AU606210B2 - Catalyst for olefin polymerization - Google Patents

Description

SIgnatture of Applicant (s) or Seal of Cornpany and Sig natures of Its Officers as prescribed by Its Articles of Association, M002 825 HOECHST AKTIENGESELLSCHAFT by D. B. Mischlewski 1 5/0~9/8 egserd!atn Attnrn" ii :4 a'

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Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class I t. Class Application Number: Lodged: ccComrplete Specification Lodged: I C.

to I S Pri9tity: Cr o c Related Art #4 4 I t1 #4 o #0 Accepted: Published: [Thiis docunictnt cotntains the 1amendnici-as miade ni Section 49 arid is c;orrect for Printing., 9 0 4 Name of Applicant, HOECHST AKTIENGESELLSCHAFT Address of Applicant: Actual inventor: Address for Service: Bruningstrasse, D-6230 Frankfurt/Main 80, Federal Republic of Germany WALTER KAMINSKY and HARTMUT MADLER EDWD. NVATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specif icatkon for the invention entitled: CATALYST FOR OLEFIN POLYMERIZATION The following statement is a full descripson of this invention, Including the best method of performing It kn~own to Ius

L

To the Commissioner of Patents HOECHST AKTIENGESELLS AFT PAT 510 Prokurist Authorized Signat ry ppa. Isenbruck i.V. Lapice -la- HOECHST AKTIENGESELLSCHAFT Dr.DA/gm HOE 87/F 269 Description Catalyst for olefin polymerization The present invention relates to a catalyst for olefin polymerization which consists of a transition metal coipound and an organometaLLic compound and in which the organometallic compound is a reaction product of a hydroxy i compound with an organoaluminum compound.

A process for the preparation of polymer masses from poly- 10 olefins and starch in which the active cocatalyst is pre- S, pared by reaction of starch with AL-trialkyls in order then to be used for the polymerization together with a metallocene is known (cf. German Patent 3,007,433,.

's Aluminoxanes are first formed here due to the residual S, 15 water content of the starch, and then further react with t 4 the OH groups of the starch (cf. Kaminsky et al. in ta Reichert, Polymer Reactions Engineering, Hanser-Verlag t9 t 1983, pages 208 220, in particular pCge 217, Figure 7).

The production of such aluminoxane-containing products by water bonded adsorptively to an organic carrier is difficult, however, because the carrier material has to be dried to a certain residual water value. This drying process is energy-consuming and the residual water content can be brought to a defined value only with difficulty.

If highly dried starch is used, the starch/AL-trialkyl/ metallocene system no longer shows any polymerization activity at all, It has now been found that a highly active ctalyst is formed if the reaction product of a compound with one or more sufficiently acid hydroxyl groups with an aluminum trialkyl is used as the cocatalyst, Suitable compounds with one or more sufficiently acid i i L. 2 hydroxyl groups are, for example, C 2 to C 10 preferably

C

6 to C 8 -polyalcohols, C 3 to C6-monosaccharides and diphenols. Compounds which may be mentioned are sorbitol, glucose, erythritol, 1,4,3,6-dianhydrosorbitol, monoanhydrosorbitoL, pyrocatechol, resorcinol, glycol, diphenols, hydroquinone and isosorbitol, preferably glucose.

These substances are reacted with an aluminum trialkyl with up to five carbon atoms in the alkyl chain, preferably aluminum trimethyl. For this, the hydroxy compound is dissolved or suspended in an inert solvent and the Saluminum trialkyl is added. The reaction is carried out Sat a temperature of 0 to 60, preferably 20 to 40 0 C and takes 15 to 240, preferably 100 to 140 minutes.

0 9° An amount of aluminum trialkyl equivalent to the number of OH groups on the carrier material (1 mole of Al per OH group) is used. Compositions which are assumed to have o 99 S the following structure, represented by the example of dianhydrosorbitol, are thereby obtained SR Al

R

OH 0 S25 (n 1) AIR 3 2nRH OH I0; I R 2 n A solvent which is also used for the polymerization is preferably used for the reaction.

