JP5290959B2 - Oxidation-modified α-olefin polymer and process for producing the same - Google Patents

Abstract

Disclosed is an oxidatively modified a-olefin polymer which is produced by oxidatively modifying a polymer of an a-olefin represented by the general formula: CH<SUB>2</SUB>=CH-C<SUB>n</SUB>H<SUB>2n+1</SUB> [wherein n is an integer of 8 or greater] and satisfies the following requirements (A) to (E): (A) the stereoregularity index value M4 is 75 mol% or less; (B) the weight average molecular weight (Mw) is 500 to 5,000,000 and the molecular weight distribution (Mw/Mn) is 4.0 or less in terms of styrene content as measured by GPC method; (C) one melting peak appears in the melting point (Tm) measurement by DSC, the amount of heat absorbed upon melting (?H) as calculated from the area of the melting peak is 20 J/g or more, and the half-width value of the melting peak is 10°C or lower; (D) the acid value is 0.01 to 50 mg KOH/g; and (E) the amount of an extract with acetone is less than 0.1 mass%. The oxidatively modified a-olefin polymer is useful as an alternative material to a wax component. Also disclosed is a method for producing the oxidatively modified a-olefin polymer with high efficiency.

Description

  The present invention relates to an oxidation-modified α-olefin polymer and a method for producing the same. Specifically, it is mainly useful as a wax component substitute material, and in particular, a toner release agent and ink component, a resin modifier, an adhesive component, an adhesive component, a lubricating oil component, an organic-inorganic composite material, a heat storage material, The present invention relates to a modifier for fuel oil such as light oil, a modifier for asphalt, an oxidation-modified α-olefin polymer useful as a high-performance wax, and a method for efficiently producing the oxidation-modified α-olefin polymer.

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, or an oxidation-modified olefin polymer obtained by oxidizing the above-mentioned polyolefin with oxygen or ozone is a variety of resins. It is used for applications such as a modifier and an adhesion-imparting agent.
As the oxidation-modified olefin polymer, for example, Patent Document 1 discloses a liquid oxidation-modified ethylene random copolymer, and Patent Documents 2 to 4 disclose polyethylene wax and polypropylene wax. In addition, as a wax-based oxidation-modified olefin polymer, a natural product-derived wax (such as carnauba wax) is used.
However, these oxidation-modified olefin polymers are all oily and have problems such as high melting point, sharp and not simple melting characteristics, and low heat resistance. For this reason, there is a demand for these improvements, but existing waxes (polyolefin-based, natural-based, synthetic-based, petroleum-based) do not satisfy all of these requests, and may be sufficient depending on the purpose of use. It is hard to say that it is performing. Accordingly, there is a strong demand for the development of an oxidation-modified olefin polymer having excellent performance.
Further, since conventional polyolefin waxes, particularly CPAO (crystalline higher α-olefin polymer) is nonpolar, the compatibility between this wax and other resins is low, and the polyolefin wax provided with a polar group The development of was requested.

Japanese Patent Publication No. 7-78096 Special Table 2000-509417 JP 2003-215835 A JP-T-2004-501246

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oxidation-modified α-olefin polymer that is useful mainly as a substitute for a wax component and a method for efficiently producing the same.

As a result of intensive studies, the present inventors have achieved the above object with an oxidatively modified α-olefin polymer having a specific property, and the α-olefin polymer having a specific property has been converted into a molecular form. It has been found that the above-mentioned oxidation-modified α-olefin polymer can be easily produced by oxidation treatment at a specific temperature in the presence of oxygen and / or ozone-containing gas until the acid value reaches a certain range. The present invention has been completed based on such findings.
That is, the present invention provides the following oxidation-modified α-olefin polymer and a method for producing the same.
1. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An oxidation-modified α-olefin polymer characterized in that the α-olefin polymer represented by the formula (1) is oxidized and modified, and satisfies the following (A) to (E).
(A) Stereoregularity index value M4 is 75 mol% or less.
(B) The styrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method is 500 to 5,000,000, and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn )) Is 4.0 or less.
(C) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
(D) Acid value is 0.01-50 mgKOH / g.
(E) The acetone extract is less than 0.1% by mass.
2. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The oxidation-modified α-olefin polymer according to 1 above, wherein the α-olefin polymer represented by the formula (1) is a polymer having 0.5 to 1.0 vinylidene groups per molecule. .
3. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An oxidation-modified α-olefin polymer characterized by being obtained by oxidation-modifying a polymer of α-olefin represented by the following formula and satisfying the following (F) to (K).
(F) Stereoregularity index value M4 is 75 mol% or less.
(G) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 5.0 dl / g.
(H) Using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. The melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is 0 to 120 ° C.
(I) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
(J) Acid value is 0.01-50 mgKOH / g.
(K) The acetone extract is less than 0.1% by mass.

