JP2002529555A - Method for producing EP (D) M using bridged pentadienyl-fluorenyl transition metal complex - Google Patents

Abstract

  (57) [Summary] The present invention relates to a process for producing ethylene-propylene copolymers and ethylene-propylene-non-conjugated diene terpolymers of the rubber type and to the use of the polymers obtained by the process for the production of all types of shaped articles.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a process for the production of rubbery ethylene / propylene copolymers and ethylene / propylene / non-conjugated diene terpolymers and to the production of all kinds of shaped articles from the polymers thus obtained. For using for.

BACKGROUND OF THE INVENTION Due to the saturated backbone, ethylene / propylene copolymers (EPM) and ethylene / propylene / non-conjugated diene terpolymers (EPDM) are important starting materials in the industry. To obtain their final properties, the polymers must be cross-linked using peroxide, radiation or sulfur / sulfur agents. The unsaturated bond content in EPDM, which is controlled by the non-conjugated diene content, is just as important in the case of sulfur crosslinking. Many catalysts have been developed for their composition and microstructure for EPM and EPDM purposes.

In the prior art, EPM and EPDM are produced using a Ziegler-Natta-based catalyst. Vanadium-containing catalysts are usually used for this. The process is performed in a solution, suspension or gas phase. In the prior art, ethylene / propylene copolymers are produced using biscyclopentadienyl zirconium compounds (EP-B-129 368), but the degree of incorporation of non-conjugated dienes is often insufficient.

[0004] US-A-4.892.851 discloses compounds in which a cyclopentadienyl ligand (Cp) is linked via a dimethylmethylene bridge to a fluorenyl ligand (Flu). The teaching of EP-A2-512 554 is also a bridged Cp-Flu compound and the use of that compound as a catalyst for olefin polymerization.

[0005] The teaching of US-A-5.158.920 is the use of bridged Cp-Flu compounds and the compounds for the preparation of stereospecific polymers. Crosslinked Cp-Flu compounds are also known from other literature, but all have the common feature that the crosslinking element is linear. However, catalysts of this kind exhibit disadvantages in the chain length of the EP (D) M obtained, often resulting in oils or waxes which cannot be used for the production of shaped articles.

DISCLOSURE OF THE INVENTION [0006] The technical problem to be solved by the present invention is therefore to provide a method for producing EPM and EPDM which does not have the disadvantages of the prior art.

This object is achieved according to the present invention, optionally in the presence of one or more cocatalysts,
A process for the polymerization of ethylene, propylene and optionally a non-conjugated diene using a metallocene as a catalyst, wherein the metallocene used has the general formula (I):

Embedded image Wherein R ¹ -R ¹² independently represent H, C ₁ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl or C ₇ -C ₁₂ aralkyl, X is H, halogen or C represents ₁ -C ₁₂ alkyl group, W is represents a first 13, 15 or 16 atom may be substituted on carbon atoms or an optionally, Y is optionally substituted C ₁ -C ₁₂ alkyl group or an optionally Represents a Group 14, 15 or 16 atom, and M represents a Group 4 metal. ] It is achieved by the method characterized by being a compound represented by these.

A C ₁ -C ₁₂ alkyl group is understood to mean all straight-chain or branched alkyl groups having 1 to 12 carbon atoms known to the expert, for example methyl, ethyl, n-propyl , Isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl and hexyl groups, each of which may also be substituted. Here possible substituents in a cycloalkyl or aryl group an alkyl or alkoxy group having halogen or C ₁ -C ₁₂ and C ₆ -C _12,
For example, benzoyl, trimethylphenyl, ethylphenyl, chloromethyl and chloroethyl groups.

A C ₁ -C ₁₂ alkoxy group is understood to mean all straight-chain or branched alkoxy groups having 1 to 12 carbon atoms known to the expert, for example methoxy, methoxy,
Ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-
Butoxy, n-pentoxy, isopentoxy, neopentoxy and hexoxy groups, each of which can also be substituted. Possible substituents here are halogen or C ₁ -C ₁₂ alkyl or alkoxy groups and C ₆ -C ₁₂ cycloalkyl or aryl groups.

A C ₆ -C ₁₂ aryl group is understood to mean all mono- or polycyclic aryl groups having 6 to 12 carbon atoms known to the expert, for example phenyl and naphthyl groups, Each can also be replaced. Possible substituents here are halogen, nitro, hydroxyl or C ₁ -C ₁₂ alkyl or alkoxy and C ₆ -C ₁₂ cycloalkyl or aryl, such as bromophenyl, chlorophenyl, toluyl and nitrophenyl. Group. A C ₇ -C ₁₂ aralkyl group is understood to mean a group in which the above-mentioned alkyl group and the above-mentioned aryl group are bonded.

