JP5466501B2 - Oxidation-modified propylene polymer and process for producing the same - Google Patents

Description

  The present invention relates to an oxidation-modified propylene homopolymer or an oxidation-modified propylene copolymer (hereinafter, both may be collectively referred to as “oxidation-modified propylene polymer”) and a method for producing the same. Specifically, the present invention relates to a sealant having high adhesiveness with a plastic material, paper, wood or the like, or a polyolefin modifier such as an inorganic filler, a dye, a toner, a polar polymer, a polar wax, a wood powder and the like. Oxidation-modified propylene-based heavy resins useful as modifiers for obtaining polyolefins with improved dispersion characteristics, compatibility characteristics, mechanical properties, and fluidity, and as surface treatment agents, primer treatment agents, and coating agent components for polyolefins. The present invention relates to a polymer, a method for efficiently producing this oxidation-modified propylene-based polymer, and a primer resin for polyolefin comprising the oxidation-modified propylene-based 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 olefin polymer obtained by oxidizing the above-mentioned polyolefin with oxygen or ozone is a modification of various resins. It is used for applications such as a texture agent and an adhesion-imparting agent.
On the other hand, low-order polypropylene obtained by using a metallocene catalyst is blended with polypropylene obtained by a magnesium-titanium catalyst to control the elastic modulus of polypropylene, as a heat seal layer in a multilayer film, etc. Applications are expected, but higher strength and higher adhesion are required.
Among various polyolefin modification methods, oxidation with oxygen or ozone (see, for example, Patent Documents 1 and 2) is less expensive than modification with an unsaturated monomer having a functional group. In the modified product, it is necessary to add a peroxide at the same time in order to promote the oxidation reaction by oxygen. However, even when peroxide is added, the modification rate is insufficient. Moreover, although the method of reduce | restoring a vinyl group containing polyolefin with a borohydride salt is disclosed as a method of modifying | denaturing polyolefin (for example, refer patent document 3), there exists a subject in cost or modification | denaturation efficiency.

Japanese Patent No. 3432511 Japanese Patent No. 2958895 JP 2006-124565 A

  The present invention has been made in view of the above circumstances, and has a high adhesion, high strength and soft oxidation-modified propylene polymer, a method for efficiently producing the same, and a polyolefin primer comprising the oxidation-modified propylene polymer. The object is to provide a resin.

As a result of intensive studies, the present inventors have achieved the above object by using an oxidatively modified propylene polymer having a specific property, and converting a propylene polymer having a specific property into molecular oxygen and / or It has been found that the oxidation-modified propylene-based polymer can be easily produced by oxidizing at a specific temperature in the presence of an ozone-containing gas. The present invention has been completed based on such findings.
That is, the present invention provides the following oxidation-modified propylene homopolymer, oxidation-modified propylene-based copolymer, a production method thereof, and a primer resin for polyolefins comprising the same.
1. An oxidation-modified propylene homopolymer satisfying the following (a) to (d).
(A) [mmmm] = 20-80 mol%
(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
(C) Acid value = 0.2-40 mgKOH / g
(D) An acetone soluble part is 0.5 mass% or less.
2. An oxidation-modified propylene homopolymer satisfying the following (e) to (i).
(E) [mmmm] = 20-80 mol%
(F) [rrrr] / (1- [mmmm]) ≦ 0.1
(G) [mm] × [rr] / [mr] ² ≦ 2.2
(H) Acid value = 0.2-40 mg KOH / g
(I) Acetone soluble part is 0.5 mass% or less.
3. An oxidation-modified propylene homopolymer satisfying the following (j) to (p).
(J) [mmmm] = 20-80 mol%
(K) [rrrr] / (1- [mmmm]) ≦ 0.1
(L) [mm] × [rr] / [mr] ² ≦ 2.2
(M) Weight average molecular weight (Mw) = 10,000 to 200,000
(N) Molecular weight distribution (Mw / Mn) ≦ 4.0
(O) Acid value = 0.2-40 mg KOH / g
(P) Acetone soluble part is 0.5 mass% or less.
4). ^{In the 1} H-NMR spectrum, the ratio of the integrated value of 4.6 to 5.3 ppm (vinyl value) to the integrated value of the peak of 0.75 to 2.00 ppm is 0.02 to 1.00%. 4. The oxidation-modified propylene homopolymer according to any one of 3 above.
5. An oxidation-modified propylene-based copolymer containing propylene units and ethylene units and / or 1-butene units in an amount of 1 to 10 mol% and satisfying the following (q) to (u).
(Q) Stereoregularity index ([mm]) = 50 to 90 mol%
(R) Weight average molecular weight (Mw) = 10,000 to 200,000
(S) Molecular weight distribution (Mw / Mn) ≦ 4.0
(T) Acid value = 0.2-40 mgKOH / g
(U) Acetone soluble part is 0.5 mass% or less.
6). ^{In 1} H-NMR spectrum, the ratio of the integrated value of 4.6 to 5.3 ppm (vinyl value) to the integrated value of the peak of 0.75 to 2.00 ppm is 0.02 to 1.00%. The oxidation-modified propylene copolymer as described.

