DE1795739A1 - METHOD OF POLYMERIZATION OF OLEFINS - Google Patents

Description

Process for the polymerization of olefins - According to the German patent 1 190 939, pure 7-allyl compounds of the transition metals of the IV. - VIII. Subgroup of the periodic table of general formula (I) in particular of titanium, zirconium, vanadium, chromium, molybdenum, tungsten, nickel, iron, cobalt, palladium and platinum. Furthermore, according to German patents 1,197,453 and 1,194,417, compounds of the transition metals of the @ -Allyl-Me-X type of the general formula (II) to produce.

In both formulas, Me denotes a transition metal of subgroup IV, - VIII of the periodic system, R to R5, which can be identical or different, hydrogen, alkyl, cycloalkyl, aralkyl or aryl, where the radicals R1 and R4 also form an olefinically unsaturated one Ring system, with preferably 5 - 12 ring members, can be closed, denotes an anionic radical in formula II, 1 denotes an integer of | are you. m and n integers from 1 to 3, where m @@@ n integers from 2 to 4 are the same In both types of compounds, so-called @ -allyl systems of the general formula (III) are bonded to transition metal atoms as characteristic groups, The simplest # -allyl system is formed by 3 carbon atoms 2, which as sp -hybrids represent a flat structure whose 3 carbon atoms are similarly bonded to a central metal atom. (C3H5) 2Ni this type of connection is represented by the following notation: Using the example of Bis-Bis-ff-Mèthallylnickels, this type of connection can be represented in terms of a formula as follows: The X-ray examination of this compound has shown that it is a "sandwich" compound whose CH3 groups on the middle carbon atom are in the anti position.

The <-Allyl system thus represents a special type of ligand which both sterically and electronically have a specific influence on the transition metal to which it is bound.

It has now been found that these # -allyl metal systems of the general Formulas I and II highly effective catalysts for the linear polymerization of olefins represent the extremely selective reactions depending on the choice of catalyst components able to trigger. The inventive catalysis can monoolefins, such as ethylene, Propylene, straight or branched butenes, pentenes or hexenes etc. or diolefins, such as butadiene or isoprene, or mixtures thereof. Depending on the catalysts and additives can polymerize to high molecular weight products such as polyethylene, Polypropylene or polybutadienes, are carried out, the polymerization in the the latter case can be directed so that either 1,2- or 1,4-polybutadienes are obtained the last exclusively or almost exclusively the 1, 4-cis structure exhibit can. Mixtures of monoolefins, e.g. Ethylene and propylene or ethylene and cyclohexene (to l-ethyl-cyclohexene and ethylidene-cyclohexane) are copolymerized. It was also found that in many cases the activity the catalysts can be increased many times over if one uses the # -Allylmetall-Systeme with Lewis acids, such as organoaluminum compounds, e.g. R2A1X or RAlX2 or such as aluminum halides, AlX3, combined, where X = Cl, Br, J and R = alkyl-, Can be cycloalkyl, aralkyl and aryl groups.

It was also found that the selectivity of the catalysts can be influenced by adding compounds that act as electron donors, i.e., able to act as Lewis bases. Electron donors include, for example, alkyl, Cycloalkyl, aralkyl or aryl compounds of the elements of main group V. Periodic Table, except nitrogen, tri-alkyl, cycloalkyl, aralkyl or aryl esters of the elements of main group V except nitrogen, as well as their triamides and e.g. dialkyl sulfoxides are also possible.

The mentioned increase in activity and selectivity through addition of Lewis acids and / or Lewis bases is mainly used in compounds of Type # -Allyl-Me-X observed.

The method according to the invention will first be explained with the aid of a few examples explained in which pure f-allyl compounds of transition metals with monoolefins respectively.

1,3-Diolefins are made to react: Tris-t-allylchrome polymerized Butadiene to high molecular weight polybutadiene, which preferably has a 1,2-structure.