4). General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The oxidation-modified α-olefin polymer as described in 3 above, wherein the α-olefin polymer represented by the formula (1) is a polymer having 0.5 to 1.0 vinylidene groups per molecule. .
5. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The α-olefin polymer formed by polymerizing the α-olefin represented by the formula (1) and the following (L) to (N) is contacted with molecular oxygen and / or ozone-containing gas at 100 to 300 ° C. The method for producing an oxidatively modified α-olefin polymer as described in 1 above, wherein the oxidation treatment is performed until the acid value reaches 0.01 to 50 mgKOH / g.
(L) Stereoregularity index value M4 is 75 mol% or less.
(M) The weight average molecular weight (Mw) in terms of styrene measured by gel permeation chromatography (GPC) is 500 to 5,000,000, and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn )) Is 4.0 or less.
(N) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
6). General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An α-olefin polymer satisfying the following (O) to (R) is brought into contact with molecular oxygen and / or ozone-containing gas at 100 to 300 ° C. The method for producing an oxidatively modified α-olefin polymer as described in 3 above, wherein the oxidation treatment is carried out until the acid value reaches 0.01 to 50 mgKOH / g.
(O) Stereoregularity index value M4 is 75 mol% or less.
(P) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 5.0 dl / g.
(Q) Using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. under a nitrogen atmosphere for 5 minutes, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. The melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is 0 to 120 ° C.
(R) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.

  The oxidation-modified α-olefin polymer of the present invention is mainly useful as a substitute for a wax component. According to the production method of the present invention, a dangerous substance such as a peroxide and an expensive reagent are not used. In addition, an oxidation-modified α-olefin polymer can be produced at low cost.

The oxidation-modified α-olefin polymer 1 of the present invention has the general formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
It is obtained by subjecting an α-olefin polymer represented by the following formula to oxidation modification. Examples of the α-olefin having 10 or more carbon atoms represented by the general formula (1) include 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- Examples include octadecene, 1-nonadecene, 1-icocene, 1-docosene, 1-hexacosene and 1-octacosene. In the present invention, an α-olefin having 12 to 40 carbon atoms is preferable.
The α-olefin polymer before oxidative modification may be an α-olefin homopolymer obtained by polymerizing one kind selected from these α-olefins, or an α-olefin copolymer obtained by polymerizing two or more kinds.

The oxidation-modified α-olefin polymer 1 satisfies the following (A) to (E). The following (A) to (E) can be adjusted according to the selection of the catalyst and the reaction conditions when producing the α-olefin polymer before oxidative modification. The same applies to (F) to (K) described later.
(A) Stereoregularity index value M4 is 75 mol% or less.
When the stereoregularity index value M4 of the oxidation-modified α-olefin polymer 1 of the present invention is 75 mol% or less, the secondary processability is good. Further, from the viewpoint of suppressing stickiness, the stereoregularity index value M4 is preferably 10 mol% or more, and more preferably 20 to 75 mol%.
The stereoregularity index value M4 is a mesopentad fraction of α-olefin chain. Asakura, M .; Demura, Y .; It is a value obtained in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama. That is, it is a value obtained by utilizing the fact that CH ₂ carbon at the side chain α-position is split and observed in the ¹³ C-NMR spectrum, reflecting the difference in stereoregularity. The larger the value of the stereoregularity index value M4, the higher the stereoregularity.
In addition, the measurement of a < ¹³ > C-NMR spectrum can be performed with the following apparatus and conditions.

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

(B) The styrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method is 500 to 5,000,000, and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn )) Is 4.0 or less.
In the oxidation-modified α-olefin polymer 1, when the weight average molecular weight is 500 or more, the occurrence of stickiness is suppressed. Moreover, since a fall of fluidity | liquidity is suppressed as a weight average molecular weight is 5,000,000 or less, a moldability becomes favorable. The weight average molecular weight is preferably 500 to 100,000.
Moreover, in the oxidation-modified α-olefin polymer 1 of the present invention, when the molecular weight distribution (Mw / Mn) is 4.0 or less, the occurrence of stickiness is suppressed. The molecular weight distribution is preferably 3.0 or less, more preferably 2.5 or less.
The said weight average molecular weight (Mw) can be calculated | required by measuring with the following apparatus and conditions by the gel permeation chromatography (GPC) method. The molecular weight distribution (Mw / Mn) can be determined from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured in the same manner.

<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<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 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(C) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
When the oxidation-modified α-olefin polymer 1 of the present invention satisfies such a relationship, stickiness hardly occurs even under industrial use conditions, and it has excellent heat resistance and is uniform at a constant temperature. It is excellent in workability because it melts.
The melting endotherm (ΔH) is determined as follows. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of the sample was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then the temperature was decreased to −10 ° C. at 5 ° C./min, and −10 The peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by maintaining the temperature at 10 ° C. for 5 minutes and then increasing the temperature to 190 ° C. at 10 ° C./min is the melting point (Tm). The melting endotherm (ΔH) is calculated from the area of the melting peak obtained in the measurement of).
In the oxidation-modified α-olefin polymer 1 of the present invention, ΔH is preferably 20 to 250 J / g, more preferably 30 to 200 J / g. ΔH is an index indicating whether or not it is soft, and when this value is large, it means that the elastic modulus is high and the softness is lowered. Moreover, melting | fusing point (Tm) is about 0-120 degreeC normally, Preferably it is 0-100 degreeC, More preferably, it is 10-90 degreeC, More preferably, it is 20-80 degreeC.
It is necessary that the melting peak observed in the temperature raising process for measuring the melting point (Tm) is one. One peak means that there is no absorption seen as other peaks or shoulders.

