JP4620205B2 - Polypropylene film - Google Patents

Polypropylene film Download PDF

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Publication number
JP4620205B2
JP4620205B2 JP2000037617A JP2000037617A JP4620205B2 JP 4620205 B2 JP4620205 B2 JP 4620205B2 JP 2000037617 A JP2000037617 A JP 2000037617A JP 2000037617 A JP2000037617 A JP 2000037617A JP 4620205 B2 JP4620205 B2 JP 4620205B2
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Japan
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group
tm
represents
component
dimethylsilylene
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JP2000037617A
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JP2001226498A (en
Inventor
裕 南
雅彦 遠藤
正実 金丸
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出光興産株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polypropylene film that can replace soft vinyl chloride, and more particularly to a novel polypropylene film that has less stickiness and is excellent in peel whitening, softness, and impact resistance.
[0002]
[Prior art]
Vinyl chloride resins are widely used as soft resins, but vinyl chloride resins are known to generate harmful substances in the combustion process, and development of alternative resins is strongly desired. In recent years, an olefin polymer produced using a metallocene catalyst has been proposed as an alternative resin. For example, a copolymer of ethylene and α-olefin may be used. However, when this copolymer is soft, there is a problem that the sticky component increases. Furthermore, there is a problem that the molded article such as a film is inferior in transparency and surface characteristics, and it is sufficient. Moreover, the moldability was also inferior.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel polypropylene film which has little stickiness and is excellent in peeling whitening property, softness and impact resistance.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that the tensile elastic modulus (TM) is in a specific range and shows a melting point Tm (° C.) in a differential scanning calorimeter (DSC) measurement. Or when the Tm is indicated, a polypropylene film having a specific relationship between TM and Tm, and having an intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent, achieves the above purpose. The present inventors have found that this can be done and have completed the present invention.
[0005]
That is, the present invention
1. (1) Tensile modulus (TM) is 5 to 500 MPa,
(2) In the differential scanning calorimeter (DSC) measurement, the melting point Tm (° C.) is not indicated, or when Tm is indicated, TM and Tm are the following relational expressions.
TM ≧ 5 × Tm-450
The filling,
(3) a polypropylene film having an intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. of 1 to 3 dl / g,
2. The polypropylene film is (1) the component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight,
(2) In DSC measurement, melting point Tm (° C.) is not shown, or when Tm is shown, Tm and melting endotherm ΔH (J / g)
ΔH ≧ 6 × (Tm−140)
The filling,
(3) The polypropylene film according to claim 1, comprising a propylene polymer [A] having an intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. of 1 to 3 dl / g,
3. The propylene polymer [A] has (1) a mesopentad fraction [mmmm] of 20 to 60 mol%,
(2) Racemic pentad fraction [rrrr] and [1-mmmm] are the following relational expressions
[[Rrrr] / [1-mmmm]] ≦ 0.1
The polypropylene film of 2 above, which is a propylene homopolymer [A-1] satisfying
4). The propylene polymer [A] and the propylene homopolymer [A-1] are (A) represented by the following general formula (I):
[0006]
[Chemical formula 2]
[0007]
[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series;1And E2Were selected from substituted cyclopentadienyl, indenyl, substituted indenyl, heterocyclopentadienyl, substituted heterocyclopentadienyl, amide, phosphide, hydrocarbon and silicon-containing groups, respectively. A ligand comprising A1And A2A cross-linked structure is formed, and they may be the same or different, X represents a σ-binding ligand, and when there are a plurality of X, a plurality of X are the same or different. Okay, other X, E1, E2Alternatively, it may be cross-linked with Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and other Y, E1, E2Or X and X may be cross-linked1And A2Is a divalent bridging group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group. Group, -O-, -CO-, -S-, -SO2-, -Se-, -NR-, -PR-, -P (O) R-, -BR- or -AlR-, wherein R is 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, which may be 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. ]
And (B) (B-1) a compound capable of reacting with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B-2) an aluminoxane. The polypropylene film of the above 1 to 3 produced by polymerizing propylene or propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of a polymerization catalyst containing a component selected from ,
5. A polypropylene film of the above 1-4, which is a cast film obtained by a T-die cast molding method,
Is to provide.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the polypropylene film of the present invention will be described in detail.
The polypropylene film of the present invention has (1) a tensile elastic modulus (TM) of 5 to 500 MPa,
(2) In the differential scanning calorimeter (DSC) measurement, the melting point Tm (° C.) is not indicated, or when Tm is indicated, TM and Tm are the following relational expressions.
TM ≧ 5 × Tm-450
The filling,
(3) A polypropylene film having an intrinsic viscosity [η] of 1 to 3 dl / g measured at 135 ° C. in a tetralin solvent.
In the polypropylene-based film of the present invention, the tensile modulus (TM) is 5 to 500 MPa, but 5 to 250 MPa is preferable from the viewpoint of flexibility.
The fact that the polypropylene film does not show the melting point Tm (° C.) in DSC measurement suggests that the heat seal temperature can be lowered, and indicates that the low temperature heat seal property is excellent. Moreover, Tm indicating that Tm and the tensile elastic modulus (TM) satisfy the above relationship indicates that the balance between the heat seal temperature and the seal strength is excellent, and the tensile elastic modulus, impact resistance, etc. of a molded product such as a film. It shows that the rigidity is excellent.
Tm and ΔH described later are obtained by DSC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample is melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to 0 ° C. at 10 ° C./min. Furthermore, the peak top of the maximum peak of the melting endothermic curve obtained by maintaining at 0 ° C. for 3 minutes and raising the temperature at 10 ° C./min is the melting point Tm, and the melting endotherm in this case is ΔH (J / g).
[0009]
When the polypropylene film shows a melting point Tm in DSC measurement, TM is
TM ≧ 5 × Tm-450
However, if TM does not satisfy this relationship, the balance between the heat seal temperature and the seal strength is not excellent. TM is preferably
TM ≧ 5 × Tm-400
More preferably,
TM ≧ 5 × Tm-350
It is. The method for measuring the tensile modulus TM (MPa) will be described in detail in the examples.
Furthermore, the polypropylene film of the present invention has an intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 1 to 3 dl / g. The intrinsic viscosity [η] is preferably 1 to 2.5 dl / g, particularly preferably 1.5 to 2.0 dl / g. If the intrinsic viscosity [η] is less than 1 dl / g, stickiness occurs. On the other hand, if it exceeds 3 dl / g, the melt fluidity is lowered and the moldability may be poor. The method for measuring [η] will be described in detail in the examples.
The polypropylene film of the present invention is a film having high rigidity and excellent low-temperature heat sealability as described above, and is suitably used for food packaging films, agricultural films (for example, greenhouses), sealant films and the like.