Xethylene is at temperatures of 0 - loo0 and pressures of 1 - loo Atom. from tris-) ¼-allylchrome to high molecular weight linear polyethylene polymerized. All the catalysts mentioned in these examples are characterized by that they contain transition metals bound to # -allyl systems.

According to the invention, further catalytic processes can be carried out, when using compounds of the type # -Allyl-Me-X, as described in DBP 1,197,453 and 1,194 417 can be produced, e.g. # -allyl metal halides as catalysts begins.

According to the invention, butadiene can, for example, with the aid of bis - # - allyl cobalt iodide polymerized very smoothly to pure 1,4-cis-polybutadiene at temperatures from -60 to + 50 ° will.

The catalytic effectiveness of the compounds of the type # -Allyl-Me-X can furthermore be increased considerably according to the invention if compounds added, which are to be referred to as Lewis acids. Accordingly, the Polymerization rate in the reaction of butadiene with bis-) -allyl cobalt iodide very much if one adds equimolecular amounts of the bis - # - allyl cobalt iodide, e.g. Aluminum bromide adds. You can activate the Kataly with equally good success sators also use diethyl aluminum chloride or ethyl aluminum dichloride.

It has also been found that very selective catalysts can be used on the basis of) ¼ allyl compounds, e.g. nickel, can be grown if the Combination of a'J) -allyl nickel halide with a Lewis acid and a Lewis base according to the definition given above.

The inventive catalytic reactions can in opposite the catalysts inert solvents are carried out. Come as a solvent e.g. saturated hydrocarbons or halogenated hydrocarbons, Aromatics or halogenated aromatics, also aliphatic or aromatic or cyclic ethers are used when catalysts are used that do not contain ethers Form complexes. If necessary, it is also possible to work without a solvent. The process according to the polymerization reactions are in the temperature range of -80 to + 100 ° and at pressures up to loo atm. executed.

Possess the products which can be prepared by the process according to the invention great technical importance. 1,4-cis-polybutadiene and polyisoprene are important technical rubbers. The polyethylene which can be produced by the claimed process or polypropylene is a completely halogen-free linear product.

All operations must be carried out with the exclusion of air and moisture, i.e. be carried out under protective gas such as argon or nitrogen, since the The catalysts used are sensitive to air and moisture.

Example 1 0.6 g = 3.4 mmol of tris- '-lylchromium are added to the cubic centimeter of hexane dissolved and in a 0.5 1 V2A autoclave with shaking at 50 atm and 20 ° with ethylene brought to reaction.

After 5 hours, the excess ethylene is blown off, the reaction product precipitated, the catalyst destroyed with methanol / hydrochloric acid and the polyethylene formed sucked off. The polymer is washed neutral and dried at 10-4 Torr and 80 °. 5 g of a linear polyethylene are obtained, the IR spectrum of which corresponds to the spectra the so-called

Ziegler polyethylene is identical. The mean molecular weight M is 1.88 106.

Example 2 The procedure is as in Example 1, but one works with one Reaction temperature of 430. After 5 hours, 32 g of linear polyethylene are obtained. Example 7 o, 6 g bis - # - Allylchromiodid are as in Example 1 in 300 cm3 hexane at 50 at and 55 - 58 ° reacted with ethylene in the course of 24 hours 40 g of linear polyethylene formed, Example 4 o, 63 g = 3.6 m @ ol tris - # - allyl chromium come in one with thermometer, cryogenic return flow meter and magnetic Stirring equipped 250 cm3 flask. Then 87 g = 1.6 @ol Butadiene condensed in. There is no reaction at the boiling point of butadiene observed, 50 cm3 of Beiizol are added, during which the boiling temperature rises to 15 °. The mixture is kept at 15 ° by external cooling.

