Process for preparing cycloolefin polymers.

The invention relates to a process for the production of homopolymers and copolymers of polycyclic olefins, with no ring opening taking place.

It is known that polycyclic olefins can be polymerized using various Ziegler catalysts. Depending on the catalyst, the polymerization proceeds via ring opening (cf. US 3,557,072 and US 4,178,424) or opening of the double bond (cf. EP 156 464, EP 283 164, EP 291 208, EP 291 970).

The disadvantage of a ring-opening polymerization is that the polymer obtained contains double bonds which can lead to chain crosslinking and thus considerably restrict the processability of the material by extrusion or injection molding.

The polymerization with the opening of the double bond leads to a relatively low polymerization rate (conversion rate) in the case of cyclic olefins.

In the case of monocyclic olefins, a stereorigid chiral metallocene compound such as ethylene bis (indenyl) zirconium dichloride can be used as the catalyst, the polymerization being carried out with the ring being retained (cf. EP 304 671).

In the propylene copolymers known to date from the aforementioned publications, the viscosity number is below 20 cm³ / g and the glass transition temperature of the copolymers of ethylene with norbornene does not exceed 100 ° C.

The object was to find a process which allows, in the copolymerization of polycyclic olefins with acyclic olefins, polymers with a viscosity number greater than 20 cm 3 / g and a glass transition temperature above 100 ° C. to be obtained.

It has been found that the object can be achieved by using a certain metallocene as a catalyst.

The invention thus relates to a method for producing a cycloolefin polymer by polymerizing 0.1 to 100% by weight, based on the total amount of monomers, of at least one monomer of the formulas I, II, III or IV<chemistry id="chem0001" num="0001"><img file="EP0407870A2_D0001.tif" /></chemistry> in which R¹ R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and denote a hydrogen atom or a C₁-C₈-alkyl radical, where the same radicals in the different formulas can have a different meaning, 0 to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula V.<chemistry id="chem0002" num="0002"><img file="EP0407870A2_D0002.tif" /></chemistry> wherein n is a number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula VI<chemistry id="chem0003" num="0003"><img file="EP0407870A2_D0003.tif" /></chemistry> wherein R⁹, R¹⁰, R¹¹ and R¹² are the same or different and represent a hydrogen atom or a C₁-C₈-alkyl radical, in solution, in suspension or in the gas phase, at a temperature of -78 to 150 ° C, at a pressure of 0 , 5 to 64 bar, in the presence of a catalyst which consists of a metallocene as transition metal component and an aluminoxane of the formula VII<chemistry id="chem0004" num="0004"><img file="EP0407870A2_D0004.tif" /></chemistry> for the linear type and / or formula VIII<chemistry id="chem0005" num="0005"><img file="EP0407870A2_D0005.tif" /></chemistry> for the cyclic type, wherein in formulas VII and VIII R¹³ is a C₁-C₆ alkyl group or phenyl or benzyl and n is an integer from 2 to 50, characterized in that the polymerization is carried out in the presence of a catalyst, the Transition metal component at least one compound of formula IX<chemistry id="chem0006" num="0006"><img file="EP0407870A2_D0006.tif" /></chemistry> is what M¹ is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R¹⁴ and R¹⁵ are the same or different and represent a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group C₇-C₄₀-arylalkyl group, a C₇-C₄₀-alkylaryl group or a C₈-C₄₀-arylalkenyl group, R¹⁶ and R¹⁷ are the same or different and a mono- or polynuclear hydrocarbon radical, which can form a sandwich structure with the central atom M¹, R¹⁸<chemistry id="chem0007" num="0007"><img file="EP0407870A2_D0007.tif" /></chemistry> = BR¹⁹ = AlR¹⁹, -Ge-, -Sn-, -O-, -S-, = SO, = SO₂, = NR¹⁹, = CO, = PR¹⁹ or = P (O) R¹⁹, where R¹⁹, R²⁰ and R²¹ are the same or are different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ fluoroalkyl group, a C₆-C₁₀ fluoroaryl group, a C₆-C₁₀ aryl group, a C₁-C₁₀ alkoxy group, a C₂-C₁₀- Alkenyl group, a C₇- C₄₀ aryl alkyl group, represent a C₈-C₄₀-arylalkenyl group or a C₇-C₄₀-alkylaryl group or R¹⁹ and R²⁰ or R¹⁹ and R²¹ each form a ring with the atoms connecting them, and M² is silicon, germanium or tin.

In the process according to the invention, at least one polycyclic olefin of the formulas I, II, III or IV, preferably a cycloolefin of the formulas I or III,<chemistry id="chem0008" num="0008"><img file="EP0407870A2_D0008.tif" /></chemistry> wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and represent a hydrogen atom or a C₁-C₈-alkyl radical, where the same radicals in the different formulas can have a different meaning, polymerized.

If appropriate, a monocyclic olefin of the formula V<chemistry id="chem0009" num="0009"><img file="EP0407870A2_D0009.tif" /></chemistry> where n is a number from 2 to 10 is used. Another comonomer is an acyclic 1-olefin of the formula VI,<chemistry id="chem0010" num="0010"><img file="EP0407870A2_D0010.tif" /></chemistry> wherein R⁹, R¹⁰, R¹¹ and R¹² are the same or different and represent a hydrogen atom or a C₁-C₈ alkyl radical. Ethylene or propylene are preferred.

In particular, copolymers of polycyclic olefins of the formulas I and III are produced.

The polycyclic olefin (I to IV) in an amount of 0.1 to 100 wt .-%, the monocyclic olefin (V) in an amount of 0 to 99.9 wt .-% and the acyclic 1-olefin (VI ) in an amount of 0 to 99.9% by weight, based in each case on the total amount of the monomers.

The monomers are preferably used in the following proportions:<ul id="ul0001" list-style="none"><li>a) the molar monomer ratio of polycyclic olefin (I to IV) to 1-olefin (VI) in the corresponding polymers is 1:99 to 99: 1, preferably 20:80 to 80:20;</li><li>b) in the case of polymers composed of polycyclic olefins (I to IV) and monocyclic olefins (V), the molar ratio of polycyclic olefin to monocyclic olefin is 10:90 to 90:10;</li><li>c) in the case of polymers composed of polycyclic olefins (I to IV), monocyclic olefins (V) and 1-olefins (VI), the molar monomer ratio of polycyclic olefin to monocyclic olefin to 1-olefin is 93: 5: 2 to 5: 93: 2 to 5: 5: 90, ie the molar ratio lies within a mixture triangle, the corners of which are determined by the molar ratios 93: 5: 2, 5: 93: 2 and 5: 5: 90;</li><li>d) in the indications a), b) and c) are as polycyclic olefins; monocyclic olefins and 1-olefins to understand mixtures of two or more olefins of the respective type.</li></ul>

The catalyst to be used for the process according to the invention consists of an aluminoxane and at least one metallocene of the formula IX<chemistry id="chem0011" num="0011"><img file="EP0407870A2_D0011.tif" /></chemistry>

In formula IX, M¹ is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium and hafnium.

