DK151889B

DK151889B - PROCEDURE FOR PREPARING AN OLEPHINE POLYMERIZATION CATALYST

Info

Publication number: DK151889B
Application number: DK496173AA
Authority: DK
Inventors: Paolo Galli; Giovanni Di Drusco; Saverio De Bartolo
Original assignee: Montedison Spa
Priority date: 1972-09-13
Filing date: 1973-09-10
Publication date: 1988-01-11
Also published as: DE2345707C2; NL7312457A; FR2198784B1; ZA737263B; SE7713028L; HU167156B; GB1434543A; YU241373A; IT969340B; SU628805A3; DK151889C; FR2198784A1; JPS604203B2; YU36344B; DE2345707A1; DD107705A5; CS181253B2; BR7307088D0; PL94433B1; AU6025773A

Description

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Opfindelsen angår en fremgangsmåde til fremstilling af en olefin polymerisationskatalysator af den i indledningen til krav 1 angivne art. De ved fremgangsmåden ifølge opfindelsen fremstillede, understøttede katalysatorer anvendes til polymerisation af alkener, de besidder en høj aktivitet,og er karakteristiske ved, at de giver anledning til dannelsen af polymere i form af sfæroidale partikler, der hverken sønderbrydes eller danner kager, når de udsættes for kompression.The invention relates to a process for preparing an olefin polymerization catalyst of the kind set forth in the preamble of claim 1. The catalysts prepared by the process of the invention are used for the polymerization of alkenes, have a high activity, and are characteristic in that they give rise to the formation of polymers in the form of spheroidal particles which do not decompose or form cakes when exposed for compression.

Takket være de særlige mekaniske egenskaber af de dannede partikler muliggør de katalysatorer, der er fremstillet ifølge opfindelsen, at man kan undgå det granuleringstrin, der normalt anvendes i forbindelse med de konventionelle processer til fremstilling af de krystallinske polymere af alkenerne.Thanks to the special mechanical properties of the particles formed, the catalysts prepared according to the invention allow to avoid the granulation step normally used in the conventional processes for preparing the crystalline polymers of the alkenes.

I betragtning af disse katalysatorers særligt høje aktivitet muliggøres det desuden, at man i mange tilfælde kan undgå det trin, som omfatter, at man renser de polymere for de katalytiske remanenser, hvorved man således frembringer en betydelig simplificering af de traditionelle processer til fremstilling af krystallinske polymere ud fra alkenerne.In addition, given the particularly high activity of these catalysts, it is possible to avoid in many cases the step of purifying the polymers for the catalytic residues, thus producing a considerable simplification of the traditional processes for producing crystalline crystals. polymers from the alkenes.

Man kender katalysatorer, der er baseret på titanhalogenider, og hvilke som bærere gør brug af vandfrie magnesiumhalogenider i aktiv form, hvorved disse katalysatorer er velegnet til polymerisation af olefiner med høje polymerudbytter.Catalysts based on titanium halides are known which as carriers make use of anhydrous magnesium halides in active form, whereby these catalysts are suitable for the polymerization of olefins with high polymer yields.

Tysk offentliggørelsesskrift nr. 2 000 586 beskriver katalysatorer, der er fremkommet ved at omsætte en metalorganisk forbindelse af et metal fra gruppe I til III af det periodiske system med et hy-dratiseret magnesiumhalogenid og med en halogenholdig titanforbindelse, hvorved det hydratiserede magnesiumhalogenid omdannes til vandfrit magnesiumhalogenid.German Publication No. 2,000 586 discloses catalysts obtained by reacting a metal-organic compound of a group I to III metal of the periodic system with a hydrated magnesium halide and with a halogen-containing titanium compound, thereby converting the hydrated magnesium halide to anhydrous magnesium.

Tysk offentliggørelsesskrift nr. 2 153 520 beskriver i høj grad aktive og selektive katalysatorer til polymerisation af alfa-ole-German Publication No. 2,153,520 describes highly active and selective catalysts for the polymerization of alpha-oleic acid.

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finer, hvilke som fast katalysatorkomponent omfatter det produkt, der fremkommer ved, at man bringer kontakt mellem en titanforbindelse og et vandfrit magnesiumhalogenid i aktiv form, idet den foretrukne metode, ved hvilken man bringer kontakt mellem forbindelserne, er fælles formaling.veneers which comprise as a solid catalyst component the product resulting from contacting a titanium compound with an anhydrous magnesium halide in active form, the preferred method of contacting the compounds being common milling.

Skønt de katalysatorer, der fremstilles under anvendelse af de i de tre foregående afsnit angivne metoder, er meget aktive og selektive, udviser de ikke nogen særpræget morfologi, og de er ikke i stand til at give anledning til dannelsen af polymere i form af kugleformede partikler, og langt mindre polymere i form af partikler, der udviser den nødvendige modstandsevne mod kompression.Although the catalysts prepared using the methods set forth in the three preceding sections are very active and selective, they do not exhibit any distinct morphology and are unable to give rise to the formation of polymers in the form of spherical particles , and much smaller polymers in the form of particles that exhibit the necessary resistance to compression.

Katalysatorer af Ziegler-Natta typen, der har form af sfæriske eller sfæroidale legemer, og som er i stand til at polymerisere ole-finerne til polymere, der har en form, der reproducerer eller "gentager" formen af katalysatorpartiklerne, er beskrevet i US patent nr. 3 594 330 og i tysk offentliggørelsesskrift nr. 1 957 705. i ! }Ziegler-Natta type catalysts which are in the form of spherical or spheroidal bodies capable of polymerizing the olefin to polymers having a form that reproduces or "repeats" the shape of the catalyst particles are disclosed in U.S. Patents No. 3 594 330 and in German Publication No. 1 957 705. i! }

De polymere korn, der frembringes med de hidtil kendte, understøttede katalysatorer, og som giver anledning til fremkomsten af "repetitions "-fænomenet, er skøre eller har høj tendens til kagedannelse, når de udsættes for kompression.The polymeric grains produced with the previously known supported catalysts, which give rise to the "repetition" phenomenon, are brittle or have a high tendency for cake formation when subjected to compression.

Det er kendt, at den granuleringsfase, der anvendes i de konventionelle processer til fremstilling af de krystallinske polymere af alkener, er en besværlig operation, der på afgørende måde påvirker processens økonomi. Man har allerede gjort et stort antal forsøg på at eliminere denne fase.It is known that the granulation phase used in the conventional processes for preparing the crystalline polymers of alkenes is a cumbersome operation that significantly affects the economy of the process. Many attempts have been made to eliminate this phase.

De eneste hidtil kendte processer, i forbindelse med hvilke det har været muligt direkte at opnå anvendelige polymere uden granulering ved transformeringsprocesser til fremstillede produkter, er karakteriseret ved anvendelsen af ikke-understøttede Ziegler-Natta-katalysatorer, hvori Ti-trichloridet, der anvendes som katalytisk komponent, fremstilles i henhold til en speciel teknik, ud fra TiCl^ ved reduktion med Al-organiske forbindelser.The only known processes in which it has been possible to directly obtain useful polymers without granulation by transformation processes for manufactured products are characterized by the use of unsupported Ziegler-Natta catalysts, wherein the Ti trichloride used as catalytic component, prepared according to a special technique, from TiCl 2 by reduction with Al-organic compounds.

De polymere, som fremstilles med sådanne katalysatorer, foreligger i form af et pulver med en snæver kornstørrelsesfordeling,The polymers prepared with such catalysts are in the form of a powder having a narrow grain size distribution,

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hvorved partiklerne ikke foreligger i nogen regelmæssig, geometrisk form, og hvorved de sønderdeles, når de udsættes for slidprøver .whereby the particles are not present in any regular geometric form and thereby disintegrate when subjected to wear samples.

Desuden finder disse ikke-granulerede pulvere kun anvendelse i forbindelse med fremgangsmåder til fremstilling af fibre.Furthermore, these non-granulated powders find use only in connection with methods of making fibers.

Det har nu overraskende vist sig, at det er muligt at fremstille understøttede katalysatorer til polymerisation af alkener, der udviser en ret høj aktivitet, og som samtidigt er i stand til at give anledning til dannelsen af krystallinske polymere i form af sfæriske eller sfæroidale partikler, der udviser en betydelig modstandsdygtighed over for smuldring og kompression.It has now surprisingly been found that it is possible to prepare supported catalysts for polymerization of alkenes which exhibit a fairly high activity and which are capable of giving rise to the formation of crystalline polymers in the form of spherical or spheroidal particles. showing considerable resistance to crumbling and compression.

Fremgangsmåden til fremstilling af katalysatoren ifølge opfindelsen, der er af den i indledningen til krav 1 angivne art, er ejendommelig ved det i den kendetegnende del af krav 1 angivne.The process for preparing the catalyst according to the invention, which is of the kind set forth in the preamble of claim 1, is characterized by the method of claim 1.

Ved den gennemsnitlige poreradius menes forholdet 2V/S · κΛ, hvor "V" betyder den totale porøsitet af partikl|rne udtrykt i cm^/g, og hvor "S" er overfladearealet udtrykt i m /g.By the mean pore radius is meant the ratio 2V / S · κΛ, where "V" means the total porosity of the particles expressed in cm 2 / g and where "S" is the surface area expressed in m / g.