After 10 hours, all of the butadiene has reacted. The polymer is dissolved in benzene in the heat and then with the addition of small amounts Antioxidant (phenylß-naphthylamine) precipitated with acetone. The polybutadiene is suctioned off and dried at 10-4 Torr. According to IR analysis, the polymer exists mainly from 1,2-polybutadiene. trans-1,4-polybutadiene contaminated Example 5 0.4 g = 1.18 mmol bis - # - allyl chromium chloride are dissolved in 100 cm3 of chlorobenzene and with 0.7 cm3 = 6 mHol of molten aluminum bromide If the solution is 1n, ethylene is passed in at 200 and normal pressure. After 3 hours the catalyst is decomposed by adding 3 cm3 of butanol. The polyethylene formed is precipitated with acetone and then suctioned off, catalyst residues are through Washing with a methanol / hydrochloric acid mixture removed. It is filtered and washed the product neutral, the polymer will be at 10- @ r gate; dried yield 2.6 g linear polyethylene, Example 6 According to German patent 1 197 453 2.38 g = 13.1 mmol tris - # - allyl cobalt in 120 cm3 ether at -600 with a solution of 1.66 g = 0.655 mmol of iodine in 100 cm3 of ether.

40-50 g of butadiene are condensed into the resulting solution. The solution is allowed to come to room temperature over a period of 12 hours. The mixture remains at room temperature for a further 2 days. Then you do not remove converted butadiene and the solvent. From the viscous residue can distill off small amounts of trimers or tetramers of butadiene. The residue is washed with methanol -4 and then dried at lo Torr. You get 30-40 g of a highly viscous polymer which, according to IR analysis, consists mainly of 1,4-cis-polybutadiene consists.

Example @ 0.234 g = 0.87 mmol to # -Allyl cobalt iodide in 20 cm3 of toluene are 'at 800 with 0.2 cm3 = 1.906 mmol of ethylaluminum dichloride in 100 cm3 of toluene offset. 60 g of butadiene are condensed into the resulting solution and then warmed the mixture to -3o0. A violent reaction occurs within a few minutes a. The mixture is kept at -20 to 300 by cooling. The polymer formed is precipitated with methanol, filtered off and dried in a high vacuum. The yield is 40 g. According to IR analysis, the polymer consists of practically pure 1,4-cis-polybutadiene, that only by traces of 1,4-trans or. 1,2-polybutadiene is contaminated.

Example 8 0.136 g = 0.504 mmol bis - # - allyl cobalt iodide in 20 cm3 toluene are at -80 ° with a solution of 0.135 g =] 0.504 mmol of aluminum bromide in 100 cm3 of toluene added.

50-60 g of butadiene are condensed into the mixture and kept then with stirring between -45 and 0 °.

After 2-6 hours, the reaction is broken and the catalyst is destroyed with methanol and the polymer precipitates. The polymer is separated off and washed and dried at 10-4 Torr and 50 °, 33 g of a rubber which according to IR analysis shows practically pure cs-1,4-polybutadiene, which only contains very small amounts trans-1,4- resp.

Contains 1,2-polybutadiene.

Example 9 0.158 g = 0.895 mmol bis - # - allyl cobalt chloride in 50 cm3 Toluene with a solution of 0.895 mmol diethylaluminum chloride in toluene offset. 40-50 g of butadiene are condensed into the mixture at -80 °, and the mixture is heated to -20 to +200, at the same time polymerisation occurs.

The polymer is worked up as usual. A mixture is obtained of cis- and trans-1,4- and 1,2-polybutadiene, Example 10 0.158 g = 0.895 mmol to - # - allyl cobalt chloride in 50 cm3 of toluene are mixed with a solution of 0.895 mmol of ethylaluminum dichloride implemented, butadiene is polymerized at -20 ° with the resulting solution, the reaction runs very quickly, a very pure 1,4-cis-polybutadiene example is obtained 11 To 200 g of liquid butadiene, @@ n gives a solution of 0.358 g = 2.025 at -80 ° mmol bis - # - allyl cobalt chloride in 50 cm3 toluene and then added to the solution 2 2.025 mmol Ethyl aluminum dichloride in 10 cm3 toluene. Han lets slowly thaw the reaction mixture overnight to room temperature then 3 l of benzene and brings the polymer into solution by heating, then the polybutadiene is precipitated with methanol, separated off and dried at 10-4 torr. 103 g of rubber-like polybutadiene are obtained, which according to IR analysis is practically pure. 1,4-cis-polybutadiene consists of very little 1,4-trans-polybutadiene contains.

