FI57766B - FOERFARANDE FOER HOMOPOLYMERISERING OCH SAMPOLYMERISERING AV ETYLEN SAMT VID FOERFARANDE ANVAEND KATALYSATOR - Google Patents

Description

['ΪΤΤΤ ^' Η Γβΐ / «« ANNOUNCEMENT rnqcs V®Ta -W <11> utlAggningssiciuft 5 / / 66 ίκ® c (4S) Patent filed 10 10 1930 .Parent g Odd e · iät '(S1) hi.W3 C 08 F 10/02, 4/02 SUOMl-FINLAND (mj νμμμμμ — ammmMi 31.6 / 72 Ρ, Η — NHM-AM **, 0ä- ° 2-72 'ΓΙ' (23) AHwplM — CMtijNed ·! 08.02.72 (41) Tullut JulkMcai - BIMt offMtNg 19.08.72 I'MMtti. I »registrlhallltui NihtMta.p« on j. ΊαΜφ.ΐΜ

Patent * oeh regl * t * r * tyrawan '' AimMcm utli | 4 och utUIrtftan pubUcand 30.06.o0 (32) (33) (31) Requested import »Mfird prtorHM l8.02.71 ^ France-France (FR) 7105656 (71) Solvay & Cie, rue du Prince Albert 33 »1050 Brussels, Belgium-Belgium (BE)" (72) Eugene Berger, Brussels, Andre Delbouille, Brussels, Pol Gerard, Braine- 1'Alleud, Jean Louis Derroitte, Brussels, Belgium- Belgien (BE) (7 ^ +) Oy Kolster Ab (5I +) Process for the homopolymerization and copolymerization of ethylene and the catalyst used in the process - Fortification with homopolymerization and shampolymerization of ethylene with the same catalyst as submitted on 17 October 1962 a process for the polymerization and copolymerization of olefins in which the reaction is carried out in the presence of a catalyst obtained by activating with an organic metal compound the reaction product between a transition metal halide derivative and a solid support, the support being a divalent metal an oxygen compound having no hydroxyl groups.

During the reaction between the halogen derivative and the solid support, complexes are formed which contain halogen, a divalent metal and a transition metal. Surface halogenation of the solid support is noted. However, this halogenation is generally quite weak, so that the total amount of halogen present is often less than 0.05 halogen atoms per divalent metal atom.

It has now been found that the choice of solid supports in a certain way results in much stronger halogenation, and much more lucrative complexes of divalent metal, transition metal and halogen.

The present invention relates to a process for the homopolymerization and copolymerization of ethylene in the presence of a catalyst prepared by activating with aluminum organo 57776 a reaction product obtained by reacting a halogen derivative of titanium with a solid support which is a divalent metal oxygen group containing less than 0.1 for.

The invention is characterized in that the solid support is an organomagnesium oxygen-nitrogen compound having magnesium-oxygen-nitrogen-carbon bonds in the molecule.

The nature of the organomagnesium oxygen-nitrogen compound is arbitrary. However, it is preferred to use compounds whose carbon radicals, which are bound to magnesium via nitrogen and oxygen, contain 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. These radicals may be saturated or unsaturated, branched, straight-chain or cyclic, and may also be substituted. They are especially selected from alkyl, alkenyl, aryl, cycloalkyl, arylalkyl, alkylaryl, acyl and aroyl radicals and their substituted derivatives.

Of the magnesium oxygen-nitrogen compounds used in the process according to the invention, oxime salts such as butyl oximates, dimethyl glyoximates and cyclohexyloximates can be mentioned in particular. Mention may also be made of salts of hydroxamic acids and alkyl- or aryl-substituted salts of hydroxylamine, as well as substituted derivatives of these compounds.

Chelates of magnesium organic oxygen-nitrogen compounds having similar types of bonds, e.g. N-nitroso-N-phenylhydroxylamine derivatives ("Cupferon"), can also be used.

Suitable organic oxygen-nitrogen compounds for carrying out the invention must be substantially free of magnesium-bonded hydroxyl groups. They should preferably have less than 0.1 hydroxyl groups per magnesium atom. However, hydroxyl groups attached to a nitrogen or carbon radical that are not attached to magnesium are not harmful and are not considered in determining whether an organic oxygen-nitrogen compound is free of hydroxyl groups.