The full width at half maximum refers to the peak width at 50% height of the endothermic peak when the melting point (Tm) is measured by DSC as described above. The smaller the full width at half maximum, the more uniform crystals are formed. This is a characteristic showing the homogeneity of α-olefin. In the oxidation-modified α-olefin polymer 1 of the present invention, the half width is preferably 7 ° C. or less, more preferably 5 to 2 ° C. When the full width at half maximum is 10 ° C. or less, the melting behavior is sharp. For example, when the α-olefin polymer of the present invention is used as a main material of a temperature-sensitive adhesive, an adhesive-non-adhesive switch temperature. The spread of the region is suppressed, so that a rapid change with the temperature of the adhesive force can be realized. That is, temperature sensitivity is improved.
(D) Acid value is 0.01-50 mgKOH / g.
When the acid value is 0.01 mg KOH / g or more, the oxidation-modified α-olefin polymer 1 has sufficient adhesive strength, and when it is 50 mg KOH / g or less, the oxidation-modified α-olefin polymer. 1 flexibility is sufficient. The acid value is preferably 0.05 to 40 mgKOH / g, more preferably 0.1 to 35 mgKOH / g. The acid value is measured according to the total acid value measuring method described in JIS K 2501-1980.
(E) The acetone extract is less than 0.1% by mass.
1 g of the oxidatively modified α-olefin polymer was dissolved in 20 ml of toluene, reprecipitated in 100 ml of acetone, and then the acetone solution was dried at 20 ° C. under reduced pressure to measure the amount of acetone extract. Acetone extract is an unreacted polar monomer. The acetone extract is preferably 0.05% by mass or less, more preferably 0.01% by mass or less. When the acetone extract is less than 0.1% by mass, the effect of polar groups bonded to the oxidatively modified α-olefin polymer is improved, and functions such as compatibility and adhesiveness are exhibited.

The oxidation-modified α-olefin polymer 2 of the present invention has the general formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The α-olefin polymer represented by the formula is oxidized and modified, and the following (F) to (K) are satisfied. In addition, about General formula (1), it is as having demonstrated in the said oxidation modification | denaturation alpha-olefin type polymer 1. FIG.
(F) Stereoregularity index value M4 is 75 mol% or less.
Same as (A) above.
(G) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 5.0 dl / g.
This intrinsic viscosity [η] is preferably 0.01 to 5.0 dl / g, more preferably 0.015 to 3.0 dl / g. When the intrinsic viscosity [η] is 0.01 dl / g or more, the form as a polymer is sufficiently maintained. Moreover, since a fluid fall is suppressed as it is 5.0 dl / g or less, coating property and applicability | paintability become favorable. This intrinsic viscosity [η] can be measured using a VMR-053 type automatic viscometer manufactured by Kouai Co., Ltd.

(H) Using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. The melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is 0 to 120 ° C.
This melting point (Tm) is measured by a method similar to the measurement method described in (C) above. The melting point (Tm) of 0 to 120 ° C. means that the oxidation-modified α-olefin polymer 2 is a crystalline resin. Melting | fusing point (Tm) becomes like this. Preferably it is 0-100 degreeC, More preferably, it is 10-90 degreeC, More preferably, it is 20-80 degreeC.
(I) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
Same as (C) above.
(J) Acid value is 0.01-50 mgKOH / g.
Same as (D) above.
(K) The acetone extract is less than 0.1% by mass.
Same as (E) above.

In the above-mentioned oxidation-modified α-olefin polymers 1 and 2 (hereinafter also referred to simply as “the oxidation-modified α-olefin polymer of the present invention”), the mesopentad fraction [mmmm] is 20 to 20%. It is preferable that it is 80 mol%, and 30-70 mol% is more preferable. When [mmmm] is 20 mol% or more, stickiness is suppressed, and when it is 80 mol% or less, the elastic modulus is not excessively high and becomes appropriate.
The above mesopentad fraction [mmmm] is based on the method proposed by A. Zambelli et al. In “Macromolecules, 6,925 (1973)”, and the methylene group and methine of the ¹³ C-NMR spectrum. It is a meso fraction in a pentad unit in a poly α-olefin molecular chain measured by a group signal. As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The ¹³ C-NMR spectrum can be measured using the same apparatus and conditions as the stereoregularity index value M4.

The oxidation-modified α-olefin polymer of the present invention preferably has a good isotactic structure, that is, the stereoregularity index value M2 is 40 mol% or more. The stereoregularity index value M2 is more preferably 45 to 90 mol%, still more preferably 50 to 85 mol%. When the stereoregularity index value M2 is 40 mol% or more, the formation of an atactic structure or a syndiotactic structure is suppressed, and an amorphous structure is suppressed, resulting in a highly crystalline structure. Deterioration of surface characteristics and strength reduction due to the above are suppressed.
This stereoregularity index value M2 is the T.W. Asakura, M .; Demura, Y .; It is a value obtained in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama. That is, M2 can be obtained by utilizing the fact that CH ₂ carbon at the side chain α-position derived from the higher α-olefin is split and observed in the ¹³ C NMR spectrum, reflecting the difference in stereoregularity. . The larger the value of M2, the higher the isotacticity.
The ¹³ C-NMR spectrum can be measured using the same apparatus and conditions as the stereoregularity index value M4.
Further, the stereoregularity index value M2 was calculated as follows. That is, six large absorption peaks based on the mixed solvent are observed at 127 to 135 ppm, and among these peaks, the fourth peak value from the low magnetic field side is set to 131.1 ppm, which is used as a reference for chemical shift. At this time, an absorption peak based on CH ₂ carbon at the α-position of the side chain is observed in the vicinity of 34 to 37 ppm. At this time, M2 is obtained using the following equation.
M2 = [(integral intensity of 36.2 to 35.3 ppm) / (integral intensity of 36.2 to 34.5 ppm)] × 100

In the method for producing an oxidation-modified α-olefin polymer of the present invention, an α-olefin polymer (α-olefin homopolymer or α-olefin copolymer) is used as a raw material polymer to be oxidized. It is done.
The α-olefin polymer preferably has 0.5 to 1.0 vinylidene groups per molecule as unsaturated end groups, and more preferably 0.55 to 1.0. By containing 0.5 to 1.0 vinylidene group, it can be efficiently oxidized and modified.