Example 12 0.2135 g = 0.243 mmol of the addition product of 2 molecules Triphenylphosphine on 1 molecule # -Allylcobaltdiiodide, (CO (C3H5) J2 - 2P (C6H5) 3), are dissolved in 70 cm3 of chlorobenzene at -80 ° and with 0.892 mmol of aluminum bromide offset. 40-50 g of butadiene are condensed into the solution. One warms up -30 to -20 °, the polymerization starts. The reaction product is in the worked out in the usual way and 25 g of a polybutadiene obtained from trans-1,4- and 1,2-polybutadiene, example 13 1.92 g = lo mmol vanadium tetrachloride are in 150 ml of ether at -80 ° with a saturated ethereal solution of allyl magnesium chloride (44 mmol) reacted with stirring. After concentrating the deep dark colored solution at .4 torr to dryness, the residue was taken up in pentane, the halogen-free Pentane extract filled into an autoclave cooled to -80 ° and 30 g of pure Pressed on propylene. The reaction mixture was allowed to slowly thaw and complete the reaction was heated to 700 for 3 hours. The excess propylene was blown off and high molecular weight propylene isolated in the usual manner. Yield: 5 g example 14 o, 25 g = 1 mmol of tetra - # - allyl zirconium are dissolved in 100 cc of liquid butadiene and heated to 90 ° in a bomb tube for 24 hours. In addition to unreacted butadiene 5 g of distillable components, 80% of which consist of n-octatriene (1,3,6). Of the The main part of the converted butadiene (40 g) consists of polybutadiene.

Example 15 0.05 g = 0.3 mmol of tris - # - allylvanadine are obtained at -80 ° dissolved in 30 cc of toluene. The solution is saturated with butadiene and then heated in the bomb tube to 800 for 8 hours. From the reaction product can be 5 g Separate polybutadiene.

Example 16 1.1 g = 8 mmol # allyl nickel chloride are added with 0.85 ccm = 8 mmol of ethyl aluminum dichloride added to 100 ccm of toluene. Two emerge Liquid layers. In this solution, butadiene is distilled at -30 ° and left the mixture stand at -30 to 0 ° for 24 h. Then all volatile components distilled off in a high vacuum. The residue is taken up in benzene and the benzene Solution washed with 2N hydrochloric acid and then with water. The dried one Benzene solution is diluted with acetone, the polybutadiene that is precipitated separates and dries. According to the IR spectrum, it is mainly 1,4-cis-polybutadiene.

Example 17 0.95 g = 7.0 mmol # -allyl nickel chloride in 100 ccm To toluene, o.74 ccm = 7.0 mmol of ethyl aluminum dichloride were added. The mix add 100 cc of isoprene at -8o0 and then let it come to 200. To the To complete the reaction, the mixture is briefly refluxed and separated then all volatiles by distillation in a high vacuum away. The residue is taken up in benzene and washed with 2N hydrochloric acid and water and dried. Acetone is added to the solution and the polyisoprene is precipitated with it which is collected and dried. According to the IR spectrum, it is predominantly around 1,4-cis-polyisoprene, to which small amounts of 3,4-polyisoprene are added.

Example 18 12 g of butadiene were mixed with 15 cc of a solution of the titanium allyl compound mixed in pentane (150 mg Ti compound) at 780 and melted, 15 hours heated at 70 ° and separated from the unreacted butadiene. The residue was dissolved in boiling benzene and the polybutadiene was precipitated with methanol (1,2-cis and 1,4-cis polybutadiene).