Ved mekanisk modstandsdygtighed over for supersoniske vibrationer menes den minimale, specifikke energi (Watt*h/1), som nødvendigvis må tilføres til partiklerne af den katalytiske komponent, der er suspenderet i en indifferent væske, for at frembringe en næsten fuldstændig desintegration deraf. Ved· udtrykket "næsten fuldstændig desintegration" (smuldring) menes, at over 80% af partiklerne udviser en gennemsnitlig størrelse, der ligger under den oprindelige størrelse. I tilfælde af katalysatoren fremstillet ved fremgangsmåden ifølge opfindelsen er målingen blevet udført ved at udsætte en suspension af partiklerne i vandfrit heptan, i en koncentration af 2 - 3 vægt-procent, anbragt i et glas-reagensglas, der dypper ned i et vandbad, for påvirkningen af de supersoniske vibrationer.By mechanical resistance to supersonic vibrations is meant the minimum specific energy (Watt * h / 1) which must necessarily be applied to the particles of the catalytic component suspended in an inert liquid to produce a near complete disintegration thereof. By the term "almost complete disintegration" (crumb ring) it is meant that over 80% of the particles exhibit an average size below the original size. In the case of the catalyst prepared by the process of the invention, the measurement has been carried out by exposing a suspension of the particles in anhydrous heptane, at a concentration of 2 to 3% by weight, placed in a glass test tube immersed in a water bath for the influence of the supersonic vibrations.

Som kilde for de supersoniske vibrationer anvendtes et apparat, der udvikler en specifik effekt, der ligger mellem 10 og 80 Watt/l, og som har en frekvens mellem 22,4 og 45 KHz.As a source of the supersonic vibrations, an apparatus was developed which develops a specific power of between 10 and 80 Watts / l and has a frequency between 22.4 and 45 KHz.

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Den specifikke effekt af apparatet udtrykkes ved forholdet mellem energien af transduceren og voluminet af den væske (hvorigennem den supersoniske energi udspredes), der indeholdes i en metaltank, i forbindelse med hvilken transduceren selv bringes IThe specific power of the apparatus is expressed by the ratio of the energy of the transducer to the volume of the liquid (through which the supersonic energy is dissipated) contained in a metal tank, to which the transducer itself is brought.

i anvendelse.in use.

Hvert prøvestykke underkastes successive behandlinger med voksende intensitet (varighed og effekt), indtil man opnår den næsten fuldstændige desintegration af partiklerne. Efter behandlingen og den forudgående separation af det meste af heptanet bliver prøverne fotograferet under et optisk mikroskop.Each sample is subjected to successive treatments of increasing intensity (duration and effect) until the near-complete disintegration of the particles is achieved. After the treatment and prior separation of most of the heptane, the samples are photographed under an optical microscope.

Det har været muligt at gennemføre en evaluering af den laveste energi, der vil frembringe en næsten fuldstændig desintegration på basis af blot en simpel sammenligning mellem de forskellige fotografier, takket være den kendsgerning, at prøvestykkerne eller prøverne efter behandlingen udviste ensartethed hvad angår partikelstørrelsesfordelingen.It has been possible to carry out an evaluation of the lowest energy which will produce an almost complete disintegration on the basis of a simple comparison between the different photographs, thanks to the fact that the samples or samples after treatment showed uniformity in the particle size distribution.

Man har opnået særligt interessante resultater med hensyn til den j mekaniske modstandsdygtighed af de sfæriske eller sfæroidale par- j i tikler af de polymere med katalysatorer, hvori bestanddel b) er karakteristisk ved supersoniske modstandsdygtighedsværdier mellem 10 og 50 Watt»h/l og ved en gennemsnitlig poreradius, der ligger mellem 35 og 60 JUog et overfladeareal mellem 3 og 70 m^/g.Particularly interesting results have been obtained with respect to the mechanical resistance of the spherical or spheroidal particles of the polymers with catalysts, wherein component b) is characterized by supersonic resistance values between 10 and 50 Watts / h and at an average pore radius between 35 and 60 JU and a surface area between 3 and 70 m 2 / g.

Man har opnået lige så tilfredsstillende resultater med de katalysatorer, hvor bestanddel b) var kendetegnet ved et overflade-areal, der var større end 70 m /g, en modstandsdygtighed over for supersoniske vibrationer, der ligger mellem 1 og 10 ¥att*h/l og en gennemsnitlig poreradius, der ligger mellem 70 og 100 Å.Equally satisfactory results have been obtained with the catalysts in which component b) was characterized by a surface area greater than 70 m / g, a resistance to supersonic vibrations ranging from 1 to 10 att att * h / 1 and an average pore radius between 70 and 100 Å.

Evnen af katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen til dannelse af krystallinske polymere af alkenerne i form af sfæriske eller sfæroidale partikler, der hverken des integrerer eller komprimeres, er endnu mere uventet, når man tager i betragtning, at de katalysatorer, der er forskellige fra katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen, kun på grund af den kendsgerning, at deres katalytisk understøttede bestanddele udviser for-The ability of the catalysts made by the process of the invention to form crystalline polymers of the alkenes in the form of spherical or spheroidal particles which neither integrate nor compress is even more unexpected considering the catalysts different from the catalysts. prepared by the process of the invention only because of the fact that their catalytically supported constituents exhibit

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skellige værdier for den mekaniske resistens over for de supersoniske vibrationer, for overfladearealet og for porernes gennemsnitlige radius, enten ikke giver anledning til fremkomsten af fænomenet "repetition", eller - hvis de gør det - giver anledning til dannelsen af skøre eller let komprimerbare, sfæriske eller sfæroidale partikler.different values for the mechanical resistance to the supersonic vibrations, for the surface area and for the average radius of the pores either do not give rise to the phenomenon of "repetition" or - if they do - give rise to the formation of brittle or easily compressible, spherical or spheroidal particles.

En særlig foretrukken udførelsesform for fremgangsmåden ifølge opfindelsen er ejendommelig ved det i den kendetegnende del af krav 7 angivne.A particularly preferred embodiment of the method according to the invention is characterized by the characterizing part of claim 7.

I tilfælde af MgCl2«6H20 bliver det smeltede chlorid sprøjtet ind i en strøm af enten varm luft eller varmt nitrogen ved hjælp af dyser med en åbningsdiameter, der er valgt på en sådan måde, at de sfærisk formede partikler, som vil dannes, vil have en partikelstørrelsesfordeling mellem 10 og 300 u.In the case of MgCl 2 6H 2 O, the molten chloride is injected into a stream of either hot air or hot nitrogen by means of nozzles having an aperture diameter selected in such a way that the spherically shaped particles which will form will have a particle size distribution between 10 and 300 u.

De således fremkomne partikler, hvorfra eventuelt både de finere og grovere partikler er separeret ved sigtning, bliver dehydratise-ret under tilstande, hvor der ikke vil forekomme nogen hydrolyse af det hydratiserede Mg-chlorid, indtil man reducerer mængden af hydratationsvand til værdier, der ligger mellem 0,5 og 3,5 mol pr. mol MgCl2, men fortrinsvis mellem 1 og 3 mol.The particles thus obtained, from which both the finer and coarser particles are optionally separated by sieving, are dehydrated under conditions where no hydrolysis of the hydrated Mg chloride will occur until the amount of hydration water is reduced to values which are present. between 0.5 and 3.5 moles per moles of MgCl2, but preferably between 1 and 3 moles.

De partielt dehydratiserede partikler bliver derpå indført i TiCl^, der er opvarmet til kogepunktet, og derpå befriet for overskuddet af TiCl^, vasket under varmepåvirkning i frisk TiCl^ og derpå vasket med heptan for at fjerne ethvert spor af TiCl^, der ikke er fikseret til bæreren. Ved at anvende denne udførelses-form for opfindelsen opnås, at de fremstillede katalysatorer udviser en særlig høj aktivitet.The partially dehydrated particles are then introduced into TiCl 2, which is heated to the boiling point, and then freed from the excess TiCl 2, washed under heat in fresh TiCl 2 and then washed with heptane to remove any trace of TiCl fixed to the wearer. By using this embodiment of the invention it is achieved that the catalysts prepared exhibit a particularly high activity.

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En anden metode til fremstillingen af den bestanddel, der har de egenskaber, der er angivet i b.l), består i, at man under anvendelse af kendt teknik og udstyr, der er velegnet til frembringelse af et produkt, der foreligger i form af sfærisk formede partikler, udsprøjter opløsninger af et vandfrit Mg-halogenid i et organisk opløsningsmiddel, såsom for eksempel en alkohol, en ether, en keton eller en ester, der har et kogepunkt mellem 60 og 150° C, under temperatur- og trykbetingelser, hvorved de 6 DK 151889 Β en kornstørrelsesfordeling, der ligger mellem 1 og 300 ji, i det væsentlige er frie for opløsningsmiddel, der ikke er kemisk bundet til Mg-halogenidet, og at man derpå i det væsentlige fuldstændiggør fjernelsen af det opløsningsmiddel, der er kombineret med bæreren, ved opvarmning, under reduceret tryk og ved en temperatur, der er større end 150° C, og som ved slutningen af behandlingen vil ligge mellem 200 og 350° G.Another method of preparing the component having the properties set out in (b) consists in using known techniques and equipment suitable for producing a product in the form of spherically shaped particles, spray solutions of anhydrous Mg halide in an organic solvent such as, for example, an alcohol, an ether, a ketone or an ester having a boiling point between 60 and 150 ° C, under temperature and pressure conditions, A grain size distribution between 1 and 300 µl is substantially free of solvent not chemically bound to the Mg halide and then substantially eliminates the removal of the solvent combined with the carrier , under heating, under reduced pressure and at a temperature greater than 150 ° C, which at the end of the treatment will be between 200 and 350 ° G.

