DD275693A1 - PROCESS FOR THE PRODUCTION OF OLEFIN POLYMERS - Google Patents

Abstract

The invention relates to a process for the preparation of olefin polymers, in particular high density polyethylenes and of ethylene copolymers, which are suitable for the production of injection molded and selected extruded products. For the process according to the invention, a modified Ziegler catalyst is prepared and used on organic carrier materials which, in a simplified production process, have a high catalytic activity which decreases only slowly in the course of the polymerization. The transition metal component of the catalyst is the reaction product of a halogen-containing organic polymer with initially a complex of an aluminum halide and an electron donor and then with a solvolysierten organomagnesium compound of the general formula RnMgX2-n x Solv., In the R is an organic radical and X is a halogen or a represent an organic radical bonded to magnesium via a heteroatom, solv. is a compound capable of forming an addition compound and n is 1 or 2. By the subsequent reaction with a transition metal compound, for. For example, titanium tetrachloride, the formation of the catalyst according to the invention, wherein the vacuum evaporation of the solvent mixture at both stages of the synthesis process for the formation of the catalyst is of fundamental importance.

Description

in the

R is an alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, alkoxy, silylalkyl, alkylsilyl

oderAmidrest, a ^p with halogen, nitrogen or oxygen hosphor functionalized aryl or terminally functionalized alkyl or alkenyl group means,

X represents halogen, alkoxy or carboxyl ligands,

η is a numerical value of 1 and 2, for example a solvated Grignard compound and

SoIv. for ethers, thioethers, tert. AmIn, tert. Phosphine or for other addition compounds

forming, ligands each having the same or different substituents

stands

and finally with a transition metal compound of the general formula

in the

M is a transition metal of the VV, VoderVI.NebengruppedesPSEI indicates,

X and Y are identical or different ligands Jer from halogen, Cyclopei .tadienyl, allyl, carbonyl, alkyl, alkenyl, aryl, alkaryl, aralkyl, cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, alkoxy, _< Aroxy, -NR'R ", - CH 2 SiRoder- N (SiR ₃ ) _{2 represent} existing ligand group, ' where R, R' and R '' stand for identical or different alkyl, cycloalkyl or aryl radicals,

m is the valency of the transition metal and

η is a number between O and mist.

2. The method according to claim 1, characterized in that the serving as a reaction medium solvent mixture or the hydrocarbon used as diluent and entrainer evaporates both after the addition of the Grignard and after the addition of the transition metal compound in vacuo and the finely powdered residue subjected to a special heat treatment becomes.

3. The method according to claim 1, characterized in that are used as starting polymers for the preparation of the organic polymer carrier polystyrene, polyalkylstyrene or their copolymers with monoolefins and diolefins, preferably with ethylene, divinylbenzene and ethyldivinylbenzene.

4. The method according to claim 1, characterized in that the organic polymer carrier is used in insoluble or in proton-free solvents soluble form.

5. The method according to claim 1, characterized in that the polymerization is carried out in the presence of the catalyst components A and B in suspension, in solution and in the gas phase, whereby olefin polymers of ethylene, propylene and higher homologs and copolymers of ethylene preferably with propylene, butene , Witches and norbornene are produced.

,, Applicable to the invention

I; The invention relates to a process for the polymerization and copolymerization of olefins with modified Ziegler.

; ' Catalyzers, which are fixed on organic carrier materials. Oils invention allows it, preferably polyethylene and

to produce ethylene copolymers with improved properties in highly effective processes.

Characteristic of the known technical solutions

The use of organic support catalysts for olefin polymerization is known (BE-PS 552550, GB-PS 834217, DE-OS 2848907, FR-PS1405371, SU-PS 473395, US-PS 4147664, US-PS 4268418, DE-OS 2922068, US Pat PS 4021599, RO-PS 66659, SU-PS 833305). It should be noted that the catalysts described have only insufficient catalytic activity. The associated relatively high transition metal content of the polyolefin gives rise to problems such as e.g. discoloration of the polymer, signs of aging or the need for subsequent removal of the catalyst from the polyolefin.