7). The oxidation according to 1 above, wherein a propylene homopolymer satisfying the following (v) and (w) is oxidized at 100 to 300 ° C. in the presence of molecular oxygen and / or ozone-containing gas: A method for producing a modified propylene homopolymer.
(V) [mmmm] = 20-80 mol%
(W) Molecular weight distribution (Mw / Mn) ≦ 4.0
8). 3. The oxidation according to 2 above, wherein a propylene homopolymer satisfying the following (x) to (z) is oxidized at 100 to 300 ° C. in the presence of molecular oxygen and / or ozone-containing gas: A method for producing a modified propylene homopolymer.
(X) [mmmm] = 20-80 mol%
(Y) [rrrr] / (1- [mmmm]) ≦ 0.1
(Z) [mm] × [rr] / [mr] ² ≦ 2.2
9. 3. The oxidation according to 3 above, wherein a propylene homopolymer satisfying the following (A) to (E) is oxidized at 100 to 300 ° C. in the presence of molecular oxygen and / or ozone-containing gas: A method for producing a modified propylene homopolymer.
(A) [mmmm] = 20-80 mol%
(B) [rrrr] / (1- [mmmm]) ≦ 0.1
(C) [mm] × [rr] / [mr] ² ≦ 2.2
(D) Weight average molecular weight (Mw) = 10,000 to 200,000
(E) Molecular weight distribution (Mw / Mn) ≦ 4.0
10. In the ¹ H-NMR spectrum, the propylene homopolymer has a ratio of the integral value of 4.6 to 5.3 ppm (vinyl value) to the integral value of the peak of 0.75 to 2.00 ppm is 0.02 to 1.00. The manufacturing method of the oxidation modification propylene homopolymer in any one of said 7-9 which is%.
11. Presence of molecular oxygen and / or ozone-containing gas containing propylene unit and ethylene unit and / or 1-butene unit in 1 to 10 mol% and satisfying the following (F) to (H) 6. The method for producing an oxidatively modified propylene copolymer as described in 5 above, wherein oxidation treatment is performed at 100 to 300 ° C.
(F) Stereoregularity index ([mm]) = 50 to 90 mol%
(G) Weight average molecular weight (Mw) = 10,000 to 200,000
(H) Molecular weight distribution (Mw / Mn) ≦ 4.0
12 In the ¹ H-NMR spectrum of the propylene copolymer, the ratio of the integral value of 4.6 to 5.3 ppm (vinyl value) to the integral value of the peak of 0.75 to 2.00 ppm is 0.02 to 1. 12. The method for producing an oxidation-modified propylene copolymer as described in 11 above, which is 00%.
13. Primer resin for polyolefin which consists of an oxidation modification propylene homopolymer in any one of said 1-3.
14 6. A primer resin for polyolefin comprising the oxidation-modified propylene-based copolymer as described in 5 above.

  The oxidation-modified propylene-based polymer of the present invention is useful as a sealant having high adhesion or as a modifier that gives a polyolefin having improved compatibility with inorganic fillers, etc. For example, an oxidation-modified propylene-based polymer can be produced without using dangerous substances such as peroxides and expensive reagents, eliminating the need to remove unreacted components, and reducing the cost of the process. The oxidation-modified propylene polymer of the present invention is excellent in the balance between performance and economy as a polyolefin primer.

  The oxidation-modified propylene homopolymer 1 of the present invention satisfies the following (a) to (d). The following (a) to (d) can be adjusted according to the selection of the catalyst and reaction conditions when producing the propylene homopolymer before oxidative modification. The same applies to (e) to (i) and (j) to (p) described later.

(A) [mmmm] = 20-80 mol%
The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic meso fraction [rmrm] described later are proposed in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. The meso fraction, the racemic fraction, and the racemic meso-racemic meso fraction in the pentad unit in the polypropylene molecular chain are measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the prepared method. As the mesopentad fraction [mmmm] increases, the stereoregularity increases. Further, the mesotriad fraction [mm], the racemic triad fraction [rr] and the mesoracemi fraction [mr] described later were also calculated by the above method.
When the mesopentad fraction [mmmm] of the oxidation-modified propylene homopolymer 1 of the present invention is 20 mol% or more, stickiness is suppressed. Become. This mesopentad fraction [mmmm] is preferably 30 to 60 mol%, more preferably 40 to 60 mol%.
The measurement of the ¹³ C-NMR spectrum can be carried out with the following apparatus and conditions in accordance with the attribution of the peak proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli et al. it can.

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

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

(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
In the oxidation-modified propylene homopolymer 1 of the present invention, when the molecular weight distribution (Mw / Mn) is 4.0 or less, the occurrence of stickiness is suppressed.
This molecular weight distribution (Mw / Mn) can be determined by measuring the mass average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC) method with the following apparatus and conditions. .