De således fremkomne sfærisk formede partikler bliver derpå bragt i kontakt med en halogeneret Ti-forbindelse for på bæreren at fiksere den ønskede mængde af Ti. Dette kan for eksempel opnås ved at suspendere partiklerne af bæreren i et indifferent opløsningsmiddel, hvori Ti-forbindelsen er opløst i en mængde svarende til den, man ønsker at udfælde på bæreren, og ved derpå at fordampe opløsningsmidlet.The spherically shaped particles thus obtained are then contacted with a halogenated Ti compound to fix to the carrier the desired amount of Ti. This can be achieved, for example, by suspending the particles of the carrier in an inert solvent, wherein the Ti compound is dissolved in an amount similar to that desired to precipitate on the carrier, and then evaporating the solvent.

En af de metoder, der også er foretrukket, til fremstilling af den be- ; •standdel, der har de egenskaber, der er angivet i b.2), består i, i at man omsætter SOC^ med sfærisk formede partikler af Mg-halogenid, j der indeholder over 4 mol krystalvand, indtil der er foregået en ; dehydratisering svarende til et vandindhold på mellem 1 og 2 mol pr. mol Mg-halogenid, og at man derpå behandler den således fremkomne bærer med TiCl^ ved kogepunktet, i henhold til den metode, der er beskrevet til fremstilling af bestanddelen svarende til punkt b.1).One of the preferred methods also for the preparation thereof; • stand having the properties given in b.2) consists of reacting SOC ^ with spherical shaped particles of Mg halide containing more than 4 moles of crystal water until one has taken place; dehydration corresponding to a water content of between 1 and 2 moles per mole of Mg halide and then treating the carrier thus obtained with TiCl 2 at the boiling point, according to the method described for the preparation of the component corresponding to item b.1).

I tilfælde af, at man anvender katalysatorerne .fremstillet ved fremgangsmåden ifølge opfindelsen til polymerisation af alfa-alkener, især propylen, vil det være hensigtsmæssigt at behandle komponent b) med elektrondonorer før eller efter understøtningen af Ti-forbindelsen. I disse tilfælde vil også den metalorganiske forbindelse, der anvendes til fremstilling af katalysatoren, blive behandlet med en elektrondonor, der fortrinsvis anvendes i mængder, der er mindre end 1 mol pr. mol metalorganisk forbindelse, især i en mængde på fra 0,1 til 0,4 mol.In the case of using the catalysts prepared by the process of the invention for the polymerization of alpha alkenes, especially propylene, it will be convenient to treat component b) with electron donors before or after the support of the Ti compound. In these cases, the metal-organic compound used to prepare the catalyst will also be treated with an electron donor, preferably used in amounts less than 1 mole per minute. moles of metal-organic compound, especially in an amount of from 0.1 to 0.4 moles.

Elektrondonorforbindelserne vælges fortrinsvis blandt esterne af organiske og uorganiske, oxiderede syrer eller blandt mono-og polyaminforbindelser, der er frie for primære aminogrupper.The electron donor compounds are preferably selected from the esters of organic and inorganic oxidized acids or from mono and polyamine compounds which are free of primary amino groups.

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Betydningsfulde eksempler på sådanne forbindelser er esterne af benzoesyre og dennes alkylderivater, Ν,Ν,Ν,Ν-tetraalkylethylen-diaminerne, piperazin etc.Significant examples of such compounds are the esters of benzoic acid and its alkyl derivatives, Ν, Ν, Ν, Ν-tetraalkylethylene diamines, piperazine, etc.

Mg-halogenidet kan anvendes i blanding med co-bærere, der er indifferente over for Mg-halogenidet, og som er udvalgt blandt forbindelserne fra grundstofferne i gruppe I til IV af det periodiske system, fortrinsvis med 20 - 80 vægt-% af sådanne co-bærere. Herved muliggøres det, at man kan fortynde Mg-halogenidet med en indifferent co-bærer, hvorved man kan nøjes med en lavere andel af Mg-halogenid, således at der findes mindre chlor eller andet korroderende halogen i systemet. Eksempler på sådanne forbindelser er: ^200^, Na2S0^, B2°3*The Mg halide can be used in admixture with co-carriers inert to the Mg halide selected from the compounds of the elements in Groups I to IV of the Periodic Table, preferably with 20 to 80% by weight of such co. carriers. This makes it possible to dilute the Mg halide with an inert co-carrier, thereby settling for a lower proportion of Mg halide, so that less chlorine or other corrosive halogen is present in the system. Examples of such compounds are: ^ 200 ^, Na2 SO4, B2 ° 3 *

De halogenerede Ti-forbindelser, der er anvendelige i katalysatorerne ifølge opfindelsen, omfatter for eksempel halogenider, halogenalkoholater, halogenamider, ammoniumhalogentitanater og halogentitanater og Ti-salte af organiske, halogenerede syrer. Fortrinsvis anvender man flydende Ti-forbindelser, såsom for eksempel TiCl^, TiCl2(OC^H^)^ og TiBr^. De faste forbindelser, såsom for eksempel TiCl^f anvendes i form af opløsninger i indifferente opløsningsmidler af deres komplekser med elektrondonorer. Mængden af anvendelig Ti-forbindelse, udtrykt som titanmetal, ligger i almindelighed mellem 0,1 og 20 vægtprocent i forhold til den understøttede, katalytiske bestanddel. Ved at anvende denne mængde af titanforbindelsen opnås, at de fremstillede katalysatorer udviser en særlig høj aktivitet.The halogenated Ti compounds useful in the catalysts of the invention include, for example, halides, halogen alcoholates, halogen amides, ammonium halogen titanates and halogen titanates, and Ti salts of organic halogenated acids. Liquid Ti compounds, such as, for example, TiCl 2, TiCl 2 (OC 2 H 2) 2 and TiBr 2 are preferably used. The solid compounds, such as, for example, TiCl 2, are used in the form of solutions in inert solvents of their complexes with electron donors. The amount of usable Ti compound, expressed as titanium metal, is generally between 0.1 and 20% by weight relative to the supported catalytic component. By using this amount of the titanium compound, it is achieved that the catalysts produced exhibit a particularly high activity.

De metalorganiske forbindelser af metallerne i gruppe II og III fra det periodiske system omfatter trialkyl-Al-forbindelserne, dialkyl-Al-halogeniderne, samt Zn- og Mg-alkylforbindelser.The metallic organic compounds of the metals in Groups II and III of the Periodic Table include the trialkyl-Al compounds, the dialkyl-Al halides, as well as Zn and Mg-alkyl compounds.

Eksempler på sådanne forbindelser er: AliCgH^)^, Α1(ϊ0^Η^)^, A1(C3H7)3, AliCgH^^Cl, Zn(02^)2» Når man er interesseret i, at katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen skal udvise en højere stereospecificitet ved polymerisationen af alfa-alkener, anvender man som allerede anført en del af de metalorganiske forbindelser i form af komplekser med elektrondonorforbindelser.Examples of such compounds are: AliCgH2) ^, Α1 (ϊ0 ^ Η ^) ^, A1 (C3H7) 3, AliCgH ^^ Cl, Zn (02 ^) 2 »When interested in the catalysts prepared by the process of the invention is to exhibit a higher stereospecificity in the polymerization of alpha alkenes, as already stated, some of the metal-organic compounds are used in the form of complexes with electron donor compounds.

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Polymerisationen af ethylen og af alfa-alkener, især propylen.og buten, 1,4-methylpenten-l, og af blandinger af ethylen/alfa-alkener med katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen gennemføres i henhold til konventionelle metoder.The polymerization of ethylene and of alpha alkenes, especially propylene and butene, 1,4-methylpentene-1, and of mixtures of ethylene / alpha alkenes with the catalysts prepared by the process of the invention is carried out according to conventional methods.

Polymerisationen gennemføres i væskefase i nærvær eller fravær af et indifferent fortyndingsmiddel eller i gasformig fase.The polymerization is carried out in liquid phase in the presence or absence of an inert diluent or in gaseous phase.

Polymerisationstemperaturen ligger i almindelighed mellem 40 og 200°C, fortrinsvis mellem 50 og 100°C.The polymerization temperature is generally between 40 and 200 ° C, preferably between 50 and 100 ° C.