Another crucial manga of these methods is the insufficient ability to control certain polymer properties, such as. As the molecular weight, molecular weight distribution and density.

Further, a high productivity polymerization catalyst is known which is prepared by grinding a mixture of magnesium compounds, titanium tetrachloride and ultrafine polyethylene as a diluent (U.S. Patent No. 4,362,648). In addition, a catalyst is known which is particularly suitable for the preparation of branched polyethylene (US Pat. No. 4,329,255). It is prepared by treating magnesium chloride precipitated magnesium chloride with titanium tetrachloride and triethylaluminum.

These methods using supported organic catalysts do not allow the regulation of several polymer characteristics at the same time high catalyst activity.

Significant progress has been made in recent times by the reaction of organic polymer carriers containing alkali metal carbon bonds with magnesium halides or organomagnesium halides and subsequent reaction with transition metal precursors (DD-WP C 08 F 234111 and 234112).

The gross conversion rates of more than 40 kgPE / g Ti xhx bar C ₁ H ₄ described with these catalysts permit a technical preparation of polyoxes

 At the same time essential polymer characteristics are adjustable.

Further improvements aimed at shortening the residence time and at the application of lower pressure with low residual catalyst content have been described in patent applications DD-WP C 08 F 245261 and 245262. The results also included the further increase in catalyst activity. Finally, in a recent invention application, a simplified production process for the last-described organically supported catalysts was disclosed for the first time (DD-WP C 08 F 247905).

However, in terms of economy and industrial practice, further simplification of catalyst preparation was warranted, and catalysts should continue to be characterized by their extraordinary effectiveness and sensitivity to the setting of polymer characteristics.

Object of the invention

The aim of the invention is the preparation of Olefinhomo- and copolymers with organically supported Ziegler catalysts, which are presented in simplified and inexpensive processes.

Explanation of the essence of the invention The technical problem which is solved by the invention

The object of the invention is to develop a process for the preparation of olefin polymers in which Ziegler catalysts are used on organic support materials which can be prepared in a simplified manner and have a high activity which drops only slowly during the course of the polymerization.

The process is intended to simultaneously allow improved controllability of the molecular weight and the production of polymers with narrow molecular weight distribution and wide density ranges

 Features of the invention

The object is achieved according to the invention by preparing and using a catalyst which consists of a solid catalyst component * A and an organometallic compound B, wherein the catalyst component A is the reaction substance r / Ines organic polymer carrier of particular morphology, the ring-halogenated or haloalkyl radicals substituted aromatic Contains structural units, initially with a complex of an aluminum halide and an electron donor, wherein as electron donors ethers, thioethers, amines or phosphines are used and then with a solvatislerten organometallic compound of the general formula

R _n MgX] ^ ₁ x SoIv.

represents, Indian

R is an alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, alkoxy, allyl alkyl, alkylsilyl or amide radical, one having Halogen, nitrogen, phosphorus or oxygen for unalkylated aryl or terminally functionalized alkyl or oxygen Alkonylr est means X represents halogen, alkoxy or carboxyllodane,

η is a numerical value of 1 and 2, for example a solvated Grignard compound and

SoIv. (For ether, thloother, tertiary amine, tertiary phosphine or for other, AdditioRsverbindungen forming, ligands each with

same substituent stands,

in a further step with a transition metal compound of the general formula MX _n Y _1n - ,,

treated, Indians

M is a transition metal of the IV., V. or Vl. Subgroup of the PSE means

X and Y are the same or different ligands selected from halogen, cyclopentadienyl, n-allyl, carbonyl, alkyl, alkenyl, aryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, alkoxy, aroxy, -NR'R ", - CH _{2 represent} SiR ₃ or -N (SiRj) ₂ existing ligand group, where R, R 'and R "represent identical or different alkyl, cycloalkyl or aryl res th,

m is the valency of the transition metal and

η is a number between O and mist.