The transition metal compound of the catalyst according to the invention is a compound of the formula I (cp) 2 MeRHal (1) in which cp denotes a cyclopentadienyl radical and Me denotes titanium, zirconium or hafnium, preferably zirconium, R is a cyclopentadienyl radical, a halogen atom, 3 3 preferably chlorine, or a C 1 to C 6 preferably C 1 to

C

3 -alkyl group, and Hal denotes a halogen atom, preferably chLorine, or a compound of the formula II VOnCL3-n

(II)

t ~C rt I I IC

II-

C C( It(: I II 4 1 1I 4.

.l in h n denotes 0 to 3.

The catalyst according to the invention is used for the polymerization of 1-olefins of the formula R-CH=CH 2 in which R denotes a hydrogen atom or an alkyl radical with 1 to 28 carbon atoms, preferably 1 to 10 carbon atoms and in particular one carbon atom, for example ethylene, propylene, but-l-ene, hex-l-ene, 4-methylpent-l-ene or oct-1-ene.

Ethylene is particularly preferred.

20 The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or discontinuously, in one or more stages at a temperature of -60 to 100 0 C, preferably -20 to 80 0 C. The pressure is 0.5 to 64 bar. The polymerization in the pressure 25 range of 5 to 64 bar, which is of particular industrial interest, is preferred.

The transition metal compound is thereby used in a concentration, based on the titanium, zirconium or vanadium, of 10 3 to 10 7 preferably 10 4 to 10- 6 mole of Ti, Zr or V per dm 3 of solvent or per liter of reactor volume. The organometallic compound is used in a concentration of to 101 mole, preferably 10 3 to 10 2 mole per dm of solvent or per dm 3 of reactor volume. In principle, however, high concentrations are also possible.

The polymerization is carried out in an inert solvent customary for the Ziegler low-pressure process, for example I S-4 in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane. A benzine or hydrogenated diesel oil fraction which has been thoroughly freed from oxygen, sulfur compounds and moisture can furthermore be used. Toluene can also be employed. Finally, it is also possible to use the polymerizing monomers as the solvent or suspending agent. The average molar mass of the polymer can be regulated in a known manner; hydrogen is preferably used for this.

SThe great advantage of these novel catalyst systems is, inter alia, that the novel cocatalysts are at the same c r S time passive fillers and active catalytic compounds.

In addition, polyolefins which have extremely high average molar masses and are of particular industrial interest can be produced with the novel catalyst systems.

S 20 Example 1 100 cm of toluene were taken in a 250 cm round-bottomed flask and 5 g of glucose (28 mmol) were suspended therein.

140 mmol of aluminum trimethyl, dissolved in 50 cm 3 of toluene, were added dropwise in the course of 30 minutes, with vigorous stirring. The mixture was allowed to afterreact at room temperature for a further 120 hours.

It was possible to use the reaction product directly as the suspension for the polymerization.

Example 2 The procedure was as in Example 1. In deviation, 5 g of sorbitol (27.4 mmol) were taken and were reacted with 165 mmol of aluminum trimethyl.

Example 3 Preparation of an aluminoxane-analogous cocataLyst from isosorbitol and AL(CH 3 3 801.4 mg (5.2 minoL) of 1,4;3,6-dianhydro-D-sorbitoL were introduced into a 250 cm 3 round-bottomed fLask and suspended in 20 cm 3 of absolute toluene. 80 cm 3 of a solution of AL(CH 3 3 in toluene (20.8 mmoL) were added dropwise as rapidly as possible at 0 100C, with vigorous stirring. The molar ratio of hydroxyl groups to ALMe 3 10 was 1:2.

f e.

4 Vigorous evolution of gas initially took place, and the S' mixture also heated up. The preliminary reaction was allowed to proceed for about a further 48 hours, with stirring. However, after a reaction time of only two So hours, the previously heterogeneous suspension had changed into a milky, cloudy solution. Undissolved isosorbitol was no longer present. When the toluene was stripped off Sat the end of the experiment, a colorless, vitreous solid 20 substance was obtained. Like methylaluminoxane, the substance was pyrophoric in air. The cryoscopically determined degree of oligomerization was n 4 (M 1120 g/mol).

Example 4 Preparation of the cocatalyst from erythritol and AL(CH 3 )3.

