WO2007091478A1 - Method for production of modified propylene polymer - Google Patents

Abstract

The object is to provide a method for production of a modified propylene polymer having a high adhesion property, a high strength and flexibility with good efficiency. Disclosed is a method for production of a modified propylene polymer, wherein the method comprises modifying a propylene polymer with a radical initiator and an olefin compound having a polar group in the absence of any solvent at 50 to 140˚C. The propylene polymer before modification satisfies the following requirements (a) to (e): (a) [mmmm] = 20 to 60 mol%; (b) [rrr]/(1-[mmmm]) ≤ 0.1; (c) [rmrm] > 2.5 mol%; (d) [mm]x[rr]/[mr]2 ≤ 2.0; and (e) the amount (W25) of a component(s) eluting at 25˚C or lower in temperature-programmed chromatography is 20 to 100% by mass. The modified propylene polymer satisfies the following requirements (1) and (2): (1) the intrinsic viscosity [η]1 of the propylene polymer after modification and the intrinsic viscosity [η]2 of the propylene polymer before modification has the following relationship: [η]1/[η]2 ≥ 0.95, wherein the both intrinsic viscosities are determined in a solvent tetralin at 135˚C; and (2) the modified propylene polymer has a molecular weight distribution (Mw/Mn) of 2.5 or more, wherein the molecular weight distribution (Mw/Mn) is determined using Mw and Mn values in terms of polystyrene as measured by GPC method.

Description

 Method for producing modified propylene polymer

 Technical field

 The present invention relates to a method for producing a modified propylene polymer, and more specifically, as a sealant having high adhesion to plastic materials, paper, wood, etc., a polyolefin modifier, for example, an inorganic filler, As a modifier to obtain polyolefins with improved dispersion characteristics, compatibility characteristics, mechanical properties, and fluidity with dyes, polar polymers, polar wax, wood flour, etc., or surface treatment agents and coating agents for polyolefins The present invention relates to a method for efficiently producing a modified propylene polymer useful as a component.

 Background art

 [0002] Conventionally, olefin-based polymers obtained by graft-modifying polyolefins such as polyethylene and polypropylene with unsaturated carboxylic acids or acid anhydrides thereof are used as modifiers for various resins, adhesiveness-imparting agents, and the like. (See, for example, Patent Documents 1 and 2). On the other hand, low-order polypropylene obtained using a meta-octane-based catalyst can be blended with polypropylene obtained using a magnesium-titanium-based catalyst to control the elastic modulus of polypropylene or as a heat seal layer in a multilayer film. Applications are expected, but higher strength and higher adhesion are required.

 When modifying a conventional propylene-based polymer based on polypropylene, a modification temperature exceeding the melting point of 160 ° C was required. On the other hand, many olefin-containing compounds used as modifiers are generally unstable because they may cause problems such as self-polymerization at temperatures exceeding the melting point. For this reason, when a modifier is added to the olefin-based polymer and reacted, a homo-homopolymer is likely to be formed, and efficient modification is often difficult. In addition, there is a demand for a higher amount of modification and a higher amount of modification of the recent polyolefin-based materials.

To solve this problem, a solution method has been proposed in which polypropylene is modified under relatively mild conditions. In this case, however, a large amount of solvent is used in the system, which increases the process load and reduces the energy intensity. There is also a problem of rising. [0003] Patent Document 1: International Publication No. 2003Z087172 Pamphlet

 Patent Document 2: JP-A-6-073250

 Disclosure of the invention

 Problems to be solved by the invention

[0004] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for efficiently producing a modified propylene polymer having high adhesiveness, high strength, and flexibility. Means to solve

[0005] As a result of intensive research, the present inventors have determined that a propylene polymer having a specific property (a propylene homopolymer or a propylene copolymer) is obtained by using a radical initiator and a polar group-containing olefin compound. The inventors have found that the object can be achieved by carrying out a modification treatment at a specific temperature in the absence of a solvent to obtain a modified propylene polymer having specific intrinsic viscosity characteristics and molecular weight distribution. The present invention has been completed based on such knowledge.

 That is, the present invention provides a method for producing the following modified propylene polymer (modified propylene homopolymer or modified propylene copolymer).

1. (a) [mmmm] = 20~60 mol _{^{0/0, (b) [}} rrrr] /. (1 - [mmmm]) ≤0 1, (c) [r mrm]> 2. 5 mole ⁰ / ₀ , (d) [mm] X [rr] / [mr] ² ≤2.0, and (e) Amount of components (W25) eluting at 25 ° C or less in temperature-programmed chromatography is 20 ~: LOO mass _^0/0 is a propylene emissions based polymer, a radical initiator and a polar group-containing Orefin based compound, in the absence of a solvent, which comprises treating reforming at temperatures 50 to 140 ° C, the following ( A method for producing a modified propylene polymer satisfying 1) and (2).

 (1) Intrinsic viscosity of the modified propylene polymer measured in a tetralin solvent at 135 ° C

 [7?] 1 and the intrinsic viscosity [7?] 2 of the propylene-based polymer before the modification have a relation of [r?] L / [r?] 2≥0.95.

(2) The molecular weight distribution (Mw / Mn) obtained from the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 2.5 or more. 2. The method for producing a modified propylene polymer as described in 1 above, wherein the polar group-containing olefin compound is an acid anhydride of an unsaturated carboxylic acid.

 The invention's effect

 [0006] According to the present invention, a modified propylene polymer having high adhesiveness, high strength, and flexibility can be efficiently produced.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0007] The propylene polymer used in the present invention (refers to a propylene polymer or a propylene copolymer; hereinafter the same) has the properties shown in the following (a) to (e).

(a) a meso pentad fraction [mmmm] is 20 to 60 mole ^_0/0.

 (b) Racemic pentad fraction [rrrr] and 1 [mmmm] satisfy the following relationship.

 [rrrr] Z (1— [mmmm]) ^ O. 1

(c) racemic meso racemic meso fraction [rmrm] is a value of greater than 2.5 mol ^_0/0.

 (d) Mesotriad fraction [mm], racemic triad fraction [rr], and triazide fraction [mr] satisfy the following relational expression.

[mm] X [rr] / [mr] ² ≤2.0,

 (e) The amount of components (W25) eluting at 25 ° C. or lower in temperature programmed chromatography is 20 to: LOO mass%.

 When the propylene polymer used in the present invention satisfies the above relationship, the balance between the amount of the sticky component of the obtained film sheet, the low elastic modulus and the transparency is excellent. In other words, it has low elasticity and excellent softness (also called flexibility), has little stickiness component, and has surface characteristics (for example, less migration of stickiness component to bleed and other products). ) And transparency are also excellent!

[0008] The meso-pentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic meso race mimeso fraction [rmrm] are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. The meso fraction, the racemic fraction and the racemic meso-racemic meso fraction in pentad units in the polypropylene molecular chain measured by the methyl group signal of the ¹³ C-NMR ^ vector in accordance with the method proposed in . As the meso-pentad fraction [mmmm] increases, the stereoregularity increases. As shown in (a) above, when the mesopentad fraction [mmmm] of the propylene polymer used in the present invention is 20 mol% or more, stickiness is suppressed. If it is 60 mol% or less, the elastic modulus will not be too high, and it will be moderate.

 The value of [rrrr] [mmmm]) is determined from the above pentad unit fraction and is an index representing the uniformity of the regular distribution of the propylene-based polymer. As this value increases, the distribution of regularity spreads, resulting in a mixture of highly ordered polypropylene and atactic polypropylene, like conventional polypropylene produced using existing catalyst systems, resulting in increased stickiness and transparency. It means to decline. As shown in the above (b), when [rrrr] Z (l- [mmmm]) of the propylene-based polymer used in the present invention is 0.1 or less, stickiness is suppressed.

 [0009] Further, as shown in the above (c), when the racemic meso racemic meso fraction [rmrm] is a value exceeding 2.5 mol%, the randomness of the polymer is increased and the transparency is further improved. To do.

The relational expression (d) above represents an index of the randomness of the polymer. The closer to 1, the higher the randomness, the more transparent, and the better balance between flexibility and elastic recovery. As shown in (d) above, when the value of [mm] X [rr] Z [mr] ² is 2.0 or less, the decrease in transparency is suppressed, and the balance between flexibility and elastic recovery is good. It becomes. [mm] X [rr] Z [mr] ² is preferably in the range of 1.8 to 0.5, more preferably 1.5 to 0.5.