The granularity of the solid carrier is not critical. However, for convenience, particles having an average diameter of 1 to 50 microns, preferably U0 to 200 microns, are best used.

The catalysts of the invention contain catalyst complexes obtained by reacting a solid support with a halogen derivative of titanium. As the halogen derivative, a halide, oxyhalide or alkoxyhalide can be used. If bromine or chlorine derivatives of titanium are used, such as TiCl 4, TiBr 2, TiCOC 3 H 2 Cl, Ti (O-iso-C 3 H 2) 2 Cl 2 and Ti (O-iso-C 3) C 13 · The best results are obtained with TiCl 3. When using derivatives containing alkoxy radicals, these are best selected from those whose straight-chain or branched alkoxy radicals contain 1 to 20 carbon atoms, in particular 1 to 10 carbon atoms.

The reaction between the solid support and the halogen derivative can be carried out in any suitable manner. The halogen derivative can be used as a vapor or as a gas, optionally diluted with an inert gas, or as a liquid or solution. As the solvent, diluents commonly used in the polymerization of olefins under low pressure are generally used. When polymerizing in solution, the halogen derivative is preferably used in high concentrations (preferably more than 50% w / w). One particularly suitable procedure is based on contacting the solid support with a pure halogen derivative kept in a liquid state. · The solid support can e.g. be suspended in a halogen derivative, or this solid support can be washed with a halogen derivative.

The temperature and pressure at which this reaction is carried out are not critical. For convenience, the operation is generally carried out at atmospheric pressure and temperature of 0 to 300 ° C, preferably 20 to 150 ° C. The reaction components are kept in contact with each other long enough to form a catalyst complex. Usually this is formed within about an hour.

After the reaction, the catalyst complex, which is also solid, is recovered separately. It can be extracted with the same halogen derivative used in the reaction and kept liquid. Finally, this catalyst complex is washed with an inert hydrocarbon derivative to remove excess reaction components.

The elemental analysis of the catalyst complex thus obtained shows that these are clearly chemically bound complexes formed as a result of chemical reactions and not as mixtures or as a result of adsorption phenomena.

In fact, it is impossible to separate the titanium derivative from these complexes by purely physical means of separation.

These complexes contain magnesium, titanium and halogen. The amount of halogen present is large. The analysis shows that the atomic ratio between halogen and titanium is higher than in the halogen derivative used as a starting material. When used as starting material TiCl 2, this atomic ratio Cl / Ti is greater than U. The ratio of halogen to magnesium is likewise high, and is generally greater than 0.5, most often greater than 1. According to the invention, the high halogen content of the catalyst complexes appears to be due to the reaction of gaseous by-products mainly with hydrogen halide and a solid support. It is thus necessary not to remove these gaseous by-products from the reaction space, without which the highly efficient catalyst complexes according to the invention cannot be obtained.

The catalysts according to the invention also contain an organoaluminium compound which acts as an activator.

Fully alkylated compounds having 1 to 20 carbon atoms in the alkyl chain and being straight-chain or branched can be used, as exemplified by aluminum trimethyl, aluminum triethyl, aluminum triisobutyl, aluminum tri-n-butyl and aluminum tri-n-Decyl. .

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It is also possible to use aluminum alkyl hydrides in which the alkyl radicals likewise contain 1 to 20 carbon atoms, in particular aluminum isobutyl hydride. Aluminum alkyl halides can also be used, the alkyl radicals of which likewise contain 1 to 20 carbon atoms, examples being aluminum ethyl sesquichloride, aluminum diethyl chloride and aluminum diisobutyl chloride.

In addition, organoaluminum compounds obtained by reacting aluminum trialkyl or aluminum dialkyl hydride having radicals having 1 to 20 carbon atoms with diolefins having 1 to 20 carbon atoms can be used, in particular those known as aluminum isoprenyl. ^

The process according to the invention is suitable for the homopolymerization of ethylene. The invention is also applicable to the copolymerization of ethylene with diolefins having from 1 to 20 carbon atoms. These diolefins can be unconjugated aliphatic diolefins, such as hexadiene-1, h, unconjugated monocyclic diolefins, such as 1,3-vinyl vinyl. -divinylcyclohexane, cyclopentadiene-1-1 and cyclooctadiene-1,5i endocyclic bridged alicyclic diolefins, such as dicyclopentadiene or norbornadiene, and conjugated aliphatic diolefins, of which

The process according to the invention is particularly well suited for the preparation of homopolymers of ethylene and mixed polymers containing at least 90 molar, preferably 95 molar, ethylene.