Reaction rate at 70 ° C: about 16 mol C4H6 / g-atom Ti / hour.

Example 19 183 mg- Pd (C3H5) 2 (0.97 mmol) were mixed with 30 g (0.56 mol) Butadiene filled into an ampoule and heated to 40o for 3 days. Subsequently was the unreacted butadiene separated and the reaction product at lo 4 Torr Distilled up to 80 ° C.

Conversion = 10.0 g (33%) butadiene residue = 6.1 g (61%) polymers example 20 1: 1 adduct of bis - # - methallylnickel and triethylphosphine To a solution of 2.27 g (13.4 m @ ol) (C4H7) 2Ni in 20 ml of pentane were 1.53 g (13.4 mmol) of triethylphosphine at -80 ° C against. The yellow solution turned red and retbr @ une Kris @ all became of a complex failed. After separation from the solvent, the crystals became dried under reduced pressure at -60 ° C.

Yield 3.024 g (78.2% of theory). Ni content: found 20.47%; calculated for (C4H7) 2-Ni.P (C2H5) 3: 20.46%.

Example 21 Ru @ 1: 1 adduct of Tris @ allyl chromium and ethylaluminum dichloro To a solution of 0.3233 g (1.85 mmol) of Cr (C3H5) 3 in 20 ml of pentane were added 0.235 g (1.85 mmol) EtAlCl2 added. After 15 minutes, a gray-brown began to precipitate Solid from the brown solution. After 2 hours the pentane was reduced Pressure removed and the precipitate dried under high vacuum at room temperature. Unbound EtAlCl2 distilled off under these conditions. The precipitation w @@ 0.567 G. The complex was formed in a yield of practically 100.00.

Example 22 1: 1 adduct of bis - # - allyl zirconium dichloride, triphenylphosphine and ethyl aluminum dichloride To a solution of 2.44 g (10 mmol) (C3H5) 2ZrCl2 in 50 ml of pentane were added to 2.62 g (10 mmol) of P (C6H5) 3 and 1.27 g (10 mmol) of C2H5AlCl2 -30 ° C given. A dark red-brown precipitate separated out from the solution. That Pentane was removed under reduced pressure, raising the temperature to 20 ° C rose. The uncomplexed ethylaluminum dichloride distilled under these conditions away. The dry residue weighed 6. 25 g, corresponding to 98% by weight of the total amount of Compounds mixed at the beginning of this experiment. Education proves this of a 1: 1: 1 adduct.

Claims (19)