R¹⁴ and R¹⁵ are the same or different and represent a hydrogen atom, a C₁-C₁₀, preferably C₁-C₃ alkyl group, a C₁-C₁₀, preferably C₁-C₃ alkoxy group, a C₆-C₁₀, preferably C₆-C₈ aryl group , a C₆-C₁₀-, preferably C₆-C₈-aryloxy group, a C₂-C₁₀-, preferably C₂-Cyl-alkenyl group, a C₇-C₄₀-, preferably C₇-C₁₀-arylalkyl group, a C₇-C₄₀-, preferably C₇-C₁₂ -Alkylaryl group, a C₈-C₄₀, preferably C₈-C₁₂ arylalkenyl group or a halogen atom, preferably chlorine.

R¹⁶ and R¹⁷ are the same or different and mean a mono- or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M¹.

Preferably R¹⁶ and R¹⁷ are either both indenyl or tetrahydroindenyl or R¹⁶ fluorenyl and R⁴ cyclopentadienyl.

R¹⁸ is a single or multi-unit bridge; which links the radicals R¹⁶ and R¹⁷ and means<chemistry id="chem0012" num="0012"><img file="EP0407870A2_D0012.tif" /></chemistry> = BR¹⁹ - AlR¹⁹, -Ge-, -Sn-, -O-, -S-, = SO, = SO₂, = NR¹⁹, = CO, = PR¹⁹ or = P (O) R¹⁹, where R¹⁹, R²⁰ and R²¹ are the same or are different and are a hydrogen atom, a halogen atom, preferably chlorine, a C₁-C₁₀-preferably C₁-C₃-alkyl group, in particular methyl group, a C₁-C₁₀-fluoroalkyl group, preferably CF₃ group, a C₆-C₁₀-fluoroaryl group, preferably pentafluorophenyl group, a C₆-C₁₀, preferably C₆-C₈ aryl group, a C₁-C₁₀, preferably C₁-C₄ alkoxy group, in particular methoxy group, a C₂-C₁₀-, preferably C₂-C₄-alkenyl group, a C₇-C₄₀-, preferably C₇-C₁₀-arylalkyl group, a C₄₀-C₄₀-, preferably C₈-C₁₂-arylalkenyl group or a c₇-C₄₀-, preferably C₇ -C₁₂-alkylaryl group, or R¹⁹ and R²⁰ or R¹⁹ and R²¹ each form a ring together with the atoms connecting them.

M² is silicon, germanium or tin, preferably silicon or germanium.

R¹⁸ is preferably = CR¹⁹R²⁰, = SiR¹⁹R²⁰, = GeR¹⁹R²⁰, -O-, -S-, = SO, = PR¹⁹ or = P (O) R¹⁹.

The metallocenes can be prepared according to the following reaction scheme:<chemistry id="chem0013" num="0013"><img file="EP0407870A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0407870A2_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP0407870A2_D0015.tif" /></chemistry>

The above reaction scheme of course also applies to the cases R¹⁶ = R¹⁷ and / or R¹⁹ = R²⁰ and / or R¹⁴ = R¹⁵.

Metallocenes used with preference are: rac-dimethylsilyl-bis- (1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis- (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis- (1-indenyl) zirconium dichloride, rac-phenylvinylsilyl-bis- (1-indenyl) zirconium dichloride, 1-silacyclobutyl-bis- (1-indenyl) zirconium dichloride, rac-ethylene-bis- (1'-indenyl) zirconium dichloride, rac-diphenylsilyl-bis- (1-indenyl) hafnium dichloride, rac-phenylmethylsilyl-bis- (1-indenyl) hafnium dichloride, rac-dimethylsilyl-bis- (1-indenyl) hafnium dichloride, rac-diphenylsilyl-bis- (1-indenyl) zirconium dichloride, Diphenylmethylene (9-fluorenyl) cyclopentadienyl zirconium dichloride, Isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride or their mixtures.

The following are particularly preferred: rac-dimethylsilyl-bis- (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis- (1-indenyl) zirconium dichloride, rac-phenylvinylsilyl-bis- (1-indenyl) zirconium dichloride, 1-silacyclobutyl-bis- (1'-indenyl) zirconium dichloride, rac-ethylene-bis (1-indenyl) zirconium dichloride, rac-diphenylsilyl-bis- (1-indenyl) zirconium dichloride, Diphenylmethylene (9-fluorenyl) cyclopentadienyl zirconium dichloride, Isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride or their mixtures.

The cocatalyst is an aluminoxane of formula VII<chemistry id="chem0016" num="0016"><img file="EP0407870A2_D0016.tif" /></chemistry> for the linear type and / or formula VIII<chemistry id="chem0017" num="0017"><img file="EP0407870A2_D0017.tif" /></chemistry> for the cyclic type. In these formulas, R¹³ represents a C₁-C₆ alkyl group, preferably methyl, ethyl or isobutyl, butyl or neopentyl, or phenyl or benzyl. Methyl is particularly preferred. n is an integer from 2 to 50, preferably 5 to 40. However, the exact structure of the aluminoxane is not known.

The aluminoxane can be made in a number of ways.

In one of the processes, finely powdered copper sulfate pentahydrate is slurried in toluene and so much aluminum trialkyl is added in a glass flask under inert gas at about -20 ° C. that about 1 mol of CuSO₄ · 5H₂O is available for every 4 Al atoms. After slow hydrolysis with elimination of alkane, the reaction mixture is left at room temperature for 24 to 48 hours, cooling being necessary, if necessary, so that the temperature does not rise above 30.degree. The aluminoxane dissolved in the toluene is then filtered off from the copper sulfate and the solution is concentrated in vacuo. It is believed that in these manufacturing processes the low molecular weight aluminoxanes condense to form higher oligomers with the elimination of aluminum trialkyl.

Furthermore, aluminoxanes are obtained if aluminum trialkyl, preferably aluminum trimethyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted with aluminum salts, preferably aluminum sulfate, containing water of crystallization at a temperature of -20 to 100.degree. The volume ratio between solvent and the aluminum alkyl used is 1: 1 to 50: 1 - preferably 5: 1 - and the reaction time, which can be controlled by splitting off the alkane, is 1 to 200 hours - preferably 10 to 40 hours.

