JP2886906B2 - Polycyclopentene and method for producing the same - Google Patents

Description

The present invention relates to a polycyclopentene and a method for producing the same. More specifically, it relates to a highly stereoregular polycyclopentene and a method for producing the same.

(Prior art)

It has been discovered by W. Kaminsky et al. That crystalline polycyclopentene can be obtained by polymerizing cyclopentene using a catalyst composed of a soluble transition metal catalyst and an aluminoxane (Transition Metal and Organometallics a).
s Catalyst for Orefin Polymerization 291-301 (198
8) Eds.W.Kaminsky). According to the above report, polymerization of cyclopentene with a catalyst having symmetrically bonded ligands gives polycyclopentene having a mixed structure of trans and cis isomers.

[Problems to be solved by the invention]

If the bond of the polycyclopentene is not a mixture of the trans form and the cis form but only one structure, it is expected that the physical properties are further excellent.

[Means for solving the problem]

The inventors of the present invention have solved the above-mentioned problems and have intensively searched for a highly stereoregular polycyclopentene, and have found that a polycyclopentene having a highly regular bond can be obtained by a specific polymerization method, thereby completing the present invention.

That is, the present invention is based on ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution, and is based on tetramethylsilane.
Highly stereoregular polycyclopentene in which only three peaks at 0.8, 38.5 and 46.7 ppm are observed. The present invention also relates to a preferred process for the preparation thereof, comprising isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride and isopropyl (cyclopentadienyl-1-fluoride).
A process for producing highly stereoregular polycyclopentene, comprising polymerizing cyclopentene using a catalyst comprising an aluminoxane and a transition metal compound containing an asymmetric ligand selected from fluorenyl) zirconium dichloride.

The highly stereoregular polycyclopentene of the present invention will be described below with reference to an example of a production method.

The catalyst used for production is reported, for example, by JAEWEN et al. (J. Am. Chen. Soc., 1988, 110, 6255).
-6256) Catalysts are exemplified.

Examples of the transition metal compound having an asymmetric ligand include the compounds described in the above literature. Specifically, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride or isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride is exemplified, and aluminoxane is represented by a general formula: (Wherein R is a hydrocarbon residue having 1 to 3 carbon atoms), in particular, a methylaluminoxane in which R is a methyl group and n is 5 or more, preferably 10 or more is used. The use ratio of the aluminoxane to the transition metal catalyst is 10 to 100,000,000 times, usually 50 to 5000 times.
The polymerization conditions for producing polycyclopentene by polymerizing cyclopentene are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method using cyclopentene as a polymerization medium in which substantially no inert medium is present, and a gas polymerization method. Phase polymerization methods can also be used. The polymerization temperature is -100 to 200
In general, the polymerization is carried out at a temperature of from 10 ° C. to 10 kg / cm ² -G. Preferably, -100 ~ 100 ° C, normal pressure ~ 5 kg / cm
²

Polycyclopentene having a relatively high stereoregularity can be produced by polymerization under the above conditions. Further, if necessary, purification can be carried out to remove portions having poor regularity by washing with a hydrocarbon solvent. However, polymerization under the above-mentioned conditions makes it possible to easily obtain highly stereoregular polycyclopentene. Highly stereoregular, for example, about 46.4 ppm
Is 0.7 or more, more preferably 0.8 or more, of the sum of the peak intensities observed at 45 to 47 ppm.

It is preferable that the molecular weight is usually 500 or more from the viewpoint of exhibiting properties as a polymer. Is calculated as More preferably, it has a molecular weight of 10,000 or more.

 Hereinafter, the present invention will be described with reference to Examples.

Example 1 Isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained by lithiation of isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method in a flask having an internal volume of 300 ml and reacting with zirconium tetrachloride. 10 mg and 0.68 g of methylaluminoxane having a degree of polymerization of about 16 manufactured by Toyo Akzo Co., Ltd. were added to 20 g of cyclopentene, polymerized at 30 ° C. for 6 hours, and then poured into a large amount of methanol to obtain 1.5 g of polycyclopentene as a methanol-insoluble component. Obtained. Waters Co., Ltd. GPC150C gel permeation chromatography measured at 135 ℃, calculated as polypropylene number average molecular weight 4800,
The weight average molecular weight was 6,800. The intrinsic viscosity measured with a tetralin solution at 135 ° C. was 0.18 dl / g. ¹³ C-NMR
In a 1,2,4 trichlorobenzene solution at 125 ° C, the absorption peak when tetramethylsilane is set to 0 ppm is as follows.
Three were observed at 30.8, 38.5, and 46.7 ppm, and 25.8 and 31.
Small peaks were observed at 8, 32.3 and 32.4 ppm. Polycyclopentene was produced by a known method (Tran
sition Metal and Organometallics as Catalyst for O
refin Polymerization 291-301 (1988) Eds.W.Kaminsk
y, JP-A-64-66216). Was obtained 3.0g can be obtained by polymerizing in the same manner using 1,2-ethylene-bis indenyl zirconium dichloride, as measured in the same manner as ¹³ C-NMR about 3
0.6, 30.8, 32.2, 38.4, 45.6, 45.7, 46.6, 46.7 and 8
A relatively strong peak in the book was observed. FIG. 1 shows the measurement results of the ¹³ C-NMR absorption spectrum. FIG. 2 shows the measurement results of X-ray diffraction (Cu-α).

〔The invention's effect〕

The polymer of the present invention can be used alone or in a mixture with other polymers for various uses, and is industrially valuable.

[Brief description of the drawings]

FIG. 1 shows ¹³ C-NMR spectra of the polycyclopentene (a) of the present invention obtained in Example 1 and the polycyclopentene (b) having low regularity obtained by the prior art. FIG. 2 is an X-ray diffraction spectrum of the polycyclopentene (a) of the present invention and the polycyclopentene (b) having low regularity obtained by the prior art.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/60-4/70 C08F 32/00-32/08 C08F 132/00-132/08 C08F 232 / 00-232/08

Claims (2)

(57) [Claims] 1. A ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution, which is 30.8% based on tetramethylsilane.
Highly stereoregular polycyclopentene in which only three peaks at 38.5 and 46.7 ppm are observed. 2. Isopropyl (cyclopentadienyl-1)
Polymerizing cyclopentene using a catalyst comprising a transition metal compound containing an asymmetric ligand selected from -fluorenyl) hafnium dichloride and isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride and aluminoxane. To produce highly stereoregular polycyclopentenes.