JPH0625357A - New propylene based copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a propylene based copolymer capable of readily modifying and excellent in adhesion, dyeing property and transparency by copolymerizing propylene with a specific alkadiene in the presence of a specific catalyst. CONSTITUTION:This copolymer has >=0.5 isotactic pentad fraction, 0.01-10dl/g intrinsic viscosity and 1.5-4.0 dispersibility (Mw/Mn) of molecular weight. The copolymer is obtained by copolymerizing propylene with preferably 0.1-20mol% one or more kinds of 6-25C alkadiene having one terminal double bond and one internal double bond in the presence of a catalyst consisting of (A) a transition metal compound of the group IV in the periodic table containing a cyclopendienyl group, an indenyl group, a fluorenyl group or one of their derivatives as a ligand and (B) a cocatalyst such as aluminoxane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel propylene-based copolymer and a method for producing the same. More specifically, it relates to a copolymer of propylene and a specific alkadiene and a method for producing the same.

[0002]

2. Description of the Related Art Polypropylene, especially isotactic polypropylene, has been used in many applications due to its excellent properties, but it has the drawback of low adhesiveness and dyeability.

On the other hand, attempts have been made to introduce an unsaturated bond into the polymer chain for the purpose of improving the adhesiveness and the dyeability thereof. JP-A-55-165907, JP-A-5
6-55409 and JP-A-62-115008, a so-called stereoregular Ziegler-Natta catalyst containing a titanium halide as a main component is used to produce propylene and a branched 1,4-diene copolymer or propylene. , Ethylene, branched 1,4-diene copolymers are described. Further, JP-A-59-155426 discloses a propylene-based block copolymer having an unsaturated bond obtained by using a so-called stereoregular Ziegler-Natta catalyst containing a titanium halide as a main component. ing.

On the other hand, a transition metal compound having a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand, a so-called metallocene compound is
It is known that poly-α-olefins can be prepared by polymerizing α-olefins with cocatalysts such as aluminoxanes.

JP-A-58-19309 discloses (Cyclopentadienyl) ₂ MeRHal (wherein R is cyclopentadienyl, C ₁ -C ₆ alkyl, halogen, and Me is a transition metal. Yes, Ha
1 is a halogen) and a method of polymerizing or copolymerizing ethylene and / or α-olefin in the presence of a catalyst composed of a transition metal compound represented by the formula (1) and aluminoxane.

Japanese Unexamined Patent Publication (Kokai) No. 60-35008 discloses that poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst composed of at least two kinds of metallocene compounds and aluminoxane.

Japanese Unexamined Patent Publication No. 61-130314 describes a method for producing a polyolefin using a catalyst composed of a sterically fixed zircon chelate compound and an aluminoxane. Further, the publication discloses a method for producing a polyolefin having a high degree of isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Have been described. JP-A-6
Japanese Unexamined Patent Publication No. 4-66124 discloses a catalyst for producing a stereoregular olefin polymer containing a transition metal compound having a silicon-crosslinked cyclopentadienyl compound as a ligand and an aluminoxane as an active ingredient.

Japanese Unexamined Patent Publication (Kokai) No. 2-41303 discloses that the following formula R ″ (CpR _n ) (CpR ′ _m ) MeQ _k (where each Cp is cyclopentadienyl or a substituted cyclopentadienyl ring) Each R _n may be the same or different and is a hydrocarbyl residue having 1 to 20 carbon atoms; each R ′ _m may be the same or different and is a hydrocarbyl residue having 1 to 20 carbon atoms R "is a structural bridge between the Cp rings that provides the catalyst with steric rigidity; Me is 4b, 5 of the Periodic Table of the Elements.
a metal of group b or 6b; each Q is a hydrocarbyl residue having 1 to 20 carbon atoms or a halogen; 0 ≦
k ≦ 3: 0 ≦ n ≦ 4: and 1 ≦ m ≦ 4; and R ′
_m is (CpR _'m) is (CpR _n) and sterically different and is selected as the metallocene catalyst used to produce the syndiotactic polyolefin is denoted by. It is described that a poly-α-olefin having good syndiotacticity can be produced by using a catalyst containing 1 component as a component.

Further, the publication describes that the syndiotactic poly-α-olefin having a wide molecular weight distribution can be produced by using two or more kinds of the above metallocene compounds.

Japanese Unexamined Patent Publication No. 2-274703 discloses the following formula (Formula 1).