The organometallic component B contains a metal of the I. to IV. Main group or II. Subgroup of the PSE and is

by activation of the catalyst component A in excess in the gram atom ratio of 10 to 600 to 1, based on the

Transition metal, after a special Vprreaktion or directly into the polymerization reactor in the presence or absence

of the olefin.

The amount of the transition metals fixed on the catalyst component A can be varied widely; it is in the range of

0.1 to 10 wt .-% of catalyst component A.

As starting polymers for the preparation of the organic polymer support polystyrene, polyalkylstyrene or their Copolymers with mono and olefins, preferably with ethylene, divinylbenzene or ethyldivinylbenzen used graze. The organic polymer carriers are the leweiligen purpose accordingly in uncrosslinked, little crosslinked to highly crosslinked

insoluble or in proton-free solvents more soluble or mixed in soluble and insoluble form.

The orgai lischo polymer carrier can, depending on its production or as a result of a grinding process in Kornf raktionon

below 50pm to coarse powder of grain size above 500pm.

Particularly suitable for the purposes of the invention are chloromethyl derivatives of styrene-divinylbenzene copolymeron with 5%

and more DVB than crosslinkers found after their reaction with the Alumlniumhalogenid adduct and the

imagneslumorganlschen compound even before treatment with the transition metal compound at temperatures up to

U63 K from the aliphatic suspending agent and the proportionate polar solvent to be liberated. Finally it is from Importance, the finished organically supported Ziegler catalyst complex for the removal of the last, the catalysis

impairing Solvensresten at elevated temperature under vacuum to heat treatment.

The olefin homo- and copolymers can be prepared in suspension, in solution or in the gas phase. According to the objective weJ the reaction temperature in the range of 343K to 413 K, preferably from 343 to 373K, the Reaction pressure in Beireich from 1 to 50 bar, preferably at 2 to 20 bar and the polymerization time in the range of 0.6 to

10 hours, preferably 0.5 to 3.0 hours chosen.

AusfOhrungsbelsplele All work was carried out under anaerobic conditions. The protective gas used was purified argon. example 1

a) Preparation of the titanium-containing catalyst component

30 g of dry poly-p-chloromethylstyrene-divinylbenzene (5% DVB) of particle size <63 pm having a chlorine content of 20.2% are suspended in hexane and admixed with stirring with 8 mmol of AICI ₁ dissolved in THF. After stirring for 30 minutes, a THF solution containing 83 mmol of n-butylmagnesium chloride is slowly added dropwise, and after further intensive mixing, the solvent is evaporated at room temperature in vacuo. The residue is re-slurried with hexane, the evaporation process repeated and the temperature carefully raised to 363K to remove the last traces of solvent. Then the residue in hexane suspension is treated dropwise with stirring 32 mmol of TiCl ₄ and after 30 minutes of continuous mixing again brought to room temperature in vacuo to dryness. After final drying at 323 K in vacuo, a dusty, reddish-gray powder with the following analyte data results: 2.71Ma .-% TI, 4.00Ma .-% Mg, 1.03Ma .-% Al, 20.9Ma, -% CI ,

b) Polymerization by means of the titanium-containing catalyst component

1. A Rflhrautoklav with 21 volume is charged with 11 hexane, in which 4 mmol 1-Bu ₁ Al and 22.1 mg of the catalyst component according to the invention are included. After pressing on 3.0 bar of hydrogen and 3.0 bar of ethylene, the mixture is heated with vigorous stirring to 358 K and made by yielding ethylene to a total pressure of 7.8 bar, corresponding to a ethylene partial pressure of 2.9 bar and a Hydrogen partial pressure of 3.7 bar. By continuous dosing of the reacted ethylene, the conditions are kept constant throughout the duration of the experiment. After 1 hour, the polymerization reaction is stopped by blocking the ethylene feed and cooling rapidly, the autoclave is depressurized and its contents are filtered.