[0010]
Specifically, as described later, the polypropylene film of the present invention uses a propylene polymer in which H25 is in a specific range and the molecular weight distribution (Mw / Mn) is narrow, thereby suppressing bleeding of the sticky component on the surface. The stickiness is low. In addition, since it is less sticky, it is a film excellent not only in surface properties but also in formability. Furthermore, the polypropylene film of the present invention has a haze measured in accordance with JIS K-7105 of usually 5% or less, preferably 3% or less, and is excellent in transparency. Furthermore, the polypropylene film of the present invention has an impact resistance of usually 10,000 J / m obtained by a measuring method using a 1/2 inch impact head in a film impact tester of Toyo Seiki Seisakusho.2Or more, preferably 15000 J / m2It is the above and it is excellent also in impact resistance.
[0011]
Specific examples of the polypropylene film of the present invention include films made of the propylene polymer [A] described below.
The propylene polymer [A] has the following (1), (2) and (3)
(1) The component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight,
(2) In DSC measurement, melting point Tm (° C.) is not shown, or when Tm is shown, Tm and melting endotherm ΔH (J / g)
ΔH ≧ 6 × (Tm−140)
The filling,
(3) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 1 to 3 dl / g.
It is a polymer which has the property shown by these.
When the propylene-based polymer [A] satisfies the above relationship, a film having excellent balance between the tensile elastic modulus and the heat seal temperature, little stickiness, and excellent moldability, transparency, and impact resistance can be obtained.
[0012]
In the propylene polymer [A] in the present invention, the component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight. Preferably, it is 0 to 50% by weight, more preferably 0 to 25% by weight, still more preferably 0 to 10% by weight, and particularly preferably 0 to 5% by weight. H25 is an index indicating whether the amount of so-called stickiness component that causes stickiness, a decrease in transparency, or the like is large or small, and the higher this value, the greater the amount of sticky component. When H25 exceeds 80% by weight, the amount of the sticky component is large, and the blocking resistance and transparency of the film may be lowered.
H25 means the weight of propylene-based polymer [A] (W0) And the polymer in 200 ml of hexane at 25 ° C. for 3 days or more and then dried (W1Is the weight loss rate calculated by the following formula.
H25 = [(W0-W1) / W0] X 100 (wt%)
[0013]
Further, the propylene-based polymer [A] in the present invention does not show a melting point Tm (° C.) in DSC measurement, or when Tm is shown, Tm and melting endotherm ΔH (J / g) are expressed by the following relational expression.
ΔH ≧ 6 × (Tm−140)
Meet. More preferably,
ΔH ≧ 3 × (Tm−120)
Particularly preferably,
ΔH ≧ 2 × (Tm−100)
It is.
Moreover, in DSC measurement, not showing melting | fusing point Tm (degreeC) suggests that heat seal temperature can be reduced, and shows that low temperature heat seal property is excellent. Also, Tm is shown, and Tm and melting endotherm ΔH (J / g) satisfying the above relationship indicates that the melting endotherm is high instead of the melting point, and the tensile elastic modulus and impact resistance of molded products such as films. It shows that the rigidity such as is excellent. The method for measuring Tm and ΔH is as described above.
[0014]
The propylene-based polymer [A] according to the present invention has an intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 1 to 3 dl / g. The intrinsic viscosity [η] is preferably 1 to 2.5 dl / g, particularly preferably 1.5 to 2.0 dl / g. If the intrinsic viscosity [η] is less than 1 dl / g, stickiness occurs. On the other hand, if it exceeds 3 dl / g, the melt fluidity is lowered and the moldability may be poor.
Further, the propylene-based polymer [A] preferably has a molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method of 2.5 to 4.0, more preferably 2 0.5 to 3.5, particularly preferably 2.5 to 3.0. If the molecular weight distribution (Mw / Mn) is less than 2.5, the moldability is lowered, and if it exceeds 4.0, stickiness may occur. In addition, about the apparatus and conditions in GPC method, it describes in an Example.
[0015]
The propylene polymer [A] in the present invention is preferably a propylene homopolymer, but the propylene homopolymer contains a small amount of ethylene and / or an α-olefin having 4 to 20 carbon atoms. Also good. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene, 1-eicocene and the like can be mentioned, and in the present invention, one or more of these can be used.
[0016]
As propylene homopolymer, the following (1) and (2)
(1) Mesopentad fraction [mmmm] is 20 to 60 mol%,
(2) Racemic pentad fraction [rrrr] and [1-mmmm] are the following relational expressions
[[Rrrr] / [1-mmmm]] ≦ 0.1
The propylene homopolymer [A-1] that satisfies the above is preferable.
In the present invention, the meso-pendad fraction [mmmm] is defined by A. Zambelli et al. As “Macromolecules,6, 925 (1973) ”,13It is a meso fraction in the pentad unit in a polypropylene molecular chain measured by the signal of the methyl group of a C-NMR spectrum. When this becomes large, it means that stereoregularity becomes high. In the present invention, the propylene homopolymer [A-1] preferably has a meso-pentad fraction [mmmm] of 30 to 60%, particularly preferably 40 to 60%, and most preferably 40 to 50%. If the mesopentad fraction [mmmm] is less than 20 mol%, the crystallinity is too low, so that the tensile elastic modulus and impact resistance may be lowered or the moldability may be poor. Moreover, when it exceeds 60%, it tends to be soft and the heat seal temperature becomes high, and the low temperature heat sealability may be impaired. Similarly, the racemic pendant fraction [rrrr] is a racemic fraction in a pentad unit in a polypropylene molecular chain. [[Rrrr] / [1-mmmm]] is an index representing the uniformity of the regularity distribution of the propylene homopolymer [A-1], which is obtained from the above pentad unit fraction. When this value is increased, the distribution of regularity is widened, which means that a mixture of highly ordered PP and APP is obtained as in the conventional polypropylene produced using an existing catalyst system, and stickiness is increased and transparency is decreased. The propylene homopolymer [A-1] in the present invention preferably has [[rrrr] / [1-mmmm]] ≦ 0.08, and more preferably [[rrrr] / [1-mmmm]] ≦ 0.06. [[Rrrr] / [1-mmmm]] ≦ 0.04 is particularly preferable. If [[rrrr] / [1-mmmm]] exceeds 0.1, stickiness may be caused. In addition,13The measurement method by C-NMR spectrum will be described in detail in Examples.
[0017]
By the way, in general, during 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 so-called 1,2 insertion polymerization in which the propylene monomer is sequentially coordinated and polymerized in the same manner. Is usually performed, but there are rarely 2, 1 insertion or 1, 3 insertion (also called abnormal insertion). The propylene homopolymer [A-1] in the present invention preferably has a small amount of 2,1 or 1,3 insertion. Moreover, the ratio of these insertions is the following relational expression (1)
[(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 5.0 (%) (1)
[Wherein (m-2, 1) is13Meso-2,1 insertion content (%), (r-2,1) measured by C-NMR is13Racemic-2,1 insertion content (%), (1,3) measured by C-NMR is13The 1,3 insertion content (%) measured by C-NMR is shown. In which the relational expression (1a) is satisfied.
[(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 1.0 (%) (1a)
It is more preferable to satisfy the above. Especially relational expression (1b)
[(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 0.1 (%) (1b)
Those satisfying the above are most preferable. If the above relational expression (1) is not satisfied, the crystallinity may be lowered more than expected and may cause stickiness.