The R ^{1 to} R ¹² groups are preferably hydrogen, methyl, ethyl, propyl, t-butyl,
Methoxy, ethoxy, cyclohexyl, benzoyl, methoxy, ethoxy, phenyl, naphthyl, chlorophenyl and toluyl groups.

When the group X represents halogen, this is understood by the expert to mean fluorine, chlorine, bromine or iodine, with chlorine being preferred. If Y represents a group 14, 15 or 16 atom, this is preferably Si,
It is understood to mean Ge, Sn, Pb, N, P, O and S. Si, N and P are particularly preferred. M represents Ti, Zr and Hf, with Zr being preferred.

General formula (II):

Embedded image Wherein R ¹ -R ¹² independently represent H, C ₁ -C ₁₂ alkyl or C ₆ -C ₁₂ aryl, X represents Cl or methyl, M is Ti or Represents Zr. ] Is preferably used.

Formula (III):

Embedded image The catalyst represented by is particularly preferably used.

The present invention also provides compounds represented by formulas (I), (II) and (III). The compounds of the formulas (I), (II) and (III) are often used in combination with a cocatalyst for the polymerization according to the invention. Possible cocatalysts are the cocatalysts known in the metallocene art, for example polymeric or oligomeric alumoxanes, Lewis acids and aluminates and borates. In this connection, in particular, Macromol.
Symp. 97, July 1995, pp. 1-246 (alumoxane) and EP 277 003, EP
277 004, Organometallics 1997, Vol. 16, pp. 842-857 (borate) and
Reference can be made to EP 573 403 (aluminate). Particularly preferred cocatalysts are: methylalumoxane, triisobutylaluminum (TIBA)
Methylalumoxane, diisobutylalumoxane, trialkylaluminum compounds (eg, trimethylaluminum, triethylaluminum, triisobutylaluminum, and triisooctylaluminum) modified with
And also dialkylaluminum compounds (eg, diisobutylaluminum hydride and diethylaluminum chloride), substituted triarylboron compounds (eg, tris (pentafluorophenyl) borane) and ionic compounds containing tetrakis (pentafluorophenyl) borate as an anion ( For example, triphenylmethyltetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, substituted triarylaluminum compounds (for example, tris (pentane) Ionic compounds containing (fluorophenyl) aluminum) and tetrakis (pentafluorophenyl) aluminate as anion (Eg, triphenylmethyltetrakis (pentafluorophenyl) aluminate and N, N-dimethylaniliniumtetrakis (
Pentafluorophenyl) aluminate). Of course, the cocatalysts can be used as a mixture with one another. The most preferred mixing ratio in each case can be determined by suitable preliminary experiments.

The polymerization according to the invention is carried out in the gas, liquid or slurry (suspension) phase.
The temperature range for the polymerization is -20C to + 200C, preferably 0C to 160C,
Particular preference is given to + 20 ° C. to + 80 ° C., the pressure range being from 1 to 50 bar, preferably from 3 to 30 bar. The polymerization inert solvent used simultaneously is, for example, a saturated aliphatic compound or a (halogeno) aromatic compound (for example, pentane, hexane,
Heptane, cyclohexane, petroleum ether, petroleum (mineral oil), hydrogenated benzene, benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like or a mixture thereof). The above reaction conditions for the polymerization are basically known to the expert.

The polymerization according to the invention is preferably carried out in the presence of an inert organic solvent. Possible inert organic solvents are, for example, aromatic, aliphatic and / or cycloaliphatic hydrocarbons, for example, preferably benzene, toluene, hexane, pentane, heptane and / or cyclohexane or mixtures thereof. The polymerization is preferably carried out as a solution polymerization or in suspension. In another preferred embodiment, the method of the invention is performed in the gas phase. Olefin polymerization in the gas phase was first technically realized in 1962 (US 3.023.203). Corresponding fluidized bed reactors are prior art.