In general, the unsaturated end 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, in the method for quantifying unsaturated terminal groups by infrared absorption spectrum method, a vinyl group, a vinylidene group, unsaturated group, such as trans (vinylene) group, respectively, of the infrared absorption spectrum 910 cm ^-1, 888 cm ^-1 , From the absorption at 963 cm ⁻¹ .
The quantitative determination of vinylidene unsaturated groups by nuclear magnetic resonance spectroscopy is performed as follows.
The number when the unsaturated terminal group is a vinylidene group 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 α-olefin polymer used in the production method of the present invention uses a metallocene catalyst and is represented by the general formula (1).
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
It can manufacture by superposing | polymerizing 1 type, or 2 or more types chosen from the alpha-olefin represented by these.
In the present invention, among the metallocene catalysts, those using a transition metal compound in which a ligand forms a crosslinked structure via a crosslinking group are preferred, and among these, crosslinking via two crosslinking groups is preferred. A method of polymerizing one or more selected from α-olefins represented by the above general formula (1) using a metallocene catalyst obtained by combining a transition metal compound forming a structure and a cocatalyst is more preferable. preferable. Specifically, (A) the following general formula (I)

And (B) (B-1) a compound capable of reacting with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B-2) an aluminoxane. In the presence of a polymerization catalyst containing a component selected from: a method of polymerizing one or more selected from α-olefins represented by the general formula (1).
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.
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 a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a 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 Examples thereof include substituted silyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl group; silicon-substituted aryl groups such as 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 dialkyl phosphide groups, diethyl phosphide groups, dipropyl phosphide groups, dibutyl phosphide groups, dihexyl phosphide groups, dicyclohexyl phosphide groups, and dioctyl phosphide groups. A diaryl phosphide group such as a dibenzyl phosphide group, a diphenyl phosphide group, and a dinaphthyl phosphide group.

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, and dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, and 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, and 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; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Can be 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 Such as phosphine, propenyl phosphine, cyclohexenyl phosphine, etc. Dialkenyl phosphine in which two alkenyls are substituted with alkenyl phosphine or phosphine hydrogen atom; Trialkenyl phosphine in which alkenyl is substituted with three alkenyl hydrogen atoms; Aryl alkyl phosphine such as benzyl phosphine, phenylethyl phosphine, phenylpropyl phosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, Anthracenylphosphine, Phenanthonylphosphine; And an aryl phosphines such as tri (alkylaryl) phosphines a hydrogen atom alkylaryl has three substituents phosphine; a hydrogen atom fin alkylaryl two substituted di (alkylaryl) phosphines. Examples of the thioethers include the aforementioned 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. Examples of such a bridging group include a general formula

(D is carbon, silicon, germanium or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisylylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable from the viewpoint of higher polymerization activity. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the above general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I). X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I). Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ 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. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.

The transition metal compound having the double-bridged cyclopentadienyl derivative as a ligand is preferably a (1,2 ′) (2,1 ′) double-bridge ligand.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) ( 2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) ( 2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, ( 1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bi (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium Dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene)- Bis (indenyl) zirconium dichloride,

(1,2′-methylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, ( 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-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2 1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4- Isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ) Bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2 ' -Dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methyl Indenyl) 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′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis ( Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-isopropylindenyl) 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'-diphenylsilylene) (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-isopropylindenyl) 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-trimethylsilylindenyl) zirconium dichloride, (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′-methylcyclopentadiene) ) Zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) ) (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-dimethylcyclopentadienyl) (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′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-eth ) (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′-isopropylidene) (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) di Conium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopenta) Dienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadi) Enyl) 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) (3-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-butyl Clopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopenta Dienyl) 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 and these compounds The thing which substituted zirconium with titanium or hafnium can be mentioned. Of course, it is not limited to these. Further, it may be an analogous compound of another group or a lanthanoid series metal element.
Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). Although it can be used, those represented by the following general formula (III) or (IV) can be preferably used.

([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R ¹⁴ M ^3. )
[In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of An anion in which the group is bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is a group 5 to 15 element in the periodic table, preferably 13 to 15 in the periodic table. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, aryloxy groups having 6 to 20 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms, 1 carbon atom ˜20 acyloxy group, organic metalloid group, or C2-C20 heteroatom-containing hydrocarbon . Two or more may form a ring .f of .G ¹ ~G ^f indicating the group represents an integer of [(valence of central metal M ¹⁾ +1]), [Z ^{2] -} Represents a conjugate base of a Bronsted acid alone or a combination of Bronsted acid and Lewis acid having a logarithm (pKa) of the acid dissociation constant of -10 or less, or a conjugate base of an acid generally defined as a super strong acid. . In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. Cyclopentadienyl group, indenyl group or fluorenyl group, R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an integer of 1 to 3 in terms of ionic valences of [L ¹ -R ¹⁰ ] and [L ² ], a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine; thioethers such as tetrahydrothiophene, benzoic acid Examples include esters such as ethyl acid; nitriles such as acetonitrile and benzonitrile.
Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl. Group, ethylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like.
Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, and methallyl. .
Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn. Etc.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al. Is mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group and the like as an alkoxy group or an aryloxy group, Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-icosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromedium ) Phenyl group, bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, diphenyl boron, and the like.