[0018]
In addition, (m-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromolecules,21617 (1988)) and Busico et al. (Macromolecules,27, 7538 (1994))13The peak content of the C-NMR spectrum is determined, and each insertion content is determined from the integrated intensity of each peak. That is, (m-2,1) is the meso-2,1 insertion content (calculated from the ratio of the integrated intensity of peaks attributed to Pα, γthreo appearing near 17.2 ppm to the integrated intensity in the entire methyl carbon region ( %). (R-2,1) is the racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensity of the peak attributed to Pα, γthreo appearing near 15.0 ppm to the integrated intensity in the entire methyl carbon region. It is. (1,3) is the 1,3 insertion content (%) calculated from the ratio of the integrated intensity of the peaks belonging to Tβ, γ + appearing in the vicinity of 31.0 ppm with respect to the integrated intensity in the entire methine carbon region.
[0019]
Further, as the propylene homopolymer [A-1] in the present invention,13In the measurement of the C-NMR spectrum, it is more preferable that a peak attributed to the molecular chain end (n-butyl group) derived from 2,1 insertion is not substantially observed. Regarding the molecular chain ends derived from this 2,1 insertion, a report by Jungling et al. (J. Polym. Sci .: Part A: Polym. Chem.,33, 1305 (1995))13The assignment of the peak in the C-NMR spectrum is determined, and each insertion content is calculated from the integrated intensity of each peak. In isotactic polypropylene, a peak appearing in the vicinity of 18.9 ppm is attributed to the unterminated methyl group carbon of the n-butyl group. Also related to abnormal insertion or molecular chain end measurement13The measurement of C-NMR may be performed in the same manner as the measurement of the mesopentad fraction [mmmm].
[0020]
The propylene-based copolymer [A] in the present invention is preferably obtained by the following production method 1 or production method 2. First, the manufacturing method 1 is demonstrated.
Manufacturing method 1
In the production method 1, (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof is ionic. Production method of polymerizing propylene or propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of a compound capable of forming a complex of (B-2) and a polymerization catalyst containing a component selected from aluminoxane It is.
[0021]
[Chemical 3]
[0022]
[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series;1And E2Were selected from substituted cyclopentadienyl, indenyl, substituted indenyl, heterocyclopentadienyl, substituted heterocyclopentadienyl, amide, phosphide, hydrocarbon and silicon-containing groups, respectively. A ligand comprising A1And A2A cross-linked structure is formed, and they may be the same or different, X represents a σ-binding ligand, and when there are a plurality of X, a plurality of X are the same or different. Okay, other X, E1, E2Alternatively, it may be cross-linked with Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and other Y, E1, E2Or X and X may be cross-linked1And A2Is a divalent bridging group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group. Group, -O-, -CO-, -S-, -SO2-, -Se-, -NR-, -PR-, -P (O) R-, -BR- or -AlR-, wherein R is 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, which may be 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. ]
And (B) (B-1) transition metal compound of the component (A)
[0023]
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. E1And E2Are substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (-N <), phosphide group (-P <), π bond, respectively. Hydrocarbon group [> CR1-,> C <] and silicon-containing group [> SiR1−,> Si <] (however, R1Represents a ligand selected from hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group), and A1And A2A crosslinked structure is formed via π-bonded hydrocarbon group [> CR1Examples of-,> C <] include a pentadienyl group and a boratabenzene group. Silicon-containing group [> SiR1-,> Si <] include -CH2-Si (CHThree) <, -Si (CHThree) <, Etc.
E1And E2They may be the same or different. This E1And E2As for, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group are preferable.
[0024]
X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and other X, E1, E2Alternatively, it may be cross-linked with 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, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, and octyl group; vinyl group, propenyl group, and cyclohexenyl. Alkenyl groups such as benzyl groups; arylalkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups; phenyl groups, tolyl groups, dimethylphenyl groups, trimethylphenyl groups, ethylphenyl groups, propylphenyl groups, biphenyl groups, naphthyl groups, Examples thereof include aryl groups such as a methylnaphthyl group, anthracenyl group, and phenanthonyl group. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable. Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group; phenylmethoxy group, phenylethoxy group, and the like. Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, methylphenoxy group, and dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, and methylethylamide group; divinylamide group, dipropenylamide group, Examples include alkenylamide groups such as dicyclohexenylamide groups; arylalkylamide groups such as dibenzylamide groups, phenylethylamide groups, and phenylpropylamide groups; and arylamide groups such as diphenylamide groups and dinaphthylamide groups. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; Of these, a trimethylsilyl group, a phenyldimethylsilylethyl group, and the like are preferable. Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Groups, alkenyl sulfide groups such as cyclohexenyl sulfide groups; arylalkyl sulfide groups such as benzyl sulfide groups, phenylethyl sulfide groups, 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 as phenanthridine Nils sulfide groups. Examples of the sulfoxide group having 1 to 20 carbon atoms include methyl sulfoxide group, methyl sulfoxide group, propyl sulfoxide group, butyl sulfoxide group, hexyl sulfoxide group, cyclohexyl sulfoxide group, and octyl sulfoxide group; vinyl sulfoxide group, propenyl sulfoxide group Group, alkenyl sulfoxide group such as cyclohexenyl sulfoxide group; arylalkyl sulfoxide group such as benzyl sulfoxide group, phenylethyl sulfoxide group, phenylpropyl sulfoxide group; phenyl sulfoxide group, tolyl sulfoxide group, dimethylphenyl sulfoxide group, trimethylphenyl sulfoxide group, Ethylphenyl sulfoxide group, propylphenyl sulfoxide group, biphenyl sulfoxide group Naphthyl sulfoxide group, methyl naphthyl sulfoxide group, anthracenyl sulfoxide group, an aryl sulfoxide group such as phenanthridine sulfonyl sulfoxide group. Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group, and other alkyl acyl groups; benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.
[0025]
On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and other Y or E1, E2Or you may bridge | crosslink with X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like. Examples of the amines include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexyl. Alkylamines such as amine and methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, and dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, and phenylpropylamine; Aryl amines such as dinaphthylamine are mentioned. Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether; cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane Can be mentioned. Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specifically, monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkylphosphines such as trihydrocarbylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, trioctylphosphine Such as phosphine, propenyl phosphine, cyclohexenyl phosphine, etc. Dialkenylphosphine in which two alkenyls are substituted with alkenylphosphine or phosphorus hydrogen atom; Trialkenylphosphine in which three alkenyls are substituted with alkenylphosphine; Arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine in which three hydrogen atoms are substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, Anthracenylphosphine, Phenanthonylphosphine; Emissions di (alkylaryl) phosphines a hydrogen atom alkylaryl and two substitutions; a hydrogen atom of phosphine alkylaryl include arylphosphine such as three substituted with tri (alkylaryl) phosphines. Examples of the thioethers include the aforementioned sulfides.
