer of 1 to 10% by mass selected from ethylene and α-olefin having 4 to 28 carbon atoms, or 90% by mass of 1-butene and ethylene, propylene and 5 to 5 carbon atoms And a butene-based copolymer of at least one selected from 28 olefins and not more than 10% by mass.
The propylene-based copolymer is preferably a propylene-based copolymer of 95% by mass or more of propylene and one or more selected from ethylene and α-olefin having 4 to 28 carbon atoms.
The butene copolymer is preferably a butene copolymer of 95% by mass or more of 1-butene and one or more selected from ethylene, propylene and α-olefin having 5 to 28 carbon atoms. It is.

The terminal unsaturated polyolefin has 0.5 to 1.0 terminal unsaturated groups per molecule, preferably 0.6 to 1.0, more preferably 0.65 to 1.0, and still more preferably. Has 0.7 to 1.0.
When the number of terminal unsaturated groups is 0.5 or more, the concentration of unsaturated groups is high, and the production efficiency of the block copolymer is increased.
The terminal unsaturated group is preferably a vinylidene group, and the vinylidene group occupying the terminal unsaturated group is usually 0.5 to 1.0, preferably 0.6 to 1.0, more preferably 0.7. It is -1.0 piece, More preferably, it is 0.8-1.0 piece.

In general, the terminal unsaturated group is measured by an infrared absorption spectrum method, a nuclear magnetic resonance spectrum method, a bromination method, or the like, and can be measured by any method.
The infrared absorption spectrum method can be performed in accordance with the method described in “New Edition Polymer Analysis Handbook”, Japan Analytical Chemistry Society, Polymer Analysis Research Roundtable.
According to it, the terminal unsaturated group by infrared absorption spectrum method, a vinyl group, a vinylidene group, trans (vinylene) unsaturated groups such as the groups, 910 cm ^-1, respectively the infrared absorption spectrum, 888cm ^-1, 963cm ^- It can be quantified from the absorption of ¹ .
The quantitative determination of vinylidene unsaturated groups by nuclear magnetic resonance spectroscopy is performed as follows.
The number of vinylidene groups as terminal unsaturated groups is determined by ¹ H-NMR measurement according to a conventional method.
Based on the vinylidene group appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, the content (C) (mol%) of the vinylidene group is calculated by a conventional method.
Furthermore, the number of vinylidene groups per molecule is calculated from the number average molecular weight (Mn) and monomer molecular weight (M) determined by gel permeation chromatography (GPC) according to the following formula.
Terminal vinylidene groups per molecule (pieces) = (Mn / M) × (C / 100)

The terminal unsaturated polyolefin has a molecular weight distribution (Mw / Mn) of 4 or less, preferably 3.5 or less, more preferably 3 or less, and still more preferably 2.5 or less.
The molecular weight distribution is preferably as narrow as possible. This is because the terminal unsaturated polyolefin forms a chain in the block copolymer of the present invention or the thermoplastic resin composition containing the copolymer. This is because a block copolymer having a controlled structure is formed.

The molecular weight distribution (Mw / Mn) can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC) method under the following apparatus and conditions.
GPC measuring device Detector: RI detector for liquid chromatography Waters 150C
Column: TOSO GMHHR-H (S) HT
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 0.3% by mass
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by the Universal Calibration method using the constants K and a in the Mark-Houwink-Sakurada formula in order to convert the polystyrene equivalent molecular weight into the molecular weight of the corresponding polymer.
Specifically, it was determined by the method described in “Size Exclusion Chromatography, Sadao Mori, P67-69, 1992, Kyoritsu Shuppan”.
K and α are described in “Polymer Handbook, John Wiley & Sons, Inc.”.
Moreover, it can determine by a usual method from the relationship of the intrinsic viscosity with respect to the newly calculated absolute molecular weight.

The terminal unsaturated polyolefin has an intrinsic viscosity [η] measured at 135 ° C. in decalin of about 0.01 to 2.5 dl / g, preferably 0.05 to 2.5, more preferably 0.05 to 2. 0.0, more preferably 0.1 to 2.0, and most preferably 0.15 to 1.8 dl / g.
When the intrinsic viscosity [η] is within the above range, the polyolefin chain length of the block copolymer is sufficient and functions such as compatibilization are sufficiently exerted, and the concentration of terminal unsaturated groups is high during block polymerization. Therefore, block copolymerizability increases.

The intrinsic viscosity [η] is calculated using the following general formula (Huggins formula) after measuring the reduced viscosity (ηSP / c) with a Ubbelohde viscometer in decalin at 135 ° C.
ηSP / c = [η] + K [η] ² c
ηSP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer concentration K = 0.35 (Haggins constant)

The terminal unsaturated polyolefin is a propylene homopolymer or a propylene copolymer of 90% by mass or more of propylene and one or more selected from ethylene and α-olefin having 4 to 28 carbon atoms (hereinafter referred to as propylene-based copolymer). In the case of a polymer), the following (a) to (c) are preferably satisfied.
(A) Mesopentad fraction [mmmm] of 30 to 80 mol%
(B) Racemic meso racemic meso fraction [rmrm]> 2.5 mol%
(C) The melting point (Tm, unit: ° C.) observed with a differential scanning calorimeter (DSC) and the mesopentad fraction [mmmm] satisfy the following relationship.
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0

The mesopentad fraction [mmmm] is preferably 30 to 75 mol%, more preferably 32 to 70 mol%.
When the mesopentad fraction is 30 mol% or more, since the propylene polymer becomes crystalline, heat resistance is exhibited, and when it is 80 mol% or less, the propylene polymer becomes moderately soft, The solubility in a solvent becomes good, and it can be widely applied to solution reactions and the like.