Molekylvægten af de polymere reguleres ved i polymerisationsfasen at anvende molekylvægtsregulatorer af den kendte type, såsom for eksempel hydrogen eller Zn-dialkyler. jThe molecular weight of the polymers is controlled by using molecular weight regulators of the known type, such as, for example, hydrogen or Zn dialkyls. j

Modstandsdygtigheden mod smuldring og kagedannelse af den sfærisk formede polymer, som dannes med katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen, bestemmes ved at arbejde med massen af partikler og ikke med den enkelte partikel, i henhold til de i det følgende angivne metoder.The resistance to crumbling and cake formation of the spherically shaped polymer formed with the catalysts prepared by the process of the invention is determined by working with the mass of particles and not with the individual particle, according to the methods set forth below.

iin

Por at bestemme modstandsdygtigheden mod smuldring indføres 20 g i polymer sammen med to små kugler af porcelæn (0 25 mm) i en metalcylinder (indvendig 0 38 mm; længde 160 mm), der er forsynet med en slæde, der har en bane på 50 mm, og som i 20 minutter udsættes for 240 oscillationer pr. minut. Derpå sammenlignes partikelstørrelsesfordelingen (med sigter af ASTM-serien nr. 4, 7, 10, 18, 35 og 70) med partikelstørrelsesfordelingen af den polymere som sådan.To determine the resistance to crumb ring, 20 g of polymer is introduced together with two small balls of porcelain (0 25 mm) into a metal cylinder (inside 0 38 mm; length 160 mm) provided with a slide having a 50 mm web and which for 20 minutes is subjected to 240 oscillations per second. minute. Then, the particle size distribution (with sieves of ASTM Series Nos. 4, 7, 10, 18, 35 and 70) is compared with the particle size distribution of the polymer as such.

De polymere, der fremstilles med katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen, udviser i det væsentlige den samme partikelstørrelsesfordeling før som efter forsøget. Man iagttager i modsætning dertil en betydelig reduktion af partikelstørrelsen i forbindelse med de polymere, der er fremstillet med katalysatorer, der ikke er fremstillet i henhold til opfindelsen.The polymers prepared with the catalysts prepared by the process of the invention exhibit substantially the same particle size distribution before as after the test. In contrast, a significant reduction in particle size is observed in connection with the polymers made with catalysts not prepared in accordance with the invention.

Med henblik på prøven til bestemmelse af modstandsdygtighed mod kagedannelse udsatte man i 6 minutter 4 tabletter, der vejede ca. 10 g, og 2 som var fremstillet ved kompression under et tryk på 394 kg/cm i en cylindrisk matrice (18 mm 0), for den samme behandling som den, man anvendte til bestemmelse af modstandsdygtigheden nod smuld-riricr.For the test of resistance to cake formation, 4 tablets were weighed for 6 minutes weighing approx. 10 g, and 2 produced by compression under a pressure of 394 kg / cm in a cylindrical die (18 mm 0), for the same treatment as that used to determine the crustal resistance of the crumb.

9 _ DK 151889 B9 _ DK 151889 B

I det tilfælde, hvor tabletterne forbliver i det væsentlige komprimeret, vejer man de fine partikler, som har separeret sig, mens partikelstørrelsesfordelingen af det smuldrede materiale i det tilfælde, hvor der har fundet en fuldstændig smuldring sted, bestemmes ved hjælp af de samme sigter, der anvendes til partiklerne af den polymere som sådan.In the case where the tablets remain substantially compressed, the fine particles which have separated are weighed, while the particle size distribution of the crumbled material in the case of complete crumbling has been determined by the same sieves. used for the particles of the polymer as such.

Tabletterne af de polymere, som fremstilles med katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen, disgregerer næsten fuldstændigt under indflydelse af behandlingen, således at der fremkommer deformerede partikler, der imidlertid har næsten de samme dimensioner som de oprindelige, små kugler.The tablets of the polymers produced with the catalysts prepared by the process of the invention almost completely disintegrate under the influence of the treatment, resulting in deformed particles having, however, nearly the same dimensions as the original small spheres.

De polymere, der i modsætning dertil er fremstillet med katalysatorer, der ikke svarer til egenskaberne af katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen, disgregerer ikke eller disgregerer kun lidt under påvirkning af rysteprøven.The polymers, in contrast, made with catalysts which do not correspond to the properties of the catalysts prepared by the process of the invention do not disregard or disregard only slightly under the influence of the shake test.

Som allerede angivet modstår partiklerne af den polymere fremstillet med katalysatorerne fremstillet ved fremgangsmåden ifølge opfindelsen både smuldreprøven og kompressionsprøven.As already stated, the particles of the polymer made with the catalysts prepared by the process of the invention withstand both the crumb test and the compression test.

Et andet træk, der kan betragtes som væsentligt for den katalysator, der anvendes ved polymerisationen, er, at partiklerne (i almindelighed har disse en diameter på 1 - 2 mm) udviser en ensartet fordeling indenfor massen af partikler af Mg-forbindelsen, der anvendes som bærer. Den residuale Ti-forbindelse, der er til stede i partiklen, foreligger i almindelighed i en mængde under 0,003% Ti.Another feature which may be considered significant for the catalyst used in the polymerization is that the particles (generally having a diameter of 1-2 mm) exhibit a uniform distribution within the mass of particles of the Mg compound used. as a carrier. The residual Ti compound present in the particle is generally present in an amount below 0.003% Ti.

Opfindelsen skal nu illustreres ved de følgende eksempler. Når intet andet er angivet, er procentangivelserne på vægtbasis. For at tydeliggøre opfindelsen i forhold til kendt teknik er de følgende eksempler 3, 4, 8 og 9 sammenligningseksempler, mens de resterende eksempler er egentlige eksempler ifølge opfindelsen.The invention will now be illustrated by the following examples. Unless otherwise indicated, the percentages are by weight. In order to clarify the invention in relation to the prior art, the following Examples 3, 4, 8 and 9 are comparative examples, while the remaining Examples are actual Examples of the invention.

10 DK 151889B10 DK 151889B

Eksempel 1Example 1

Fremstilling af MgClg^^HgO i sfærisk formPreparation of MgClg 3 H 2 O in spherical form

Smeltet MgCl2*2H20 "blev i modstrøm besprøjtet med varm luft i et apparat af sprøjtekølingstypen fra firmaet Uiro Atomizer. Diameteren af sprøjtedysen var 0,34 mm. Overtrykket blev etableret med nitrogen. ;The molten MgCl2 * 2H20 "was sprayed countercurrently with hot air in a Uiro Atomizer spray-type apparatus. The diameter of the spray nozzle was 0.34 mm. The overpressure was established with nitrogen .;

De sfærisk formede partikler blev opsamlet på bunden af tørreren og blev derpå sigtet for at opnå en fraktion mellem 53 og 105 u. |The spherically shaped particles were collected on the bottom of the dryer and then sieved to obtain a fraction between 53 and 105 µl.

De således separerede fraktioner blev derpå tørret i en ovn ved 130° C i en nitrogenstrøm. iThe thus separated fractions were then dried in an oven at 130 ° C in a stream of nitrogen. in

Efter tørring viste det sig, at produktet bestod af MgClg·21^0.After drying, it was found that the product consisted of MgClg · 21 °.

Fremstilling af den understøttede katalysatorbestanddelPreparation of the supported catalyst component

Det anvendte udstyr bestod af en reaktor af Pyrex-glas, der har en volumenkapacitet på ca. 3 liter, og som på sin bund har en filterplade af sintret glas. Opvarmningen blev udført ved hjælp af en elektrisk modstand, der er viklet omkring den lavere, tubu- i lært formede del af reaktoren. Desuden blev reaktoren forsynet j med en tilbagesvaler, en omrører, et termometer og et reserve- j lungesystem med vandfrit Kg· Tilførslen af bærer i form af pulver j foregik gennem et indløb ved hjælp af et reagensglas, der kunne sættes'under tryk med Hg·The equipment used consisted of a Pyrex glass reactor having a volume capacity of approx. 3 liters and which has a sintered glass filter plate on its bottom. The heating was carried out by means of an electrical resistor wound around the lower tubular shaped part of the reactor. In addition, the reactor was provided with a reflux condenser, a stirrer, a thermometer and a reserve pulmonary system with anhydrous Kg. The supply of carrier in the form of powder j proceeded through an inlet using a test tube which could be pressurized with Hg. ·

En glasflaske, der var tilsluttet til bunden af reaktoren, opsamler reaktions- og vaskevæskerne fra filtratet, mens en anden i flaske, der er anordnet lateralt og tilsluttet til reaktorens hoved, tjener til at opvarme og tilføre vaskevæskerne.One glass bottle connected to the bottom of the reactor collects the reaction and wash liquids from the filtrate, while another in bottle arranged laterally and connected to the head of the reactor serves to heat and supply the wash liquids.

33

Understøtningsreaktionen fandt sted ved at indføre 2500 cm TiCl^ i reaktoren og ved derpå at bringe temperaturen af TiOl^ til kogepunktet deraf, 136,5° C. Efter få minutters kogning indføres der i reaktoren 120 g bærer under kraftig omrøring. Temperaturen faldt derpå, hovedsageligt hidrørende fra virkningen af den HC1, der udvikledes i reaktionen, og som opløstes i TiOl^, hvorved der frembragtes en sænkning af kogepunktet deraf.The support reaction took place by introducing 2500 cm @ 2 of TiCl3 into the reactor and then bringing the temperature of TiOl4 to its boiling point, 136.5 ° C. After a few minutes of boiling, 120 g of carrier were introduced into the reactor with vigorous stirring. The temperature then decreased, mainly due to the action of the HCl which developed in the reaction, which was dissolved in TiO1, thereby producing a lowering of the boiling point thereof.

n DK 151889 Βn DK 151889 Β

Gradvist steg temperaturen til 138° O, kogepunktet af TiCl^, som indeholder en vis mængde TiOCl2 som reaktionsbiprodukt. Denne temperatur blev bibeholdt i 1 time for at fuldføre reaktionen.Gradually, the temperature rose to 138 ° O, the boiling point of TiCl 2, which contains a certain amount of TiOCl2 as the reaction by-product. This temperature was maintained for 1 hour to complete the reaction.