[0026]
Next, A1And A2Is a divalent bridging group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group. Group, -O-, -CO-, -S-, -SO2-, -Se-, -NR-, -PR-, -P (O) R-, -BR- or -AlR-, wherein R is 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, which may be the same or different; Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms. Examples of such a bridging group include a general formula
[0027]
[Formula 4]
[0028]
(R2And RThreeAre each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same as or different from each other, and may be bonded to each other to form a ring structure. e shows the integer of 1-4. )
The thing represented by is mentioned. Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH2═C═), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisylylene group, diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable. In the general formula (I), q is an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
[0029]
In the transition metal compound represented by the general formula (I), E1And E2Is a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, A1And A2The bonding of the crosslinking group is preferably a (1,2 ') (2,1') double-crosslinking type. Among the transition metal compounds represented by the general formula (I), the general formula (Ia)
[0030]
[Chemical formula 5]
[0031]
The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the above general formula (Ia), M, A1, A2, Q and r are the same as above. X represents a σ-bonding ligand, and 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 the same as those exemplified in the description of X in formula (I). Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y or X. Specific examples of this Y include the same as those exemplified in the description of Y in the general formula (I). RFour~ R9Represents 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, at least one of which is not a hydrogen atom It is necessary. RFour~ R9They may be the same or different, and adjacent groups may be bonded to each other to form a ring. Above all, RFiveAnd R6Form a ring and R8And R9Preferably form a ring. RFourAnd R7As such, a group containing a hetero atom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.
The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand is preferably a (1,2 ') (2,1') double-bridge ligand.
[0032]
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2, '-Ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1 , 2'-ethylene) (2,1'-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3-methyl-4 -Isopropylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1 '-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) di Conium dichloride, (1,2'-methylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) ) Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-i-propylindenyl) zirconium dichloride, (1,2 ' -Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) ) Bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethyl) Silylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-) i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl) Silylene) bis (4-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis ( Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethyl) Lucylylene) (2,1′-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethyl) Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 ' -Isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichlor Lido, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1 , 2′-Diphenylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichlor , (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'- Diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 -Isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methylcyclopentadi Enyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) Zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconi Um dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene) ) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3,4 Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-di Tylsilylene) (2,1′-ethylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Methylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) ) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopenta Dienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) ( 3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2, 1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 '-Dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) ( 2,1′-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2, 1'-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclo Ntadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propyl) Cyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'- n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5 ' -Phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl 5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5- i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl- 5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3- Methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethyl) Silylene) (2,1′-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ( 2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′- Dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) Luconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclo) Pentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propyl) Cyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) ( '-, methyl-5'-i-propyl-cyclopentadienyl) zirconium dichloride and zirconium in these compounds may include those obtained by substituting titanium or hafnium. Of course, it is not limited to these. Further, it may be an analogous compound of another group or a lanthanoid series metal element.
[0033]
Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). The following general formulas (II) and (III)
([L1-RTen]k +)a([Z]-)b          ... (II)
([L2]k +)a([Z]-)b                ... (III)
(However, L2Is M1, R11R12M2, R13 ThreeC or R14M2It is. )
[In formulas (II) and (III), L1Is Lewis base, [Z]-Is a non-coordinating anion [Z1]-And [Z2]-, Where [Z1]-Is an anion in which a plurality of groups are bonded to an element, ie, [MThreeG1G2... Gf]-(Where MThreeRepresents a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table. G1~ GfAre 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, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryloxy group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, Or a C2-C20 heteroatom containing hydrocarbon group is shown. G1~ GfTwo or more of them may form a ring. f is [(center metal MThreeValence) +1]. ), [Z2]-Is a Bronsted acid alone having a logarithm of the reciprocal of the acid dissociation constant (pKa) of -10 or less, or a conjugate base of a combination of Bronsted acid and Lewis acid, or a conjugate base of an acid generally defined as a super strong acid. Show. In addition, a Lewis base may be coordinated. RTenRepresents 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 R11And R12Are respectively cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group or fluorenyl group, R13Represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R14Represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is [L1-RTen], [L2] Is an integer of 1 to 3, and a is an integer of 1 or more, and b = (k × a). M1Includes elements of Group 1 to 3, 11 to 13 and 17 of the periodic table, and M2Represents a Group 7-12 element of the Periodic Table. ]
What is represented by these can be used conveniently.
[0034]
Where L1Specific examples of ammonia include methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, and p-bromo. -N, N-dimethylaniline, amines such as p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate And nitriles such as acetonitrile and benzonitrile.
[0035]
RTenSpecific examples of hydrogen include methyl, methyl, ethyl, benzyl, and trityl groups.11, R12Specific examples thereof include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and the like. R13Specific examples of these include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, and the like.14Specific examples of these include tetraphenylporphine, phthalocyanine, allyl, and methallyl. M2Specific examples of Li, Na, K, Ag, Cu, Br, I, IThreeMThreeAs specific examples, Mn, Fe, Co, Ni, Zn, and the like can be given.
[0036]
[Z1]-That is, [MFourG1G2... Gf], MFourSpecific examples of B, Al, Si, P, As, Sb, etc., preferably B and Al. G1, G2~ GfSpecific examples of the dialkylamino group include dimethylamino group, diethylamino group, etc., alkoxy group or aryloxy group as methoxy group, ethoxy group, n-butoxy group, phenoxy group, etc., hydrocarbon group as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethyl Fluorine, chlorine, bromine, iodine as a halogen atom such as phenyl group, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group as a hetero atom-containing hydrocarbon group , Pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl And 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.
[0037]
Non-coordinating anion, ie, a Bronsted acid alone having a pKa of -10 or less or a conjugate base of a combination of Bronsted acid and Lewis acid [Z2]-Specific examples of trifluoromethanesulfonate anion (CFThreeSOThree)-, Bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClOFour)-, Trifluoroacetate anion (CFThreeCO2)-, Hexafluoroantimony anion (SbF6)-, Fluorosulfonate anion (FSOThree)-, Chlorosulfonate anion (ClSOThree)-, Fluorosulfonate anion / 5-antimony fluoride (FSOThree/ SbFFive)-, Fluorosulfonate anion / 5-arsenic fluoride (FSOThree/ AsFFive)-, Trifluoromethanesulfonic acid / 5-antimony fluoride (CFThreeSOThree/ SbFFive)-And so on.
[0038]
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, Such as trifluoromethanesulfonic silver can be given.
The compound that can react with the transition metal compound of the component (A), which is the component (B-1), to form an ionic complex may be used singly or in combination of two or more. .
On the other hand, as the aluminoxane of the component (B-2), the general formula (IV)
[0039]
[Chemical 6]
[0040]
(Wherein R15Represents a hydrocarbon group or halogen atom such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12, and w represents an average degree of polymerization, usually 2 to 50, preferably Is an integer from 2 to 40. Each R15May be the same or different. )
A chain aluminoxane represented by the general formula (V)
[0041]
[Chemical 7]
[0042]
(Where R15And w are the same as those in formula (IV). )
The cyclic aluminoxane shown by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means 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, water adsorbed on an inorganic or organic substance with an organoaluminum compound, and (4) a method of reacting a tetraalkylaluminoxane with a trialkylaluminum and further reacting with water. . The aluminoxane may be insoluble in toluene.