The above-mentioned mesopentad fraction [mmmm], racemic pentad fraction [rrrr] and racemic mesoracemimeso fraction [rmrm], which will be described later, are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli and others. The meso fraction, the racemic fraction and the racemic meso-racemic meso fraction in the pentad unit in the polypropylene molecular chain measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the method proposed in (1).
As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The ¹³ C-NMR spectrum can be measured according to the following apparatus and conditions in accordance with the attribution of peaks proposed by “Macromolecules, 8, 687 (1975)” by A. Zambelli and the like. it can.
Further, the mesotriad fraction [mm], the racemic triad fraction [rr] and the mesoracemi fraction [mr] described later were also calculated by the above method.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<Calculation formula>
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

When the racemic meso racemic meso fraction [rmrm] of the propylene polymer exceeds 2.5 mol%, randomness increases and transparency is further improved.
Further, the above relational expression between the melting point (Tm, unit: ° C.) observed by a differential scanning calorimeter (DSC) and the mesopentad fraction [mmmm] is preferably 1.76 [mmmm] −20.0 ≦ Tm. ≦ 1.76 [mmmm] +3.0
More preferably 1.76 [mmmm] -15.0 ≦ Tm ≦ 1.76 [mmmm] +2.0
It is.
When the melting point (Tm) exceeds (1.76 [mmmm] +5.0), it indicates that there are partially highly stereoregular sites and sites that do not have stereoregularity.
Moreover, when melting | fusing point (Tm) does not reach (1.76 [mmmm] -25.0), there exists a possibility that heat resistance may not be enough.
The mesopentad fraction [mmmm] is measured as an average value, and it cannot be clearly distinguished whether the mesopentad fraction distribution is wide or narrow, but the relationship with the melting point (Tm) By limiting to a specific range, a preferable highly uniform reactive propylene polymer can be defined.
The melting point (Tm) is determined by DSC measurement.
That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of a sample was melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to −40 ° C. at 10 ° C./min.
Further, the melting point (Tm) is the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by maintaining the temperature at −40 ° C. for 3 minutes and then increasing the temperature at 10 ° C./min.

The propylene polymer preferably further satisfies the following (d) to (f).
(D) [rrrr] / (1- [mmmm]) ≦ 0.1
When the above relationship is satisfied, stickiness is suppressed.
(E) [mm] × [rr] / [mr] ² ≦ 2.0
When the value of [mm] × [rr] / [mr] ² is 2.0 or less, a decrease in transparency is suppressed, and the balance between flexibility and elastic recovery is improved.
[Mm] × [rr] / [mr] ² is preferably in the range of 1.8 to 0.5, more preferably 1.5 to 0.5.
(F) The amount of components (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100 mass%.
The component amount (W25) of the propylene-based polymer eluted at 25 ° C. or lower in the temperature rising chromatography is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
W25 is an index indicating whether or not the propylene-based polymer is soft, and when this value is small, a component having a high elastic modulus increases or the mesopentad fraction [mmmm] is uneven.
In the said propylene polymer, a softness | flexibility is maintained as W25 is 20 mass% or more.
W25 is not adsorbed by the packing material at a column temperature of 25 ° C. of TREF (temperature rising elution fractionation) in an elution curve obtained by measurement by temperature rising chromatography with the following operation method, apparatus configuration and measurement conditions. This is the amount (% by mass) of the eluted component.

(1) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C, then gradually cooled to 0 ° C at a temperature decrease rate of 5 ° C / hour, held for 30 minutes, and the sample is crystallized on the surface of the filler. Let
Thereafter, the column is heated to 135 ° C. at a temperature increase rate of 40 ° C./hour to obtain an elution curve.
(2) Apparatus configuration TREF column: Silica gel column (4.6φ × 150 mm) manufactured by GL Science
Flow cell: GL Science Co., Ltd. optical path length 1 mm KBr cell Liquid feed pump: Senshu Kagaku Co., Ltd. SSC-3100 pump Valve oven: GL Science Co., Ltd. MODEL 554 oven (high temperature type)
TREF oven: GL Sciences 2 series temperature controller: Rigaku Kogyo REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO MIRAN 1A CVF
10-way valve: Barco Electric valve Loop: Barco 500 μl loop (3) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / L
Injection volume: 500 μl
Pump flow rate: 2.0 ml / min Detection wave number: 3.41 μm
Column packing: Chromosolv P (30-60 mesh)
Column temperature distribution: Within ± 0.2 ° C

The terminal unsaturated polyolefin is a butene homopolymer or a butene copolymer of 90% by mass or more of 1-butene and one or more selected from ethylene, propylene and olefin having 5 to 28 carbons (hereinafter, In the case of a butene polymer), the mesopentad fraction [mmmm] is preferably in the range of 20 to 90 mol%.
The mesopentad fraction [mmmm] is more preferably 30 to 85 mol%, and further preferably 30 to 80 mol%.
When the mesopentad fraction is within the above range, the transparency is good, and the decrease in flexibility, the decrease in low-temperature heat sealability, and the decrease in hot tack property are suppressed.

The mesopentad fraction [mmmm] of the butene-based polymer is described in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum to determine the mesopentad fraction in the poly (1-butene) molecule.
The stereoregularity index {[mmmm] / [mmrr] + [rmmr]} to be described later is obtained by calculating the mesopentad fraction [mmmm], the mesomesolemic racemic fraction [mmrr], and the racemic mesomesolemic fraction [rmmr] according to the above method. Calculated from the measured values.
^{The 13} C nuclear magnetic resonance spectrum was measured by the following apparatus and conditions.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The butene polymer preferably further satisfies the following (g) and (h).
(G) A melting point (Tm) measured by a differential scanning calorimeter (DSC) is not observed, or the melting point (Tm) is a crystalline resin having a temperature of 0 to 100 ° C.
In the butene polymer, when a melting point (Tm) is observed, the melting point is preferably 0 to 80 ° C.
In addition, melting | fusing point is calculated | required with the measuring method mentioned above.
(H) {[mmmm] / [mmrr] + [rmmr]} ≦ 20
When the stereoregularity index {[mmmm] / [mmrr] + [rmmr]} is 20 or less, deterioration of flexibility, low-temperature heat sealability and hot tackiness is suppressed.
This stereoregularity index is preferably 18 or less, more preferably 15 or less.