Derpå blev det omsatte TiCl^, som indeholder biprodukterne, filtreret i varmen. Derpå gennemførtes der to vaskninger med TiCl^ i varmen og derpå 5 gange med heptan, der var dehydratiseret ved destillation med metallisk natrium.Then the reacted TiCl 2 containing the by-products was filtered in the heat. Then two washings were carried out with TiCl 2 in the heat and then 5 times with heptane which was dehydrated by distillation with metallic sodium.

Den kemiske analyse af den understøttede katalysatorbestanddel, der var tørret under vakuum, frembragte følgende resultater:The chemical analysis of the supported catalyst component dried in vacuo produced the following results:

Ti = 2,95 i«, Cl = 69 Mg = 20,5 %, H20 = 2,85 Rontgenstråle-analysen viste tilstedeværelsen af MgCl2 og MgCl2»H20. Overfladearealet af den understøttede bestanddel androg 33,7 m /g.Ti = 2.95 in «, Cl = 69 Mg = 20.5%, H 2 O = 2.85 The X-ray analysis showed the presence of MgCl2 and MgCl2» H20. The surface area of the supported component was 33.7 m / g.

Den minimale, specifikke supersoniske energi, der var nødvendig til opnåelse af fuldstændig sønderbrydning (smuldring) af partiklerne, androg 10,3 Watt»h/liter. Den gennemsnitlige poreradius var 59 Å.The minimum specific supersonic energy needed to achieve complete disintegration (crumbling) of the particles was 10.3 Watts / h. The average pore radius was 59 Å.

Polymerisation 1 en autoklav, der havde en volumenkapacitet på 4,5 liter, og som var forsynet med en bladomrører, et oliekredsløb til opvarmning og et vandkredsløb til afkøling, indførtes der 2000 cm^ renset heptan, der indeholder 4 g Al-tri-isobutyl. Temperaturen blev hævet til ca. 75° C, og derpå indførte man under et H2-tryk, katalysatorbestanddelen dispergeret i heptan. Den indførte mængde androg 0,00452 g svarende til 0,00452 g Ti. Derpå indførte man 7,5 kg/cm H2 og 5,5 kg/cm ethylen, mens temperaturen blev bragt til at stige til 85° C.Polymerization In an autoclave having a volume capacity of 4.5 liters and equipped with a leaf stirrer, an oil circuit for heating and a water circuit for cooling, 2000 cm 2 of purified heptane containing 4 g of Al-tri-isobutyl was introduced. . The temperature was raised to approx. 75 ° C and then under a H2 pressure, the catalyst component dispersed in heptane was introduced. The amount introduced was 0.00452 g corresponding to 0.00452 g Ti. Then 7.5 kg / cm H2 and 5.5 kg / cm ethylene were introduced while the temperature was raised to 85 ° C.

Trykket blev holdt konstant ved kontinuerlig tilførsel af ethylen. Polymerisationen blev gennemført i et tidsrum af 4 timer. Efter afgasning og afkøling udtoges der 740 g polyethylen. Den polymere forelå i form af sfærisk formede partikler med en diameter på 1 - 2 mm, hvilke var i stand til at bestå de sædvanlige smuldre- og kompressionsprøver, der er beskrevet i det foregående.The pressure was kept constant by continuous supply of ethylene. The polymerization was carried out for a period of 4 hours. After degassing and cooling, 740 g of polyethylene were extracted. The polymer was in the form of spherically shaped particles having a diameter of 1 to 2 mm, which were capable of passing the usual crumbling and compression tests described above.

12 DK 151889 B12 DK 151889 B

Eksempel 2Example 2

Den anvendte bærer var den samme som bæreren fra eksempel 1. Også metoden til fremstilling af den katalytiske bestanddel og de omsatte mængder var de samme.The carrier used was the same as the carrier of Example 1. Also, the method of preparing the catalytic component and the quantities reacted were the same.

Med denne co-katalysator gennemførte man polymerisationsforsøg med propylen i flydende propylen, med og uden komplekseringsmidler.This co-catalyst carried out polymerization experiments with propylene in liquid propylene, with and without complexing agents.

Polymerisation uden komplekseringsmidler I den allerede beskrevne 4 liter autoklav indførte man under Ho- 3 c atmosfære 3,1 g Al-tri-isobutyl i ca. 10 cm heptan. Ved hjælp af en 2 liter flaske indførte man i autoklaven 1150 g propylen. Temperaturen androg 30° C. Derpå indførte man ved 3 injektion med et Hg-overtryk ved hjælp af en 50 cm flaske 0,0141 g co-katalysator svarende til 0,00045 g Ti og 0,9 g Al-tri-isobutyl i 20 cm^ heptan. iPolymerization without Complexing Agents In the 4 liter autoclave already described, 3.1 g of Al-tri-isobutyl was introduced into ca. 10 cm of heptane. Using a 2 liter bottle, 1150 g of propylene was introduced into the autoclave. The temperature was 30 ° C. Then, by 3 injection with a Hg overpressure, a 50 cm bottle of 0.0141 g of co-catalyst corresponding to 0.00045 g of Ti and 0.9 g of Al-tri-isobutyl was introduced into 20 ml. cm 2 of heptane. in

Temperaturen blev derpå bragt op på 60° C, og ved denne temperatur viste trykket sig at være 27 atm. (overtrykket skyldtes det injicerede H^)· Under 4 timers polymerisation faldt trykket til 21 atm.The temperature was then brought up to 60 ° C and at this temperature the pressure was found to be 27 atm. (The pressure was due to the injected H 2) · During 4 hours of polymerization, the pressure dropped to 21 atm.

rr

Efter afkøling og udluftning af propylenet udtog man 750 g polypropylen. Udbytterne viste sig at være 1.670.000 g polymer/g Ti.After cooling and venting the propylene, 750 g of polypropylene were withdrawn. The yields were found to be 1,670,000 g polymer / g Ti.

Remanensen fra heptan-ekstraktionen androg 18,8 %.The residue from heptane extraction was 18.8%.

Efter ekstraktion af den amorfe substans forelå den polymere i form i af sfæriske partikler, der havde en diameter på ca. 1 mm, og som udviste god modstandsdygtighed både over for kompressions- og smuldringsprøven.After extraction of the amorphous substance, the polymer was in the form of spherical particles having a diameter of approx. 1 mm, and showed good resistance to both the compression and crumb test.

Polymerisation med komplekseringsmidlet triphenylphosphin I dette eksempel anvendtes den samme autoklav og den samme metode som den, der er beskrevet i forsøgene uden komplekseringsmidler.Polymerization with the triphenylphosphine complexing agent In this example, the same autoclave and the same method as that described in the experiments without complexing agents were used.

13 DK 151889 B13 DK 151889 B

3 I en Hg-strøm tilførtes der 4 g Al-tri-isobutyl i ca. 15 cm heptan; derpå indførtes der 1150 g propylen. Der afvejedes 0,009 g katalysator (svarende til 0,00029 g Ti), som indførtes i den lille ^ 3 50 cm flaske, der indeholdt 0,02 g triphenylphosphin i 20 cm heptan; disse materialer hlev holdt i kontakt med hinanden i ca.3 In a Hg stream, 4 g of Al-tri-isobutyl was added for approx. 15 cm of heptane; then 1150 g of propylene was introduced. 0.009 g of catalyst (equivalent to 0.00029 g of Ti) was weighed into the small 35 cm bottle containing 0.02 g of triphenylphosphine in 20 cm of heptane; these materials kept in contact with each other for approx.

15 minutter. Derpå blev katalysatoren og phosphinet injiceret i autoklaven under Hg-tryk. Derpå blev temperaturen hævet fra 50 til 60° C, og trykket steg til 26 atm. Efter 4 timers forløb blev reaktionsblandingen afkølet, propylenet blev udluftet, og der blev udtaget 145 g polymer. Udbytterne androg 500.000 g poly-mer/g Ti. Remanensen fra heptanekstraktionen var 29,5 1°· Efter ekstraktion af den amorfe substans forelå den polymere i form af sfæriske partikler, der var modstandsdygtige over for de sædvanlige smuldrings- og kompressionsprøver.15 minutes. Then, the catalyst and phosphine were injected into the autoclave under Hg pressure. Then the temperature was raised from 50 to 60 ° C and the pressure increased to 26 atm. After 4 hours, the reaction mixture was cooled, the propylene was vented and 145 g of polymer was withdrawn. The yields were 500,000 g polymer / g Ti. The residue from heptane extraction was 29.5 1 °. After extraction of the amorphous substance, the polymer was present in the form of spherical particles resistant to the usual crumbling and compression tests.