[0011]

[Chemical 1] [In the formula, M ¹ is titanium, zirconium, vanadium, niobium or tantalum, R ¹ and R ² may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom
An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a carbon atom. A C 7-40 alkylaryl group or a C 8-40 arylalkenyl group, wherein R ³ and R ⁴ are different and the central atom M
¹ means a mononuclear- or polynuclear hydrocarbon group capable of forming a sandwich structure together with ^1, and R ⁵ is

[0012]

[Chemical 2] ^{= BR 6, = AlR 6,} -Ge -, - Sn -, - O-,
-S -, = SO, = SO , = NR 6, = CO, = PR
⁶ or = mean P (O) R ^6, this time R ^6, R ⁷ and R ⁸ may be the same or different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms Group, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms or an alkylaryl group having 7 to 40 carbon atoms, or R ⁶ and R ⁷ or R ⁶ and R Each ⁸ together with its attached atom forms a ring, and M ² is silicon, germanium or tin. ] A method for producing a high molecular weight syndiotactic polyolefin by polymerizing an olefin in the presence of a catalyst composed of a transition metal component represented by the following formula and an aluminoxane is described.

Further, in Japanese Patent Laid-Open No. 2-274704.
Is a high-molecular-weight syndyne using a similar hafnium compound.
A method of making tactical polyolefins is described.
ing. On the other hand, the so-called Kaminsky type as described above
The active species of the catalyst is [Cp '₂MR] ⁺(Where Cp '= Shiku
Lopentadienyl derivative, M = Ti, Zr, Hf, R =
A transition metal cation represented by
Since it was suggested that aluminoxanes should not be used as co-catalysts.
Some catalytic systems have also been reported.

Taube et al., J. Organometall. Chem., 34 .
7 , C9 (1988) [Cp ₂ TiMe (THF)] ⁺ [B
Ethylene polymerization has been successful using a compound represented by Ph ₄ ] ^- (Me = methyl group, Ph = phenyl group).

Jordan et al., J. Am. Chem. Soc., 109 , 41.
11 (1987) show that zirconium complexes such as [Cp ₂ ZrR (L)] ⁺ (R = methyl group, benzyl group, L = Lewis base) polymerize ethylene.

Japanese Patent Publication No. 1-501950, Japanese Patent Publication No.
-502036 describes a method for polymerizing olefins using a catalyst composed of a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. Zambel
li et al. reported in Macromolecules, 22 , 2186 (1989) that isotactic polypropylene can be produced by a catalyst that combines a zirconium compound having a cyclopentadiene derivative as a ligand and trimethylaluminum and fluorodimethylaluminum. is doing. JP-A-3-179005 discloses an olefin polymerization catalyst comprising a) a metallocene compound, b) an aluminum alkyl, and c) a Lewis acid.

[0017]

The method for producing a propylene-based copolymer having an unsaturated bond using the Ziegler-Natta type catalyst as described above has a poor copolymerization efficiency, and an unsaturated bond is formed in the produced polymer. In order to introduce it, it is necessary to introduce a large amount of diene comonomer into the polymerization system. Moreover, the obtained copolymer had a wide molecular weight distribution and was inferior in transparency and mechanical properties.

[0018]

Means for Solving the Problems The inventors of the present invention have made intensive studies on a method for solving the above problems and efficiently producing an isotactic propylene-diene copolymer having excellent physical properties. It has been found that the above-mentioned object can be achieved by copolymerizing propylene and a diene compound in the presence of the present invention, and the present invention has been completed.

[0019] The present invention comprises a propylene and alkadienes having at least one one having 6 to 25 carbon atoms of the terminal double bond and one internal double bond, ¹³
The isotactic pentad fraction measured by C-NMR is 0.5 or more, and the content rate of the above-mentioned alkadiene is 0.
01 to 30 mol%, the intrinsic viscosity [η] measured with a tetralin solution at 135 ° C. is 0.01 to 10 dl / g, and gel permeation chromatography (G
The molecular weight dispersity (Mw / Mn) measured by PC) is 1.5.
The present invention further provides (A) a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand. In the presence of a catalyst consisting of a transition metal compound (B) cocatalyst of Group 4 of the periodic table, propylene and at least one alkadiene having one terminal double bond and one internal double bond having 6 to 25 carbon atoms are prepared. The method for producing the novel propylene-based copolymer is characterized in that it is copolymerized.

The novel propylene-based copolymer of the present invention contains propylene in an amount of 0.01 to 30 mol%, preferably 0.1 to 30 mol%.
It is composed of an alkadiene having a content of 20 mol% and having at least one terminal double bond having 6 to 25 carbon atoms and one internal double bond. It is a propylene-based copolymer having a substantially isotactic structure.

The novel propylene-based copolymer of the present invention has a methyl group isotactic pentad chain fraction of 0.5 or more, preferably 0.6, as measured by ¹³ C-NMR.
The intrinsic viscosity [η] measured with a tetralin solution at 135 ° C. is 0.01 to 10 dl / g, preferably 0.1.
It has a value of 1 to 10 dl / g and a molecular weight dispersity (Mw / Mn) measured by gel permeation chromatography (GPC) of 1.5 to 4.0, preferably 2.0.
Has a value of ~ 3.5.