3.175 g of erythritol (dry, 26 mmol) was suspended in 100 cm 3 of absolute toluene. 100 cm 3 of a solution of AL(cH 3 3 in toluene (104 mmol) was rapidly added dropwise at 0OC. After one hour, the batch was heated to room temperature and allowed to further-react for another 48 hours. For a typical polymerization, 1/5 of such a batch was used as the cocatalyst for the polymerization.

Example Polymerization with the modified catalyst system 6 1,4;3,6-dianhydrosorbitol/AL(CH 3 3 -VCl 3 504 mg (3.2 x 10 3 mol/dm 3 of VCL 3 310 cm 3 of absolute toluene and 10 cm 3 of a solution, previously prepared in accordance with Example 3, of the reaction product of 1,4;3,6-dianhydrosorbitol and AL(CH 3 3 were added in succession to a previously evacuated, thoroughly heated 1 dm 3 gLass autoclave flushed with argon, in a countercurrent of argon.

.After adjusting the temperature of the solution to 70 0

C,

4' the polymncrization was started by forcing in ethylene r t (8 bar) and was continued for 2 hours.

Yield: 34.7 g 3 Productivity: 212 g of PE/g of V Viscosity number: 34.1 cm 3 /g o 9 Example 6 o The cocatalyst prepared in Example 1 was suspended in toluene. 10 2 mole of this suspension, based on the aluminum, were introduced into a glass autoclave filled 3 4 with 300 cm of toluene. The temperature of the suspension was adjusted to 70 0 C, 3 x 106 mole of dicyclopentadienyl-zirconium dichloride were added and polymerization was carried out with ethylene under a pressure of 7 bar for 1 hour.

Yield: 3.1 g Productivity: 11230 g of PE/g of Zr i Molar mass: 80,000 Density: 0.98 g/cm 3

Claims (4)

1. -7- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A catalyst for olefin polymerization consisting of a transition metal compound and an organometallic compound, in which the transition metal compound is a compound of the formula I (cp)2 MeRHal (I) t in which Scp denotes a cyclopentadienyl radical, Me denotes titanium, zirconium or hafnium, I R is a cyclopentadienyl radical, a halogen atom or a C to C 6 -alkyl group and Hal denotes a halogen atom, or a compound of the formula II 0nC 3n (II) in which n denotes 0 to 3, and the organometallic compound has been obtained by reaction of a Cg 10 polyalcohol, C 3 6 monosaccharide or C,_ 6 diphenol with an aluminum trialkyl.

2. A process for the preparation of a catalyst for olefin polymerization by bringing together a transition metal compound as defined in claim 1 with an organometallic compound, which comprises using the reaction product of a C 2 -1 0 C3 6 monosaccharide or C_ 6 diphenol with an aluminum trialkyl as the organometallic compound.

3. Use of a catalyst as claimed in claim 1 for polymerization of a 1-olefin of the formula R-CH-CH 2 in which R denotes a hydrogen atom or an alkylene radical with 1 to 28 carbon atoms. 4 T 8

4. A process for the preparation of a 1-olefin polymer by polymerization of a 1-olefin of the formula R-CH=CH 2 in which R is a hydrogen atom or an alkyl group with 1 to 28 carbon atoms, at a temperature of -60 to 100 C under a pressure of 0.5 to 64 bar solution, in suspension or in the gas phase, in the presence of a catalyst which con- sists of a transition metal compound and an organometallic compound, which comprises carrying out the polymerization in the presence of a catalyst, the transition metal com- pound of which is a compound of the formula I s '(cp)2 MeRHal (1) in which cp denotes a cyclopentadienyl radical, Me denotes titanium, zirconium or hafnium, R is a cyclopentadienyl radical, a halogen atom or a CI- to C 6 -aLkyl group and Hal denotes a halogen atom, or a compound of the formula II VOnCl3-n (II) in which n denotes 0 to 3, and the organometallic compound of which has been obtained by c a-io Pcnaq^-^ol C3-ep ^OnOiQCe.otc reaction of a compound, r=th jr C- 'pV I nc tB- p with an aluminum trialkyL. DATED this 14th day of September 1988. IIOECHST AKTIENGESELLSCHAFT EDWD. WATERS SONS PATENT ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000. S, i