The yield to polyothylene is equal to 10% of the gross volume of the feedstock. EkgPE / gTi xhx barC ₁ H ₄ or 1.724 kg PE / gKot, χ hx bar C ₁ H ₄ . Dor melt index at 5kg load is 18.3g / 10mln.

2. An ethylene-hydrogen partial pressure ratio of 1.2 * u 1.6bar is used in a two-part polymer dispersion, the experiment being carried out as above, but with the difference that the test duration is now 2 hours. 14.8 mg of the catalyst component described under a) produce 53.8 g of polyethylene in 2 hours, which corresponds to an average gross conversion rate of 55.9 kg PE / g Tl xhx bor CjH ₄ or 1.514 kg PE / g cat, xhx barC] H ₄ . MFIt "18,2g / 10min.

3. In a third experiment, an ethylene-hydrogen partial pressure ratio of 2.1 to 2.7 bar is used. The dissolution is carried out as described under 1., but with the change that the polymerization time now lasts 4 hours. 19 mg of the lower) described catalyst component yield 178 g of polyethylene in 4 hours, which corresponds to a productivity of 345.9 kg PE / g Ti or 9.37 kg PE / g cat. MFI ₆ = 15.2 g / 10 min.

Example 2

a) Preparation of the titanium-containing catalyst component

The procedure for preparing the catalyst component is similar to that of Example 1, except that instead of 83mmol n-butylmagnesium chloride 62 mmol ethyl magnesium bromide are used and the amount of titanium tetrachloride is reduced to 19 mmol. The resulting light brown powder contains 1.66Ma% TI; 3.08Ma .-% Mg; 0.27 Ma .-% Al; 18.1 mass% Cl; 11.5Ma .-% Br.

b) polymerization

The polymerization is carried out according to Example 1 b), but with the modification that not 4 mmol of i-BujAI, but 6mmol are used as cocatalyst. 18.1 mg of the catalyst component described under a) give at a ethylene-hydrogen partial pressure ratio of 2.9 to 3.7 bar in 1 hour 51. g of polyethylene, corresponding to a gross conversion rate of 58.8 kg PE / g Ti xhx bar C ₂ H ₄ or 0.975 kg PE / g cat. Xhx χ bar C ₂ H ₄ · MFI ₆ = 13.9 g / 10 min.

Beisplei 3

a) Preparation of the titanium-containing catalyst component

The preparation of the catalyst component corresponds to the procedure given in Example 1, with the difference that 30 g of the finely powdered poly-p-chloromethylstyrene derivative (20.2% Cl) are now mixed with 23 mmol aluminum chloride, 62 mmol n-butylmagnesium chloride and 6.3 mmol! Converts titanium tetrachloride. The light gray dust powder contains 0.6iMa .-% TI; 3.66Ma .-% Mg; 1,06Ma .-% Al; 21,1Ma .-% CI.

b) polymerization

The polymerization corresponds in detail to the procedure given in Example 1. 20.7 mg of the catalyst component described under a) give 40.4 g of polyethylene, corresponding to a gross conversion rate of 110.3 kg PE / g Ti xh χ bar C ₂ H ₄ or 0.673 kg PE / g cat. Xhx bar C ₂ H ₄ · MFI ₆ «17,9g / 10min.

Example 4

a) Preparation of the titanium-containing catalyst component

The catalyst component is prepared according to the procedure given in Example 2, but with the Modification that the amount of aluminum chloride is increased to 23 mmol. The result is a hello-brown powder with the following Analytical data:

. ~ 1,74Ma% Ti; 2,62Ma .-% Mg; 0,84Ma .-% Al; 18.5Ma .-% C1; 8.3mA .-% B (.

b) polymerization

The polymerization succeeds; According to Example 2.25.6 mg of the untar a) described, with 6mmol i-BujAI activated catalyst component produce 60.6 g of polyethylene, resulting in a gross conversion rate of 46.9 kg PE / g Ti χ hx bar C ₂ H ₄ or 0.817kg PE / g cat. xhx bar C ₂ H ₄ equals. The MFI ₍ 13,9g / 10rnin.