Of the aluminum salts containing water of crystallization, those which have a high content of water of crystallization are used in particular. Aluminum sulfate hydrate is particularly preferred, especially the compounds Al₂ (SO₄) ₃ · 16H₂O and Al₂ (SO₄) ₃ · 18H₂O with the particularly high crystal water content of 16 or 18 mol H₂O / mol Al₂ (SO₄) ₃.

A further variant for the preparation of aluminoxanes consists in dissolving aluminum trialkyl, preferably aluminum trimethyl, in the suspension medium, preferably in the liquid monomer, in heptane or toluene, which is then placed in the polymerization vessel, and then reacting the aluminum compound with water.

In addition to the previously described processes for the production of aluminoxanes, there are others which are useful. Regardless of the type of production, all aluminoxane solutions have in common a changing content of unreacted aluminum trialkyl, which is present in free form or as an adduct. This content has a not yet clarified influence on the catalytic activity, which differs depending on the metallocene compound used.

It is possible to preactivate the metallocene with an aluminoxane of the formula II and / or III before use in the polymerization reaction. This significantly increases the polymerization activity.

The preactivation of the transition metal compound is carried out in solution. The metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon. Toluene is preferably used.

The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total solution. The metallocene can be used in the same concentration, but it is preferably used in an amount of 10-1 mol per mol of aluminoxane. The preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 ° C to 100 ° C, preferably 0 to 70 ° C.

A significantly longer pre-activation is possible, but it usually does not increase activity or reduce activity, but it can be useful for storage purposes.

The polymerization is carried out in an inert solvent customary for the Ziegler low-pressure process, for example in an aliphatic or cycloaliphatic hydrocarbon; such as, for example, butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane. Furthermore, a gasoline or hydrogenated diesel oil fraction that has been carefully freed from oxygen, sulfur compounds and moisture can be used. Toluene can also be used.

Finally, the monomer to be polymerized can also be used as a solvent or suspending agent. In the case of norbornene, such bulk polymerizations are carried out at a temperature above 45 ° C. The molar mass of the polymer can be regulated in a known manner; hydrogen is preferably used for this purpose.

The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more stages at a temperature of -78 to 150 ° C., preferably -20 to 80 ° C. The pressure is 0.5 to 64 bar and is obtained either by the gaseous olefins or with the aid of inert gas.

Continuous and multi-stage processes are particularly advantageous because they enable the polycyclic olefin to be used rationally. In the case of continuous processes, the polycyclic olefin, which can be obtained as a residual monomer together with the polymer, can also be recovered and returned to the reaction mixture.

The metallocene compound is used in a concentration, based on the transition metal, of 10⁻³ to 10⁻⁷, preferably 10⁻⁵ to 10⁻⁶ mol transition metal per dm³ reactor volume. The aluminoxane is used in a concentration of 10⁻⁴ to 10⁻¹, preferably 10⁻⁴ to 2 · 10⁻² mol per dm³ reactor volume, based on the aluminum content. In principle, however, higher concentrations are also possible. In order to combine the polymerization properties of different metallocenes, it is possible to use mixtures of several metallocenes.

Compared to the known state of the art, the method according to the invention is characterized in that the zirconium compounds used with preference are very temperature-stable in dilute solution, so that they can also be used at temperatures up to 80.degree.

In the preparation of copolymers, the molar ratios of the polycyclic olefin to the 1-olefin used can be varied within a wide range. The incorporation rate of comonomer can be controlled almost arbitrarily by the choice of the polymerization temperature, the concentration of the catalyst components and the molar ratio used. An incorporation rate of more than 40 mol% is achieved with norbornene.

The average molecular weight of the copolymer formed can be varied in a known manner by varying the catalyst concentration or the temperature.

The polydispersity M_w/ M_n the copolymers are quite narrow with values ​​between 2.9 - 6.0 (4.5), but differ from the molar mass distributions of the polyethylenes and polypropylenes M produced with this catalyst system_w/ M_n = 2 clearly. This results in a property profile of the polymers, which makes them particularly suitable for injection molding.

The copolymerization of the polycyclic olefins with the acyclic olefins, especially with propylene, results in polymers with a viscosity number greater than 20 cm³ / g. For copolymers of norbornene with acyclic olefins, especially ethylene, the glass transition temperature is above 100 ° C.

In the polymerization of cyclopentene, polymers with a high stereoregular structure are formed due to the properties of the ethylene bis (1-indenyl) zirconium dichloride catalyst. It can be assumed that the other polymers produced by means of the process according to the invention also have a high stereoregularity in their structure.

The process described can be used to produce amorphous copolymers. The copolymers are transparent and hard. For example, they are soluble in decahydronaphthalene at 135 ° C and in toluene at room temperature. The polymers according to the invention can be processed thermoplastically. No remarkable degradation or viscosity build was found in either extrusion or injection molding.

The materials according to the invention are particularly suitable for the production of extrusion parts such as foils, hoses, tubes, rods and fibers as well as for the production of injection molded articles of any shape and size. An important property of the materials according to the invention is their transparency. As a result, the optical applications of the extruded or injection molded parts made of these materials are particularly important. The refractive index of the reaction products described in the following examples, determined with an Abbe refractometer and mixed light, is in the range between 1.520 and 1.545. Since the refractive index is very close to that of Kronglas (n = 1.51), the products according to the invention can be used as a replacement for glass, for example lenses, prisms, carrier plates and foils for optical data storage, for video disks, for compact disks, as a deck - and focusing disks for solar cells, as cover and diffusing disks for performance optics, as optical fibers in the form of fibers or foils.

The polymers according to the invention can also be used for the production of polymer alloys. The alloys can be made in the melt or in solution. The alloys each have a favorable combination of properties of the components for certain applications. The following polymers can be used for alloys with the polymers according to the invention: Polyethylene, polypropylene, (ethylene-propylene) copolymers, polybutylene, poly (4-methyl-1-pentene), polyisoprene, polyisobutylene, natural rubber, poly (methyl methacrylate), other polymethacrylates, polyacrylates, (acrylate-methacrylate) copolymers , Polystyrene, (styrene-acrylonitrile) copolymers, bisphenol A polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates nylon-6, nylon-66, further polyamides, polyaramides, Polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, polyvinylidene fluoride.

The glass transition temperatures (Tg) given in the following examples were determined by means of DSC (differential scanning calorimetry) at a heating rate of 20 ° C./min. The specified viscosity numbers were determined in accordance with DIN 53 728.

example 1

Preparation of rac-dimethylsilyl-bis- (1-indenyl) zirconium dichloride (metallocene A)

All subsequent work operations were carried out in an inert gas atmosphere using absolute solvents (Schlenk technique).

