AU622980B2 - Process for the preparation of a random propylene copolymer - Google Patents

Description

i i. i CIL_~3 i LI- -~lli- 622980 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class In Application Number: Lodged: Form it. Class 0 0 00 0 *0* 0 0 0 0o 0 Complete Specification Lodged: Accepted: Published: Priority Related Art Name of Applicant HOECHST AKTIENGESELLSCHAFT S Address of Applint 0,0 0, Address of Applicant 50 Bruningstrasse, D6230 Frankfurt/Main Germany 80, Federal Republic of *J 0 00 l 00 Actual Inventor o0 0*00 Address for Service VOLKER DOLLE, MARTIN ANTBERG, JUREN ROHRMANN and ANDREAS WINTER WATERMARK PATENT TRADEMARK ATTORNEYS.

LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Complete Specification for the invention entitled: PROCESS FOR THE PREPARATION OF A RANDOM PROPYLENE COPOLYMER The following statement is a full description of this invention, including the best method of performing it known to u 1.

VC

HOECHST AKTIENGESELLSCHAFT HOE 89/F 053 Dr.DA/bs Description Process for the preparation of a random propylene copolymer The polymerization of olefins, depending on the process used, gives copolymers with different properties and different proportions of comonomers: a) random copolymers with a low proportion of comonomers, b) polymer blends containing a larger proportion of incorporated comonoiers than the random copolymers and c) copolymer rubbers containing the comonomers incorporated in similar proportions.

As a rule, random copolymers differ from the correspond- 5, o ing homopolymers in having a lower crystallinity and a 15 lower hardness. It is desirable for the random copolymers to have as random a chain structure as possible. The prior art olefin copolymers which are prepared with the aid of heterogeneous catalysts can only fulfil this.

requirement to a very limited extent.

Q 20 Random terpolymers of C 2

/C

3

/C

n with n 3 have been 0'1, described and were obtained using heterogeneous catalysts (cf. EP 263,718). The proportion of C 3 is 97 to 86 mol the proportion of C 2 is 0.5 to 6 and the proportion of Cn (n 3) is 2 to 13 mol The material has good heat sealing properties but is obtained in a two step process .with a suspension polymerization step and a gas phase polymerization step. In order to obtain the desired antiblocking properties, a terpolymer with a high proportion of the third monomer has to be prepared. However bipolymers are however required since these are easier to manipulate and have a chemically homogeneous chain structure.

Furthermore, random C 2

/C

3 copolymers are known, prepared by suspension polymerization (cf. EP 74,194). In order to _i 2 obtain the desired properties, the polymers obtained must be broken down. Moreover, the proportion of ethylene is greater than 6 This high proportion of C 2 is necessary in order to reduce the chemical inhomogeneity of a heterogeneous catalyst system, this inhomogeneity tending to produce a relatively high proportion of crystallizable sequences in the polymer.

Finally, an ethylene/propylene copolymer with a high proportion of ethylene and a process for its preparation has been described (cf. JP 62/121,707). The process is carried out using ethylenebisindenylzirconium dichloride at a temperature of less than -10°C and is consequently unsuitable for industrial production. Apart from that, the activity of the catalyst is very low.

I 04 00 0 0 04 O* 0 o 4 0O 00 e o 0 4 ooo o 0 0 460S «I o 4.

II*

15 The object was therefore to provide a process for the preparation of a propylene copolymer, which can be carried out within an industrially relevant temperature range with adequate catalyst activity and provides a copolymer which is suitable for thermoforming and blowmolding.

It was found that this object can be achieved by copolymerization of propylene with other olefins in the presence of certain metallocene catalysts.

The invention accordingly provides a process for the preparation of a propylene copolymer composed of 99.9 to 80.0 mol relative to the total polymer, of propylene units and 0.1 to 20.0 mol relative to the total polymer, of units which are derived from ethylene or from an olefin with at least 4 carbon atoms of the formula

R"-CH=CH-R

1 6 where R 1 5 and R 16 are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms or R' 5 and R 1 6 with the carbon atoms bonding them form a ring having 4 to 28 carbon atoms, by polymerizing 50 to 99.5 by weight, relative to the total amount of monomers, of propylene and 0.5 to 50 by i i I N -3 weight, relative to the total amount of monomers, c~f at least one representative of the group consi3tj ethylene and olef ins having at least 4 carbon. atom. of the formula R 15 -CH=CH-Rlr', where R'1 5 and R 1 6 '1have the meaning given above, at a temperature of 300C to 1500C at a pressure of 0.5 to 100 bar in solution, in suspension or in the gas phase in the presence of a catalyst composed of a metallocene and an aluminoxane, wherein the metallocene is a compound of the formula I R4- -(CRR 9 R1 R73~ I 0 0R 2

