JP2005171139A - Modified polypropylene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polypropylene having high affinity between polypropylene and a polar material, excellent in storage stability of a solution and having high surface smoothness after coating when used for primer, etc. and to provide a method for producing the modified polypropylene. <P>SOLUTION: The modified polypropylene is obtained by graft-bonding 0.1-100 units derived from a one or more kinds of modifying agents selected from a group consisting of (meth)acrylic acid, styrene, dicarboxylic acid, dicarboxylic anhydride and derivatives thereof on a polypropylene in which the value of a racemic dyad fraction [r] measured by<SP>13</SP>C-NMR is 0.12-0.49 and the weight average molecular weight is 5,000-500,000 . <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a modified polypropylene, and more specifically, has high affinity with polypropylene and polar materials, and when used as a primer or the like, it has excellent storage stability and surface properties after coating, paint, primer, adhesive, The present invention relates to a modified polypropylene useful for adhesives, inks, compatibilizers, reactive polymers and the like.

  Polyolefins such as polypropylene and polyethylene have high crystallinity and nonpolarity, and therefore have little affinity with other substrates, for example, polar polymers such as acrylic resins and vinyl acetate resins. Therefore, there is a problem that blending, painting, adhesion and printing of these resins are difficult.

  In order to solve this problem, many studies have been made on the chlorination of polymers and the modification with dicarboxylic anhydrides. For example, it has been proposed to graft copolymerize a polypropylene resin with a dicarboxylic anhydride such as maleic anhydride and then chlorinate (see Patent Document 1).

However, chlorinated polypropylene modified with dicarboxylic anhydride has a low chlorine affinity when the chlorine content is high, and as a result, the ability to adhere to polyolefin deteriorates. On the other hand, when the chlorine content is low, when used by dissolving in a solvent, the solution properties deteriorate, such as precipitation of solids and decrease in fluidity, particularly at low temperatures.
Therefore, even in the case of polymers having polar groups such as dicarboxylic acid anhydrides, the problems as described above due to the chlorinated polymer of the main chain cannot be solved in many cases. In the future, the chlorination process and chlorinated polypropylene are expected to be difficult to use due to environmental constraints.

In order to improve the solution properties, it has been proposed to use very low molecular weight isotactic polypropylene as the base polymer.
However, highly stereoregular isotactic polypropylene (see, for example, Patent Document 2) usually has insufficient solubility in a solvent even if it has a low molecular weight. For this reason, there are problems such as poor storage stability, difficulty in use because solids precipitate during storage, and insufficient surface smoothness of the coating.

  Then, in order to improve the solubility to a solvent, using the thing which copolymerized ethylene and propylene with another alpha olefin as base polyolefin is examined.

  However, when a propylene-ethylene-α-olefin copolymer is used (see Patent Document 3), since the copolymer itself has a low affinity with polypropylene, if this is modified, the affinity with polypropylene further decreases. Often, it is difficult to obtain sufficient adhesion. In particular, when a large number of polar groups such as dicarboxylic acid anhydride are introduced, the affinity with polypropylene is remarkably reduced, and when the amount of modification is small, the affinity with a polar material becomes insufficient.

As described above, when isotactic polypropylene having crystallinity is used, even if it has a low molecular weight, as in the case of chlorinated polypropylene, the solubility in a solvent is not sufficient. Problems arise in terms of surface smoothness and paint. In addition, when a propylene-ethylene-α-olefin copolymer is used to solve the crystallinity problem, the storage stability and the surface smoothness of the coating are improved, but the affinity with the polypropylene material or the polar material Will be sacrificed.
Japanese Patent Laid-Open No. 2002-20672 Japanese Patent Application Laid-Open No. 11-100412 JP 2002-173514 A ([0040] to [0043])

  In view of the above situation, the object of the present invention is a modified polypropylene useful as a primer or the like because of its high affinity with polypropylene and polar materials, excellent solution storage stability, and high surface smoothness after coating. Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have focused on soluble isotactic polypropylene in which the value of racemic dyad fraction [r] measured by ¹³ C-NMR is in a specific range. By reacting this with a specific compound to make a modified polypropylene, not only the affinity with polypropylene and polar materials is improved, but also the storage stability of the polymer solution containing this modified polypropylene, and the surface smoothness after coating. As a result, the present invention has been completed.

That is, according to the first invention of the present invention, the value of the racemic dyad fraction [r] measured by ¹³ C-NMR is in the range of 0.12 to 0.49, and the weight average molecular weight is 5,000 to 500. There is provided a modified polypropylene characterized in that 0.1 to 100 units represented by the following general formula (1) are graft-bonded to polypropylene having a molecular weight of 1,000.

(In the formula, ^{R 1} is H, or an alkyl group of _{C 1 to 10;} ^{R 2} is ^OR 4, Cl, Br, halogen selected from F or I, ^NR _{1 2} or ^R 5 ^-NR _{1 2} groups; R ³ is H or —COR ² group, and n is 0.1 to 100, where R ⁴ is H or a C _1-10 alkyl group that may have halogen; groups _{;-( CH 2) a-O-} P (O) (oR 1) 2, or ^{_{- (CH 2) a-O}} -P (O) (O -) (O- (CH 2) b-N ⁺ R ¹ ₃ (a and b are each an integer of 1 to 5); an alkali metal M selected from Li, Na, or K; a C _5-10 alicyclic hydrocarbon; a glycidyl group; R ⁵ —COCR ^{1 _{= CH 2; R 5 oR 1}} ; R 5 Si (oR 1) 3, or indicates ^R 5 -NCO, also, ^{R 5} is _{C 1 to 1} Alkylene group or _{- [(CH 2) q-} O-] a r-, q and r is an integer of respective 1-5).

According to the second invention of the present invention, the value of the racemic dyad fraction [r] measured by ¹³ C-NMR is in the range of 0.12 to 0.49, and the weight average molecular weight is 5,000 to 500, There is provided a modified polypropylene characterized in that 0.1 to 100 units represented by the following general formula (2) are graft-bonded to polypropylene of 000.

Wherein R ⁶ is H, or a C _1-10 alkyl group, or a halogen selected from Cl, Br, F or I; R ⁷ is Ar—X ′, OCO—R ⁶ , CHO, COR ⁶ , CN, pyridyl group, pyrrolidonyl group, Si (OR ¹ ) ₃ , C _1-10 alkyl halide, halogen, OR ⁶ , OSO ₃ M or NH—CO—R ⁶ , m is 0.1-100. Here, X ′ is R ⁶ , OH, COOH, NH ₂ , CN, NO ₂ , C _1-10 alkyl halide, CH═CH ₂ , or OCO—R ⁶ , R ¹ is H, or C _1-10 alkyl group, M is the aforementioned alkali metal.)

Furthermore, according to the third aspect of the present invention, the value of the racemic dyad fraction [r] measured by ¹³ C-NMR is in the range of 0.12 to 0.49, and the weight average molecular weight is 5,000 to 500. There is provided a modified polypropylene characterized in that 0.1 to 100 units of one or two or more units selected from dicarboxylic acid or dicarboxylic acid anhydride are graft-bonded to polypropylene of 1,000.

Preferred embodiments of the present invention include the following.
(1) The modified polypropylene according to the first invention, wherein n in the general formula (1) is 0.5 to 50.
(2) In the first invention, a modified polypropylene characterized in that the unit represented by the general formula (1) is a unit derived from (meth) acrylic acid, an alkyl ester or a glycidyl ester thereof.
(3) A modified polypropylene according to the first invention, wherein the unit represented by the general formula (1) is a unit derived from an alkali metal salt of (meth) acrylic acid or a halide thereof.
(4) In the first invention, the unit represented by the general formula (1) is a unit derived from a (meth) acrylic acid derivative containing either an OH group, an alkoxy group, an amino group, or an isocyanate group. Characterized modified polypropylene.
(5) The modified polypropylene according to the second invention, wherein m in the general formula (2) is 0.5 to 50.
(6) The modified polypropylene according to the second invention, wherein the unit represented by the general formula (2) is a unit derived from a styrene derivative.
(7) The modified polypropylene according to the second invention, wherein the unit represented by the general formula (2) is a unit derived from a vinyl compound.
(8) A modified polypropylene according to the third invention, wherein the dicarboxylic acid unit is a unit derived from maleic acid, fumaric acid, itaconic acid, or citraconic acid.
(9) In the third invention, the unit of the dicarboxylic acid anhydride is derived from any of maleic anhydride, itaconic anhydride, citraconic anhydride, endomethylenetetrahydrophthalic anhydride, or methylendomethylenetetrahydrophthalic anhydride. A modified polypropylene characterized in that
(10) A modified polypropylene characterized in that, in the first to third inventions, the racemic dyad fraction [r] value of polypropylene is 0.16 to 0.45.
(11) The modified polypropylene according to any one of the first to third inventions, wherein the polypropylene has a weight average molecular weight (Mw) of 10,000 to 250,000.
(12) The modified polypropylene according to any one of the first to third aspects, wherein the polypropylene has an absorption peak observed at 973 cm ⁻¹ in IR measurement at room temperature.
(13) The modified polypropylene according to (12), wherein an absorption peak derived from a crystal part of polypropylene is not observed.
(14) The modified polypropylene according to (13), wherein the absorption peaks derived from the crystal part of the polypropylene are 770 cm ⁻¹ , 842 cm ⁻¹ , and 998 cm ⁻¹ .
(15) The racemic dyad fraction measured by ¹³ C-NMR after polymerizing polypropylene using a homogeneous metal complex catalyst or heterogeneous catalyst and separating and removing crystalline polypropylene as necessary. A polypropylene having a rate [r] value of 0.12 to 0.49 and a weight average molecular weight of 5,000 to 500,000 is represented by at least 1 represented by the general formula (3) in the presence of a radical reaction initiator. A process for producing a modified polypropylene, characterized by reacting with a seed compound.

(In the formula, ^{R 1} is H, or an alkyl group of _{C 1 to 10;} ^{R 2} is ^OR 4, Cl, Br, halogen selected from F or I, ^NR _{1 2} or ^R 5 ^-NR _{1 2} groups; R ³ is H or —COR ² group, and n is 0.1 to 100, where R ⁴ is H or a C _1-10 alkyl group that may have halogen; groups _{;-( CH 2) a-O-} P (O) (oR 1) 2, or ^{_{- (CH 2) a-O}} -P (O) (O -) (O- (CH 2) b-N ⁺ R ¹ ₃ (a and b are each an integer of 1 to 5); an alkali metal M selected from Li, Na, or K; a C _5-10 alicyclic hydrocarbon; a glycidyl group; R ⁵ —COCR ^{1 _{= CH 2; R 5 oR 1}} ; R 5 Si (oR 1) 3, or indicates ^R 5 -NCO, also, ^{R 5} is _{C 1 to 1} Alkylene group or _{- [(CH 2) q-} O-] a r-, q and r is an integer of respective 1-5).

(16) A method for producing a modified polypropylene according to the above (15), wherein the compound represented by the general formula (3) is (meth) acrylic acid, an alkyl ester thereof, or a glycidyl ester.
(17) A method for producing a modified polypropylene according to the above (15), wherein the compound represented by the general formula (3) is an alkali metal salt of (meth) acrylic acid or a halide thereof.
(18) The modification according to (15), wherein the compound represented by the general formula (3) is a (meth) acrylic acid derivative containing any one of an OH group, an alkoxy group, an amino group, and an isocyanate group. A method for producing polypropylene.
(19) The racemic dyad fraction measured by ¹³ C-NMR after polymerizing polypropylene using a homogeneous metal complex catalyst or heterogeneous catalyst, and separating and removing crystalline polypropylene as necessary. Polypropylene having a rate [r] value of 0.12 to 0.49 and a weight average molecular weight of 5,000 to 500,000 is represented by at least 1 represented by the general formula (4) in the presence of a radical reaction initiator. A process for producing a modified polypropylene, characterized by reacting with a seed compound.

Wherein R ⁶ is H, or a C _1-10 alkyl group, or a halogen selected from Cl, Br, F or I; R ⁷ is Ar—X ′, OCO—R ⁶ , CHO, COR ⁶ , CN, pyridyl group, pyrrolidonyl group, Si (OR ¹ ) ₃ , C _1-10 alkyl halide, halogen, OR ⁶ , OSO ₃ M or NH—CO—R ⁶ , m is 0.1-100. Here, X ′ is R ⁶ , OH, COOH, NH ₂ , CN, NO ₂ , C _1-10 alkyl halide, CH═CH ₂ , or OCO—R ⁶ , R ¹ is H, or C _1-10 alkyl group, M is the aforementioned alkali metal.)