<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) Acid value = 0.2-40 mgKOH / g
When the acid value is 0.2 mgKOH / g or more, the oxidized modified propylene homopolymer 1 has sufficient adhesive strength, and when it is 40 mgKOH / g or less, the flexibility of the oxidized modified propylene homopolymer 1 is increased. Is enough. The acid value is preferably 0.5 to 35 mgKOH / g, more preferably 1.0 to 25 mgKOH / g. The acid value is measured according to the total acid value measuring method described in JIS K 2501-1980.
(D) An acetone soluble part is 0.5 mass% or less.
The acetone soluble part is prepared by dissolving 0.5 g of sample in 10 ml of toluene, reprecipitating in 50 ml of acetone, filtering the precipitate, and drying the filtrate at 25 ° C. under reduced pressure. Say percentage. The acetone soluble part is preferably 0.1% by mass or less, more preferably 0.05% by mass or less. When the acetone soluble part is 0.5% by mass or less, generation of odor is suppressed, and even when it comes into contact with the human body, there is no adverse effect, and stickiness is suppressed, so that surface characteristics are improved. .

The oxidation-modified propylene homopolymer 2 of the present invention satisfies the following (e) to (i).
(E) [mmmm] = 20-80 mol%
Same as (a) above.
(F) [rrrr] / (1- [mmmm]) ≦ 0.1
The value of [rrrr] / (1- [mmmm]) is obtained from the above pentad unit fraction, and is an index representing the uniformity of the regularity distribution of the oxidatively modified propylene homopolymer 2. As this value increases, the distribution of regularity spreads, resulting in a mixture of highly ordered polypropylene and atactic polypropylene, like conventional polypropylene produced using existing catalyst systems, resulting in increased stickiness and reduced transparency.
When [rrrr] / (1- [mmmm]) is 0.1 or less in the oxidation-modified propylene homopolymer 2, stickiness is suppressed.
(G) [mm] × [rr] / [mr] ² ≦ 2.2
When the value of [mm] × [rr] / [mr] ^{2 in} the oxidation-modified propylene homopolymer 2 is 2.2 or less, a decrease in transparency is suppressed, and the balance between flexibility and elastic recovery rate is good. Become. [Mm] × [rr] / [mr] ² is preferably in the range of 0.5 to 2.2, more preferably 1.0 to 2.2.
(H) Acid value = 0.2-40 mg KOH / g
Same as (c) above.
(I) Acetone soluble part is 0.5 mass% or less.
Same as (d) above.

The oxidation-modified propylene homopolymer 3 of the present invention satisfies the following (j) to (p).
(J) [mmmm] = 20-80 mol%
Same as (a) above.
(K) [rrrr] / (1- [mmmm]) ≦ 0.1
The same as (f) above.
(L) [mm] × [rr] / [mr] ² ≦ 2.2
Same as (g) above.
(M) Weight average molecular weight (Mw) = 10,000 to 200,000
In the oxidation-modified propylene homopolymer 3, when the weight average molecular weight is 10,000 or more, the occurrence of stickiness is suppressed. Moreover, since the viscosity of a melt degree will fall that a weight average molecular weight is 200,000 or less, workability | operativity at the time of applying to various uses becomes favorable.
(N) Molecular weight distribution (Mw / Mn) ≦ 4.0
Same as (b) above.
(O) Acid value = 0.2-40 mg KOH / g
Same as (c) above.
(P) Acetone soluble part is 0.5 mass% or less.
Same as (d) above.

The oxidation-modified propylene-based copolymer of the present invention satisfies the following (q) to (u). The following (q) to (u) can be adjusted according to the selection of the catalyst and the reaction conditions when producing the propylene-based copolymer before oxidative modification.
(Q) Stereoregularity index ([mm]) = 50 to 90 mol%
Stereoregularity index ([mm]) is used the JEOL Ltd. JNM-EX400 type device, the ¹³ C-NMR spectra were measured in the same manner as the above conditions, the propylene chain meso triad ([mm ]) The value obtained by measuring the fraction.
The larger the value of the stereoregularity index ([mm]), the higher the stereoregularity.
In the propylene-based copolymer of the present invention, the stereoregularity index ([mm]) is preferably 50 to 80 mol%. When the stereoregularity index ([mm]) is 50 mol% or more, the occurrence of stickiness is suppressed, and when it is 90 mol% or less, the secondary workability is improved.
(R) Weight average molecular weight (Mw) = 10,000 to 200,000
The same as (m) above.
(S) Molecular weight distribution (Mw / Mn) ≦ 4.0
Same as (b) above.
(T) Acid value = 0.2-40 mgKOH / g
Same as (c) above.
(U) Acetone soluble part is 0.5 mass% or less.
Same as (d) above.