RS

a too (CRE3R3')n, t~~0 R 6

R

6 .00 in which t0*0R 1 and R 2 are identical or different and denote a hydrogen atom, a C 1

-C

10 )-aJlcy3. group, a P-CI-alkoxy group, Pa

C

6 -Cl-aryl group, a C.-Cl.-aryloxy group, a 2C, alkenyl group, a C 7

-C

4 -arylalkyl group, a 0*00*alkylaryl group, a C 8

-C

40 -arylalkenyl group or a halogen atom, 00*R R 4, R 5 and R 6 are identical or different and denote a 0 hydrogen atom, a halogen atom, a C,-Cl.-alkyl group, a radical -NR,' 0

-SR'

0 -OSiR" 0 -SiR' 0 or -PR' 0 in which

R

10 is a Cl-Cl-alkyl group, a C 6 -Cl-aryl group or if the 00 radical contains Si or P may also be a halogen atom, or each pair of adjacent radicals R 3 R 4, R 5 or R 6 forms a ring with the carbon atoms linking them, R 7 is R11 R 11

R

11 R1R1 I I 1 13 1 M M 1

M

1

CR

2 0-M I I I I

I

R12 R 12 R1 2 R1R2 -C-0 MI I I R12 R 12 -4 0 0 0 0 00 0 00 *4 o 0 0 o o@0~ 15 o 0 0 00 0 0006 *000

=BR

1 1 =A1R 1 1 =SO, =S0 2

=NR

1 1

=CO,

=PR11or =P(O)R11 where

R

11 R 12 and R' 3 are identical or different and denote a hydrogen atom, a halogen atom, a Cl-C 30 -alkyl group, a Cl-C-fluoroalkyl group, a C 6

-C

1 0 -aryl group, a C6-C 10 -fluoroaryl group, a C 1 -C.,-alkoxy group, a

C

2 -Cl-alkenyl group, a C 7

-C

40 -arylalkyl group, a C 8

C

4 0 -arylalkenyl group, a C 7

-C

4 0 -alkylaryl group or R and R 12 or R" and R 13 in each case form a ring with the atoms bonding them, Mi is silicon, germanium or tin,

R

8 and R 9 are identical or different and have the meaning given for R 11 m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and the aluminoxane is one of-the formula (II)

R

1 4 R1 Al o--Al-0 .Al R1

(II)

0 00 0 4000 o 04 00 4 00 0 0 0 4 04 01 4 2'0~ 0 in the instance of the linear type and/or of the formula

(III)

FR14p+2

(III)

in the instance of the cyclic type, R14 in the formulae (II) and (III) denoting a Cl-C.-alkyl group and p denoting an integer from 2 to The invention furthermore relates to the copolymer prepared by the above process and to its use f or the preparation of thermoforming sheets and for the blow- 5 molding of hollow articles.

The catalyst which is to be used for the process according to the invention is composed of an aluminoxane and a metallocene of the formula I.

R

4

R

4

(CRBR

9 )m

R

3

R

3

R

1 R7

H

R (I) R2F RSR5 R R

(CRRS

9 )n So R R 6 FR' and R 2 are identical or different and denote a hydrogen atom, a C-Clo-, preferably Ci-C 3 -alkyl group, a Ci-Clo-, preferably Ci-C 3 -alkoxy group, S. Wa C 6

-C

10 preferably C.-C-aryl group, a C6-C, 0 preferably C 6 -C-aryloxy group, a C 2 -Co 1 preferably C 2

-C

4 -alkenyl group, a C 7

-C

40 preferably C 7 -Cio-arylalkyl group, a C 7

-C

40 preferably C 7

-C

1 2 -alkylaryl group, a C 8

-C

40 preferably C 8 -Ci2-arylalkenyl group, or a halogen atom, preferably chlorine.

R

3 R R 5 and R 6 are identical or different and denote a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -Clo-, preferably Ci-C 3 -alkyl group, a radical NRi-, -SR 10 -OSiR' 0 -SiR'o- or -PR2where R i o is a Ci-Cio, preferably Ci-C 3 -alkyl group or

C

6

-C

10 preferably C.-Cs-aryl group, or in the case of radicals containing Si or P may also be a halogen atom, preferably a chlorine atom, or each adjacent pair of radicals R 3

R

4

R

5 or R 6 forms a ring with the carbon atoms bonding them. Particular preference is given to indenyl, flucrenyi and cyclopentadienyl ligands.