(20) The method for producing a modified polypropylene according to the above (19), wherein the compound represented by the general formula (4) is a styrene derivative.
(21) The method for producing a modified polypropylene according to the above (19), wherein the compound represented by the general formula (4) is a vinyl compound.
(22) A racemic dyad fraction measured by ¹³ C-NMR after polymerizing polypropylene using a homogeneous metal complex catalyst or a heterogeneous catalyst and separating and removing crystalline polypropylene as necessary. A polypropylene having a rate [r] value of 0.12 to 0.49 and a weight average molecular weight of 5,000 to 500,000 is selected from dicarboxylic acid or dicarboxylic anhydride in the presence of a radical reaction initiator. A method for producing a modified polypropylene, comprising reacting with at least one compound.
(23) The method for producing a modified polypropylene according to the above (22), wherein the dicarboxylic acid is any one of maleic acid, fumaric acid, itaconic acid, or citraconic acid.
(24) In the above (22), the dicarboxylic acid anhydride is any of maleic anhydride, itaconic anhydride, citraconic anhydride, endomethylenetetrahydrophthalic anhydride, or methylendomethylenetetrahydrophthalic anhydride. A method for producing modified polypropylene.
(25) Adhesive, ink, paint, primer, sealing agent, surface modifier, coating agent, adhesive, reactive polymer, or compatibilizer comprising the modified polypropylene of any one of the first to third inventions .

In the modified polypropylene of the present invention, a specific number of specific modifiers are graft-bonded per one polypropylene molecule having a racemic dyad fraction [r] value measured by ¹³ C-NMR in the range of 0.12 to 0.49. Therefore, the affinity with the polypropylene material, the storage stability of the solution are improved, and the coating surface smoothness is also excellent.

  Hereinafter, the modified polypropylene of the present invention and the production method thereof will be described in detail for each item.

1. Base polymer (polypropylene)
In the present invention, a polypropylene having a racemic dyad fraction [r] value measured by ¹³ C-NMR in the range of 0.12 to 0.49 is used as the base polymer of the modified polypropylene.

  The racemic dyad fraction [r] value defined in the present invention is an index of the stereoregularity of polypropylene (an index indicating continuous methyl groups in alternating planes), and represents the degree of isotacticity of polypropylene. is there.

For example, if the racemic dyad fraction [r] value is 0, ie 0%, the polypropylene is all isotactic polypropylene, and if the [r] value is 0.5, ie 50%, the polypropylene Becomes atactic polypropylene. In addition, the racemic dyad fraction [r] value prescribed | regulated by this invention can be obtained from the integral value of the peak intensity resulting from the structure of the stereoregularity measured by the method well-known to those skilled in the art, ie, ¹³ C-NMR.

  In the present invention, the polypropylene needs to have a racemic dyad fraction [r] value in the range of 0.12 to 0.49, preferably 0.16 to 0.45, and particularly preferably 0.17 to 0.47. 0.43.

Also, the polypropylene, the peak of the IR absorption spectrum (at room temperature) ^{is, 770cm -1, 842cm -1,} not observed in any of the positions of 998 ^-1. The peaks appearing at these positions are characteristic peaks derived from the crystal part of isotactic polypropylene.
Furthermore, this polypropylene has an absorption peak at 973 cm ⁻¹ derived from the amorphous part of isotactic polypropylene in the IR absorption spectrum (room temperature). However, these IR absorption peaks may shift somewhat depending on the measurement conditions and equipment.

The polypropylene according to the present invention is a copolymer copolymerized with ethylene, α-olefin, or diolefin as long as the racemic dyad fraction [r] value measured by ¹³ C-NMR is in the range of 0.12 to 0.49. May be contained in an amount of less than 10 mol%. Examples of the α-olefin include olefins having 4 to 8 carbon atoms such as 1-butene, 1-hexene, 4-methyl-1-pentene, and diolefins. , 5-hexadiene, 1,7-octadiene, 1,9-decadiene and the like.

  When the propylene-α-olefin copolymer is contained in an amount of 10 mol% or more, the affinity with the polypropylene material is lowered. In order to have sufficient affinity with polypropylene, it is preferable to use a homopolymer of propylene.

  Although the polypropylene which concerns on this invention can be manufactured by said method, weight average molecular weights (Mw) are 5,000-500,000, and 10,000-250,000 are more preferable. The molecular weight distribution (Mw / Mn) is 1.01-10.0, preferably 1.01-7.0, more preferably 1.01-5.0.

^The method for producing polypropylene having a racemic dyad fraction [r] value in the range of 0.12 to 0.49 measured by ¹³ C-NMR is a production method capable of keeping the racemic dyad fraction [r] value within this range. If there is, it is not particularly limited, but the following production method is preferable.

  That is, using a homogeneous or heterogeneous metal complex catalyst, saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane; benzene, toluene, xylene Polymerize propylene in a solvent such as THF. Polymerization in a so-called propylene bulk or gas phase polymerization using propylene itself as a solvent is also possible.

The homogeneous metal complex catalyst is a catalyst composed of an organometallic compound and an organoaluminum compound, or a metal complex composed of an organic compound containing a hetero atom such as oxygen or nitrogen and a transition metal, for example,
(I) a catalyst comprising at least one complex selected from the group consisting of titanium, zirconium, hafnium alkoxy complexes, alkylamide complexes, and acetylacetone complexes, and aluminoxanes, boron compounds, or organoaluminum compounds,
(Ii) a catalyst comprising two cycloalkadienyl groups of a metal selected from the group consisting of titanium, zirconium and hafnium or a derivative thereof, a complex having a halogen or an alkyl group, and an aluminoxane, a boron compound or an organoaluminum compound , Etc.

  In the catalyst (i), at least one complex selected from an alkoxy complex of titanium, zirconium, hafnium, an alkylamide complex, or an acetylacetone complex is represented by, for example, the following general formulas (5) to (10): Compounds.

M (OR) _a X _4-a (5)
M (NR ₂ ) _a X _4-a (6)
M (acac) ₂ X ₂ (7)
[OR ⁴ O] MX ₂ (8)
[OR ⁴ N (R ⁵ )] MX ₂ (9)
[N (R ⁵ ) R ⁴ N (R ⁵ )] MX ₂ (10)

In the general formulas (5) to (10), M represents Ti, Zr, or Hf. X represents F, Cl, Br, or I. R represents a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ represents a divalent aromatic or alicyclic, aliphatic hydrocarbon group, and / or a divalent oxygen-containing group, a divalent nitrogen-containing group, Represents a divalent group containing different elements such as oxygen, nitrogen and silicon other than C and H, such as a divalent silicon-containing group, and R ⁵ represents a monovalent aromatic or alicyclic, aliphatic carbonization. Represents a hydrogen group. acac is acetylacetone ligand, methylbutanedione ligand, butanedione ligand, benzoylacetone ligand, benzoyltrifluoroacetone ligand, dibenzoylmethane ligand, furoylacetone ligand, trifluoroacetylacetone A ligand, 3-phenylacetylacetone ligand, 2,4-hexanedione ligand, trifluorodimethyl-2,4-hexanedione ligand and the like; a is an integer of 2-4.

Further, examples of the hydrocarbon group ^{R 4} _is, -C _{n H 2n} - divalent saturated hydrocarbon group such _as, -C _{n H 2n-2} - or _-C n _{H 2n-4} - like Examples thereof include a divalent aliphatic unsaturated hydrocarbon group, a divalent alicyclic hydrocarbon group such as -cycloC _m H _2m-2- , and a divalent hydrocarbon group containing an aromatic ring. In addition, n is an integer of 1-10, Preferably it is 2-5, m is an integer of 5-15, Preferably it is 8-12. The saturated hydrocarbon group may be branched as well as a straight chain. Examples of the branched hydrocarbon group include a dialkylmethylene group (R ₂ C =), —CH (R) CH (R) —, — CH (R) CH ₂ CH (R) — and the like can be mentioned. Furthermore, R ⁴ has an oxygen or nitrogen atom such as — (CH ₂ ) _n O (CH ₂ ) _n —, — (CH ₂ ) _n NR (CH ₂ ) _n —, or C ₆ H ₄ OC ₆ H ₄ —. Or a group having a silicon atom such as a dialkylsilylene group (R ₂ Si =). Of these, a divalent saturated hydrocarbon group such as —C _n H _2n — is preferable.

As specific compounds of the compounds represented by M (OR) _a X _4-a , M (NR ₂ ) _a X _4-a , and M (acac) ₂ X ₂ in the general formulas (5) to (7), _{, Ti (OC 2 H 5)} 4, Ti (On-C 3 H 7) 4, Ti (Oi-C 3 H 7) 4, Ti (On-C 4 H 9) 4, Ti (Oi-C 4 H _{9) 4, Ti (Os-} C 4 H 9) 4, Ti (Ot-C 4 H 9) 4, Ti (OcycloC 5 H 9) 4, Ti (OC 5 H 11) 4, Ti (OC 6 H 5 ) ₄ , Ti (OcycloC ₆ H ₁₁ ) ₄ , Ti (OC ₆ H ₁₃ ) ₄ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (Oi-C ₃ H ₇ ) ₂ Cl ₂ , Ti (On-C) _{3 H 7) 2 Br 2,} Ti (On-C 4 H 9) 2 Cl 2, Ti (Oi-C 4 H _{) 2 Br 2, Ti (Os} -C 4 H 9) 2 I 2, Ti (OC 5 H 11) 2 Cl 2, Ti (OcycloC 6 H 11) 2 F 2, Ti [N (C 2 H 5) 2 ] ₄ , Ti [N (n-C ₃ H ₇ ) ₂ ] ₄ , Ti [N (i-C ₃ H ₇ ) ₂ ] ₄ , Ti [N (n-C ₄ H ₉ ) ₂ ] ₄ , Ti [ _{N (i-C 4 H 9} ) 2] 4, Ti [N (s-C 4 H 9) 2] 4, Ti [N (t-C 4 H 9) 2] 4, Ti [N (cycloC 5 H ₉ ) ₂ ] ₄ , Ti [N (C ₅ H ₁₁ ) ₂ ] ₄ , Ti [N (C ₆ H ₅ ) ₂ ] ₄ , Ti [N (cycloC ₆ H ₁₁ ) ₂ ] ₄ , Ti [N (C _{6 H 13) 2] 4,} Ti [n (C 2 H 5) 2] 2 Cl 2, Ti [n (n-C 3 H 7) 2] 2 Cl 2, _{i [N (i-C 3} H 7) 2] 2 Br 2, Ti [N (s-C 4 H 9) 2] 2 Cl 2, Ti [N (n-C 4 H 9) 2] 2 Br 2 , Ti [N (t—C ₄ H ₉ ) ₂ ] ₂ I ₂ , Ti [N (C ₅ H ₁₁ ) ₂ ] ₂ F ₂ , Ti [N (C ₅ H ₁₁ ) ₂ ] ₂ Cl ₂ , Ti ( _{acetylacetonato)} 2 _Cl 2, Ti (methyl butanedioate _{isocyanatomethyl)} 2 _Cl 2, Ti _{(butanedionate)} 2 _Cl 2, Ti (benzoyl _acetonate) 2 _Br 2, Ti (benzoyl trifluoroacetamido _{isocyanatomethyl)} 2 _F 2, Ti (Dibenzoylmethanato) ₂ I ₂ , Ti (furoyl acetonato) ₂ Br ₂ , Ti (trifluoroacetylacetonato) ₂ Br ₂ , Ti (2,4-hexanedionate) ₂ Cl ₂ , Zr (OC ₂ H _{5) 4,} Z _{(On-C 3 H 7)} 4, Zr (Oi-C 3 H 7) 4, Zr (On-C 4 H 9) 4, Zr (Oi-C 4 H 9) 4, Zr (Os-C 4 H ₉ ) ₄ , Zr (Ot-C ₄ H ₉ ) ₄ , Zr (OcycloC ₅ H ₉ ) ₄ , Zr (OC ₅ H ₁₁ ) ₄ , Zr (OC ₆ H ₅ ) ₄ , Zr (OcycloC ₆ H ₁₁ ) ₄ , Zr (OC ₆ H ₁₃ ) ₄ , Zr (OC ₂ H ₅ ) ₂ Cl ₂ , Zr (Oi—C ₃ H ₇ ) ₂ Cl ₂ , Zr (On—C ₃ H ₇ ) ₂ Br ₂ , Zr (On _{-C 4 H 9) 2 Cl 2} , Zr (Oi-C 4 H 9) 2 Br 2, Zr (Os-C 4 H 9) 2 I 2, Zr (OC 5 H 11) 2 Cl 2, Zr (OcycloC _{6 H 11) 2 F 2,} Zr [N (C 2 H 5) 2] 4, Zr _{[N (n-C 3 H} 7) 2] 4, Zr [N (i-C 3 H 7) 2] 4, Zr [N (n-C 4 H 9) 2] 4, Zr [N (i- _{C 4 H 9) 2] 4} , Zr [N (s-C 4 H 9) 2] 4, Zr [N (t-C 4 H 9) 2] 4, Zr [N (cycloC 5 H 9) 2] ₄ , Zr [N (C ₅ H ₁₁ ) ₂ ] ₄ , Zr [N (C ₆ H ₅ ) ₂ ] ₄ , Zr [N (cycloC ₆ H ₁₁ ) ₂ ] ₄ , Zr [N (C ₆ H ₁₃ ) _{2] 4, Zr [n (} C 2 H 5) 2] 2 Cl 2, Zr [n (n-C 3 H 7) 2] 2 Cl 2, Zr [n (i-C 3 H 7) 2] 2 _{Br 2, Zr [n (s} -C 4 H 9) 2] 2 Cl 2, Zr [n (n-C 4 H 9) 2] 2 Br 2, Zr [n (t-C 4 H 9) 2] ₂ I ₂ , Zr [N (C ₅ H ₁₁ ) ₂ ] ₂ F ₂ , Zr [N (C ₅ H ₁₁ ) ₂ ] ₂ Cl ₂ , Zr (acetylacetonato) ₂ Cl ₂ , Zr (methylbutanedionato) ₂ Cl ₂ , Zr (butanedionato) ₂ Cl ₂ , Zr (benzoylacetonato) ₂ Br ₂ , Zr (benzoyltrifluoroacetonato) ₂ F ₂ , Zr (dibenzoylmethanato) ₂ I ₂ , Zr (furoylacetonato) ₂ Br ₂ , Zr (trifluoroacetylacetonato) ₂ Br ₂ , Zr (2,4-hexanedionate) ₂ Cl ₂ , Hf (OC ₂ H ₅ ) ₄ , Hf (On—C ₃ H ₇ ) ₄ , _{Hf (Oi-C 3 H 7} ) 4, Hf (On-C 4 H 9) 4, Hf (Oi-C 4 H 9) 4, Hf (Os-C 4 H 9) 4, Hf (Ot-C 4 H _{) 4, Hf (OcycloC 5 H} 9) 4, Hf (OC 5 H 11) 4, Hf (OC 6 H 5) 4, Hf (OcycloC 6 H 11) 4, Hf (OC 6 H 13) 4, Hf ( _{OC 2 H 5) 2 Cl 2} , Hf (Oi-C 3 H 7) 2 Cl 2, Hf (On-C 3 H 7) 2 Br 2, Hf (On-C 4 H 9) 2 Cl 2, Hf ( _{Oi-C 4 H 9) 2} Br 2, Hf (Os-C 4 H 9) 2 I 2, Hf (OC 5 H 11) 2 Cl 2, Hf (OcycloC 6 H 11) 2 F 2, Hf [N ( _{C 2 H 5) 2] 4} , Hf [n (n-C 3 H 7) 2] 4, Hf [n (i-C 3 H 7) 2] 4, Hf [n (n-C 4 H 9) _{2] 4, Hf [N (} i-C 4 H 9) 2] 4, Hf [N (s-C 4 H _{) 2] 4, Hf [N} (t-C 4 H 9) 2] 4, Hf [N (cycloC 5 H 9) 2] 4, Hf [N (C 5 H 11) 2] 4, Hf [N ( C ₆ H ₅ ) ₂ ] ₄ , Hf [N (cycloC ₆ H ₁₁ ) ₂ ] ₄ , Hf [N (C ₆ H ₁₃ ) ₂ ] ₄ , Hf [N (C ₂ H ₅ ) ₂ ] ₂ Cl ₂ , _{Hf [n (n-C 3} H 7) 2] 2 Cl 2, Hf [n (i-C 3 H 7) 2] 2 Br 2, Hf [n (s-C 4 H 9) 2] 2 Cl 2 _{, Hf [n (n-C} 4 H 9) 2] 2 Br 2, Hf [n (t-C 4 H 9) 2] 2 I 2, Hf [n (C 5 H 11) 2] 2 F 2, Hf [N (C ₅ H ₁₁ ) ₂ ] ₂ Cl ₂ , Hf (acetylacetonato) ₂ Cl
₂ , Hf (methylbutanedionato) ₂ Cl ₂ , Hf (butanedionato) ₂ Cl ₂ , Hf (benzoylacetonato) ₂ Br ₂ , Hf (benzoyltrifluoroacetonato) ₂ F ₂ , Hf (dibenzoylmethanato) ₂ I ₂ , Hf (furoyl acetonato) ₂ Br ₂ , Hf (trifluoroacetylacetonato) ₂ Br ₂ , Hf (2,4-hexanedionato) ₂ Cl ₂ , and the like.

