DK151892B - PROCEDURE FOR CATALYTIC POLYMERIZATION OF PROPYL - Google Patents
PROCEDURE FOR CATALYTIC POLYMERIZATION OF PROPYL Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Description
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Opfindelsen angår en fremgangsmåde til katalytisk polymerisation af propylen ved at anvende katalysatorer, der indeholder titan, magnesium, aluminium og halogener.The invention relates to a process for catalytic polymerization of propylene using catalysts containing titanium, magnesium, aluminum and halogens.
Fra italiensk patent nr. 932.438 kender man katalysatorer, der er i stand til på stereoregulær måde at polymerisere alfa-alke-ner, især propylen, som udviser en høj aktivitet, og som består af reaktionsproduktet af et aluminiumalkyl, især komplexeret med en Lewis-base, med en særlig katalytisk bestanddel, der omfatter forbindelser og/eller blandinger, der indeholder titan, magnesium og fortrinsvis en Lewis-base, fremkommet ved at bringe en halogeneret titanforbindelse i kontakt med en bærer omfattende et magnesiumhalogenid, der er til stede i en særlig aktiveret form. I disse katalysatorer forekommer kontakten mellem titanforbindelsen og magnesiumhalogenidet i almindelighed ved samtidig formaling.Italian Patent No. 932,438 discloses catalysts capable of stereoregular polymerization of alpha alkenes, especially propylene, which exhibit high activity and which consist of the reaction product of an aluminum alkyl, especially complexed with a Lewis compound. base, with a particular catalytic component comprising compounds and / or mixtures containing titanium, magnesium and preferably a Lewis base, obtained by contacting a halogenated titanium compound with a support comprising a magnesium halide present in a particularly activated form. In these catalysts, the contact between the titanium compound and the magnesium halide generally occurs during co-milling.
Hvis man i de ovenfor angivne katalysatorer forsøger som en bestanddel, der indeholder et magnesiumhalogenid i den aktiverede form, at anvende et produkt, der er fremkommet ved omsætning mellem en titanforbindelse (f.eks. TiCl^) og et magnesiumalkoholat, opnår man katalysatorer, der ikke udviser helt tilfredsstillende aktiviteter og stereospecificiteter.If, in the above catalysts, an ingredient containing a magnesium halide in the activated form is attempted to use a product obtained by reaction between a titanium compound (e.g. TiCl 3) and a magnesium alcoholate, catalysts are obtained, that do not exhibit wholly satisfactory activities and stereospecifics.
Når på analog måde den katalytiske bestanddel, der indeholder et magnesiumhalogenid i den aktiverede form, fremstilles ved omsætning mellem TiCl^ og en magnesiumforbindelse med formlen RMgX, hvor R er et carbonhydridradikal og X kan være R eller et halogen, er aktiviteten og stereoregulariteten af den således fremkomne katalysator ikke helt tilfredsstillende.Analogously, when the catalytic component containing a magnesium halide in the activated form is prepared by reaction between TiCl 2 and a magnesium compound of formula RMgX wherein R is a hydrocarbon radical and X may be R or a halogen, the activity and stereoregularity of the catalyst thus obtained is not entirely satisfactory.
Det er opfindelsens formål at angive en fremgangsmåde til katalytisk polymerisation af propylen, af den i indledningen til kravet angivne art, hvor den anvendte katalysator udviser en bedre aktivitet end de hidtil kendte katalysatorer, der anvendes til dette formål, og hvor samtidigt stereoregulariteten af det dannede polymerisat er upåklagelig.It is an object of the invention to provide a process for catalytic polymerization of propylene, of the kind set forth in the preamble of claim, wherein the catalyst used exhibits a better activity than the known catalysts used for this purpose and at the same time the stereoregularity of the resulting polymerisate is impeccable.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved det i den 2The process according to the invention is peculiar to that of the invention
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kendetegnende del af kravet angivne. Det har overraskende vist sig, at den katalysator, der anvendes ved fremgangsmåden ifølge opfindelsen, udviser en bedre aktivitet end de hidtil kendte katalysatorer, der anvendes til dette formål, og at tillige stereoregulariteten af det dannede polymerisat er upåklagelig.characteristic part of the claim stated. Surprisingly, it has been found that the catalyst used in the process of the invention exhibits a better activity than the known catalysts used for this purpose, and that the stereoregularity of the resulting polymerisate is impeccable.
Det har således overraskende vist sig, at det er muligt at poly-merisere propylen med katalysatorer, der er i besiddelse af forbedrede egenskaber hvad angår aktivitet og stereoregularitet, når man går ud fra en katalytisk bestanddel, hvori magnesiumha-logenid i den aktiverede form er fremstillet ud fra Mg-alkohola-ter eller Mg-dialkyler.Thus, it has surprisingly been found that it is possible to polymerize propylene with catalysts possessing improved activity and stereoregularity properties when starting from a catalytic component wherein magnesium halogenide in the activated form is prepared from Mg alcoholates or Mg dialkyls.
Man kender ganske vist fra dansk patent nr. 125 599 og fransk patent nr. 2 093 306 en fremgangsmåde til polymerisation af alfa-olefiner, der indeholder mindst 3 carbonatomer, og blandinger af sådanne med ethylen under anvendelse af katalysatorer, der består af A) en organoaluminiumforbindelse og B) et fast stof opnået ved først at omsætte et magnesiumalkoholat med en organoaluminiumforbindelse, og dernæst lade reaktionsproduktet heraf reagere med en overgangsmetalhalogenforbindelse. Ifølge opfindelsen gør man imidlertid brug af en komponent B, der er af en principielt anden type. Herved fremkommer der polymerisater med høje iso-taktiske værdier. I forbindelse med polypropylen er høje værdier for isotakticiteten af stor vigtighed i kommercielle produkter.It is admittedly known from Danish Patent No. 125 599 and French Patent No. 2 093 306 a process for polymerizing alpha-olefins containing at least 3 carbon atoms and mixtures thereof with ethylene using catalysts consisting of A) an organoaluminum compound and B) a solid obtained by first reacting a magnesium alcoholate with an organoaluminum compound and then reacting the reaction product thereof with a transition metal halide compound. However, according to the invention, a component B which is of a different principle is used. This results in polymerisates with high iso-tactical values. In the case of polypropylene, high values of isotacticity are of great importance in commercial products.