The terminal unsaturated polyolefin of the present invention is preferably produced by a metallocene catalyst.
Examples of the metallocene catalyst include (A) a transition metal compound composed of a metal element of 3 to 10 in the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and the like, and (B) a transition. Examples of the catalyst include a compound that can react with a metal compound to form an ionic complex, and can generate a terminal unsaturated group.
Examples of the transition metal compound include compounds composed of biscyclopentadienyl ligands such as zirconocene chloride and pentamethylcyclopentadienylzirconium dichloride, ethylenebisindenylzirconium dichloride, dimethylsilylene-bis- [2-methyl-4- [Phenylindenyl] zirconium dichloride, dimethylsilylene-bis- [2-methyl-4,5-benzoindenyl] zirconium dichloride, and other compounds comprising a bridged indenyl ligand, pentamethylcyclopentadienyltrimethoxytitanium, pentamethyl A compound comprising a monocyclopentadienyl ligand such as cyclopentadienyltrichlorotitanium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] Funium, dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H -1-Azulenyl)] A compound composed of an azurenium ligand such as hafnium.
Furthermore, the double bridge | crosslinking transition metal compound represented by the following general formula (I) is mentioned.

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table. Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. A metal etc. are mentioned.
Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of yield of terminal vinylidene group and catalytic activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different from each other.
As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y.
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
Specific examples of the 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 cyclohexenyl group. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like.
Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group, phenylmethoxy group, and phenylethoxy group.
Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group.
Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a 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 A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group;
Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include methyl sulfide groups, ethyl sulfide groups, propyl sulfide groups, butyl sulfide groups, hexyl sulfide groups, cyclohexyl sulfide groups, octyl sulfide groups and the like; vinyl sulfide groups, propenyl sulfides Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide , Anthracenyl Nils sulfide group, an aryl sulfide groups such as phenanthridine Nils sulfide groups.

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, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide , Anthracenyl Nils sulfide group, an aryl sulfide groups such as phenanthridine Nils sulfide groups.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl 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.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X.
Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
Examples of the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine. Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, phenylpropylamine; And arylamines such as naphthylamine.

  Examples of 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, Aliphatic hybrid ether compounds such as methyl-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 Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; , Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, cyclic compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane An ether compound is mentioned.

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specifically, 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, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Phosphine, propenylphosphine, cyclohexenylphosphine, etc. Noalkenylphosphine or dialkenylphosphine in which two alkenyl hydrogen atoms are substituted; Trialkenylphosphine in which three alkenyl hydrogen atoms are substituted; Phosphoryl arylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine in which three hydrogen atoms of phosphine are substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methyl Naphthylphosphine, anthracenylphosphine, phenanthonylphosphine; And an aryl phosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphines; alkyl aryl hydrogen atom fin two substituted di (alkylaryl) phosphines. Examples of the thioethers include the above sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms.
As such a crosslinking group, for example, the general formula (a)

(D is a group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium and tin. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other, and may be bonded to each other to form a ring structure.
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH2 = C =), Dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

  Specific examples of the double-bridged transition metal compound represented by the general formula (I) include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3 '-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride , (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2 , 1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′- Tylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′ -Methylcyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,4-dimethylcyclopentadie (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl) (3' , 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclo Pentadienyl) zirconium dichloride,

(1,2′-ethylene) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene ) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1 ′ -Methylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′- Sopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3- Methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl -5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl- 5-Isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium Chloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) Zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3′-Methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3 ′ -Methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl -5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl -5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( -Methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl -5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2′-ethylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) ) Zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) Zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride and the like In which zirconium in the compound is substituted with titanium or hafnium, and represented by the general formula (II) described later Mention may be made of the compound.
Moreover, the analogous compound of the metal element of another group may be sufficient. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.
Among the transition metal compounds represented by the general formula (I), the compound represented by the general formula (II) is preferable.

In the above general formula (II), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and A ^1a and A ^2a each represent a bridging group represented by the general formula (a) in the above general formula (I). CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C (CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si are preferred.
A ^1a and A ^2a may be the same as or different from each other.
R ^{4 to} R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group.
Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the general formula (I).
Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like.
Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as a dimethylamino group, a diethylamino group, and a diphenylamino group; a phenylsulfide group, a methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups.
Among these, as R ⁴ and R ⁵ , groups containing heteroatoms such as halogen, oxygen and silicon are preferable because of high polymerization activity.
R ^{6 to} R ¹³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
X and Y are the same as in general formula (I). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Among the double-bridged transition metal compounds represented by the general formula (II), when both indenyl groups are the same, the transition metal compounds belonging to Group 4 of the periodic table include (1,2'-dimethylsilylene). ) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2 '-Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-ethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-isopropylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethyl) Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (4-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (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-ethoxymethylindene Nyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl) Silylene) bis (3-ethoxyethylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methoxymethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis ( 3-methoxyethylindenyl) zirconium dichloride, (1,2′-phenylmethylsilylene) (2,1′-phenylmethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-phenylmethylsilylene) (2, 1'-phenylmethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (indenyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-isopropylidene) bis (3-methylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-isopropylidene) bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) bis (3-phenylindenyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'- Styrene) (indenyl) zirconium dichloride,

(1,2'-dimethylsilylene) (2,1'-methylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-isopropyl Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 ' -Methylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenyl) Silylene) (2,1′-methylene) bis (indenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) bis (3-n-butylindenyl) zirconium dichloride, ( 1,2′-diphenylsilylene) (2,1′-methylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) bis (3-trimethylsilyl) Indenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium, are not limited thereto.
Further, it may be a compound similar to a metal element other than Group 4.
A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

