For a long time, isotactic polymers have been of interest as plastic materials for manufacturing articles of relatively good deformation resistance, such as e. g. sheathings of household appliances. In general, such isotactic polymers with propylene as monomer are of highly crystalline nature and, therefore, relatively hard with little or no impact resistance at all so that they will come into question only for application fields in which those characteristics are desirable.

Most recently, various attempts have been made, aiming at preparing also polypropylene with elastic characteristics. European Printed Publication 0 707 016 Al specifies a catalyst composition and a process for preparing polyolefins. The catalysts specified in European Printed Publication 0 707 016 A1 are, in substance, made up of a metallocene compound having an indene ring and a fluorene ring which are bridged via C, Si or Ge. In case of the metallocene compound, it, in this connexion, is obviously essential that, in the indene ring system, at least the residue denoted with R4 not be hydrogen. When that residue R4 is hydrogen, the effects, such as specified in the aforementioned European Patent Application, will not be attained (P 6, from L 57 up to P 7, L 3). The polymers specified in European Printed Publication 0 707 016 Al and prepared with metallocenes, here espe- cially the polypropylene prepared with those metallocenes, however, show as can be drawn from the examples and the graphs, but unsatisfactory characteristics in regard of the elastic behaviour.

Departing from all these facts, it is the object of the present invention to find a new catalysator combination and to suggest a process to make polymers from olefinically unsaturated compounds available, not only showing thermoplastic but, at the same time, thermoplastic-elastic characteristics and, thus, being applicable for many application fields.

That object is, in regard of the catalysator combination, solved by the characterising features of Claim 1; in regard of the process for preparing the polymers, it is solved by the characterising features of Claim 5.

The invention relates to a new catalyst combination containing a metal complex and an activator.

The metal complex is a metallocene compound.

Herewith, metal compounds of the Fourth Auxiliary Group of the Periodic System Table IVB generally come into question, which compounds may be present as defined metal complexes and with which compounds activators are mixed. In general, the metals are present in the complexes in formally positively charged manner.

As regards the metals, titanium, zirconium, hafnium, vanadium, niobium, and tantalum specifically come into question, the metal atom preferably showing <BR> <BR> <BR> <BR> halogen or a Ci-Cs alkyl, aryl or benzyl as residue X.

The metallocene is defined by general Formula I.

wherein the residues R1-R'are a linear or branched Ci-Cio alkyi, a 5-7-linked cycloalkyl that, in its <BR> <BR> <BR> turn, may carry one or several Ci-Ce alkyl residues<BR> <BR> <BR> <BR> <BR> as substituents, a C6-Cis aryl, aryl alkyl or alkyl aryl, in which case Rl, R2; R3, R4; and R6, R, here again, may be partially or simultaneously integrated

into 5-7-linked cycloalkyl or aryl rings fused thereto.

In case of the metallocene compound according to general Formula I, it is essential that, in general Formula I, the carbon atom adjacent to the residue R7 and the carbon atom adjacent to the residue R6 be, with the indene ring system, only hydrogen. Thereby, it is ensured that, with the indene ring system, a linear system can form by the residues R6 and R, which system, obviously, will prove to be especially advantageous when preparing the isotactic elastomers according to the invention. In contrast to the metallocene complex according to European Printed Publication 0 707 016 Al, only hydrogen atoms and no carbon atoms with further residues, as is imperative in the aforementioned European laying-open specification, can, thus, be found at the positions mentioned in the aforegoing.

In this connexion, suitable bridging structural units E are 1.2-ethyl, 1.3-propyl, 1.4-butyl, carbon, silicon or germanium. For the case that E is carbon, silicon or germanium, the bridging structural unit E may, herewith, additionally carry the residues R9 and R10 which, then, are a C1-Ca alkyl, a 4-7-linked cycloalkyl or aryl, R9 and R1° being able to also form a 4-7-linked cycloalkyl or aryl jointly with E.

A particularly preferred embodiment of the invention resides in that such a metallocene complex is used as reflected by general Formula VII. wherein all the residues have the significations indicated above. In contrast to the metallocene complex according to general Formula I, it, however, now is imperative here on the indene ring system that another ring fused thereto be at hand which is bridged via two E2 groups.

E2 therewith, signifies CH2, oxygen or sulphur and n is 1 or 2.

As defined in Patent Claim 1, it certainly is furthermore provided in accordance with the invention, to additionally use at least also one activator, apart from the metallocene compounds specified above. The invention, herewith, generally encompasses all the activators that have as yet become known in the state-of-the-art for metallocene compounds. Such activators have also been specified by European Printed Publication 0 707 016 Al. As activator, at least one compound of general Formulas II to VI is, however, used with special preference.