A solution of 30 g (0.23 mol) of indene (technical grade 91%) filtered through aluminum oxide in 200 cm³ of diethyl ether was cooled with ice with 80 cm³ (0.20 mol) of a 2.5 molar solution of n-butyllithium in hexane transferred. The mixture was stirred for a further 15 min at room temperature and the orange solution was added via cannula to a solution of 13.0 g (0.10 mol) of dimethyldichlorosilane (99%) in 30 cm 3 of diethyl ether within 2 hours. The orange suspension was stirred overnight and shaken three times with 100-150 cm³ of water. The yellow organic phase was dried twice over sodium sulfate and evaporated in a rotary evaporator. The remaining orange oil was kept in an oil pump vacuum at 40 ° C. for 4 to 5 hours and freed from excess indene, a white precipitate being formed. By adding 40 cm³ of methanol and crystallization at -35 ° C, a total of 20.4 g (71%) of the compound (CH₃) ₂Si (Ind) ₂ could be isolated as a white to beige powder. Mp 79-81 ° C (2 diastereomers).

A solution of 5.6 g (19.4 mmol) (CH₃) ₂Si (Ind) ₂ in 40 cm³ THF was slowly at room temperature with 15.5 cm³ (38.7 mmol) of a 2.5 molar hexane solution of Butyllithium added. 1 hour after the end of the addition, the deep red solution was added dropwise to a suspension of 7.3 g (19.4 mmol) of ZrCl₄ · 2THF in 60 cm³ of THF within 4-6 hours. After 2 hours of stirring, the orange precipitate was suction filtered through a glass frit and recrystallized from CH₂Cl₂. 1.0 g (11%) of rac- (CH₃) ₂Si (Ind) ₂ ZrCl₂ were obtained in the form of orange crystals which gradually decompose from 200 ° C. Correct elementary analysis. The E1 mass spectrum showed M⁺ = 448. 1 H-NMR spectrum (CDCl₃): 7.04 - 7.60 (m, 8, aromatic H), 6.90 (dd, 2, β-Ind H), 6.08 (d, 2, α-Ind H), 1.12 (s, 6, SiCH₃).

Examples 2-9

The metallocenes B, C, D, E, F, G, H and I according to Table 1 were prepared analogously to Example 1, with a dihalogen compound according to Table 2 instead of dimethyldichlorosilane and HfCl₄ for the hafnium compounds (metallocenes G, H and I) was used instead of ZrCl₄.

Example 10

Preparation of diphenylmethylene (9-fluorenyl) -cyclopentadienyl-zirconium dichloride - (metallocene L)

A solution of 5.10 g (30.7 mmol) of fluorene in 60 cm 3 of THF was slowly mixed with 12.3 cm 3 (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium at room temperature. After 40 min, 7.07 g (30.7 mmol) of diphenylfulven was added to the orange solution and the mixture was stirred overnight. 60 cm 3 of water were added to the dark red solution, the solution turning yellow and the solution etherifying. The ether phase dried over MgSO₄ was concentrated and left to crystallize at -35 ° C. 5.1 g (42%) of 1,1-cyclopentadienyl- (9-fluorenyl) -diphenylmethane were obtained as a beige powder.

2.0 g (5.0 mmol) of the compound were dissolved in 20 cm³ of THF and 6.4 cm³ (10 mmol) of a 1.6 molar solution of butyllithium in hexane were added at 0 ° C. After stirring for 15 min at room temperature, the solvent was stripped off, the red residue was dried in an oil pump and washed several times with hexane. After drying in an oil pump vacuum, the red powder was added at -78 ° C to a suspension of 1.16 g (5.00 mmol) ZrCl₄. After slowly warming up, the mixture was stirred for a further 2 h at room temperature. The pink suspension was filtered through a G3 frit. The pink residue was washed with 20 cm³ CH₂Cl₂, dried in an oil pump vacuum and extracted with 120 cm³ toluene. After stripping off the solvent and drying in an oil pump vacuum, 0.55 g of the zirconium complex was obtained in the form of a pink-red crystal powder.

The orange-red filtrate of the reaction mixture was concentrated and left to crystallize at -35 ° C. A further 0.45 g of the complex crystallize from CH₂Cl₂. Total yield 1.0 g (36%). Correct elementary analysis. The mass spectrum showed M⁺ = 556. 1 H-NMR spectrum (100 MHz, CDCl₃): 6.90 - 8.25 (m, 16, Flu-H, Ph-H), 6.40 (m, 2, Ph -H), 6.37 (t, 2, Cp-H), 5.80 (t, 2, Cp-H).

Example 11

Preparation of isopropylene- (9-fluorenyl) -cyclopentadienylzirconium dichloride - (Metallocen M)

Metallocen M was based on the literature reference J. Am. Chem. Soc.<u style="single">110</u> (1988) 6255.

Example 12

A clean and dry 1.5 dm³ polymerization reactor with stirrer was purged with nitrogen and then with ethylene and filled with a solution of 25 g of norbornene in 750 cm³ of toluene. The reactor was then brought to a temperature of 20 ° C. with stirring and 1 bar of ethylene was injected.

Then 20 cm³ of toluene solution of methylaluminoxane (10.1% by weight of methylaluminoxane with a molecular weight of 1,300 g / mol after cryoscopic determination) were metered into the reactor and the mixture was stirred at 20 ° C. for 15 minutes, the ethylene pressure being kept at 1 bar by metering in further amounts (saturation of the toluene with ethylene). At the same time, 30.5 mg of metallocene A were dissolved in 10 cm 3 of toluene methylaluminoxane solution (concentration and quality see above) and preactivated by standing for 15 minutes. The solution of the complex was then metered into the reactor. The mixture was then polymerized for 1 hour at 20 ° C. with stirring (750 rpm), the ethylene pressure being kept at 1 bar by metering in further quantities. The contents of the reactor were then quickly drained into a stirred vessel in which 100 cm 3 of isopropanol had been placed. This mixture was mixed with 2 dm³ of acetone, stirred for 10 min and then the suspended polymeric solid was filtered off. The filtered polymer was then placed in 300 cm³ of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and this suspension was stirred for 2 hours. The polymer was then filtered off again, washed neutral with water and dried at 80 ° C. and 0.2 bar for 15 hours. A product amount of 55 g was obtained. A viscosity number VZ of 244 cm³ / g and a glass transition temperature Tg of 32 ° C. were measured on the product.

Examples 13-16

Polymerization tests were carried out analogously to Example 12. Compared to Example 12, the following were varied: - Type of metallocene used - Amount of metallocene used.

All other parameters remained constant. Varyed parameters and polymerization results are shown in Table 3.