[0043]
These aluminoxanes may be used alone or in combination of two or more.
The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. The range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit weight polymer becomes high, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit weight polymer becomes high, which is not practical. Moreover, as a catalyst component (B), (B-1) and (B-2) can also be used individually or in combination of 2 or more types.
[0044]
The polymerization catalyst in the production method of the present invention can use an organoaluminum compound as the component (C) in addition to the components (A) and (B).
Here, as the organoaluminum compound of component (C), the general formula (VI)
R16 vAlJ3-v      ... (VI)
[In the formula, R16Is an alkyl group having 1 to 10 carbon atoms, J is 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 is an integer of 1 to 3]
The compound shown by these is used.
Specific examples of the compound represented by the general formula (VI) 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.
[0045]
In the production method of 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 the component (B), for example. 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 catalytic activity and reducing the proportion of the (B) promoter. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight is also seen in addition to the above effect. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an inert hydrocarbon, aliphatic hydrocarbon, aromatic hydrocarbon, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons.
The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, 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 it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.
[0046]
In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
As an inorganic oxide carrier, specifically, SiO2, Al2OThree, MgO, ZrO2, TiO2, Fe2OThree, B2OThree, CaO, ZnO, BaO, ThO2And mixtures thereof, such as silica alumina, zeolite, ferrite, glass fiber and the like. Among these, especially SiO2, Al2OThreeIs preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, as a support other than the above, MgCl2, Mg (OC2HFive)2General formula MgR represented by17 xX1 yThe magnesium compound represented by these, its complex salt, etc. can be mentioned. Where R17Is 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, X1Represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is an integer of 0 to 2, y is an integer of 0 to 2, and x + y = 2. Each R17And each X1May be the same or different.
[0047]
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.
As the carrier used in the present invention, MgCl2, MgCl (OC2HFive), Mg (OC2HFive)2, SiO2, Al2OThreeEtc. are preferable. The properties of the carrier vary depending on the type and production method, but 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 50-500m2/ G, pore volume is usually 0.1-5cmThree/ G, preferably 0.3-3 cmThree/ G.
When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). reference).
Furthermore, it is desirable that the carrier is used after being usually fired at 150 to 1000 ° C, preferably 200 to 800 ° C.
[0048]
When at least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .
The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (1) at least one of the component (A) and the component (B) is mixed with the carrier. 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, and (3) the support and (A) Method of reacting component and / or component (B) with organoaluminum compound or halogen-containing silicon compound, (4) (B) component or (A) after component (A) or component (B) is supported on a carrier ) Method of mixing with component, (5) Method of mixing contact reaction product of component (A) with component (B) with carrier, (6) During contact reaction of component (A) with component (B), carrier Is a way to coexist It is possible to use.
In the above reactions (4), (5) and (6), an organoaluminum compound (C) can also be added.
[0049]
In the present invention, when contacting the (A), (B), and (C), the catalyst may be prepared by irradiating elastic waves. Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for polymerization after removing the solvent once and taking out as a solid, or may be used for polymerization as it is.
Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within a polymerization system. For example, at least one of the component (A) and the component (B), a carrier, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 2 MPa, and the temperature is 1 to -20 to 200 ° C. A method of preliminarily polymerizing for about min.
[0050]
In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of weight ratio. -2) The ratio of use of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50, by weight. When using 2 or more types as a component (B), it is desirable that the use ratio of each (B) component and a support | carrier is in the said range by weight ratio. Further, the ratio of the component (A) to the carrier used is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of weight ratio.
If the ratio of component (B) [component (B-1) or component (B-2)] to the carrier or the proportion of component (A) to the carrier departs from the above range, the activity may decrease. . The average particle diameter of the polymerization catalyst thus prepared in the present invention is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m.2/ G, preferably 50-500m2/ 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. Specific surface area is 20m2If it is less than / g, the activity may decrease, and 1000 m2When the amount exceeds / g, the bulk density of the polymer may decrease. In the catalyst according to 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.
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. Next, manufacturing method 2 will be described.
[0051]
Manufacturing method 2
Production method 2 includes (A) a transition metal compound of Group 4 of the periodic table represented by the following general formula (VII), (B) (B-1) an aluminumoxy compound, and (B-2) the above transition metal compound. Propylene or propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing at least one selected from ionic compounds that can be converted into cations by reaction. This is a production method for polymerization.
[0052]
[Chemical 8]
[0053]
[In the formula, R18~ R28, X1And X2Are each independently 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, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or phosphorus Indicates the containing group, R20And Rtwenty oneAnd Rtwenty fiveAnd R26They may be bonded to each other to form a ring. Y1Is a divalent bridging group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group. Group, -O-, -CO-, -S-, -SO2-, -NR-, -PR-, -P (O) R-, -BR- or -AlR-, wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 to 20 halogen-containing hydrocarbon groups are shown. MFourRepresents titanium, zirconium or hafnium. ]
This transition metal compound is a single bridge type complex.
[0054]
In the general formula (VII), R18~ R28, X1And X2Examples of the halogen atom include chlorine, bromine, fluorine, and iodine atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, and n-decyl group. An alkyl group, a phenyl group, an aryl group such as a 1-naphthyl group and a 2-naphthyl group, an aralkyl group such as a benzyl group, and the like, and examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include trifluoromethyl. And a group in which one or more hydrogen atoms of the hydrocarbon group are substituted with an appropriate halogen atom. Examples of the silicon-containing group include a trimethylsilyl group and dimethyl (t-butyl) silyl group. Examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. Examples of the nitrogen-containing group include a dimethylamino group, and examples of the phosphorus-containing group include a phenylphosphine group. R20And Rtwenty oneAnd Rtwenty fiveAnd R26They may be bonded to each other to form a ring such as fluorene. R20And Rtwenty oneAnd Rtwenty fiveAnd R26As a specific example of the above, R18~ R28And the like except for the hydrogen atom from those mentioned above. R20, R26Are preferably a hydrogen atom and an alkyl group having 6 or less carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a cyclohexyl group, and even more preferably a hydrogen atom. R20, Rtwenty one, Rtwenty fiveAnd R26Is preferably an alkyl group having 6 or less carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, or a cyclohexyl group, and even more preferably an isopropyl group. Rtwenty one, Rtwenty two, Rtwenty four, R26And R27Is preferably a hydrogen atom. A particularly preferred combination is R18Is an alkyl group other than hydrogen and Rtwenty fourIs a hydrogen atom.
X1, X2Are preferably a halogen atom, a methyl group, an ethyl group, or a propyl group. Y1Specific examples of methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, tetramethyldisylylene, dimethylgermylene, methylborylidene (CHThree-B =), methylaluminidene (CHThree-Al =), phenylphosphilidene (Ph-P =), phenylphospholidene (PhPO =), 1,2-phenylene, vinylene (-CH = CH-), vinylidene (CH2= C =), methylimide, oxygen (-O-), sulfur (-S-), and the like. Among these, methylene, ethylene, ethylidene, and isopropylidene are preferable in terms of achieving the object of the present invention.