On the other hand, among the double bridged transition metal compounds represented by the general formula (II), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, the transition metal compound of Group 4 of the periodic table is ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ( Indenyl) (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) (indenyl) (3-phenylindenyl) zirconium dichloride, (1,2′-dimethyl) Rylene) (2,1′-dimethylsilylene) (indenyl) (3-benzylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-neopentyl) Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-phenethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Ethylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) (indenyl) (3-methylindenyl) zirconium dichloride, (1,2 '-Ethylene) (2,1'-ethylene) (indenyl) (3-trimethylsilylindenyl) zyl Conium dichloride, (1,2′-ethylene) (2,1′-ethylene) (indenyl) (3-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) ( Indenyl) (3-benzylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) (indenyl) (3-neopentylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) (indenyl) (3-phenethylindenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium, are not limited thereto. .
Further, it may be a compound similar to a metal element other than Group 4.
A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

As a compound capable of reacting with the transition metal compound (B) constituting the catalyst used in the present invention to form an ionic complex, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and A borate compound is preferable in terms of high catalyst activity.
Examples of borate compounds include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyl (tri-n-butyl) ammonium tetraphenylborate. , Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) borate trie Ruammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) ) Tetraethylammonium borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate , Tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) dimethylanilinium borate, tetra Scan (pentafluorophenyl) borate trimethyl anilinium,

  Methyl pyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2- Cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Nitrogen, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis Tafluorophenyl) triphenylcarbenium borate, methylanilinium tetrakis (perfluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocete) Nium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (penta Fluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate and the like. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.

The catalyst used in the production method of the present invention may be a combination of the component (A) and the component (B). In addition to the component (A) and the component (B), an organoaluminum compound is used as the component (C). Also good.
As the organoaluminum compound of component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormal hexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride.
These organoaluminum compounds may be used alone or in combination of two or more.
Among these, in the present invention, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum and trimethylaluminum Normal octyl aluminum is more preferred.

The amount of component (A) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L, More preferably, it is 0.2 × 10 ^{−6 to} 1.2 × 10 ⁻⁵ mol / L, and particularly preferably 0.3 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mol / L.
When the amount of component (A) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the heat of polymerization is easy. Can be removed.
The use ratio (A) / (B) of the component (A) and the component (B) is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio.
When (A) / (B) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed.
Further, there is no fear that a large amount of boron exists in the target terminal unsaturated olefin polymer.
The use ratio (A) / (C) of the component (A) and the component (C) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, and further preferably 1 in terms of molar ratio. / 10 to 1/1000.
By using the component (C), the polymerization activity per transition metal can be improved. When (A) / (C) is in the range of 1/1 to 1/10000, the balance between the effect of addition of component (C) and economy is good, and the intended terminal unsaturated olefin polymer There is no fear that a large amount of aluminum is present inside.
In the production method of the present invention, the preliminary contact may be performed using the above-described component (A) and component (B), or component (A), component (B) and component (C).
The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used.
Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the component (B) used as the cocatalyst.

  The terminal unsaturated polyolefin of the present invention is a propylene homopolymer produced by a catalyst containing a bicrosslinked complex represented by the above general formula (I), or 90% by mass or more of propylene, ethylene and α having 4 to 28 carbon atoms. -Propylene-based copolymer, butene homopolymer of 1 to 10% by mass selected from olefins, or 90% by mass or more of 1-butene and ethylene, propylene, and olefins having 5 to 28 carbon atoms. One type of homopolymer or two or more types of copolymers selected from a butene-based copolymer with a mass% or less, an α-olefin having 5 to 28 carbon atoms is preferred.

The terminal unsaturated olefin of the present invention is preferably one having little catalyst residue.
In particular, the transition metal content is 5 mass ppm or less, the aluminum content is 300 mass ppm or less, and the boron content is 5 mass ppm or less.
Examples of the transition metal include titanium, zirconium and hafnium, and the total amount thereof is 5 ppm by mass or less.
The content of aluminum is preferably 280 mass ppm or less.
These metal components can be measured by an ICP (High Frequency Inductively Coupled Plasma Spectroscopy) measuring device.
When a terminal unsaturated olefin with little catalyst residue is used, the obtained block copolymer or the thermoplastic resin composition containing the copolymer is preferable because of its high purity.

Examples of the terminal saturated polyolefin of the present invention include those obtained using a Ziegler catalyst, a metallocene catalyst, and the like, which are substantially free of terminal unsaturated groups. For example, reactive polyolefins containing unsaturated groups may be used. Hydrogenated polyolefins containing no unsaturated groups, polyolefins containing no unsaturated groups produced without using a polyene component, and more specifically, the following polyolefins (1) to (3): .
(1) Polyethylene resins such as high density polyethylene (HDPE), low density (LDPE), and L-LDPE (2) isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, propylene and ethylene, 4 to 12 carbon atoms Copolymer composed of one or more α-olefins, polypropylene resin such as block polypropylene (3) Polymer composed of one or more olefins having 6 to 28 carbon atoms

In the combination of the terminal unsaturated polyolefin and the terminal saturated polyolefin of the present invention, the form includes a molten mixture with the terminal unsaturated polyolefin, a powdery mixture, a dry blend mixture such as pellets, a solution dissolved in a hydrocarbon solvent or A mixture in a suspended state generated by cooling or reprecipitation after dissolution.
The mixing ratio is 20 to 100% by weight of terminal unsaturated polyolefin and 0 to 80% by weight of terminal saturated polyolefin, preferably 30 to 100% by weight of terminal unsaturated polyolefin and 0 to 70% by weight of terminal saturated polyolefin, more preferably Is 40 to 100% by mass of terminal unsaturated polyolefin and 0 to 60% by mass of terminally saturated polyolefin, more preferably 50 to 100% by mass of terminally unsaturated polyolefin and 0 to 50% by mass of terminally saturated polyolefin.
When the content is 20% by mass or more of the terminal unsaturated polyolefin, the amount of the block copolymer produced after the polymerization reaction is preferably increased.
From another point of view, when a graft copolymer or a thermoplastic resin composition containing a graft polymer is added to the same type of resin as the terminal saturated polyolefin, the block copolymer is contained in the terminal saturated polyolefin. A sufficient amount and a good dispersion state are preferable because the block copolymer is easily dispersed in the entire composition obtained.
Accordingly, when the terminal saturated polyolefin is 80% by mass or less, the terminal saturated polyolefin becomes an appropriate amount, which is preferable from the viewpoint of dispersibility.

