JP2010150265A - Propylene-based polymer, transition metal compound, catalyst, and resin composition and molded article consisting of the polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-based polymer giving a molded article having less stickiness, and excellent in softness and transparency, catalyst giving the above polymer, transition metal compound suitable as a component of the catalyst, and resin composition and molded article consisting of the polymer. <P>SOLUTION: This propylene-based polymer is provided by having 20 to 80 mol% racemic pentad fraction (rrrr), &le;4 molecular weight distribution (Mw/Mn) measured by a gel permeation chromatography (GPC) and 100,000 to 1,000,000 weight-average molecular weight (Mw). The transition metal compound having a specific double crosslinked type biscyclopentadienyl derivative as a ligand, the catalyst consisting of the transition metal compound and an assistant catalyst, the resin composition obtained from the polymer and polyolefines, and its molded articles are provided. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a propylene-based polymer, a catalyst and a transition metal compound, a resin composition comprising the polymer, and a molded body, and more specifically, a propylene-based polymer that provides a molded body with less stickiness and excellent flexibility and transparency. The present invention relates to a polymer, a catalyst for giving the polymer, a transition metal compound suitable as the catalyst component, a resin composition comprising the polymer, and a molded article.

  Conventionally, vinyl chloride resin has been widely used as a soft resin. However, vinyl chloride resin is known to generate harmful substances in the combustion process, and development of alternative products is strongly desired. There is a propylene polymer as an alternative to the soft vinyl chloride resin. Propylene polymers are produced in the presence of various catalysts, but propylene polymers produced using conventional catalyst systems have many sticky components when trying to make them soft (that is, those having a low elastic modulus). There is a drawback of becoming. Since the atactic polypropylene (APP) component that is the cause of the sticky component increases, the surface properties of the resulting molded article deteriorate. In addition, when a molded body in the form of a sheet or a film is developed for foods, medical uses, various problems may occur. Therefore, a propylene polymer having an improved balance between the low elastic modulus and the amount of the sticky component is desired.

  The present invention relates to a propylene-based polymer that gives a molded article with less stickiness and excellent flexibility and transparency, a catalyst that gives the polymer, a transition metal compound that is suitable as the catalyst component, and a resin composition comprising the polymer The object is to provide a product and a molded body.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have obtained a racemic pentad fraction (rrrr), a molecular weight distribution measured by a gel permeation chromatograph (GPC) method, and a weight average molecular weight (Mw). ) In a specific range is excellent in the balance between the amount of sticky component, low elastic modulus and transparency, and transition with specific double-bridged biscyclopentadienyl derivatives as ligands It has been found that the propylene polymer can be obtained by using a catalyst containing a metal compound, and the present invention has been completed.

That is, the present invention provides the following propylene polymer, transition metal compound and catalyst, a resin composition comprising the polymer, and a molded article.
1. (1) Racemic pentad fraction (rrrr) is 20 to 80 mol%, (2) Molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4 or less, (3) Weight average A propylene-based polymer having a molecular weight (Mw) of 100,000 to 1,000,000.

2. The transition metal compound represented by the following general formula (I).

(In the formula, M represents a group 3 to 10 of the periodic table or a metal element of the lanthanoid series, X represents a σ-binding ligand bonded to M, and when there are a plurality of X, a plurality of X are They may be the same or different, or may be cross-linked with Y. Y represents a Lewis acid, and when there are a plurality of Y, the plurality of Y may be the same or different, R ^{1 to} R ⁵ , or X may be bridged with X. A represents a substituent whose skeleton is composed of an element of Group IV of the Periodic Table, p is an integer of 1 to 20, q is an integer of 1 to 5, and [(M atom 2), and r represents an integer of 0 to ^3. R ¹ , R ² , R ⁴ , and R ⁵ are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen having 1 to 20 carbon atoms. containing hydrocarbon group, a silicon-containing group, or a hetero atom-containing group .R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 4 carbon atoms 20 halogen-containing hydrocarbon group, a silicon-containing group, or a heteroatom value containing group. Further, R ¹ to R ⁵ may be the same or different, or may be formed adjacent groups and rings. )

3. 3. The transition metal compound according to 2 above, wherein A in the general formula (I) is R ⁶ ₂ C or R ⁶ ₂ Si (R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms).
4). A is, CH _2, in formula _{(I) (CH 3) 2} C, CH 2 CH 2, (CH 3) 2 C (CH 3) 2 C, (CH 3) 2 Si, (C 6 H 5) _2. The transition metal compound according to 2 above, which is at least one substituent selected from Si.

5). (A) the transition metal compound according to any one of 2 to 4 above and (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex ( B-2) A catalyst for producing a propylene polymer, on which a catalyst component composed of a component selected from aluminoxane is supported.
6). (A) the transition metal compound according to any one of 2 to 4 above, (B) (B-1) a compound that can react with the transition metal compound of the component (A) to form an ionic complex on the carrier; (B-2) The catalyst for producing a propylene-based polymer as described in 5 above, which comprises a component selected from aluminoxane and a catalyst component comprising (C) an organoaluminum compound.