Det er ganske vist også fra engelsk patent nr. 1 387 885 kendt ved polymerisation af olefiner at anvende katalysatorer bestående af A) en organoaluminiumforbindelse og en elektrondonor og B) en overgangsmetalhalogenforbindelse afsat på magnesiumhaloge-nid. Imidlertid er den specifikke overflade af de kendte katalysatorer langt mindre end den specifikke overflade af de katalysatorer, der anvendes ved fremgangsmåden ifølge opfindelsen. Desuden anvender man som udgangsmateriale ved fremstillingen af de katalysatorer, der anvendes ved fremgangsmåden ifølge opfindelsen, Al-alkylhalogenider, hvilket ikke er tilfældet i forbindelse med den fra det engelske patent kendte katalysator. Den katalysator, der anvendes ved fremgangsmåden ifølge opfindelsen, udviser en 3It is admittedly also known from the use of catalysts consisting of A) an organoaluminum compound and an electron donor and B) a transition metal halide compound deposited on magnesium halide. However, the specific surface of the known catalysts is far smaller than the specific surface of the catalysts used in the process of the invention. In addition, as starting material in the preparation of the catalysts used in the process of the invention, Al-alkyl halides are used, which is not the case with the catalyst known from the English patent. The catalyst used in the process of the invention exhibits a 3
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betydeligt bedre aktivitet end den fra det engelske patent kendte katalysator.significantly better activity than the catalyst known from the English patent.
Betegnelsen "additions- og/eller substitutionsprodukter" af elektrondonorforbindelser med aluminiumalkyler betyder produkter, der henholdsvis består af eller omfatter komplexerne af elektrondonorforbindelserne med aluminiumalkyler og de forbindelser, der er et resultat af reaktionen mellem aluminiumtrialkyler og elektrondonorforbindelser, der indeholder mobile hydrogenatomer, der er i stand til at reagere med aluminiumtrialkyler til frembringelse af substitutionsreaktioner, såsom f.eks.The term "addition and / or substitution products" of electron donor compounds with aluminum alkyls means products which respectively consist of or comprise the complexes of the electron donor compounds with aluminum alkyls and those compounds which result from the reaction between aluminum trialkyls and electron donor compounds containing mobile hydrogen atoms contained in capable of reacting with aluminum trialkyls to produce substitution reactions such as e.g.
2A1R3 + R'NH0-R2A1-N-A1R2 + 2R-H.2A1R3 + R'NHO-R2A1-N-A1R2 + 2R-H.
2 I2 I
R'R
Enhver Lewis-base, der er i stand til at tilvejebringe additions-og/eller substitutionsforbindelser med aluminiumalkyler, er velegnet til dannelse af bestanddel A af de katalysatorer, der anvendes ved fremgangsmåden ifølge opfindelsen.Any Lewis base capable of providing addition and / or substitution compounds with aluminum alkyls is suitable for forming component A of the catalysts used in the process of the invention.
Forbindelser, der er anvendelige til dette formål, er aminer, amider, ethere, estere, ketoner, nitriler, phosphiner, stibiner, arsiner, phosphoramider, thioethere, aldehyder, alkoholater, amider og salte af organiske syrer af metaller af de første fire grupper af det periodiske system.Compounds useful for this purpose are amines, amides, ethers, esters, ketones, nitriles, phosphines, stibins, arsines, phosphoramides, thioethers, aldehydes, alcoholates, amides and salts of organic acids of metals of the first four groups of the Periodic Table.
De mest interessante resultater, hvad angår både aktivitet og stereospecificitet, opnås under anvendelse af estere eller diaminer.The most interesting results, in terms of both activity and stereospecificity, are obtained using esters or diamines.
Typiske eksempler på sådanne forbindelser er ethylbenzoat, ethyl-p-methoxybenzoat, diethylcarbonat, ethylacetat, dimethylmaleat, triethylborat, ethyl-o-chlorbenzoat, ethyl-naphthenat, ethyl-to-luat, ethyl-p-butoxybenzoat, ethyl-cyclohexanoat, ethyl-pivalat, Ν,Ν,Ν',N'-tetramethylen-diamin, 1,2,4-trimethylpiperazin og 2,5-dimethylpiperazin.Typical examples of such compounds are ethyl benzoate, ethyl p-methoxybenzoate, diethyl carbonate, ethyl acetate, dimethyl maleate, triethyl borate, ethyl o-chlorobenzoate, ethyl naphthenate, ethyl toluate, ethyl p-butoxybenzoate, ethyl cyclohexanoate, ethyl acetate. pivalate, Ν, Ν, Ν ', N'-tetramethylene diamine, 1,2,4-trimethylpiperazine and 2,5-dimethylpiperazine.
Det foretrukne forhold Lewis-base/aluminiumtrialkyl er almindeligvis under 0,8 og i tilfælde af estere eller diaminer varierer det mellem 0,1 og 0,6.The preferred ratio of Lewis base / aluminum trialkyl is generally below 0.8 and in the case of esters or diamines it varies between 0.1 and 0.6.