Specific examples of the compound represented by [OR ⁴ O] MX ₂ in the general formula (8) include [OCH ₂ CH ₂ O] TiCl ₂ , [OCH ₂ CH ₂ CH ₂ O] TiCl ₂ , [OCH _{2 CH 2 CH 2 CH 2 O} ] TiCl 2, [OCH 2 CH 2 OCH 2 CH 2 O] TiCl 2, [OCH 2 CH 2 O] Ti (CH 3) 2, [OCH 2 CH 2 CH 2 O] Ti (CH ₃ ) ₂ , [OCH ₂ CH ₂ CH ₂ CH ₂ O] Ti (CH ₃ ) ₂ , [OCH ₂ CH ₂ OCH ₂ CH ₂ O] Ti (CH ₃ ) ₂ , [OCH ₂ CH ₂ O] Ti (C ₆ H ₅ ) ₂ , [OCH ₂ CH ₂ CH ₂ O] Ti (C ₆ H ₅ ) ₂ , [OCH ₂ CH ₂ CH ₂ CH ₂ O] Ti (C ₆ H ₅ ) ₂ , [OCH ₂ CH ₂ OCH ₂ CH _{O] Ti (C 6 H 5} ) 2, [OCH 2 CH 2 O] Ti (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 O] Ti (CH 2 C 6 H 5) 2, [ _{OCH 2 CH 2 CH 2 CH 2} O] Ti (CH 2 C 6 H 5) 2, [OCH 2 CH 2 OCH 2 CH 2 O] Ti (CH 2 C 6 H 5) 2, [OCH (C 6 H 5 ) CH (C ₆ H ₅ ) O] Ti (CH ₃ ) ₂ , [OCH ₂ C (C ₆ H ₅ ) ₂ CH ₂ O] Ti (CH ₃ ) ₂ , [OCH ₂ CH ₂ O] ZrCl ₂ , [ _{OCH 2 CH 2 CH 2 O]} ZrCl 2, [OCH 2 CH 2 CH 2 CH 2 O] ZrCl 2, [OCH 2 CH 2 OCH 2 CH 2 O] ZrCl 2, [OCH 2 CH 2 O] Zr (CH 3 _{) 2, [OCH 2 CH 2} CH 2 _{] Zr (CH 3) 2,} [OCH 2 CH 2 CH 2 CH 2 O] Zr (CH 3) 2, [OCH 2 CH 2 OCH 2 CH 2 O] Zr (CH 3) 2, [OCH 2 CH 2 O _{] Zr (C 6 H 5)} 2, [OCH 2 CH 2 CH 2 O] Zr (C 6 H 5) 2, [OCH 2 CH 2 CH 2 CH 2 O] Zr (C 6 H 5) 2, [OCH _{2 CH 2 OCH 2 CH 2 O} ] Zr (C 6 H 5) 2, [OCH 2 CH 2 O] Zr (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 O] Zr (CH 2 C _{6 H 5) 2, [OCH} 2 CH 2 CH 2 CH 2 O] Zr (CH 2 C 6 H 5) 2, [OCH 2 CH 2 OCH 2 CH 2 O] Zr (CH 2 C 6 H 5) 2, _{[OCH (C 6 H 5)} CH (C 6 H 5) O] _{Zr (CH 3) 2, [} OCH 2 C (C 6 H 5) 2 CH 2 O] Zr (CH 3) 2, [OCH 2 CH 2 O] HfCl 2, [OCH 2 CH 2 CH 2 O] HfCl 2 _{, [OCH 2 CH 2 CH 2} CH 2 O] HfCl 2, [OCH 2 CH 2 OCH 2 CH 2 O] HfCl 2, [OCH 2 CH 2 O] Hf (CH 3) 2, [OCH 2 CH 2 CH 2 _{O] Hf (CH 3) 2} , [OCH 2 CH 2 CH 2 CH 2 O] Hf (CH 3) 2, [OCH 2 CH 2 OCH 2 CH 2 O] Hf (CH 3) 2, [OCH 2 CH 2 _{O] Hf (C 6 H 5} ) 2, [OCH 2 CH 2 CH 2 O] Hf (C 6 H 5) 2, [OCH 2 CH 2 CH 2 CH 2 O] Hf (C 6 H 5) 2, [ OCH ₂ CH ₂ OCH _{CH 2 O] Hf (C 6} H 5) 2, [OCH 2 CH 2 O] Hf (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 O] Hf (CH 2 C 6 H 5) 2 _{, [OCH 2 CH 2 CH 2} CH 2 O] Hf (CH 2 C 6 H 5) 2, [OCH 2 CH 2 OCH 2 CH 2 O] Hf (CH 2 C 6 H 5) 2, [OCH (C 6 _{H 5) CH (C 6 H} 5) O] Hf (CH 3) 2, [OCH 2 C (C 6 H 5) 2 CH 2 O] Hf (CH 3) 2, and the like.

Specific examples of the compound represented by [OR ⁴ N (R ⁵ )] MX ₂ in the general formula (9) include [OCH ₂ CH ₂ N (CH ₃ )] TiCl ₂ , [OCH ₂ CH ₂ CH _{2 N (C 6 H 5)} ] TiCl 2, [OCH 2 CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] TiCl 2, [OCH 2 CH 2 OCH 2 CH 2 N (cycloC ₆ H ₁₁ )] TiCl ₂ , [OCH ₂ CH ₂ N (CH ₃ )] Ti (CH ₃ ) ₂ , [OCH ₂ CH ₂ CH ₂ N (C ₆ H ₅ )] Ti (CH ₃ ) _{2 , [OCH 2 CH 2 CH 2} CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] Ti (CH 3) 2, [OCH 2 CH 2 OCH 2 CH 2 N (cycloC 6 H 11) _{] Ti (CH 3) 2,} [OCH _{2 CH 2 N (CH 3)} ] Ti (C 6 H 5) 2, [OCH 2 CH 2 CH 2 N (C 6 H 5)] Ti (C 6 H 5) 2, [OCH 2 CH 2 CH 2 CH _{2 N ((i-C 3} H 7) 2 C 6 H 3)] Ti (C 6 H 5) 2, [OCH 2 CH 2 OCH 2 CH 2 N (CH 3)] Ti (C 6 H 5) 2 _{, [OCH 2 CH 2 n (} i-C 3 H 7)] Ti (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 n (n-C 6 H 13)] Ti (CH 2 C 6 _{H 5) 2, [OCH 2} CH 2 CH 2 CH 2 N (C 6 H 5)] Ti (CH 2 C 6 H 5) 2, [OCH 2 CH 2 OCH 2 CH 2 N ((i-C 3 H _{7) 2 C 6 H 3)} ] Ti (CH 2 C 6 H 5) 2, [OCH (C 6 H 5) CH ( _{6 H 5) N (i-} C 3 H 7)] Ti (CH 3) 2, [OCH 2 C (C 6 H 5) 2 CH 2 N (C 6 H 5)] Ti (CH 3) 2, [ _{OCH 2 CH 2 N (CH 3} )] ZrCl 2, [OCH 2 CH 2 CH 2 N (C 6 H 5)] ZrCl 2, [OCH 2 CH 2 CH 2 CH 2 N ((i-C 3 H 7) _{2 C 6 H 3)] ZrCl} 2, [OCH 2 CH 2 OCH 2 CH 2 N (cycloC 6 H 11)] ZrCl 2, [OCH 2 CH 2 N (CH 3)] Zr (CH 3) 2, [OCH _{2 CH 2 CH 2 N (C} 6 H 5)] Zr (CH 3) 2, [OCH 2 CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] Zr (CH 3 ) ₂ , [OCH ₂ CH ₂ OCH ₂ CH ₂ N (cycl) _{oC 6 H 11)] Zr (} CH 3) 2, [OCH 2 CH 2 N (CH 3)] Zr (C 6 H 5) 2, [OCH 2 CH 2 CH 2 N (C 6 H 5)] Zr ( _{C 6 H 5) 2, [} OCH 2 CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] Zr (C 6 H 5) 2, [OCH 2 CH 2 OCH 2 CH _{2 N (CH 3)] Zr} (C 6 H 5) 2, [OCH 2 CH 2 N (i-C 3 H 7)] Zr (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 N _{(n-C 6 H 13)} ] Zr (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 CH 2 n (C 6 H 5)] Zr (CH 2 C 6 H 5) 2, [OCH _{2 CH 2 OCH 2 CH 2 N} ((i-C 3 H 7) 2 C 6 H 3)] Zr (CH 2 _{6 H 5) 2, [OCH} (C 6 H 5) CH (C 6 H 5) N (i-C 3 H 7)] Zr (CH 3) 2, [OCH 2 C (C 6 H 5) 2 CH _{2 N (C 6 H 5)} ] Zr (CH 3) 2, [OCH 2 CH 2 N (CH 3)] HfCl 2, [OCH 2 CH 2 CH 2 N (C 6 H 5)] HfCl 2, [OCH _{2 CH 2 CH 2 CH 2 N} ((i-C 3 H 7) 2 C 6 H 3)] HfCl 2, [OCH 2 CH 2 OCH 2 CH 2 N (cycloC 6 H 11)] HfCl 2, [OCH 2 _{CH 2 N (CH 3)]} Hf (CH 3) 2, [OCH 2 CH 2 CH 2 N (C 6 H 5)] Hf (CH 3) 2, [OCH 2 CH 2 CH 2 CH 2 N ((i _{-C 3 H 7) 2 C 6} H 3)] Hf (CH 3) 2, _{[OCH 2 CH 2 OCH 2 CH} 2 N (cycloC 6 H 11)] Hf (CH 3) 2, [OCH 2 CH 2 N (CH 3)] Hf (C 6 H 5) 2, [OCH 2 CH 2 CH _{2 N (C 6 H 5)} ] Hf (C 6 H 5) 2, [OCH 2 CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] Hf (C 6 H 5 ) ₂ , [OCH ₂ CH ₂ OCH ₂ CH ₂ N (CH ₃ )] Hf (C ₆ H ₅ ) ₂ , [OCH ₂ CH ₂ N (i-C ₃ H ₇ )] Hf (CH ₂ C ₆ H _{5 ) 2, [OCH 2 CH 2} CH 2 n (n-C 6 H 13)] Hf (CH 2 C 6 H 5) 2, [OCH 2 CH 2 CH 2 CH 2 n (C 6 H 5)] Hf ( _{CH 2 C 6 H 5) 2} , [OCH 2 CH 2 OCH 2 CH 2 N (( _{-C 3 H 7) 2 C 6} H 3)] Hf (CH 2 C 6 H 5) 2, [OCH (C 6 H 5) CH (C 6 H 5) N (i-C 3 H 7)] Hf (CH ₃ ) ₂ , [OCH ₂ C (C ₆ H ₅ ) ₂ CH ₂ N (C ₆ H ₅ )] Hf (CH ₃ ) ₂ , and the like.