Examples 17-21 and comparative experiments a and b

Polymerization tests were carried out analogously to Example 12. Compared to Example 12, the following were varied: - Type of metallocene used - Amount of metallocene used - Type of solvent for norbornene solution - Amount of norbornene used - polymerization time (t) - polymerization temperature (T) - ethylene pressure (p).

All other parameters remained constant. Varyed parameters and polymerization results are shown in Table 4.

Example 22

The polymerization was carried out according to Example 12, with the difference that nitrogen was used instead of ethylene and a mixture of 94.16 g of norbornene and 84.16 g of 4-methyl-1-pentene was used instead of 25 g of norbornene. Deviating from Example 12, 61.4 mg of metallocene A were used and the polymerization time was 3 hours. 3.5 g of product with a glass transition temperature of 80 ° C. were obtained.

Example 23

The polymerization was carried out according to Example 12, with the difference that instead of norbornene, a mixture of 94.16 g of norbornene and 84.16 g of 4-methyl-1-pentene was used. Deviating from Example 12, 62.2 mg of metallocene A were used and the polymerization time was 3 hours. 11.8 g of product with a glass transition temperature of 55 ° C. were obtained.

Example 24

A polymerization experiment was carried out analogously to Example 12. However, the norbornene solution charged into the reactor was a solution of 15 g of norbornene in 750 cm 3 of hexane; 29.6 mg of metallocene were used. 8 g of polymer were obtained with VZ = 116 cm³ / g and Tg = 36 ° C.

Example 25

A clean and dry 1.5 dm³ polymerization reactor with stirrer was purged with nitrogen and then with propylene and filled with a solution of 30 g of norbornene in 750 cm³ of toluene. The reactor was then brought to a temperature of 20 ° C. with stirring and 1 bar of propylene was injected. Then 20 cm³ of toluene solution of methylaluminoxane (10.1% by weight of methylaluminoxane with a molecular weight of 1,300 g / mol after cryoscopic determination) were metered into the reactor and the mixture was stirred at 20 ° C. for 15 minutes, the propylene pressure being kept at 1 bar by metering in further amounts (saturation of the toluene with propylene). At the same time, 30.9 mg of metallocene A were dissolved in 10 cm³ of toluene methylaluminoxane solution (concentration and quality see above) and preactivated by standing for 15 minutes. The solution of the complex was then metered into the reactor. The mixture was then polymerized for 3 hours at 20 ° C. with stirring (750 rpm), the propylene pressure being kept at 1 bar by metering in more. The contents of the reactor were then quickly drained into a stirred vessel in which 100 cm 3 of isopropanol had been placed. This mixture was mixed with 2 dm³ of acetone, stirred for 10 min and then the suspended polymeric solid was filtered off. The filtered polymer was then placed in 300 cm³ of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and this suspension was stirred for 2 hours. Then the stirred mixture was mixed with 200 cm³ of toluene and after a further 5 min stirring the toluene phase was separated with 1 dm³ of acetone. The polymer dissolved in toluene by extraction of the hydrochloric acid mixture was precipitated in this way. The precipitated polymeric solid was then filtered off and dried at 80 ° C. and 0.2 bar for 15 h.

A product amount of 5.4 g was obtained. A viscosity number VZ = 23 cm³ / g and a glass transition temperature Tg = 96.6 ° C. were measured on the product.

Examples 26-37

Polymerization tests were carried out analogously to Example 19. The following were varied compared to Example 19: - Type of metallocene used - Amount of metallocene used. - Amount of norbornene used - Polymerization temperature (T).

In Verusch 28-30, a toluene solution of methylaluminoxane with 10.3% by weight methylaluminoxane with a molar mass of 750 g / mol was used after cryoscopic determination. All other parameters remained constant. Varyed parameters and polymerization results are shown in Table 5.

Example 38

A polymerization experiment was carried out analogously to Example 25. However, the norbornene solution charged into the reactor was a solution of 15 g of norbornene in 750 cm 3 of hexane; the amount of metallocene A used was 31.6 mg and the polymerization temperature 40 ° C.

5.3 g of polymer were obtained with VZ = 7 cm³ / g and Tg = 87 ° C.

Example 39

A clean and dry 1.5 dm³ polymerization reactor with stirrer was purged with nitrogen and then with propylene and filled with a solution of 107 g of norbornene in 750 cm³ of toluene. The reactor was then brought to a temperature of 20 ° C. with stirring and 1 bar of propylene was injected. Then 20 cm³ of toluene methylaluminoxane solution (10.1% by weight methylaluminoxane with a molecular weight of 750 g / mol after cryoscopic determination) were metered into the reactor and the mixture was stirred for 15 min at 20 ° C., the propylene pressure being kept at 1 bar by metering in more (Saturation of the toluene with propylene). At the same time, 64.1 mg of metallocene A were dissolved in 10 cm 3 of toluene methylaluminoxane solution (for concentration and quality, see above) and preactivated by standing for 15 minutes. The solution of the complex was then metered into the reactor. The mixture was then polymerized for 3 hours at 20 ° C. with stirring (750 rpm), the propylene pressure being kept at 1 bar by metering in more. The contents of the reactor were then quickly drained into a stirred vessel in which 100 cm 3 of isopropanol had been placed. This mixture was mixed with 2 dm³ of acetone, stirred for 10 min and then the suspended polymeric solid was filtered off. The filtered polymer was then placed in 300 cm³ of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and this suspension was stirred for 2 hours. The polymer was then filtered off again, washed neutral with water and dried at 80 ° C. and 0.2 bar for 15 hours.

A product amount of 2 g was obtained. A viscosity number VZ of 26.1 cm 3 / g and a glass transition temperature Tg of 129.5 ° C. were measured on the product.

Examples 40-43

Polymerization tests were carried out in accordance with Example 39. The following were varied compared to Example 39: - Molecular weight of methylaluminoxane - Type of metallocene used - Amount of metallocene used - Amount of norbornene used - Propylene pressure (P).

All other parameters remained constant, varied parameters and polymerization results are shown in Table 6.

Example 44

A polymerization experiment was carried out in accordance with Example 12, with 110 g of 1,4,3,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene instead of norbornene and 61.5 instead of 30.5 mg mg of metallocene A were used. 17 g of polymer was obtained. A viscosity number VZ = 120 cm³ / g and a glass transition temperature Tg = 124 ° C. were measured on the polymer.

Example 45

A polymerization experiment was carried out according to Example 17, using a mixture of 94 g of norbornene and 68 g of cyclopentene instead of norbornene. 17.4 g of polymer were obtained. A viscosity number VZ = 137 cm³ / g and a glass transition temperature Tg = 117 ° C. were measured on the polymer.