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of −10 or less or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acids and Lewis acids include trifluoromethanesulfonic acid anions (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonate anion (FSO ₃ ) ⁻ , chlorosulfonate anion (ClSO ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅₎ ) ^-, fluorosulfonic acid Ani On / 5- fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - , and the like.

  Specific examples of the ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) include triethylammonium tetraphenylborate, tetraphenyl Tri-n-butylammonium borate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyl tetraphenylborate Diphenylammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl ruborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) ) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (penta Fluorophenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate Tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (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, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, Silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluoropheny ) Ferrocenium borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) tetraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. This compound of the component (B-1) may be used singly or in combination of two or more.
On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, an alkenyl group, an aryl group, or an arylalkyl group, or a halogen atom, and w represents an average degree of polymerization, Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method. For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There are methods such as crystal water contained in salt, water adsorbed on inorganic and organic substances and reaction with organoaluminum compound, (4) method of reacting tetraalkyldialuminoxane with trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in hydrocarbon solvents such as toluene. These aluminoxanes may be used alone or in combination of two or more.

The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit weight polymer becomes high, which is not practical.
When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical. As the catalyst component (B), (B-1) and (B-2) may be used alone or in combination of two or more.

As a polymerization catalyst in the production of the α-olefin polymer used in the present invention, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 It is an integer. ]
The compound represented by these is used.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used alone or in combination of two or more.

In the production of the α-olefin polymer used in the present invention, preliminary contact may be performed using the above-mentioned component (A), component (B) and component (C). The preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (B), but the method is not particularly limited, and a known method can be used. This preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component used as the promoter. Moreover, the molecular weight improvement effect is seen with the said effect by making (A) component and (B-2) component contact.
The preliminary contact temperature is usually about -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.
The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount may remain in the polymer.
In the preliminary contact, an olefinic compound may coexist. Examples of the olefin compound to be coexisted include ethylene or an α-olefin compound having 3 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. The amount of the olefinic compound added is about 0.5 to 20% by mass, preferably 1 to 15% by mass of the solvent used in the preliminary contact.

In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, glass fiber and the like. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, examples of the carrier other than the above include a magnesium compound represented by the general formula MgR ¹⁷ _x X ¹ _y represented by magnesium compounds such as MgCl ₂ and Mg (OC ₂ H ₅ ) ₂ , and complex salts thereof. it can. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

As the carrier used in the present invention, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) _{2 and the} like are preferable. Moreover, although the shape of a support | carrier changes with the kind and manufacturing method, an average particle diameter is 1-300 micrometers normally, Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there. When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease.
The specific surface area and pore volume of the support can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983). )reference).
Further, when the carrier is an inorganic oxide carrier, it is usually desirable to use it after baking at 150 to 1000 ° C, preferably 200 to 800 ° C.
When at least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .

  The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (1) At least one of the component (A) and the component (B) is mixed with the carrier. (2) A method in which the support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (3) the support and (A (4) Method of reacting component and / or component (B) with an organoaluminum compound or halogen-containing silicon compound, (4) (B) component or (B) A) a method of mixing with the component, (5) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, and (6) in the contact reaction of the component (A) with the component (B). A method of allowing a carrier to coexist can be used. In the above reactions (4), (5) and (6), an organoaluminum compound (C) can also be added.

In the present invention, when contacting the above (A), (B), and (C), a catalyst may be prepared by irradiating elastic waves. Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for polymerization after once removing the solvent and taken out as a solid, or may be used for polymerization as it is. Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within a polymerization system.
For example, at least one of the component (A) and the component (B), a support, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa, and the temperature is -20 to 200 ° C. A method of preliminarily polymerizing for about 1 minute to 2 hours to produce catalyst particles can be used.

In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio. When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio.
In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500. If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there.
The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50-500 m ² / g. When the average particle size is 2 μm or more, increase of fine powder in the polymer is suppressed, and when it is 200 μm or more, increase of coarse particles in the polymer is suppressed. Moreover, the fall of activity is suppressed as a specific surface area is 20 m < ² > / g or less, and the fall of the bulk density of a polymer is suppressed as it is 1000 m < ² > / g or less.
In the catalyst used in the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. When the amount of transition metal is within the above range, a decrease in activity is suppressed.
In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.

The α-olefin polymer used in the present invention is produced by homopolymerizing or copolymerizing an α-olefin using the above-described polymerization catalyst. In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legal is particularly preferred.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , preferably from raw material monomer / component (A) (molar ratio). Furthermore, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is preferably from normal pressure to 20 MPa (G), particularly preferably from normal pressure to 10 MPa (G).
Examples of the method for adjusting the molecular weight of the polymer include selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen. When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, the reaction can be carried out in the absence of a solvent.

In the method for producing the oxidation-modified α-olefin polymer of the present invention, the acid value of the α-olefin polymer reaches 0.01 to 50 mgKOH / g in the presence of molecular oxygen and / or ozone-containing gas. Oxidize until. By using the α-olefin polymer satisfying the following conditions, the oxidation-modified α-olefin polymer of the present invention can be obtained.
For the production of the oxidation-modified α-olefin polymer 1, the general formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
And an α-olefin polymer satisfying the following (L) to (N) is used.
(L) Stereoregularity index value M4 is 75 mol% or less.
(M) The styrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method is 500 to 5,000,000, and the molecular weight distribution (Mw / Mn) is 4.0 or less.
(N) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
These are the same as (A), (B) and (C), respectively.

