IL35020A - Catalysts for the polymerization of olefines - Google Patents

Description

Catalysts for the polymerization of EDISON 33295 2 The present invention relates to catalysts for the polymerization of particularly to their preparation and to methods for the polymerization of ethylene and its mixtures with The of ethylene has been carried out so far with the help of various One of the best known is formed by the product obtained by the reaction of a titanium or vanadium compound with an organometallic derivative of a metal of groups II and III of the Periodic This invention relates to polymerization catalysts for olefins that show a considerably higher catalytic activity than that of the catalysts of the prior art allow to achieve an extraordinary increase of the amount of polymer produced with respect to the catalyst In a few previous still pending Patent Applications by the same there have been described polymerization catalysts for which with a very high catalytic activit the product of reaction between a hydride or an organometallic compound of a metal of groups II or III of the Periodic System with a product obtained by contacting a titanium or vanadium compound with a carrier consisting of an anhydrous or Sn under such conditions that an activation of the anhydrous halide or by using the halide in an already activated It has now unexpectedly been found that it is possible to obtain catalysts with an activity comparable to that of the catalysts described in the above mentioned Patent Specifications 3 The invention thus provides a catalyst for the polymerization of particularly ethylene comprising a product of reaction between a hydride or an organometallic compound of Be and alkali metals with the product obtained by contacting a titanium with a carrier consisting of or containing an anhydrous manganese in a preactivated form or obtained in the active form in the course of the formation of the catal tic component the active form being characterized in that the highest intensity diffraction line of its spectrum which appears in the spectrum of the normal manganese halide is replaced by a halo of lower having a surface area greater 2 than In the case of anhydrous manganese dichloride the active form is characterized by the fact that in its the diffraction line appearing at a lattice distance of d which is the most intense in the spectrum of normal becomes less intense while in its place a broadened halo Such catalysts have valuable in particular a very high activity which in many cases makes it not necessary to purify the polymer at the end of the The halides in the active form may be obtained by various One of the most suitable ones consists in dissolving the anhydrous halides in ethers or other anhydrous organic solvents and then removing most of the solvent by rapid evaporation and thereafter completing 4 the of the solvent at reduced pressure and at tures in general greater than preferably comprised between and Activated forms of halides may be obtained also by means of very fine and in by any other mechanical method in which the particles of the carrier are subjected to the action of frictional The preferred od the preparation of the supported catalytic component consists in dispersing the Ti compound on the anhydrous already being in the active form by the of mixtures of the two operating according to known grinding is preferably carried out in ball by operating in dry conditions in the absence of inert the preparation may be also carried out by simply mixing the Ti compound with the anhydrous Another suitable od for the preparation of the halide in an active and which at the time allows to obtain the supported catalytic component according to this consists in treating the anhydrous not activated with Ti compounds which normally are or with solutions of compounds in organic under conditions in which a certain quantity of Ti compound remains fixed on the For instance it is possible to obtain supported catalytic components directly usable in the polymerization phase by treating anhydrous of the normal type with an excess of at the boiling and thereafter removing the As has been the preparation of the supported catalytic components according to this invention allows to obtain simultaneously the activation of the halide and also supporting the Ti without the need to carry out a mechanical activation of the carrier the dispersion of the Ti Titanium compounds suitable the preparation of the new catalysts according to the invention are halogen halogen titanates or and alkylaamonium titanites or titanites of alkali titanium amides and titanium titanium salts of organic as well as the addition compounds of and titanium with compounds in which the atoms are in general 0 and S such as for the amines and Other suitable Ti compounds are those obtainable from the above mentioned Ti compounds and from alcoholates and amides of alkali metals such for indicates the earbazyl of Ti compounds suitable for the preparation of the catalysts of this invention ares 6 Ti The quantity of Ti compound usablo for the preparation of the supported catalytic may be comprised wide whose lower limit may down to values for instance below by with respect to the carrier and whoso upper limit tain greater by Particularly interesting resultsjas far as the yield in mer of the catalyst with rofaronoe both to the Ti compound as well as