The ¹³ C-NMR ^ vector was measured according to the following apparatus and conditions according to the attribution of the peak proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli et al. It can be carried out.

[0010] Apparatus: JEOL Ltd. Heng NM— EX400 type ¹³ C— NMR system

 Method: Proton complete decoupling method

 Concentration: 220mgZml

 Solvent: 1, 2, 4 90:10 (volume ratio) mixed solvent of triclonal benzene and heavy benzene Temperature: 130 ° C

 Panores width: 45 °

 Norse repeat time: 4 seconds

Accumulation: 10000 times [0011] <Calculation formula>

 M = (m / S) X IOO

 R = (y / S) X IOO

 S: Signal strength of side chain methyl carbon atoms of all propylene units

 P β β Λ9. 8-22.5 ppm

 P a j8: 18.0〜17.5ppm

 Ρ α γ: 17.5-17.lppm

 γ: Race pentad chain: 20. 7 to 20.3 ppm

 m: Mesopentad chain: 21.7-72.5 ppm

[0012] The propylene-based polymer used in the present invention has a propylene-based polymer component amount (W25) eluting at 25 ° C or lower in a temperature-enhanced chromatography as shown in the above)) of 20 to 100 masses. %, Preferably 30 to: L00 mass%, more preferably 50 to: L00 mass%.

 W25 is an index indicating whether or not the propylene-based polymer has a soft force. When this value is small, a component having a high elastic modulus increases or the stereoregularity distribution is widened. In the present invention, flexibility is maintained when W25 is 20% by mass or more.

 Note that W25 is the TREF (temperature rising elution fractionation) column temperature 25 ° C in the elution curve obtained by measuring with the temperature rising chromatography of the following operating method, equipment configuration and measurement conditions! Don't be absorbed by the filler! This is the amount (% by mass) of the component that elutes with boil.

[0013] (1) Operation method

 The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C, and then gradually cooled to 0 ° C at a temperature drop rate of 5 ° CZ and held for 30 minutes to crystallize the sample on the surface of the packing material. Make it. After that, the column is heated up to 135 ° C at a heating rate of 40 ° CZ time to obtain an elution curve.

 (2) Device configuration

TREF column: GL Sciences silica gel column (4.6 φ 150 mm) Flow cell: GL Sciences optical path length lmm KBr cell Liquid feed pump: SSC-3100 pump manufactured by Senshu Science Co., Ltd.

 Valve oven: MODEL554 oven (high temperature type) manufactured by GL Science

TREF oven: GL Sciences

 Two series temperature controller: REX-C100 temperature controller manufactured by Rigaku Corporation

 Detector: IR detector for liquid chromatography MIRA made by FOXBORO

N 1A CVF

 10-way valve: Electric valve manufactured by PARCO

 Loop: 500cm / lepe made by PARCO

 (3) Measurement conditions

 : ο dichroic benzene

 Sample concentration: 7.5 g / L

 Injection volume: 500 μ 1

 Pump flow rate: 2. OmlZ min

 Detection wave number: 3. 41 m

 Column packing material: Chromosolve P (30-60 mesh)

 Column temperature distribution: Within ± 0.2 ° C

[0014] Further, in the present invention, it is preferable that the propylene-based polymer power satisfies the following requirements (a ') to (e') according to the above requirements (a) to (e)! .

(a,) a meso pentad fraction [mmmm] is 30 to 50 mole ^_0/0.

 (b ') Racemic pentad fraction [rrrr] and 1 [mmmm] satisfy the following relationship.

 [rrrr] / (1-[mmmm]) ≤ 0.08

(c ') the racemic meso racemic meso fraction [rmrm] is 2. is a value greater than 7 mol ^_0/0.

 (d ') Mesotriad fraction [mm], racemic triazide fraction [rr] and mesoracemi fraction [mr] satisfy the following relational expression.

[mm] X [rr] / [mr] ² ≤l. 8

 (e ′) The amount of components (W25) eluting at 25 ° C. or lower in temperature-programmed chromatography is 30 to: LOO mass%.

[0015] Furthermore, in the present invention, the propylene-based polymer power described above requirements (a) to (e) Anyway, those satisfying the following (a ") to (e") are preferred!

(a ") a meso pentad fraction [mmmm] is 30 to 50 mole ^_0/0.

 (b〃) Racemic pentad fraction [rrrr] and 1- [mmmm] satisfy the following relationship.

 [rrrr] / (1— [mmmm]) ^ O. 06

(C〃) racemic meso racemic meso fraction [rmrm] is 2. is a value greater than 8 mol ^_0/0.

 (d ") Mesotriad fraction [mm], racemic triaz fraction [rr], and meso racemic fraction [mr] satisfy the following relational expression.

 [mm] X [rr] / [mr] ≤ 丄. 5

 (e ") The amount of component (W25) eluting at 25 ° C or lower in temperature programmed chromatography is 50 ~: LO 0% by mass.

 [0016] In addition to the above-mentioned requirements, the propylene-based polymer used in the present invention has (f) a molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method of 5 or less, and (g) a tetralin solvent. Preferably, the intrinsic viscosity [7?] Measured at 135 ° C satisfies at least one of 0.1 ldl / g or more. The molecular weight distribution (MwZMn) is more preferably 4 or less, and still more preferably 3.5 or less. When the molecular weight distribution (MwZMn) is 5 or less, stickiness in the film sheet is suppressed.

 The molecular weight distribution (MwZMn) was calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polyethylene measured by the gel permeation chromatography (GPC) method using the following apparatus and conditions. Value.

[0017] <GPC measurement device>

 Column: TOSO GMHHR—H (S) HT

 Detector: RI detector for liquid chromatogram WATERS 150C

 <Measurement conditions>

 Solvents: 1, 2, 4 Trichrome mouth benzene

 Measurement temperature: 145 ° C

 Flow rate: 1.0mlZ min

 Sample concentration: 2. 2mg / ml

Injection volume: 160 1 Calibration curve: Universal Calibration

[0018] By the way, in general, in the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the propylene monomer is sequentially coordinated and polymerized in the same manner. Insertion polymerization is usually performed, but in rare cases 2, 1 or 1, 3 insertion (also called abnormal insertion). The propylene homopolymer used in the present invention preferably has a small amount of 2,1 or 1,3 insertion. In addition, the ratio of these insertions is the following relational expression (1)

 [(m-2, l) + (r-2, 1) + (1, 3)] ≤5.0 (%) (1)

Wherein, (m- 2, 1) is ¹³ C- meso measured in NMR - 2, 1 insert content (%), (r- 2, 1) is racemic were measured by ¹³ C- NMR - 2, 1 Insertion content (%) and (1, 3) indicate 1,3 insertion content (%) measured by ¹³ C-NMR. ]

 (2)

 [(m-2, l) + (r-2, 1) + (1, 3)] ≤1.0 (%) (2)

 It is more preferable to satisfy the above. In particular, relational expression (3)

 [(m-2, l) + (r-2, 1) + (1, 3)] ≤0.1 (%) (3)

 The most preferable one is satisfied. When the above relational expression (1) is satisfied, the decrease in crystallinity is suppressed, and stickiness can be suppressed.

[0019] The above (m-2, 1), (r-2, 1) and (1, 3) are reported by Grassi et al. [Macromolucules, 21, p.617 (1988)] and by Busico et al. Based on the report [Macromolucules, 27, p.753 8 (1994)], the assignment of the ¹³ C—NMR ^ vector peak was determined, and each insertion content was determined from the integrated intensity of each peak. That is, (m−2, 1) is the meso 2, 1 insertion calculated as the specific power of the integrated intensity of the peak belonging to P α, y threo that appears around 17.2 ppm relative to the integrated intensity in the entire methyl carbon region. Content rate (%).

(r-2, 1) is the specific power of the integrated intensity of the peak attributed to Ρα, γ threo that appears near 15. Oppm of the integrated intensity in the chill carbon region. ). (1, 3) is the 1,3 insertion content (%) where the specific power of the integrated intensity of the peak attributed to Τ | 8, γ + that appears near 31. Oppm of the integrated intensity in the chin carbon region is also calculated. is there. [0020] Further, the propylene-based polymer used in the present invention has a substantial peak attributed to the end of the molecular chain (n-butyl group) derived from 2, 1 insertion in the measurement of ¹³ C-NMR spectrum. Those that are not observed are more preferred. Regarding the molecular chain ends derived from this 2, 1 insertion, a ¹³ C-NMR ^ vector based on the report of Jungling et al., I. Polym. Sci .: Part A: Polym. Chem., 33, P1305 (1995)] And determine the content of each insertion from the integrated intensity of each peak.