Example 46

Two ethylene-norbornene copolymers according to the invention, which have a glass transition temperature of 55 or 115 ° C. and a viscosity number of 240 or 230 cm³ / g, were determined by means of C¹³-NMR (Nuclear Magnetic Resonance) on the basis of the ratio between the number determined by tertiary and secondary carbon atoms norbornene incorporation rates of 27 and 41.5 mol%.

Example 47

40 g of a polymer prepared according to Example 20 were kneaded at 200 ° C. for 1 hour in a measuring kneader (from HAAKE) under inert gas (Ar). The torque had stabilized after filling and had remained constant for 45 minutes.

Example 48

Analogously to Example 46, 20 g of a polymer prepared according to Example 20 were kneaded together with 20 g of a polymer prepared according to Example 21. The alloy thus obtained was transparent. Using DSC at a heating rate of 20 ° C / min, only one glass step at 149 ° C could be identified.<tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">connection</entry><entry namest="col2" nameend="col2" align="center">Short name</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">rac-dimethylsilyl-bis- (1-indenyl) zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene A</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-dimethylgermyl-bis- (1-indenyl) zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene B</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-phenylmethylsilyl-bis- (1-indenyl) zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene C</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-phenylvinylsilyl-bis- (1-indenyl) zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene D</entry></row><row><entry namest="col1" nameend="col1" /></row><row><entry namest="col1" nameend="col1" align="left">1-silacyclobutyl-bis- (1'-indenyl) zirconium dichloride (mixture of isomers: 57% rac isomer, 43% meso isomer)</entry><entry namest="col2" nameend="col2" align="left">Metallocen E</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-ethylene-bis (1-indenyl) zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene F</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-diphenylsilyl-bis- (1-indenyl) hafnium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocen G</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-phenylmethylsilyl-bis- (1-indenyl) hafnium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocen H</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-dimethylsilyl-bis- (1-indenyl) hafnium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene I</entry></row><row><entry namest="col1" nameend="col1" align="left">rac-diphenylsilyl-bis- (1-indenyl) zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocen K</entry></row><row><entry namest="col1" nameend="col1" align="left">Diphenylmethylene (9-fluorenyl) cyclopentadienyl zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocene L</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride</entry><entry namest="col2" nameend="col2" align="left">Metallocen M</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Metallocene</entry><entry namest="col2" nameend="col2" align="left">Dihalogen compound</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">A</entry><entry namest="col2" nameend="col2" align="left">Dimethyldichlorosilane</entry></row><row><entry namest="col1" nameend="col1" align="left">B</entry><entry namest="col2" nameend="col2" align="left">Dimethyl germanium dichloride (dimethyl dichloro german)</entry></row><row><entry namest="col1" nameend="col1" align="left">C.</entry><entry namest="col2" nameend="col2" align="left">Phenylmethyldichlorosilane</entry></row><row><entry namest="col1" nameend="col1" align="left">D</entry><entry namest="col2" nameend="col2" align="left">Phenylvinyldichlorosilane</entry></row><row><entry namest="col1" nameend="col1" align="left">E</entry><entry namest="col2" nameend="col2" align="left">Cyclotrimethylene dichlorosilane</entry></row><row><entry namest="col1" nameend="col1" align="left">F</entry><entry namest="col2" nameend="col2" align="left">1,2-dibromoethane</entry></row><row><entry namest="col1" nameend="col1" align="left">G</entry><entry namest="col2" nameend="col2" align="left">Diphenyldichlorosilane</entry></row><row><entry namest="col1" nameend="col1" align="left">H</entry><entry namest="col2" nameend="col2" align="left">Phenylmethyldichlorosilane</entry></row><row><entry namest="col1" nameend="col1" align="left">I.</entry><entry namest="col2" nameend="col2" align="left">Dimethyldichlorosilane</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">J</entry><entry namest="col2" nameend="col2" align="left">Diphenyldichlorosilane</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>Table 3</title><tgroup cols="7" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">example</entry><entry namest="col2" nameend="col2" align="center">Metallocene</entry><entry namest="col3" nameend="col3" align="center">Amount of metallocene (mg)</entry><entry namest="col4" nameend="col4" align="center">T (° C)</entry><entry namest="col5" nameend="col5" align="center">Product quantity (g)</entry><entry namest="col6" nameend="col6" align="center">VZ (cm³ / g)</entry><entry namest="col7" nameend="col7" align="center">Tg (DSC) (° C)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">13</entry><entry namest="col2" nameend="col2" align="left">B</entry><entry namest="col3" nameend="col3" align="char" char=",">31,4</entry><entry namest="col4" nameend="col4" align="right">20</entry><entry namest="col5" nameend="col5" align="char" char=",">3,3</entry><entry namest="col6" nameend="col6" align="right">337</entry><entry namest="col7" nameend="col7" align="char" char=",">23,5</entry></row><row><entry namest="col1" nameend="col1" align="right">14</entry><entry namest="col2" nameend="col2" align="left">K</entry><entry namest="col3" nameend="col3" align="char" char=",">33,5</entry><entry namest="col4" nameend="col4" align="right">20</entry><entry namest="col5" nameend="col5" align="char" char=",">14,0</entry><entry namest="col6" nameend="col6" align="right">96</entry><entry namest="col7" nameend="col7" align="char" char=",">31,2</entry></row><row><entry namest="col1" nameend="col1" align="right">15</entry><entry namest="col2" nameend="col2" align="left">L</entry><entry namest="col3" nameend="col3" align="char" char=",">43,7</entry><entry namest="col4" nameend="col4" align="right">20</entry><entry namest="col5" nameend="col5" align="char" char=",">9,0</entry><entry namest="col6" nameend="col6" align="right">121</entry><entry namest="col7" nameend="col7" align="char" char=",">37,6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">16</entry><entry namest="col2" nameend="col2" align="left">M</entry><entry namest="col3" nameend="col3" align="char" char=",">29,3</entry><entry namest="col4" nameend="col4" align="right">20</entry><entry namest="col5" nameend="col5" align="char" char=",">12,0</entry><entry namest="col6" nameend="col6" align="right">99</entry><entry namest="col7" nameend="col7" align="char" char=",">32,2</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><title>Table 4</title><tgroup cols="11" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="14.31mm" /><colspec colnum="2" colname="col2" colwidth="14.31mm" /><colspec colnum="3" colname="col3" colwidth="14.31mm" /><colspec colnum="4" colname="col4" colwidth="14.31mm" /><colspec