-6 k 7 is R11

I

M1 R 12 R11

I

C

I

R12

R

1 1

R

1 1 R1 '1 '1 '1 13 M M-M

CR

2

I

R

1 2

R

1 2 R'12 -0

I

0-

=BR

1 1 =A1R 1 1 -SO, =S0 2 =NR1, =CO, =R or =P R1, where R11, R1 2 and R 1 3 are identical or' different and denote a hydrogen atom, a halogen atom, a 0 4 Q0 preferably Cl-C 4 -alkyl group, in particular a 0, methyl group, a Cl-C 10 -f luoroalkyl group, preferably a CF 3 group, a Cr-C-fluoroaryl group, preferably a pentaf luorophenyl group, a C 6

-C

1 9 preferably Cr-C-aryl group, OZ a Cl-Cl.- pref erably C 1

-C

4 -alkoxy group, in particular a methoxy group, a C2-C 1 0 preferably C 2

-C

4 -alkenyl group, a C 7

-C

4 preferably C 7 -C-arylalkyl group, a C 8

-C

40 preferably C.-C 2 -arylalkenyl group or a C 7

-C

4 preferably ooo 0 C 7

-C

1 2 -alkylaryl group, or R1 and R 12 or R' 1 and Rl 1 in each case together form a ring with the atoms bonding them.

0 0 00 0 0 15 M 1 is silicon, germanium or tin, preferably silicon and germanium.

is preferably =CR' 1

R

12 =SiR"R' 2 =GeR"R' 2 11 =SO, =PR 11 or =P(0)R Ra and RG are identical or different and have the meaning given for R 11 m and n are identical or different and denote zero, 1 or 2, pref erably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.

The metallocenes described above can be prepared by the following general reaction scheme: -7

H

2 Ra ButylLi -4 a~j

H

2 Rb ButylLi- jbLi Ha_ (CR 8

R

9 )m-R 7 (CR8R?)n-RbH LiRa- (CR 8

R

9 )m,-R 7 (CR8R 9 )n-RbLi X- (CR 8

R

9 )m,-R 7

(CR

8

R

9 2 ButylL

L+

Hf Cl 4 a 04 40*0 0,44 4, I0

(CRBR

9 )m,,Ra R7 Hf I Cl .,PR9R)n-Rb

R

1 L 1

(CRBR

9 )m,,Ra R7 Hf, (CR R n-RD R1

R

2 Li (CR8R 9 )m-Ra

KR

Hf

(CBR)-R

4441 a 0044 a 0.4000 a 0 R 3 (X =Cl, Br, I, 0-tosyl, HRa=RH R R4 R

=I

6 Preferred metallocenes are those of the formula I in which the radical -(CR 8

R

9 7 -(CRaRg),- denotes -Ge(CH 3 2 -Si(CH 3 2 2 or -Si(CH 3 (Cr1 5 Particular preference is given to the use of the following metallocene ccornjovnnds: ethylenebisin~denylhafnium dichloride 1) and bisindenyldimi-thylsilylhafnium dichloride 2).

-8- The cocatalyst is an aluminoxane of the formula II

R

1 4

R

1 4

R

14 Al 0 Al 0 Al (I) 14 R14

LP

in the instance of the linear type and/or of the formula

(III)

0 DI l

(II)

L p+2 4 1 in the instance of the cyclic type. In these formulae,, 14 denotes a C 1 -C.-alkyl group, preferably methyl, ethyl or %tit isobutyl, in particular methyl, and p denotes an integer I from 2 to 50, preferably 5 to 40. However, the exact 10 structure of the aluminoxane is not known.

0 The aluminoxane can be prepared by various methods.

One possibility is the careful addition of water to a 0000 dilute solution of a trialkylaluminum by adding the 0solution of the trialkylaluminum, preferably trimethylaluminum, and the water each in small portions to a previously introduced relatively large amount of an inert solvent and at each stage waiting until gas evolution has ended.

In another process, a slurry of finely powdered copper sulfate pentahydrate is prepared in toluene and admixed in a glass flask, under inert gas at about -20"C, with an amount of trialkylaluminum such that for every 4 gram 9 atoms of Al there is available about 1 mole of CuSO 4 .5H 2 0.