Specific examples of the compound represented by [N (R ⁵ ) R ⁴ N (R ⁵ )] MX ₂ in the general formula (10) include [N (CH ₃ ) CH ₂ CH ₂ N (CH ₃ ) _{] TiCl 2, [N ((} i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3] TiCl 2, [N (C _{6 H 5) CH 2 CH 2} CH 2 CH 2 N (C 6 H 5))] TiCl 2, [N (cycloC 6 H 11) CH 2 CH 2 OCH 2 CH 2 N (cycloC 6 H 11)] TiCl 2 _{, [N (CH 3) CH} 2 CH 2 N (CH 3)] Ti (CH 3) 2, [N (C 6 H 5) CH 2 CH 2 CH 2 N (C 6 H 5)] Ti (CH 3 ) ₂ , [N ((i-C ₃ H ₇ ) ₂ C ₆ H ₃ ) CH ₂ CH ₂ CH _{2 CH 2 N ((i-C} 3 H 7) 2 C 6 H 3)] Ti (CH 3) 2, [N (cycloC 6 H 11) CH 2 CH 2 OCH 2 CH 2 N (cycloC 6 H 11)] Ti (CH ₃ ) ₂ , [N (CH ₃ ) CH ₂ CH ₂ N (CH ₃ )] Ti (C ₆ H ₅ ) ₂ , [N (C ₆ H ₅ ) CH ₂ CH ₂ CH ₂ N (C _{6 H 5)] Ti (C 6} H 5) 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H _{3)] Ti (C 6 H} 5) 2, [N (CH 3) CH 2 CH 2 OCH 2 CH 2 N (CH 3)] Ti (C 6 H 5) 2, [N (i-C 3 H 7 _{) CH 2 CH 2 n (i} -C 3 H 7)] Ti (CH 2 C 6 H 5) 2, [n (n-C 6 H 13) C _{2 CH 2 CH 2 N (n} -C 6 H 13)] Ti (CH 2 C 6 H 5) 2, [N (C 6 H 5) CH 2 CH 2 CH 2 CH 2 N (C 6 H 5)] _{Ti (CH 2 C 6 H 5} ) 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 OCH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H _{3)] Ti (CH 2 C} 6 H 5) 2, [N (i-C 3 H 7) CH (C 6 H 5) CH (C 6 H 5) N (i-C 3 H 7)] Ti ( _{CH 3) 2, [N (} C 6 H 5) CH 2 C (C 6 H 5) 2 CH 2 N (C 6 H 5)] Ti (CH 3) 2, [N (CH 3) CH 2 CH 2 _{N (CH 3)] ZrCl 2} , [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 _{3] ZrCl 2, [N (} C 6 H 5) CH 2 CH 2 CH 2 CH 2 N (C 6 H 5))] ZrCl 2, [N (cycloC 6 H 11) CH 2 CH 2 OCH 2 CH 2 N (CycloC ₆ H ₁₁ )] ZrCl ₂ , [N (CH ₃ ) CH ₂ CH ₂ N (CH ₃ )] Zr (CH ₃ ) ₂ , [N (C ₆ H ₅ ) CH ₂ CH ₂ CH ₂ N (C _{6 H 5)] Zr (CH} 3) 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H ₃ )] Zr (CH ₃ ) ₂ , [N (cycloC ₆ H ₁₁ ) CH ₂ CH ₂ OCH ₂ CH ₂ N (cycloC ₆ H ₁₁ )] Zr (CH ₃ ) ₂ , [N (CH ₃ ) CH _{2 CH 2 N (CH 3)]} Zr (C 6 H 5) 2 _{[N (C 6 H 5)} CH 2 CH 2 CH 2 N (C 6 H 5)] Zr (C 6 H 5) 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 _{CH 2 CH 2 N ((i} -C 3 H 7) 2 C 6 H 3)] Zr (C 6 H 5) 2, [N (CH 3) CH 2 CH 2 OCH 2 CH 2 N (CH 3)] _{Zr (C 6 H 5) 2} , [n (i-C 3 H 7) CH 2 CH 2 n (i-C 3 H 7)] Zr (CH 2 C 6 H 5) 2, [n (n-C _{6 H 13) CH 2 CH 2} CH 2 n (n-C 6 H 13)] Zr (CH 2 C 6 H 5) 2, [n (C 6 H 5) CH 2 CH 2 CH 2 CH 2 n (C _{6 H 5)] Zr (CH} 2 C 6 H 5) 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 OCH 2 CH 2 N ( _{i-C 3 H 7) 2} C 6 H 3)] Zr (CH 2 C 6 H 5) 2, [N (i-C 3 H 7) CH (C 6 H 5) CH (C 6 H 5) N _{(i-C 3 H 7)} ] Zr (CH 3) 2, [N (C 6 H 5) CH 2 C (C 6 H 5) 2 CH 2 N (C 6 H 5)] Zr (CH 3) 2 _{, [N (CH 3) CH} 2 CH 2 N (CH 3)] HfCl 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 CH 2 N ((i-C 3 _{H 7) 2 C 6 H 3} ] HfCl 2, [N (C 6 H 5) CH 2 CH 2 CH 2 CH 2 N (C 6 H 5))] HfCl 2, [N (cycloC 6 H 11) CH 2 _{CH 2 OCH 2 CH 2 N (} cycloC 6 H 11)] HfCl 2, [N (CH 3) CH 2 CH 2 N (CH 3 _{] Hf (CH 3) 2,} [N (C 6 H 5) CH 2 CH 2 CH 2 N (C 6 H 5)] Hf (CH 3) 2, [N ((i-C 3 H 7) 2 C _{6 H 3) CH 2 CH 2} CH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] Hf (CH 3) 2, [N (cycloC 6 H 11) CH 2 CH 2 OCH 2 _{CH 2 N (cycloC 6 H 11} )] Hf (CH 3) 2, [N (CH 3) CH 2 CH 2 N (CH 3)] Hf (C 6 H 5) 2, [N (C 6 H 5) _{CH 2 CH 2 CH 2 N (} C 6 H 5)] Hf (C 6 H 5) 2, [N ((i-C 3 H 7) 2 C 6 H 3) CH 2 CH 2 CH 2 N ((i _{-C 3 H 7) 2 C 6} H 3)] Hf (C 6 H 5) 2, [N (CH 3) CH 2 CH 2 OCH _{CH 2 N (CH 3)]} Hf (C 6 H 5) 2, [N (i-C 3 H 7) CH 2 CH 2 N (i-C 3 H 7)] Hf (CH 2 C 6 H 5) _{2, [n (n-C} 6 H 13) CH 2 CH 2 CH 2 n (n-C 6 H 13)] Hf (CH 2 C 6 H 5) 2, [n (C 6 H 5) CH 2 CH _{2 CH 2 CH 2 N (C} 6 H 5)] Hf (CH 2 C 6 H 5) 2, [
_{N ((i-C 3 H} 7) 2 C 6 H 3) CH 2 CH 2 OCH 2 CH 2 N ((i-C 3 H 7) 2 C 6 H 3)] Hf (CH 2 C 6 H 5) _{2, [N (i-C} 3 H 7) CH (C 6 H 5) CH (C 6 H 5) N (i-C 3 H 7)] Hf (CH 3) 2, [N (C 6 H 5 _{) CH 2 C (C 6 H} 5) 2 CH 2 N (C 6 H 5)] Hf (CH 3) 2, and the like.

  Examples of aluminoxanes include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and dry aluminoxane obtained by removing and purifying unreacted aluminum compounds in these aluminoxanes. Instead of aluminoxanes, boron compounds such as triphenylborane, trispentafluorophenylborane, triphenylmethyltrispentafluoroborate, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, dioctylaluminum chloride, etc. The organoaluminum compound can also be used.

  Examples of the organoaluminum compound include dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride, and other alkylaluminum halides; Aluminoxanes.

The amount of the above components used is 1 × 10 ^{−5 to} 0.5 mol, preferably 1 × 10 ^{−4 to} 0.1 mol of metal complex per mol of propylene used, and aluminoxanes, boron compounds or organic compounds are used. The aluminum compound is 1 × 10 ^{−6 to} 0.5 mol, preferably 1 × 10 ^{−5 to} 0.1 mol.
The polymerization reaction is performed at a temperature of −100 to 100 ° C. for 0.5 to 50 hours, preferably at −80 to 80 ° C. for 1 to 30 hours.

  (Ii) a catalyst comprising a metal having a cycloalkadienyl group or a derivative thereof selected from the group consisting of titanium, zirconium and hafnium, a complex having a halogen or an alkyl group, and an aluminoxane, a boron compound or an organoaluminum compound. In the complex, two cycloalkadienyl groups or derivatives thereof may be crosslinked or not. The crosslinkable compound is preferably a monocrosslinked metallocene compound.

  Examples of the non-crosslinked metallocene compound include compounds represented by general formulas (11) to (13).

In the general formulas (11) to (13), R ¹ is a hydrogen atom or a substituent of an aliphatic, aromatic and alicyclic hydrocarbon group having 1 to 8 carbon atoms, or SiR ₃ (R is 1 carbon atom. ˜5 alkyl groups, aromatic groups, or alicyclic substituents, which may be the same or different at the same time.
X represents a halogen or an alkyl group having 1 to 10 carbon atoms. Here, when X is halogen, fluorine, chlorine, bromine and iodine are exemplified, and when X is an alkyl group, methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, s- Examples thereof include a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Among these, chlorine and a methyl group are preferable, and a methyl group is particularly preferable. M is any metal of Ti, Zr, and Hf. n shows the integer of 1-3.

  In addition, although the indenyl group and the phenyl group of the fluorenyl group in the general formulas (12) to (13) may have a substituent, a monocrosslinked cyclopentadienyl, fluorenyl or a derivative thereof, and a monocrosslinked bisindenyl or Compounds having a ligand developed for the production of highly crystalline polypropylene such as derivatives thereof are not preferred.

  The non-bridged metallocene compounds represented by the general formulas (11) to (13) are substituted products in which each cyclopentadienyl group is substituted with 1 to 4 substituents, preferably 1 to 3 substituents. It is a substituted product substituted with. Only atactic polypropylene can be obtained from those having no substituents or having 5 substituents, which is not preferable.