7). 7. The propylene-based polymer production catalyst according to 5 or 6 above, wherein (B-1) is a compound represented by the following general formula (III) and / or the following general formula (IV).
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
[In the formulas (III) and (IV), L ¹ is a Lewis base, and L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R ¹⁴ M ³ . [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is an anion having a plurality of groups bonded to the element, ie, [M ¹ G ¹ G ^2. G ^f ] ⁻ (where M ¹ represents an element of Group 5 to 15 of the periodic table, preferably Group 13 to 15 of the periodic table. G ^{1 to} G ^f represent a hydrogen atom, a halogen atom, and carbon, respectively. An alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms 40 alkylaryl groups, 7-7 carbon arylalkyl groups, C1-C20 halogen-substituted hydrocarbon groups, C1-C20 acyloxy groups, organic metalloid groups, or C2-C20 heteroatoms two or more rings of .G ¹ ~G ^f indicating a hydrocarbon group containing Optionally form .f represents an integer of [(valence of central metal M1) +1]), [Z ^{2] -.} The logarithm of the reciprocal of the acid dissociation constant (pKa) -10 following Bren A conjugate base of Sted acid alone or a combination of Bronsted acid and Lewis acid, or an acid conjugate base generally defined as a super strong acid. In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]

8). (B-2) For producing a propylene polymer as described in 5 or 6 above, wherein the aluminoxane is a chain aluminoxane represented by the following general formula (V) and / or a cyclic aluminoxane represented by the following general formula (VI): catalyst.

(In the formula, R ¹⁵ represents a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, or an arylalkyl group, or a halogen atom, w represents an average degree of polymerization, and is an integer of 2 to 50. (Note that each R ¹⁵ may be the same or different.)

9. (C) The catalyst for producing a propylene-based polymer according to the above 8, wherein the organoaluminum compound is a compound represented by the following general formula (VII).
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
10. 2. A resin composition obtained from the propylene polymer according to 1 and polyolefins.
11. 11. A molded product obtained from the propylene polymer described in 1 or the resin composition described in 10 above.

The propylene-based polymer of the present invention, the resin composition comprising the polymer, and the molded article have little stickiness, excellent flexibility and transparency, films, sheets, containers, automobile interior materials, and housing materials for home appliances. Used for etc.
In particular, the propylene-based polymer of the present invention and the resin composition comprising the polymer have an improved balance between the low elastic modulus and the amount of the sticky component, and are suitable for food, medical use and the like.

  Hereinafter, [1] a propylene polymer, [2] a transition metal compound suitable as a component of a catalyst for producing a propylene polymer, [3] a catalyst for producing a propylene polymer, and [4] a propylene polymer. The resin composition consisting of [5] molded body will be described in detail.

[1] Propylene polymer The propylene polymer of the present invention is obtained by copolymerizing a propylene homopolymer obtained by homopolymerizing propylene with propylene and ethylene or an α-olefin having 4 to 20 carbon atoms. There is a propylene-based copolymer obtained, and a propylene homopolymer is preferably used.
Examples of the α-olefin other than propylene constituting the propylene-based copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene. , 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like, and one or more of them can be used.
As the propylene-based copolymer in the present invention, a random copolymer is preferable. Moreover, it is preferable that the structural unit obtained from propylene is 90% mol or more, More preferably, it is 95 mol% or more. When the structural unit obtained from propylene is less than 90 mol%, stickiness of the surface of the molded article or a decrease in transparency may occur.

The propylene polymer of the present invention is a polymer having the following (1) to (2) as requirements.
(1) Racemic pentad fraction (rrrr) is 20 to 80 mol%, preferably 20 to 60 mol%.
(2) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4 or less, preferably 3.5 or less, more preferably 3.0 or less.
(3) The weight average molecular weight (Mw) is 100,000 to 1,000,000, preferably 100,000 to 500,000.

The racemic pentad fraction (rrrr) in the propylene-based polymer used in the present invention is a racemic fraction in a pentad unit in a polypropylene molecular chain. This racemic pentad fraction (rrrr) According to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al., It is measured by the signal of the methine group of the ¹³ C nuclear magnetic resonance spectrum.
When the racemic pentad fraction (rrrr) of the propylene-based polymer used in the present invention is less than 20 mol%, stickiness is caused. If it exceeds 80 mol%, the elastic modulus increases, which is not preferable.

Note that the measurement of ¹³ C nuclear magnetic resonance spectrum is described in V.V. According to the assignment of peaks proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

In addition to the above requirements, the propylene-based polymer in the present invention has a molecular weight distribution (Mw / Mn) measured by GPC method of 4 or less, preferably 3.5 or less, particularly preferably 3.0 or less. . If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur.
In addition to the above requirements, the propylene-based polymer of the present invention has a weight average molecular weight measured by GPC method of 100,000 to 1,000,000, preferably 100,000 to 500,000. . If Mw is less than 100,000, stickiness may occur. On the other hand, if it exceeds 1,000,000, the fluidity is lowered and the moldability may be poor.