After slow hydrolysis with alkane elimination the reaction mixture is left for 24 to 48 hours at room temperature, which may require cooling so that the temperature does not exceed 30 C. The aluminoxane dissolved in toluene is then separated from the copper sulfate by filtration and the solution is concentrated in vacuo. It is assumed that during this preparation the low molecular weight aluminoxanes condense with elimination of trialkylaluminum to form higher oligomers.

Furthermore, aluminoxanes are obtained if trialkylaluminum, preferably trimethylaluminum, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is brought into reaction at a temperature of S' 15 -20 to 100°C with aluminum salts containing water of crystallization, preferably aluminum sulfate. In this process, the ratio by volume between the solvent and the alkylaluminum used is 1:1 to 50:1, preferably 5:1, and the reaction time, which can be monitored from the elimination of the alkane, is 1 to 200 hours, preferably to 40 hours.

Particular preference is given to aluminum salts containing a high proportion of water of crystallization.

Hydrated aluminum sulfate is especially preferred, particularly the compounds A1 2 (S0 4 316H 2 0 and A1 2

(SO

4 3 .18H 2 0 with the particularly high proportion of water of crystallization of 16 and 18 moles of H 2 0/mole of A1 2

(SO

4 3 A Another alternative for the preparation of aluminoxane is to dissolve trialkylaluminum, preferably trimethylaluminum, in a suspension medium which has bein previously introduced into the polymerization vessel, preferably in liquid monomer in heptane or toluene and then to react the aluminum compound with water.

In addition to the processes which have been described 7 0 00 84*0 o 0 4r 4 o *4 0* r 4*4u4 4qc 10 above for the preparation of aluminoxanes, there are other usable processes.

Whatever the method of preparation, all solutions of aluminoxane contain a variable amount of unconverted trialkylaluminum which is present in the free state or as an adduct.

The metallocene can be preactivated before use in the polymerization reaction with an aluminoxane of the formula (II) and/or (III). This significantly increases the polymerization activity and improves the particle morphology.

The preactivation of the transition metal compound is carried out in solution. Here, it is preferable to dissolve the metallocene in a solution of the aluminoxane 15 in an inert hydrocarbon. Suitable hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferably used.

The concentration of the aluminoxane in the solution is in the range of from about 1 by weight up to the 20 saturation limit, preferably of 5 to 30 by weight, relative in each case to the total solution. The metallocene can be tsed in the same concentration, but is preferably used in an amount of 10 4 1 mole per mole of aluminoxane. The preactivation time is 5 minutes to 25 60 hours, preferably 5 to 60 minutes. Preactivation is carried out at a temperature of -78C to 100 0 C, preferably 0 to 0401 40*4 B04$ 0 04 40 4 00a 0+ 4 0 44I 41 0r 0404 The polymerization is carried out in a known manner in solution, suspension or in the gas phase, continuously or batchwise, in one or more steps at a temperature of 30 to 150"C, preferably 30 to 80°C. Propylene is copolymerized with at least one representative of the group consisting of ethylene and olefins having at least 4 carbon atoms of the formula R" 5 -CH=CH-R1 6 In this formula, R 15 and R 1 6 are identical or different and denote a hydrogen atom or an i

C-~

11 alkyl radical having 1 to 28 carbon atoms. However, R 1 and R 16 may also form a ring with the carbon atoms bonding them which contains 4 to 28 carbon atoms. Examples of olefins of this type are 1-butene, 1-hexene, 4-methyl-lpentene, 1-octene, norbornene, norbornadiene, cyclopentene, cyclohexene and cyclooctene. The amount of propylene used is 50 to 99.5, preferably 60 to 99 by weight, relative to the total amount of monomers, and the amount of comonomer, there being at least one, is 0.5 to 50, preferably 1 to 40 by weight relative to the total amount of monomers.

If necessary, hydrogen is added as a molecular weight regulator. The total pressure in the polymerization system is 0.5 to 100 bar. Preference is given to polymer- 1 15 ization in the industrially particularly relevant pres- I sure range of 5 to 64 bar.

In polymerization, the metallocene compound is used in a concentration, relative to the transition metal, of 10 3 to 10 7 preferably 10 4 to 10 moles, of transition metal per dm 3 of solvent or per dm 3 of reactor volume. The aluminoxane is used in a concentration of 10 s 5 to 10-1 moles, preferably 10 to 10- 2 moles per dm 3 of solvent or per dm 3 of reactor volume. However, in principle higher concentrations can also be used.