The organometallic compounds of the formulas (I), (II) or (III) and, optionally, cocatalysts are also applied to inorganic supports and are used in heterogeneous form when used in suspension or gas phase. Used in. Suitable inert inorganic solids are, in particular, silica gels, clays, aluminosilicates, talc, zeolites, carbon blacks, inorganic oxides (eg silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide) or silicon carbide, preferably Silica gel, zeolite and carbon black. The described inert inorganic solids can be used alone or as a mixture with one another. In another preferred embodiment, the organic carriers are used alone or as a mixture with one another or with an inorganic carrier. Examples of organic carriers are porous polystyrene, porous polypropylene or porous polyethylene.

Possible non-conjugated dienes are all dienes known to the expert whose double bond has a different reactivity towards the catalyst system used, for example 5-ethylidene-2-norbornene (END), 5-vinyl norbornene, 1,4-hexadiene, 7-methyl
-1,6-octadiene and dicyclopentadiene. 5-Ethylidene-2-norbornene and 1,4-hexadiene are preferred.

It may be advantageous to purify the starting materials and remove impurities (eg, oxygen, water or polar substances). The polymerization is generally carried out under inert conditions.

The rubbery EPM and EPDM that can be produced according to the invention are distinguished by a low crystal content. The crystal content is generally less than 30%, preferably 20%
%, Particularly preferably less than 10%, particularly preferably in the range from 0 to 10%. The crystal content can be determined by measuring the melting enthalpy ratio and by the DSC method. The following factors have proven to be relevant here:

(Equation 1)

Uncrosslinked EPM and EPDM are readily soluble in common solvents such as hexane, heptane or toluene. The ethylene content ranges from 5 to 95% by weight, preferably from 40 to 90% by weight. The propylene content ranges from 5 to 95% by weight, preferably from 9.5 to 59.5% by weight. The content of the non-conjugated diene is in the range of 0 to 20% by mass, preferably 0.5 to 12% by mass. Naturally, the sum of the individual monomer contents must be 100%, so that the expert will select an appropriate content from the range of individual mass%.

A particular advantage of the process of the invention is that the catalyst can remain in the final product and does not cause interference during further processing or use.

[0024] Further processing of EPMs and EPDMs that can be produced in accordance with the present invention typically involves a crosslinking step using a peroxide, sulfur / sulfur donor or high energy radiation. This process is known to the expert, but in this regard, in particular, Bayer AG (Le
verkusen), Handbuch fuer die Gummi-Industie, 2nd edition, 1991
Year, pages 231 et seq. If desired, EPM and EPDM can be oil-extended.

The present invention relates to rubbery EPMs and EPDMs that can be produced according to the present invention.
For the manufacture of all types of shaped articles. Examples of shaped articles are seals, O-rings, cross-sections, sheets, covers and damping elements for other substances. For applications in the low temperature range, it may be advantageous to use products having a degree of crystallinity in the range 0-5%.

Of course, the rubbery EPMs and EPDMs according to the present invention can be combined with other polymers or rubbers (eg, SBR, BR, CR, NBR, ABS, HNBR, polyethylene,
Polypropylene, polyethylene copolymer, LDPE, LLDPE, HDPE,
HMWPE, polysiloxanes, silicone rubbers and fluorinated rubbers). The corresponding mixture is known to the expert and can be optimized by several experiments.

[0027] It may also be advantageous to add fillers such as carbon black, silica, talc, silicates and metal oxides. These fillers and their use are known to the expert, but in particular the Encyclopedia of Polymer Science and Engineeri
ng, Volume 4, pages 66 et seq.

EXAMPLES All work up to the completion of the polymer was performed in an inert gas atmosphere using Schlenk, spray and glove box techniques. The inert gas used was argon from Linde having a purity of more than 99.996%, which was post-purified with an Oxisorb cartridge from Messer-Griesheim (Germany). Toluene having a purity of 99.5% or more used for the polymerization and for the preparation of the catalyst and cocatalyst stock solution,
Obtained from Riedel-de-Haeen (Germany). For use, the toluene was pre-dried over potassium hydroxide for several days, degassed, heated to reflux over a sodium / potassium alloy for at least one week, and finally distilled.