MFourRepresents titanium, zirconium or hafnium, with hafnium being particularly preferred.
[0055]
Specific examples of the transition metal compound represented by the general formula (VII) include 1,2-ethanediyl (1- (2-isobutylindenyl)) (2-indenyl) hafnium dichloride, 1,2-ethanediyl (1 -(2-butylindenyl)) (2-indenyl) hafnium dichloride, 1,2-ethanediyl (1- (2-butylindenyl)) (2- (4,7-dimethylindenyl)) hafnium dichloride, 1 , 2-ethanediyl (1- (2-isopropylindenyl)) (2- (4,7-dimethylindenyl)) hafnium dichloride, 1,2-ethanediyl (1- (2-isopropylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium dichloride and the like, dimethylsilylene (1- (2-isobutylindenyl)) (2-indenyl ) Hafnium dichloride, dimethylsilylene (1- (2-butylindenyl)) (2-indenyl) hafnium dichloride, dimethylsilylene (1- (2-butylindenyl)) (2- (4,7-dimethylindenyl) ) Hafnium dichloride, methylsilylene (1- (2-isopropylindenyl)) (2- (4,7-dimethylindenyl)) hafnium dichloride, methylsilylene (1- (2-isopropylindenyl)) (2- ( 4,7-diisopropylindenyl)) hafnium dichloride and the like, 1,3-propanediyl (1- (2-isopropylindenyl)) (2-indenyl) hafnium dichloride, 1,3-propanediyl (1- (2- Isobutylindenyl)) (2-indenyl) hafnium dichloride, 1,3-propa Diyl (1- (2-butylindenyl)) (2-indenyl) hafnium dichloride, 1,3-propanediyl (1- (2-butylindenyl)) (2- (4,7-dimethylindenyl)) Hafnium dichloride, 1,3-propanediyl (1- (2-isopropylindenyl)) (2- (4,7-dimethylindenyl)) hafnium dichloride, 1,3-propanediyl (1- (2-isopropylindenyl) Nyl)) (2- (4,7-diisopropylindenyl)) hafnium dichloride, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl) Hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-diisopropylindenyl) hafnium dichloride Lido, isopropylidene (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2- (4,7-Diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-dimethylindenyl)) hafnium dichloride, isopropylidene (1- (4,7 -Dimethylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (2-indenyl) (1- (2-isopropylindenyl)) hafnium dichloride, dimethylsilylene- (2 -Indenyl) (1- (2-isopropylindenyl)) hafnium dichloride, etc. And there may be mentioned those obtained by replacing hafnium in the zirconium or titanium in these compounds, but is not limited thereto.
The transition metal compound represented by the general formula (VII) can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 11-130807 previously filed by the present applicant. As the component (A-1), two or more kinds of these transition metal compounds may be used in combination.
[0056]
The component (B) used in the production method 2 is the same as the component (B) used in the production method 1 described above. In addition, as the olefin polymerization catalyst in the present invention, like the olefin polymerization catalyst in Production Method 1, it may be supported on a carrier, may have been subjected to prepolymerization, or as required ( C) An organoaluminum compound may be used.
The method for producing the propylene polymer [A] or the propylene homopolymer [A-1] in the present invention is not particularly limited, and a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method. Any method such as a suspension polymerization method may be used, but a slurry polymerization method or a gas phase polymerization method is preferred. Examples of the α-olefin having 4 to 20 carbon atoms include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like can be mentioned, and in the present invention, one or more of these can be used.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably raw material monomer / the above component (A) (molar ratio), preferably 1 to 10.8, Especially 100-10FiveIt is preferable that Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is normal pressure to 20 MPa, preferably normal pressure to 10 MPa.
[0057]
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 a chain transfer agent. Examples of the chain transfer agent include hydrogen; silane compounds such as phenylsilane and phenyldimethylsilane; and organoaluminum compounds such as trimethylaluminum. Of these, hydrogen is preferable. The addition amount of the chain transfer agent is 10 times mol or more, preferably 50 times mol or more with respect to the transition metal component of the catalyst used.
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.
[0058]
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 preliminarily polymerized product has an intrinsic viscosity [η] (measured in decalin at 135 ° C.) of 0.2 dl / g or more, particularly 0.5 dl / g or more, and the pre-polymerization product with respect to 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the polymerization product is 1 to 10000 g, particularly 10 to 1000 g.
[0059]
If necessary, a nucleating agent may be added to the propylene polymer [A] or the propylene homopolymer [A-1] in the present invention. There is no restriction | limiting in particular as a nucleating agent, What is necessary is just to have the effect of improving the progress speed of a crystal nucleation process. Substances that have the effect of improving the progress rate of the crystal nucleation process include substances that have the effect of promoting molecular chain orientation through the process of adsorbing molecular chains of polymers.
Specific examples of the nucleating agent include a high melting point polymer, a carboxylic acid or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic phosphate compound or a metal salt thereof, dibenzylidene sorbitol or a derivative thereof, and a rosin acid partial metal. Examples thereof include salts, inorganic fine particles, imides, amides, quinacridones, quinones, and mixtures thereof.
[0060]
Examples of the high melting point polymer include polyolefins such as polyethylene and polypropylene, polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, syndiotactic polystyrene, poly-3-methylpentene-1, poly-3-methylbutene-1, and polyalkenylsilane. Can be mentioned.
Examples of the metal salt include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrolecarboxylate.
Dibenzylidene sorbitol or derivatives thereof include dibenzylidene sorbitol, 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-2,4- Dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-chlorobenzylidene) sorbitol, 1,3: 2,4 -Dibenzylidene sorbitol etc. are mentioned. Specific examples include Gelall MD, Gelall MD-R (trade name) manufactured by Shin Nippon Rika.
Examples of the rosin acid partial metal salt include Pine Crystal KM1600, Pine Crystal KM1500, Pine Crystal KM1300 (trade name) manufactured by Arakawa Chemical Industries, and the like.
Inorganic fine particles include talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, and pumice. Examples thereof include powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide.
Examples of the amide compound include adipic acid dianilide and peric acid dianilide.
One type of these nucleating agents may be used, or two or more types may be used in combination.
In the present invention, the following general formula is used as a nucleating agent.
[0061]
[Chemical 9]
[0062]
(Wherein R29Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R30And R3 1Each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. MFiveRepresents any of alkali metal, alkaline earth metal, aluminum and zinc;FiveWhen m is an alkali metal, m represents 0, n represents 1, MFiveIs an alkaline earth metal or zinc, n represents 1 or 2, m is 1 when n is 1, m is 0 when n is 2, MFiveWhen is aluminum, m is 1 and n is 2. )
It is preferable to use inorganic fine particles such as an organic phosphate metal salt and / or talc represented by the formula shown below because of less odor generation and is suitable for food applications.