In addition, said molecular weight distribution (Mw / Mn) is a value calculated from the mass average molecular weight Mw and the number average molecular weight Mn measured by the GPC method with the following apparatus and conditions.
GPC measurement device Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

  In addition to the above requirements, the propylene-based polymer in the present invention preferably has a tensile modulus of 100 MPa or less, more preferably 70 to 5 MPa.

  The method for producing a propylene polymer in the present invention includes a method of homopolymerizing propylene using a catalyst system called a metallocene catalyst or a method of copolymerizing propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms. Can be mentioned. Examples of the metallocene catalyst include JP-A-58-19309, JP-A-61-130314, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, and special tables. Transition metal compounds having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and the like, as described in JP-A-1-502036 Examples thereof include a catalyst obtained by combining a transition metal compound whose ligand is geometrically controlled and a promoter.

[2] Transition metal compound suitable as a component of a catalyst for producing a propylene polymer In the method for producing a propylene polymer of the present invention, a ligand forms a crosslinked structure through a crosslinking group among metallocene catalysts. A catalyst comprising a transition metal compound is preferable, and in particular, a method of polymerizing propylene using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure via two bridging groups and a promoter. Is more preferable. Next, the transition metal compound used for production of the propylene polymer of the present invention will be described.
The transition metal compound of the present invention is a novel double-bridged metallocene complex represented by the following general formula (I).

  In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity.

X represents a σ-binding ligand, and Y represents a Lewis base. q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
When there are a plurality of X, the plurality of X may be the same or different, and may be cross-linked with other X or Y. Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. On the other hand, when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, a cyclopentadienyl group or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

In the general formula (I), R ¹ , R ² , R ⁴ and R ⁵ are each 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 hetero atom containing group is shown. R ³ represents 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 hetero atom value-containing group. R ^{1 to} R ⁵ may be the same as or different from each other, and may form a ring with an adjacent group.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group, a vinyl group, a propenyl group, and a cyclo group. Alkenyl groups such as hexenyl group, arylalkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group And aryl groups such as a methylnaphthyl group, anthracenyl group, and phenanthonyl group.

  Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilino group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group; triethylsilyl group; Propylsilyl group: Trihydrocarbon-substituted silyl group such as dimethyl (t-butyl) silyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl groups; silicon-substituted aryl groups such as trimethylsilylphenyl groups; dimethylhydrosilyl groups and methyldihydrosilyl groups. Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include dimethyl phosphide group, diethyl phosphide group, di (n-propyl) phosphide group, diisobutyl phosphide group, di (sec-butyl) phosphide group, and di (t-butyl). Phosphide group, dipentyl phosphide group, dihexyl phosphide group, dioctyl phosphide group, diphenyl phosphide group, dibenzyl phosphide group, methyl ethyl phosphide group, (t-butyl) trimethylsilyl phosphide group, methyl trimethylsilyl phosphide group Further, it may contain a halogen atom such as chlorine, bromine or iodine.

  Examples of the hetero atom-containing group include a hetero atom-containing hydrocarbon group. Hetero atom-containing hydrocarbon groups include p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Methyl) phenyl group, bis (trimethylsilyl) methyl group and the like.

As a C1-C20 alkoxy group mentioned as a specific example of X, alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenylmethoxy group, a phenylethoxy group, etc. are mentioned.
Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group.
Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.

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

Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmidoyl group, stearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.
X is preferably an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group.

  Specific examples of the Lewis base of Y include amines such as methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine, methylethylamine, Alkylamines such as trimethylamine, triethylamine, tri-n-butylamine, and alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, and dicyclohexenylamine; phenylamine, phenylethylamine, phenylpropylamine, etc. Arylalkylamines; arylamines such as diphenylamine and dinaphthylamine; or ammonia, aniline, N-methyl Le aniline diphenylamine, N, N- dimethylaniline, methyl diphenyl amine pyridine, p- bromo -N, like N- dimethylaniline.

  Examples of ethers include fatty ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl -Aliphatic mixed ether compounds such as n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl vinyl ether, Aliphatic unsaturated ether compounds such as methyl allyl ether, ethyl vinyl ether, and ethyl allyl ether; anisole, Aromatic ether compounds such as enetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane, etc. Can be mentioned. Examples of the esters include ethyl benzoate.