In isotactic polypropylene, the peak appearing around 18.9 ppm is attributed to the unterminated methyl group carbon of the n-butyl group. In addition, ¹³ C-NMR measurement relating to abnormal insertion or molecular chain end measurement may be carried out using the above-mentioned apparatus and conditions.

 In addition to the above requirements, the propylene-based polymer used in the present invention preferably further has an extraction amount of boiling jetyl ether, which is an index of elastic modulus, of 5% by mass or more. The amount of boiling jetyl ether extracted can be measured using a Soxhlet extractor under the following conditions.

 [0021] Measurement conditions

 Extraction sample: l ~ 2g

 Sample shape: powder (Pellet toy is crushed and used as powder) Extraction solvent: Jetyl ether

 Extraction time: 10 hours

 Number of extractions: 180 times or more

 Extraction amount calculation method: Calculated by the following equation.

[Extracted amount to getyl ether ( _g ) Z powder weight (g)] X 100

[0022] Further, in addition to the above, the propylene polymer used in the present invention preferably further has a tensile modulus of 1 OOMPa or less, more preferably 70 MPa or less.

 In addition to the above requirements, the propylene-based polymer in the present invention preferably has excellent flexibility when the melting endotherm Δ Δ by DSC measurement is 20 jZg or less. Δ 指標 is an index indicating whether or not it is soft, and as this value increases, it means that the softness with a high elastic modulus decreases.

The propylene polymer may or may not have a melting point (Tm) and a crystallization temperature (Tc). Although it is good, it is preferable that it is not soft or has a low value, in particular, Tm is 100 ° C or less. Tm, Tc and Δ Η are obtained by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin 'Elma Co., Ltd.), 10 mg of a sample was melted at 230 ° C for 3 minutes in a nitrogen atmosphere and then cooled to 0 ° C at 10 ° CZ. . The peak top of the maximum peak of the crystallization exothermic curve obtained at this time is the crystallization temperature: Tc. Furthermore, the maximum peak of the melting endothermic curve obtained by holding at 0 ° C for 3 minutes and then raising the temperature at 10 ° CZ is the melting point: Tm. In this case, the melting endotherm is ΔΗ. is there.

 [0023] Among the propylene-based polymers used in the present invention, the propylene-based copolymer includes a copolymer of propylene and ethylene and Z or a-olefin having 4 to 20 carbon atoms. Α-olefins with 4 to 20 carbon atoms include 1-butene, 1-pentene, 4-methyl 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and one Xadecene, 1-octadecene, 1 eicosene and the like can be mentioned, and one or more of these can be used in the present invention. The propylene-based copolymer in the present invention is preferably a random copolymer.

 Further, the structural unit capable of obtaining propylene power is preferably 90 mol% or more, more preferably 95 mol% or more.

 [0024] The propylene-based polymer used in the present invention can be produced by homopolymerizing or copolymerizing propylene using a meta-octane-based catalyst.

 In the present invention, it is preferable to use a transition metal compound in which a ligand forms a cross-linked structure via a cross-linking group among the meta-octacene catalysts. More preferred is a method in which propylene is homopolymerized or copolymerized using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure with a co-catalyst via a catalyst.

 For example,

 (Α) —General formula (I)

[0025] [Chemical 1]

 [0026] and (B) (B-1) a compound that can react with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B — 2) Aluminoxane Power A method in which propylene is homopolymerized or copolymerized in the presence of a polymerization catalyst containing a selected component.

 In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and Forces including lanthanoid metals Among these, point powers such as olefin polymerization activity Titanium, zirconium and hafnium are preferred.

E ¹ and E ² are substituted cyclopentagel group, indur group, substituted indenyl group, heterocyclopentagel group, substituted heterocyclopentagel group, amide group (-N <), Phosphine group (1P), hydrocarbon group [>CR—,> C] and silicon-containing group [>SIR—,> Si <] (where R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or This is a ligand selected from the group (which is a hetero atom-containing group), and forms a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As E ¹ and E ² , a substituted cyclopentagel group, an indur group and a substituted indur group are preferable.

[0027] X represents a sigma-binding ligand, and when there are a plurality of X, a plurality of X may be the same or different from each other,

It may be cross-linked with Ε ² or Υ. Specific examples of X include a nitrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

On the other hand, Υ indicates a Lewis base, and when there are multiple Υ, the multiple Υ are the same or different. It may be cross-linked with other Y, E ¹ E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, and thioethers. Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon -Containing group, germanium-containing group, tin-containing group, O, 1 CO, 1 S, 1 SO —, 1 Se, 1 NR ¹ —,

 2

— PR ¹ —, — P (0) Ri—, —BR ¹ or — AIR ¹ where R ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen having 1 to 20 carbon atoms. The hydrocarbon groups contained are the same or different. q represents an integer of 1 to 5 and represents [(M valence) 2], and r represents an integer of 0 to 3.

 Among such crosslinking groups, at least one is preferably a crosslinking group having a hydrocarbon group having 1 or more carbon atoms. Examples of such a crosslinking group include a general formula

 [0028] [Chemical 2]

[0029] (D is carbon, silicon, germanium or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and are bonded to each other. And e may represent an integer of 1 to 4.)

 Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, and bilidene. Group (CH = C =), dimethylsilylene group, diphenylsilylene group, methyl

 2

 Examples thereof include a lucylsilylene group, a dimethylgermylene group, a dimethylstarylene group, a tetramethyldisylylene group, and a diphenyldisylylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

In the transition metal compound represented by the general formula (I), when E ¹ and E ² are a substituted cyclopentaenyl group, an indenyl group, or a substituted indenyl group, a bridging group of A ¹ and A ² The bond of (1, 2 ′) (2, 1 ′) is preferably a double bridge type. Among the transition metal compounds represented by the general formula (I), the general formula (II)

 [0030] [Chemical 3]

[0031] A transition metal compound having a double-bridged biscyclopentaenyl derivative represented by the following formula as a ligand is preferred.

In the above general formula (II), M,

q and r are the same as in general formula (I). X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Upsilon ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I). Upsilon ¹ represents a Lewis base, Upsilon ^{if 1} there are a plurality, have good ¹ more Upsilon can be crosslinked with Yogu other Upsilon ¹ or X ¹ may be the same or different. As the specific examples of Upsilon ^1, general formula Rukoto include the same as those exemplified in the description of Upsilon of (I) leaves at.

R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.

[0032] In the transition metal compound having the double-bridge type cyclopentagel derivative as a ligand, the ligand may be a (1, 2 ') (2, 1') double-bridge type. preferable.

Specific examples of the transition metal compound represented by the general formula (I) include (1, 2'-ethylene) (2, 1'-ethylene) monobis (indul) zirconium dichloride, (1, 2'-methylene) (2, 1'-methylene) bis (indul) zirconium dichloride, (1, 2'-isopropylidene) (2, 1 '—Isopropylidene) monobis (indulur) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) monobis (3-methylindulur) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) bis (4,5 benzoindulur) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) monobis (4-isopropylindulur) zirconium dichloride, ( 1,2'-ethylene) (2,1'-ethylene) one bis (5,6 dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) one bis (4,4 7 Dipropyl Prodyl) Zirconium Dichloride, (1, 2'-Ethylene) (2, 1'-Ethylene) —Bis (4 Phenol Indur) Zirconium Dichloride, (1, 2'-Ethylene) (2, 1 ' — Ethylene) bis (3-methyl 4-— Sopropylindul) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) monobis (5,6 benzoindulur) zirconium dichloride, (1,2'-ethylene) (2,1'- Isopropylidene) bis (indul) zirco-mudichloride,

 [0033] (1, 2'-methylene) (2, 1'-ethylene) monobis (indul) zirconium dichloride, (1, 2'-methylene) (2, 1'-isopropylidene) monobis (indul) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indul) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methylethyl) Ndur) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-n-butylindulur) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 ' —Dimethylsilylene) bis (3-isopropylindulur) zirconium dichloride, (1, 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3 trimethylsilylmethylindulur Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3 ferrule) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,5 benzoindulur) zirconium dichloride, (1,2 'dimethylsilylene) (2,1' dimethylsilylene) bis (4 isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2, 1 '—Dimethylsilylene) bis (5,6-dimethylindulur) zirconium dichloride,