Specific examples of the organic phosphate metal salt include ADK STAB NA-11 and ADK STAB NA-21 (manufactured by Asahi Denka Co., Ltd.).
[0063]
Further, in the present invention, it is preferable to use inorganic fine particles such as talc as a nucleating agent because, when formed into a film, it is excellent in slip property and printing characteristics and the like are improved. Furthermore, it is preferable to use the dibenzylidene sorbitol or a derivative thereof as a nucleating agent because of excellent transparency. Furthermore, it is preferable to use the amide compound as a nucleating agent because it is excellent in rigidity.
In the present invention, a nucleating agent and various additives used as desired may be dry blended using a Henschel mixer or the like. Alternatively, it may be melt kneaded using a single 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.
The addition amount of the nucleating agent in the present invention is usually 10 ppm or more, preferably in the range of 10 to 10,000 ppm, more preferably relative to the propylene-based copolymer [A] or [A-1]. It is the range of 10-5000 ppm, More preferably, it is 10-2500 ppm. If it is less than 10 ppm, the improvement of the moldability of the film is not observed. On the other hand, even if an amount exceeding 10,000 ppm is added, the preferable effect may not increase.
[0064]
Examples of film forming methods include general compression molding methods, extrusion molding methods, blow molding methods, cast molding methods, and the like. Especially, the cast film manufactured by the cast molding method is preferable. Moreover, the film may process the surface as needed, may enlarge surface energy, or may make the surface polar. For example, the treatment method includes corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone and ultraviolet irradiation treatment, and the like. Examples of the surface unevenness method include a sand blast method and a solvent treatment method.
The film can be blended with an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, an antistatic agent, or the like as required.
Furthermore, since films containing inorganic fine particles such as talc are excellent in slipping properties, secondary processability such as bag making and printing is improved, and it can be applied to all general-purpose packaging films in high-speed production equipment such as various automatic filling and packaging laminates. Is preferred.
A film formed by molding a propylene-based polymer containing dibenzylidene sorbitol or a derivative thereof as a nucleating agent is particularly excellent in transparency and has a large display effect, and is therefore suitable for packaging toys and stationery.
A film formed by molding a propylene-based polymer containing the above amide compound as a nucleating agent is particularly excellent in rigidity and is unlikely to cause problems such as curling in high-speed bag making. Suitable as a packaging film.
[0065]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by the following Examples.
First, a method for evaluating resin properties and physical properties of the polymer of the present invention will be described.
(1) Measurement of [η]
It was measured at 135 ° C. in a tetralin solvent using a VMR-053 type automatic viscometer manufactured by Kosei Co., Ltd.
(2) Measurement of pentad fraction, triad fraction and abnormal insertion fraction
13The measurement of the C nuclear magnetic resonance spectrum was performed by A. Zambelli et al., “Macromolecules,8, 687 (1975) ", the following apparatus and conditions were used.
Apparatus: JNM-EX400 type manufactured by JEOL Ltd.13C-NMR apparatus
Method: Proton complete decoupling method
Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene
Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds
Integration: 10,000 times
(3) Measurement of molecular weight distribution (Mw / Mn)
Mw / Mn is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polyethylene measured by the GPC method using the following apparatus and conditions.
GPC measuring device
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
Measurement condition
Solvent: 1,2,4-trichlorobenzene
Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min
Sample concentration: 2.2 mg / ml
Injection volume: 160 microliters
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver. 1.0)
(4) DSC measurement
Using a differential scanning calorimeter (Perkin Elmer, DSC-7), 10 mg of a sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, cooled to 0 ° C. at 10 ° C./min, and further at 0 ° C. After holding for 3 minutes, the melting endotherm obtained by raising the temperature at 10 ° C./min was defined as ΔH. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as the melting point Tm (° C.).
(5) Amount of component eluted in hexane (H25)
H25 was determined by measurement under the following measurement conditions.
Sample: 0.1-5g
Sample shape: powder
(The pelletized material is pulverized and used as a powder)
Solvent: Hexane
Elution conditions: 25 ° C, left for 3 days or more
Elution amount calculation method: Calculated by the following formula.
H25 = [(W0-W1) / W0  ] X 100 (%)
[0066]
Evaluation method of film quality
After film formation, the film was subjected to an aging treatment of 40 ° C. × 24 hours, and then conditioned at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 10% for 16 hours or more. And measured.
(1) Tensile modulus and elongation at break
Based on JIS K-7127, it measured by the tension test on the conditions shown below.
Crosshead speed: 500mm / min
Load cell: 15kg
Measurement direction: Machine direction (MD direction)
(2) Impact resistance
In the Toyo Seiki Seisakusho film impact tester
It was evaluated by impact fracture strength using a lid.
(3) Haze
It evaluated by the test based on JISK-7105.
(4) Anti-blocking property
About two films, one metal roll surface and another anti-metal roll are adhered to each other under the following adhesion conditions, and each is fixed to a 10 cm × 10 cm jig, and peel strength at an area of 10 cm × 10 cm Was measured by the following peeling test.
The smaller the peel strength, the better the anti-blocking property.
Adhesion conditions: temperature 60 ° C., 7 days, load 15 g / cm2, Area 10cm × 10cm
Peel test: Test speed: 20 mm / min, Load cell: 2 kg
[0067]
Example 1
(1) Preparation of catalyst component [(1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-n-butylindenyl)2Synthesis of zirconium dichloride] (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indene) in a Schlenk bottle2Of 0.83 g (2.8 mmol) and 50 ml of ether were cooled to −78 ° C., and 3.1 ml (5.0 mmol) of n-butyllithium (hexane solution: 1.6 mol) was added. Thereafter, the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane to obtain 1.1 g (2.3 mmol) of a lithium salt as an ether adduct. The obtained lithium salt was dissolved in 50 ml of tetrahydrofuran (THF) and cooled to -78 ° C. To this, 0.57 ml (5.3 mmol) of n-butyl bromide was slowly added dropwise and stirred at room temperature for 12 hours. After the solvent was distilled off and extraction was performed with 50 ml of hexane, the hexane was distilled off to obtain (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-n-butylindene).2Of 0.81 g (1.77 mmol) was obtained (yield 74%).
Next, the (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-n-butylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream.2Of 0.81 g (1.77 mmol). This was cooled to −78 ° C., 2.7 mL (4.15 mmol) of n-butyllithium (hexane solution: 1.54 mol) was added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with hexane to obtain 0.28 g (1.43 mmol) of a lithium salt as an ether adduct.
The obtained lithium salt was dissolved in 50 ml of toluene under a nitrogen stream, cooled to −78 ° C., and 0.33 g (1.42 mol) of zirconium tetrachloride preliminarily cooled to −78 ° C. (50 ml). ) Was added dropwise. After completion of dropping, the mixture was allowed to stand at room temperature for 6 hours. The solution was filtered and the solvent of the filtrate was distilled off. The obtained solid was recrystallized from dichloromethane to obtain (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-n-butylindenyl).20.2 g (0.32 mol) of zirconium dichloride was obtained (22% yield).