Examples of phosphines include methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, octyl phosphine and other monohydrocarbon substituted phosphines, dimethyl phosphine, diethyl phosphine, dipropyl phosphine, dibutyl phosphine, dihexyl phosphine, dicyclohexyl. Diphosphine substituted phosphines such as phosphine and dioctyl phosphine, alkyl phosphines such as tri hydrocarbon phosphine such as trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, trihexyl phosphine, tricyclohexyl phosphine and trioctyl phosphine, vinyl Phosphine, propenyl phosphine, cyclohexenyl phosphite Monoalkenylphosphine such as dialkenylphosphine substituted with two alkenyl hydrogen atoms; trialkenylphosphine substituted with three alkenyl hydrogen atoms; arylalkyl such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine Phosphine; Diarylalkylphosphine or aryldialkylphosphine in which three hydrogen atoms of phosphine are substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine , Methylnaphthylphosphine, anthracenylphosphine, phenanthrylphosphine Fins; a hydrogen atom alkylaryl two substituted di (alkylaryl) phosphines phosphine; aryl phosphine such as tri (alkylaryl) phosphines alkylaryl hydrogen phosphine has three substituents and the like.
Examples of the thioethers include the aforementioned sulfides. Examples of nitriles include acetonitrile and benzonitrile.

  In the general formula (I), A represents a substituent whose skeleton is composed of an element of Group IV of the periodic table, and they may be the same as or different from each other. p is an integer of 1-20. As the group IV element of the periodic table, carbon, silicon, tin, and germanium are preferable. Examples of the substituent whose skeleton is composed of an element of Group IV of the periodic table include, for example, the following general formula:

(E represents carbon, silicon, tin, germanium, and R ⁷ and R ⁸ are each 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, A silicon-containing group having 1 to 20 carbon atoms, which may be the same as or different from each other, and may be bonded to each other to form a ring, and e represents an integer of 1 to 4.
The group represented by these is mentioned.

Hydrocarbon group having 1 to 20 carbon atoms of R ⁷ and R ^8, an alkoxy group having 1 to 20 carbon atoms, aryloxy group and a silicon-containing group having 1 to 20 carbon atoms of 6 to 20 carbon atoms, said R ¹ It includes the same as those in to R ^5. Specifically, methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, diphenylsilylene, tetramethyldisilylene, dimethylgermylene, dimethylstannylene, 1,2-phenylene, Vinylene, vinylidene, ethynylidene (CH ₂ = C =), and the like. Among these, methylene [CH ₂ ], isopropylidene [(CH ₃ ) ₂ C], ethylene [CH ₂ CH ₂ ], ethylidene [(CH ₃ ) ₂ C (CH ₃ ) ₂ C], dimethylsilylene [(CH ₃ ) ₂ Si], and diphenylsilylene [(C ₆ H ₅ ) ₂ Si] are easy to synthesize and yield in transition metal compounds. However, it is preferable.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged ligand.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ' , 4′-Diisopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ′, 4′-dimethyl) Cyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,5-diphenylcyclopentadienyl) (3 ', '-Dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3', 4'-diethylcyclopenta Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropyl-4-methylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadiene) Enyl) zirconium dichloride, and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium, but of course are not limited thereto.
Further, a transition metal compound similar to the above in which zirconium is substituted with a transition metal of another group, or a compound similar to the above in which zirconium is substituted with a lanthanoid series metal element may be used.
This transition metal compound is synthesized, for example, by the method described in “J. Organomet. Chem.” 369, 359 (1989). That is, the reaction of the corresponding substituted cycloalkenyl anion with the aforementioned M halide is preferred.

[3] Catalyst for Propylene Polymer Production The propylene polymer production catalyst of the present invention comprises (A) the above transition metal compound, and (B) (B-1) the transition metal compound of component (A) A catalyst containing a compound capable of forming an ionic complex by reaction and a catalyst component comprising a component selected from (B-2) aluminoxane, and (A) the above transition metal compound, (B) ( B-1) a compound capable of reacting with the transition metal compound of component (A) to form an ionic complex, a component selected from (B-2) aluminoxane, and a catalyst component comprising (C) an organoaluminum compound. A supported catalyst is preferred.

Of these components (B), any component can be used as long as it is a compound that can react with the transition metal compound of component (A) to form an ionic complex. Are represented by the following general formula (III) and general formula (IV):
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R ¹⁴ M ^3.)
[In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of Anion in which the group is bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table) G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Aryl group, aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms An acyloxy group, an organic metalloid group, or a heteroatom-containing carbon having 2 to 20 carbon atoms . Two or more may form a ring .f of .G ¹ ~G ^f represents a hydrogen group represents an integer of [(valence of central metal M1) +1]), [Z ^{2] -} Represents a conjugate base of a Bronsted acid alone or a combination of Bronsted acid and Lewis acid having a logarithm (pKa) of an acid dissociation constant of -10 or less, or an acid conjugate base generally defined as a super strong acid. Show. In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. Cyclopentadienyl group, indenyl group or fluorenyl group, R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ -R ¹⁰ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]
What is represented by these can be used conveniently.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, Fe, Co, Ni, and Zn. And so on.

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

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

  Specific examples of such an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the component compound (B-1), include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) tetraethylammonium borate, benzyl (tri-n-butyl) ammonium borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluoro) Phenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate, Dimethylanilinium trakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetrapheni Silver ruborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) ) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Teoraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, silver Such as trifluoromethanesulfonic silver can be given.