In the oxidation-modified propylene polymer of the present invention such as the above-mentioned oxidation-modified propylene homopolymers 1 to 3 and the oxidation-modified propylene copolymer, [rmrm] is preferably 1.0 mol% or more. When [rmrm] is 1.0 mol% or more, the randomness of the stereoregularity of the oxidation-modified propylene polymer increases, and the balance between low-temperature processability and adhesion is improved.
The oxidation-modified propylene-based polymer of the present invention is obtained by using a differential scanning calorimeter (DSC), holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve is preferably a crystalline resin having a temperature of 60 to 120 ° C. The melting endotherm (ΔH) obtained by calculation from the area of the melting peak obtained in the measurement of the melting point (Tm) is preferably 5 to 80 J / g, more preferably 10 to 60 J / g. is there.
In the ¹ H-NMR spectrum of the oxidation-modified propylene polymer of the present invention, the ratio of the integral value of 4.6 to 5.3 ppm (vinyl value) to the integral value of the peak of 0.75 to 2.00 ppm is 0.00. It is preferable that it is 02 to 1.00%, and 0.03 to 0.90 is more preferable. When the vinyl value is 0.02% or more, the efficiency of the oxidation reaction is good, and when it is 1.00% or less, crosslinking during the oxidation reaction is suppressed.

In the method for producing an oxidation-modified propylene homopolymer and an oxidation-modified propylene-based copolymer of the present invention, a propylene homopolymer, a propylene unit, an ethylene unit, and / or a 1-butene unit are used as a raw material polymer to be oxidized. A propylene-based copolymer containing is used. Hereinafter, these may be referred to as “propylene polymers”.
The propylene polymer used in the production method of the present invention can be produced by homopolymerizing propylene using a metallocene catalyst or by copolymerizing propylene with ethylene and / or 1-butene.
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 in which propylene is homopolymerized or copolymerized using a metallocene catalyst obtained by combining a transition metal compound forming a structure and a cocatalyst is more 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. And a method of homopolymerizing or copolymerizing propylene in the presence of a polymerization catalyst containing a component selected from:
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 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 biscyclopentadienyl derivative as a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged 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 a non-coordinating anion, that is, a Bronsted acid alone having a pKa of −10 or less or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acid and Lewis acid include a trifluoromethanesulfonate anion ( 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₎ ^-, anion fluorosulfonic acid / 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 propylene-based 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 propylene-based polymer used in the present invention, preliminary contact may be performed using the above-described 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, (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 propylene-based polymer used in the present invention is produced by homopolymerizing or copolymerizing propylene 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. In addition, depending on the polymerization method, the reaction can be performed without a solvent.

In the method for producing an oxidation-modified propylene polymer of the present invention, the propylene polymer is oxidized in the presence of molecular oxygen and / or ozone-containing gas. By using a propylene polymer satisfying the following conditions, the oxidation-modified propylene polymer of the present invention can be obtained.
For the production of the oxidation-modified propylene polymer 1, a propylene homopolymer satisfying the following (v) and (w) is used.
(V) [mmmm] = 20-80 mol%
(W) Molecular weight distribution (Mw / Mn) ≦ 4.0
These are the same as the above (a) and (b), respectively.
For the production of the oxidation-modified propylene polymer 2, a propylene homopolymer satisfying the following (x) to (z) is used.
(X) [mmmm] = 20-80 mol%
(Y) [rrrr] / (1- [mmmm]) ≦ 0.1
(Z) [mm] × [rr] / [mr] ² ≦ 2.2
These are the same as (a), (f) and (g), respectively.
Propylene homopolymer satisfying the following (A) to (E) is used for the production of the oxidation-modified propylene polymer 3.
(A) [mmmm] = 20-80 mol%
(B) [rrrr] / (1- [mmmm]) ≦ 0.1
(C) [mm] × [rr] / [mr] ² ≦ 2.2
(D) Weight average molecular weight (Mw) = 10,000 to 200,000
(E) Molecular weight distribution (Mw / Mn) ≦ 4.0
These are the same as (a), (f), (g), (m) and (b), respectively.
In the production of the above-mentioned oxidation-modified propylene copolymer, a propylene copolymer containing 1 to 10 mol% of a propylene unit, an ethylene unit and / or a 1-butene polymer unit and satisfying the following (F) to (H) is satisfied. A polymer is used.
(F) Stereoregularity index ([mm]) = 50 to 90 mol%
(G) Weight average molecular weight (Mw) = 10,000 to 200,000
(H) Molecular weight distribution (Mw / Mn) ≦ 4.0
These are the same as (q), (m) and (b), respectively.
In the ¹ H-NMR spectrum, the propylene-based polymer used in the present invention has an integral value ratio (vinyl value) of 4.6 to 5.3 ppm with respect to the integral value of the peak of 0.75 to 2.00 ppm is 0.02. It is preferable that it is -1.00%, and 0.03-0.90 is more preferable. Here, the peak at 0.75 to 2.00 ppm is derived from an alkyl group such as a methyl group on the side chain, a methylene group or methine group on the main chain, and the peak at 4.6 to 5.3 ppm is at the end of the polymer. This is derived from the unsaturated bond. Therefore, the vinyl value is a value related to the amount of unsaturated bonds, and when the vinyl value is 0.02% or more, an oxidation-modified propylene-based polymer can be easily produced.

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 propylene 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 propylene-type polymers, Preferably it is the range of 0.01-5 mass parts.