If the polymerization is a suspension or solution polyi merization, an inert solvent customary for the Ziegler process is used. The polymerization may be carried out Sfor example in an aliphatic or cycloaliphatic hydrocarbon; examples of these are butane, pentane, hexdne, heptane, isooctane, cyclohexane, and methylcyclohexane.

A naphtha fraction or hydrogenated diesel oil fraction may also be used. It is also possible to use toluene.

Preference is given to polymerization in liquid monomer.

If inert solvents are used, the monomers are metered in in the gaseous or liquid form. If only one monomer is 1-- 12 used as the suspending medium, the comonomer(s) is/are metered in in the gaseous or liquid form. Furthermore, it is possible to carry out the polymerization in a mixture of different monomers as the suspending medium; a further monomer can then be metered in liquid or gaseous form. It is advantageous when using ethylene to charge part of the ethylene initially and then to meter in the remainder during the polymerization.

The duration of the polymerization is optional, since the catalyst system which is to be used according to the invention has only a slight loss of polymerization activity over time.

0 b B0 o 09 08 308 4O14 0 48 04 ri r r F 't' e, i

L

A feature of the process according to the invention is that the hafnium compounds used are very heat stable so 15 that they can also be used with high activity at temperatures up to 90 0 C. Moreover, the aluminoxanes used as cocatalysts can be added in lower concentrations than hitherto. Finally, it has now become possible to prepare random copolymers at industrially relevant temperatures.

w//cA may d.

20 The copolymer (or terpolymer)(prepared according to the invention is a copolymer (terpolymer) composed of 99.9 to 80.0 mol relative to the total polymer, of propylene units and 0.1 to 20.0 mol relative to the total polymer, of units which are derived from the above comonomers in which the comonomers are incorporated in blocks with an average sequence length n 1.25. The copolymers have a uniform composition i.e. no distribution of composition is observed. The polydispersity M,/Mn is in the range of 2.5 to 5.5 and the molecular weight is in the range of about 100,000 to 360,000 g/mole. Due to these molecular properties, the copolymers have, in addition to low crystallinity, a high transparency, are not tacky and have an enormous tensile strength.

The sequence length of the comonomer blocks in the copolymers according to the invention are preferably 13 below 1.25, particularly below 1.2 and especially below 1.1.

The invention is described in more detail in the following examples.

The following symbols are used: VZ viscosity number in cm'/g M weight average mole- determined by gel permeacular weight tion chromatography (data Mn number average mole- in units of g/mole) cular weight S°Mw/Mn polydispersity average block length ncz 2 polyethylene (the block lengths were determined by 3 C-NMR spectro- 15 scopy) Example 1 A dry 16 dm 3 vessel was purged with nitrogen and charged with 10 dm 3 of liquid propylene. Then 35 cm 3 of methylaluminoxane solution in toluene MAO, corresponding to 50.7 mmols of Al, having an average degree of oligomerization n 30) were added and the batch was stirred at for 15 minutes. 12 g of ethylene were then added.

S.r. Meanwhile, 52.5 mg 0.103 mmols) of bisindenylethylenei hafnium dichloride were dissolved in 16 cm 3 of MAO 23.2 mmols of Al) and preactivated by being left to stand for 15 minutes.

The solution was then added to the vessel. The polymerization system was brought to a temperature of 60C and the polymerization begun. During the following 120 minutes, 38 g of ethylene were added in small portions and the temperature maintained.

14 1.33 kg of random ethylene-propylene copolymer were obtained. The activity was thus 12.7 kg of PP/g of metallocene/h or 6.5 PP/mmols of Hf/h.

The following analytical data were determined from the polymer: VZ 168 cm 3 M, 196000 g/mole, Mn 44550 g/mole, 4.4, n2 1.0, 3.5 by weignt of incorporated ethylene, T. 126.5 0 C, AH 65 J/g.

Example 2 6o o The procedure of Example 1 was followed. 23 g of ethylene S to were charged. During the polymerization, 68 g of ethylene were metered in.

The polymerization time was likewise 2 hours. 40.0 mg (0.078 mmols) of metallocene compound were used. 1.42 kg of random ethylene-propylene copolymer were obtained. The activity of the metallocene was thus 17.8 kg of PP/g of metallocene/h or 9.0 kg of PP/mmol of Hf/h.

VZ 182 cm 3 M, 207000 g/mole, M, 46000 g/mole, Mw/Mn 4.5, n 2 1.0, 6.4 by weight of incorporated ethylene, Tm 127°C, AH 67 J/g.