  (B-1) may be used alone or in combination of two or more. On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

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

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.

  Examples of the aluminoxane include methylaluminoxane, emethylaluminoxane, isobutylaluminoxane, t-butylaluminoxane, and the like. These may be used alone or in combination of two or more.

  Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method. For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There are a method of reacting crystallization water contained in a salt or the like, water adsorbed on an inorganic or organic material with an organoaluminum compound, and (4) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. . The aluminoxane may be insoluble in toluene.

The proportion of the (A) catalyst component and the (B) catalyst component used in the propylene-based polymer production catalyst of the present invention is the molar ratio when the (B-1) compound is used as the (B) catalyst component. The range is preferably 10: 1 to 1: 100, more preferably 2: 1 to 1:10. When deviating from this range, the catalyst cost per unit mass polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical.
Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).

In the polymerization catalyst of the present invention, an organoaluminum compound is preferably used as the component (C) in addition to the components (A) and (B).
Here, as the organoaluminum compound of the component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

  In the production of the polymerization catalyst of the present invention, it is preferable to perform preliminary contact using the above-described component (A), component (B) and component (C). The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the promoter (B) used. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above effect. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, and more preferably 0 ° C to 80 ° C. In the preliminary contact, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon or the like can be used as a solvent. Of these, particularly preferred are aliphatic hydrocarbons.

  The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

  In the catalyst of the present invention, it is preferable to use at least one catalyst component supported on a suitable carrier. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.

Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

As a carrier other than the above, a magnesium compound represented by the general formula MgR ¹⁷ _x X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ , or a complex salt thereof can be given. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.
As the support in the catalyst of the present invention, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O _{3 and the} like are preferable.

Although the properties of the carrier vary depending on the type and production method, the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there. When either the specific surface area or the pore volume deviates from the above range, the catalyst activity may decrease.
The specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method, for example.

In the case where the carrier is an inorganic substance, it is usually desirable to use it after firing at 150 to 1000 ° C, preferably 200 to 800 ° C.
Further, when at least one of the catalyst components is supported on the carrier, at least one of (A) the catalyst component and (B) the catalyst component, preferably both (A) the catalyst component and (B) the catalyst component are supported. Is desirable.

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

  In the production of the catalyst of the present invention, the catalyst may be prepared by irradiating elastic waves when contacting the (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 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.

The catalyst thus obtained may be used for polymerization after removing the solvent once and taking out as a solid, or may be used for polymerization as it is.
Further, in the production of the catalyst of the present invention, the catalyst can be produced by carrying out the supporting operation of at least one of the component (A) and the component (B) on the carrier. For example, at least one of the component (A) and the component (B), a carrier, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa (gauge), and -20 to 200 A method of preliminarily polymerizing at about 1 minute to 2 hours to form catalyst particles can be used.

  The ratio of the component (B-1) to the support used in the catalyst of the present invention is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio. When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio. In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.

If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g. , Preferably it is 50-500 m < ² > / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. When the specific surface area is less than 20 m ² / g, the activity may decrease, and when it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of 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. If the amount of transition metal is outside the above range, the activity may be lowered.

By using the catalyst supported on the carrier in this way, a polymer having an industrially advantageous high bulk density and excellent particle size distribution can be obtained.
The propylene-based polymer of the present invention is preferably produced by homopolymerizing propylene or copolymerizing propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms using the polymerization catalyst described above. The

  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, or a suspension polymerization method may be used. A polymerization method is particularly preferred.

About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. In addition, the ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , and particularly preferably 100 to 10 ⁵ with respect to the raw material monomer / the component (A) (molar ratio). (Note that this raw material monomer is propylene, or further added with ethylene or an α-olefin having 4 to 20 carbon atoms.) Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to The pressure is 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).

Examples of the method for adjusting the molecular weight of the polymer include selection of the type, amount used, and polymerization temperature of each catalyst component, and further polymerization in the presence of hydrogen.
When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, it can be carried out without solvent.

  In the polymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and examples thereof include those similar to those exemplified above, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used.

  Moreover, prepolymerization temperature is -20-200 degreeC normally, Preferably it is -10-130 degreeC, More preferably, it is 0-80 degreeC. In the prepolymerization, an inert hydrocarbon, aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.

  In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and per 1 millimole of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10000 g, particularly 10 to 1000 g.

[4] Resin composition comprising propylene polymer The resin composition comprising the propylene polymer of the present invention is obtained from the propylene polymer and polyolefins.
Examples of the polyolefins used in the resin composition include polyethylene, polypropylene, poly α-olefins composed of α-olefins having 4 or more carbon atoms, polyvinyl cycloalkane, syndiocta polystyrene, and polyalkenyl silanes.