Examples of the anionic polymerizable monomer of the present invention include the following compounds.
[I] Acrylic acid derivatives (1) Acrylic esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, normal octyl acrylate, 2-ethylhexyl acrylate, etc. (2) Sodium acrylate, acrylic acid Acrylic acid salt composed of acrylic acid and typical metal elements such as potassium, magnesium acrylate, calcium acrylate, etc. (3) Acrylic acid esters containing oxygen, nitrogen, sulfur and silicon atoms in the ester residue, such as glycidyl acrylate Acrylates having functional groups such as acryloyloxyethyl isocyanate and methacryloyloxyethyl isocyanate (4) acrylamide (5) Substituents containing oxygen, nitrogen, sulfur and silicon atoms, for example, N-methylacrylamide, N- Ethyla Kurylamide, N-isopropylacrylamide, N-cyclohexylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N, N-dicyclohexylacrylamide, N- (2-hydroxy N) -substituted acrylamides such as ethyl) -acrylamide, N- (2-hydroxypropyl) -acrylamide, N, N-dimethylaminoethylacrylamide, N-methylolacrylamide,
(6) Acrylonitrile [II] methacrylic acid derivative Monomer [III] styrene having an alkyl group such as a methyl group at the α-position of the monomer [I] above, and further α-methylstyrene, p-methyl Styrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o -Isopropyl styrene, m-methyl styrene, m-ethyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2.4-dimethyl styrene, 2.5-dimethyl styrene, 3.5-dimethyl styrene, etc. Alkylstyrenes; p-methoxystyrene, o-methoxystyrene, m-methoxys Alkoxy styrenes such as len; halogenated styrenes such as p-chlorostyrene, m-chlorostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene Styrene derivatives such as trimethylsilylstyrene [IV] conjugated diolefins containing 4 to 12 carbon atoms, such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4- Diene derivatives such as dimethyl-1,3-hexadiene and 4,5-diethyl-1,3-octadiene, preferably 1,3-butadiene and isoprene.
As the anionic polymerizable monomer, one or more selected from the above [I] to [IV] can be used.

The metallizing agent for terminally unsaturated polyolefin is composed of an alkyl lithium compound (AkLi) / alkali metal alkoxide (AkOM) (M represents sodium, potassium, rubidium or cesium metal) or amines.
As an alkyl lithium compound, alkyl lithium which consists of C1-C10 hydrocarbon groups, such as normal butyl lithium and sec-butyl lithium, is mentioned.
In the alkali metal alkoxide, the metal is as described above, and alcohols corresponding to the alkoxide include isopropanol, sec-butanol, tert-butanol, 2-pentanol, 3-pentanol, tert-pentanol, 3-methyl- 3-pentanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-heptanol, 3-heptanol, 1 (-)-menthol, heptanol, 3-methyl-3-hexanol, 2-ethyl- 2-hexanol, 3-ethyl-3-hexanol, 2-propyl-2-pentanol, 2-isopropyl-2-pentanol, 3-propyl-3-pentanol, 3-isopropyl-3-pentanol, methanol Can be mentioned.
In particular, it is preferable to use an alkali metal alkoxide soluble in a nonpolar hydrocarbon solvent and an alcohol precursor thereof.
Most preferred alkali metal alkoxides are alkali metal alkoxides obtained from tert-butanol, 2-ethyl-2-hexanol (2-EtHexOH), menthol (MenOH) and tertiary pentanol (tert-PeOH), and preferred metals As for, potassium and cesium.
The amines can be selected from trialkylamines, diamines, etc., but N, N, N ′, N′-tetramethylethylenediamine is preferred.
The molar ratio of the alkyllithium compound (ii) to the terminal unsaturation amount (i) of the terminal unsaturated polyolefin is (i) / (ii) = 1 to 2, preferably 1 to 1.5, more preferably 1 to 1.5. 1.3.
Further, the molar ratio of the alkyl lithium compound (ii) to the alkali metal alkoxide compound (iii) is about (iii) / (ii) = 1 to 4, preferably side reactions other than the desired metalation, for example, fragrance In order to suppress ring metallization, (iii) / (ii) = 1.2-3.
The molar ratio of the alkyl lithium compound (ii) to the amines (iv) is (ii) / (iv) = 1 to 2, preferably 1 to 1.5.
Examples of the nonpolar hydrocarbon solvent include hydrocarbon solvents having a boiling point of 0 to 200 ° C., and preferred solvents include pentane, n-hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane.
As a usage-amount of a solvent, it is used in the range of 1-50 ml of solvent with respect to 1 g of terminal unsaturated polyolefins.

In the reaction for metallizing the terminal unsaturated polyolefin of the present invention, the reaction temperature is usually in the range of room temperature (about 20 to 25 ° C.) to 40 ° C., and the reaction time is usually within 60 minutes.
In the block polymerization conditions, the molar ratio of the alkyl lithium compound (ii) and the anion polymerizable monomer (v) is about (v) / (ii) = 10 to 100,000, preferably 50 to 80,000, more preferably 80 to 60000, more preferably 100 to 50000.
When the molar ratio is 10 or more, the amount of block polymerization is sufficient, and when it is 100,000 or less, unreacted anionic polymerizable monomers do not remain, and the homopolymer not involved in block polymerization is preferably reduced.
The block polymerization temperature is about −80 to 100 ° C., preferably 20 to 90 ° C., more preferably 30 to 80 ° C. The reaction time is usually about 0.1 to 30 hours, preferably 0.2. ~ 20 hours.