to the carrier itself is are obtained with quantities of Ti compound on the carrier betwoen 1 and by pound is not In the case of the polymerization of ethylene this ratio preferably comprised between 7 The catalysts according to this invention are used in the of in a liquid in the presence or absence of an inert or in a gaseous The temperature may be comprised between and but preferably between and at atmospheric pressure or below atmospheric The regulation of the molecular weight of the polymer during the is effected in known by carrying out the polymerization in the presence of a an organometallic cadmium or zinc compound or such regulators to the catalytic activity of normal catalysts from a compound a transition sad an compound of a metal of 1 to catalysts of invention are as to activity by tho presence of such substances for regulation of molecular In polymerisation of for it possible to of the polymer within of practical corresponding to values of in ralia at about 1 to t tho yield polymer dropping to valuesbelow it necessary at tho end of to purify tho polymer from catalyst thus obtained is generally linear and highly crystalline density values equal to or greater and with la particular with to injection which is very in that of the polyethylene obtained aid of content is than 10 parte per 8 The intrinsic viscosity o the polymer was measured in tetralin at EXAMPLE 1 JO g of anhydrous were dissolved in 100 co of anhydrous By a rapid evaporation of the alcohol and subsequent at under a reduced of there was obtained a powder with a specific surface of 22 g of this powder and g of ground together in a for at a of in a glass mill 100 diameters 50 containing g of steel having a 5 g of the mixture thus ground and 1500 cc of were introduced together with 2 cc of under a nitrogen into a 3 litres autoclave of stainless steel fitted with an and heated to a temperature of Thereto were then added hydrogen up to a pressure of 5 atm and then ethylene up to a pressure of 10 atm and this pressure was maintained constant throughout the test by continuously introducing ethylene into the After 5 hours the polymerization was interrupted and the polymer obtained was filtered and g of granular polyethylene having an apparent density of and an intrinsic viscosity in tetralin at of were The yield in ol mer to 9 EXAMPLE 2 g of prepared according to example 1 and g of vrere ground together for 20 hours under a 7 atmosphere at a temperature of By using g of the mixture thus prepared and tho po ymerization of tho ethylene to tho procedures cribed in example 1 there obtained 88 g of polyethylene ving an intrinuic in tetralin at oft The in polymer amounted to 000 of EXAMPLE 3 g of the prepared in example 1 and g o were ground together under a nitrogen atmosphere 16 hours at a temperature of carrying out Using O268 g of the mixture thus prepared and the polymerization of the ethylene following the described in example 1 there were obtained 149 g of granular polyethylene ving an intrinsic determined in tetralin at 2β2 yield in polymer amounted to of EXAMPLE 4 g of prepared according to example 1 and 2380 grams of CO ground together in a nitrogen for 3 hours at By using g of the mixture thus obtained and by conducting the polymerization of the ethylene following the the procedures described in example 1 there wore obt ined g of polyethylene having an intrinsic determined in tetralin at The yield in polymer amounted to of EXAMPLE i A prepared by dissolving 25 of anhydrous in 100 cc of anhydrous slowly into a cylindrical vessel heated up to and maintained at a The powder thus obtained then dried through heating at at a reduced pressure of 5 mm g of MnBr2 thus treated and g of together for under a nitrogen atmosphere at a temperature of Using g of this mixture and conducting the zation of the ethylene following the procedures described in example 1 there were obtained 5 of a polyethylene with an intrinsic visco sity determined in tetralin at of The yield in polymer amounted to of EXAMPLE 6 t Into a 1000 oc glass flask cooler fitted with a stirrer and a eflux were introduced under an anhydrous nitrogen atmosphere g of and co of an hydrous tetrahyd The resulting suspension maintained at point for After cooling the overlaying liquid by tion and the insoluble product dried at a reduced pressure of at a temperature of 7779 the obtained according to t described previously and of ground together a nitrogen for hours at a of 12 By using of re thus prepared and by ing out the polymerization of the ethylene following the described example there were obtained 68 g of a polyethylene having intrinsic determined in tetralin at of The yield in polymer amounted to of 7 g of prepared according to Example and g of obtained by reduction of with and having a were together under a nitrogen atmosphere for at a of Using g of the and by out the polynorization of the ethylene by following tho procedureo in vrcro obtained of a had an intrinsic viscosity determined in tetralin at oft The yield in to of process g of according to in ample and g of were ground together stream of for hours at a temperature of thus prepared and by using here were obtained g of a polyethylene which had an intrinsic determined in lin at of The yield in polymer amointed to gg of EXAMPLE 9 The example 8 was repeated instead of By using g of the mixture prepared according to example there were