Examples of polypropylene include homopolypropylene, which is a propylene-only polymer, such as propylene-ethylene random polypropylene, such as propylene / propylene-ethylene block polypropylene, and polyethylene includes high-density polyethylene, low-density polyethylene, such as ethylene- Examples include linear low density polyethylene such as butene-1, ethylene-hexene-1, and ethylene-octene-1. Examples of the poly α-olefin include polybutene-1, poly (4-methylpentene-1), poly (3-methylpentene-1), and poly (3-methylbutene-1). Preferred examples of the polyvinylcycloalkane include polyvinylcyclohexane and polyvinylcyclopentane. Examples of the polyalkenyl silane include those having an alkenyl group having 2 to 20 carbon atoms, such as vinyl silane, butenyl silane, and allyl silane.
Among these, polypropylene, polyethylene and poly α-olefin are preferable from the viewpoint of compatibility, and polypropylene is more preferable from the viewpoint of heat resistance and flexibility. The weight average molecular weight of the polyolefins in the present invention is 10,000 to 1,000,000 from the viewpoint of practicality.

  As a method for producing a resin composition comprising the propylene polymer of the present invention, the propylene polymer, polyolefins, and various additives used as desired are dry blended using a Henschel mixer or the like. It may be. Alternatively, it may be melt kneaded using a single-screw or twin-screw extruder, a Banbury mixer, or the like. Alternatively, when a high melting point polymer is used as the nucleating agent, the high melting point polymer may be added simultaneously or sequentially in the reactor at the time of producing the propylene polymer. Examples of various additives used as desired include an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, and an antistatic agent.

[4] Molded body The molded body of the present invention is a molded body obtained from the propylene polymer or the resin composition. The molded article of the present invention has softness (also referred to as flexibility), high elastic recovery rate (property that returns to its original state even when pulled), softness, that is, low elastic modulus and excellent transparency. There are features.

  Examples of the molded body of the present invention include a film, a sheet, a container, an automobile interior material, and a housing material for an electrical product. Examples of the film include a food packaging film and an agricultural film (an example of a greenhouse). As a container, since it is excellent in transparency, a transparent case, a transparent box, a decorative box, etc. are mentioned.

Examples of the molding method include a molding method, a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, and a blow molding method.
The molding conditions are not particularly limited as long as the temperature conditions allow the resin to melt and flow, and can usually be performed at a resin temperature of 50 ° C. to 300 ° C. and a mold temperature of 60 ° C. or less. When forming a film as the molded article of the present invention, it can be performed by a general compression molding method, extrusion molding method, blow molding method, cast molding method, or the like.

EXAMPLES Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
In the following examples and comparative examples, measurement of resin properties and evaluation of physical properties of polymers were performed as follows.
(1) Resin characteristics of polymer Racemic pentad fraction (rrrr), molecular weight distribution (Mw / Mn), and weight average molecular weight (Mw) were measured by the methods described in the specification.
(2) Tensile elastic modulus A test piece was prepared by press-molding a propylene-based polymer, and measured by a tensile test based on JIS K-7113.
-Test piece (No. 2 dumbbell) Thickness: 1mm
・ Crosshead speed: 50mm / min
・ Load cell: 100kg
(3) Internal haze A propylene polymer was press-molded to prepare a test piece, which was measured by a test based on JIS K-7105. The smaller this value, the better the transparency.
Test piece: 15 cm × 15 cm × 1 mm (test piece thickness = 1 mm)

Production Example [Production of Transition Metal Compound]
According to the following method, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ′, 4′-dimethylcyclo) which is the transition metal compound of the present invention is used. Pentadienyl) hafnium dichloride was synthesized.

(1) Production of 6,6-dimethylfulvene 300 mL of methanol, 70 mL (852 mmol) of cyclopentadiene, and 63 mL (859 mmol) of acetone are added to a 1 L three-necked flask, and 85 mL (1018.3 mmol) of pyrrolidine is added thereto at room temperature using a dropping funnel. And slowly dropped. After completion of dropping, the mixture was stirred for 1 hour and neutralized with 84 mL of acetic acid. The mixture was diluted with 200 mL each of water and ether and separated with a separatory funnel, and the organic phase was washed with 200 mL each of brine and water and then dried over anhydrous magnesium chloride. After distilling off the solvent, 66.55 g (627 mmol) of 6,6-dimethylfulvene was obtained by distillation under reduced pressure. (Yield 74%)

(2) Production of Isopropylcyclopentadiene 200 mL of ether was added to 24.8 g (653 mmol) of lithium aluminum hydride, and 66.55 g (627 mmol) of 6,6-dimethylfulvene was slowly added dropwise thereto using a dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Hydrolysis was performed at 0 ° C., ether extraction was performed, and the solvent was distilled off after drying over anhydrous magnesium chloride. Distillation under reduced pressure gave 36,61 g (338.4 mmol) of isopropylcyclopentadiene. (Yield 39%)

(3) Production of 3-isopropyl-6,6-dimethylfulvene 36.61 g (338.4 mmol) of isopropylcyclopentadiene and 27.3 mL (372 mmol) of acetone were added to 200 mL of methanol, and 36 mL (431 mmol) of pyrrolidine using a dropping funnel. Was dripped. After stirring at room temperature for 1 hour, the mixture was neutralized with acetic acid and diluted with 200 mL of water and ether. The organic phase was separated, the solvent was distilled off, and the resulting yellow oil was distilled under reduced pressure to obtain 36.81 g (248 mmol) of 3-isopropyl-6,6-dimethylflupene. (Yield 73%)