In the present invention, for example, a propylene-based polymer is used in a molecular form 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. The propylene-based polymer can be oxidized by a method in which a gas containing oxygen and / or ozone is reacted by melting and kneading in the presence of a gas containing molecular oxygen and / or ozone.
The oxidation-modified propylene-based polymer of the present invention has high adhesion to polyolefin and the like, and can impart high strength, softness and the like to the adherend. Therefore, the oxidation-modified propylene-based polymer of the present invention is useful as a sealant or adhesive base material having high adhesiveness, or as a modifier that gives a polyolefin having improved compatibility with inorganic fillers. is there.

The primer resin for polyolefin of the present invention comprises the above-mentioned oxidation-modified propylene polymer.
The polyolefin primer resin of the present invention can contain an organic solvent as desired in order to improve ease of preparation and workability of the coating process. The organic solvent is not particularly limited as long as it is inactive with respect to the oxidation-modified propylene polymer and has an appropriate volatility. Examples of the organic solvent include methyl ethyl ketone, dimethylacetamide, acetone, ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, n-hexane, isohexane, methylene chloride, tetrahydrofuran, ethyl ether, and dioxane. These may be used alone or in combination of two or more. Of these, methyl ethyl ketone, ethyl acetate, butyl acetate, isohexane and toluene are preferred. Moreover, when it is difficult to use an organic solvent, it can also be used as an aqueous dispersion.
In order to improve the weather resistance, the primer resin of the present invention may contain additives such as an organic pigment, an inorganic pigment, and an ultraviolet absorber as necessary.
The primer resin of the present invention can be applied to an adherend using a commonly applied application method such as a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method, or a dipping method. .
The primer resin of the present invention can be suitably used for a sealing material. Specifically, the primer resin of the present invention exhibits stable adhesiveness to adherends of polyolefin-based materials, which are difficult-to-adhere members, as well as glass and aluminum, and is silicone, polyurethane, and modified silicone. Stable adhesiveness is also shown for system sealants. In addition, any combination of these adherends and sealing materials can be suitably used because of any combination.
In the primer resin of the present invention, in order to improve the balance between performance and economy, polypropylene, maleic anhydride, an acrylic monomer, or polypropylene modified with chlorine is mixed in an amount of 50 mass% or less based on the primer resin. May be.

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 propylene homopolymer (I) In a heat-dried stainless steel autoclave having an internal volume of 1 L, heptane 400 ml, triisobutylaluminum 1.0 mmol, methylanilinium tetrakis (perfluorophenyl) borate 1.5 μmol, And 0.5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylindenyl) zirconium dichloride (complex a) prepared in (1) above was added.
While stirring, the temperature was raised to 70 ° C., and propylene gas was introduced up to 0.8 MPa in total pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 60 minutes. After completion of the polymerization, 5 ml of methanol was added, and after depressurization, the polymerization solution was taken out and dried under reduced pressure to obtain 40 g of a propylene homopolymer (I).
About the obtained propylene homopolymer (I), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(3) Production of oxidation-modified propylene homopolymer (Ia) Propylene alone 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 30 g of polymer (I) was charged and placed in an oil bath at 180 ° C. while stirring at a rotation speed of 50 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 27 g of light yellow to white oxidized modified propylene homopolymer (Ia).
About the obtained oxidation modification | denaturation propylene homopolymer (Ia), the physical property was measured by the method mentioned above except peelability and wetting tension. Peelability and wetting tension were measured by the following methods. The results are shown in Table 2.

(1) Peelability 0.5 g of an oxidation-modified propylene polymer was dissolved in 5 ml of heptane to prepare a heptane solution of the oxidation-modified propylene polymer. On the other hand, on a 150 mm × 150 mm × 1 mm press plate obtained by press-molding polypropylene (manufactured by Prime Polymer Co., Ltd., J-762HP), the heptane solution of the above oxidation-modified propylene polymer is dropped and flattened with a glass rod. The film was smoothed and dried to prepare a 10 to 20 μm film of an oxidation-modified propylene polymer. On this film, an acrylic paint was further applied and dried to prepare a 90-100 μm paint film. Then, 4 lines were drawn vertically and 4 lines horizontally with a cutter knife so that a square of about 2 mm square could be formed. Then, after attaching cello tape (registered trademark) to the eye, the cello tape (registered trademark) was peeled off, and the following evaluation was made based on the ratio of the remaining paint.
○: The area of the remaining paint film is 90 to 100%.
Δ: The area of the remaining paint film is 50 or more and less than 90%.
X: The area of the remaining coating film is less than 50%.
(2) Wetting tension Wetting tension, which is a measure of the ability of the surface of a plastic film to retain ink, coating, or adhesive, was evaluated. It has been empirically known that as the wetting tension on the surface of the plastic film increases, the holding ability of ink, coating, adhesive, etc. is improved.
The evaluation was based on “Plastic-film and sheet-wetting tension test method” defined in JIS K6768. An oxidation-modified propylene-based polymer is sandwiched between Teflon (registered trademark) sheets and pressed at 180 ° C. using a 0.3 mm spacer to produce an evaluation film. This film is placed in a desiccator at room temperature for 8 hours or more. I left it alone.
Wet mixture test solution manufactured by Wako Pure Chemical Industries, Ltd. is used as the test mixture, and the mixture is applied to the film with a cotton swab containing the mixture, and the liquid film does not break after 2 seconds. Thus, when the original state was maintained, it was determined to be “wet”. Tests were sequentially performed from a test liquid mixture having a low surface tension, and the surface tension of the maximum liquid mixture determined to be “wet” was defined as the wetting tension of the film.