Accordingly, the activator may be an open-chai or cyclic alumoxane compound of general Formula II or III, such as is reflected hereinafter:

wherein RB is a Ci-C4 alkyl group and n is a number between 5 and 30.

In case of the catalyst combination according to the invention, also the above-specified compounds of general Formulas II and III can, alone or in combination with the subsequent activators such as are reflected by general Formulas IV to VI, be used.

R93C[B(C6F5)4](V)B(C6F5)3(IV) H][B(C6F5)4](VI)R9CN In general Formulas IV to VI, R9, in this connexion, signifies a Ci-C4 alkyl group or an aryl group.

It has, therewith, proven to be especially favourable when the metallocene complex according to general Formula I and the activator according to general Formulas II to VI are employed in such quantities that the atomic ratio between aluminium from the alumoxane or boron from the cationic activator and the transition metal from the metallocene complex is within the range of from 1: 1 to 106: 1.

The invention furthermore relates to a process for preparing linear, thermoplastic-elastic polymers from olefinically unsaturated compounds with an isotactic arrangement of the monomer unit and a statistic dis- tribution of isolated stereoscopic errors along the

individual chains, tacticity varying within the range <BR> <BR> <BR> of between 25 and 60 % [mmmm] pentad concentration. A regular sequence of isotactic and atactic blocks, therewith, is excluded. In many cases, it was found that the [rmrm] pentad was totally missing or present with a maximum of 2.5 % of the entire pentad area.

Furthermore, it became evident that, in most cases, the [rrrr] and [rrrm] pentads are always greater than the [rmrm] pentad. The process according to the invention is specifically characterised in that a specially selected catalyst combination is used as described before.

Pressures of from 1 to 100 bars, preferably of from 3 to 20 bars and in particular of from 5 to 15 bars, have proven to be suitable reaction parameters for preparing the linear, thermoplastic, elastomeric olefin polymers. Favourable temperatures are within the range of from-50 °C to 200 °C, of preference at from 100 to 150 °C and of high preference at from 20 to 50 °C.

The polymerisation reactions can be carried out in the gas phase, in suspension and in supercritical monomers and especially in solvents inert under polymerisation conditions. In particular the solution polymerisation has proven to be the clearly superior thing for the present preparation process. Suitable inert solvents for that purpose are such solvents that do not contain any reactive groups in the molecule, i. e. aromatic solvents like benzole, <BR> <BR> <BR> toluol, xylol, ethyl benzole or alkanes such as e. g. propane, n-butane, i-butane, pentane, hexane, heptane or mixtures thereof.

The polymers prepared according to the invention are linear, thermoplastic, elastic polymers from an

olefinically unsaturated compound with an isotactic arrangement of the monomer units and a statistic distribution of isolated stereoscopic errors along the individual chains and a mean molecular weight Mw of the polymers within the range of from 100,000 to 800,000 gms/mol and a TG of from-50 to +30.

With the polymer prepared according to the invention, it is essential that the stereoscopic errors be situated in the polymer chain itself and that, thus, a specific pentad concentration result. In this connexion, it was found that, with the polymers prepared according to the invention, the [rmrm] pentad with a maximum of 2.5 % of the entire pentad area will, in general, be present. In many cases, it was also found that that [rmrm] pentad was completely missing.

Furthermore, it became evident that, in most cases, the [rrrr] and [rrrm] pentads are always greater than the [rmrm] pentad. Determination of the pentad concentration in case of polymers has, properly speaking, become known from the state-of-the-art and is specified e. g. in J. A. Ewen,"Catalytic Polymerisation of Olefins", Eds. T. Keii, K. Soga; Kodanska Elsevier Pub.; Tokyo, 1986, P 271 et seqq.

Also the pentad concentration determination according to the invention now present was carried out by means of the method specified in the above-mentioned piece of pertinent literature.

Apart from the above-mentioned specific pentad concentration, the linear, isotactic polymers have a molecular weight within the range of from 100,000 to 800,000, of preference from 110,000 to 500,000 and of special preference within the range of from 120,000 to 300,000 gms/mol. The mean molecular weights Mw

(mean weight value) of the polymers were measured by means of the gel permeation chromatography (GPC) method at 135 °C with microstyragel as column material and 1,2,4-trichlorobenzole as solvent against closely distributed polypropylene standards.