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I almindelighed påvirkes katalysatorens aktivitet og stereospecificitet i modsat retning af det molære forhold Lewis-base/alumi-nium-trialkyl, i den forstand, at aktiviteten er desto lavere, jo højere dette forhold er, og vice versa, hvad angår stereospecificiteten.In general, the activity and stereospecificity of the catalyst are adversely affected by the Lewis-base / aluminum trialkyl molar ratio in the sense that the activity is lower, the higher this ratio, and vice versa as to the stereospecificity.
De aluminium-trialkyler, der anvendes i henhold til opfindelsen, kan udvælges fra et stort sortiment af forbindelser.The aluminum trialkyls used in accordance with the invention can be selected from a wide range of compounds.
Særligt velegnede forbindelser er de, som omfatter alkyler, der har en lineær eller forgrenet kæde, der indeholder op til 20 car-bonatomer, eller reaktionsprodukter deraf med vand, ammoniak eller primære aminer og følgelig indeholdende to eller flere aluminiumatomer, der er bundet til hinanden ved hjælp af oxygen- eller nitrogenatomer.Particularly suitable compounds are those comprising alkyls having a linear or branched chain containing up to 20 carbon atoms, or reaction products thereof with water, ammonia or primary amines, and consequently containing two or more aluminum atoms bonded together by means of oxygen or nitrogen atoms.
Nogle typiske eksempler på sådanne forbindelser er aluminium-tri-ethyl, aluminium-trimethyl, aluminium-tri-n-butyl, aluminium-tri-n-propyl, aluminium-triisohexyl, aluminium-triisooctyl, (ci2H25^3' (CjHg^Al-O-Al (C2H5^2' ^C2H5 ^ ^C2H5 ^ 2 og aluminiumisoprenyl.Some typical examples of such compounds are aluminum triethyl, aluminum trimethyl, aluminum tri-n-butyl, aluminum tri-n-propyl, aluminum triisohexyl, aluminum triisooctyl, (ci 2 H 25 3) (C -O-Al (C2H5 ^ 2 '^ C2H5 ^^ C2H5 ^ 2 and aluminum isoprenyl.
έ6Η5έ6Η5
Komponent A) af katalysatoren anvendt ved fremgangsmåden ifølge opfindelsen kan fremstilles i henhold til forskellige metoder.Component A) of the catalyst used in the process of the invention can be prepared by various methods.
En foretrukken metode består i først at omsætte Lewis-basen med aluminiumalkyl i et passende molært forhold, og derpå at omsætte komponent A fremkommet på denne måde med komponent B.A preferred method consists of first reacting the Lewis base with aluminum alkyl to a suitable molar ratio, and then reacting component A thus obtained with component B.
En anden metode består i, at man omsætter et aluminiumtrialkyl med komponent B) og derpå tilsætter Lewis-basen til det således ! fremkomne reaktionsprodukt. j iAnother method consists of reacting an aluminum trialkyl with component B) and then adding the Lewis base to it thus! reaction product obtained. j i
Aluminium-, magnesium- og titanforbindelserne, der er velegnede til dannelse af komponent B) af katalysatorerne anvendt ved fremgangsmåden ifølge opfindelsen, kan udvælges blandt et stort sortiment af forbindelser.The aluminum, magnesium and titanium compounds which are suitable for forming component B) of the catalysts used in the process of the invention can be selected from a wide range of compounds.
Nogle typiske eksempler på forbindelser af type (a^) er haloge-nider, oxyhalogenider, alkoxyhalogenider af titan, og især TiCl^.Some typical examples of compounds of type (a ^) are halides, oxyhalides, alkoxy halides of titanium, and especially TiCl 2.
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Nogle typiske eksempler på forbindelser af type (a2) er magnesi-um-alkoholater og især sådanne, der har lineære eller forgrenede alkoxy-grupper indeholdende 1-20, fortrinsvis 1-10 carbon-atomer; halogen-alkoholater og især chlor-alkoholater af magnesium med alkoxy-grupper af den før angivne type; acetylacetonat, methylglyoximat af magnesium, Mg(C2H^)2 og Mg(CgH5)2·Some typical examples of compounds of type (a2) are magnesium alcoholates and especially those having linear or branched alkoxy groups containing 1-20, preferably 1-10 carbon atoms; halo-alcoholates and especially magnesium chloro-alcohols with alkoxy groups of the type previously specified; acetylacetonate, methylglyoxime of magnesium, Mg (C2H2) 2 and Mg (CgH5) 2 ·
Nogle typiske eksempler på forbindelser af type (a^) er aluminium-halogenider med formel AlRnX'3_n, hvor X' er chlor, og R er et alkyl-radikal med en lineær eller forgrenet kæde indeholdende op til 20 og fortrinsvis 1-10 carbonatomer og især aluminiumethyl-sesquichlorid og aluminiumethyl-dichlorid.Some typical examples of compounds of type (a ^) are aluminum halides of formula AlRnX'3_n wherein X 'is chloro and R is an alkyl radical with a linear or branched chain containing up to 20 and preferably 1-10 carbon atoms. and in particular aluminum ethyl sesquichloride and aluminum ethyl dichloride.
Nogle typiske eksempler på forbindelser af type (b^) er, ved siden af de, der er anført i forbindelse med forbindelserne af type (a-j), aluminiumtrihalogenider og især AlCl^·Some typical examples of compounds of type (b ^) are, besides those listed in connection with the compounds of type (a-j), aluminum trihalides and especially AlCl
Nogle typiske eksempler på forbindelser af type (b2) er magnesi-umhalogenider, enten vandfri eller hydratiseret, og især magnesium-chlorid og -oxychlorid.Some typical examples of type (b2) compounds are magnesium halides, either anhydrous or hydrated, and in particular magnesium chloride and oxychloride.