For the production of the oxidation-modified propylene polymer 2, the general formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An α-olefin polymer satisfying the following (O) to (R) is used.
(O) Stereoregularity index value M4 is 75 mol% or less.
(P) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 5.0 dl / g.
(Q) Using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. under a nitrogen atmosphere for 5 minutes, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. The melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is 0 to 120 ° C.
(R) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
These are the same as (A), (G), (H) and (C), respectively.

At the time of the oxidation reaction with a gas containing molecular oxygen or ozone, a radical initiator may coexist as necessary. The radical initiator is not particularly limited, and is appropriately selected from conventionally known radical initiators such as various organic peroxides and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Of these, organic peroxides are preferred.
Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t- Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Α, α′bis (t-butylperoxy) diisopropylbenzene Oxides, peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxyoct , Alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di Examples thereof include peroxycarbonates such as -sec-butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The radical initiator may be diluted with water, an inert solvent, or an emulsion solution of an inert inorganic compound. Specific examples of the inert solvent include octane, decane, xylene, and silicone oil. Examples of the inert inorganic compound include silica gel, alumina, calcium carbonate, and aluminum hydroxide. By performing this dilution, the risk of the radical initiator can be reduced. Moreover, since the solid radical initiator has a specific gravity different from that of the base polymer, classification is likely to occur at the time of feeding, but there is also an effect of suppressing this.
There is no restriction | limiting in particular as the usage-amount of the said radical initiator, According to the desired physical property of the target oxidation modification | denaturation alpha-olefin type polymer, it selects suitably. The usage-amount of a radical initiator is about 0.01-10 mass parts normally with respect to 100 mass parts of alpha olefin polymers, Preferably it is the range of 0.01-5 mass parts.

In the present invention, for example, the α-olefin polymer is used at a temperature of 100 to 300 ° C., preferably 120 to 200 ° C., for about 0.01 to 10 hours, using a roll mill, a Banbury mixer, an extruder, or the like. Oxidation treatment of an α-olefin polymer by a method in which a gas containing molecular oxygen and / or ozone is reacted by melting and kneading in the presence of a gas containing molecular oxygen and / or ozone. it can.
The oxidation-modified α-olefin polymer of the present invention is mainly useful as a substitute for a wax component, and in particular, a release agent and an ink component for toner, a resin modifier, an adhesive component, an adhesive component, and a lubricating oil. It is useful as a component, organic-inorganic composite material, heat storage material, modifier for fuel oil such as light oil, asphalt modifier, and high-performance wax.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
(1) Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (complex a)
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 tetrahydrofuran (THF) and brought 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-butyltylium (n-BuLi) (1.54 mol / L, 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)

(2) Production of α-olefin polymer (I) A heat-dried stainless steel autoclave with an internal volume of 1 L, linearene 18 (trade name, Idemitsu Kosan Co., Ltd., 1-octadecene) 400 ml, triisobutylaluminum 0 0.5 mmol, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylindenyl) zirconium dichloride (complex a) 0.5 μmol prepared in (1) above, and methylaniline 4.0 μmol of nitrotetrakis (perfluorophenyl) borate was added.
Further, 0.15 MPa of hydrogen was introduced, and polymerization was performed at a polymerization temperature of 90 ° C. for 240 minutes. After completion of the polymerization reaction, the reaction product was precipitated with acetone, and then heated and dried under reduced pressure to obtain 220 g of an α-olefin polymer (I).
About the obtained alpha-olefin type polymer (I), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(3) Production of Oxidation Modified α-Olefin Polymer (Ia) Produced in (2) above in a Separa glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade. 130 g of α-olefin polymer (I) was charged, and the temperature was raised to 180 ° C. while stirring at a rotational speed of 400 rpm. Next, dry air was introduced for 5 hours through an air blowing tube. Thereafter, the blowing of air was stopped, purged with nitrogen, and then cooled to room temperature to obtain 128 g of light yellow to white oxidation-modified α-olefin polymer (Ia).
The physical properties of the obtained oxidation-modified α-olefin polymer (Ia) were measured by the method described above. Moreover, peelability was evaluated by the following method. The results are shown in Table 1.

<Peelability>
An aluminum plate is divided into 10 square grids (2 × 5 squares) each having a size of 1 cm × 1 cm, and the molten oxidatively modified α-olefin polymer is 0.5 mm thick. It was applied with. After solidifying for 3 hours, “cellophane tape” manufactured by Nichiban Co., Ltd. was brought into close contact, and then peeled off. Check the number of squares where the oxidation-modified α-olefin polymer was peeled off and the number of remaining squares in the grid on the aluminum plate when the tape was peeled off. Calculated.