S Example 3 The procedure of Example 1 was followed. 1.5 g of ethylene were charged. During the polymerization, 4.5 g of ethylene were metered in.

The polymerization time was likewise 2 hours. 49.0 mg (0.096 mmols) of metallocene compound were used. 2.43 kg of random ethylene-propylene copolymer were obtained. The activity of the metallocene was thus 22.8 kg of PP/g of metallocene/h or 11.6 kg of PP/mmol of Hf/h.

VZ 137 cm 3 M, 151000 g/mole, M 30200 g/mole, Mv/M. 5.0, nr2 1.0, 2.4 of incorporated ethylene, Tm 126:C, AH 69 J/g.

Example 4 The procedure of Example 1 was followed, but 13.5 g of ethylene were charged. During the polymerization, 40 g of ethylene were metered in.

The polymerization time was likewise 2 hours. 53.4 mg (0.105 mmol) of metallocene compound were used. 2.53 kg o10 of random ethylene-propylene copolymer were obtained. The activity of the metallocene was therefore 23.7 kg of PP/g of metallocene/h or 12.0 kg of PP/mmol of Hf/h.

VZ 154 cm 3 M, 168000 g/mole, Mn 303500 g/mole, M./Mn 5.8, nc 2 1.0, 2.1 by weight of incorporated ethylene, Tm 126.8"C, AH 70 J/g.

Example The procedure of Example 1 was followed, but 30.5 g of ethylene were charged. During the polymerization, 92 g of ethylene were metered in.

The polymerization time was likewise 2 hours. 56.5 mg (0.ill mmol) of metallocene compound were used. 1.45 kg of random ethylene-propylene copolymer were obtained. The activity of the metallocene was thus 15.5 kg of PP/g of metallocene/h or 7.9 kg of PP/mmol of Hf/h.

VZ 190 cm 3 M, 217000 g/mole, M, 41750 g/mole, 5.2, nc2 1.0, 8.4 of incorporated ethylene, Tm 127°C, AH, 61 J/g.

Example 6 The procedure of Example 1 was followed. 13 g of ethylene 16 were charged and then 120 g of 1-butene. During the polymerization, 40 g of ethylene were metered in.

The polymerization time was likewise 2 hours. 64.5 mg (0.127 mmol) of metallocene compound were used.

2.05 kg of random ethylene-propylene-butene terpolymer were obtained. The activity of the metallocene was thus 15.9 kg of PP/g of metallocene/h or 8.1 kg of PP/mmol of Hf/h.

SVZ 160 cm 3 M, 179000 g/mole, Mn 40000 g/mole, I *10 M,/Mn 4 n 2 1.0, 2.6 of incorporated ethylene, T. 126.5 0 C, AH. 65 J/g.

Example 7 S The procedure of Example 1 was followed, 35 g of ethylene were charged and then 70 g of 1-butene. During the polymerization, 105 g of ethylene were metered in.

The polymerization time was likewise 2 hours. 64.5 mg (0.127 mmol) of metallocene compound were used. 2.70 kg of random ethylene-propylene-butene terpolymer were obtained. The activity of the metallocene was thus 21.0 kg of PP/g of metallocene/h or 10.6 kg of PP/mmol of Hf/h.

VZ 130 cm 3 M, 142000 g/mole, M, 26320 g/mol, M,/M 5.4, n, 1.0, 5.2 of incorporated ethylene, T. 126°C, AH, 67 J/g.

Example 8 The procedure of Example 1 was followed, but 50°C was selected as the polymerization temperature. 30 g of ethylene were charged. During the polymerization, 95 g of ethylene were metered in.

-17- The polymerization time was likewise 2 hours. 55.7 mg (0.110 mmol) of metallocene compound iiere used. 2.15 kg of random ethylene/propylene copolymer were obtained. The activity of the metallocene was thus 19.3 kg of PP/g of j 5 metallocene/h or 9.8 kg of PP/mmol of Hf/h.

VZ 134 cm 3 M, 115000 g/mole, M, 20900 g/mole, Mw/M 5.5, ncr 1.0, 5.7 of incorporated ethylene, Tm 1270C, AHm 69 J/g.

Example 9 The procedure of Example 1 was followed, but 70 0 C was o selected as the polymerization temperat.re. 11 g of ethylene were charged. During the polymerization, 35 g of ethylene were metered in.

oo: The polymerization time was likewise 2 hours. 45.5 mg (0.089 mmol) of metallocene compound were used. 1.74 kg of random ethylene/propylene copolymer were obtained. The activity of the metallocene was thus 19.1 kg of PP/g of metallocene/h or 9.7 kg of PP/mmol of Hf/h.