The novel propylene-based copolymer of the present invention comprises a group (A) cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand of Group 4 of the periodic table. Transition metal compounds, and (B)
It can be produced by copolymerizing propylene and an alkadiene in the presence of a catalyst composed of a promoter.

The transition metal compound used as the component (A) in the present invention is a metallocene compound capable of providing polypropylene having a substantially isotactic structure. Such metallocene compounds are disclosed, for example, in JP-A-61-130314 and JP-A-1-197490.
Japanese Patent Application Laid-Open No. 1-203409, Japanese Patent Application Laid-Open No. 1-240409
Examples of known compounds include those described in JP-A-75608, JP-A-1-301704, JP-A-2-131488, JP-A-3-12406, and JP-A-3-12407. it can. More specifically, for example, ethylenebis (1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, dimethylsilylenebis (1-indenyl) zirconium dichloride, dimethyl Silylene bis (methylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (
In addition to zirconium compounds such as dimethylcyclopentadienyl) zirconium dichloride, similar hafnium compounds can be mentioned.

As the cocatalyst used with the transition metal compound, known cocatalysts used with the metallocene compound as described above can be used in the copolymerization of the present invention. Examples of such a cocatalyst include, for example, in addition to the known aluminoxane, JP-A-1-5019.
Ionic compounds as described in Japanese Patent Publication No. 50 and Japanese Patent Publication No. 1-502036, JP-A-3-17900.
Mention may be made of co-catalysts composed of aluminum alkyls and Lewis acids as described in JP-A-5.
General formula for aluminoxanes

[0025]

[Chemical 3] (Wherein R represents a hydrocarbon group having 1 to 3 carbon atoms, and n represents an integer of 2 or more), and particularly methylaluminoxane in which R is a methyl group, n is 5 or more, preferably Ten or more are used. The aluminoxanes may be mixed with some alkylaluminum compounds.

In the present invention, the ratio of aluminoxane to the transition metal compound used is 10 to 10,000.
It is 0 mol times, usually 50 to 10000 mol times. In the present invention, the alkadiene supplied with propylene during copolymerization is an alkadiene having one terminal double bond and one internal double bond having 6 to 25 carbon atoms, and among them, a branched alkadiene is copolymerized with propylene. It has good properties and is suitable for use. Specific examples of such suitable alkadienes include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 2-methyl-2,7-octadiene and the like. The amount of these alkadienes used varies depending on the alkadiene content in the intended copolymer, but is usually 1/10000 to 1/10 of propylene.

The polymerization method and polymerization conditions used in the method of the present invention are not particularly limited, and known methods used in the polymerization of α-olefins can be used. Solvent polymerization method using an inert hydrocarbon medium, or substantially A bulk polymerization method or a gas phase polymerization method in which an inert hydrocarbon medium does not exist can also be used, and it is general to carry out at a polymerization temperature of −100 to 200 ° C. and a polymerization pressure of normal pressure to 100 kg / cm ^2. . The pressure is preferably −50 to 100 ° C. and atmospheric pressure to 50 kg / cm ² .

Examples of the hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, and benzene. Aromatic hydrocarbons such as toluene, xylene, etc. can also be used.

In the present invention, not only propylene homopolymerization, but also propylene and ethylene, propylene and 1-, as long as they have a substantially syndiotactic structure,
Ethylene having 2 to 25 carbon atoms such as butene or α-
It can also be used when producing a copolymer with an olefin.

The copolymer according to the present invention has an unsaturated bond in the molecular chain, and therefore, for example, in JP-A-57-57.
726, Japanese Patent Application Laid-Open No. 57-59934, it can be used for the synthesis of a polymer having a polar group by a polymer reaction and a crosslinking reaction as performed in EPDM. Since the polymer can be easily obtained, a polymer having excellent physical properties can be obtained, which is industrially valuable.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 3.0 mg of ethylenebis (1-indenyl) zirconium dichloride synthesized by the method described in JP-A-61-130314 and a methylaluminoxane manufactured by Tosoh Akzo Co., Ltd. 17.7) 0.8 g, liquid propylene 0.75 l and JP-A-60-89436.
Then, 21.9 g of methyl-1,4-hexadiene synthesized by the method described in Japanese Patent Publication No. 1994-242242 was added. After polymerizing at 40 ° C. for 1 hour, the obtained polymer was washed with heptane and dried to obtain 77.5 g of a propylene-diene copolymer. The intrinsic viscosity (hereinafter abbreviated as [η]) measured with a 135 ° C. tetralin solution of this copolymer was 0.18 d.
The molecular weight dispersity (Mw / Mn) measured by gel permeation chromatography (GPC) was 2.7. ^The isotactic pentad fraction determined by ¹³ C-NMR is 0.811, and the ¹ H-NMR measurement shows that
The diene content determined from the peak intensity observed at 5.0 to 5.2 ppm based on tetramethylsilane using benzene-d ₆ as a solvent was 1.1 mol%.