Example 2
(1) Production of α-olefin polymer (II) A heat-dried stainless steel autoclave with an internal volume of 1 L was subjected to linearene 2024 (trade name, manufactured by Idemitsu Kosan Co., Ltd., α-olefin having 18 to 26 carbon atoms). Mixture) 400 ml, triisobutylaluminum 0.5 mmol, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride prepared in Example 1 (1) (Complex a) 1 μmol and dimethylanilinium tetrakispentafluorophenylborate 4 μmol were added.
Further, 0.15 MPa of hydrogen was introduced, and polymerization was performed at a polymerization temperature of 90 ° C. for 240 minutes. After completion of the polymerization reaction, the reaction product was precipitated with acetone, and then heated and dried under reduced pressure to obtain 180 g of an α-olefin polymer (II).
About the obtained alpha-olefin type polymer (II), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(2) Production of oxidation-modified α-olefin polymer (II-a) α produced in (1) above in a separa type glass reactor (500 ml) equipped with an air blowing tube, an exhaust port and a thermometer. -130 g of olefin polymer (II) was charged and heated to 180 ° C while stirring at a rotational speed of 400 rpm. Next, dry air was introduced for 5 hours through an air blowing tube. Thereafter, the blowing of air was stopped, purged with nitrogen, and then cooled to room temperature to obtain 125 g of a light yellow to white solid oxidation-modified α-olefin polymer (II-a).
About the obtained oxidation modification | denaturation alpha-olefin type polymer (II-a), the physical property was measured by the method mentioned above. The results are shown in Table 1.

Example 3
(1) Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-trimethylsilylmethyl-indenyl) indenylzirconium dichloride (complex b)
Under a nitrogen stream, 50 ml of ether and 3.5 g (10.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bisindene were added to a Schlenk bottle having an internal volume of 200 ml, and this was added at −78 ° C. The n-BuLi hexane solution (1.60 mol / L, 12.8 ml) was added dropwise. After stirring for 8 hours at room temperature, the ether was distilled off. 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 THF, and 1.4 ml of iodomethyltrimethylsilane was added dropwise thereto at room temperature. Next, it hydrolyzed with 10 mL of water, and after extracting 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. Then, the mixture was raised to room temperature and stirred for 3 hours, and then 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, and the residue was washed with 50 ml of hexane and then recrystallized with 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, trimethylsilyl, 9H), 0.89, 0.86, 1.03, 1.06 (s, dimethylsilylene, 12H), 2.20, 2.65 (d, methylene, 2H), 6.99 (s, CH, 1H), 7.0-7.8 (m, Ar-H, 8H)

(2) Production of α-olefin polymer (III) Into a 1 L stainless steel autoclave heated and dried, Linearlen 2024 (trade name, manufactured by Idemitsu Kosan Co., Ltd., mixed with α-olefin having 18 to 26 carbon atoms) Body) 400 ml, triisobutylaluminum 0.5 mmol, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-trimethylsilylmethyl-indenyl) indenylzirconium dichloride (complex) prepared in (1) above b) 1 μmol and 4 μmol of dimethylanilinium tetrakispentafluorophenylborate were added.
Further, 0.15 MPa of hydrogen was introduced, and polymerization was performed at a polymerization temperature of 80 ° C. for 240 minutes. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure, to obtain 190 g of an α-olefin polymer (III).
About the obtained alpha-olefin type polymer (III), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(3) Production of Oxidation Modified α-Olefin Polymer (III-a) It was produced in the above (2) in a Separa type glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade. 130 g of α-olefin polymer (III) was charged, and the temperature was raised to 180 ° C. while stirring at a rotational speed of 400 rpm. Next, dry air was introduced for 5 hours through an air blowing tube. Thereafter, the blowing of air was stopped, purged with nitrogen, and then cooled to room temperature to obtain 130 g of an oxidation-modified α-olefin polymer (III-a).
About the obtained oxidation modification | denaturation alpha-olefin type | system | group polymer (III-a), the physical property was measured by the method mentioned above. The results are shown in Table 1.

Example 4
(1) Synthesis of (1,1′-Me ₂ SiSiMe ₂ ) (2,2 ′-(i-Pr) ₂ NB) bis (indenyl) zirconium dichloride 1,1′-Me ₂ SiSiMe ₂ ) (2,2 '-(I-Pr) ₂ NB) bis (indene) 1.4 g (3.1 mmol) was dissolved in 30 ml of ether, and 3.9 ml of a hexane solution of n-butyllithium (1.58 mol / L) at −78 ° C. Was added dropwise and stirred at room temperature for 8 hours. After the solvent was distilled off under reduced pressure, the resulting solid was washed with 30 ml of hexane to obtain a dilithio salt as a pale orange solid.
This was suspended in 20 ml of toluene, and 0.72 g (3.1 mmol) of zirconium tetrachloride suspended in 10 ml of toluene was added dropwise at 0 ° C. The mixture was stirred overnight at room temperature, the precipitate was filtered off, the solvent was concentrated in half, and 5 ml of hexane was added to give (1,1′-Me ₂ SiSiMe ₂ ) (2,2 ′-(i- 0.29 g of Pr) ₂ NB) bis (indenyl) zirconium dichloride was obtained.