Example 1: Preparation of 1,3,3-trimethyl-2,3-dihydropentalene 600 ml of methanol, 50 ml of freshly distilled cyclopentadiene (0.61
mol) and 75 ml (0.61 mol) of diacetone alcohol are placed in a 1 L N ₂ flask under argon. After adjusting the temperature of the mixture to 0 ° C., 80 ml of freshly distilled pyrrolidine are added. After warming to room temperature, the mixture is stirred for 18 hours. The dark yellow solution is concentrated to 200 ml and distilled through a 30 cm Vigreux column. 16.9 g of a yellow-orange viscous oil (distillation temperature 64-70 ° C.) are isolated at an oil bath temperature of 130-160 ° C. under oil pump vacuum. This fraction is distilled through a mirrored 25 cm digestion column. 2.1 g (14 mmol) of the desired product are obtained at a distillation temperature of 66-69 ° C. and an oil bath temperature of 150 ° C. under 11 mbar. ¹ H-NMR
The spectrum shows a 5: 1 ratio of product to 6,6-dimethylfulvene. ¹ H-NMR (100 MHz, CDCl ₃ , J [Hz], TMS): δ [ppm] 6.72 (1H, d, ³ J = 5.0, Cp olefin proton) 6.06 (2H, dd, ³ J = 5.0, ⁴ J = 0.8, Cp olefin proton) 2.82 (2H, s, methylene proton) 2.14 (3H, s, methyl proton) 1.26 (6H, s, methyl proton)

Example 2 Preparation of 1-fluorenyl-1,3,3-trimethyl-1,2,3,6-tetrahydropentalene 9.56 ml (15.3 mmol) of 1.6N solution of n-butyllithium in hexane
) In 50 ml of THF in a 250 ml N ₂ flask with dropping funnel and reflux condenser
To a mixture of 2.54 g (15.3 mmol) of fluorene in 1 is added dropwise at -50 ° C over 30 minutes. After warming to room temperature, the solution is stirred for a further 8 hours and then briefly heated at the boiling point. After cooling to −50 ° C., 1,3,3-trimethyl-2 in 20 ml of THF
1.68 g (11.5 mmol) of 1,3-dihydropentalene are added dropwise over 2 hours and the mixture is stirred overnight at room temperature. After boiling briefly, 20 ml of semi-concentrated hydrochloric acid are added. The lower aqueous phase is saturated with NaCl and extracted with diethyl ether. The combined organic phases are washed twice with 20 ml each of a saturated solution of NaCl. Then, the organic phase is dried over Na ₂ SO _4. After distilling off all the solvent in a rotary evaporator, 5.0 g of crude product are obtained as an orange-yellow viscous oil. The ligand was subjected to column chromatography (silica gel 60, particle size 0.015 to 0.040 mm
, Petroleum ether 60/70). Yield: 1.10 g (3.5 mmo
l; 30% based on pentalene). ¹ H-NMR (100 MHz, CDCl ₃ , TMS): δ [ppm] 7.83 to 6.97 (8H, m, aromatic ring proton) 6.65 to 6.32 (2H, m, Cp olefin proton) 4 0.05 (1H, s, fluorene aliphatic proton) 3.40, 3.02, 2.72 (2H, m, Cp aliphatic proton) 1.73 or 1.69 (3H, s, methyl proton (2 isomers) 1.34 to 1.18 (2H, m, methylene proton) 0.98 (3H, s, methyl proton) 0.30 (3H, s, methyl proton) Mass spectrum: m / z 312 (molecular peak) )

[0031] Example 3: [1- (η ⁵ - fluorenyl) -1,3,3-trimethyl eta ⁵ - tetrahydrophthalic Pen sauce sulfonyl] zirconium dichloride n- butyl lithium in hexane manufacturing 1.8M Lido 4.4ml (8.0 mmol)
Is added dropwise at room temperature to a mixture of 1.1 g (3.2 mmol) of 1-fluorenyl-1,3,3-trimethyl-1,2,3,6-tetrahydropentalene in 25 ml of THF. 4
After a day, the mixture is heated briefly at the boiling point. After the solvent has been completely distilled off, the precipitate formed is washed twice with 10 ml each of pentane. After decanting the pentane, 0.75 g (3.2 mmol) of zirconium tetrachloride and 35 m of pentane at -60 ° C.
Add l. The mixture is stirred at room temperature for 3.5 days. After decanting the pentane, the residue is extracted with a total of 60 ml of methylene chloride. After concentrating the solution, 1.9
4 g of crude product are obtained. After recrystallization from methylene chloride, 150 mg of product (
0.3 mmol (10% based on zirconium tetrachloride) is obtained as a crystalline red photosensitive solid (FIG. 3 shows an X-ray crystal structure analysis diagram). Mass spectrum: m / z 472 (molecular peak)

Polymerization: Methylaluminoxane from Witco was used as cocatalyst. This is 100m
g / ml as a toluene solution. The gaseous monomers used, ethylene (Linde) and propylene (Gerling, Holz)
& Co.) has a purity of 99.8% or more. Before being introduced into the reactor, ethylene and propylene were passed in each case through two purification columns in order to remove traces of oxygen and sulfur. The two columns had dimensions of 3.300 cm ³ , an operating pressure of 8.5 bar and an operating temperature of 25 ° C., ensuring a volume flow of about 10 L / min. First in each case
Were packed with Cu catalyst (BASF R3-11) and in each case the second column was packed with molecular sieves (10 °).