Example 2 Instead of methyl-1,4-hexadiene, 2-methyl-
Polymerization was carried out in the same manner as in Example 1 except that 22.4 g of 2,7-octadiene (manufactured by Shell Chemical Co., Ltd.) was used. The obtained copolymer was 61.4 g, and [η] of this copolymer was obtained.
Was 0.20 dl / g, Mw / Mn was 2.6, the isotactic pentad fraction was 0.820, and the diene content was 0.4 mol%.

Example 3 Polymerization was carried out in the same manner as in Example 1 except that 2.0 mg of dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride was used instead of ethylenebis (1-indenyl) zirconium dichloride. The obtained polymer was 94.6 g, and [η] of this polymer was 0.
84 dl / g, Mw / Mn was 2.8, and the isotactic pentad fraction was 0.937. The diene content was 0.9 mol%.

Example 4 Instead of methyl-1,4-hexadiene, 2-methyl-
Polymerization was carried out in the same manner as in Example 3 except that 22.4 g of 2,7-octadiene (manufactured by Shell Chemical Co., Ltd.) was used. The obtained copolymer was 107.2 g, [η] of this copolymer was 0.77 dl / g, Mw / Mn was 2.7, isotactic pentad fraction was 0.905, and diene content was 1.7 mol. %Met.

Example 5 Polymerization was carried out in the same manner as in Example 3 except that the amount of methyl-1,4-hexadiene used was 7.3 g. The obtained polymer was 89.2 g, and [η] of this polymer was 0.
97 dl / g, Mw / Mn was 2.4, the isotactic pentad fraction was 0.956, and the diene content was 0.3 mol%.

Example 6 The amount of 2-methyl-2,7-octadiene used was 7.5.
Polymerization was performed in the same manner as in Example 4 except that g was used. The obtained polymer was 114.2 g.
Was 0.96 dl / g, Mw / Mn was 2.3, the isotactic pentad fraction was 0.932, and the diene content was 0.9 mol%.

Comparative Example 1 Preparation of solid catalyst component 20 g of magnesium chloride, 6 m of diisobutyl phthalate
1 and 7 ml of titanium tetrachloride were co-ground for 40 hours using a vibration mill and then treated with boiling toluene to obtain a solid catalyst component.

Polymerization 10 mg of the solid catalyst component prepared above, 0.03 ml of diphenyldimethoxysilane, and 0.3 of triethylaluminum.
An attempt was made to copolymerize propylene with methyl-1,4-hexadiene in the same manner as in Example 1 except that 1 ml was used as a catalyst. However, the produced polymer is treated with ¹ H-NM
As a result of R measurement, a peak attributed to an unsaturated bond was not observed.

Comparative Example 2 Propylene and methyl-1,4 were prepared in the same manner as in Example 1 except that 50 mg of titanium trichloride manufactured by Marubeni Solvay and 27 mg of diethylaluminum chloride were used as catalysts.
-Tried to copolymerize with hexadiene. However, as a result of ¹ H-NMR measurement of the produced polymer, no peak attributed to an unsaturated bond was observed.

[0040]

By carrying out the method of the present invention, a polypropylene copolymer having an unsaturated bond in the polymer can be efficiently obtained. Further, since the copolymer of the present invention has an unsaturated bond in the molecular chain, a polymer having improved properties can be obtained by a known method of modifying the unsaturated bond in the polymer.

Claims (2)

[Claims] 1. An isotactic pentad fraction comprising propylene and at least one alkadiene having at least one terminal double bond having 6 to 25 carbon atoms and one internal double bond, and having an isotactic pentad fraction measured by ¹³ C-NMR. It is 0.5 or more, and the content rate of the alkadiene is 0.01 to 30 mol%.
And the intrinsic viscosity [η] measured with a tetralin solution at 135 ° C. is 0.01 to 10 dl / g, and the molecular weight dispersity (Mw / Mn) measured by gel permeation chromatography (GPC) is A novel propylene-based copolymer characterized by having a content of 1.5 to 4.0. 2. A catalyst comprising (A) a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand, a transition metal compound of Group 4 of the periodic table (B) a cocatalyst. The novel propylene-based copolymer according to claim 1, characterized in that propylene is copolymerized with at least one alkadiene having one terminal double bond having 6 to 25 carbon atoms and one internal double bond. Method for producing polymer.