Specific examples of monosubstituted compounds in which each cyclopentadienyl group has one substituent include, for example, (methylcyclopentadienyl) ₂ ZrCl ₂ , (methylcyclopentadienyl) ₂ ZrBr ₂ , (ethylcyclopenta Dienyl) ₂ ZrCl ₂ , (ethylcyclopentadienyl) ₂ Zr (methyl) ₂ , (isopropylcyclopentadienyl) ₂ ZrCl ₂ , (isopropylcyclopentadienyl) ₂ ZrI ₂ , (n-propylcyclopentadi Enyl) ₂ ZrCl ₂ , (n-propylcyclopentadienyl) ₂ Zr (phenyl) ₂ , (n-butylcyclopentadienyl) ₂ ZrCl ₂ , (i-butylcyclopentadienyl) ₂ Zr (benzyl) ₂ , _{(i-butylcyclopentadienyl)} 2 Zr _(methyl) 2, (s-butyl _{Cyclopentadienyl)} 2 Zr _(benzyl) 2, _{(t-butylcyclopentadienyl) 2} ZrCl 2, _{(t- butylcyclopentadienyl) 2} ZrBr 2, (neopentyl _{cyclopentadienyl)} 2 ZrCl _2, (Neopentylcyclopentadienyl) ₂ Zr (methyl) ₂ , (cyclopentylcyclopentadienyl) ₂ ZrCl ₂ , (cyclopentylcyclopentadienyl) ₂ ZrCl ₂ , (n-hexylcyclopentadienyl) ₂ ZrCl ₂ , (N-hexylcyclopentadienyl) ₂ Zr (phenyl) ₂ , (cyclohexylcyclopentadienyl) ₂ ZrCl ₂ , (cyclohexylcyclopentadienyl) ₂ Zr (methyl) ₂ , (phenylcyclopentadienyl) ₂ ZrCl ₂ , (trimethylsilylsik Lopentadienyl) ₂ ZrCl ₂ , (triphenylsilylcyclopentadienyl) ₂ ZrCl ₂ , (diphenylmethylsilylcyclopentadienyl) ₂ ZrCl ₂ , (methylcyclopentadienyl) ₂ HfCl ₂ , (methylcyclopentadienyl) ₂ HfBr _{2, (ethylcyclopentadienyl)} 2 HfCl _{2, (ethylcyclopentadienyl)} 2 Hf _(methyl) 2, _{(isopropylcyclopentadienyl)} 2 HfCl _{2, (isopropylcyclopentadienyl)} 2 HFI ₂ , (N-propylcyclopentadienyl) ₂ HfCl ₂ , (n-propylcyclopentadienyl) ₂ Hf (phenyl) ₂ , (n-butylcyclopentadienyl) ₂ HfCl ₂ , (i-butylcyclopentadienyl) _enyl) 2 Hf (benzylidene ) _{2, (i-butylcyclopentadienyl)} 2 Hf _(methyl) 2, _{(s-butylcyclopentadienyl)} 2 Hf _(benzyl) 2, _{(t-butylcyclopentadienyl) 2} HfCl 2, (t - _{butylcyclopentadienyl)} 2 HfBr _2, (neopentyl _{cyclopentadienyl)} 2 HfCl _2, (neopentyl _{cyclopentadienyl)} 2 Hf _(methyl) 2, (cyclopentyl _{cyclopentadienyl)} 2 HfCl _2, ( cyclopentyl _{cyclopentadienyl)} 2 HfCl _2, (n-hexyl _{cyclopentadienyl)} 2 HfCl _2, (n-hexyl _{cyclopentadienyl)} 2 Hf _(phenyl) 2, (cyclohexyl _{cyclopentadienyl)} 2 HfCl _2, (Cyclohexylcyclopentadienyl) ₂ Hf (methyl ) ₂ , (phenylcyclopentadienyl) ₂ HfCl ₂ , (trimethylsilylcyclopentadienyl) ₂ HfCl ₂ , (triphenylsilylcyclopentadienyl) ₂ HfCl ₂ , (diphenylmethylsilylcyclopentadienyl) ₂ HfCl ₂ , (Methylcyclopentadienyl) ₂ TiCl ₂ , (methylcyclopentadienyl) ₂ TiBr ₂ , (ethylcyclopentadienyl) ₂ TiCl ₂ , (ethylcyclopentadienyl) ₂ Ti (methyl) ₂ , (isopropyl Cyclopentadienyl) ₂ TiCl ₂ , (isopropylcyclopentadienyl) ₂ TiI ₂ , (n-propylcyclopentadienyl) ₂ TiCl ₂ , (n-propylcyclopentadienyl) ₂ Ti (phenyl) ₂ , ( n-Butylcyclopen _{Dienyl) 2} TiCl 2, (i- butyl _{cyclopentadienyl)} 2 Ti _(benzyl) 2, _{(i-butylcyclopentadienyl)} 2 Ti _(methyl) 2, _{(s-butylcyclopentadienyl)} 2 Ti ( (Benzyl) ₂ , (t-butylcyclopentadienyl) ₂ TiCl ₂ , (t-butylcyclopentadienyl) ₂ TiBr ₂ , (neopentylcyclopentadienyl) ₂ TiCl ₂ , (neopentylcyclopentadienyl) ₂ Ti (methyl) ₂ , (cyclopentylcyclopentadienyl) ₂ TiCl ₂ , (cyclopentylcyclopentadienyl) ₂ TiCl ₂ , (n-hexylcyclopentadienyl) ₂ TiCl ₂ , (n-hexylcyclopentadienyl) ) ₂ Ti (phenyl) ₂ , (cyclohexylcyclopentadi) Enyl) ₂ TiCl ₂ , (cyclohexylcyclopentadienyl) ₂ Ti (methyl) ₂ , (phenylcyclopentadienyl) ₂ TiCl ₂ , (trimethylsilylcyclopentadienyl) ₂ TiCl ₂ , (triphenylsilylcyclopentadienyl) ) ₂ TiCl ₂ , (diphenylmethylsilylcyclopentadienyl) ₂ TiCl ₂ , and the like.

Specific examples of the disubstituted product in which the cyclopentadienyl group has two substituents include, for example, (dimethylcyclopentadienyl) ₂ ZrCl ₂ , (dimethylcyclopentadienyl) ₂ ZrBr ₂ , (methylethylcyclopenta Dienyl) ₂ ZrI ₂ , (methylpropylcyclopentadienyl) ₂ Zr (methyl) ₂ , (dipropylcyclopentadienyl) ₂ Zr (phenyl) ₂ , (diphenylcyclopentadienyl) ₂ Zr (benzyl) ₂ , _(indenyl) 2 ZrCl _{2, (dimethylcyclopentadienyl)} 2 HfCl _{2, (dimethylcyclopentadienyl)} 2 HfBr _2, (methyl ethyl _{cyclopentadienyl)} 2 _HFI 2, (methylpropyl cyclopentadienyl) ₂ Hf _(methyl) 2, (di propylcyclopentadienyl _Enyl) 2 Hf _(phenyl) 2, (diphenyl _{cyclopentadienyl)} 2 Hf _(benzyl) 2, _(indenyl) 2 HfCl _{2, (dimethylcyclopentadienyl)} 2 TiCl _{2, (dimethylcyclopentadienyl)} 2 TiBr ₂ , (methylethylcyclopentadienyl) ₂ TiI ₂ , (methylpropylcyclopentadienyl) ₂ Ti (methyl) ₂ , (dipropylcyclopentadienyl) ₂ Ti (phenyl) ₂ , (diphenylcyclopentadienyl ) ₂ Ti (benzyl) ₂ , (indenyl) ₂ TiCl ₂ , and the like.

Specific examples of the tri- or tetrasubstituted body each cyclopentadienyl group has 3 or 4 substituents, for example, (trimethyl _{cyclopentadienyl)} 2 ZrCl _{2, (indenylmethyl)} 2 ZrCl _2, (tetra (Methylcyclopentadienyl) ₂ ZrCl ₂ , (fluorenyl) ₂ ZrCl ₂ , (trimethylcyclopentadienyl) ₂ HfCl ₂ , (indenylmethyl) ₂ HfCl ₂ , (tetramethylcyclopentadienyl) ₂ HfCl ₂ , ( _{fluorenyl) 2} HfCl 2, _{(trimethylcyclopentadienyl) 2} TiCl 2, _{(indenylmethyl) 2} TiCl 2, _{(tetramethylcyclopentadienyl) 2} TifCl 2, _(fluorenyl) 2 TiCl _2, include like.

  Examples of the monocrosslinked metallocene compound include a compound represented by the general formula (14).

In the general formula (14), R ⁴ represents a divalent aromatic or alicyclic group, an aliphatic hydrocarbon group, and / or a divalent oxygen-containing group, a divalent nitrogen-containing group, or a divalent silicon-containing group. Represents a divalent group containing different elements such as oxygen, nitrogen and silicon other than C and H, and R ^{5 to} R ⁸ are each a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. May be the same or different. Further, at least one of R ^{5 to} R ⁸ of both cyclopentadiene rings is a hydrogen atom. X represents a halogen, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. M is any metal of Ti, Zr, and Hf.