(4) Production of 1,3-diisopropylcyclopentadiene 9.4 g (248 mmol) of lithium aluminum hydride was added to 200 mL of ether, and 35.26 g (237.8 mmol) of 3-isopropyl-6,6-dimethylfulvene was slowly added thereto. It was dripped. After dropping, the mixture was stirred at room temperature for 1 hour, hydrolyzed at 0 ° C., and extracted with ether. The organic phase was dried over anhydrous magnesium chloride, the solvent was distilled off, and 27.58 g (183.5 mmol) of 1,3-diisopropylcyclopentadiene was obtained by distillation under reduced pressure. (Yield 74%)

(5) Production of 3,5-diisopropylcyclopentadienyldimethylchlorosilane To 9.6 g (63.4 mmol) of 1,3-diisopropylcyclopentadiene, 100 mL of toluene and 50 mL of hexane were added, and n-BuLi (1. 45 mL of 55M hexane solution) was added dropwise. After stirring at room temperature for 8 hours, the white precipitate was filtered off and dried under reduced pressure. The resulting white solid was dissolved in 80 mL of THF at −78 ° C., and 10.8 mL (89 mmol) of dimethyldichlorosilane was added dropwise thereto. It returned to room temperature and stirred for 2 hours. After the solvent was distilled off, extraction was performed with 100 mL of hexane. The solvent was distilled off to obtain 14.4 g (59 mmol) of 3,5-diisopropylcyclopentadienyldimethylchlorosilane. (Yield 93%)

(6) Preparation of (2,3-dimethylcyclopentadienyl) (2,4-diisopropylcyclopentadienyl) dimethylsilane 50 mL of THF was added to 14.4 g (59 mmol) of 3,5-diisopropylcyclopentadienyldimethylchlorosilane. This was added dropwise to a THF solution of 1,2-dimethylcyclopentadienyllithium (59 mmol) that had been synthesized separately. After stirring overnight, the solvent was distilled off and extracted with 100 mL of hexane. The solvent was distilled off to obtain 7.55 g (25.1 mmol) of (2,3-dimethylcyclopentadienyl) (2,4-diisopropylcyclopentadienyl) dimethylsilane. (Yield 43%)

(7) Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadiene) (2,3- 100 mL of ether was added to 7.55 g (25.1 mmol) of dimethylcyclopentadienyl) (2,4-diisopropylcyclopentadienyl) dimethylsilane, and n-BuLi (hexane solution, 1.61 M) at −78 ° C. 2 mL was added. After stirring at room temperature for 8 hours, the solvent was distilled off, washed with 100 mL of hexane, and dried under reduced pressure. 80 mL of THF was added to this, 3.0 mL (24.7 mmol) of dimethyldichlorosilane was added at 0 degreeC, and it stirred at room temperature for 20 hours. The solvent of the obtained yellowish cloudy solution was distilled off and extracted with 80 mL of hexane. When the solvent of the extract was distilled off, a yellow oily substance was obtained. When this was subjected to Kugel distillation (0.06 torr, 160 ° C.), (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropylcyclopentadiene) was obtained as a viscous light yellow oily substance. Enyl) (3 ′, 4′-dimethylcyclopentadiene) was obtained.

(8) Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) hafnium dichloride 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadiene) 2.04 g (5.7 mmo1) with 50 mL of THF. In addition, 8.5 mL (13.7 mmol) of n-BuLi (hexane solution, 1.61 M) was added dropwise at 0 ° C. After completion of dropping, the mixture was stirred at room temperature for 2.5 hours. After the solvent was distilled off, it was washed with 30 mL of hexane. This was filtered off and dried under reduced pressure to obtain a white powder. 1.17 g (3.2 mmol) of this powder was suspended in 50 mL of dichloromethane and cooled to −78 ° C. A suspension of 1.0 g of hafnium tetrachloride in 30 mL of dichloromethane was added dropwise thereto and stirred at room temperature for 8 hours. After the solvent was distilled off, extraction was performed with 40 mL of toluene. After filtration, the solution is concentrated and refrigerated when (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl). Colorless crystals of (enyl) hafnium dichloride were precipitated.

Example 1
In a stainless steel autoclave with an internal volume of 10 liters, 6 liters of heptane, 5 mmol of triisobutylaluminum, 20 mmol of methylaluminoxane (manufactured by Albemarle), (1,2'-dimethylsilylene) (2,1 ') obtained in the production example -Dimethylsilylene) (3,5-diisopropylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) hafnium dichloride was charged in an amount of 20 μmol. Here, propylene gas was introduced to a total pressure of 7.8 MPa-G, and polymerization was carried out at a polymerization temperature of 40 ° C. for 60 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 160 g of a propylene polymer. The resin characteristics of the propylene-based polymer were as follows: racemic pentad fraction (rrrr) was 22.3, molecular weight distribution (Mw / Mn) was 2.14, and weight average molecular weight (Mn) was 100,000.
The obtained propylene-based polymer was extruded and granulated with a single screw extruder (manufactured by Tsukada Juiki Seisakusho: TLC35-20 type) to obtain pellets. The test piece obtained by press molding had a tensile strength of 20 MPa and an internal haze of 5%.

