JP3208156B2 - Novel propylene-based copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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. More specifically, the present invention mainly relates to a propylene-alkadiene copolymer having a syndiotactic structure.

[0002]

2. Description of the Related Art JP-A-2-41303 and JP-A-2-41303
No. 41305, etc. syndiotactic polypropylene has high syndiotacticity,
Although it is a polymer excellent in physical properties, it has a drawback that adhesiveness and dyeability are low.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have previously solved the above-mentioned problems by copolymerizing a cyclic diolefin or a linear diolefin with propylene to introduce a double bond into the polymer. The use of a cyclic diolefin as a comonomer leads to a decrease in polymerization activity, and a decrease in the molecular weight of the produced polymer, which lowers the good physical properties of the inherent syndiotactic polypropylene. There was a problem.

[0004]

Means for Solving the Problems The present inventors have solved the above-mentioned problems, and as a result of earnestly studying a syndiotactic propylene-diene copolymer having excellent physical properties, as a result of using a specific alkadiene as a comonomer,
The inventors have found that the above-mentioned objects have been achieved and completed the present invention.

That is, the present invention relates to a syndiotactic pen which comprises propylene and at least one branched alkadiene having one terminal double bond and one internal double bond having 6 to 25 carbon atoms, and which is measured by ¹³ C-NMR. The tod fraction is 0.5 or more, the content 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 provided a novel propylene-based copolymer having a substantially syndiotactic structure,
(A) General formula [I]

[0006]

Embedded image (Where A ¹ and A ² represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof, and A ¹ and A ² are selected to be different from each other. A ³ and A ⁴ Is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an aryl halide group or oxygen, nitrogen,
It is a hydrocarbon group containing a hetero atom such as sulfur or silicon or a hydrogen atom. Q is a compound containing carbon, silicon, germanium, or tin that connects A ¹ and A ² . Also,
A ³ and A ⁴ may be connected to each other to form a ring structure among A ³ , A ⁴ and Q. R ¹ and R ² are a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
-20, aryl, alkylaryl and arylalkyl groups. M is titanium, zirconium, hafnium. Propylene and at least one branched alkadiene having at least one terminal double bond having 6 to 25 carbon atoms and one internal double bond in the presence of a catalyst comprising (B) a cocatalyst; A method for producing the novel propylene-based copolymer, characterized by copolymerizing.

[0007] The novel propylene-based copolymer of the present invention contains propylene and 0.01 to 30 mol%, preferably 0.1 to 30 mol%.
It consists of a branched 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 syndiotactic structure.

Further, the novel propylene-based copolymer of the present invention has a syndiotactic pentad chain fraction of methyl group of 0.5 or more, preferably 0.1 M, 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 to 10 dl / g.

The measurement of the syndiotactic pentad fraction (rrrr) by ¹³ C-NMR is described in, for example,
It can be measured by a known method as described in JP-A-41303, JP-A-2-41305 and the like.

The novel propylene polymer of the present invention is obtained by copolymerizing propylene and an alkadiene in the presence of a catalyst comprising (A) the transition metal compound represented by the general formula [I] and (B ) an aluminoxane. It can be manufactured by doing.

In the general formula [I], A ¹ and A ^{2 each} represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof, and A ¹ and A ² are selected to be different from each other. . Examples of suitable combinations for obtaining a propylene-based polymer having a substantially syndiotactic structure according to the present invention include A ¹ is a cyclopentadienyl group, A ² is a fluorenyl group, or 2,7-di-t -A butylfluorenyl group. A ³ and A ^{4 each} have 1 to 10 carbon atoms
, An aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogenated aryl group, or a hydrogen atom. Specific examples of A ³ and A ⁴ include:
Examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenyl group, a toluyl group, a chlorophenyl group, a fluorophenyl group, and a benzyl group. Q is A ¹ ,
Is a carbon linking the A ^2. R ¹ and R ² are a halogen atom,
Hydrogen atom, alkyl group having 1 to 10 carbon atoms, 6 to 2 carbon atoms
0 represents an aryl group, an alkylaryl group or an arylalkyl group, preferably a chlorine atom or a methyl group. M
Is titanium, zirconium and hafnium.

The transition metal compound represented by the general formula [I] is described in, for example, JP-A-2-41303 and JP-A-2-2-230.
The compound can be synthesized using a method similar to the method for synthesizing a transition metal compound described in, for example, Japanese Patent No. 74703.

A preferred example of the transition metal compound represented by the general formula [I] used in the present invention is described in JP-A-2-413.
No. 03, JP-A-2-274703 and the like.

In the copolymerization, a catalyst composed of a transition metal compound and known aluminoxanes is used.

The aluminoxanes are represented by the general formula (3)

[0016]

Embedded image Wherein R is a hydrocarbon group having 1 to 3 carbon atoms, and n is an integer of 2 or more. In particular, R is a methylaluminoxane in which methyl is a methyl group, and n is 5 or more, preferably More than 10 are used. The above-mentioned aluminoxanes may contain some alkylaluminum compounds.

In the present invention, the use ratio of aluminoxane to the above transition metal compound is from 10 to 10,000.
It is 0 mole times, usually 50 to 10000 times.