The molecular weight distribution Mw/Mn (mean weight value/mean numerical value) of the polymers was likewise measured by means of the gel permeation chromatography method and generally amounts to from 1.2 to 3.5.

In addition to all that, the polymers show a glass transition temperature Tg within the range of from -50 °C to +30 °C, of special preference a Tg of from -20 °C to +10 °C. The glass transition temperature was determined by means of the DSC method.

The linear, isotactic polymers prepared according to the invention present, after all, a structure of one <BR> <BR> <BR> or several C2-Cao olefins. In this case, the olefin<BR> <BR> <BR> <BR> is preferred to be a C3-C20-Alk-l-ene. Examples of<BR> <BR> <BR> <BR> such C3-C20-Alk-l-enes are: propene, 1-butene, 2- butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1- decene, 1-dodecene, 1-hexadecene, 1-octadecene, 1- eicosene.

Apart from the already mentioned olefins, also Cs- Czo cycloolefins are of the especially suitable kind.

Examples thereof are cyclopentene, cyclohexene, norbornadiene and its derivatives.

In case of the linear, isotactic polymers, polypropylene is especially preferred. Further suitable polymers are copolymers from propylene and a <BR> <BR> <BR> C4-C20 olefin or a cycloolefin. It is also possible to prepare terpolymers which show the characteristics defined in Patent Claim 1 when they present a

structure of propylene, a C2-C20 olefin and a cycloolefin.

The polymers prepared according to the invention are e. g. soluble in toluol at a temperature within the range of from 20 to 80 °C; they show a distinct elastic behaviour in a tensile-strength test, measured with a"Standard Universal Testing Machine ZWICK 1445", as specified in the examples, and, in general, possess a crystallisation melting temperature, measured by means of the"Differential Scanning Calometry" (DSC) method within the range of from-50 °C to 150 °C. In particular, it has to be emphasised that, also in this case, the polymers clearly differ, in regard of their elastic- thermoplastic behaviour, from the state-of-the-art, i. e. from European Printed Publication 0 707 016 A1 mentioned in the introductory part to the Description. This being so, the polymers prepared according to the invention are particularly suited for the manufacture of articles of relatively good deformation resistance, such as e. g. sheathings for household appliances. Furthermore, it is worth mentioning that the polymers can be used in polymer mixtures for impact resistance modification. Due to their elastic characteristics, the polymers are especially suited for elastic sheets, moulded bodies, and gaskets.

The present invention will, hereinafter, be explained in more detail on the basis of several preparation examples of the catalysts and on the basis of polymerisation examples. Herewith, there show: Fig. 1 tensile-strength measurements on two polymers prepared according to the

invention, as compared to two polymers from European Printed Publication 0 707 016 Al, Fig. 2 an X-ray structure analysis of a metallocene complex according to the invention, Fig. 3 a nuclear magnetic resonance (NMR) spectrum of a polymer prepared according to the invention, and Fig. 4 a nuclear magnetic resonance (NMR) spectrum of another polymer prepared according to the invention.

Fig. 1 now illustrates the tensile-strength measurements of two selected examples from European Printed Publication 0 707 016 Al, as compared to two polymers prepared in accordance with the invention.

By the remarks"Cf. Fig. 4"and"Cf. Fig. 5"in Fig.

1, the corresponding examples from European Printed Publication 0 707 016 Al are meant in this case. As can be drawn from a comparison of those tensile- strength curves with the tensile-strength curves of the polymers (PP 36 and PP 45) prepared according to the invention, the polymers according to the invention show a distinctive, rubber-elastic plateau.

Contrary thereto, the polymers according to European Printed Publication 0 707 016 A1 present either a flow behaviour (Fig. 4) or the polymer breaks in case of higher expenditures of force (Fig. 5). It is just that comparison that clearly illustrates the surprising characteristics of the polymers prepared according to the invention and showing a distinctive, rubber-elastic behaviour.

Catalyst preparation Obtaining of 5.6-cyclopenta-2-methyl-indane-1-one 40.4 mL of methacryl acid chloride (387.9 mmols) are, together with 62.06 gms of anhydrous aluminium chloride (20 mol% in excess), incorporated into 250 mL of CH2Cl2, cooled down to-78 °C, and slowly mixed with 50.0 mL of indane (45.84 gms, 387.9 mmols). As the indane is added, the colour changes from bright yellow to orange. The mixture is carefully quenched with diluted HCl*aq, washed with hydrous KzCOa solution and water, and dried through Na2SO4.