Specific examples of the monocrosslinked metallocene compound include, for example, CH ₂ CH ₂ (methylcyclopentadienyl) ₂ ZrBr ₂ , (CH ₃ ) ₂ Si (cyclopentadienyl) (dimethylcyclopentadienyl) ₂ ZrBr _2. , (C ₆ H ₅ ) C (ethylcyclopentadienyl) ₂ ZrCl ₂ , CH ₂ CH ₂ CH ₂ (ethylcyclopentadienyl) (trimethylcyclopentadienyl) Zr (methyl) ₂ , CH ₂ CH ₂ ( i-propylcyclopentadienyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (i-propylcyclopentadienyl) ₂ ZrI ₂ , (CH ₃ ) ₂ Si (n-propylcyclopentadienyl) (tetramethylcyclo _{pentadienyl) 2 ZrCl 2, (CH 3} ) 2 Si (n- propyl cyclopentadienylide ) ₂ Zr _{(phenyl) 2, (C 6 H 5} ) 2 Si (n- _{butylcyclopentadienyl) 2 ZrCl 2, (CH 3} ) 2 Si (i- butyl _{cyclopentadienyl)} 2 Zr _{(benzyl) 2} CH ₂ CH ₂ (methylcyclopentadienyl) (i-butylcyclopentadienyl) Zr (methyl) ₂ , (CH ₃ ) ₂ Si (s-butylcyclopentadienyl) ₂ Zr (benzyl) ₂ , ( CH _{3) 2} Si (t- _{butylcyclopentadienyl) 2 ZrCl 2, (CH 3} ) 2 Si (t- _{butylcyclopentadienyl) 2 ZrBr 2, (CH 3} ) 2 Si ( neopentyl cyclopentadienyl ) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (neopentylcyclopentadienyl) (dimethylcyclopentadienyl) Zr (methyl) ₂ , (CH ₃ ) ₂ Si (cyclopentylcyclopentadienyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (cyclopentylcyclopentadienyl) ₂ ZrI ₂ , (CH ₃ ) ₂ Si (n-hexylcyclopentadienyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (n-hexylcyclopentadienyl) ₂ Zr (phenyl) ₂ , (CH ₃ ) ₂ Si (cyclohexylcyclopentadienyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si ( (Cyclohexylcyclopentadienyl) ₂ Zr (methyl) ₂ , (CH ₃ ) ₂ Si (phenylcyclopentadienyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (dimethylcyclopentadienyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (dimethylcyclopentadienyl) ₂ ZrBr ₂ , (CH ₃ ) ₂ Si (dimethylcyclopentadienyl) (diethylcyclopentadienyl) ₂ ZrI ₂ , (CH ₃ ) ₂ Si (methylpropylcyclopentadienyl) ₂ Zr (methyl) ₂ , (CH ₃ ) ₂ Si (dipropylcyclo) Pentadienyl) ₂ Zr (phenyl) ₂ , (CH ₃ ) ₂ Si (diphenylcyclopentadienyl) ₂ Zr (benzyl) ₂ , CH ₂ CH ₂ CH ₂ (indenyl) ₂ ZrCl ₂ , (CH ₃ ) ₂ Si (Trimethylcyclopentadienyl) ₂ ZrCl ₂ , CH ₂ CH ₂ CH ₂ (indenylmethyl) ₂ ZrCl ₂ , (CH ₃ ) ₄ Si ₂ (cyclopentadienyl) (tetramethylcyclopentadienyl) ZrCl ₂ , CH ₂ CH ₂ CH ₂ (methylcyclopentadienyl) (fluorenyl) Zr l _{2, CH 2 CH 2 (methylcyclopentadienyl) 2 HfBr 2, (CH 3} ) 2 Si ( cyclopentadienyl) (dimethyl _{cyclopentadienyl) 2 HfBr 2, (C 6} H 5) C ( ethyl Cyclopentadienyl) ₂ HfCl ₂ , CH ₂ CH ₂ CH ₂ (ethylcyclopentadienyl) (trimethylcyclopentadienyl) Hf (methyl) ₂ , CH ₂ CH ₂ (i-propylcyclopentadienyl) ₂ HfCl ₂ , (CH ₃ ) ₂ Si (i-propylcyclopentadienyl) ₂ HfI ₂ , (CH ₃ ) ₂ Si (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl) ₂ HfCl ₂ , (CH _{3) 2} Si (n- propyl _{cyclopentadienyl)} 2 Hf _{(phenyl) 2, (C} 6 _{H 5 2} Si _{(n-butylcyclopentadienyl) 2 HfCl 2, (CH 3} ) 2 Si (i- butyl _{cyclopentadienyl)} 2 Hf _{(benzyl) 2, CH} 2 _CH 2 (methylcyclopentadienyl) (i -Butylcyclopentadienyl) Hf (methyl) ₂ , (CH ₃ ) ₂ Si (s-butylcyclopentadienyl) ₂ Hf (benzyl) ₂ , (CH ₃ ) ₂ Si (t-butylcyclopentadienyl) _{2 HfCl 2, (CH 3)} 2 Si (t- _{butylcyclopentadienyl) 2 HfBr 2, (CH 3} ) 2 Si ( neopentyl _{cyclopentadienyl) 2 HfCl 2, (CH 3} ) 2 Si ( neopentyl cyclopentadienyl) (dimethyl cyclopentadienyl) Hf _{(methyl) 2, (CH 3) 2} Si ( cyclopentyl consequent _{Pentadienyl) 2 HfCl 2, (CH 3} ) 2 Si ( cyclopentyl _{cyclopentadienyl) 2 HfI 2, (CH 3} ) 2 Si (n- hexyl _{cyclopentadienyl) 2 HfCl 2, (CH 3} ) 2 Si (n - hexyl _{cyclopentadienyl)} 2 Hf _{(phenyl) 2, (CH 3) 2} Si ( cyclohexyl _{cyclopentadienyl) 2 HfCl 2, (CH 3} ) 2 Si ( cyclohexyl _{cyclopentadienyl)} 2 Hf _{(methyl) 2} , _{(CH 3)} 2 Si _{(phenyl cyclopentadienyl) 2 HfCl 2, (CH 3} ) 2 Si ( _{dimethylcyclopentadienyl) 2 HfCl 2, (CH 3} ) 2 Si ( _{dimethylcyclopentadienyl)} 2 HfBr _{2, (CH 3) 2 Si} ( dimethylcyclopentadienyl) (di Chill _{cyclopentadienyl) 2 HfI 2, (CH 3} ) 2 Si ( methylpropyl _{cyclopentadienyl)} 2 Hf _{(methyl) 2, (CH 3) 2} Si ( dipropyl _{cyclopentadienyl)} 2 Hf (phenyl) ₂ , (CH ₃ ) ₂ Si (diphenylcyclopentadienyl) ₂ Hf (benzyl) ₂ , CH ₂ CH ₂ CH ₂ (indenyl) ₂ HfCl ₂ , (CH ₃ ) ₂ Si (trimethylcyclopentadienyl) ₂ HfCl ₂ , CH ₂ CH ₂ CH ₂ (indenylmethyl) ₂ HfCl ₂ , (CH ₃ ) ₄ Si ₂ (cyclopentadienyl) (tetramethylcyclopentadienyl) HfCl ₂ , CH ₂ CH ₂ CH ₂ (methylcyclo pentadienyl) _{(fluorenyl) HfCl 2, CH 2 CH 2} ( methylcyclopentadienyl pen _{Dienyl) 2 TiBr 2, (CH 3} ) 2 Si ( cyclopentadienyl) (dimethyl _{cyclopentadienyl) 2 TiBr 2, (C 6} H 5) C ( _{ethylcyclopentadienyl) 2} TiCl 2, _CH 2 _{CH 2} CH ₂ (ethylcyclopentadienyl) (trimethylcyclopentadienyl) Ti (methyl) ₂ , CH ₂ CH ₂ (i-propylcyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (i-propyl) Cyclopentadienyl) ₂ TiI ₂ , (CH ₃ ) ₂ Si (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (n-propylcyclopentadienyl) ) ₂ Ti (phenyl) ₂ , (C ₆ H ₅ ) ₂ Si (n-butylcyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (i-butylcyclopentadienyl) ₂ Ti (benzyl) ₂ , CH ₂ CH ₂ (methylcyclopentadienyl) (i-butylcyclopentadienyl) Ti (methyl) ₂ , (CH ₃ ) ₂ Si (s-butylcyclopentadienyl) ₂ Ti (benzyl) ₂ , (CH ₃ ) ₂ Si (t-butylcyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si ( t- _{butylcyclopentadienyl) 2 TiBr 2, (CH 3} ) 2 Si ( neopentyl _{cyclopentadienyl) 2 TiCl 2, (CH 3} ) 2 Si ( neopentyl cyclopentadienyl) (dimethyl cyclopentadienyl ) Ti _{(methyl) 2, (CH 3) 2} Si ( cyclopentyl _{cyclopentadienyl) 2} TiCl 2, (CH ) ₂ Si (cyclopentyl _{cyclopentadienyl) 2 TiI 2, (CH 3} ) 2 Si (n- hexyl _{cyclopentadienyl) 2 TiCl 2, (CH 3} ) 2 Si (n- hexyl _{cyclopentadienyl)} 2 Ti (Phenyl) ₂ , (CH ₃ ) ₂ Si (cyclohexylcyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (cyclohexylcyclopentadienyl) ₂ Ti (methyl) ₂ , (CH ₃ ) ₂ Si (phenyl) Cyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (dimethylcyclopentadienyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (dimethylcyclopentadienyl) ₂ TiBr ₂ , (CH ₃ ) ₂ Si ( dimethyl cyclopentadienyl) (diethyl _{cyclopentadienyl)} 2 _TiI 2, CH _{3) 2} Si (methylpropyl _{cyclopentadienyl)} 2 Ti _{(methyl) 2, (CH 3) 2} Si ( dipropyl _{cyclopentadienyl)} 2 Ti _{(phenyl) 2, (CH 3) 2} Si ( diphenyl cyclo Pentadienyl) ₂ Ti (benzyl) ₂ , CH ₂ CH ₂ CH ₂ (indenyl) ₂ TiCl ₂ , (CH ₃ ) ₂ Si (trimethylcyclopentadienyl) ₂ TiCl ₂ , CH ₂ CH ₂ CH ₂ (indenyl) Methyl) ₂ TiCl ₂ , (CH ₃ ) ₄ Si ₂ (cyclopentadienyl) (tetramethylcyclopentadienyl) TiCl ₂ , CH ₂ CH ₂ CH ₂ (methylcyclopentadienyl) (fluorenyl) TiCl ₂ , etc. Is mentioned.

In the case of an unbridged metallocene compound, RCp ₂ TiCl ₂ in which R is 3 or more carbon atoms (for example, t-Bu) is preferable. Moreover, when the metallocene compound is a monocrosslinked product such as Me ₂ CRCp ₂ TiCl ₂ , it is preferable that R is C _1-8 (for example, t-Bu).

  Moreover, the above-mentioned (i) can be used for the aluminoxanes, boron compounds and organoaluminum compounds.

The amount of the component used is 5.0 × 10 ⁻⁷ to 5.0 × 10 ⁻³ mol, preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻⁴ mol of metallocene compound per mol of propylene. The aluminoxane, boron compound or organoaluminum compound is 1.0 × 10 ^{−5 to} 5.0 mol, preferably 1.0 × 10 ^{−3 to} 0.1 mol.

The polymerization reaction is performed at a temperature of −100 to 200 ° C. for 0.1 to 100 hours, preferably at −50 to 150 ° C. for 1 to 50 hours. Further, in the above non-bridged metallocene compound RCp ₂ TiCl ₂ , when R is 3 or more carbon atoms, it is 0 ° C. or less, and Me ₂ CRCp ₂ TiCl ₂ is a mono-bridged metallocene compound having a small carbon number of R Is preferably polymerized at around 100 ° C.

  The polypropylene of the present invention can be produced using the above homogeneous catalyst, and hydrogen, diethyl zinc, and a Si—H bond-containing compound can be added as a molecular weight regulator. These catalysts can be used by being supported on a carrier such as silica, alumina, zirconia, titania and the like.

On the other hand, in the present invention, polypropylene can be synthesized using a heterogeneous catalyst.
Examples of the heterogeneous catalyst include (a) a titanium compound or zirconium compound, a hafnium compound and (b) an Mg compound or Mn compound, a Co compound, (c) an organoaluminum compound, and (d) an electron as necessary. Examples thereof include a catalyst comprising a donor compound.

  (I) Examples of ligands such as titanium compounds include halogens, alkoxy groups and derivatives thereof, cyclopentadienyl groups and derivatives thereof, acetylacetone and derivatives thereof, and their valence is 2 to 4, especially Tetravalent is preferable. Examples of the tetravalent ligand titanium compound include compounds represented by the general formula (15).

_{TiX a (OR) b Cp c} (acac) d (15)
(X represents halogen, R represents an alkyl group having 1 to 4 carbon atoms, Cp represents a cyclopentadienyl group, acac represents an acetylacetone ligand, and a, b, c and d represent 0 to 4) An integer of a + b + c + d = 4.)
Specific compounds include TiCl ₄ , Ti (OBu) ₄ , Cp ₂ TiCl ₂ , (acac) ₂ TiCl _{2 and the} like.

(B) Examples of ligands such as Mg compounds include halogens, alkyl groups and derivatives thereof, alkoxy groups and derivatives thereof. As an example of a magnesium compound, the compound represented by General formula (16) is mentioned, for example.
MgX _e R _f (OR) _g (16)
(X represents halogen, R represents an alkyl group having 1 to 4 carbon atoms, e, f, and g represent integers of 0 to 2, and e + f + g = 2.)

  Moreover, (c) As an organoaluminum compound, the compound similar to the compound used with the said homogeneous catalyst is mentioned.

  Furthermore, (d) electron donating compounds include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, Examples include alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, and carbonates. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, and ethers are preferably used.

  Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, malonic acid, and succinic acid. , Glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexamonocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid Fragrances such as acids, alicyclic carboxylic acids such as cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tert-butylbenzoic acid, naphthoic acid, cinnamic acid Monocarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid Pyromellitic acid, and aromatic polycarboxylic acids such as mellitic acid.

As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.
As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, acrylic Ethyl acetate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate , Dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, di tartrate Chill, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, α-naphthoic acid Isobutyl, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, Diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitic acid, tributyl trimellitic acid, tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetra pyromellitic acid tetra Chill, and the like.

  As the carboxylic acid halide, acid halides of the above carboxylic acids can be used. Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid promide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, succinic acid chloride, succinic acid bromide , Glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid Luric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cyclo-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride, Benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid Examples include dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, and phthalic acid butyl chloride can be used.

  Alcohols are represented by the general formula ROH. In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl, aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, bezyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethyl phenol, isopropyl. Phenol, p-tertiary butyl phenol, n-octyl phenol and the like.

  Ethers are represented by the general formula ROR ′. In the formula, R and R ′ are alkyl, alkenyl, cycloalkyl, aryl, and aralkyl having 1 to 12 carbon atoms, and R and R ′ may be the same or different and may form a ring. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether. , Tetrahydrofuran and the like.

  Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxylane, Methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltrif Enoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltripheno Sisilane, methyltriallyloxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyl Diphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, diphenyl Benzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimeth Shishiran, chloro phenylalanine diethoxy silane and the like.

Specific examples of the electron-donating compound containing a hetero atom include 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6 as compounds containing a nitrogen atom. -Diisopropylpiperidine, 2,2,5,5-tetramethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methyl Pyridine, 1,2,4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-methylpyrrole, 2,5-dimethylpyrrole, imidazole, toluic acid Amide, benzonitrile, acetonitrile, aniline, paratoluidine, Lutotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc. are compounds containing sulfur atoms such as thiophenol, thiophene, ethyl 2-thiophenenecarboxylate, ethyl 2-thiophenenecarboxylate, 2-methylthiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl mercaptan, diethyl thioether, diphenyl thioether, methyl benzenesulfonate, methylsulfite, ethylsulfite, etc. include tetrahydrofuran, 2 -Methyltetrahydrofuran, 3-methyltetrahydrofuran, 2-ethyltetrahydrofuran, dioxane, dimethyl ether, diethyl ether, di- Tyl ether, diisoaluminum ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, ethyl 2-furalate, isoamyl 2-furalate, methyl 2-furalate, propyl 2-furalate, etc. Examples of the compound to be included include triphenyl phosphine, tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphite, and diphenyl phosphite.
Of these electron donating compounds, ether compounds are particularly preferable. Moreover, it may be used at the time of preparation of Mg, Ti, halogen-based catalyst components, may be used at the time of polymerization, or two or more kinds may be used.

  The heterogeneous catalyst may be used by being supported on a metal oxide such as silica and alumina, and specifically, Japanese Patent Publication Nos. 7-12970, 7-121971, and 7-121972. And JP-A-62-295909, JP-A-63-54407, JP-A-63-54408 and the like.

  The polymerization conditions using the heterogeneous catalyst can be performed under the same conditions as those for the homogeneous catalyst (ii).

  In addition, when a heterogeneous catalyst is used, a polymer insoluble in toluene at room temperature, such as crystalline polypropylene, may be produced as a by-product. In such a case, it can be used after being removed.

2. Modified Polypropylene The modified polypropylene of the present invention is a polypropylene having a racemic dyad fraction [r] value measured by ¹³ C-NMR in the range of 0.12 to 0.49. Or a dicarboxylic acid or a dicarboxylic acid anhydride is grafted.

  This modified polypropylene is characterized by having good affinity with polypropylene and high solubility in a solvent because the base polymer is a polypropylene having a racemic dyad fraction [r] value of 0.12 to 0.49. have.

  In the modified polypropylene of the present invention, the modifier is grafted to the polypropylene main chain. When the modifier is introduced at two or more locations, the modifier is randomly introduced as a pendant structure into the main chain polypropylene.