Nogle typiske eksempler på forbindelser af type (b^) er Ti(O-iC^H^)^, Ti(0-nC3H7)4, Ti(0-iC4H9)4, Ti(0-nC4H9)4, Ti(OC6H5)4 og Ti0(0-iC3H7)g.Some typical examples of compounds of type (b ^) are Ti (O-iC ^ H ^) ^, Ti (0-nC3H7) 4, Ti (0-iC4H9) 4, Ti (0-nC4H9) 4, Ti (OC6H5) ) 4 and TiO (O-1C3H7) g.
Disse forbindelser kan eventuelt anvendes i blanding med mindre mængder af vanadinforbindelser, såsom V0C13 og VC14·These compounds may optionally be used in admixture with smaller amounts of vanadium compounds, such as VOC1 and VC14.
Nogle typiske eksempler på forbindelser af type (b4) er aluminium-alkoholater, alkyl-alkoholater og halogen-alkoholater, hvori alkylet indeholder op til 10 carbonatomer og halogenet er chlor og især aluminiumtriisobutylat.Some typical examples of compounds of type (b4) are aluminum alcoholates, alkyl alcoholates and halogen alcoholates wherein the alkyl contains up to 10 carbon atoms and the halogen is chlorine and especially aluminum triisobutylate.
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De sluttelige forhold mellem Ti, Mg og Al i komponent B af katalysatorerne anvendt ved fremgangsmåden ifølge opfindelsen kan variere over brede intervaller. I tilfælde I) (reaktionsprodukt af a^ med + a^)) opnås særligt profitable resultater med Mg/Ti forhold fra 0,5 til 30, især fra 1 til 20, og med Mg/Al forhold fra 0,5 til 5, fortrinsvis fra 0,8 til 3. i i I tilfælde II) (reaktionsprodukterne af b^ med (b£ + b^ og eventuelt b^)) opnås især profitable resultater med Mg/Ti forhold \ mellem 0,5 og 30, fortrinsvis mellem 0,5 og 20, med Mg/Al forhold mellem 0,5 og 15, fortrinsvis mellem 0,8 og 10, og med Ti/Al (som b^) forhold mellem 0,01 og 2, især mellem 0,01 og 0,5.The final ratios of Ti, Mg and Al in component B of the catalysts used in the process of the invention may vary over wide ranges. In case I) (reaction product of a ^ with + a ^)), particularly profitable results are obtained with Mg / Ti ratios of 0.5 to 30, especially from 1 to 20, and with Mg / Al ratios of 0.5 to 5, preferably from 0.8 to 3. ii In case II) (the reaction products of b ^ with (b £ + b ^ and optionally b ^)) in particular, profitable results are obtained with Mg / Ti ratios \ between 0.5 and 30, preferably between 0.5 to 20, with Mg / Al ratio between 0.5 and 15, preferably between 0.8 and 10, and with Ti / Al (as b ^) ratio between 0.01 and 2, especially between 0.01 and 0.5.
Altid i tilfælde II) (reaktionsprodukt af b^ og (a2 + b^)) °Pn^s særligt profitable resultater med Mg/Ti forhold mellem 0,5 og 50, især mellem 1 og 30, og med Mg/Al forhold mellem 0,5 og 15, fortrinsvis mellem 1 og 10.Always in Case II) (reaction product of b ^ and (a2 + b ^)) ° Pn ^ s particularly profitable results with Mg / Ti ratios between 0.5 and 50, especially between 1 and 30, and with Mg / Al ratios between 0.5 to 15, preferably between 1 and 10.
I katalysatorerne anvendt ved fremgangsmåden ifølge opfindelsen er forholdet Al/Ti højere end 1; særligt fordelagtige resultater opnås med forhold Al/Ti, der ligger over mellem 10 og 10.000.In the catalysts used in the process of the invention, the ratio Al / Ti is higher than 1; particularly advantageous results are obtained with ratios Al / Ti exceeding 10 to 10,000.
Disse katalysatorer kan anvendes til at polymerisere propylen.These catalysts can be used to polymerize propylene.
Polymerisationsbetingelserne er kendt for sagkyndige og omfatter temperaturer mellem -80 og +150°C, fortrinsvis mellem 0 og 100°C, hvorved partialtrykkene af propylen er højere end atmosfærisk tryk. Polymerisationen kan gennemføres enten i flydende fase, i nærværelse eller i fravær af et som fortyndingsmiddel tjenende carbonhydrid, eller i gasfase.The polymerization conditions are known to those skilled in the art and include temperatures between -80 and + 150 ° C, preferably between 0 and 100 ° C, whereby the partial pressures of propylene are higher than atmospheric pressure. The polymerization can be carried out either in the liquid phase, in the presence or in the absence of a dilute hydrocarbon, or in the gas phase.
Ved polymerisationen af propylen opnår man særligt tilfredsstillende resultater ved at arbejde i nærværelse af et som fortyndingsmiddel tjenende, indifferent alifatisk eller aromatisk carbonhydrid, der er flydende under polymerisationsbetingelserne eller ved at arbejde i flydende propylen som reaktionsmedium.In the polymerization of propylene, particularly satisfactory results are obtained by working in the presence of a diluent, inert aliphatic or aromatic hydrocarbon, which is liquid under the polymerization conditions or by working in liquid propylene as the reaction medium.
De følgende eksempler er angivet for bedre at illustrere hoved- 7The following examples are given to better illustrate main 7
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trækkene ved den foreliggende industrielle opfindelse.features of the present industrial invention.