Example 5

a) Preparation of the titanium-containing catalyst component

In a modification of the given in Example 1 synthesis rule comes as a carrier now less strongly chloromethylated poly-p-chloromethylstyrenedivinylbenzene (5% DVB) are used. 30 g of strongly dried, ultrafine powdered product with a chlorine content of 12.8% Cl are treated as described in Example 3 with 23 mmol of aluminum chloride, 62 mmol of n-butylmagnesium chloride, dissolved in THF, and 6.3 mmol of titanium tetrachloride, dissolved in hexane. The resulting light gray colored catalyst component contains 0.66Ma.% Ti; 3.35Ma.% Mg; 1,27Ma .-% Al; 17,85Ma .-% CI.

b) polymerization

The polymerization is carried out according to Example 1. 18.1 mg of the catalyst component described above give 22.6 g of polyethylene, which corresponds to a catalyst activity of 65.2 kg PE / g Ti xhx bar C ₂ H ₄ or 0.431 kg PE / g cat. Xh χ bar C ₂ H ₄ . MFI ₆ " 14.9 g / 1 OmIn.

Verglichsbelsplel 1

a) Preparation of the titanium-containing catalyst component

16g sharply dried and up to particle size <63pm milled Polyrtyrendivlnylbenzen (5% DVB) are reacted according to the procedure described in Beisplei 2 with 4mmol aluminum chloride, 31 mmol Ethylmngneaiumbromid and 9.5mmol titanium tetrachloride. A light brown powder was obtained with the following analytical values: 1.66Ma.% Ti; 3.04% by weight of Mg; 0.26 mass% Al; 6.3% by weight of Cl; 9.5Ma .-% Br.

b) polymerization

Under the polymerization conditions according to Example 1, 23.8 g of polyethylene are obtained with 23.8 mg of the above-described catalyst component. This corresponds to a catalyst activity of 21.4 kg PE / g Tiχhx bar C ₂ H ₄ or 0.333 kg PE / g KM. xhx bar C ₂ H ₄ · MFI ₅ - 6.5g / 10mln.

Verglelchsbelsptel 2

a) Preparation of the titanium-containing catalyst component

In the present case, the catalyst component is prepared without using βίηβ3 organic carrier. By reaction of 24mmol of aluminum chloride, 186mmol of ethyl magnesium bromide and 57mmol of titanium tetrachloride according to the procedure generally employed, a dark gray colored product containing 5.86% by weight of Ti is obtained.

b) polymerization

In the polymerization carried out according to Example 1, 25.3 mg of the above catalyst component yielded, upon application of an ethylene-hydrogen partial pressure ratio of 2.9 to 3.7 bar in 1 hour, a yield of 54.2 g of polyethylene, a catalytic actor of 12 , 6kg PE / g Tiχhx bar C ₂ H, or 0.739 kg PE / gKat. χ h χ bar CjH ₄ corresponds. The melt index at 5kg load is 12.5g / 10mln.

Claims (1)

1. A process for the preparation of olefin homo- and copolymers by preparing and using a modified Ziegler catalyst of a solid catalyst component A based on an organic polymer support of certain morphology, the ring-halogenated or haloalkyl radicals substituted aromatic compounds and an organometallic component B, characterized in that the catalyst component A of the catalyst is prepared by reacting the organic polymer support first with the complex of an aluminum halide and an electron donor, using ethers, thioethers, amines or phosphines as electron donors, then with a solvolysed organomagnesium compound of the general formula R _n MgX _2. ,, x SoIv.