5-Ethylidene-2-norbornene (ENB) was obtained from Aldrich as a mixture of endo and exo forms (> 99% purity), degassed, and mixed with 1 ml of n-tributylaluminum (Witco, 20 ml per L of ENB). Stirred for a week and condensed.

[0034] First procedure was a leak test of the device. During the test, both the applied vacuum and the introduced argon pressure of 4 bar must be kept constant for a few minutes. Only then was the apparatus completely heated at 95 ° C. for 1 hour under oil pump vacuum. Then, the reactor was
Alternatively, a reaction temperature of 60 ° C. was reached and the reactants were charged. During the reaction, the temperature was maintained with an accuracy of ± 1 ° C.

For the terpolymerization, 500 ml of toluene and 10 ml of MAO solution were first introduced in countercurrent with argon, and then a predetermined amount of the desired liquid monomer (ENB) was added. The solution was first saturated with propylene and then with ethylene. When saturation was reached, polymerization was initiated by spraying the metallocene solution. Ethylene was replenished during the reaction so that the total pressure was constant during the reaction, but the monomer composition of the batch constantly changed. Therefore, the reaction was interrupted at a low conversion. The reaction was terminated by spraying 5 ml of ethanol to deactivate the catalyst and the gaseous monomer was carefully removed in a ventilator. A stock solution of 1.0 × 10 ⁻³ M of the given catalyst compound in toluene was used for the polymerization.

Examples 4 to 9: The product from Example 3 in homogeneous form was used as the catalyst compound. Table 1 shows the monomer compositions, partial monomer partial pressures, and reaction temperatures of the examples.

Example 10 (Comparative Example) [(Cp) C (CH ₃ ) ₂ (Flu)] ZrCl ₂ in a uniform form was used as a catalyst compound. Table 1 shows the monomer compositions, partial monomer partial pressures, and reaction temperatures of the examples.

[0038]

[Table 1]

The polymer toluene solutions from Examples 4 to 10 were removed from the reactor and stirred overnight with 200 ml of 5% aqueous hydrochloric acid. The toluene phase was separated, neutralized with 50 ml of a saturated solution of sodium hydrogen carbonate and washed three times with 100 ml each of distilled water. Then, toluene and liquid monomer were removed at 30 ° C. and 40 mbar by a rotary evaporator, and then an attempt was made to precipitate the polymer by adding 100 ml of ethanol. If this was successful, the polymer was removed from the solution and dried. If the polymer remained a highly viscous liquid, residual toluene, monomers and ethanol were removed on a rotary evaporator and the polymer was dried. Drying was performed overnight at 60 ° C. under reduced pressure of an oil pump.

Analysis of the polymer: An Ubbelohde viscometer (capillary 0a, K = 0.005) temperature-controlled to 135 ° C. was used for the determination of the viscosity average molecular weight M _η . Decahydronaphthalene (decalin) prepared using 1 g / l of 2,6-di-t-butyl-4-methylphenol as a stabilizer was used as a solvent. The flow time was measured using a Viskoboy 2.

For the preparation of the polymer solution, 50 ml of decahydronaphthalene was added to 50 m of the polymer.
g, the solid was dissolved in a sealed flask at 135 ° C. without stirring overnight, and the solution was filtered hot before measurement. The capillary was flushed twice with the polymer solution to wash the capillary. Measurements were repeated until stable at a constant value or until enough measurements were obtained to obtain an average. Molecular weights M _η for EPM and EPDM were calculated using the Mark-Houwink constant for PE (k = 4.75 × 10 ⁻⁴ , a = 0.725).

[0042]

Table 2 Activity and molecular weight M _η

Values for dimethylmethylene bridged (Cp) (Flu) ZrCl ₂ (M. Arndt, W.
Kaminsky, A.-M. Schauwienold, U. Weingarten: Macromol. Chem. Phys. 199
Vol. 1135 (1988)) so that the molecular weights of EP can be compared using the modifications proposed by Scholte (TG Scholte, NLJ Meijerink, HM Schoffeleers, AM
G. Brands: J. Appl. Polym. Sci. Vol. 29 (1984) p. 3763). The comparison is shown in the graphs of FIGS. When the method of the present invention (Examples 4 to 9) is used, it is found that the molecular weight is considerably higher than the literature value. Table 3 shows various degrees of introduction.