[0018]

[0019]

[0020]

[0021]

In the present invention, the transition metal catalyst component and / or
Alternatively , the aluminoxane can be used as it is as SiO ₂ or Al ₂
It may be used by being supported on a known carrier that supports a Ziegler-type catalyst component such as O ₃ and MgCl ₂ .

In the present invention, the branched alkadiene supplied together with propylene at the time of copolymerization is an alkadiene having one terminal double bond and one internal double bond having 6 to 25 carbon atoms. Specific examples of such suitable alkadienes include, for example, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 2-methyl-
2,7-octadiene and the like can be mentioned. The amount of these alkadienes used depends on the alkadiene content in the desired copolymer, but is usually 1/10000 to 1/10 of propylene.

The polymerization method and the polymerization conditions carried out in the method of the present invention are not particularly limited, and a known method carried out in the polymerization of α-olefin is used, and a solvent polymerization method using an inert hydrocarbon medium or a substantial method is used. In addition, a bulk polymerization method or a gas phase polymerization method in which an inert hydrocarbon medium does not exist can be used, and the polymerization is generally performed at a polymerization temperature of −100 to 200 ° C. and a polymerization pressure of normal pressure to 100 kg / cm ^2. . Preferably, it is -50 to 100 ° C and normal pressure to 50 kg / cm ² . As the hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention, for example, in addition to saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, benzene, toluene, Aromatic hydrocarbons such as xylene can also be used.

In the present invention, the olefin to be copolymerized with the branched alkadiene is not limited to propylene alone, but may be, for example, propylene and ethylene, or propylene and 1-butene having 2 carbon atoms as long as it has a substantially syndiotactic structure. It can also be used when producing a copolymer with about 25 to about 25 ethylene or α-olefin.

Since the copolymer according to the present invention has a double bond, for example, Japanese Patent Application Laid-Open Nos. 57-57726 and 57-5
It can be used for the synthesis of a polar polymer by a polymer reaction usually carried out with isotactic polypropylene as disclosed in 9934, and a cross-linking reaction carried out with EPDM. Since a polymer can be easily obtained, a polymer having excellent physical properties can be obtained, which is industrially high.

[0027]

The present invention will be specifically described below with reference to examples. Example 1 A 1.5-liter autoclave sufficiently purged with nitrogen was placed in a
No.-41303, 3.0 mg of isopropylidenecyclopentadienylfluorenylzirconium dichloride and 0.8 g of methylaluminoxane (degree of polymerization 17.7) manufactured by Tosoh Akzo Co., Ltd. 0.75 l and JP-A-60
21.9 g of 4-methyl-1,4 hexadiene synthesized by the method described in JP-A-89436 was added. 1 at 40 ° C
After polymerization for an hour, the obtained polymer was washed with heptane and dried to obtain 110.7 g of a propylene-diene copolymer. The intrinsic viscosity (hereinafter abbreviated as [η]) of this copolymer measured in a tetralin solution at 135 ° C. is 1.18 dl / g, the syndiotactic pentad fraction determined by ¹³ C-NMR is 0.868, and ¹ H -NM
In R measured, the diene content was determined from the peak intensity observed in 5.0~5.2ppm benzene -d ₆ relative to tetramethylsilane as a solvent was 0.9 mol%.

Example 2 Instead of 4-methyl-1,4 hexadiene, 22.4 g of 2-methyl-2,7-octadiene (manufactured by Shell Chemical Company)
Polymerization was carried out in the same manner as in Example 1 except for using. The obtained copolymer was 77.4 g, [η] of the copolymer was 1.25 dl / g, the syndiotactic pentad fraction was 0.851, and the diene content was 1.9 mol%.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that no diene compound was used. The obtained polymer was 84.0 g, [η] of the polymer was 1.27 dl / g, and the syndiotactic pentad fraction was 0.872. As described above, even when the diene compound was used as a comonomer, a decrease in polymerization activity and a decrease in the molecular weight of the produced polymer were hardly observed.

[0030]

Since the propylene copolymer of the present invention has a double bond in the molecular chain, a polymer having improved properties can be obtained by a known method for modifying the double bond in the polymer.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsunosuke Shiomura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Shuji Sasaki (58) Field surveyed (Int.Cl. ⁷ , DB name) ) C08F 210/06 C08F 4/642 CA, REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A syndiotactic pentad fraction comprising propylene and at least one branched alkadiene having one terminal double bond and one internal double bond having 6 to 25 carbon atoms, as measured by ¹³ C-NMR. Is at least 0.5, the content 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. A novel propylene copolymer having a syndiotactic structure. (A) A compound represented by the following general formula [I]: (Here, A ¹ and A ² represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof, and A ¹ and A ² are selected to be different from each other.
A ³ and A ⁴ are an alkyl group having 1 to 10 carbon atoms, and 6 to 2 carbon atoms.
And 0 is an aryl group, an alkylaryl group, an arylalkyl group, a halogenated aryl group, or a hydrogen atom. Q
Is a carbon linking A ¹ and A ² . R ¹ and R ^{2 each} represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. M is titanium, zirconium, hafnium. ) And a branched alkadiene having at least one terminal double bond having 6 to 25 carbon atoms and one internal double bond in the presence of a catalyst comprising a transition metal compound represented by the formula (B) aluminoxane: 2. The method for producing a novel propylene copolymer according to claim 1, wherein said method is carried out.