The polymerization can be carried out by any process known in the art by applying it in solution or suspension with a solvent or hydrocarbon diluent or even in the gas phase. In the case of solution or suspension processes, the same solvents or diluents are used as in the washing of the catalyst complexes, suitable as aliphatic or cycloaliphatic hydrocarbons, such as butane, pentane, hexane, heptane, cyclohexane, methylcyclohexane or mixtures thereof. The polymerization can also be carried out in a liquid which is considered to be liquid or in one of the monomers.

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The polymerization pressure is generally between atmospheric pressure and 100 kp / cm, preferably 50 kp / cm. The temperature is generally selected in the range of 20 to 200 ° C, preferably in the range of 6 ° to 120 ° C. The polymerization can be carried out as a continuous process or in batches.

The organometallic compound and the catalyst complex may be added separately to the polymerization medium. They can also be contacted with each other at a temperature in the range of -J + 0 ° C .. .80 ° C for up to 2 hours before being fed to the polymerization reactor. They can also be contacted with each other in several steps, but it is also possible to add a part of the organometallic compound to the reactor in advance or to add several different organometallic compounds to it.

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The total amount of organoaluminum compound used is not critical »but is usually 0.02 to 50 mol per liter of solvent, diluent or reactor.

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per crude, and preferably 0.2 to 5 mmol / dm.

The amount of catalyst complex used is calculated as a function of the titanium content of the complex. This amount is generally selected to be from 0.001 to 2.5, suitably 0.01 to 0.25 milliatom grams of titanium per liter of solvent, diluent or reactor volume.

The relationship between the amounts of the organoaluminum compound and the catalyst complex is also not critical. This ratio is generally chosen such that the ratio of the organoaluminum compound to titanium, expressed in moles per gram of atom, is greater than 1 and preferably greater than 10.

The average molecular weight and melt index of the polymers prepared by the process of the invention can be adjusted by adding to the polymerization state "one or more molecular weight modifiers, such as hydrogen, zinc or calcium diethyl, alcohols or carbon dioxide.

The specific gravity of the homopolymers prepared by the process of the invention can likewise be adjusted by adding to the polymerization space a metal alkoxide belonging to groups IVa and Va of the Periodic Table. Thus, polyethylenes can be prepared having a specific gravity between the specific gravity of high polyethylenes and low-pressure polyethylenes prepared in a known manner.

Of the alkoxides suitable for this adjustment, titanium and vanadium alkoxides with radicals containing 1 to 20 carbon atoms are particularly effective. These include TiO2CH2, TiO2 (H2O2), Ti / OCH2CH2Cl2, TiO2

Thanks to the process according to the invention, polyethylene can be produced with considerable results. The homopolymerization of ethylene has a productivity, expressed in grams of polyethylene per gram of catalyst complex, in some cases exceeding 2000. Due to these high productivitys and the relatively small amount of total content in the catalyst complexes, the polymers do not require post-purification.

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The amount of titanium contained as a residue in the polymers prepared by the process of the invention is particularly small, and is generally less than 20 ppm. Titanium derivatives are disadvantageous in catalyst residues mainly because they form colored complexes with phenols conventionally used as antioxidants in polyolefins. Thus, the purification step can be omitted from the finishing of the polymer and thus a considerable saving can be achieved.

The polyethylenes produced by the process of the invention are well suited for conventional uses of polyolefins: injection molding, compression molding, blow molding, etc.

The following examples illustrate the invention.

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Example 1

Suspend 5 g of MgCONCl 2 H 2 O (magnesium butyloximate) in 25 ml of pure TiCl 2 and heat the suspension to 130 ° C. Keep the suspension at this temperature with vigorous stirring for one hour. Separate by filtration the solid complex formed as a result of the reaction between Mg / CH 2 Cl 2 and TiCl 2 and wash this complex with hexane until all residues of TiCl 4 have disappeared from the wash solvent. The complex is then washed under a stream of dry nitrogen at 10 ° C for 16 hours.