[0034] (1, 2'-dimethylsilylene) (2, 1'-dimethylsilylene) bis (4,7 diisopropylisopropyl) zirconium dichloride, (1,2'-dimethylsilylene) (2, 1'- Dimethylsilile ) Bis (4-phenolindulyl) zirconium dichloride, (1,2'dimethylsilylene) (2,1'dimethylsilylene) bis (3-methyl-4-isopropylindulur) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1'-dimethylsilylene) bis (5,6 benzoindulur) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (indulur) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-isopropylidene) one bis (3-methylindulyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) one bis (3— Isopropylindul) Zircoyu dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-n-butylindulur) Luconium dichloride, (1, 2'-dimethylsilylene) (2, 1'-isopropylidene) -bis (3 trimethylsilylmethylindul) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1'-isopropylidene Redene) bis (3 trimethylsilylindulur) zirconium dichloride,

 [0035] (1, 2'-Dimethylsilylene) (2, 1'-Isopropylidene) monobis (3-phenolindul) zirconium dichloride, (1, 2'-Dimethylsilylene) (2, 1'-methylene) Bis (indyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1'-methylene) monobis (3 methylindul) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1 '—Methylene) monobis (3-isopropylindulur) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-methylene) bis (3-n-butylindulur) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1'-methylene) monobis (3 trimethylsilylmethylindyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1'-methylene) monobis (3-trimethylsilyl) Inn Dur) zirconium dichloride, (1, 2'-diphenyl-silylylene) (2,1'-methylene) bis (indul) zirconium dichloride, (1,2'-diphenyl-silylene) (2, 1'-methylene) Bis (3-methylindul) zirconium dichloride, (1, 2'-diphenylsilylene) (2, 1'-methylene) monobis (3-isopropylindul) zirco dimudichloride, (1, 2 'diphe- Lucylylene) (2,1'-methylene) bis (3-n-butylindulur) zirconium dichloride,

[0036] (1, 2'-Diphenyl-silylene) (2, 1'-methylene) monobis (3 trimethylsilylmethylindul) zirconium dichloride, (1, 2'-diphenyl-silylene) (2, 1'-methylene Ibi (3-Trimethylsilylindulur) Zirconium Dichloride, (1, 2'-Dimethylsilylene) (2, 1 'Dimethylsilylene) (3-Methylcyclopentagel) (3'-Methylcyclopentagel) Zirconium Dichloride, (1, 2'-Dimethylsilylene) (2, 1'-Isopropylidene) (3-Methylcyclopentagel) (3'-Methylcyclopentagel) zirco-dichloride, (1, 2 ' —Dimethylsilylene) (2, 1'-ethylene) (3-methylcyclopentadienyl) (3'-methylcyclopentagel) zirconium dichloride, (1, 2 'ethylene) (2, 1'-methylene) (3-methylcyclopentagel) (3'-methylcyclopentagel) zirconium dichloride, (1, 2 ethylene) (2, 1 isopropylidene) (3-methylcyclopentagel) (3 ' —Methylcyclopentagel) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methylcyclopentagel) (3'-methylcyclopentagel) zirconium dichloride, ( 1,2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentagel) (3'-methylcyclopentagel) zirconium dichloride,

 [0037] (1, 2 isopropylidene) (2, 1 isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadiene) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1 'dimethylsilylene) (3,4 dimethylcyclopentagel) (3', 4 'dimethylcyclopentagel) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1' —Isopropylidene) (3, 4-dimethylcyclopentagel) (3 ', 4'-dimethylcyclopentagel) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1'-ethylene) ( 3,4-dimethylcyclopentagel) (3 ', 4'-dimethylcyclopentaenyl) dinoleconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3, 4 Dimethinorecyclobenzene) (3 ', 4' Dimethylsic) Pentagel) zirconium dichloride, (1, 2 ethylene) (2, 1 isopropylidene) (3,4 dimethylcyclopentagel) (3 ', 4'-dimethylcyclopentagel) zirconium dichloride, (1 , 2'-methylene) (2, 1'-methylene) (3,4-dimethylcyclopentagel) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride,

 [0038] (1, 2'-methylene) (2, 1'-isopropylidene) (3,4 dimethylcyclopentagel)

(3 ', 4'-dimethylcyclopentagel) zirconium dichloride, (1, 2'-isopropylidene ) (2, 1 isopropylidene) (3,4 dimethylcyclopentagel) (3 ', 4' dimethylcyclopentagel) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1 Dimethylsilylene) (3-methyl-5-ethylcyclopentagel) (3'-methyl-5'-ethylcyclopentagel) zirconium dichloride, (1, 2'-dimethylsilylene) (2, 1 ' Dimethylsilylene) (3-methyl-5-ethylcyclopentagel) (3'-methyl-5-ethylcyclopentagel) zirconium dichloride, (1, 2 'dimethylsilylene) (2, 1'-dimethyl Silylene) (3-Methyl-5-isopropylpropylpentaene) (3'-Methyl-5 isopropylcyclopentagel) zirconium dichloride, (1,2'dimethylsilylene) (2,1'dimethylsilylene) ( 3— Chile-5-n-butylcyclobenzene) (3'-methyl-5'-n-butylcyclopentagel) zirconium chloride, (1, 2'-dimethylsilylene) (2, 1'-dimethylsilylene) ) (3-methyl-5-phenylcyclopentagel) (3'-methyl-5'-phenylcyclopentagel) zirconyl dichloride,

(1, 2 'dimethylsilylene) (2, 1 isopropylidene) (3-methyl-5-ethylcyclopentagel) (3'-methyl-5'-ethylcyclopentagel) zirconium dichloride, (1, 2' Dimethylsilylene) (2, 1 isopropylidene) (3-methyl-5-isopropylcyclopentagel) (3'-methyl-5'-isopropylcyclopentagel) dimethyl dimethyl chloride, (1, 2'- Dimethylsilylene) (2, 1'-isopropylidene) (3-methyl-5-n-butylcyclopentagel) (3'-methyl-5'-n-butylcyclopentagel) zirconium dichloride, (1 , 2'-dimethylsilylene) (2, 1'-isopropylidene) (3-methyl-5-phenylcyclopentagel) (3'-methyl-5'-phenol cyclopentagel) zirconium dichloride , (1 , 2'-dimethylsilylene) (2, 1'-ethylene) (3-methyl-5-ethylcyclopentagel) (3'-methyl-5'-ethylcyclopentagel) zirconium dichloride, (1, 2 '-Dimethylsilylene) (2,1'-ethylene) (3-methyl-5-isopropylpropylcyclopentagel) (3'-methyl-5'-isopropylcyclopentagel) zirconium dichloride, ( 1,2'-dimethylsilylene) (2,1 ethylene) (3-methyl-5-n-butylcyclopentagel) (3'-methyl-5'-n-butylcyclopentagel) zirconium dichloride, [0040] (1, 2'-dimethylsilylene) (2, 1'-ethylene) (3-methyl-5-phenylcyclopentaenyl) (3'-methyl-5'-phenylcyclopentagel) zirconium dichloride, (1, 2 'dimethylsilylene) (2, 1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentagel) zirconium dichloride, (1 , 2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-isopropylpropylpentaenyl) (3'-methyl-5'-isopropylcyclopentagel) zirconium dichloride, (1 , 2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-η-butylcyclopentagel) (3'-methyl-5'-η-butylcyclopentagel) zirconium dichloride, ( 1, 2'—dimethylsilylene) (2, 1'— Tylene) (3-Methyl-5-Phenol Methyl Pentagel) (3'-Methyl-5'-Phenolcyclopentagel) Zirconium Dichloride, (1, 2'-Ethylene) (2, 1'- Methylene) (3-methyl-5-isopropylpropylene) (3'-methyl-5'-isopropylcyclopentagel) zirconium dichloride, (1,2'-ethylene) (2,1'- Isopropylidene) (3-methyl-5-isopropylcyclopentagel) (3'-methyl-5'-isopropylcyclopentagel) zirco didichloride, (1, 2'-methylene) (2, 1'-methylene ) (3-Methyl-5-isopropylcyclopentagel) (3'-Methyl-5'-isopropylpropylcyclopentagel) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene ) (3-Methyl 5-Isopropyl (Robilyl cyclopentagel) (3'-methyl-5'-isopropyl cyclopentagel) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. Moreover, the analogous compound of the metal element of another group or a lanthanoid series may be sufficient.