colnum="5" colname="col5" colwidth="14.31mm" /><colspec colnum="6" colname="col6" colwidth="14.31mm" /><colspec colnum="7" colname="col7" colwidth="14.31mm" /><colspec colnum="8" colname="col8" colwidth="14.31mm" /><colspec colnum="9" colname="col9" colwidth="14.31mm" /><colspec colnum="10" colname="col10" colwidth="14.31mm" /><colspec colnum="11" colname="col11" colwidth="14.31mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">example</entry><entry namest="col2" nameend="col2" align="center">Metallocene</entry><entry namest="col3" nameend="col3" align="center">Amount of metallocene (mg)</entry><entry namest="col4" nameend="col4" align="center">Amount of norbornene (g)</entry><entry namest="col5" nameend="col5" align="center">T (° C)</entry><entry namest="col6" nameend="col6" align="center">P (bar)</entry><entry namest="col7" nameend="col7" align="center">d (h)</entry><entry namest="col8" nameend="col8" align="center">Solvents</entry><entry namest="col9" nameend="col9" align="center">Product quantity (g)</entry><entry namest="col10" nameend="col10" align="center">VZ (cm³ / g)</entry><entry namest="col11" nameend="col11" align="center">Tg (DSC) (° C)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">17</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="char" char=",">60</entry><entry namest="col4" nameend="col4" align="right">107</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">1</entry><entry namest="col7" nameend="col7" align="right">3</entry><entry namest="col8" nameend="col8" align="left">toluene</entry><entry namest="col9" nameend="col9" align="char" char=",">54,1</entry><entry namest="col10" nameend="col10" align="right">177</entry><entry namest="col11" nameend="col11" align="right">105</entry></row><row><entry namest="col1" nameend="col1" align="right">18</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="char" char=",">66,5</entry><entry namest="col4" nameend="col4" align="right">214</entry><entry namest="col5" nameend="col5" align="right">70</entry><entry namest="col6" nameend="col6" align="char" char=",">1,5</entry><entry namest="col7" nameend="col7" align="right">3</entry><entry namest="col8" nameend="col8" align="left">Petrol fraction bp. 110-130 ° C</entry><entry namest="col9" nameend="col9" align="char" char=",">9,5</entry><entry namest="col10" nameend="col10" align="right">55</entry><entry namest="col11" nameend="col11" align="right">163</entry></row><row><entry namest="col1" nameend="col1" align="right">19</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="char" char=",">60</entry><entry namest="col4" nameend="col4" align="right">107</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">1</entry><entry namest="col7" nameend="col7" align="right">3</entry><entry namest="col8" nameend="col8" align="left">toluene</entry><entry namest="col9" nameend="col9" align="char" char=",">6,0</entry><entry namest="col10" nameend="col10" align="right">62</entry><entry namest="col11" nameend="col11" align="right">156</entry></row><row><entry namest="col1" nameend="col1" align="right">20</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="char" char=",">60</entry><entry namest="col4" nameend="col4" align="right">180</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">1</entry><entry namest="col7" nameend="col7" align="right">1</entry><entry namest="col8" nameend="col8" align="left">toluene</entry><entry namest="col9" nameend="col9" align="char" char=",">7,6</entry><entry namest="col10" nameend="col10" align="right">65</entry><entry namest="col11" nameend="col11" align="right">146</entry></row><row><entry namest="col1" nameend="col1" align="right">See a</entry><entry namest="col2" nameend="col2" align="left">F</entry><entry namest="col3" nameend="col3" align="char" char=",">60</entry><entry namest="col4" nameend="col4" align="right">180</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">1</entry><entry namest="col7" nameend="col7" align="right">1</entry><entry namest="col8" nameend="col8" align="left">toluene</entry><entry namest="col9" nameend="col9" align="char" char=",">35,0</entry><entry namest="col10" nameend="col10" align="right">157</entry><entry namest="col11" nameend="col11" align="right">134</entry></row><row><entry namest="col1" nameend="col1" align="right">21</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="char" char=",">60</entry><entry namest="col4" nameend="col4" align="right">214</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">1</entry><entry namest="col7" nameend="col7" align="right">3</entry><entry namest="col8" nameend="col8" align="left">toluene</entry><entry namest="col9" nameend="col9" align="char" char=",">16,8</entry><entry namest="col10" nameend="col10" align="right">110</entry><entry namest="col11" nameend="col11" align="right">154</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">See b</entry><entry namest="col2" nameend="col2" align="left">F</entry><entry namest="col3" nameend="col3" align="char" char=",">60</entry><entry namest="col4" nameend="col4" align="right">214</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">1</entry><entry namest="col7" nameend="col7" align="right">3</entry><entry namest="col8" nameend="col8" align="left">toluene</entry><entry namest="col9" nameend="col9" align="char" char=",">34,4</entry><entry namest="col10" nameend="col10" align="right">191</entry><entry namest="col11" nameend="col11" align="right">141</entry></row></tbody></tgroup></table></tables><tables id="tabl0005" num="0005"><table frame="all"><title>Table 5</title><tgroup cols="8" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="19.68mm" /><colspec colnum="2" colname="col2" colwidth="19.68mm" /><colspec colnum="3" colname="col3" colwidth="19.68mm" /><colspec colnum="4" colname="col4" colwidth="19.68mm" /><colspec colnum="5" colname="col5" colwidth="19.68mm" /><colspec colnum="6" colname="col6" colwidth="19.68mm" /><colspec colnum="7" colname="col7" colwidth="19.68mm" /><colspec colnum="8" colname="col8" colwidth="19.68mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">example</entry><entry namest="col2" nameend="col2" align="center">Metallocene</entry><entry namest="col3" nameend="col3" align="center">Amount of metallocene (mg)</entry><entry namest="col4" nameend="col4" align="center">Amount of norbornene (g)</entry><entry namest="col5" nameend="col5" align="center">T (° C)</entry><entry namest="col6" nameend="col6" align="center">Product quantity (g)</entry><entry namest="col7" nameend="col7" align="center">VZ (cm³ / g)</entry><entry namest="col8" nameend="col8" align="center">Tg (DSC) (° C)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">26</entry><entry namest="col2" nameend="col2" align="left">C.