I de nedenfor angivne eksempler bestemmes smelte-flyde-index (MIL) i henhold til metoden i ASTM D-1238/73; bøjningsstiv-heden måles i henhold til metoden i ASTM D-747/70 på prøvestykker fremstillet ved støbning ved hjælp af en pladepresse ved 200°C og ved hærdning ved 140°C i 2 timer.In the examples given below, the melt flow index (MIL) is determined according to the method of ASTM D-1238/73; the bending stiffness is measured according to the method of ASTM D-747/70 on specimens made by casting by a plate press at 200 ° C and by curing at 140 ° C for 2 hours.
Løs massefylde, der altid bestemmes på polypropylenet i pulverform, grænseviskositetstal og overfladeareal måles omvendt ved anvendelse af ikke-standardiserede metoder.Loose density, always determined on the polypropylene in powder form, intrinsic viscosity and surface area is inversely measured using non-standard methods.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at bestanddel A) af katalysatoren er et additionsprodukt af alumi-nium-trialkyler med elektrondonorforbindelser, der er udvalgt blandt esterne og diaminerne.The process of the invention can be carried out in that component A) of the catalyst is an addition product of aluminum trialkyls with electron donor compounds selected from the esters and diamines.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at forbindelsen (a^) er TiCl^, forbindelsen ^2) er et magnesiumdial-koholat, hvori alkoxy-grupperne, der enten er lineære eller forgrenede, indeholder fra 1 til 10 carbonatomer, og at forbindelsen (a^) er et aluminium-alkyldichlorid, hvori alkylet indeholder 1-10 carbonatomer.The process of the invention can be carried out by the compound (a ^) being TiCl4, the compound ^ 2) being a magnesium dialkoolate wherein the alkoxy groups, which are either linear or branched, contain from 1 to 10 carbon atoms and that the compound ( a ^) is an aluminum alkyl dichloride wherein the alkyl contains 1-10 carbon atoms.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at Mg/Ti forholdet i reaktionsproduktet B (I) ligger mellem 0,5 og 30, fortrinsvis mellem 1 og 20, og at forholdet Mg/Al ligger mellem 0,5 og 10, fortrinsvis mellem 0,8 og 3.The process of the invention can be carried out by the Mg / Ti ratio in the reaction product B (I) being between 0.5 and 30, preferably between 1 and 20, and the ratio Mg / Al being between 0.5 and 10, preferably between 0, 8 and 3.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at forbindelsen (b^) er et aluminium-alkyl-dichlorid, hvori alkylet indeholder mellem 1 og 10 carbonatomer, og at forbindelsen (a2) er udvalgt blandt magnesium-dialkoholaterne, hvori de lineære eller forgrenede alkoxylgrupper indeholder mellem 1 og 10 carbonatomer, og blandt magnesiumhalogeniderne, og fortrinsvis magnesiumchlorid, og at forbindelsen (b^) er et titan-te-traalkoholat, og forbindelsen (b^) er et aluminium-trialkoholat.The process of the invention can be carried out by the compound (b ^) being an aluminum alkyl dichloride wherein the alkyl contains between 1 and 10 carbon atoms and the compound (a2) is selected from the magnesium dialcoholates wherein the linear or branched alkoxyl groups contain between 1 and 10 carbon atoms, and among the magnesium halides, and preferably magnesium chloride, and the compound (b ^) is a titanium tetrahydrocarbonate and the compound (b ^) is an aluminum trialcoholate.
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Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at forbindelsen (b3) er udvalgt blandt Ti(o-iC3H7)4, Ti(o-nC3H7)4, Ti(0-iC4Hg)4, Ti(0-nC4Hg)4, Ti(OCgH5)4 og Ti20(0-iC3H7)g, og a't forbindelsen (b4) er Al (0-iC4Hg ) 3.The process of the invention can be carried out by the compound (b3) selected from Ti (o-iC3H7) 4, Ti (o-nC3H7) 4, Ti (0-iC4Hg) 4, Ti (0-nC4Hg) 4, Ti (OCgH5) ) And Ti 2 O (O-1C 3 H 7) g and the compound (b4) is Al (O-1C 4 Hg) 3.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at Mg/Ti forholdet i produktet B (II) ligger mellem 0,5 og 30, fortrinsvis mellem 0,5 og 20, og at forholdet Mg/Al ligger mellem 0,5 og 15, fortrinsvis mellem 0,8 og 10, og at forholdet Ti/Al (som b4) ligger mellem 0,01 og 2, fortrinsvis mellem 0,01 og 0,5.The process according to the invention can be carried out in that the Mg / Ti ratio in product B (II) is between 0.5 and 30, preferably between 0.5 and 20, and that the ratio Mg / Al is between 0.5 and 15, preferably between And the ratio Ti / Al (as b4) is between 0.01 and 2, preferably between 0.01 and 0.5.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at Ti forbindelsen af bestanddel B (I) foreligger i form af et kompleks med en Lewis-base.The process of the invention can be carried out by the Ti compound of component B (I) being in the form of a complex with a Lewis base.
Fremgangsmåden ifølge opfindelsen kan gennemføres ved, at den udøves ved temperaturer, der ligger mellem -80 og +150°C, under et tryk af propylen, der er højere end atmosfæretryk.The process of the invention can be carried out by operating at temperatures ranging from -80 to + 150 ° C under a pressure of propylene higher than atmospheric pressure.
Fremgangsmåden ifølge opfindelsen kan udøves i nærværelse af et indifferent, som fortyndingsmiddel tjenende carbonhydrid.The process according to the invention can be practiced in the presence of an inert, diluent hydrocarbon.
Fremgangsmåden ifølge opfindelsen kan udøves i en flydende monomer.The process of the invention can be practiced in a liquid monomer.