For example, when one modifier monomer is bonded to one position of the polypropylene main chain, it becomes a modified polypropylene in which one unit of n or m = 1 is bonded, and one modifier monomer is bonded to three positions of the polypropylene main chain. When bonded one by one, it becomes a modified polypropylene in which three units of n or m = 1 are bonded. In addition, when 10 locations (units) of the polypropylene main chain are modified, 2 units with n or m = 1, 3 units with n or m = 2, and 4 units with n or m = 3 , N or m is a modified polypropylene having a modified amount of 2 + 6 + 12 = 20.
In the present invention, the average modification amount per molecular chain of polypropylene is 0.1 to 100, preferably 0.3 to 80, more preferably 0.5 to 50, and particularly preferably 1.0 to 30. It is.

The modified polypropylene of the present invention is a radical in which a polypropylene having a racemic dyad fraction [r] value measured by ¹³ C-NMR in a range of 0.12 to 0.49 is dissolved in an organic solvent or in a kneader. It can be obtained by reacting with a denaturing agent in the presence of a reaction initiator.

  Usually, one type of modifier is used, but two or more types can also be used. When using 2 or more types, 2 or more types are selected from either the compound represented by the following general formula (3) and (4), or dicarboxylic acid (anhydride). Further, two or more kinds of modifiers may be mixed in advance and reacted with polypropylene, or may be reacted in two or more stages.

In formula (3), R ¹ , R ² and R ³ are the same as described above.

In formula (4), R ⁶ and R ⁷ are the same as described above.

The modification reaction is performed in a temperature range of −50 to 200 ° C., preferably −30 to 180 ° C., as long as the polymer is dissolved in an organic solvent. If it is less than −50 ° C., the reaction rate is slow. On the other hand, if it exceeds 200 ° C., the molecular chain of the olefin copolymer is cleaved, which is not preferable. Particularly preferably, the denaturing reaction is performed in a temperature range of 0 ° C to 180 ° C.
The reaction time is 1 minute or longer, preferably 5 minutes to 10 hours, particularly preferably 10 minutes to 5 hours. The longer the reaction time, the better the amount of modifier introduced into the polymer. Usually, the denaturation reaction is performed in one step, but the reaction may be performed in two or more steps.

  Examples of the organic solvent include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, nonane, decane, and dodecane; saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane; benzene, toluene, xylene, and the like An aromatic hydrocarbon etc. are mentioned.

  Moreover, as a radical reaction initiator, azo type such as azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, t-butylperoxy-2-ethylhexano Peroxides such as acrylate and 2,5-dimethyl-2,5-di-t-butylperoxyhexane can be used, and two or more kinds of radical reaction initiators may be used.

  On the other hand, when using a kneading machine for modification reaction such as an extrusion kneader, the inside of the apparatus is 30 to 250 ° C., preferably 50 to 200 ° C. The modification reaction varies depending on the molecular weight of polypropylene, the type and amount of the modifier and radical reaction initiator, the reaction solvent used, etc., but the reaction rate is slow at less than 30 ° C., whereas the polymer molecular chain exceeds 250 ° C. Since it is cut, it is not preferable. The reaction temperature of the modification reaction may be maintained at the same temperature or may be changed during the modification reaction.

  The reaction time (residence time in the kneader) is 0.1 to 30 minutes, and more preferably 0.2 to 20 minutes. If the residence time is shorter than 0.1 minutes, the efficiency of the modification reaction is poor. On the other hand, as the residence time is longer, the amount of the modifier introduced into the polypropylene is improved. However, if the residence time is longer than 30 minutes, the molecular weight reduction and coloring due to polymer deterioration become significant.

  Examples of the modifier include, as the compound represented by the general formula (3), in addition to (meth) acrylic acid, derivatives of (meth) acrylic acid include the following.

Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, triphenylmethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , T-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, alkyl esters such as triphenylmethyl methacrylate; glycidyl esters such as glycidyl acrylate, glycidyl methacrylate; sodium acrylate, potassium acrylate, acrylic acid Lithium salt, sodium methacrylate salt Alkali metal salts of (meth) acrylic acid such as potassium methacrylate and lithium methacrylate; acrylic acid chloride, acrylic acid bromide, α-chloro-methyl acrylate, methacrylic acid chloride, methacrylic acid bromide, α-chloro-methyl methacrylate (Meth) acrylic acid halides; acrylamide, N, N-dimethylacrylamide, N, N-diisopropylacrylamide, methacrylamide, N, N-dimethylmethacrylamide, N, N-diisopropylmethacrylamide, N, N-dimethyl Amino group-containing (meth) acrylic acid derivatives such as aminoethyl acrylate and N, N-dimethylaminoethyl methacrylate; ethylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol Diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol Di (meth) acrylates such as dimethacrylate; 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, trimethoxysilylpropyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy OH groups such as propyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, trimethoxysilylpropyl methacrylate, etc. Coxy group-containing (meth) acrylic acid derivatives; isocyanate group-containing (meth) acrylic acid derivatives such as 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl acrylate; ethylene glycol methacrylate phosphate, 2-methacryloyloxyethyl phosphorylcholine, etc. P-containing (meth) acrylic acid derivatives. Furthermore, as other P-containing (meth) acrylic acid derivatives, CH ₂ ═C (CH ₃ ) CO—O—CH ₂ —CH ₂ (CH ₂ Cl) —O—PO (OH) ₂ , CH ₂ ═C _{(CH 3) CO-O-} CH 2 -CH 2 -O-PO (OH) -O-NH 3 (CH 2 CH 2 OH), also include such.

  In the present invention, the compound represented by the general formula (3) is preferably acrylic acid, methacrylic acid, or an alkyl ester, glycidyl ester thereof, and an OH group or alkoxy group-containing (meth) acrylic acid derivative.

Moreover, as a compound represented by the said General formula (4), the following are mentioned, for example.
Nitrile compounds such as acrylonitrile and methacrylonitrile; vinyl chloride, vinyl bromide, vinyl fluoride, vinyl iodide, vinylidene chloride, sodium vinyl sulfonate, potassium vinyl sulfonate, lithium vinyl sulfonate, methyl vinyl ether, ethyl Vinyl ether, isobutyl vinyl ether, vinyl pyridine, N-vinyl pyridine, vinyl pyrrolidone, acrolein, methyl vinyl ketone, isobutyl vinyl ketone, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethylsilane, vinyl triethoxysilane, vinyl acetamide, N- Vinyl compounds such as vinylacetamide and allyl chloride; styrene, hydroxystyrene, aminostyrene, divinylbenzene, vinyl benzoic acid, cyanostyrene, nitrile Styrene, chloromethylstyrene, alpha-methyl styrene, p- methyl styrene, acetoxystyrene, and styrene derivatives such as p- dimethylaminomethyl styrene.
In the present invention, a styrene derivative is particularly preferable as the compound of the general formula (4).

  Dicarboxylic acids that can be used as modifiers include unsaturated aliphatic dicarboxylic acids such as maleic acid, citraconic acid, fumaric acid, itaconic acid, mesaconic acid, glutaconic acid, vinyl maleic acid, and allyl succinic acid, dimethyl maleate, and fumaric acid. Examples thereof include derivatives such as unsaturated aliphatic dicarboxylic acid esters such as diethyl, cycloalkene dicarboxylic acids such as tetrahydrophthalic acid and tetrahydroterephthalic acid, and derivatives thereof. Preferred are maleic acid, citraconic acid, fumaric acid and itaconic acid, and particularly preferred are maleic acid and fumaric acid.

  Further, dicarboxylic acid anhydrides that can be used as modifiers include dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylendomethylenetetrahydrophthalic anhydride. Things.

  The modified polypropylene of the present invention is an unmodified soluble isotactic polypropylene and / or unmodified syndiotactic polypropylene (the racemic dyad fraction [r] has a value of 0.51 to 0.51) within a range not impairing the object of the present invention. 0.88) can also be used as a mixture.

  The modified polypropylene of the present invention can be used as an adhesive, ink, paint, primer, sealing agent, surface modifier, coating agent, pressure-sensitive adhesive, reactive polymer, or compatibilizing agent. Particularly preferred applications are paints, surface modifiers, primers or coating agents.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
In addition, the polymer in a present Example and a comparative example was analyzed and evaluated by the method shown next.

(1) Measurement of molecular weight The molecular weight was measured using a GPC (gel permeation chromatography) model 150 manufactured by Waters. The measurement conditions are solvent: o-dichlorobenzene, measurement temperature: 135 ° C., solvent flow rate: 1.0 ml / min, and the column uses a monodisperse polystyrene standard sample manufactured by Tosoh Corporation to obtain a polystyrene calibration curve. Thus, a calibration curve for polypropylene was prepared by the universal method.

(2) Measurement of racemic dyad fraction [r] The racemic dyad fraction [r] is 50 MHz, 120 ° C., pulse width 8.2 μsπ / 3, pulse using Varian XL-200 NMR with PFT pulse Fourier transform device. ¹³ C-NMR was measured under the conditions of an interval of 4 seconds and an integration count of 5000. The sample was prepared by dissolving in a mixed solution of trichlorobenzene and benzene (2: 1).

(3) Measurement of modifier introduction amount (number of molecules per polypropylene molecule) The modifier introduction amount per polypropylene molecule is the functional group content and GPC curve of the modifier obtained by infrared absorption spectrum (IR) measurement. It calculated from the value of the number average molecular weight obtained from this. For IR measurement, a polymer made into a film using FT / IR-470 manufactured by JASCO Corporation was used.

(4) Affinity for polypropylene Affinity for polypropylene was determined by applying a toluene solution of the obtained modified polymer to a PP plate at room temperature and drying it at 100 ° C. for 1 hour, and then testing it according to JIS K-5400. Went. Evaluation was made as follows: ◯: adhesion rate 100%, Δ: adhesion rate ≧ 90%, x: adhesion rate <90%.

(5) Affinity for polar materials Affinity for polar materials was evaluated by measuring the contact angle with water. The measurement method is to apply the obtained modified polypropylene on a polypropylene plate, measure the contact angle with water at 25 ° C., contact angle ≦ 30 °: ○, 30 ° <contact angle ≦ 60 °: Δ, 60 ° <contact angle ≦ 90 °: evaluated as x.

(6) Surface smoothness of coating The PP plate coated with the modified polymer obtained in (4) above and dried was exposed to light to visually observe the irregularities on the surface.

(7) Storage stability The storage stability was determined by visually observing a solution stored at room temperature for 2 weeks to confirm the presence or absence of solid precipitation.

[Example 1]
(1) Polymerization of propylene 150 mL of toluene was placed in a 2 L autoclave equipped with a stirrer and sufficiently substituted with nitrogen gas, and kept at -50 ° C. At the same temperature, 80 mmol of MMAO was added in terms of aluminum monomer. Next, 8.3 mol of propylene was introduced while stirring. Finally, 1 mL of 0.1 mol / L t-BuCp ₂ ZrCl ₂ in toluene was added to initiate polymerization. The polymerization was carried out for 5 hours.
Polymerization was stopped by putting the reaction solution in 5 L of methanol cooled to −60 ° C. and precipitating the polymer. The polymer obtained was washed 5 times with methanol and dried at room temperature.
The yield of the obtained polymer was 8.2 g, its GPC curve was unimodal, the weight average molecular weight Mw was 32,000, and the value of Mw / Mn was 2.0. Moreover, the value of the racemic dyad fraction [r] measured by ¹³ C-NMR was 0.17. When IR measurement was performed at room temperature, no peak due to crystalline isotactic PP was observed.
Table 1 shows the polymerization conditions of propylene, and Table 2 shows the analysis results of the obtained polymer.