This one1When H-NMR was determined, the following results were obtained.
1H-NMR (90 MHz, CDClThree) (Δ, ppm): 0.88, 0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1-1.5 (18H, n-butyl), 7.0-7. 6 (8H, benzene ring proton)
[0068]
(2) Production of propylene polymer
In a polymerization tank having an internal volume of 200 liters, the catalyst component obtained in the above (1) was 46.7 micromol / hour, triisobutylaluminum (TIBA) was 117 mmol / hour, and methylaluminoxane (MAO) was 46. 7 mmol / h, heptane 46.7 l / h, propylene 3.4 kg / h and hydrogen (H2/ CThree= 0.20), and polymerization was carried out at 60 ° C. and 0.8 MPa. Next, the polymer solution was sent to a deaeration tank, and 10 ml / hour of methanol was added to deaerate propylene and hydrogen. Antioxidants (Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd. and Irgaphos 168 manufactured by Ciba Specialty Chemicals Co., Ltd.) and a stabilizer were added to the obtained polymer solution and heated and degassed. Extrusion granulation was carried out using a single screw extruder (manufactured by Tsukada Juki Seisakusho: TLC35-20) to obtain a propylene polymer composition pellet.
[0069]
[0070]
(3) Film formation
Using the obtained pellets, a film having a thickness of 70 μm was formed under the following molding conditions using a TLC35-20 type 20 mmφ molding machine manufactured by Tsukada Juki Seisakusho.
T-die outlet temperature: 220 ° C
Take-off speed: 3.0m / min
Chill roll temperature: 30 ° C
Chill roll: Mirror surface
The obtained film was measured according to the film quality evaluation method. The results are shown in Table 1.
Example 2
Except that the additive formulation was changed to the following in Example 1, pellets of a propylene-based polymer composition were obtained in the same manner as in Example 1, and a film having a thickness of 70 μm was formed in the same manner as in Example 1. And evaluated. The results are shown in Table 1.
[0071]
[0072]
Comparative Example 1
After fully replacing the glass reactor with an internal volume of 6 liters with a stirrer with nitrogen gas, about 2430 g of ethanol, 16 g of iodine and 160 g of metal magnesium were charged into this reaction vessel and heated with stirring under reflux conditions. The reaction was continued until the generation of hydrogen gas from the inside ceased to obtain a solid product. The magnesium compound was obtained by drying the reaction liquid containing this solid product under reduced pressure.
A glass reactor having an internal volume of 5 liters sufficiently substituted with nitrogen gas was charged with 160 g of the above magnesium compound (not pulverized), 80 ml of purified heptane, 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate. Was kept at 80 ° C., 770 ml of titanium tetrachloride was added with stirring and reacted at 110 ° C. for 2 hours, and then the solid components were separated and washed with purified heptane at 90 ° C. Further, 1220 ml of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then thoroughly washed with purified heptane to obtain a solid catalyst component.
In a polymerization tank having an internal volume of 200 liters, the solid catalyst component was added at 6.0 g / hour, triisobutylaluminum (TIBA) at 0.2 mol / hour, and 1-allyl-3,4-dimethoxybenzene (ADMB). At 0.012 mol / hour, cyclohexylmethyldimethoxysilane (CHMDMS) was supplied at 0.012 mol / hour and propylene was fed at 37 kg / hour, and polymerization was carried out at 2.7 MPa · G to obtain polypropylene.
The obtained propylene was evaluated in the same manner as in Example 1, and a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 2
A film was molded and evaluated in the same manner as in Example 1 using pellets of affinity PL1880 (trade name) manufactured by Dow Chemical Japan as the propylene polymer. The results are shown in Table 1.
[0073]
[Table 1]
[0074]
【The invention's effect】
The polypropylene film of the present invention has little stickiness and is excellent in peel whitening property, softness and impact resistance, and can be suitably used in the food packaging field and the medical field.

Claims (5)

  1. (1) Tensile modulus (TM) is 5 to 500 MPa,
    (2) In the differential scanning calorimeter (DSC) measurement, the melting point Tm (° C.) is not indicated, or when Tm is indicated, TM and Tm are the following relational expressions.
    TM ≧ 5 × Tm-450
    The filling,
    (3) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 1 to 3 dl / g,
    (4) The amount of component (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight,
    (5) In DSC measurement, the melting point Tm (° C.) is not shown, or when Tm is shown, Tm and melting endotherm ΔH (J / g)
    ΔH ≧ 6 × (Tm−140)
    The filling,
    (6) Mesopentad fraction [mmmm] is 20 to 60 mol%,
    (7) Racemic pentad fraction [rrrr] and [1-mmmm] are the following relational expressions
    [[Rrrr] / [1-mmmm]] ≦ 0.1
    Polypropylene film consisting of propylene emissions alone polymer [A-1] satisfying.
  2. The polypropylene film according to claim 1, wherein the propylene homopolymer [A-1] has a molecular weight distribution (Mw / Mn) of 2.5 to 4.0.
  3. The polypropylene film according to claim 1 or 2, wherein the propylene homopolymer [A-1] satisfies the following relational expression (1).
    [(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 5.0 (%) (1)
    [Wherein (m-2, 1) is 13 Meso-2,1 insertion content (%), (r-2,1) measured by C-NMR is 13 Racemic-2,1 insertion content (%), (1,3) measured by C-NMR is 13 The 1,3 insertion content (%) measured by C-NMR is shown. ]
  4. Propylene homopolymer [A-1] is (A) the following general formula (I)
    [Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E 1 and E 2 represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A 1 and A 2 In addition, they may be the same or different, X represents a σ-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E 1 , E 2 or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E 1 , E 2 or X, and A 1 and A 2 are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR -, - PR -, - P (O) R -, - BR- or -AlR- indicates, R represents A hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, and a C1-C20 halogen-containing hydrocarbon group are shown, and they may be 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. ]
    And (B) (B-1) a compound capable of reacting with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B-2) an aluminoxane. Any one of Claims 1-3 manufactured by polymerizing a propylene or propylene, ethylene, and / or a C4-C20 alpha-olefin in presence of the polymerization catalyst containing the component chosen from these. The polypropylene film described in 1.
  5. It is a polypropylene-type film in any one of Claims 1-4, Comprising: The cast film obtained by the T dacast molding method.
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CN 00814904 CN1322034C (en) 1999-10-26 2000-10-24 Polypropylene film and multilayered laminate
PCT/JP2000/007409 WO2001030891A1 (en) 1999-10-26 2000-10-24 Polypropylene film and multilayered laminate
EP20000970017 EP1231236B1 (en) 1999-10-26 2000-10-24 Polypropylene film and multilayered laminate
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US20140106638A1 (en) 2011-06-02 2014-04-17 Idemitsu Kosan Co., Ltd Multilayer elastic film
WO2013183611A1 (en) * 2012-06-04 2013-12-12 出光興産株式会社 Alpha-olefin polymer
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