EKSEMPEL 1 (a) Ii§rostilling_af_komponent_B_i_katalysatoren 25,4 g Mg(OC2H5)2 behandledes med 140 ml af en opløsning indeholdende 60 g Al(C2Hg)Cl2 i 91 ml n-hexan (Cl/Mg atomforhold = 1,6) ved en temperatur på 25°C i 2 timer. Reaktionen var exotherm, og af denne årsag var det tilrådeligt at afkøle. Ved afslutningen blev det faste reaktionsprodukt gentagne gange vasket ved dekantering med n-hexan og derpå tørret under vakuum ved 45°C.EXAMPLE 1 (a) Preparation of Component_B_i_ Catalyst 25.4 g of Mg (OC2H5) 2 was treated with 140 ml of a solution containing 60 g of Al (C2Hg) Cl2 in 91 ml of n-hexane (Cl / Mg atomic ratio = 1.6) at temperature of 25 ° C for 2 hours. The reaction was exothermic and for this reason it was advisable to cool. At the end, the solid reaction product was repeatedly washed by decantation with n-hexane and then dried under vacuum at 45 ° C.
Det opsamlede, faste produkt (23,9 g) blev underkastet en elementæranalyse, hvorved der fremkom følgende resultater:The collected solid product (23.9 g) was subjected to an elemental analysis to give the following results:
DK 151892 BDK 151892 B
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Mg = 20,9 g/100 gMg = 20.9 g / 100 g
Al = 5 g/100 g 01 = 44,95 g/100 g.Al = 5 g / 100 g 01 = 44.95 g / 100 g.
Dette produkt blev derpå “behandlet med TiCl^ i overskud i 1 time ved 136°C, derpå gentagne gange vasket med n-hexan, hvorved man fjernede ethvert spor af frit TiCl^, og slutteligt tørret under vakuum ved 50°C.This product was then "treated with TiCl 2 in excess for 1 hour at 136 ° C, then repeatedly washed with n-hexane, removing any trace of free TiCl 2, and finally dried under vacuum at 50 ° C.
Det således fremkomne faste produkt blev udsat for elementæranalyse, hvorved der fremkom følgende resultater:The solid product thus obtained was subjected to elemental analysis, yielding the following results:
Mg = 16,95 g/100 gMg = 16.95 g / 100 g
Al = 3,5 g/100 g li = 7,75 g/100 g 01 = 65,5 g/100 g, pAl = 3.5 g / 100 g li = 7.75 g / 100 g 01 = 65.5 g / 100 g, p
Overfladearealet var 160 m /g.The surface area was 160 m / g.
(b) Polymerisation af propylen i et opløsningsmiddel 310 mg af det faste produkt (eksempel 1a) blev indført i en 2,5 liter autoklav, der er af rustfrit stål, og som indeholder 1 liter heptan og 1,135 g AliCgH^)^, forblandet med 572 mg ethyl-anisat.(b) Polymerization of propylene in a solvent 310 mg of the solid product (Example 1a) was introduced into a 2.5 liter stainless steel autoclave containing 1 liter of heptane and 1.135 g of AliCgH with 572 mg of ethyl anisate.
Polymerisationen blev udført ved 60°C under et manometertryk på 5 kg/cm2 med propylen og hydrogen (1,5$ volumenprocent af gasfasen) , i 5 timer. Trykket blev holdt konstant ved kontinuerlig tilførsel af propylen. Ved afslutningen og efter at opløsningsmidlet var fjernet ved stripping med damp fremkom der 263 g tør polymer, hvorved udbyttet var 10.950 g polypropylen/g Ti i 5 timer; denne polymer udviste en remanens efter ekstraktion i kogende heptan på 81$ og en løs massefylde på 0,33 kg/liter.The polymerization was carried out at 60 ° C under a pressure gauge of 5 kg / cm 2 with propylene and hydrogen (1.5% v / v of the gas phase), for 5 hours. The pressure was kept constant by continuous supply of propylene. At the end and after the solvent was removed by stripping with steam, 263 g of dry polymer was obtained, yielding 10,950 g of polypropylene / g Ti for 5 hours; this polymer exhibited a residual post-extraction in boiling heptane of $ 81 and a bulk density of 0.33 kg / liter.
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(c) Polymerisation af propylen i_en flydende monomer(c) Polymerization of propylene in a liquid monomer
Til en 30 liter autoklav af rustfrit stål tilførtes 10 kg propylen sammen med 12,5 g Al(C2H^)^ i 90 ml n-heptan, 7,20 g ethylanisat i 120 ml n-heptan, 900 mg af det faste produkt (eksempel 1a) i 130 ml n-heptan og 15 NI hydrogen. Polymerisationstemperaturen hlev indstillet på 65°C, og manometertrykket hlev indstillet på 26,5 kg/cm . Efter 5 timer og efter at have fjernet overskud af propylen fremkom der 2,95 kg polypropylen, svarende til et udbytte på 42.300 g polymer/g Ti, med en remanens efter ekstraktion med kogende heptan på 78,51° og en løs massefylde på 0,32 kg/li- ter.To a 30 liter stainless steel autoclave, 10 kg of propylene was added together with 12.5 g of Al (C 2 H 2) 2 in 90 ml of n-heptane, 7.20 g of ethyl anisate in 120 ml of n-heptane, 900 mg of the solid product ( Example 1a) in 130 ml of n-heptane and 15 N of hydrogen. The polymerization temperature was set to 65 ° C and the pressure gauge was set to 26.5 kg / cm. After 5 hours and after removing excess propylene, 2.95 kg of polypropylene, corresponding to a yield of 42,300 g of polymer / g Ti, was obtained with a residue after extraction with boiling heptane of 78.51 ° and a loose density of 0 , 32 kg / liter.