The block copolymer of the present invention is described below.
In the primary structure, the polyolefin chain is one kind of homopolymer or two or more kinds of copolymers selected from α-olefin having 2 to 28 carbon atoms as described above.
The anionic polymerizable monomer chain side chain is a polymerization chain composed of one or more selected from acrylic acid derivatives, methacrylic acid derivatives, styrene derivatives, and diene derivatives.
As for the molecular weight of the block copolymer, the weight average molecular weight (Mw) determined from GPC is usually 2,000 to 500,000, preferably 2,500 to 400,000, more preferably 4,000 to 350,000. .
Moreover, the molecular weight distribution (Mw / Mn) is 1.5-4 normally, Preferably it is 1.6-3.8, More preferably, it is 1.7-3.0.
Furthermore, it is preferable that the block copolymer of the present invention does not contain a gel component.
(Method for measuring gel component)
Using a solvent that dissolves both the polyolefin component of the block copolymer and the chain component consisting of an anionic polymerizable monomer, a stainless steel 400 mesh (mesh 0.034 mm) mesh of a glass separable flask with a stirrer 50 mg of the block copolymer is put into the finished bowl and fixed to the stirring blade.
A solvent containing 0.1% by mass of an antioxidant (BHT) is added and dissolved with stirring at the boiling point for 4 hours.
After dissolution, the collected soot is sufficiently dried in vacuum, and the insoluble part is determined by weighing.
The gel component defined as the insoluble part is calculated by the following formula.
[Remaining amount in mesh (g) / Amount of charged sample (g)] × 100 (unit:%)
Examples of the solvent include paraxylene and toluene.
Usually, in the above formula, it is defined that the gel component is not included with a range of 0 to 1.5 mass%.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1
(1) Synthesis of transition metal compound (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was synthesized as follows.
In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF (tetrahydrofuran) and heated to -78 ° C. Cooled down.
2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution.
After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Obtained (yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of ether.
The mixture was cooled to −78 ° C., and a hexane solution of n-BuLi (1.54M, 7.6 ml (1.7 mmol)) was added dropwise. After raising to room temperature and stirring for 12 hours, ether was distilled off.
The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows.
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene). 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2-7.7 (m, 8H, Ar-H)

Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 ml of toluene.
The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise thereto.
After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to obtain 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)

Production Example 2
Synthesis of (1,2′-SiMe ₂ ) (2,1′-SiMe ₂ ) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride Under a nitrogen stream, 50 ml of ether and (1,2 ′ -SiMe ₂ ) (2,1′-SiMe ₂ ) bisindene (3.5 g, 10.2 mmol) was added thereto, and a hexane solution (1.60 mol / L, n-butyllithium (n-BuLi)) at −78 ° C. 12.8 ml) was added dropwise.
After stirring at room temperature for 8 hours, the solvent was distilled off, and the obtained solid was dried under reduced pressure to obtain 5.0 g of a white solid.
This solid was dissolved in 50 ml of tetrahydrofuran (THF), and 1.4 ml of iodomethyltrimethylsilane was added dropwise thereto at room temperature.
After hydrolysis with 10 ml of water and extraction of the organic phase with 50 ml of ether, the organic phase was dried and the solvent was distilled off.
50 ml of ether was added thereto, and a hexane solution of n-BuLi (1.60 mol / L, 12.4 ml) was added dropwise at −78 ° C. After raising to room temperature and stirring for 3 hours, the ether was distilled off.
The obtained solid was washed with 30 ml of hexane and then dried under reduced pressure.
5.11 g of this white solid was suspended in 50 ml of toluene, and 2.0 g (8.60 mmol) of zirconium tetrachloride suspended in 10 ml of toluene in another Schlenk was added.
After stirring at room temperature for 12 hours, the solvent was distilled off, the residue was washed with 50 ml of hexane, and the residue was recrystallized from 30 ml of dichloromethane to obtain 1.2 g of yellow fine crystals. (Yield 25%)
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.09 (s, -SiMe ₃ , 9H); 0.89, 0.86, 1.03, 1.06 (s, -Me ₂ Si-, 12H); 2.20, 2.65 ( _{d, -CH 2 -, 2H)} ; 6.99 (s, CH, 1H); 7.0-7.8 (m, ArH, 8H)

Production Example 3 [Production of terminal unsaturated polypropylene (1)]
In a heat-dried stainless steel autoclave with an internal volume of 1.4 L, 0.4 L of dry heptane, 10 ml of a toluene solution of 20 mmol of methylaluminoxane, (1,2′-dimethylsilylene) (2,1 ′) synthesized in Production Example 1 above -Dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride 1 ml of a heptane solution of 20 μmol was added, and the temperature was raised to 90 ° C. with stirring.
Propylene gas was introduced into this so that the partial pressure was 0.1 Mpa.
During the polymerization reaction, propylene gas was supplied by a pressure regulator so as to keep the pressure constant, polymerization was performed for 120 minutes, and then cooled, unreacted propylene was removed by depressurization, and the contents were taken out.
The contents were put into a large amount of methanol and washed, and then the polypropylene was recovered and dried to obtain 75.3 g.
The results are shown in Table 1.

Production Example 4 [Production of terminal unsaturated polypropylene (2)]
A terminal unsaturated polypropylene was obtained in the same manner as in Production Example 3 except that the transition metal compound synthesized in Production Example 2 was used instead of the transition metal compound synthesized in Production Example 1.
The results are shown in Table 1.

Production Example 5
In a heat-dried stainless steel autoclave with an internal volume of 1.4 L, 0.4 L of dry heptane, 1 mL of heptane solution of 0.5 mmol of triisobutylaluminum, and 2 mL of heptane slurry of 1.5 μmol of methylanilinium tetrakis (perfluorophenyl) borate In addition, the mixture was stirred for 10 minutes while controlling at 50 ° C.
Furthermore, 0.5 μmol of heptane of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex prepared in Production Example 1 above. 2 ml of slurry was charged.
Next, the temperature was raised to 70 ° C. while stirring, and propylene gas was introduced up to 0.8 MPa in total pressure.
During the polymerization reaction, propylene gas was supplied by a pressure regulator so as to keep the pressure constant, polymerization was performed for 120 minutes, and then cooled, unreacted propylene was removed by depressurization, and the contents were taken out.
The contents were air-dried and further dried under reduced pressure at 80 ° C. for 8 hours to obtain 123 g of polypropylene.
The results are shown in Table 1.

