DE1595623A1 - Process for the preparation of polyolefins with broad molecular weight distribution - Google Patents

Description

Frankfurt (M) -Hoechst

Appendix I.

to the patent application Fw

April 21, 1960 Dr.Gi/br

5067

Process for the preparation of polyolefins with a broad molecular weight distribution

It is known that ethylene can be used at lower pressures Can polymerize organoaluminum compounds and titanium compounds to form polyethylene.

A technically important catalyst system exists

a) from the solid reaction product of TiCl ^ with chlorine-containing Aluminum alkyl compounds such as diethylaluminum mono-

chloride or ethylaluminum sesquichloride and -Di

b) made of lithium aluminum monochloride as an activator. To the rain

of the molecular weight, hydrogen is used.

According to the German Pat. No. 1,049,584 the reaction of TiCl ^ and organoaluminum compounds in the weiten.Temperaturbereich from -50 ° C BLS can be carried +150 ⁰ C.

The polyethylene produced with the aid of this catalyst system has a relatively broad molecular weight distribution.

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The molecular weight distribution particularly influences the flow behavior of the melt. By widening the Molecular weight distribution can increase the flow rate of the melt. In extrusion processing In many cases, therefore, polymers with a broad molecular weight distribution are drawn to those with a narrower molecular weight distribution because of the higher flow rate before. However, a higher flow rate can also be achieved by using polymers. a lower one Molecular weight obtained. However, the vom Molecular weight dependent mechanical properties.

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According to Belgian patent / 655 984, polymers with a broad molecular weight distribution are obtained during the polymerization in at least 2 zones or reactors in which different reaction conditions are maintained, such as different amounts of regulators, such as hydrogen, or different contact concentrations. According to a proposal that does not belong to the state of the art, a polyethylene with a broad molecular weight distribution is obtained if a mixture of trivalent titanium compounds is used as the titanium-containing component, which are produced by reducing TiCl ^ and Ti (OR) ₂ Cl ₂ by chlorine-containing organoaluminum compounds.

The present invention relates to a process for the production of polyolefins with a very broad molecular weight distribution (Mw _ ^ η) and high flowability through

Mn
Polymerization of ethylene alone or ethylene with up to 5 wt -.% Butene (l) or propylene after the low-pressure process in an inert solvent using Ziegler-mixed catalysts consisting of reduced titanium compounds and Aluminiumdläthylmonochlorid as an activator, wherein the molecular weight is regulated by hydrogen, which is characterized in that the reduced titanium compounds are a mixture of trivalent titanium compounds

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a) «us 1 part of the ^{solid reaction product produced at -20 0} C to + 25 ° C of titanium tetrachloride with chlorine-containing aluminum alkyl compounds and

b) is used from 0.1-1 parts of the solid reaction product prepared at +30 ⁰ C to +100 ⁰ C titanium tetrachloride »it Aluminiu chlorine-containing" alkyl compounds.

For the preparation of the titanium catalyst of the invention can ■ to 1 part of the b "i -20 ⁰ C to + 25 ° C produced a solid reaction product of tick eit Aluminiuealkylverbindungen chlorine-containing, suspended in an inert solvent, with 0.1 to 1 part of at +30 ⁰ CbIs +100 ⁰ C produced solid reaction product of TiCK with chlorine-containing aluminum alkyl compounds, suspended in an »inert solvent, ■ tables and used in the polymerization.

The production of the reduced titanium compound is carried out in a known manner in an inert solvent, in particular Ib saturated hydrocarbons such as hexane, or heptane hydrogenated diesel oil fractions of the boiling range of 14dc- 220 C carried out, either the titanium tetrachloride undiluted or dissolved in a de »inert solvent in a solution of the halogen-containing organo-aluminum compound added dropwise to the inert solvent or vice versa Solution of the halogen-containing alueiniuraorgani see connection in the titanium tetrachloride solution is added dropwise. As halogen-containing organoaluminum compounds are advantageous Aluminum diethyl monochloride or aluminum ethyl sesquichloride, (an equimolecular mixture of aluminumdläthylonochlald and aluminum ethyl dichloride) are used. The molar ratio

Al (C ₀ H ^) ₀ Cl to TICl should be 0.5 to 1.0. * - j £ ή

The polymerization takes place in a known manner, in inert dispersants such as hexane, cyclohexane or hydrogenated IMeselölfraktionen the above Siedebereicha, wherein Te "Perat \ irish between 50 - 12 <° C, preferably 70 - 85 ⁰ C and at LHIeken from 1-20 at-, preferably 1 - 6 at.

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The organometallic chlorine-containing aluminum compound is used Diethylaluminiummonochlorld in question for the polymerization.

All gaseous olefins are ethylene or mixtures of Ethylene with up to 5% by weight of butene (l) or propylene is used.

The setting of the molecular weights is carried out in a known manner Way through hydrogen.

The polyolefins obtained have a particularly broad molecular weight distribution, the polymer melt therefore shows excellent flowability and is therefore suitable especially for extrusion processing. The received Cables, bottles, etc. show excellent application technology Properties.

The degree of molecular non-uniformity (U-value), which according to GV Schulz, J.makrom. Ch. 1, 1J51 / J9 ^^ 7 as the ratio of Mw. is defined.