EKSEMPEL 2 (a) Eremstilling af komponent B af katalysatoren 20,4 g Ti(OnBu)^ (titan-tetranormalhutylat) hlev blandet med 11,4 g vandfrit MgCl2 i pulverform, idet man holdt en temperatur på 165°C i 3 timer. Der fremkom et halvflydende produkt, hvori en del af magnesiumchloridet var til stede i den opløste form. I kold tilstand blev det før angivne reaktionsprodukt tilsat med 240 ml n-hexan, og man fik det til grundigt at disgregere ved hjælp af omrøring. Suspensionen blev blandet med 38,2 g A1C2H^C12 (aluminium-ethyl-dichlorid) i en n-heptan-opløsning ved en koncentration af 478 g/liter. Blandingens temperatur blev indstillet på 70°0 og holdt på denne værdi i 1 time. Efter afkøling dekanteredes det faste bundfald, indtil overskud af aluminium-alkyl forsvandt.EXAMPLE 2 (a) Preparation of component B of the catalyst 20.4 g of Ti (OnBu) 3 (titanium tetranormal butylate) was mixed with 11.4 g of anhydrous MgCl 2 in powder form, maintaining a temperature of 165 ° C for 3 hours. A semi-liquid product was obtained in which part of the magnesium chloride was present in the dissolved form. In the cold state, the aforementioned reaction product was added with 240 ml of n-hexane and it was thoroughly disregarded by stirring. The suspension was mixed with 38.2 g of AlCl 2 H 2 Cl 2 (aluminum ethyl dichloride) in an n-heptane solution at a concentration of 478 g / liter. The temperature of the mixture was set to 70 ° and maintained at this value for 1 hour. After cooling, the solid precipitate was decanted until excess aluminum-alkyl disappeared.
. Det faste produkt blev tørret under vakuum ved 50°C. Elementær- ‘ analyse udviste følgende resultater:. The solid product was dried under vacuum at 50 ° C. Elemental analysis showed the following results:
Mg = 11,45 g/100 gMg = 11.45 g / 100 g
Al - 3,45 g/100 gAl - 3.45 g / 100 g
Ti = 12,1 g/100 gTi = 12.1 g / 100 g
Cl = 63,75 g/100 g.Cl = 63.75 g / 100 g.
i ii i
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(¾) Polymerisation af_ propylen i en flydende monomer 10 kg propylen sammen med 12,5 g A1(C2H^)^ i 90 ml n-heptan, 6,36 g ethylanisat i 120 ml n-heptan, 860 mg af det faste produkt (eksempel 2a) i 130 ml n-heptan og 15 NI hydrogen blev indført i en 30 liter autoklav af rustfrit stål. Temperaturen hlev indstillet på 65°C, og trykket hlev indstillet på 26,5 kg/cm2 .(¾) Polymerization of propylene in a liquid monomer 10 kg of propylene together with 12.5 g of Al (C 2 H (Example 2a) in 130 ml of n-heptane and 15 N of hydrogen was introduced into a 30 liter stainless steel autoclave. The temperature was set to 65 ° C and the pressure was set to 26.5 kg / cm 2.
Efter 5 timers polymerisation og efter at have fjernet overskuddet af propylen fremkom der 0,6 kg polypropylen (udbytte = 5.770 g polymer/g Ti) med en remanens efter ekstraktion med kogende heptan på 68,6$ og en løs massefylde på 0,20 kg/liter.After 5 hours of polymerization and after removing the excess propylene, 0.6 kg of polypropylene (yield = 5.770 g polymer / g Ti) was obtained with a residual post extraction with boiling heptane of $ 68.6 and a loose density of 0.20 kg / liter.
EKSEMPEL· 3 (a) Eremstilling_af_komponent_B_af_katalysatoren 11,65 g vandfrit MgCl2 i pulverform hlev blandet med 29,55 g Al(Osek.Bu)^ (aluminium-sek.tributylat) og 4,08 g Ti(On.Bu)^ (titan-n-tetrabutylat), idet man arbejdede ved 165°0 i 6 timer.EXAMPLE 3 (a) Preparation of Component_B_of_Catalyst 11.65 g of anhydrous MgCl2 in powder form mixed with 29.55 g Al (Osek.Bu) ^ (aluminum sec tributylate) and 4.08 g Ti (On.Bu) ^ (titanium -n-tetrabutylate), working at 165 ° for 6 hours.
På denne måde fremkom der en pasta, der var halvfast i varm tilstand og fast i kold tilstand.In this way, a paste was obtained which was semi-solid in hot state and solid in cold state.
Bette faste produkt blev disgregeret ved omrøring i et opløsningsmiddel (n-hexan i 240 ml) under kolde betingelser.Better solid product was disregarded by stirring in a solvent (n-hexane in 240 ml) under cold conditions.
Ved en temperatur på 20°0 tilsatte man den ovenfor angivne suspension med 38,15 g A1C2H^C12 (aluminium-ethyldichlorid) i en n-heptan opløsning i en koncentration på 478 g/liter. Blandingens temperatur blev indstillet på 70°C og holdt på denne værdi i 1 time. Efter afkøling dekanterede man det faste produkt, det blev gentagne gange vasket med n-hexan· ved dekantering for at fjerne overskydende aluminiumalkyl. Bet faste produkt blev tørret under vakuum ved 50°C. Elementæranalysen udviste følgende resultater:At a temperature of 20 ° 0, the above suspension was added with 38.15 g of AlCl 2 H 2 Cl 2 (aluminum ethyl dichloride) in an n-heptane solution at a concentration of 478 g / liter. The temperature of the mixture was adjusted to 70 ° C and maintained at this value for 1 hour. After cooling, the solid product was decanted, it was repeatedly washed with n-hexane · by decantation to remove excess aluminum alkyl. Bet solid product was dried under vacuum at 50 ° C. The elemental analysis showed the following results:
Mg = 16,15 g/100 gMg = 16.15 g / 100 g
Al = 7,05 g/100 gAl = 7.05 g / 100 g
Ti = 3 g/100 gTi = 3 g / 100 g
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Overfladearealet var 46 m /g.The surface area was 46 m / g.