Example 2
(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, .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 Propylene Homopolymer (II) A 1 L stainless steel autoclave heated and dried was charged with 400 mL of heptane, 1 mmol of triisobutylaluminum, 3 μmol of methylanilinium tetrakis (perfluorophenyl) borate and (1 1 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene)-(3-trimethylsilylmethylindenyl) indenylzirconium dichloride (complex b) prepared in (1) was added.
While stirring, the temperature was raised to 75 ° C., and propylene gas was introduced up to 0.8 MPa in total pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 60 minutes. After completion of the polymerization, 5 ml of methanol was added, and after depressurization, the polymerization solution was taken out and dried under reduced pressure to obtain 70 g of a propylene homopolymer (II).
About the obtained propylene homopolymer (II), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(3) Production of oxidation-modified propylene homopolymer (II-a) Propylene alone 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 30 g of polymer (II) was charged and placed in an oil bath at 180 ° C. while stirring at a rotation speed of 50 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 28 g of light yellow to white oxidized modified propylene homopolymer (II-a).
About the obtained oxidation modification propylene homopolymer (II-a), the physical property was measured by the method mentioned above. The results are shown in Table 2.

Example 3
(1) Production of propylene copolymer (III) In a 1 L stainless steel autoclave heated and dried, 400 ml of heptane, 20 ml of 1-butene, 0.5 mmol of triisobutylaluminum, methylanilinium tetrakis (perfluorophenyl) ) Borate 0.8 μmol and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) (complex a) prepared in Example 1 (1). 2 μmol was added.
Further, 0.2 MPa of hydrogen was introduced. Next, propylene was continuously introduced until the total pressure became 0.8 MPa, and polymerization was performed at 70 ° C. for 15 minutes. After completion of the polymerization, 10 ml of methanol was added, and after depressurization, the polymerization solution was taken out and dried under reduced pressure to obtain 57 g of a propylene copolymer (III).
About the obtained propylene-type copolymer (III), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(2) Production of oxidation-modified propylene-based copolymer (III-a) Propylene produced in (1) above in a separa-type glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade. 30 g of the copolymer (III) was charged and placed in an oil bath at 180 ° C. while stirring at a rotational speed of 50 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 28 g of light yellow to white oxidation-modified propylene copolymer (III-a).
About the obtained oxidation modification propylene-type copolymer (III-a), the physical property was measured by the method mentioned above. The results are shown in Table 2.

Comparative Example 1
(1) Production of propylene homopolymer (IV) In a heat-dried stainless steel autoclave having an internal volume of 1 L, 400 ml of heptane, 1 mmol of triisobutylaluminum, 0.6 mmol of toluene solution of methylaluminoxane manufactured by Albemarle (in terms of aluminum), And 0.6 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (complex a) prepared in Example 1 (1) was added. .
Further, after adding 0.5 MPa of hydrogen, the temperature was raised to 60 ° C. while stirring, and propylene gas was introduced up to 0.8 MPa in total pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 60 minutes. After completion of the polymerization, 5 ml of methanol was added, and after depressurization, the polymerization solution was taken out and dried under reduced pressure to obtain 32 g of a propylene homopolymer (IV).
About the obtained propylene homopolymer (IV), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(2) Production of oxidation-modified propylene homopolymer (IV-a) Propylene alone produced in (1) above in a separa glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade 30 g of polymer (IV) was charged and placed in an oil bath at 180 ° C. while stirring at a rotation speed of 50 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 29 g of light yellow to white oxidized modified propylene polymer (IV-a).
About the obtained oxidation modification propylene homopolymer (IV-a), the physical property was measured by the method mentioned above. The results are shown in Table 2.

Comparative Example 2
(1) Production of propylene homopolymer (V) In a heat-dried stainless steel autoclave having an internal volume of 1 L, 400 mL of heptane, 1 mmol of triisobutylaluminum, 0.6 mmol of toluene solution of methylaluminoxane manufactured by Albemarle (in terms of aluminum), And 0.6 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene)-(3-trimethylsilylmethylindenyl) indenylzirconium dichloride (complex b) prepared in Example 2 (1). did.
Further, 0.01 MPa of hydrogen was added, and then the temperature was raised to 60 ° C. while stirring, and propylene gas was introduced up to 0.8 MPa in total pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 60 minutes. After completion of the polymerization, 5 ml of methanol was added, and after depressurization, the polymerization solution was taken out and dried under reduced pressure to obtain 80 g of a propylene homopolymer (V).
About the obtained propylene homopolymer (V), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(2) Production of oxidation-modified propylene homopolymer (Va) Propylene alone produced in (1) above in a separa glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade 30 g of polymer (V) was charged and placed in an oil bath at 180 ° C. while stirring at a rotational speed of 50 rpm. Next, dry air was introduced for 5 hours through an air blowing tube. Air blowing was stopped, purged with nitrogen, and then cooled to room temperature to obtain 28 g of light yellow to white oxidized modified propylene polymer (Va).
About the obtained oxidation modification propylene homopolymer (Va), the physical property was measured by the method mentioned above. The results are shown in Table 2.