Yield: 70.07 gms (376.2 mmols) of oily product, 97.0 <BR> <BR> <BR> % of the theory NMR (200 mcps, CDC13 7.24 ppm): 8<BR> <BR> <BR> <BR> <BR> 1.25 ppm d (J = 6.9 cps) 3 H methyl group, 8 2.10 ppm m (J = 3.7 to 7.6 cps) 2 H aliphatic protons of the cycles, 8 2.62 ppm m 2 H aliphatic protons of the indanone ring, 8 2.86 ppm m (J = 11 to 14 cps) 4 H aliphatic protons of the cycles, 8 3.25 ppm m (J = 7.0 cps) 1 H aliphatic proton of the indanone system, <BR> <BR> <BR> 8 7.21 and 7.51 ppm s 2 H aromatic MS (GC-MS) m/z 186 (M+ 100 %), (186,251 mol-1).

Obtaining of 5.6-cyclopenta-2-methylindane-1-ole 70.07 gms (376.2 mmols) of the 2-methyl-5.6- cyclopentylindane-1-one are, with 5 gms of LiAlH4, reduced in 200 mL of EtaO by letting the ketone drip (2 hrs) slowly towards an ice-cooled suspension of LiAlH4. Agitating is effected all through the night and quenching with Hz0 is carried out, the colour of the solution changing from lime green to bright yellow. Now 15 mL of HCl are added in concentrated manner and the emulsion is agitated for 1 h. The etherial phase is separated, neutralised with 200 mL of KzCO3 solution, and three times washed with water.

Thereafter, drying is effected through Na2SO4 and the solvent is completely removed. A crystalline mixture of the diastereomeric 1-indanoles is obtained. NMR <BR> <BR> <BR> <BR> (200 mcps, CDCl3): 6 1.13 ppm d 3 H methyl group, 8<BR> <BR> <BR> <BR> <BR> <BR> 1.76 ppm wide 1 H OH group, 6 2.05 ppm m 2 H aliphatic protons of the cycles, 8 2.15 to 2.71 ppm m 2 H aliphatic protons of the indanole ring, 8 2.87 ppm m 4 H aliphatic protons of the cycles, 8 3.08 ppm 1 H aliphatic proton of the indanole system, 6 4.17 and 4.93 ppm d 2 H with OH function on the indanole ring, 8 7.08 and 7.23 ppm d 2 H aromatic.

Yield: 69.62 gms, 369.8 mmols, 98.3 % of the theory MS (GC-MS) m/z 188 (M+ 100 %), (188.267 gms mol~1).

Obtaining of 5.6-cyclopenta-2-methylindene 69.62 gms (369.8 mmols) of the diastereomer mixture of the 2-methyl-5.6-cyclopentylindene-1-oles are dissolved in 500 mL of benzole; and then 3 to 5 gms <BR> <BR> <BR> <BR> of p-TosOH are added and the emulsion is, for three quarters of an hour, boiled on the water separator under reflux. The organic phase is separated, neutralised with 200 mL of KzC03 solution, and three times washed with water. Thereafter, drying is effected through Na2SO4 and the solvent is completely removed.

The product colourlessly crystallises from n-pentane; yield: 57.67 gms, 338.7 mmols corresponding to 91.6 % of the theory MS (GC-MS) m/z 170 (M+ 100 %), (170.225 gms mol-1). NMR (200 mcps, CDC13 7,24 ppm): 8 2.23 ppm m/s 5 H methylene and 2-methyl group of the indene <BR> <BR> <BR> <BR> system, b 3.01 ppm t 4 H methylene groups, 8 3.32 ppm<BR> <BR> <BR> <BR> <BR> <BR> s 2 H methylene group acids, 8 6.51 ppm s 1 H ole- finic indene system, 8 7.20 and 7.34 ppm s 2 H

aromatic, 13-NMR (200 mcps, CDC13): 8 16.8 ppm methyl group, 5 25.8 ppm methylene group of Cycle 5, <BR> <BR> <BR> 8 32.66 and 32.72 ppm methylene groups of the Cycle,<BR> <BR> <BR> <BR> 8 42.2 ppm methylene group of the indene system, 6<BR> <BR> <BR> <BR> <BR> 127.1 ppm tertiary C-atom of the indene system, 8 115.5 and 119.5 (each with H) ppm aromatic C-atoms, the same without H for 139.6,141.7,142.1,144.4, and 145.0 ppm incl 4° olefinic C-atom of the indene system (cf. CH correlation and HH-COSY).