obtained 49 g of a pplyethylene had an intrinsic vis cosity of The yield in polymer amounted to of EXAMPLE t g of prepared according to example 1 and g of ground under a nitrogen for 16 hours at a of Using g of the mixture thus and by carrying out the polymerization of the ethylene by following the procedures cribed in example 1 there were obtained g of a polyethylene had an intrinsic determined in tetralin at of The yield in polymer amounted to of EXAMPLE 11 g of by reacting equimolar titie3 of in xylol at Ti Calculated Ti 2 Pound K were ground together under a nitrogen atmosphere for 16 at a temperature of By using g of the mixture thus and by carrying out the polymerization of the ethylene following the procedures cribed in example there obtained 54 g of a polymer having an intrinsic determined in tetral n at a temperature of The yield in polymer to 210j000 of EXAMPLE Into the same already described in example 1 were d for 16 hours at a temperature of g of and MnCl prepared according to example By using 0 g of such a mixture and by carrying out the po lymerization of the ethylene by following the procedures de3cribdd in example there were obtained 222 g of a polyethylene had an intrinsic in tetralin at The ield in ol mer amounted to of EXAMPLE 15 i S prepared according to example 1 and of ground together for 3 hours at a temperature of in the mill as that described in 1 g of the mixture thus ground were introduced together with 1000 cc of and 2 cc of under a nitrogen into a stainless steel autoclave of 2 fitted with stirrer and heated up to To this then added ethylene and hydrogen the pressure was maintained constant throughout te3t by continuously introducing After 8 rs the polymerisation was the tion product was filtered and the obtained Thereby wore obtained g of a polyethylene which had an in trinsic determined in tetralin at of d The yield in polymer amounted to 000 of EXAMPLE 14 g of prepared according to example 1 and of were ground together for hours at a temperature of in the same mill already described in example 1 By using g of the thus prepared and by ing out the polymerization of the ethylene according to the procedures described in there were obtained 137 β of polyethylene having an intrinsic determined in n at g of dried at under a reduced pressure of were treated with 100 of for This was then and tho so lid washed with until all chlorine ions in tho te have disappeared and finally it was dried under In the isolated present of By using g of produot and carrying out the polymerization of the ethylene according to the prooedure3 in there were g of a polyethylene ving an intrinsic viscositydetermined i tetralin at The yiold in amounted to of insufficientOCRQuality

Claims (1)

17 CLAIMS Catalyst for the polymerization of alpha particularly comprising a product of reaction between a hydride or an organo metallic compound of Be and a alkali metals with the product obtained by contacting a titanium compound chosen from amongst halogen halogen or ammonium and alky1 titanites or titanites of alkali titanium amides and titanium titanium salts of organic as well as addition compounds of and tetravalent with compounds a support consisting of an anhydrous manganese and more particularly a preactiyated form or obtained in the active in the course of the formation of the catalytic the active form being characterized in that the highest intensity diffraction line of its spectrum which appears in the spectrum of the normal manganese halide is replaced by a halo of lower having a surface area greater than 3m Catalyst according to Claim 1 wherein the titanium compound is one of the CO W 18 Catalyst according to Claims 1 and wherein the titanium compound is contacted with an anhydrous manganese particularly and in an active obtained by dissolving the anhydrous manganese halide in an organic more particularly an alcohol or an the greatest part of which is rapidly and the removal of the solvent is thereafter completed reduced and at a temperature in general greater than Catalyst according to Claim wherei the titanium compound is contacted with an activated anhydrous manganese by the two compounds in a ball mill in the absence of any inert Catalyst according to Claim wherein the supported catalytic component is obtained by treating an anhydrous manganese dihalide of normal type with a liquid titanium compound or with a of a titanium in an organic solvent under conditions in which the titanium compound is attached to the Catalyst according to Claim wherein the anhydrous manganese halide is contacted with an excess of at the boiling and the excess is subsequently Catalyst according to any of Claims 1 to wherein the titanium compound is present on the carrier is an amount of from to but preferably to by weight with respect to the 19 Catalyst according to any of Claims 1 to wherein an in particular an is used as the organometallie A process for the polymerization of in particular ethylene or of its mixtures in which the polymerization is conducted in the presence of a catalyst according to any of Claims 1 to Process according to Claim which the polymerization is carried out at temperatures from and in the presence of a regulator for the weight of the and the polymer thus obtained is not subjected to any purification treatment from catalyst Polyethylene obtained by a process according to Claim insufficientOCRQuality