Example 1 (Production of polypropylene / methyl methacrylate block copolymer)
In a dry 200 ml three-necked flask equipped with a stirrer, 7.5 g of polypropylene synthesized in Production Example 3 and 31 ml of cyclohexane were charged and dissolved while stirring at room temperature.
Further, this solution was bubbled with nitrogen for 10 minutes for dehydration.
The cyclohexane decreased by this treatment was compensated by newly adding dehydrated cyclohexane.
0.95 ml of a cyclohexane solution containing 4 mmol of cyclohexane slurry of 2 mmol of tert-butoxide potassium and 1 mmol of sec-butyllithium was added, followed by stirring at 70 ° C. for 60 minutes for metallization.
Thereafter, it was cooled to room temperature, 7.1 g of dehydrated and distilled and purified methyl methacrylate was added over 5 minutes, and the temperature was raised to 40 ° C. and reacted for 2 hours.
After completion of the reaction, the reaction mixture was added to 1 L of methanol containing 1% by volume of 12 mol / L hydrochloric acid to precipitate the polymer, followed by washing.
Further, methanol washing was performed, and 13.9 g of a polymer was obtained by filtration and drying.
When GPC measurement of this product was performed, the weight average molecular weight (Mw) was 10500, the molecular weight distribution (Mw / Mn) was 1.85, which was increased compared to the molecular weight of the terminally unsaturated polypropylene of the precursor, No expansion of the molecular weight distribution was observed, and the molecular weight distribution profile was shifted to the high molecular weight side as a whole, confirming the formation of a block copolymer.

Example 2 (Production of polypropylene / methyl methacrylate block copolymer)
In a dry 200 ml three-necked flask equipped with a stirrer, 5.0 g of polypropylene synthesized in Production Example 4 and 39 ml of cyclohexane were charged and dissolved while stirring at room temperature.
Further, this solution was bubbled with nitrogen for 10 minutes for dehydration.
The cyclohexane decreased by this treatment was compensated by newly adding dehydrated cyclohexane.
0.95 ml of a cyclohexane solution containing 1.0 mmol of N, N, N ′, N ′,-tetramethylethylenediamine and 1 mmol of sec-butyllithium was added, followed by stirring at 20 ° C. for 120 minutes for metallization.
Thereafter, 7.1 g of dehydrated and distilled and purified methyl methacrylate was added over 5 minutes and reacted at 25 ° C. for 2 hours.
After completion of the reaction, the reaction mixture was added to 1 L of methanol containing 1 mol% of 12 mol / L hydrochloric acid, and the polymer was washed and recovered.
Further, methanol washing was performed, and 11.4 g of a polymer was obtained by filtration and drying.
When GPC measurement of this product was performed, the weight average molecular weight (Mw) was 5700, the molecular weight distribution (Mw / Mn) was 1.58, which was increased compared to the precursor molecular weight, and the molecular weight distribution was further expanded. Further, since the molecular weight distribution profile was shifted to the high molecular weight side as a whole, it was confirmed that a block copolymer was formed.

Example 3 (Production of polypropylene / methyl methacrylate block copolymer)
In a dry 200 ml three-necked flask equipped with a stirrer, 5.0 g of the polypropylene synthesized in Production Example 3 and 50 ml of cyclohexane were charged and dissolved while stirring at room temperature.
Further, this solution was bubbled with nitrogen for 10 minutes for dehydration.
The cyclohexane decreased by this treatment was compensated by newly adding dehydrated cyclohexane.
0.95 ml of cyclohexane solution containing 4 mmol of cyclohexane slurry of 2 mmol of tert-butoxide potassium and 1 mmol of sec-butyllithium was added, and the mixture was stirred at 20 ° C. for 15 minutes for metallization.
Thereafter, 7.1 g of dehydrated and distilled and purified methyl methacrylate was added over 5 minutes, and the reaction was carried out at 25 ° C. for 2 hours.
The reaction mixture was treated in the same manner as in Example 1 to obtain 11.5 g of polymer.
In order to clarify the structure of this product, solvent fractionation and composition analysis were performed.
First, the obtained polymer was dissolved in heptane and separated into a soluble part and an insoluble part by filtration.
As a result, the soluble part (C7S) was 36.8% by mass, and the insoluble part (C7IS) was 63.2% by mass.
Further, the insoluble part (C7IS) was similarly extracted with acetone and separated by a centrifuge. As a result, the ratio of the soluble part (C7IS / AS) to the insoluble part (C7IS) was 58.8% by mass, insoluble The ratio of the part (C7IS / AIS) to the insoluble part (C7IS) was 41.2% by mass.
Table 2 shows the results of the composition analysis of each component determined by ¹ H-NMR.

Moreover, the terminal unsaturated polypropylene of Production Example 3 is soluble in heptane and insoluble in acetone, and polymethyl methacrylate is insoluble in heptane and soluble in acetone.
Since the polypropylene component and the polymethyl methacrylate component coexist in all the components, it was confirmed that the block copolymer was formed in all fractions.
Moreover, when the insoluble part (C7IS / AIS) in which it was confirmed that a free polypropylene component and a polymethylmethacrylate component do not exist was evaluated, weight average molecular weight (Mw) 7600, molecular weight distribution (Mw / Mn) 1.70. The block rate was 66.9%.