</entry><entry namest="col3" nameend="col3" align="char" char=",">60,9</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">1,4</entry><entry namest="col7" nameend="col7" align="right">19</entry><entry namest="col8" nameend="col8" align="char" char=",">91,1</entry></row><row><entry namest="col1" nameend="col1" align="right">27</entry><entry namest="col2" nameend="col2" align="left">D</entry><entry namest="col3" nameend="col3" align="char" char=",">51,6</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">1,5</entry><entry namest="col7" nameend="col7" align="right">22</entry><entry namest="col8" nameend="col8" align="char" char=",">89,7</entry></row><row><entry namest="col1" nameend="col1" align="right">28</entry><entry namest="col2" nameend="col2" align="left">E</entry><entry namest="col3" nameend="col3" align="char" char=",">56,2</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">1,1</entry><entry namest="col7" nameend="col7" align="right">22</entry><entry namest="col8" nameend="col8" align="char" char=",">103,6</entry></row><row><entry namest="col1" nameend="col1" align="right">29</entry><entry namest="col2" nameend="col2" align="left">K</entry><entry namest="col3" nameend="col3" align="char" char=",">38,0</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">2,0</entry><entry namest="col7" nameend="col7" align="right">14</entry><entry namest="col8" nameend="col8" align="char" char=",">91,8</entry></row><row><entry namest="col1" nameend="col1" align="right">30</entry><entry namest="col2" nameend="col2" align="left">G</entry><entry namest="col3" nameend="col3" align="char" char=",">351,0</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">70</entry><entry namest="col6" nameend="col6" align="char" char=",">1,2</entry><entry namest="col7" nameend="col7" align="right">30</entry><entry namest="col8" nameend="col8" align="char" char=",">50,0</entry></row><row><entry namest="col1" nameend="col1" align="right">31</entry><entry namest="col2" nameend="col2" align="left">H</entry><entry namest="col3" nameend="col3" align="char" char=",">100,2</entry><entry namest="col4" nameend="col4" align="right">40</entry><entry namest="col5" nameend="col5" align="right">70</entry><entry namest="col6" nameend="col6" align="char" char=",">1,1</entry><entry namest="col7" nameend="col7" align="right">26</entry><entry namest="col8" nameend="col8" align="char" char=",">48,2</entry></row><row><entry namest="col1" nameend="col1" align="right">32</entry><entry namest="col2" nameend="col2" align="left">I.</entry><entry namest="col3" nameend="col3" align="char" char=",">177,0</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">3,0</entry><entry namest="col7" nameend="col7" align="right">24</entry><entry namest="col8" nameend="col8" align="char" char=",">61,0</entry></row><row><entry namest="col1" nameend="col1" align="right">33</entry><entry namest="col2" nameend="col2" align="left">I.</entry><entry namest="col3" nameend="col3" align="char" char=",">302,0</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">50</entry><entry namest="col6" nameend="col6" align="char" char=",">7,0</entry><entry namest="col7" nameend="col7" align="right">4</entry><entry namest="col8" nameend="col8" align="char" char=",">70,4</entry></row><row><entry namest="col1" nameend="col1" align="right">34</entry><entry namest="col2" nameend="col2" align="left">L</entry><entry namest="col3" nameend="col3" align="char" char=",">30,6</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">50,0</entry><entry namest="col7" nameend="col7" align="right">14</entry><entry namest="col8" nameend="col8" align="char" char=",">26,5</entry></row><row><entry namest="col1" nameend="col1" align="right">35</entry><entry namest="col2" nameend="col2" align="left">L</entry><entry namest="col3" nameend="col3" align="char" char=",">30,1</entry><entry namest="col4" nameend="col4" align="right">40</entry><entry namest="col5" nameend="col5" align="right">40</entry><entry namest="col6" nameend="col6" align="char" char=",">110,0</entry><entry namest="col7" nameend="col7" align="right">27</entry><entry namest="col8" nameend="col8" align="char" char=",">23,7</entry></row><row><entry namest="col1" nameend="col1" align="right">36</entry><entry namest="col2" nameend="col2" align="left">L</entry><entry namest="col3" nameend="col3" align="char" char=",">15,0</entry><entry namest="col4" nameend="col4" align="right">40</entry><entry namest="col5" nameend="col5" align="right">50</entry><entry namest="col6" nameend="col6" align="char" char=",">23,0</entry><entry namest="col7" nameend="col7" align="right">4</entry><entry namest="col8" nameend="col8" align="char" char=",">62,0</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">37</entry><entry namest="col2" nameend="col2" align="left">M</entry><entry namest="col3" nameend="col3" align="char" char=",">30,3</entry><entry namest="col4" nameend="col4" align="right">80</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" align="char" char=",">1,3</entry><entry namest="col7" nameend="col7" align="right">22</entry><entry namest="col8" nameend="col8" align="char" char=",">26,6</entry></row></tbody></tgroup></table></tables><tables id="tabl0006" num="0006"><table frame="all"><title>Table 6</title><tgroup cols="9" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">example</entry><entry namest="col2" nameend="col2" align="center">Metallocene</entry><entry namest="col3" nameend="col3" align="center">Amount of metallocene (mg)</entry><entry namest="col4" nameend="col4" align="center">Amount of norbornene (g)</entry><entry namest="col5" nameend="col5" align="center">Pressure (bar)</entry><entry namest="col6" nameend="col6" align="center">Mw (MAO) (g / mol)</entry><entry namest="col7" nameend="col7" align="center">Product quantity (g)</entry><entry namest="col8" nameend="col8" align="center">VZ (cm³ / g)</entry><entry namest="col9" nameend="col9" align="center">Tg (DSC) (° C)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">40</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="right">89</entry><entry namest="col4" nameend="col4" align="right">107</entry><entry namest="col5" nameend="col5" align="right">3</entry><entry namest="col6" nameend="col6" align="right">750</entry><entry namest="col7" nameend="col7" align="char" char=",">3,1</entry><entry namest="col8" nameend="col8" align="char" char=",">31</entry><entry namest="col9" nameend="col9" align="right">107</entry></row><row><entry namest="col1" nameend="col1" align="right">41</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col4" align="right">50</entry><entry namest="col5" nameend="col5" align="right">1-3*</entry><entry namest="col6" nameend="col6" align="right">750</entry><entry namest="col7" nameend="col7" align="char" char=",">5,2</entry><entry namest="col8" nameend="col8" align="char" char=",">25,6</entry><entry namest="col9" nameend="col9" align="right">101</entry></row><row><entry namest="col1" nameend="col1" align="right">42</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col4" align="right">107</entry><entry namest="col5" nameend="col5" align="right">1-3*</entry><entry namest="col6" nameend="col6" align="right">1 300</entry><entry namest="col7" nameend="col7" align="char" char=",">5,3</entry><entry namest="col8" nameend="col8" align="char" char=",">21,0</entry><entry namest="col9" nameend="col9" align="right">120</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">43</entry><entry namest="col2" nameend="col2" align="left">F</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col4" align="right">107</entry><entry namest="col5" nameend="col5" align="right">1-3*</entry><entry namest="col6" nameend="col6" align="right">1 300</entry><entry namest="col7" nameend="col7" align="char" char=",">12,0</entry><entry namest="col8" nameend="col8" align="char" char=",">20,0</entry><entry namest="col9" nameend="col9" align="right">129</entry></row></tbody></tgroup><tgroup cols="9" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col9" align="justify">* the pressure was increased linearly from 1 to 3 bar within 1 hour during the polymerization.</entry></row></tbody></tgroup></table></tables>