Polymerisation med komplekseringsmidlet ethylbenzoat I den allerede beskrevne autoklav indførte man under HL-tryk 3 ά 3 g Al-triethyl i 11 cm heptan og 1,5 g ethylbenzoat. 1 autoklaven indførte man derpå 950 g propylen, og co-katalysa-toren, nemlig 0,0171 g i 20 cm heptan (svarende til 0,00055 g Ti), blev injiceret ved hjælp af den flaske, der var sat under tryk med H2· Temperaturen blev derpå bragt op til 65° C, og trykket blev holdt på 28 atm. Efter 4 timers polymerisation blev polymerisationsmassen afkølet, gasserne blev udluftet, og der blev udtaget 43 g polymer, der forelå i form af frit strømmende, små kugler, der modstod smuldrings- og kompressionsprøverne, mens udbyttet androg 78.000 g/g Ti, og remanensen af ekstraktionen med heptan var lig 63,6Polymerization with the ethylbenzoate complexing agent In the autoclave already described, 3 ά 3 g of Al triethyl in 11 cm heptane and 1.5 g of ethyl benzoate were introduced under HL pressure. 950 g of propylene was then introduced into the autoclave and the co-catalyst, namely 0.0171 g in 20 cm of heptane (corresponding to 0.00055 g of Ti), was injected by means of the bottle pressurized with H2 · The temperature was then brought to 65 ° C and the pressure maintained at 28 atm. After 4 hours of polymerization, the polymerization mass was cooled, the gases vented, and 43 g of polymer available in the form of free flowing, small beads that withstood the crumb and compression tests were withdrawn while the yield was 78,000 g / g Ti and the residue of the extraction with heptane was equal to 63.6

Eksempel 3-7Examples 3-7

Eksempel 3 og 4 er sammenligningseksempler. Fremstillingen af det hydratiserede Mg-chlorid med sfærisk form blev gennemført i en 6 liter kappeautoklav, der var forsynet med et sifon-udtag i væskefasen, og desuden med et termoelement til måling af temperaturen og med et manometer til trykket.Examples 3 and 4 are comparative examples. The preparation of the hydrated Mg chloride of spherical form was carried out in a 6 liter jacket autoclave equipped with a siphon outlet in the liquid phase, and additionally with a thermocouple for measuring the temperature and with a pressure gauge.

14 DK 151889 B14 DK 151889 B

På sifon-udtaget er der anordnet et ydre, med en bøsning forsynet rør, hvis ende er tilsluttet til sprøjtedysen (0,64 mm 0) ved på-skruning. Opvarmningen gennemføres under anvendelse af damp, der har et tryk på 4,5 atm., og som cirkulerer i en varmekappe.On the siphon socket there is provided an outer, bushing tube whose end is connected to the spray nozzle (0.64 mm 0) by screw-in. The heating is carried out using steam having a pressure of 4.5 atm and circulating in a heating jacket.

I autoklaven indførtes der 4 kg MgClg^E^O. Temperaturen blev hævet til 128° C ved hjælp af cirkulerende damp i kappen. Ved indføring af nitrogen i autoklaven blev trykket bragt op på 22 atm. Efter opvarmning med dampen af den externe del af den sifon, der fører til sprøjtedysen, blev ventilen åbnet, og det smeltede chlorid blev sprøjtet.Into the autoclave 4 kg of MgCl 2 The temperature was raised to 128 ° C by circulating steam in the jacket. When introducing nitrogen into the autoclave, the pressure was brought up to 22 atm. After heating with the steam of the external part of the siphon leading to the spray nozzle, the valve was opened and the molten chloride was sprayed.

Det sprøjtede chlorid blev opsamlet i en lukket beholder med ni- , trogenlunge og indeholdende vandfrit heptan. Ved slutningen af ; sprøjtningen blev de sfæriske pulvere separeret fra opløsningsmidlet og tørret i en ovn ved en temperatur under 80° C i en strøm af nitrogen for at eliminere opløsningsmidlet.The sprayed chloride was collected in a sealed container of ni, trogen lung and containing anhydrous heptane. At the end of; spraying, the spherical powders were separated from the solvent and dried in an oven at a temperature below 80 ° C in a stream of nitrogen to eliminate the solvent.

Det viste sig, at bæreren bestod af kugler med en diameter, der var mindre end 350 u; ca. 30 i» var under 150 μ.It was found that the carrier consisted of spheres of less than 350 microns in diameter; ca. 30 i »was below 150 µ.

Efter sigtning af bæreren og efter at have valgt den fraktion, der ligger mellem 105 og 149 p, blev denne sidste tørret i en i ovn ved forskellige temperaturer.After sieving the carrier and after selecting the fraction between 105 and 149 µm, the latter was dried in an oven at various temperatures.

De data, der står i forbindelse med dehydratiseringen af det sfæriske chlorid, og som viser, hvad der er nødvendigt for at opnå de forskellige grader af hydratisering, er angivet i tabel i I. i iThe data related to the dehydration of the spherical chloride, showing what is needed to obtain the various degrees of hydration, are given in Table I.

Premstillingen af de understøttede, katalytiske bestanddele blev IThe premix of the supported catalytic constituents became I

gennemført ved at udnytte de dehydratiserede bærere og ved at 1 arbejde i overensstemmelse med den i eksempel 1 beskrevne metode. ;carried out by utilizing the dehydrated carriers and by working according to the method described in Example 1. ;

Reaktionsbetingelserne, mængderne af reaktanter og de analytiske - data af de understøttede bestanddele er alle blevet angivet i tabel II.The reaction conditions, the amounts of reactants and the analytical data of the supported constituents have all been given in Table II.

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1515

Polymerisationerne med ethylen blev gennemført med det samme udstyr og under anvendelse af den samme metode som angivet i de foregående eksempler.The polymerizations with ethylene were carried out with the same equipment and using the same method as set forth in the previous examples.

De relevante data i forbindelse med polymerisationsbetingelserne, de opnåede resultater og egenskaberne af de polymere er sammenstillet i tabel III.The relevant data related to the polymerization conditions, the results obtained and the properties of the polymers are summarized in Table III.

Tabel ITable I

t r _Eksempel 3 iEksempel 4 1Eksempel 5 Eksempel 6 Eksempel 7 iExample 3 Example 1 Example 5 Example 6 Example 7 i

Dehydratise- 80 °0 95° 0 115° C 135° C 135° CDehydration 80 ° 0 95 ° 0 115 ° C 135 ° C 135 ° C

ringsbetingelser 4 timer 4 timer 4 timer 4 timer 8 timerring conditions 4 hours 4 hours 4 hours 4 hours 8 hours

Cl 36,45 $ 40,95 $ 46,35$ 53,75 $ 60,95 $ H20 51,40 $ 43,05 $ 37,20 $ 26,80 $ 16,00 $ RX: krystal- ; linsk form MgCl2«6H2C MgCl2*4H20 HgCl2«4H2° MgCl2.2H20 MgCl2*H20Cl 36.45 $ 40.95 $ 46.35 $ 53.75 $ 60.95 $ H20 51.40 $ 43.05 $ 37.20 $ 26.80 $ 16.00 $ RX: crystal-; lineal form MgCl2 «6H2C MgCl2 * 4H20 HgCl2« 4H2 ° MgCl2.2H20 MgCl2 * H20

MgCl2-2H20MgCl2-2H20

Teoretisk $ af Cl 34,85 42,9 48,5 54,1 62,7Theoretical $ of Cl 34.85 42.9 48.5 54.1 62.7

Teoretisk $ af H20 53,2 42,4 34,9 27,4 15,9Theoretical $ of H 2 O 53.2 42.4 34.9 27.4 15.9

is DK 151889 Bis DK 151889 B

Tabel IITable II

Eksempel nummer Eksempel 3 jEksempel 4 Eksempel 5 -Eksempel 6 Eksempel 7 --1---------- ------ - Mængde af bærer 80 g j 80 g 60 g · 80 g 39 gExample Number Example 3 Example 4 Example 5 Example 6 Example 7 - 1 ---------------- Amount of Carrier 80 g j 80 g 60 g · 80 g 39 g

Mængde af TiClÆ 2000 em^ I 2000 cm^ 2000 cm^ 2000 cm^ 2000 cm^ Temperatur 137° C j 137° C 137 C 138 C 137 CAmount of TiClÆ 2000 cm ^ In 2000 cm ^ 2000 cm ^ 2000 cm ^ 2000 cm ^ Temperature 137 ° C j 137 ° C 137 C 138 C 137 C

Varighed 1 time j 1 time 1 time j 1 time 1 timeDuration 1 hour j 1 hour 1 hour j 1 hour 1 hour

Vask med TiCl^ 2 2 2 j 2 1Wash with TiCl2 2 2 2 j 2 1

Vask med Ογ- 5 5 5 | 5 5 ——----Γ"Wash with Ογ- 5 5 5 | 5 5 ——---- Γ "

Analyse: i fAnalysis: i f

Ti 3,50 % 4,15 f 3,00 f ; 3,20 f 1,55 f 'Ti 3.50% 4.15 f 3.00 f; 3.20 f 1.55 f

Cl 69,00 f 70,25 i> 68,95 % ! 69,15 f 68,15 f 'Cl 69.00 f 70.25 i> 68.95%! 69.15 f 68.15 f '

Mg 20,95 1o 20,95 # 21,55 % - 22,25 # :Mg 20.95 1o 20.95 # 21.55% - 22.25 #:

Specifik over- > ! flade i m^/g 98,2 109,9 64,9 j 21,3 11,4 _ !__iSpecific over->! surface in m ^ / g 98.2 109.9 64.9 j 21.3 11.4 _! __ i