Comparative Example 3
50 g of the propylene homopolymer (I-a) produced in Example 1 was melted with stirring at 140 ° C. in a nitrogen atmosphere in a Separa glass reactor (internal volume 500 ml). Thereafter, 4 g of maleic anhydride and 2 g of catalyst (Nippon Yushi Co., Ltd., Parroyl TCP) were added and stirred for 10 minutes. Then, in order to remove unreacted maleic acid, the reaction product was dissolved in 400 ml of trichlorobenzene at 100 ° C., allowed to cool, then poured into 2 L of acetone, the precipitate was filtered off and dried, and the modified propylene alone 49 g of polymer (Ib) was obtained.
About the obtained modified propylene homopolymer (Ib), the physical property was measured by the method mentioned above. The results are shown in Table 2.
Moreover, when the total amount of maleic acid (ring closure and ring opening) was measured by the following method about the obtained modified propylene homopolymer (Ib), it was 1.0 mass%. The amount of maleic acid (ring opening) was 0.6% by mass.

<Calculation method of maleic acid modification amount>
The amount of modification is measured by pressing a blend of propylene polymer and organic acid before modification with a 0.1 mm spacer and measuring IR with an IR measuring instrument (manufactured by JASCO Corporation, FT / IR-5300). Then, a calibration curve was prepared from the characteristic carbonyl (1600 to 1900 cm ⁻¹ ) absorption amount and the amount of organic acid charged, and IR measurement was performed on the acid-modified press plate. That is, the ratio of the peak of 4480 to 3950 cm ^{−1 in} the IR spectrum and the peak area near 1780 cm ⁻¹ was determined, and using the calibration curve prepared in advance, total maleic acid (ring closure and ring opening) and maleic acid (opening) of the sample were obtained. Ring) was quantified. This calibration curve should be prepared in advance using a sample of polyolefin / maleic anhydride (concentration (mass%): 0.05, 0.1, 0.5, 1.0, 2.0). Created by.
Samples were quantified for total maleic acid (ring-closing and ring-opening) and maleic acid (ring-opening) by the following procedure. When there are three peaks near 1600 cm ⁻¹ , this indicates that unreacted maleic acid remains.
(1) 1600 cm ^-1 confirmed that peak is not in the vicinity (2) 4250cm ^-1 vicinity thickness correction peak (3) 1780 cm ^-1 (all maleate: opening + closed) No (4) 1710 cm ^-1 ( (5) Maleic acid concentration (mass%) = calibration curve slope × 1710 cm cm ⁻¹ area ratio (6) Maleic acid concentration (mass%) = calibration curve slope × 1710 cm cm ⁻¹ area ratio

Example 4
(1) Production of propylene homopolymer (VI) In a heat-dried stainless steel autoclave having an internal volume of 1 L, heptane 400 ml, triisobutylaluminum 1.0 mmol, methylanilinium tetrakis (perfluorophenyl) borate 1.5 μmol, In addition, 0.5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylindenyl) zirconium dichloride (complex a) prepared in Example 1 (1) was added.
After adding 0.01 MPa of hydrogen while stirring, the temperature was raised to 78 ° C. and at the same time, propylene gas was introduced up to 0.6 MPa in total pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 30 minutes. After completion of the polymerization, 5 ml of methanol was added, and after depressurization, the polymerization solution was taken out and dried under reduced pressure to obtain 65 g of propylene homopolymer (VI).
About the obtained propylene homopolymer (VI), the physical property was measured by the method mentioned above. The results are shown in Table 1.
(2) Production of oxidation-modified propylene homopolymer (VI-a) Propylene alone produced in (1) above in a separa glass reactor equipped with an air blowing pipe, an exhaust port and a stirring blade (internal volume 500 ml) 30 g of the polymer (VI) was charged and placed in an oil bath at 210 ° C. while stirring at a rotation speed of 50 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 26 g of light yellow to white oxidized modified propylene homopolymer (VI-a).
About the obtained oxidation modification | denaturation propylene homopolymer (VI-a), the physical property was measured by the method mentioned above. The results are shown in Table 2.

  From the above results, it can be seen that the wettability of the oxidation-modified propylene polymer of the example is improved by the oxidation treatment. For this reason, when the propylene oxide polymer of the example is applied to an adhesive or the like, it is expected that the adhesive strength is improved. In addition, since no polar group-containing monomer is used in the oxidation treatment, it is expected that unreacted monomers need not be removed and can be produced at low cost.

  The oxidation-modified propylene-based polymer of the present invention is useful as a sealant having high adhesion or as a modifier or the like that gives a polyolefin having improved compatibility with inorganic fillers.