 [0041] Next, the component (B-1) in the component (Β) is any compound that can react with the transition metal compound of the component (Α) to form an ionic complex. The force which can be used even if it is The thing represented by the following general formula (III), (IV) can be used conveniently.

([L ¹ R ^{1 ()} ] ^{K +} ) ([Z] —)---(III)

 a b

([L ² ] ^{K +} ) ([Z] —)---(IV)

 a b

(However, L ² is ^{M 2, R U R 12 M} 3, R 13 C or R ¹⁴ M ^3.)

 Three

[In formulas (III) and (IV), L ¹ is a Lewis base, [z] — is a non-coordinating key [z ¹ ] — and [zT, where Where [Z ¹ ] — is a key-ion with multiple groups bonded to the element, that is, [Μ ^^ ² · · — (where M ¹ is an element in groups 5 to 15 of the periodic table, preferably the periodic rule Table ¹ represents elements in Groups 13 to 15. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , Aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkyl aryl group having 7 to 40 carbon atoms, aryl alkyl group having 7 to 40 carbon atoms, halogen-substituted carbonization having 1 to 20 carbon atoms A hydrogen group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms Even ^if two or more of Gi to G ^f form a ring . good f represents an integer of [(valence of central metal M ¹⁾ + 1]), [Z ^2] -. the inverse of the logarithm (pKa of acid dissociation constant) Gar 1 0 following Conjugate bases of a combination of Bronsted acid alone or Bronsted acids and Lewis acids, or generally exhibit conjugate base of an acid defined as superstrong acid. Further, a Lewis base group may be coordinated. R ^1Q represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl aryl group, or an aryl alkyl group, and R ¹¹ and R ¹² are each a cyclopentagel. A group, a substituted cyclopentagel group, an indur group or a fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl aryl group or an aryl alkyl group. R ¹⁴ represents a macrocyclic ligand such as tetrafluoro-porphyrin or phthalocyanine. k is an integer of 1 to 3 in terms of [L ¹ R ^{1 (>} ], [L ² ], a is an integer of 1 or more, and b = (k X a) M ² is a periodic table 1 to 3, 11 to 13, and 17 group elements, M ³ represents a group 7 to 12 element in the periodic table.]

Here, specific examples of L ¹ include ammonia, methylamine, amino, dimethylamine, dimethylamine, N-methylaniline, diphenylamine, N, N dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyl. Amines such as diphenylamine, pyridine, p-bromo N, N dimethylamine, p-tro-N, N dimethylamine, and phosphine such as triethylphosphine, triphenylphosphine, diphenylphosphine Thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, and -tolyls such as acetonitrile and benzo-tolyl.

Specific examples of R ^1Q include hydrogen, methyl group, ethyl group, benzyl group, trityl group, etc. Specific examples of R ^U and R ¹² include cyclopentagel group, methylcyclopenta Examples include tagel group, ethylcyclopentagel group, pentamethylcyclopentagel group and the like.

Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, and methallyl. be able to.

Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and f. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn, and the like. Can be mentioned.

[0043] Further, in [Z ¹ ] —that is, [M ^ ² ′ · −G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al Is mentioned. Also,

Specific examples of G ^{2 to} G ^f include a dialkylamino group such as a dimethylamino group and a jetylamino group, an alkoxy group or an allyloxy group as a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group, and the like, and a hydrocarbon group as methyl. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-icosyl group, phenol group, p-tolyl group, benzyl group, 4t-butylphenol group, 3, 5-dimethylphenyl group, etc., halogen, fluorine, chlorine, bromine, iodine, heteroatom-containing hydrocarbon group, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenol group, 3, 4, 5-trifluorophenyl group, pentafluorophenyl group, 3, 5-bis (trifluoromethyl) phenol group, bis (trimethylsilyl) methyl Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron and the like.

[0044] Further, as a specific example of a non-coordinating key-on, that is, a conjugate base [Z ² ] —a Bronsted acid alone having a pKa of 10 or less or a combination of Bronsted acid and Lewis acid, L-methanesulfonic acid-one (CF 2 SO 4)-, bis (trifluoromethanesulfol) methyl

 3 3

 Luoone, bis (trifluoromethanesulfol) benzylaone, bis (trifluorophenol methanesulfuryl) amide, perchlorate ion (CIO)-, trifluoroacetate ion (CF

 4 3

CO) ―, Hexafluoroantimonone (SbF) ―, Fluorosulfonic acid (F)

2 6

 SO)-, chlorosulfonic acid ion (C1SO)-, fluorosulfonic acid ion Z5—

3 3

Antimony fluoride (FSO / SbF) —, fluorosulfonate anion Z5—arsenic fluoride (FSO / AsF) ―, trifluoromethanesulfonic acid Z5—antimony fluoride (CF 2 SO 4 / SbF)

3 5 3 3 5 etc.

 [0045] Specific examples of such an ionic compound that reacts with the transition metal compound of component (A) to form an ionic complex, that is, a compound of component (B-1), include triphenylammonium tetraphenylborate. -UM, tetraphenylborate tri-n-butylammonium, trimethylammonium tetraborate, tetraethylammonium tetraborate, methyl tetrahydroborate (tree n-butyl) Ammonium, benzyl tetraborate (tri-n-butyl) ammonium, dimethyldiphenyl borate, tetraphenylborate, triphenyl (methyl) ammonium, tetraphenylborate Trimethyl triborate, methyl pyridinium tetraphenylborate, benzylpyridium tetraborate, methyl tetraphenylborate (2-cyanopyridine -Um), tetrakis (pentafluoro oral) triethylammonium borate, tetrakis (pentafluorophenyl) boric acid tri-n-butylammonium, tetrakis (pentafluorophenol) boric acid Triphenyl-molybdenum, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenol) tetraethylammonium borate, tetrakis (pentafluorophenyl) ) Benzyl borate (tri-n-butyl) ammonium, tetrakis (pentafluorophenol) methyl diphenyl borate, tetrakis (pentafluorophenol) triborate (methyl) ammonium borate , Tetrakis (pentafluorophenyl) borate methyl linoleum, tetrakis (pentafluorophenol) dimethylborate borate Tetrakis (pentafluorophenyl) trimethylborium borate,

 [0046] Tetrakis (pentafluorophenyl) methylpyridium borate, tetrakis (pentafluorophenyl) benzil pyridinium borate, tetrakis (pentafluorophenyl) methyl borate (2- Cyanopyridinium), Tetrakis (pentafluorophenyl) benzil borate (2-cyanopyridine), Tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridine)

-Um), tetrakis (pentafluorophenyl) boric acid triphenylphosphorane, tetrakis [bis (3,5-ditrifluoromethyl) phenol] dimethyl boric acid, tetraphenyl Ferroacetate borate, silver tetrafluoroborate, trityl tetrafluoroborate, tetraphenyltetraborateporphyrinmanganese tetraborate, tetrakis (pentafluorophenol) boron Acid ferroceum, tetrakis (pentafluorophenol) boric acid (1, 1'-dimethyl ferrocere

-Um), tetrakis (pentafluorophenyl) borate decamethyl ferroaceum, tetrakis (pentafluorophenol) silver borate, tetrakis (pentafluorophenyl) tritium borate Tetrakis (pentafluorophenyl) lithium borate, Tetrakis (pentafluorophenyl) sodium borate, Tetrakis (pentafluorophenyl) borate tetraphenylporphyrin Manganese, Silver tetrafluoroborate, Hexafluorophosphoric acid Examples thereof include silver, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. These (B-1) component compounds may be used singly or in combination of two or more.

 On the other hand, as an aluminoxane of the component (B-2), the general formula (V)

 [0047] [Chemical 4]

[In the formula, R represents a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a alkenyl group, an aryl group, an arylalkyl group, or a halogen atom, and w represents Shows the average degree of polymerization and is usually an integer of 2 to 50, preferably 2 to 40. Each R ¹⁵ may be the same or different.

 A chain aluminoxane represented by the general formula (VI)

[0049] [Chemical 5]

[Wherein, R ¹⁵ and w are the same as those in the general formula (V).]

The cyclic aluminoxane shown by these can be mentioned. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The means may be reacted according to a known method without any particular limitation. For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There is a method of reacting water of crystallization, water adsorbed on inorganic or organic substances with organoaluminum compounds, and (4) a method of reacting tetraalkylaluminoxane with trialkylaluminum and further reacting with water. .