Elemental analysis of the catalyst complex shows that it contains 203 g of magnesium, 1 + 5 g of titanium and 6 and 6 g of chlorine per kg. The Cl / Ti atomic ratio is thus about 20.2 and the Cl / Mg atomic ratio is about 2.3 ·

63 mg of catalyst complex and 200 mg of aluminum triisobutyl as hexane solution are introduced into a 1 liter flask. The reaction mixture is kept at 80 ° C for 10 min. The contents of the flask are then transferred to a 3-liter stainless steel autoclave with 1 liter of hexane. The temperature of the autoclave is raised to about 80 ° C. Ethylene is introduced into the autoclave at a partial pressure of 10 kp / cm and hydrogen at a partial pressure of 2 H kp / cm.

The polymerization is continued for one hour by keeping the pressure constant by continuously adding ethylene. After one hour, the gas is removed from the autoclave and 11 + 0 g of polyethylene are recovered.

The hourly productivity is thus 2200 g of polyethylene (PE) per gram of catalyst complex. The specific activity of the catalyst complex in relation to the weight of titanium used and the pressure of ethylene at 1 kp / cm is thus about 5000 g PE / h.g Ti.kp/cm2 C ^.

The polyethylene obtained has a melt index of 0.33 g / 10 min, measured according to ASIM D 1238 57 T.

Example 2

Suspend 5 g of magnesium dimethyl glyoximate in 25 ml of pure TiCl 4 and continue the preparation of the catalyst complex in the same manner as in Example 1.

Elemental analysis of the resulting catalyst complex shows that it contains 201 g of magnesium, 39 g of titanium and 665 g of chlorine per kg. The Cl / Ti atomic ratio is thus about 23.1 and the Cl / Mg atomic ratio is about 2.1+.

The polymerization test is then performed as in Example 1 except that 18 mg of catalyst complex is used. The polymerization is stopped after 0.5 hours. 1Hl of polyethylene is recovered.

The hourly productivity is thus 15,700 g of polyethylene (PE) per gram of catalyst complex. The specific activity is thus 1 + 0 500 g PE / h.g Ti. kp / cm2 CgH2.

The polyethylene obtained has a melt index of 0.83 g / 10 min.

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Example 3

Suspend 5 g of the magnesium salt of N-nitroso-N-phenylhydroxylamine ("Cupferonate") of the formula Mg / oN (NO) CH 2 Cl 2> 25 ml in TiCl 2 and continue the preparation of the catalyst complex in the same manner as in Example 1.

Elemental analysis of the resulting catalyst complex shows that it contains 180 g of magnesium, 42 g of titanium and 6 100 g of chlorine per kg. The Cl / Ti atomic ratio is thus about 21.6 and the Clyfog atomic ratio about 2.5. The polymerization test is then carried out as in Example 1, except that 9 ®g of catalyst complex is used. After one hour, 202 g of polyethylene are recovered.

- The hourly productivity is thus 22,400 g of polyethylene (PE) per gram of catalyst complex, and the specific activity is about 54,000 g PE / h.g Ti.kp/cm

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__ The polyethylene obtained has a melt index of 0.68 g / 10 min.

Claims (3)

8 57766 A process for homopolymerizing and copolymerizing ethylene in the presence of a catalyst prepared by activating with a organoaluminum compound a reaction product obtained by reacting a halogen derivative of titanium with a solid support which is a divalent metal oxygen compound and containing less than 0.1 hydroxyl the carrier is an organomagnesium oxygen-nitrogen compound having magnesium-oxygen-nitrogen-carbon bonds in the molecule. Process according to Claim 1, characterized in that the solid support is a salt of okayim, hydroxamic acid or N-substituted hydroxylamine. Catalyst for use in the process according to claim 1, prepared by activating with an organoaluminum compound the reaction product obtained by reacting a titanium halogen derivative with a solid support which is a divalent metal oxygen compound and contains less than 0.1 hydroxyl groups per molecule, characterized in that the solid support is an organomagnesium oxygen-nitrogen compound having magnesium-oxygen-nitrogen-carbon dioxide in the molecule.