...... I...... I

Modstandsdyg- s tighed over for supersoniske vibrationer i : ¥att*h/liter 3 - 3,17 2 - 3,2 10,3 25,6 25,6Resilience to supersonic vibrations in: ¥ att * h / liter 3 - 3.17 2 - 3.2 10.3 25.6 25.6

Gennemsnitlig poreradius 41 1 36 Å 45 Å 38 Å 63 Å 1Average pore radius 41 1 36 Å 45 Å 38 Å 63 Å 1

Tabel IIITable III

17 DK 151889B17 DK 151889B

_jBksempel 3 jEksempel 4 Eksempel 5 Eksempel 6 Eksempel 7 Mæng de af kata- ! lytisk forbindel- i se b,0165 g |0,0153 g 0,0245 g 0,029 g 0,0343 g Mængde af Ti 10,00056 g jO,00064 g 0,00073 g 0,00093 g 0,00058 g Mængde af jExample 3 Example 4 Example 5 Example 6 Example 7 Mix those of the cat! lytic compound see b, 0165 g | 0.0153 g 0.0245 g 0.029 g 0.0343 g Amount of Ti 10,00056 g jO, 00064 g 0.00073 g 0.00093 g 0.00058 g Amount of j

Al(iC^Hg)5 4 g 4 g 4 g 4 g 4 gAl (iC ^ Hg) 5 4 g 4 g 4 g 4 g 4 g

Temperatur 85° C 85° C 85° C 85° C 85° CTemperature 85 ° C 85 ° C 85 ° C 85 ° C 85 ° C

Varighed - timer 5 timer 5 timer 5 timer 5 timer 5 timerDuration - hours 5 hours 5 hours 5 hours 5 hours 5 hours

Ethylen-tryk 8,5 ata 8,5 ata 8,5 ata 8,5 ata 8,5 ata E^-tryk 5,5 ata 5,5 ata 5,5 ata 5,5 ata 5 , 5 ata Mængde af polymer 508 g 840 g 310 g 195 g 234 gEthylene pressure 8.5 ata 8.5 ata 8.5 ata 8.5 ata 8.5 ata E ^ pressure 5.5 ata 5.5 ata 5.5 ata 5.5 ata 5.5 ata Amount of polymer 508 g 840 g 310 g 195 g 234 g

Udbytte, g pol./g Ti 900,000 1,300,000 425,000 210,000 400,000 g pol./g katalysator 31,000 55,000 12,600 6,700 6,850Yield, g pol / g Ti 900,000 1,300,000 425,000 210,000 400,000 g pol / g catalyst 31,000 55,000 12,600 6,700 6,850

Tilsyneladende * _ , , 3 massefylde 0,268 g/cm0,300 g/cnr 0,400 g/cnr 0,435 g/cnr 0,400 g/cmApparently *, 3 density 0.268 g / cm0.300 g / cm 0.400 g / cm 0.435 g / cm 0.400 g / cm

Polymer Modstandsdygtighed over for: smuldring nej nej ja * ja ja kompression nej nej ja ja ja _ i i _Polymer Resistance to: crumbling no no yes * yes yes compression no no yes yes yes _ i i _

Eksempel 8-10Examples 8-10

Eksempel 8 og 9 er sammenlignende eksempler. Den katalytiske bestanddel, som anvendes i disse eksempler, er fremkommet ved at anvende fraktionen med en kornstørrelsesfordeling mellem 62 og 105 pn, fremstillet ud fra henholdsvis hexahydratet, tetrahydratet og di-hydratet af magnesiumchlorid fra eksempel 3, 4 og 5.Examples 8 and 9 are comparative examples. The catalytic component used in these examples is obtained by using the fraction having a grain size distribution between 62 and 105 µm, prepared from the hexahydrate, tetrahydrate and dihydrate of magnesium chloride of Examples 3, 4 and 5, respectively.

De katalytiske bestanddele er blevet fremstillet under anvendelse af den samme metode i henhold til eksempel 3, 4 og 6.The catalytic components have been prepared using the same method of Examples 3, 4 and 6.

Også de polymere forsøg er blevet gennemført under de samme betingelser som betingelserne i henhold til de ovenfor angivne eksempler.Also, the polymeric experiments have been carried out under the same conditions as the conditions of the above examples.

18 DK 151889 B18 DK 151889 B

I tabel IV har man anført de relevante data for egenskaberne af de understøttede, katalytiske bestanddele, for resultaterne af polymerisationsforsøgene og for egenskaberne af de fremkomne polymere.Table IV lists the relevant data for the properties of the supported catalytic constituents, for the results of the polymerization experiments and for the properties of the resulting polymers.

Tabel IVTable IV

i Eksempel 8 Eksempel 9 Eksempel 10 iExample 8 Example 9 Example 10 i

Analyse af understøttet bestanddelSupported component analysis

Ti fo 3,69 3,25 2,55Ti fo 3.69 3.25 2.55

Cl % 66,7 68,35 67,85Cl% 66.7 68.35 67.85

Mg % 18,9 19,85 21,40Mg% 18.9 19.85 21.40

Specifik overflade i m2/g 156,1 82,9 12Specific surface area in m2 / g 156.1 82.9 12

Modstandsdygtighed mod smuldring, ¥att*h/liter 3,8 - 6,4 6,4 25,6 ;Crack Resistance, ¥ att * h / liter 3.8 - 6.4 6.4 25.6;

Gennemsnitlig ; radius, 1 38 34 40 1Average ; radius, 1 38 34 40 1

Polymerisation: udbytte i g pol./gPolymerization: yield in g pol./g

Ti 760,000 1,066,000 435,000Ti 760,000 1,066,000 435,000

Modstandsdygtighed af den polymere over for: smuldring nej nej ja kompression nej nej jaResistance of the polymer to: crumbling no no yes compression no no yes

Eksempel 11Example 11

Smeltet MgCl^e^o blev udsprøjtet i henhold til den i eksempel 1 beskrevne metode. Det således fremkomne produkt blev sigtet for at separere fraktionen med partikelstørrelser mellem 105 og 149 pm·The molten MgCl 2 e 2 0 was sprayed according to the method described in Example 1. The product thus obtained was screened to separate the fraction with particle sizes between 105 and 149 µm.

Denne fraktion blev derpå tørret i en ovn ved 80° 0 i 4 timer i en nitrogenstrøm. En Rontgenstråleanalyse af produktet viste, at det bestod af MgC^^HgO.This fraction was then dried in an oven at 80 ° for 4 hours in a stream of nitrogen. An X-ray analysis of the product showed that it consisted of MgCl3 HgO.

80 g af dette produkt blev derpå bragt til at reagere med 2000 cm Tid. i det apparat, der allerede er beskrevet i eksempel 1.80 g of this product was then reacted with 2000 cm Time. in the apparatus already described in Example 1.

19 DK 151889B19 DK 151889B

Efter 1 times reaktion blev overskuddet af TiCl. fjernet, mens 3 4 der yderligere tilsattes 2000 cm frisk TiCl^, der var opvarmet til 120° 0, og temperaturen blev bibeholdt på 137° C i yderligere en time. TiCl^ blev derpå udtaget, og produktet blev vasket tre gange med varm TiCl^ og seks gange med heptan.After 1 hour of reaction, the excess TiCl became. removed while further adding 2000 cm of fresh TiCl 2, heated to 120 ° 0, and maintaining the temperature at 137 ° C for an additional hour. TiCl 3 was then removed and the product washed three times with hot TiCl 2 and six times with heptane.

Ved analyse af det tørre produkt fandt man følgende: Ti = 8,55 01 = 61,45 f°, Mg = 17,25 nAnalysis of the dry product found the following: Ti = 8.55 01 = 61.45 f °, Mg = 17.25 n

Den specifikke overflade af produktet var 27,4 m /g, og resistensen mod smuldring af partiklerne var lig 12,8 Watt»h/liter.The specific surface of the product was 27.4 m / g and the resistance to crumbling of the particles was equal to 12.8 Watts / h.

0,0151 g af dette produkt blev anvendt ved polymerisationen af ethylen« under de i eksempel 1 angivne betingelser.0.0151 g of this product was used in the polymerization of ethylene under the conditions of Example 1.

Derved fremkom der 150 g polymer, der i det væsentlige bestod af sfærisk formede partikler, men hvori der også forelå korn med en uregelmæssig geometrisk form. Ved at udsætte den polymere for sædvanlige smuldrings- og kompressionsprøver viste det sig, at den hverken smuldrede eller blev komprimeret.There were thus obtained 150 g of polymer which consisted essentially of spherically shaped particles, but also containing grains of irregular geometric shape. By subjecting the polymer to conventional crumbling and compression tests, it was found that it was neither crumbly nor compressed.

Eksempel 12 60 g MgClg^^O i form af sfærisk formede partikler med størrelsen 53 - 105 /im og fremkommet ved sprøjtning med det i eksempel 1 beskrevne apparat blev bragt til at reagere med 2500 cm SOC^» som forelå i en 3 liter beholder, der var forsynet med en omrører og en tilbagesvaler. Reaktionen initieredes ved 55° C under gasudvikling. Under reaktionen steg temperaturen langsomt til 70° C.Example 12 60 g of MgClg 2 O in the form of spherical shaped particles of the size 53 - 105 µm and obtained by spraying with the apparatus described in Example 1 was reacted with 2500 cm 2 of SOC 2 which was available in a 3 liter container. , which was equipped with a stirrer and a reflux condenser. The reaction was initiated at 55 ° C during gas evolution. During the reaction, the temperature slowly increased to 70 ° C.