Polyethylene, which compares with a catalyst system, existing

a) from the solid Umsetzungeprodukt of tick with chlorine-containing Alkylaiuminiumverbindungen, at 20 ⁰ C, and ""

b) is produced from diethylaluminum monochloride as an activator, shows ^{a U-value of 6-8 with a ^^ d "** * 1} ** ^{of 2} * 7 (measured in 0.1 Jfjger solution in xylene).

If the reduced titanium compound is produced comparatively at 50 ° or 70 ° C., the activation is obtained Polymerization with diethylaluminum monochloride a polyethylene, that at the same molecular weight the same degree of exhibits molecular non-uniformity.

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On the other hand, the mixture according to the invention succeeds old trivalent titanium compounds, the

a) from 1 part of the solid reaction product of TiCl ^ produced at -20 ° to + 25 ° C with chlorine-containing aluminum alkyl compounds

b) au "0.1 to 1 parts of the üesetxungsproduktes prepared at +30 ⁰ C to C 4-100 of TiCl ^ old chlorinated aluminum alkyl compounds, in the presence of £ thylaluminlummonochlorid as activator" polyethylenes or copolymers of ethylene with 5 Qew .- $ To produce butene (l) or propylene »the at have a «^ X _re <j *" ^{value of 2} * 7 (g · »·« »·« in some solution in xylene) U-values of 9-2?

was

It is surprising and / cannot be foreseen by the skilled person

that the broad molecular weight distribution which is solid with the Katalysatorsysten reaction product of TiCl with chlorine-containing alkylaluminum compounds, the reaction can be carried out in the wide temperature range from -20 ⁰ C to +100 ⁰ C, obtained with diethylaluminum monochloride as an activator, can be substantially broadened if the reduced titanium compound is a mixture in the composition according to the invention of solid reaction products prepared in different temperature ranges from TiCIi, with chlorine-containing alkylaluminum compounds in

⁴ Di compound with ethylaluminum monochloride as an activator or begins.

The large technical port step of the process according to the invention for the production of polyolefins with a very broad Molecular weight distribution consists in the fact that no changes in the polymerization conditions, as described in i ^ / Belgian patent / 655 984, must be carried out, and therefore a simple continuous implementation of the process is guaranteed.

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Versuohsbeispiele

l) a) Production of the solid Uasetzungproduct of ■ it Äthylalueiniueseaqulchlorid at 20 ⁰ C,

In a "500 esr four-necked flask, 200 ml of an inert olefin-free diesel oil fraction Voe boiling point l8o be exclusion of air and moisture - submitted to 21O ⁰ C and 37 g (150" mol) Xthylalueiniuesesquiohlorid and at 20 ° C 38 g (200 "mol) of TlCl ₄ trains within 4 hours drips. A fine brown precipitate separates out. For secondary reaction is 10 hrs. Further stirred at 20 ⁰ C and then decant the mother liquor and the precipitate 4 "washed al old 200" 1 Diesel oil.

b) Production of the solid conversion product of TiCIb »it Ethylaluminum quichloride at 50 ° C. The reaction is carried out at 50 ^° C. as indicated under a).

c) Production of the solid reaction product of TiCl ^ ■ with ethylaluminiumesquichloride at OC. The reaction is carried out at 0 ^° C. as indicated under a).

d) polymerization

In a 10 1 Polyeerizationagefläß are excluded of air and moisture 7 1 of a diesel oil fraction (bp. 180-210 ° C) submitted. Then a solution of 16.8 g (14o nmol) DÜtthylaluBiniusanonochlorld in 200 cm Diesel oil fraction added and heated to 80 ° C. at at this temperature the amounts of the titanium catalysts prepared according to ac added and the polymerization carried out by introducing ethylene and hydrogen. After 5 hours At 70 C, the catalyst is decomposed by adding 200 carbons of n-butanol and stirred 3 <** 1 with water. 009834/1740

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After filtration, steam distillation and drying receives aan the amounts of polyethylene given in the table.

The molecular weights (ft _{re (J} , geaessen 0, IJiig in xylene) aowle the U-values can be seen from the table. When processing into bottles, the in the presence of mixtures of TiCl, -catalysts, which are produced at different temperatures Polyethylenes obtained by high flowability, and the bottles show a smooth, pebble-free surface.

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Claims (1)

- 9 - Fw 5067 Claim The method for producing polyolefins "it a particularly broad molecular weight distribution and high PlieifMhigkelt by polymerization of ethylene and copolymerization of ethylene with up to 5 wt -.% Butene (l) or propylene after de" low-pressure process in inert solvents using Ziegler-mixed catalysts consisting of reduced titanium compounds, produced by reacting titanium tetrachloride in inert solvents at temperatures from ^ 20 ⁰ C to +100 C and washing out the solid reaction product, and diethylalurainium monochloride as activator, the molecular weight is regulated by hydrogen, characterized in that the reduced titanium compound a mixture of titanium compounds, consisting of a) 1 part of the solid Uesetzung produced at -20 to + 25 ° C product of titanium tetra chloride with chlorine-containing aluminum alkyl compounds and b) 0.1 to 1 part of the ^{solid reaction product produced at +30 to +100 0} C of titanium tetrachloride with chlorine-containing aluminum alkyl compounds is used. .0 (1983 A / 174 0