 The aluminoxane may be insoluble in hydrocarbon solvents such as toluene. These aluminoxanes may be used singly or in combination of two or more.

 [0051] The use ratio of the (A) catalyst component and the (B) catalyst component is preferably 10: 1 to 1: in a molar ratio when the compound (B-1) is used as the (B) catalyst component. If the range of 100, more preferably 2: 1 to 1:10 deviates from the above range, the catalyst cost per unit weight polymer increases, which is not practical.

 When the (B-2) compound is used, a range force S of preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000 in terms of molar ratio is desirable. If it is in this range, the catalyst cost per unit mass polymer does not become so high and is practical. As the catalyst component (B), (B 1) and (B-2) can be used alone or in combination of two or more.

 [0052] As the polymerization catalyst in the production of the propylene-based polymer used in the present invention, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of component (C), the general formula (VII)

R ¹⁶ AU (VII)

 3—

[Wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and V represents 1 to 3 carbon atoms. It is an integer. The compound represented by these is used.

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, trie Til aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, jetyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, jetyl aluminum sesquichloride and ethyl aluminum sesquichloride Etc. These organoaluminum compounds may be used singly or in combination of two or more.

 In the production of the propylene-based polymer used in the present invention, preliminary contact can be carried out using the above-mentioned component (A), component (B) and component (C). The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B), and a known method with no particular limitation can be used. This preliminary contact is effective in reducing catalyst costs, such as improvement in catalyst activity and reduction in the proportion of the (B) component used as a promoter. In addition to the above effects, the effect of increasing the molecular weight can be seen by contacting the components (A) and (B-2).

 The pre-contact temperature is usually about −20 ° C. to 200 ° C., preferably −10 ° C. to 150 ° C., and more preferably 0 ° C. to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Of these, aliphatic hydrocarbons are particularly preferred.

 The use ratio of the above (A) catalyst component and (C) catalyst component is preferably 1: 1 to 1: 10000, more preferably <ί 1: 5 to L: 2000, and more preferably in molar ratio. <ί until 1: 10 to 1: 1000 Range power S Desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and there is a possibility that it will remain in the polymer in a large amount.

In the preliminary contact, an olefin-based compound may coexist. Examples of the olefin compounds to be coexisted include ethylene or a3-olefin compounds having 3 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dedecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. The addition amount of the olefinic compound is about 0.5 to 20% by mass, preferably 1 to 15% by mass of the solvent used in the preliminary contact. In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. There are no particular restrictions on the type of the carrier, and any inorganic oxide carrier and other inorganic carrier and organic carrier can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferred.

 Specific examples of inorganic oxide carriers include SiO 2, AI 2 O 3, MgO, ZrO 3, TiO 2, and Fe 2

 2 2 3 2 2 2 3

, Β Ο, CaO, ΖηΟ, BaO, ThO and their mixtures such as silica alumina, zeolite

2 3 2

 Light, ferrite, glass fiber, etc. are mentioned. Among these, especially SiO 2, A1

 2 o is preferred. The inorganic oxide carrier contains a small amount of carbonate, nitrate, sulfate, etc.

twenty three

 Contain it.

 On the other hand, as a carrier other than the above, magnesium compounds such as MgCl and Mg (OC H)

 2 2 5 2

And a magnesium compound represented by the general formula MgR "X ¹ and complex salts thereof. R ¹⁷ is an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. Group or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, X is 0 to 2, y is 0 to 2, and x + y = 2 Each R "and each X ¹ may be the same or different.

 Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and vigor.

 [0055] The carrier used in the present invention includes MgCl

 2, MgCl (OC H), Mg (OC H)

 2 5 2 5 2 and the like are preferable. The shape of the carrier varies depending on the type and production method. The force average particle diameter is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to LOO μm. If the particle size is small, fine particles in the polymer increase, and if the particle size is large, coarse particles in the polymer increase, resulting in a decrease in bulk density and clogging of the hopper.

The specific surface area of the carrier is usually 1 to 1000 m ² Zg, preferably 50 to 500 m ² Zg, and the pore volume is usually 0.1 to 5 cm ³ / g, preferably 0.3 to ³ cm ³ / g. When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may be lowered.

The specific surface area and pore volume of the support can be obtained, for example, by determining the volume force of nitrogen gas adsorbed according to the BET method (Journal of the American American Chemical Society). Ii, 60, 309 (1983)).

 Further, when the carrier is an inorganic oxide carrier, it is usually desired to use it after firing at 150 to 1000 ° C, preferably 200 to 800 ° C! /.

 When at least one of the catalyst components is supported on the carrier, it is desirable to support at least one of (A) the catalyst component and (B) the catalyst component, preferably both (A) the catalyst component and (B) the catalyst component. .

 [0056] The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the component (1) A) and the component (B) and the carrier (2) A method in which the carrier is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (3) the carrier and A method of reacting the component (A) and the component Z or component (B) with an organoaluminum compound or a halogen-containing silicon compound; (4) after the component (A) or component (B) is supported on a carrier (B ) Component or (A) component mixing method, (5) (A) component and (B) component contact reaction mixture with carrier, (6) (A) component and (B) component In the contact reaction, a method in which a carrier coexists can be used. In the above reactions (4), (5) and (6), an organoaluminum compound (C) can also be added.

 [0057] In the present invention, the catalyst may be prepared by irradiating elastic waves when contacting the above (A), (B), and (C). Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave.

 Specifically, an ultrasonic wave having a frequency of 1 to: LOOOkHz, preferably 10 to 500 kHz is mentioned.

 The catalyst thus obtained may be once distilled off as a solid and taken out as a solid and used for force polymerization, or may be used for polymerization as it is. In the present invention, the catalyst can be generated by carrying out the supporting operation of at least one of the component (A) and the component (B) on the carrier.

For example, add at least one of component (A) and component (B), a carrier, and, if necessary, the organoaluminum compound of component (C) above, add olefins such as ethylene at normal pressure to 2 MPa, and -20 to 200 ° C. To produce catalyst particles by prepolymerization for about 1 minute to 2 hours Can be used.

 [0058] In the present invention, the ratio of the component (B-1) and the carrier used is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. It is desirable that the use ratio of the Magashi (B-2) component and the carrier is, as a mass ratio, preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50. When two or more types are used as the component (B), it is desirable that the ratio of the component (B) to the carrier is within the above range in terms of mass ratio.

 Further, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to L: 500. If the proportion of component (B) [(B-1) component or (B-2) component] and carrier, or (A) component and carrier deviates from the above range, the activity decreases. Sometimes.

The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 m, preferably 10 to 150 μm, particularly preferably 20 to LOO μm, and the specific surface area is usually 20 to: L000m ² Zg, preferably 50 to 500 m ² Zg. When the average particle size is 2 m or more, increase of fine powder in the polymer is suppressed, and when it is 200 m or more, increase of coarse particles in the polymer is suppressed. Further, when the specific surface area is 20 m ² Zg or less, the decrease in activity is suppressed, and when it is 1000 m ² Zg or less, the decrease in bulk density of the polymer is suppressed.

 In the catalyst used in the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. When the amount of transition metal is within the above range, the decrease in activity is suppressed.

 In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.

[0059] The propylene-based polymer used in the present invention is produced by homopolymerizing or copolymerizing propylene using the polymerization catalyst described above. In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legal is particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually −100 to 250 ° C., preferably −50 to 200 ° C., more preferably 0 to 130 ° C. The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , preferably the raw material monomer / the component (A) (molar ratio). preferable. Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (G), particularly preferably normal pressure to lOMPa (G).

 Methods for adjusting the molecular weight of the polymer include selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen. In the case of using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, pentane, hexane, heptane, octane, etc. Aliphatic hydrocarbons, halogenated hydrocarbons such as chloroform, dichloromethane and the like can be used. These solvents may be used alone or in combination of two or more. A monomer such as a-olefin may be used as a solvent. In addition, depending on the polymerization method, the reaction can be performed without a solvent.

 In the method for producing a modified propylene polymer of the present invention, the propylene polymer is modified using a radical initiator and a polar group-containing olefin compound. As the polar group-containing olefin-based compound used for the modification treatment, an organic acid such as unsaturated carboxylic acid or a derivative thereof can be used. In the present invention, an olefin-based compound containing a glycidyl group, An olefin compound containing a hydroxyl group and an acid anhydride of an unsaturated carboxylic acid are preferred. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid and angelic acid.

Desaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like, such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, sodium methacrylate, glycidyl acrylate Examples thereof include chill, allyloyloxysethyl isocyanate, methacryloyloxyethyl isocyanate, and 2-hydroxyethyl acrylate. Of these, maleic anhydride, glycidylethyl acrylate, and 2-hydroxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more. These polar group-containing olefin-based compounds can also be used after diluted with a solvent. By diluting with a solvent, uneven distribution of the polar group-containing olefin-based compound in the propylene-based polymer can be suppressed. As the solvent, methanol, ethanol, acetone, methyl ethyl ketone, hexane, heptane, octane, toluene, xylene, ethylbenzene and the like can be used.

 [0061] On the other hand, the radical initiator is not particularly limited and may be a conventionally known radical initiator, for example, various organic peroxides, azo compounds such as azobisisobutyryl-tolyl, azobisisovalero-tolyl, etc. Of these, organic peroxides can be suitably selected and used.

Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, di ( 2,4 Diclonal Benzoyl) Disilveroxides such as Peroxide, t-Butinorehydroperoxide, Cumenehydroperoxide, Diisopropylbenzenehydroperoxide, 2,5 Dimethylhexane 2,5 Dihydroperoxide Hydroperoxides such as di-t-butyl peroxide, dicumyl peroxide, 2,5 dimethyl-2,5 di (t-butylperoxy) hexane, 2,5 dimethyl-2,5 di (t-butyl peroxide) Hexin 3, dialkyl peroxides such as α, α 'bis (t-butylperoxy) diisopropylbenzene, 1, 1 bis-t-butylperoxide Shi -3, 3, 5 hexane bird methylcyclohexane, 2, 2-bis (t - Buchirupaokishi) Paokishiketa Lumpur such as butane, _t-butyl peroxide O carboxymethyl O transfected benzoate, t-butylperoxy O alkoxy Viva rate, t chromatography Bed Alkyl peresters such as tilperoxyneodecanoate and t-butylperoxybenzoate, di-2-ethylhexyloxydicarbonate, diisopropylperoxydicarbonate, disec butylperoxydicarbonate, and peroxycarbonates such as tert-butylperoxyisopropyl carbonate. Of these, dialkyl peroxides are preferred. These may be used alone or in combination of two or more.

[0062] The radical initiator may be diluted with water, an inert solvent, or an inert inorganic compound emulsion solution. Specific examples of inert solvents include Decane, xylene, silicone oil, etc. Examples of the inert inorganic compound include silica gel, alumina, calcium carbonate, and aluminum hydroxide. By performing this dilution, the risk of the radical initiator can be reduced. Further, since the solid radical initiator has a specific gravity different from that of the base polymer, classification tends to occur at the time of feeding, but it also has an effect of suppressing this.

 The amount of the polar group-containing olefinic compound and radical initiator used is appropriately selected according to the desired physical properties of the target modified propylene polymer without any limitation. The amount of the polar group-containing olefin-based compound used is usually in the range of about 0.1 to 70 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the propylene polymer. When the amount used is 0.1 parts by mass or more, the adhesive strength required for the modified propylene polymer, the dispersibility of additives such as fillers, and the improvement of paintability are sufficient. Further, when the amount used is 70 parts by mass or less, the properties of the propylene-based polymer are not impaired. On the other hand, the use amount of the radical initiator is usually in the range of about 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the propylene polymer.

 In the present invention, for example, the propylene-based polymer, the polar group-containing olefin-based compound and the radical initiator are 50 to 140 using a roll mill, a Banbury mixer, an extruder, or the like. C, preferably 80-140. The propylene-based polymer can be modified in the absence of a solvent by a method of melting and kneading and reacting at a temperature of C for about 0.01 to 0.5 hours.

 Here, in the absence of solvent, the polar group-containing olefin compound is diluted with a small amount of solvent as described above, or the radical initiator is diluted with water, an inert solvent, or an emulsion solution of an inorganic compound. It also includes the case where it is used. The amount of these solvents and inorganic compounds used is about 0 to 10% by mass of the propylene polymer.

In addition, when the reforming reaction is performed under normal high temperature conditions, the molecular weight and viscosity of the modified propylene polymer are equal to or lower than those of the propylene polymer before modification, and the molecular weight distribution changes. There is a tendency not to. However, in the present invention, since the reforming reaction is performed at a relatively low temperature of 50 to 140 ° C., the molecular weight and viscosity do not decrease. Such an effect is achieved by the fact that the added polar group-containing olefinic compound has a relatively high molecular weight while being propylene-based. It is expected that this is caused by branching into a polymer, or terminal olefins of a propylene polymer copolymerize with a polar group-containing olefin compound to form a crosslinked structure.

 In the present invention, this modification treatment can be performed in the presence of a styrene compound. Examples of the styrene compound include styrene, a-methylstyrene, p-methylstyrene, dibutenebenzene and the like. These styrene compounds may be used alone or in combination of two or more. The amount of use is usually in the range of about 0.1 to about L0, preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of the propylene polymer. By using a styrenic compound, the modification process can be performed more efficiently.

 In the present invention, the propylene polymer after the modification treatment has the following physical properties (1) and (2).

 (1) Intrinsic viscosity of the modified propylene polymer measured in a tetralin solvent at 135 ° C

[7?] 1 and the intrinsic viscosity [7?] 2 of the propylene-based polymer before modification have the relationship [r?] L / [r?] 2≥0.95.

 (2) The molecular weight distribution (Mw / Mn) obtained from the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 2.5 or more.

 In the above (1), [7?] 1 / [7?] 2 [preferably, 0.95 to 7.0, and more preferably 0.95 to 5.0. [7?] 17 [7?] 2 being 0.95 or more indicates that the decomposition reaction of the propylene-based polymer is suppressed, and the reaction not desired in the present invention is suppressed. In addition, [r?] 1Z [r?] 2 of 7.0 or less indicates that the progress of the crosslinking reaction of the propylene polymer is moderate, and modified propylene with improved solubility. This shows that a polymer was obtained.

In the above (2), the molecular weight distribution (MwZMn) of the modified propylene polymer is preferably 2.5 to: L0.0, more preferably 2.5 to 8.0. A molecular weight distribution (MwZMn) of 2.5 or more indicates that the reforming reaction has proceeded effectively, and appropriate amounts of the modified propylene polymer and crosslinked polymer have been produced. To modified propylene polymer In this case, high adhesiveness, high strength and softness are exhibited. A molecular weight distribution (MwZMn) of 10.0 or less indicates that the crosslinking reaction has proceeded moderately, and that the modified propylene polymer exhibits solubility, fluidity, and compatibility when combined. Indicates that The above molecular weight distribution (MwZMn) is obtained from the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) method using the same apparatus and conditions as described above. It is a calculated value.

[0065] The physical properties can be adjusted by appropriately selecting the type of radical initiator in addition to the temperature conditions in the reforming process, and controlling the concentration of the radical initiator and the time of the reforming reaction. . When the reforming reaction is performed in the presence of a styrenic compound, these physical properties can be adjusted by appropriately selecting the type of the styrenic compound and adjusting the amount used. .

 The modified propylene polymer thus modified is capable of imparting high adhesion, high strength, softness, etc. to a resin such as polyolefin, and is present as a sealant having high adhesion. Is useful as a modifier or the like to give polyolefin having improved compatibility with inorganic fillers. Example

 Next, the power to explain the present invention in more detail with reference to examples. The present invention is not limited to these examples.

 Production Example 1 (Production of propylene homopolymer)

 (1) Synthesis of metal complex compounds

 (1,2,1-dimethylsilylene) (2,1,1-dimethylsilylene) bis (3-trimethylsilylmethylindul) zirconium dichloride was synthesized as follows.

 In a Schlenk bottle, 3.0 g (6. 97 mmol) of the lithium salt of (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) monobis (indene) was dissolved in 50 ml of THF (tetrahydrofuran). Cooled to 8 ° C. 2. 1 ml (14.2 mmol) of odomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.

The solvent was distilled off, and 50 mL of ether was collected and washed with a saturated salt ammonia solution. After separation, the organic phase is dried and the solvent is removed to give (1, 2'-dimethylsilylene) (2, 1'-dimethyl). 3.04 g (5.88 mmol) of lucylylene) -bis (3-trimethylsilylmethylindene) was obtained (yield 84%).