Reaktionen fortsatte, indtil der havde dannet sig et produkt, hvis sammensætning var MgC^· 1,5H20.The reaction continued until a product had formed, the composition of which was MgC ^ · 1.5H₂O.

30 g af dette produkt blev derpå bragt til at reagere med TiCl^ under de samme betingelser som anført i eksempel 1.30 g of this product was then reacted with TiCl 3 under the same conditions as set forth in Example 1.

Ved analyse af produktet, som blev tørret under vakuum ved 70° c, fandtes følgende resultat: Ti = 2,80 fo, 01 = 67,80 fo.Analysis of the product, which was dried under vacuum at 70 ° C, found the following result: Ti = 2.80 fo, 01 = 67.80 fo.

Det specifikke overfladeareal var 77,2 myg. ModstandsdygtighedenThe specific surface area was 77.2 mosquitoes. The resistance

ao DK 151889Bao DK 151889B

mod smuldring af partiklerne var 3,9 Watt*h/liter, mens den gennemsnitlige radius af porerne var 92 A.against crumbling of the particles was 3.9 Watt * h / liter, while the average radius of the pores was 92 A.

0,0372 g af dette produkt blev anvendt til polymerisation af ethylen under de samme betingelser som demf der blev anvendt i eksempel 1. Derved opnåede man 290 g af en polymer i form af sfæroidale partikler, i forbindelse med hvilke det viste sig, at de ved at blive udsat for sædvanlige smuldrings- og kompressionsprøver hverken blev sønderbrudt eller komprimeret.0.0372 g of this product was used for polymerization of ethylene under the same conditions as those used in Example 1. This gave 290 g of a polymer in the form of spheroidal particles, in which it was found that by being subjected to usual crumbling and compression tests were neither broken nor compressed.

Eksempel 13 50 g af det sfærisk formede produkt med sammensætningen MgCl2·1,5H20 fremstillet under de i eksempel 12 herskende betingelser blev bragt til at reagere med 50 cm^ ethylbenzoat.Example 13 50 g of the spherical shaped product of the composition MgCl 2 · 1.5 H 2 O prepared under the conditions of Example 12 were reacted with 50 cm 3 of ethyl benzoate.

Efter 16 timers forløb var væsken fuldstændigt absorberet. Det faste produkt blev fortyndet med heptan og suspensionen blev tørret under højt vakuum ved ca. 70° C.After 16 hours, the liquid was completely absorbed. The solid product was diluted with heptane and the suspension was dried under high vacuum at ca. 70 ° C.

Det tørrede produkt blev sigtet på en 200 μια sigte for at fjerne fraktionen af grove partikler.The dried product was screened on a 200 μια screen to remove the fraction of coarse particles.

3 30 g af det således fremkomne produkt blev omsat med 2000 cm TiCl^ under de i eksempel 1 herskende betingelser. Produktet, der var tørret under vakuum, udviste følgende analyse: Ti =2,5 f>,3 30 g of the product thus obtained were reacted with 2000 cm of TiCl 3 under the conditions of Example 1. The product dried under vacuum showed the following analysis: Ti = 2.5 f>,

Cl = 64 f>, Mg = 21,2 fo.Cl = 64 f>, Mg = 21.2 fo.

Den specifikke overflade var 118,9 m /g, og modstanden mod smuldring af partiklerne viste sig at være 1,7 Watt»h/liter. Den gennemsnitlige radius af porerne var 92 Å.The specific surface area was 118.9 m / g and the resistance to crumbling of the particles was found to be 1.7 Watt / h / liter. The average radius of the pores was 92 Å.

0,041 g af produktet blev anvendt til polymerisation af ethylen under de i eksempel 1 angivne betingelser. Den således fremkomne polymer forelå i form af sfæriske partikler med en diameter på 1-2 μια, og når disse partikler blev udsat for de sædvanlige prøver for bestemmelse af modstanden mod smuldring og kompression, viste det sig, at de hverken smuldrede eller blev komprimeret.0.041 g of the product was used for polymerization of ethylene under the conditions of Example 1. The polymer thus obtained was in the form of spherical particles having a diameter of 1-2 μια, and when these particles were subjected to the usual tests for determining the resistance to crumb and compression, they were found not to crumble or to be compressed.

Eksempel 14Example 14

MgGl9*0,45Ho0 i form af sfæroidale partikler blev fremstillet vedMgGl9 * 0.45Ho0 in the form of spheroidal particles was prepared by

21 DK 151889B21 DK 151889B

i en strøm af gasformigtHC1 ved 110° C at dehydratisere partikler af MgC^’fiELjO med størrelsen 53 - 105 yarn, fremkommet ved den i eksempel 1 beskrevne sprøjtemetode.in a stream of gaseous HCl at 110 ° C to dehydrate particles of MgCl2 -FEL2O of the size 53 - 105 yarns, obtained by the spraying method described in Example 1.

45 g af produktet blev derpå bragt til at reagere med TiCl^ under de samme betingelser som angivet i eksempel 1.45 g of the product was then reacted with TiCl 3 under the same conditions as in Example 1.

Efter tørring udviste den understøttede, katalytiske bestanddel følgende analyse: 2After drying, the supported catalytic component performed the following analysis:

Det specifikke overfladeareal viste sig at være 3,7 m /g; modstandsdygtigheden mod smuldring var 6,4 Watt«h/liter.The specific surface area was found to be 3.7 m / g; crumble resistance was 6.4 watts «h / liter.

0,1902 g af dette produkt blev anvendt til polymerisation af ethylen under de samme betingelser som betingelserne i eksempel 1.0.1902 g of this product was used for polymerization of ethylene under the same conditions as the conditions of Example 1.

Derved opnåedes 70 g polymer i form af sfæroidale partikler med en diameter på 1 - 2 mm; når disse partikler blev underkastet de sædvanlige prøver for bestemmelse af modstandsdygtigheden mod smuldring og kompression, viste det sig, at de hverken smuldrede eller komprimeredes.Thereby 70 g of polymer was obtained in the form of spheroidal particles having a diameter of 1-2 mm; when these particles were subjected to the usual tests to determine the resistance to crumbling and compression, it was found that they were neither crumbly nor compressed.

Claims

A process for preparing an olefin polymerization catalyst by reaction of an organometallic compound of a group I-III metal, an anhydrous magnesium halide and a halogen-containing Ti compound, characterized in that a) a metal organic compound of a group metal II and .III of the periodic system are reacted with b) a product consisting of a carrier which is an anhydrous Mg halide or a mixture of Mg halide and a M IV group, and of a halogen-containing Ti compound chemically fixed on the carrier or dispersed thereon, the product being in the form of spherically shaped particles having a diameter between 1 and

350 Jim, and is characterized by the following values of the mechanical resistance to supersonic vibrations expressed in watts «h / liter, of the average pore radius and of the surface area: (1) mechanical resistance to supersonic vibrations between 5 and 40 watts« h / liter , average pore radius between 30 and 70 Å and surface area between 3 and 70 m / g or (2) mechanical resistance to supersonic vibrations between 1 and 20 Watts h / liter, average pore radius between 70 and 150 Å 2 and surface area greater than 70 m / g.

Method according to claim 1, characterized in that a component b) is used which exhibits a resistance to super-sonic vibrations between 10 and 30 Watt-h / liter, an average pore radius between 35 and 60 Å and a surface area 2. between 3 and 70 m / g. j

Method according to claim 1, characterized in that a component b) is used which is resistant to supersonic vibrations between 1 and 10 Watt-h / liter, an average pore radius between 70 and 100 Å and a surface area that is greater than 70 m / g. DK 151889B

Process according to the preceding claims, characterized in that the carrier before or after the reaction with the Ti compound is modified by reaction with an electron donor compound and that the metal-organic compound is an Al trialkyl partially complexed with an electron donor compound. connection.

Process according to claims 1 to 4, characterized in that the carrier consists of Mg chloride and that the Ti compound, which is chemically fixed on the carrier or dispersed therein, is a Ti halide, especially TiCl 2.

Process according to the preceding claims, characterized in that the Ti compound present in the carrier is present in an amount between 0.1 and 20% by weight, expressed as metallic Ti.

Process according to claim 1, characterized in that a magnesium dihalide hexahydrate, optionally pretreated with an electron donor compound, is subjected to an injection according to known methods for obtaining spherical shaped particles having a diameter from 1 to 350. pmr, the resulting particles are dehydrated to obtain a residual crystal water content of between 0.5 and 3.5 moles, that the resulting partially dehydrated particles are reacted with a titanium halide or with a solution thereof at a temperature above 100 ° C. produced with an inert solvent, that the excess titanium halide not fixed on the support and any solvent present is removed and that the resulting spherical particles are treated with the organic aluminum compound, optionally in the presence of an co-catalyst.

Process according to claim 7, characterized in that the particles of the hydrated Mg halide containing between 0.5 and 3.5 moles of crystal water are reacted in a liquid medium consisting of heated TiCl to the boiling point.