9,4.

VZ 158 cm 3 M, 158000 g/mole, Mn 32400 g/mole, i| :2 0 M/M, 4.9, nc 2 1.0, 2.6 by weight of incorporated ethylene, Tm 128 0 C, AH 68.5 J/g.

Example The procedure of Example 1 was followed, but the catalyst used was bisindenyldimethylsilylhafnium dichloride. 10 g of ethylene were charged. During the polymerization, 35 g of ethylene were metered in. Polymerization was carried out for two hours at 600C. 53 mg (0.099 mmol) of metallocene compound were used. 0.88 kg of random ethylene-propylene copolymer were obtained. The activity of the metallocene was thus 8.3 kg of PP/g of metallocene/h or 4.4 kg of PP/mmol of Hf/h.

18 VZ 285 cm 3 M, 336000 g/mole, M. 65900 g/mole, M./M 5.1, ncz 1.0, 4.9 of incorporated ethylene, T. 127.5°C, AH, 62 J/g.

Example 11 The procedure of Example 10 was followed. 1 g of ethylene was charged. During the polymerization, 5 g of ethylene were metered in. Polymerization was carried out for two hours at 60 0 C. 47.2 mg (0.088 mmol) of metallocene compound were used. 2.4 kg of random ethylene-propylene copolymer were obtained. The activity of the metallocene was thus 25.4 kg of PP/g of metallocene/h or 13.6 kg of qq PP/mmol of Hf/h.

Q 0 VZ 272 cm 3 M, 310000 g/mole, Mn 68000 g/mole, 4.7, nc 1.0, 0.2 of incorporated ethylene, T. 126.5"C, AH. 65 J/g.

Example 12 The procedure of Example 10 was followed. 7.5 g of ethylene were charged. During the polymerization, 25 g of ethylene were metered in. Polymerization was carried out for two hours at 60 0 C. 53.3 mg (0.103 mmol) of metallocene compound were used. 2.3 kg of random ethylenepropylene copolymer were obtained. The activity of the ,metallocene was thus 20.8 kg of PP/g of metallocene/h or S11.2 kg of PP/mmol of Hf/h.

VZ 295 cm 3 M, 349000 g/mole, M. 79000 g/mole, sM/M 4.4, n 2 1.0, 1.3 of incorporated ethylene, Tm 128"C, AHm 67 J/g.

Example 13 The procedure of Example 10 was followed. 11 g of ethylene were charged. During the polymerization, 36 g of ethylene were metered in. Polymerization was carried out 19 for two hours at 60°C. 57.8 mg (0.108 mmol) of metallocene compound were used. 1.7 kg of random ethylenepropylene copolymer were obtained. The activity of the metallocene was thus 14.7 kg of PP/g of metallocene/h or 7.8 kg of PP/mmol of Hf/h.

VZ 277 cm 3 M, 320000 g/mole, M 77600 g/mole, 4.2, nC 2 1.0, 2.7 of incorporated ethylene, Tm 127"C, AH. 63 J/g.

Example 14 The procedure of Example 1 was followed. 37 g of ethylene were charged. During the polymerization, 112 g of ethylene were metered in. Polymerization was carried out for two hours at 60 0 C. 53.6 mg (0.100 mmol) of metallocene compound were used. 2.0 kg of random ethylene-propylene copolymer were obtained. The activity of the metallocene was thus 18.7 kg of PP/g of metallocene/h or 10.0 kg of PP/mmol of Ff/h.

VZ 284 cm 3 M, 334000 g/mole, M n 67000 g/mole, M,/Mn 5.0, nc 2 1.0, 7.4 of incorporated ethylene, S 20 Tm 126.5 0 C, AH m 64.5 J/g.