 Next, the (1, 2'-dimethylsilylene) (2, 1, 1-dimethylsilylene) monobis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream 3.04 g (5.88 mmol) And 50 mL of ether. — The mixture was cooled to 78 ° C., and 7.6 mL (l l. 7 mmol) of n-BuLi hexane solution (1.54 mol / L) was added. After stirring for 12 hours at room temperature, the ether was distilled off. The obtained solid was washed with 40 mL of hexane to obtain 3.06 g (5.07 mmol) of a lithium salt as an ether adduct (yield 73%).

 The results of measurement by 'H-NMROOMHz, THF-d) are as follows.

 8

 δ: 0.04 (s, 18H, trimethylsilyl); 0.48 (s, 12H, dimethylsilylene); 1.10 (t, 6H, methyl); 2.59 (s, 4H, methylene); 3.38 (q, 4H, methylene); 6.2- 7.7 (m, 8H, Ar- H)

[0067] Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 mL of toluene. After cooling to -78 ° C, a suspension of 1.2 g (5 lmmol) of zirconium tetrachloride (20 ml), which had been cooled to -78 ° C in advance, was added dropwise. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. By recrystallizing the resulting residue from dichloromethane, (1, 2'-dimethylmethylylene) (2, 1, -dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride 0.9 g ( l. 33 mmol) was obtained (yield 26%).

 The results of measurement by 'H-NMROOMHz, CDC1) are as follows.

 Three

 δ: 0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd, 4H, methylene); 7.1-7.6 (m, 8H, Ar-H)

[0068] (2) Polymerization of propylene:

 A heat-dried stainless steel autoclave with an internal volume of 10 L was synthesized with 5 L of heptane, 5 mmol of triisobutylaluminum, 15 mol of methyl gallium tetrakis (perfluorophenol) borate and the above (1) (1, 2, —Dimethylsilylene) (2,1, -dimethylsilylene) -bis (3-trimethylsilylmethylindul) zirconium dichloride 3 μmol was added.

Next, 0.03 MPa of hydrogen was introduced, the temperature was raised to 70 ° C. while stirring, and propylene gas was introduced to a total pressure of 0.8 MPa. In the pressure regulator so that the pressure remains constant during the polymerization reaction More propylene gas was supplied for polymerization for 90 minutes, and after 20 minutes, the contents were taken out and dried under reduced pressure to obtain 2000 g of polypropylene. The physical properties of the obtained polypropylene were measured by the following methods. The results are shown in Table 1.

[0069] (1) Intrinsic viscosity [7?]

 Measurement was performed at 135 ° C. in a tetralin solvent using a VMR-053 type automatic viscometer manufactured by Kosei Co., Ltd.

 (2) Mesopentat fraction [mmmm], racemic pentad fraction [rrrr], racemic meso racemic meso fraction [rmrm], mesotriato fraction [mm], racemic triad fraction [rr], triad fraction [mr] ゝAbnormal insertion fraction and elution components (W25)

 It was measured by the method described above.

 (3) Molecular weight distribution (Mw / Mn)

 As described above, weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were measured by gel permeation chromatography (GPC) method to obtain molecular weight distribution (Mw / Mn).

 (4) Heat of fusion (Δ Η)

 Using a differential scanning calorimeter (Perkin Elmer Co., Ltd., DSC7), the measurement was performed by the method described above.

[0070] [Table 1]

[0071] Example 1

 38 g of polypropylene produced in Production Example 1 3.04 g of powdered maleic anhydride and bis (4- (tert-butylcyclohexyl) peroxydicarbonate (manufactured by Nippon Oil & Fats Co., Ltd., Paryl TCP) as a radical initiator 1 52g was mixed and shaken thoroughly until homogeneous, using a batch-type kneader (Toyo Seiki Co., Ltd., Labo Plast Mill), temperature setting 120 ° C, rotation speed 100 rpm, kneading time The modified polypropylene was kneaded for about 3 minutes, and the resulting modified polypropylene was vacuum dried at 150 ° C for 4 hours to remove residual maleic acid, and then measured for physical properties by the following methods. The results are shown in Table 2.

[0072] (1) Intrinsic viscosity [7?] 1 and Intrinsic viscosity [7?] 2

 Using a VMR-053 type automatic viscometer manufactured by Kosei Co., Ltd., at 135 ° C in a tetralin solvent, the intrinsic viscosity [η] 1 of the propylene polymer after modification and the limit of the propylene polymer before modification Viscosity [r?] 2 was measured.

 (2) Measurement of denaturation amount

The amount of modification was determined by pressing a blend of propylene polymer and organic acid before modification with a 0.1 mm spacer and measuring IR with an IR measuring instrument (FTZIR-5300 manufactured by JASCO Corporation). , characteristic carbo - le charge of absorption and organic acids (1600~1900cm ^_1) A calibration curve was prepared from the amount and determined by performing IR measurement on the acid-modified press plate. (3) Wetting tension measurement

 Wet tension was evaluated as a measure of the ability of the plastic film surface to hold ink, coating, or adhesive. It has been empirically known that as the wetting tension on the surface of a plastic film increases, the holding capacity of ink, coating, or adhesive improves.

 The evaluation was stipulated in JIS K6768 !, “Plastic film and sheet wettability tension test method”. A modified propylene polymer is sandwiched between Teflon (registered trademark) sheets and pressed at 180 ° C using a 0.3 mm spacer to produce a film for evaluation. This film is placed in a desiccator at room temperature. Left for more than 8 hours.

 Wet mixture test mixture manufactured by Wako Pure Chemical Industries, Ltd. was used as the test mixture, and the mixture was applied to the film with a cotton swab containing the mixture. In addition, when the original state was maintained, it was determined to be “wet”. The tests were conducted in order from the test mixture with a low surface tension, and the surface tension of the mixture that was determined to be “wetted” was taken as the wetting tension of the film.

[0073] Example 2

 Mix 1 kg of polypropylene produced in Production Example 1 with 80 g of powdered maleic anhydride and 40 g of dibenzoylperoxide (manufactured by Yizaku Akuso, Power Dox B-40ES) as a radical initiator. Shake well. This was kneaded using a twin screw extruder (manufactured by Nippon Steel, Labotex 30) at a temperature setting of 120 ° C. and a residence time of about 2 minutes to obtain a modified polypropylene. The obtained modified polypropylene was vacuum-dried at 150 ° C. for 4 hours to remove residual maleic acid, and then the physical properties were measured by the above methods. The results are shown in Table 2.

[0074] Comparative Example 1

In Example 1, instead of bis (41- (tert-butylcyclohexyl) peroxydicarbonate (manufactured by NOF Corporation, Parolyl TCP), 1,3-bis (t-butylperoxypropyl) benzene ( A modified polypropylene was obtained in the same manner as in Example 1 except that 1.52 g was used and the kneading temperature was set to 180 ° C. About the obtained modified polypropylene, the physical property was measured by said method. The results are shown in Table 2.

[0075] [Table 2] Table 2

 *: In the measurement of surface tension, the lower limit of measurement is 30 mN / m. Industrial applicability

[0076] The modified propylene-based polymer of the present invention is useful as a sealant having high adhesiveness, or as a modifier or the like that gives polyolefin having improved compatibility with an inorganic filler.

Claims

Claims [1] (a) [mmmm] = 20-60 mol 0 / o, (b) [rrrr] / (1-[mmmm]) ≤0.1, (c) [rmr m]> 2. 5 mol 0/0, (d) [mm] X [rr] / [mr] 2≤2.0, and (e) The amount of components (W25) eluting at 25 ° C or lower in temperature-programmed chromatography is 20 ~ : LOO mass% propylene-based polymer is modified with a radical initiator and a polar group-containing olefin-based compound in the absence of a solvent at a temperature of 50 to 140 ° C. A method for producing a modified propylene-based polymer satisfying 1) and (2).

 (1) Intrinsic viscosity of the modified propylene polymer measured in a tetralin solvent at 135 ° C

 [7?] 1 and the intrinsic viscosity [7?] 2 of the propylene-based polymer before the modification have a relation of [r?] L / [r?] 2≥0.95.

 (2) The molecular weight distribution (Mw / Mn) obtained from the polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 2.5 or more.

 [2] The process for producing a modified propylene polymer according to [1], wherein the polar group-containing olefinic compound is an acid anhydride of an unsaturated carboxylic acid.