Example 4
A separable flask equipped with a stirrer with an internal volume of 1 L was charged with 50 g of terminal unsaturated polypropylene of Production Example 5 and 400 ml of dehydrated heptane and dissolved at room temperature with stirring.
After dissolution, the solution was bubbled with nitrogen for 30 minutes for dehydration.
The heptane decreased by this treatment was compensated by newly adding dehydrated heptane.
3.6 ml of a cyclohexane slurry of 1.82 mmol of potassium tert-butoxide and 0.87 ml of a cyclohexane solution containing 0.91 mmol of sec-butyllithium were added and metallized by stirring at 20 ° C. for 15 minutes.
Thereafter, 9.0 g of dehydrated and purified glycidyl methacrylate was added over 5 minutes, and the reaction was performed at 70 ° C. for 2 hours.
The reaction mixture was treated in the same manner as in Example 1, and 53.2 g of a block copolymer was obtained by extraction with acetone, washing, and filtration and drying.
The graft ratio was 6.0%, the weight average molecular weight was 120,000, and the molecular weight distribution (Mw / Mn) was 2.10.

  The block copolymer of the present invention or the thermoplastic resin composition containing the copolymer is a polyolefin modifier, such as an inorganic filler or dye, as a sealant having high adhesion to plastic materials, paper, wood, etc. , As a modifier for obtaining polyolefins with improved compatibility with polar polymers, polar wax, wood powder, metal, etc., mechanical properties, and fluidity, or polyolefin surface treatment agent, primer treatment, coating agent components It is useful as such.

Claims (9)

And end edge metallized polyolefin to the unsaturated polyolefin obtained by metallization, at least one anionically polymerizable monomer and a body reacted, terminal unsaturation polyolefin to the anionic polymerizable monomer chain block copolymer to form a Propylene copolymer in which the terminal unsaturated polyolefin is a propylene homopolymer, propylene copolymer of 90% by mass or more and one or more selected from ethylene and α-olefin having 4 to 28 carbon atoms. , A butene homopolymer, or a butene copolymer of 90% by mass or more of 1-butene and one or more but 10% by mass or less selected from ethylene, propylene, and olefin having 5 to 28 carbon atoms. The manufacturing method of the block copolymer which satisfies these .
(A) Mesopentad fraction [mmmm] of 30 to 80 mol% The method for producing a block copolymer according to claim 1, wherein the terminal unsaturated polyolefin further satisfies the following (2) to (4).
( 2) having 0.5 to 1.0 terminal unsaturated groups per molecule;
(3) Molecular weight distribution (Mw / Mn) is 4 or less (4) Intrinsic viscosity [η] measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g Anionic polymerizable monomers include (meth) acrylic acid esters, (meth) acrylic acid metal salts, (meth) acrylic acid esters containing oxygen, nitrogen, sulfur and silicon atoms in the ester residue, (meth) acrylamide N-substituted (meth) acrylamide, (meth) acrylonitrile, styrene, alkyl styrenes, alkoxy styrenes, halogenated styrenes, trimethylsilyl styrene, conjugated diolefins containing 4 to 12 carbon atoms A method for producing a block copolymer according to 1 or 2. The method for producing a block copolymer according to any one of claims 1 to 3, wherein the terminal unsaturated group is a vinylidene group. The terminal unsaturated polyolefin is a propylene homopolymer, or a propylene-based copolymer of 90% by mass or more of propylene and one or more types selected from ethylene and α-olefin having 4 to 28 carbon atoms. The manufacturing method of the block copolymer in any one of Claims 1-4 which satisfies (a) and (b) .
(A) Mesopentad fraction [mmmm] of 30 to 80 mol%
(B) Racemic meso racemic meso fraction [rmrm]> 2.5 mol% Terminally unsaturated polyolefin is, butene homopolymer, or ethylene and 1-butene 90% by weight or more, Ru butene copolymer der with one or more 10 wt% or less selected from olefins of propylene and 5 to 28 carbon atoms process for producing the block copolymer according to any one of 請 Motomeko 2-4. A propylene homopolymer, or a propylene-based copolymer of 90% by mass or more of propylene and one or more and 10% by weight or less selected from ethylene and α-olefin having 4 to 28 carbon atoms, and the following (a) and The propylene polymerization site satisfying (b) contains (meth) acrylic acid esters, (meth) acrylic acid metal salts, and oxygen, nitrogen, sulfur and silicon atoms in the ester residues as anionic polymerizable monomers (meta) ) Acrylates, (meth) acrylamide, N-substituted (meth) acrylamide, (meth) acrylonitrile, styrene, alkyl styrenes, alkoxy styrenes, halogenated styrenes, trimethylsilyl styrene, containing 4-12 carbon atoms chained and block binding consisting of one or more selected from conjugated diolefins that, following (6) to the block copolymer which satisfies (7).
(A) Mesopentad fraction [mmmm] of 30 to 80 mol%
(B) Racemic meso racemic meso fraction [rmrm]> 2.5 mol%
( 6) Weight average molecular weight is 2,000 to 500,000
(7) Molecular weight distribution (Mw / Mn) is 1.5-4 A butene homopolymer or a butene copolymer of 90% by mass or more of 1-butene and one or more but 10% by mass or less selected from ethylene, propylene, and olefin having 5 to 28 carbon atoms, and a mesopentad fraction [mmmm ] Is a butene polymerization site in the range of 30 to 80 mol%, (meth) acrylic acid ester, (meth) acrylic acid metal salt as an anionically polymerizable monomer , oxygen, nitrogen, sulfur, silicon in the ester residue (Meth) acrylic acid esters containing atoms, (meth) acrylamide, N-substituted (meth) acrylamide, (meth) acrylonitrile, styrene, alkylstyrenes, alkoxystyrenes, halogenated styrenes, trimethylsilylstyrene, 4-12 chain and blocks consisting of one or more selected from conjugated diolefins containing carbon atoms Bound, block copolymer which satisfies the following (6) to (7).
( 6) Weight average molecular weight is 2,000 to 500,000
(7) Molecular weight distribution (Mw / Mn) is 1.5-4 The block copolymer obtained by the manufacturing method in any one of Claims 1-6 .