Obtaining of 1- (9 fluorenyl)-2 (1- (5. 6-cyclopenta-2- methyl) indenyl) ethane 3.89 gms of 2-methyl-5.6-cyclopentylindene-1 (22.85 mmols) are, with 14.3 mL of n-BuLi, deprotonated in 150 mL of dioxane and then mixed with a solution of 25.13 mmols of 2- (9'-fluorenyl) ethyltrifluoromethane sulphonate in 100 mL of dioxane. Agitating is effected all through the night, heating up to 60 °C is carried out for half an hour and the solution is quenched with ca. 3 mL of H20. The dioxane is removed and the product is extracted with three times 200 mL of Et20. Without chromatographic processing, 6.49 gms (17.9 mmols, 78.3 % of the theory) of a colourless, crystalline Product are obtained.

NMR (200 mcps, CDC13,7.24 ppm): 8 1.89 ppm s 3 H methyl group, 8 1.41 ppm to 1.72 ppm m 4 H aliphatic protons of the bridge, 8 2.10 ppm pseudo-t 2 H <BR> <BR> <BR> aliphatic protons of the cycle, 8 2.90 ppm pseudo-t 4 H aliphatic protons of the cycle, 8 3.87 ppm t 1 H <BR> <BR> <BR> aliphatic proton of the fluorene system, 8 6.40 ppm s<BR> <BR> <BR> <BR> <BR> 1 H indene proton, 8 6.98 and 7.07 ppm aromatic pro- tons of the indene system, 8 7.31 to 7.77 ppm m 8 H aromatic of the fluorene. MS (FD) m/z 362.5 (M+ 100 %).

Obtaining of 1- (9 fluorenyl)-2 » (5.6-cyclopenta-2- methyl) indenyl) ethane zirconocene dichloride 1.711 gms of 1- [1'- (2'-methyl) 5', 6'- cyclopentylindenyl-2- (9"-fluorenyl)] ethane (4.72 mmols) are dissolved in 100 mL of toluol, mixed with 10 mL of dioxane, and deprotonated, at low temperature, with 5.9 mL of n-BuLi. Agitating is effected for ca. 1 hour and then the suspension is again cooled down to-78 °C. Now 1.10 gm of ZrCl4 is added. That suspension is agitated, at room temperature, for another 14 hours, in which case a fine red powder forms that can be crystallised after a separation of formed LiCl from toluol.

Yield: 2.148 gms (4.11 mmols, 87.1 % of the theory).

NMR (500 mcps, ChCl4 80 °C); 8 2.00 ppm m 2 H methylene group cyclopentane ring (J = 6.8 to 7.5 cps),. 8 2.15 ppm s 3 H methyl group, 8 2.79 to 2.94 ppm m 4 H methylene groups cyclopentane ring adjacent to the aromatic system (J = 7.5 to 9.7 cps), 8 4.05 ppm m (J = 3.5 to 13.2 cps) 2 H aliphatic protons of the bridge (in case of the fluorene), 8 3.83 and 4.57 ppm m (J = 4.2 to 10.0 cps) 1 H aliphatic protons of <BR> <BR> <BR> the bridge (diastereotopic) at a time, 8 6.05 ppm s 1 H indene proton, 8 7.03 to 7.85 ppm m 10 H aromatic.

MS (El) m/z 5,22,6 isotopic pattern corresponding EA CH-combustion analysis: calculated 64.35 % C 4, 63 % H Found: 64.08/63.89% 4.53/4.63%

Polymerisation example All the polymerisations were carried out in 300 mL of toluol under the conditions indicated in Table 1.

The NMR data were measured by means of a Bruker AMX 500 device and evaluated on the basis of literature data.

Toble 1 Run No. Catalyst Amount# Tp [°C] C3 [mol(#-1) Yield [g] tp [min] ctivity* Tg [°C] Tm[°C] M1 P 36 Flu-Et-Ilnd 7,5 30 2,9 36,87 33 3080 -5,9 50,2 171.@ P 45 Flu-Et-Ilnd 10 35 4,92 115,23 39 3603 -7,5 51,7 95.@ Run No. Pentaden mmmm mmmr rmmr mmrr mmrm + rmrr rmrm rrrr rrrm mr in % P 36 36,7 18,5 2,1 21,1 5,0 0,0 2,5 3,7 1 P 45 36,5 17,9 1,7 21,0 5,8 0,3 3,1 3,6 1 #in µmol *kgPP/mol[Zr]mol[C3]h