Claims (3)

1. A process for the preparation of a propylene copoly- mer composed of 99.9 to 80.0 mol relative to the total polymer, of propylene units and 0.1 to

20.0 mol relative to the total polymer, of units which are derived from ethylene or from an olef in with at least 4 carbon atoms of the formula R -CH=CH-R where R1 5 and R6 are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms or R1 5 and R 1 6 with the carbon atoms bonding them form a ring having 4 to 28 carbon atoms, by polymerizing 50 to

99.5 by weight, relative to the total amount of monomers, of propylene and 0.5 to 50 by weight, relative to the total amount of monomers. of at least one representative of the group COIAiiting of ethylene and olefinis having at least 4 carbon atoms of the formula R' 5 -CH=CH-R1', where R15 and R1 6 have the meaning given above, at a temperature of 300C to 1500C at a pressure of 0.5 to 100 bar in solution, in suspension or in the gas phase in the presence of a catalyst comppsed of a metallocene and an alumin- oxane, wherein the metallocene is a compound of the formula I I F 'I p S *4 50 0 444 044* O 44 0 4444 0 4444 *44 o 4~ 44 0 44 44444444 0 44 4 044 4 0441 44 *4*44 4444 4 4 4444 4444 44 14 44 4 44. .44441 I R 7 (CRSR 9 )r (I) m1 1 Ra8 in which R1 and R 2 are identical or different and denote a hydrogen atom, a Cl-Cl-alkyl group, a C3.- C o-alkoxy group, a CO-C 1 -aryl group, a Cr- C 10 -aryloxy group, a C 2 -Co-alkenyl group, a C 7 -C 0 -arylalkyl group, a C 7 -C 4 -alkylaryl 4 I 21 group, a Ce-C 40 -arylalkenyl group~ or a halogen atom, R 3 R 4 R 5 and R 6 are identical or different and denote a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group, a radical -NR2 0 -SR' 0 -OSiR3 I SiR- 10 3 or -PR 2 in which R1 0 is a C 1 -Cl 0 -alkyl group, a Cr,-Cl-aryl group or if the radical contains Si or P may also be a halogen atom, or each pair of adjacent radicals R 3 R4, R' or R forms. a ring with the carbon atoms linking them, R 7 is 00 0 0* R11 I M1 R 12 R11 R 1 1 M I i I R 1 2 R 1 2 '1 13 M 4- CR 2 -0 M- I R12 I I 0 M1- 0 -C R12 R12 00 00 00 =BR 11 =A1R 11 =S0, =S0 2 R, =CO, -PR 11 Or =P(0)R 1 oo where R11, R 1 2 and R 13 are identical or different and denote a hydrogen atom, a halogen atom, a Cl-C 3 -alkyl group, a Cl-C-fluoroalkyl group, a CB-Cl-aryl group, a Cb-Clo-fluoroaryl group, a C,-Cl.-alkoxy group, a C?--Cl-alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group, a C7-C4-alkyl- 121 aryl group or R 11 and R 1 or R' 1 and R 1 in each case form a ring with the atoms bonding them, Mis silicon, germanium or tin, R 8 and R I are identical or different and have the meaning given for R 11 m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and the aluminoxane is one of the formula (II) then to react the aluminum compound with water. In addition to the processes which have been described 22 R14 Rl4 R 14 Al- 0 Al O Al (II) l- oP R14 p R 14 in the instance of the linear type and/or of the formula (III) R14 (III) .Al in the instance of the cyclic type, R 1 in the formulae (II) and (III) denoting a Ci-C-alkyl group and p denoting an integer from 2 to 2. The process as claimed in claim 1, wherein the metallocene is a compound of the formula I in which the radical (CR 8 eR).-R 7 (CR 8 denotes -CH 2 -CH 2 -Ge(CH 3 2 -Si(CH 3 2 -Si(C6H,) 2 or -Si(CH 3 )(C 6 H 5 3. The process as claimed in claim 1, wherein the metallocene is ethylenebisindenylhafnium dichloride or bisindenyldimethylsilylhafnium dichloride. 4. A random propylene copolymer composed of 99.9 to 80.0 mol relative to the total polymer, of propylene units and 0.1 to 20.0 mol relative to the total polymer, of units which are derived from ethylene or from an olefin with at least 4 carbon atoms of the formula R"-CH=CH-R 16 where R 1 and R l6 are identical or different and denote a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms or R 15 and R 16 form a ring of 4 to 28 carbon atoms with the atoms bonding them, the said copolymer having an average molecular weight of more than 23 100000 g/mole, a polydispersity of 2.5 to 5.5 and a sequence length of below 1.25. The use of the propylene copolymer prepared as claimed in claim 1 for the preparation of sheets for thermoforming, and for the blowmolding of hollow articles. 2 0- I 0 0 4 o 0 v* 0I 0 DATED this 13th day of February 1990. HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 'THE ATRIUM" 290 BURWOOD ROAD HAWTHORN. VIC. 3122. @040 0#4* R 5554 it It 55155 III I *4 4 L