Example 2
25% by weight of the polypropylene polymer obtained in Example 1 was blended with Idemitsu Petrochemicals Polypropylene El05GM.
Pellets were obtained from the obtained resin composition by the same method as in Example 1. The test piece obtained by press molding had a tensile strength of 1100 MPa and an internal haze of 35%.

Comparative Example 1
Pellets were obtained from Idemitsu Petrochemical's polypropylene El05GM by the same method as in Example 1. The test piece obtained by press molding had a tensile strength of 1500 MPa and an internal haze of 45%.

Claims (8)

The transition metal compound represented by the following general formula (I).

(In the formula, M represents a group 3 to 10 of the periodic table or a metal element of the lanthanoid series, X represents a σ-binding ligand bonded to M, and when there are a plurality of X, a plurality of X are They may be the same or different, or may be cross-linked with Y. Y represents a Lewis acid, and when there are a plurality of Y, the plurality of Y may be the same or different, R ^{1 to} R ⁵ , or X may be cross-linked with X. A represents a substituent having an element of group IV of the periodic table, p is an integer of 1 to 20, q is an integer of 1 to 5 [(valence of M ) -2], and r represents an integer of 0 to ^3. R ¹ , R ² , R ⁴ and R ⁵ are each a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen containing 1 to 20 carbon atoms. indicating hydrocarbon group, a silicon-containing group, or a heteroatom containing group .R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms 0 containing hydrocarbon group, a silicon-containing group, or a heteroatom value containing group. Further, R ¹ to R ⁵ may be the same or different, or may be formed adjacent groups and rings. ) The transition metal compound according to claim 1, wherein A in the general formula (I) is R ⁶ ₂ C or R ⁶ ₂ Si (R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). A is, CH _2, in formula _{(I) (CH 3) 2} C, CH 2 CH 2, (CH 3) 2 C (CH 3) 2 C, (CH 3) 2 Si, (C 6 H 5) The transition metal compound according to claim 1, which is at least one substituent selected from ₂ Si.   (A) It can react with the transition metal compound according to any one of claims 1 to 3 and (B) (B-1) the transition metal compound of the component (A) to form an ionic complex. A catalyst for producing a propylene-based polymer comprising a catalyst component comprising a compound and a component selected from (B-2) aluminoxane.   The carrier reacts with (A) the transition metal compound according to any one of claims 1 to 3, and (B) (B-1) the transition metal compound of the component (A) to form an ionic complex. A catalyst for producing a propylene-based polymer according to claim 4, wherein a catalyst component comprising a compound selected from (B-2) aluminoxane and (C) an organoaluminum compound is supported. The catalyst for producing a propylene-based polymer according to claim 4 or 5, wherein (B-1) is a compound represented by the following general formula (III) and / or the following general formula (IV).
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
[In the formulas (III) and (IV), L ¹ is a Lewis base, and L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R ¹⁴ M ³ . [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is an anion having a plurality of groups bonded to the element, ie, [M ¹ G ¹ G ^2. G ^f ] ⁻ (where M ¹ represents an element of Group 5 to 15 of the periodic table, preferably Group 13 to 15 of the periodic table. G ^{1 to} G ^f represent a hydrogen atom, a halogen atom, and carbon, respectively. An alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms 40 alkylaryl groups, 7-7 carbon arylalkyl groups, C1-C20 halogen-substituted hydrocarbon groups, C1-C20 acyloxy groups, organic metalloid groups, or C2-C20 heteroatoms two or more rings of .G ¹ ~G ^f indicating a hydrocarbon group containing Optionally form .f represents an integer of [(valence of central metal M1) +1]), [Z ^{2] -.} The logarithm of the reciprocal of the acid dissociation constant (pKa) -10 following Bren A conjugate base of Sted acid alone or a combination of Bronsted acid and Lewis acid, or an acid conjugate base generally defined as a super strong acid. In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ] (B-2) The propylene heavy polymer according to claim 4 or 5, wherein the aluminoxane is a chain aluminoxane represented by the following general formula (V) and / or a cyclic aluminoxane represented by the following general formula (VI). Catalyst for coalescence production.

(In the formula, R ¹⁵ represents a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, or an arylalkyl group, or a halogen atom, w represents an average degree of polymerization, and is an integer of 2 to 50. (Note that each R ¹⁵ may be the same or different.) The catalyst for producing a propylene-based polymer according to claim 5, wherein the organoaluminum compound (C) is a compound represented by the following general formula (VII).
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)