(2) Production of α-olefin polymer (IV) In a 1 L autoclave that has been heat-dried, 400 ml of linearene 2024 (trade name, manufactured by Idemitsu Kosan Co., Ltd., a mixture of α-olefins having 18 to 26 carbon atoms), Triisobutylaluminum 0.5 mmol, (1,1′-Me ₂ SiSiMe ₂ ) (2,2 ′-(i-Pr) ₂ NB) bis (indenyl) zirconium dichloride 1 μmol, dimethylanilinium synthesized in (1) above Tetrakis pentafluorophenyl borate (4 μmol) was added, and 0.2 MPa of hydrogen was further introduced, followed by polymerization at a polymerization temperature of 80 ° C. for 240 minutes. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 213 g of a higher α-olefin polymer.
About the obtained alpha-olefin type polymer (IV), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(3) Production of Oxidation Modified α-Olefin Polymer (IV-a) It was produced in the above (2) in a Separa type glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade. 130 g of α-olefin polymer (IV) was charged, and the temperature was raised to 180 ° C. while stirring at a rotational speed of 400 rpm. Next, dry air was introduced for 5 hours through an air blowing tube. Thereafter, the blowing of air was stopped, purged with nitrogen, and then cooled to room temperature to obtain 130 g of an oxidation-modified α-olefin polymer (IV-a).
About the obtained oxidation modification | denaturation alpha-olefin type polymer (IV-a), the physical property was measured by the method mentioned above. The results are shown in Table 1.

  From the above results, it can be seen that the oxidatively modified α-olefin polymers of the examples have improved peelability due to oxidation treatment. For this reason, when the oxidation-modified α-olefin polymer of the example is applied to a release agent for toner and an ink component, it is expected that the adhesive strength is improved.

  The oxidation-modified α-olefin polymer of the present invention is mainly useful as a substitute for a wax component, and in particular, a release agent and an ink component for toner, a resin modifier, an adhesive component, an adhesive component, and a lubricating oil. It is useful as a component, organic-inorganic composite material, heat storage material, modifier for fuel oil such as light oil, asphalt modifier, and high-performance wax. In addition to the above, cosmetics (lipsticks, pomades, creams, eyebrows, eye shadows, tics, packs, shampoos, rinses), medical (ointments, suppositories, emulsions, surgical dressings, poultices), stationery (crayons) , Crepes, pencils, carbon paper), for glazing (wood, furniture, leather, automobiles, paper, confectionery, textiles), for candles, skin cream, textile oils, confectionery materials, model materials, sculpture materials, leather finishing materials, Insulation material Wax paper, musical instruments, grafting wax printing, mold article manufacturing Fruit wax coating, various greases, ski wax, wax dyeing, polish, car wax, metalworking oil, rubber anti-aging agent, tire, adhesion Agent, processed paper, heat storage agent, agricultural chemical, fertilizer, abrasive (metal, stainless steel), oil lubricant <grease, mold release agent, paint), dental dental wax, fixed use (lens, embedding), As a modifier to obtain polyolefins with improved dispersion characteristics, compatibility characteristics, mechanical properties, and fluidity with inorganic fillers, dyes, toners, polar polymers, polar waxes, wood flour, etc., and surface treatment of polyolefins It is useful as a component such as an agent, a primer treatment agent and a coating agent component.

Claims (6)

General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An oxidation-modified α-olefin polymer characterized in that the α-olefin polymer represented by the formula (1) is oxidized and modified, and satisfies the following (A) to (E).
(A) Stereoregularity index value M4 is 75 mol% or less.
(B) The styrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method is 500 to 5,000,000, and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn )) Is 4.0 or less.
(C) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
(D) Acid value is 0.01-50 mgKOH / g.
(E) The acetone extract is less than 0.1% by mass. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The polymer of α-olefin represented by the formula (1) is a polymer having 0.5 to 1.0 vinylidene groups per molecule, Coalescence. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An oxidation-modified α-olefin polymer characterized by being obtained by oxidation-modifying a polymer of α-olefin represented by the following formula and satisfying the following (F) to (K).
(F) Stereoregularity index value M4 is 75 mol% or less.
(G) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 5.0 dl / g.
(H) Using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. The melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is 0 to 120 ° C.
(I) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.
(J) Acid value is 0.01-50 mgKOH / g.
(K) The acetone extract is less than 0.1% by mass. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The polymer of the α-olefin represented by the formula (1) is a polymer having 0.5 to 1.0 vinylidene groups per molecule. Coalescence. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
The α-olefin polymer formed by polymerizing the α-olefin represented by the formula (1) and the following (L) to (N) is contacted with molecular oxygen and / or ozone-containing gas at 100 to 300 ° C. 2. The method for producing an oxidation-modified α-olefin polymer according to claim 1, wherein the oxidation treatment is performed until the acid value reaches 0.01 to 50 mg KOH / g.
(L) Stereoregularity index value M4 is 75 mol% or less.
(M) The weight average molecular weight (Mw) in terms of styrene measured by gel permeation chromatography (GPC) is 500 to 5,000,000, and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn )) Is 4.0 or less.
(N) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), and the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less. General formula (1)
_{CH 2 = CH-C n H} 2n + 1 (1)
(In the formula, n is an integer of 8 or more.)
An α-olefin polymer satisfying the following (O) to (R) is brought into contact with molecular oxygen and / or ozone-containing gas at 100 to 300 ° C. The method for producing an oxidation-modified α-olefin polymer according to claim 3, wherein the oxidation treatment is performed until the acid value reaches 0.01 to 50 mgKOH / g.
(O) Stereoregularity index value M4 is 75 mol% or less.
(P) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 5.0 dl / g.
(Q) Using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. under a nitrogen atmosphere for 5 minutes, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. The melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is 0 to 120 ° C.
(R) There is one melting peak obtained in the melting point (Tm) measurement by a differential scanning calorimeter (DSC), the melting endotherm (ΔH) calculated from the area of the melting peak is 20 J / g or more, and The full width at half maximum is 10 ° C. or less.