[0044]

Table 3 Composition of the product

It can be seen that the degree of introduction of propylene in Example 4 is considerably improved as compared with the case of Example 10.

To determine the melting point range T _m , melting enthalpy ΔH _m, and glass transition point T _g , DSC measurements were performed using a DSC 821e manufactured by Mettler-Toledo. Calibration was performed using indium (T _m = 156.6 ° C.). 5-20 mg of substance for measurement
Is weighed in an aluminum pan, temperature range -100 ° C to 200 ° C, heating rate 20 ° C /
Measured in minutes. Of the data obtained by two heatings via intermediate cooling (−20 ° C./min), the data from the second heating was used. The values are summarized in Table 4.

[0047]

Table 4 DSC value of the product

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (71 Applicant D-51368 Leverkusen, Germany (72) Inventor Peter Shelter, Federal Republic of Germany Day-51373 Reefel Kusen, Karl-Lefex-Strase 42 (72) Inventor Walter Kaminsky, Federal Republic of Germany 25421 Pinneberg, Bushweg No. 52 (72) Inventor Ulrich Weingarten Germany Day 22145 Hamburg, Alaska Welk No. 8 (72) Inventor Ralph Werner Federal Republic of Germany Day 41539 Dolmagen, Walhofener-Strasse 37 F-term (reference) 4F071 AA15X AA20X AA21X AH19 BC01 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA00A BA00B BA01B BA02B BB00BBC BCBC BCB BCB BCB BCB BCB BC BC CA27A CA28A CA29A CA30A EB02 EB03 EB16 EB18 EC03 EC05 FA02 FA03 FA04 GA01 GA19 GA26 GB01 4J128 AA01 AB00 AB01 AC01 AC10 AC28 AD00 BA00A BA00B BA01B BA02B BB00A BB01B BB02B BC12B BC13BCA12A BC12A BC13A BC12A EC05 FA02 FA03 FA04 GA01 GA19 GA26 GB01

Claims (12)

[Claims] 1. A process for the polymerization of ethylene, propylene and optionally a non-conjugated diene using a metallocene as a catalyst, optionally in the presence of one or more cocatalysts, wherein the metallocene used is generally Formula (I): Wherein R ¹ -R ¹² independently represent H, C ₁ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl or C ₇ -C ₁₂ aralkyl, W is a carbon atom or optionally represents optionally substituted first 13, 15 or 16 atom, X is, H, halogen or C ₁ -C ₁₂ alkyl group, Y is optionally substituted C ₁ -C ₁₂ alkyl group or an optionally Represents a Group 14, 15 or 16 atom, and M represents a Group 4 metal. ] The compound characterized by the above-mentioned. 2. The method according to claim 1, wherein Y represents a carbon atom. 3. The method according to claim 2, wherein W represents a carbon atom and X represents a halogen atom. 4. The process according to claim 1, wherein 5-ethylidene-2-norbornene or 1,4-hexadiene is used as the non-conjugated diene. 5. The method according to claim 1, wherein the polymerization is carried out in a solution. 6. The process according to claim 1, wherein the polymerization is carried out in suspension. 7. The process according to claim 1, wherein the polymerization is carried out in the gas phase. 8. The method according to claim 1, wherein the compound represented by the general formula (I) is used in a supported form. 9. The process according to claim 1, wherein alumoxane is used as a cocatalyst. 10. The process according to claim 1, wherein one or more borates are used as cocatalysts. 11. A compound of the general formula (I): Wherein R ¹ -R ¹² independently represent H, C ₁ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl or C ₇ -C ₁₂ aralkyl, W is a carbon atom or optionally represents optionally substituted first 13, 15 or 16 atom, X is, H, halogen or C ₁ -C ₁₂ alkyl group, Y is optionally substituted C ₁ -C ₁₂ alkyl group or an optionally Represents a Group 14, 15 or 16 atom, and M represents a Group 4 metal. ] The compound represented by these. 12. Use of an ethylene / propylene copolymer or an ethylene / propylene / non-conjugated diene terpolymer which can be produced by the process according to claim 1 for the production of shaped articles of all kinds. .