P a t e n t a n s p r ü c h e 1) Process for the polymerization of Olefins, characterized in that one monoolefins or diolefins or their Mixtures with # -allyl compounds of transition metals, especially metal - # - allyls or # -Allyl metal halides treated as catalysts. 2) Process according to claim 1, characterized in that # -Allyl metal catalysts of the general Porirel used, in which X is an anionic radical, Me is a transition metal of subgroups IV to VIII of the Periodic Table, up to R5, which can be identical or different, are hydrogen, alkyl, cycloalkyl, aralkyl or aryl, where the radicals or R2 with the radicals R4 or R5 can also be closed to form an olefinically unsaturated ring system, preferably with 5 to 12 ring members, n is 1 to 4, m is 0 to 3 and n + m is 2 to 4. 3) Method according to claim 2, characterized in that Me titanium, Zircon, vanadium, chromium, molybdenum, tungsten, nickel, iron, cobalt, palladium or Platinum and X is dromide, chloride or iodide, 4) Proceed according to Claims 1 to 3, characterized in that to increase the activity and further influencing the selectivity of the # -allyl metal catalysts Lewis acids and / or Lewis bases added. 5) Process according to claim 4, characterized in that one Lewis acids of the general formula R2AlY, RA1Y2 and AiY5-, where Y C1, Br, J and R are alkyl, cycloalkyl, Aralkyl and aryl groups are used. 6) Method according to claims 4 and 5, characterized in that one is aluminum brimide, aluminum chloride, aluminum iodide or ethylaluminum dichloride used. 7) Method according to claim 4, characterized in that with identical or different alkyl, cycloalkyl, aralkyl or aryl radicals Phosphines, phosphites, phosphoric acid triamides, arsines, arsinites, arsenic acid triamides, Stibine, Stibite, Antimonsäuretriamide, Bismuthtne, Bismuthite, Bismuthsäuretriamide or sulfoxides used as Lewis bases. 8) Method according to claims 1 to 7, characterized in that the reactions are carried out with solutions of the starting materials in inert solvents are, preferably in aliphatic, aromatic or cyclic ethers, saturated, aliphatic or aromatic hydrocarbons or halogenated aromatic Hydrocarbon. 9) Catalysts for the polymerization of olefins, consisting of adducts of Lewis acids, Lewis bases and # -alllyl compounds of transition metals, 10. Catalysts for the polymerization of olefins, consisting of adducts of Lewis acids and # -alllyl compounds of excess metals. 11. Catalysts according to claims 9 and lo, characterized in that that the Lewis acids have the general formulas R2AlY, RAlY2 or A1Y3, in which R is alkyl, cycloalkyl, aralkyl and aryl and Y is chloride, bromide and iodide. 12. Catalysts according to claims 9 to 11, characterized in that that the Lewis acid is aluminum bromide, aluminum chloride, aluminum iodide or ethyl aluminum dichloride is. 13. Catalysts according to claim 9, characterized in that the Lewis bases substituted identically or differently to alkyl, cycloalkyl, aryl and / or Aralkyl compounds of phosphines, phosphites, phosphoric acid triamides, arsines, Arsinites, arsenic acid triamides, stibines, stibites, antimonic acid triamides, bismuthines, Bismuthites, bismuth acid triamides or sulfoxides. 14. Catalysts according to claims 9 and 13, characterized in that that the Lewis base triphenylphosphine, tricyclohexylphosphine, diphenylphosphine, triisopropylphosphine, Tri-n-butyl phosphine, triethyl phosphine, trimethyl phosphite, tris (o-oxy-diphenyl) phosphite, Tri-o-cresyl phosphite, triphenyl arsine, tri- (ophenyl-phenyl) -phosphite or phosphorous acid tri-diethylamide is. 15. Catalysts for the polymerization of olefins, consisting of Adducts of Lewis bases and # -allyl compounds of transition metals of the general Formula BC, where B for phosphites, phosphorus triamides, Arsine, Arsinite, Arsenic triamide, stibine, stibite, antimony triamide, bismuthine, bismuthite, bismuth triainide and sulfoxides, the same different alkyl, cycloalkyl, aryl or aralkyl substituents have, and C is a # -allyl compound of transition metals of IV., V., VI. and VIII. Subgroup of the periodic system means. 16. Catalysts according to claim 15, wherein B is methyl phosphite, tris (o-oxydiphenyl) phosphite, Tri-ooresylphosphite, triphenylarsine or phosphorous acid = -tridiäthylamid is. 17. Catalysts according to Claims 9 to 16, characterized in that the # -allyl compounds of transition metals are pre-bonds of the general formula are in which X is an anionic radical, Me a transition metal of IV., V., VI. and VIII. Subgroup of the periodic system means n 1 to 4, m 0 to 3 and n + m are 2 to 4 and R1 to R5, which can be the same or different, Signify hydrogen, alkyl, cycloalkyl, aralkyl or aryl, where the radicals R1 or with the radicals R4 or R5 also to an olefinically unsaturated Ririgsystem with preferably 5 to 12 ring members can be closed. 18 * Catalysts according to Claim 17, characterized in that X Is chloride, bromide or iodide. 19. Catalysts according to claims 17 and 18, characterized in that that Me titanium, zirconium, vanadium, chromium, molybdenum, tungsten, nickel, iron, cobalt, Is palladium or platinum.