Claims (12)

An oxidation-modified propylene homopolymer satisfying the following (a) to (d).
(A) [mmmm] = 20-80 mol%
(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
(C) Acid value = 0.2-40 mgKOH / g
(D) An acetone soluble part is 0.5 mass% or less. An oxidation-modified propylene homopolymer satisfying the following (e) to (i).
(E) [mmmm] = 20-80 mol%
(F) [rrrr] / (1- [mmmm]) ≦ 0.1
(G) [mm] × [rr] / [mr] ² ≦ 2.2
(H) Acid value = 0.2-40 mg KOH / g
(I) Acetone soluble part is 0.5 mass% or less. An oxidation-modified propylene homopolymer satisfying the following (j) to (p).
(J) [mmmm] = 20-80 mol%
(K) [rrrr] / (1- [mmmm]) ≦ 0.1
(L) [mm] × [rr] / [mr] ² ≦ 2.2
(M) Weight average molecular weight (Mw) = 10,000 to 200,000
(N) Molecular weight distribution (Mw / Mn) ≦ 4.0
(O) Acid value = 0.2-40 mg KOH / g
(P) Acetone soluble part is 0.5 mass% or less. ^{In the 1} H-NMR spectrum, the ratio (vinyl value) of the integrated value of 4.6 to 5.3 ppm to the integrated value of the peak of 0.75 to 2.00 ppm is 0.02 to 1.00%. The oxidation-modified propylene homopolymer according to any one of -3. An oxidation-modified propylene-based copolymer containing propylene units and ethylene units and / or 1-butene units in an amount of 1 to 10 mol% and satisfying the following (q) to (u).
(Q) Stereoregularity index ([mm]) = 50 to 90 mol%
(R) Weight average molecular weight (Mw) = 10,000 to 200,000
(S) Molecular weight distribution (Mw / Mn) ≦ 4.0
(T) Acid value = 0.2-40 mgKOH / g
(U) Acetone soluble part is 0.5 mass% or less. The ratio (vinyl value) of an integrated value of 4.6 to 5.3 ppm to an integrated value of a peak of 0.75 to 2.00 ppm in a ¹ H-NMR spectrum is 0.02 to 1.00%. The oxidation-modified propylene-based copolymer described in 1. In the ¹ H-NMR spectrum satisfying the following (v) and (w), the ratio (vinyl value) of the integral value of 4.6 to 5.3 ppm to the integral value of the peak of 0.75 to 2.00 ppm is 0. The oxidation-modified propylene according to claim 1, wherein 0.02 to 1.00% of propylene homopolymer is oxidized at 100 to 300 ° C in the presence of molecular oxygen and / or ozone-containing gas. A method for producing a homopolymer.
(V) [mmmm] = 20-80 mol%
(W) Molecular weight distribution (Mw / Mn) ≦ 4.0 In the ¹ H-NMR spectrum satisfying the following (x) to (z), the ratio (vinyl value) of the integral value of 4.6 to 5.3 ppm to the integral value of the peak of 0.75 to 2.00 ppm is 0. The oxidation-modified propylene according to claim 2, wherein 0.02 to 1.00% of propylene homopolymer is oxidized at 100 to 300 ° C in the presence of molecular oxygen and / or ozone-containing gas. A method for producing a homopolymer.
(X) [mmmm] = 20-80 mol%
(Y) [rrrr] / (1- [mmmm]) ≦ 0.1
(Z) [mm] × [rr] / [mr] ² ≦ 2.2 In the ¹ H-NMR spectrum satisfying the following (A) to (E), the ratio (vinyl value) of the integral value of 4.6 to 5.3 ppm to the integral value of the peak of 0.75 to 2.00 ppm is 0. The oxidation-modified propylene according to claim 3, wherein 0.02 to 1.00% of propylene homopolymer is oxidized at 100 to 300 ° C in the presence of molecular oxygen and / or ozone-containing gas. A method for producing a homopolymer.
(A) [mmmm] = 20-80 mol%
(B) [rrrr] / (1- [mmmm]) ≦ 0.1
(C) [mm] × [rr] / [mr] ² ≦ 2.2
(D) Weight average molecular weight (Mw) = 10,000 to 200,000
(E) Molecular weight distribution (Mw / Mn) ≦ 4.0 And propylene unit comprises 1 to 10 mol% of ethylene units and / or 1-butene units, satisfying the following items (F) ~ (H), in ¹ H-NMR spectrum, the peaks of 0.75~2.00ppm In the presence of molecular oxygen and / or ozone-containing gas, a propylene-based copolymer having a ratio of the integral value of 4.6 to 5.3 ppm (vinyl value) to the integral value of 0.02 to 1.00% is obtained in the presence of molecular oxygen and / or ozone-containing gas. The method for producing an oxidation-modified propylene-based copolymer according to claim 5, wherein the oxidation treatment is performed at ˜300 ° C.
(F) Stereoregularity index ([mm]) = 50 to 90 mol%
(G) Weight average molecular weight (Mw) = 10,000 to 200,000
(H) Molecular weight distribution (Mw / Mn) ≦ 4.0   Primer resin for polyolefin which consists of an oxidation modification propylene homopolymer in any one of Claims 1-3.   A polyolefin primer resin comprising the oxidation-modified propylene copolymer according to claim 5.