(2) Introduction of methyl methacrylate into polypropylene 20 g of cyclohexane was added to 2 g of polypropylene obtained by the above polymerization, and stirred with a stirrer until the polypropylene was completely dissolved. Thereafter, nitrogen was bubbled through the cyclohexane solution for 20 minutes. Under a nitrogen atmosphere, 1.0 g of methyl methacrylate and 0.05 g of t-butylperoxy-2-ethylhexanoate as a radical reaction initiator were added and mixed for 2 minutes. After the temperature in the system reached 60 ° C., stirring was continued for 1 hour. Here, 0.05 g of t-butylperoxy-2-ethylhexanoate was added, and stirring was further continued for 1 hour. This operation was repeated once more. After a total of 3 hours, the oil bath was lowered and immediately 50 ml of cooled cyclohexane was added. This cyclohexane solution was poured into 600 ml of methanol to precipitate a polymer, and then the polymer was taken out and dissolved in 150 ml of cyclohexane. The cyclohexane solution was transferred to a separatory funnel, 50 ml of methanol was added, the separatory funnel was shaken well, allowed to stand and separated. After repeating this operation three times, only the cyclohexane layer was recovered and sufficiently dried to obtain a polymer. When the obtained polymer was subjected to IR measurement, absorption derived from an ester was observed in the vicinity of 1730 cm ⁻¹ . When the amount of introduction was determined from the absorption intensity, it was found to be 3.2 / chain.
Table 3 shows the modification conditions of polypropylene and the modification amount of the resulting modified polymer. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Example 2]
(1) Polymerization of propylene The same procedure as in Example 1 was performed.
(2) Introduction of ethylene glycol dimethacrylate into polypropylene The solvent was changed to methylcyclohexane, and ethylene glycol dimethacrylate was used instead of methyl methacrylate as a modifier, and the modification was performed under the conditions shown in Table 3. The amount of the modifying agent that could be introduced was 4.0 / chain.
Table 3 shows the modification conditions of polypropylene and the modification amount of the resulting modified polymer. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Example 3]
(1) Polymerization of propylene 150 mL of toluene was placed in a 2 L autoclave equipped with a stirrer and sufficiently substituted with nitrogen gas, and kept at 21 ° C. At the same temperature, 90 mmol of ethylaluminum sesquichloride was added in terms of aluminum monomer. Next, 3 mL of a 1 mol / L Ti (OBu) ₄ toluene solution was added, and 8.3 mol of propylene was introduced while stirring. The time when the introduction was completed was regarded as the start of polymerization. The polymerization was carried out for 8 hours. Polymerization was stopped by putting the reaction solution in 5 L of methanol cooled to −60 ° C. and precipitating the polymer. The polymer obtained was washed 5 times with methanol and dried at room temperature. The polymerization results are shown in Table 2.
(2) Introduction of acrylic acid into polypropylene Modification was performed under the conditions shown in Table 3 using octane as a solvent and acrylic acid as a modifier. The amount of the modifying agent that can be introduced is shown in Table 3.
Table 3 shows the modification conditions of polypropylene and the modification amount of the resulting modified polymer. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Example 4]
(1) Polymerization of propylene The same procedure as in Example 3 was performed.
(2) Introduction of fumaric acid into polypropylene Modification was performed under the conditions shown in Table 3 using decane as a solvent and fumaric acid as a modifier. After the denaturation reaction, 50 mL of cooled decane was added. Unreacted fumaric acid was filtered off, and the filtrate was poured into methanol to precipitate a polymer. Subsequent steps were performed in the same manner as in Example 1. The amount of modifier that could be introduced is shown in Table 3.
Table 3 shows the modification conditions of polypropylene and the modification amount of the resulting modified polymer. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Example 5]
(1) Preparation of heterogeneous catalyst component 1 (see FIG. 1) As described in Japanese Patent Publication No. 7-121970 (Example 14), first, silicon oxide and n-butylethylmagnesium were brought into contact with each other. A heterogeneous catalyst component 1 was prepared by contacting with tetraethoxysilane, then with 2,2,2-trichloroethanol, and finally with anisole and titanium tetrachloride.
(2) Polymerization of propylene 150 mL of toluene was placed in a 2 L autoclave equipped with a stirrer and sufficiently substituted with nitrogen gas, and kept at 40 ° C. 10 mmol of triethylaluminum was added at the same temperature. Next, 10 mg of the prepared heterogeneous catalyst component 1 was added. While stirring, 2 L of hydrogen was introduced, and 8.3 mol of propylene was further introduced. The time when the introduction was completed was regarded as the start of polymerization. The polymerization was carried out for 1 hour. Propylene was purged and methanol was added to terminate the polymerization. The reaction slurry was poured into 5 L of methanol cooled to −60 ° C. to precipitate a polymer. The polymer obtained was washed 5 times with methanol and dried at room temperature. 24.9 g of polypropylene was obtained.
(3) Removal of crystalline polypropylene 3.5 g of the above polypropylene was added to 46.5 g of toluene, and stirred for one day. Centrifugation gave a clear supernatant. When a part of the supernatant was taken out and poured into methanol to precipitate a polymer, the polymer concentration was 5.7 wt. %Met. Moreover, the weight average molecular weight Mw of this polymer was 22,000, and the value of Mw / Mn was 4.8. The analysis results of the polymer are shown in Table 2.
(4) Introduction of 2-isocyanatoethyl methacrylate into polypropylene Nitrogen was bubbled into a toluene solution of the obtained polypropylene (supernatant 20 g) for 20 minutes. Modification was performed under the conditions shown in Table 3 using 2-isocyanatoethyl methacrylate in a nitrogen atmosphere. For the purification of the polymer, acetone bubbled with nitrogen was used instead of methanol, and all operations were performed in a nitrogen stream. The amount of modifier that could be introduced is shown in Table 3.
Table 3 shows the modification conditions of polypropylene and the modification amount of the resulting modified polymer. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Example 6]
(1) Preparation of heterogeneous catalyst component 1 (see FIG. 1) The same procedure as in Example 5 was performed.
(2) Polymerization of propylene The same procedure as in Example 5 was performed.
(3) Removal of crystalline polypropylene The same procedure as in Example 5 was performed.
(4) Introduction of glycidyl methacrylate into polypropylene The conditions shown in Table 3 were used. Table 3 shows the amount of modification of the resulting modified polymer.
Further, Table 4 shows the results of evaluating the affinity of the modified polymer, the surface smoothness of the coating, and the storage stability.

[Example 7]
(1) Preparation of heterogeneous catalyst component 2 (see FIG. 1) As described in Japanese Examined Patent Publication No. 7-121971 (Example 7), first, silicon oxide and n-butylethylmagnesium were brought into contact with each other, and this was converted to HC. Contact with a hydrocarbyloxy group-containing compound represented by (OC ₂ H ₅ ) ₃ , then contact with 2,2,2-trichloroethanol, and finally contact with titanium tetrachloride to prepare heterogeneous catalyst component 2 did.
(2) Polymerization of propylene 150 mL of toluene was placed in a 2 L autoclave equipped with a stirrer and sufficiently substituted with nitrogen gas, and kept at 40 ° C. At the same temperature, 10 mmol of triisobutylaluminum and 1 mmol of di-n-butyl ether were added. Next, 10 mg of the previously prepared heterogeneous catalyst component 2 was added. While stirring, 2.3 L of hydrogen was introduced, and 8.3 mol of propylene was further introduced. The time when the introduction was completed was regarded as the start of polymerization. The polymerization was carried out for 1 hour. Propylene was purged and methanol was added to terminate the polymerization. Thereafter, the same operation as in Example 5 was performed to obtain polypropylene.
(3) Removal of crystalline polypropylene 3.5 g of the above polypropylene was added to 46.5 g of xylene and stirred for one day. Centrifugation gave a clear supernatant. A part of the supernatant was taken out and poured into methanol to precipitate a polymer. The polymer concentration was 6.0 wt. %Met. Moreover, the weight average molecular weight Mw of this polymer was 16,000, and the value of Mw / Mn was 4.4. The value of [r] for the racemic diad fraction was 0.41. The analysis results of the polymer are shown in Table 2.
(4) Introduction of Acetoxystyrene into Polypropylene Nitrogen was bubbled into 20 g of the supernatant of the obtained polypropylene xylene solution for 20 minutes. Modification was performed under the conditions shown in Table 3 using acetoxystyrene under a nitrogen atmosphere. The amount of the modifying agent that can be introduced is shown in Table 3.
Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Example 8]
(1) Preparation of heterogeneous catalyst component 3 (see FIG. 1) As described in Japanese Patent Publication No. 7-121971 (Example 13), first, silicon oxide and di-n-butylmagnesium-TEAL complex were contacted. This was contacted with tetraethoxysilane, then with 2,2,2-trichloroethanol, and finally with titanium tetrachloride to prepare heterogeneous catalyst component 3.
(2) Polymerization of propylene 150 mL of toluene was placed in a 2 L autoclave equipped with a stirrer and sufficiently substituted with nitrogen gas, and kept at 40 ° C. 10 mmol of triisobutylaluminum was added at the same temperature. Next, 10 mg of the previously prepared heterogeneous catalyst component 3 was added. While stirring, 1.5 L of hydrogen was introduced, and 8.3 mol of propylene was further introduced. The time when the introduction was completed was regarded as the start of polymerization. The polymerization was carried out for 0.5 hours. Propylene was purged and methanol was added to terminate the polymerization. Thereafter, the same operation as in Example 5 was performed to obtain polypropylene.
(3) Removal of crystalline polypropylene 3.5 g of the above polypropylene was added to 46.5 g of toluene, and stirred for one day. Centrifugation gave a clear supernatant. A part of the supernatant was taken out and poured into methanol to precipitate a polymer. The polymer concentration was 5.5 wt. %Met. Moreover, the weight average molecular weight Mw of this polymer was 33,000, and the value of Mw / Mn was 5.2. The analysis results of the polymer are shown in Table 2.
(4) Introduction of hydroxyethacrylate to polypropylene Modification was performed under the conditions shown in Table 3. The amount of modifier that could be introduced is shown in Table 3. Table 4 shows the results of evaluating the affinity of the modified polymer, the surface smoothness of the coating, and the storage stability.

[Example 9]
(1) Preparation of heterogeneous catalyst component 1 (see FIG. 1) The same procedure as in Example 5 was performed.
(2) Polymerization of propylene The same procedure as in Example 5 was performed.
(3) Removal of crystalline polypropylene The same procedure as in Example 5 was performed.
(4) Introduction of maleic anhydride into polypropylene Modification was performed under the conditions shown in Table 3. The polymer was purified in the same manner as in Example 1 except that acetone sufficiently substituted with nitrogen was used instead of methanol. The amount of modifier that could be introduced is shown in Table 3. Table 4 shows the results of evaluating the affinity of the modified polymer for polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Comparative Example 1]
(1) Polymerization of propylene Polymerization was carried out under the conditions shown in Table 1 using a catalyst prepared according to the description in JP-A-63-264607 (Example 1). This catalyst was prepared by first preparing a magnesium-containing solid, contacting with 2,2,2-trichloroethanol, and then contacting with titanium tetrachloride and di-n-butyl phthalate. The results are shown in Table 2.
(2) Introduction of ethylene glycol dimethacrylate into polypropylene The polymer was not dissolved in a solvent, but the same operation as in Example 2 was performed. As shown in Table 3, the modifier could not be introduced. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

[Comparative Example 2]
The same operation as in Example 8 was performed except that the operation for removing crystalline polypropylene was not performed. The amount of modifier that could be introduced is shown in Table 3. Further, Table 4 shows the results of evaluating the affinity of the modified polymer to polypropylene and polar materials, the surface smoothness of the coating, and the storage stability.

It is explanatory drawing which shows the preparation method and its use of the heterogeneous catalyst for polypropylene polymerization.

Claims (3)

A polypropylene having a racemic diad fraction [r] value measured by ¹³ C-NMR in a range of 0.12 to 0.49 and a weight average molecular weight of 5,000 to 500,000 is represented by the following general formula (1). A modified polypropylene characterized in that 0.1 to 100 units represented by the formula are graft-bonded.

(In the formula, ^{R 1} is H, or an alkyl group of _{C 1 to 10;} ^{R 2} is ^OR 4, Cl, Br, halogen selected from F or I, ^NR _{1 2} or ^R 5 ^-NR _{1 2} groups; R ³ is H or -COR ² group, n is 0.1-100.
Here, R ⁴ is H or a C _1-10 alkyl group that may have halogen; an aromatic group that may have an alkyl substituent; — (CH ₂ ) aO—P (O) (OR ¹ ). _2, or ^{_{- (CH 2) a-O}} -P (O) (O -) (O- (CH 2) b-N + R 1 3 (a and b are each an integer of 1 to 5); Li, Na Or an alkali metal M selected from K; C _5-10 alicyclic hydrocarbon; glycidyl group; R ⁵ —COCR ¹ ═CH ₂ ; R ⁵ OR ¹ ; R ⁵ Si (OR ¹ ) ₃ , or R ⁵ represents -NCO, and R ⁵ represents a C _1-10 alkylene group or — [(CH ₂ ) q—O—] r—, and q and r each represents an integer of 1 to 5.) A polypropylene having a racemic diad fraction [r] value measured by ¹³ C-NMR in a range of 0.12 to 0.49 and a weight average molecular weight of 5,000 to 500,000 is represented by the following general formula (2). A modified polypropylene, wherein 0.1 to 100 units represented by the formula are graft-bonded.

Wherein R ⁶ is H, or a C _1-10 alkyl group, or a halogen selected from Cl, Br, F or I; R ⁷ is Ar—X ′, OCO—R ⁶ , CHO, COR ⁶ , CN, pyridyl group, pyrrolidonyl group, Si (OR ¹ ) ₃ , C _1-10 alkyl halide, halogen, OR ⁶ , OSO ₃ M or NH—CO—R ⁶ , m is 0.1-100.
Here, X ′ is R ⁶ , OH, COOH, NH ₂ , CN, NO ₂ , C _1-10 alkyl halide, CH═CH ₂ , or OCO—R ⁶ , R ¹ is H, or C _1-10 alkyl group, M is the alkali metal. ) Dicarboxylic acid or dicarboxylic anhydride is added to polypropylene having a racemic diad fraction [r] value measured by ¹³ C-NMR in the range of 0.12 to 0.49 and a weight average molecular weight of 5,000 to 500,000. A modified polypropylene, wherein 0.1 to 100 units of one or more units selected from those are graft-bonded.

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