119 mg af det faste produkt (eksempel 3a) "blev indført i en 2.5 liter autoklav, der var fremstillet af rustfrit stål, og som indeholdt 1 liter n-heptan og 1,135 g A1(C2H^)^ forblandet med 447 mg ethylanisat.119 mg of the solid product (Example 3a) was introduced into a 2.5 liter stainless steel autoclave containing 1 liter of n-heptane and 1.135 g of Al (C 2 H 2) 3 premixed with 447 mg of ethyl anisate.
_ n_ n
Polymerisationen blev udført ved 60°C under et tryk på 5 kg/cnr med' propylen og hydrogen (1,5$ volumenprocent af gasfasen) i 5 timer.The polymerization was carried out at 60 ° C under a pressure of 5 kg / cm with propylene and hydrogen (1.5% v / v of the gas phase) for 5 hours.
Trykket blev holdt konstant ved kontinuerlig tilførsel af propylen.The pressure was kept constant by continuous supply of propylene.
Ved afslutningen og efter fjernelse af opløsningsmidlet ved stripping med damp fremkom der 74 g tørt polypropylen, der havde en remanens efter ekstraktion med kogende heptan lig 77,6 $, hvorved udbyttet er 20.700 g polymer/g Ti i løbet af 5 timer.At the end and after removing the solvent by stripping with steam, 74 g of dry polypropylene was obtained which had a residue after extraction with boiling heptane equal to $ 77.6, yielding 20,700 g of polymer / g Ti over 5 hours.
(o) £2i25£risation_af_propylen_i_en_flydende_monomer(o) £ 2i25 £ risation_of_propylene_in_fluid_monomer
Til en autoklav, der var fremstillet af rustfrit stål, og som havde en volumenkapacitet på 30 liter, tilførtes 10 kg propylen, 12.5 g AliC.gH^)^ i 90 ml n-heptan, 6,36 g ethylanisat i 120 liter n-heptan, 856 mg af det faste produkt (eksempel 3a) i 130 ml n-heptan og 15 NI hydrogen.To a stainless steel autoclave having a volume capacity of 30 liters, 10 kg of propylene, 12.5 g of AliC.gH 2) in 90 ml of n-heptane, 6.36 g of ethyl anisate in 120 liters of n-heptane were added. heptane, 856 mg of the solid product (Example 3a) in 130 ml of n-heptane and 15 N of hydrogen.
Polymerisationstemperaturen indstilledes på 65°0, og trykket 2 indstilledes på 26,5 kg/cm .The polymerization temperature was set to 65 ° 0 and the pressure 2 was set to 26.5 kg / cm.
Efter 5 timers forløb fjernedes overskydende propylen, hvorefter der fremkom 1,61 g polypropylen (udbytte 62.600 g polymer/g Ti), som udviste en remanens efter ekstraktion med kogende heptan på 78,5$, en løs massefylde på 0,29 kg/liter, et grænseviskositets- : tal på 2 dl/g, et smelteflydeindeks på 3,7 g/101 og en bøjnings-stivhed på 10.310 kg/cm^.After 5 hours, excess propylene was removed, yielding 1.61 g of polypropylene (yield 62,600 g of polymer / g of Ti), which exhibited a residual post-extraction with boiling heptane of $ 78.5, a loose density of 0.29 kg / a liter viscosity: 2 dl / g, a melt flow index of 3.7 g / 101 and a bending stiffness of 10,310 kg / cm 2.
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EKSEMPEL 4 (a) l£emstilling_af _kom£onent__B_af ^katalysatoren 23 g vandfrit MgC^ i pulverform Blandedes med 59 g Al(Osek.Bu)^ (aluminium-sek.tributylat) og med 4,08 g Ti(OnBu)^ (titan-n-tetrabutylat), idet man arbejdede ved 165°C i 6 timer. På denne måde fremkom der en halvfast pasta, som blev dispergeret i kold tilstand, under omrøring, i 180 ml n-hexan. Ved en temperatur på 20°C tilblandedes 76,2 g A1C 2^012 (aluminiumethyl-dichlorid) i en n-heptanopløsning ved en koncentration på 478 g/liter til suspensionen, temperaturen blev indstillet på 70°0 under intens omrøring i 1 time.EXAMPLE 4 (a) Preparation of the catalyst 23 g of anhydrous MgCl 3 in powder form Mixed with 59 g Al (Osek.Bu) ^ (aluminum sec tributylate) and with 4.08 g Ti (OnBu) titanium n-tetrabutylate), operating at 165 ° C for 6 hours. In this way, a semi-solid paste which was dispersed in cold state, with stirring, was obtained in 180 ml of n-hexane. At a temperature of 20 ° C, 76.2 g of AlCl 2 0 012 (aluminum ethyl dichloride) in an n-heptane solution at a concentration of 478 g / liter was added to the suspension, the temperature was adjusted to 70 ° 0 with intense stirring for 1 hour. .
Efter afkøling blev det faste produkt dekanteret og gentagne gange vasket med n-hexan ved dekantering for at fjerne overskydende aluminiumalkyl. Det faste produkt blev derpå tørret under vakuum ved 50°C.After cooling, the solid product was decanted and repeatedly washed with n-hexane by decantation to remove excess aluminum alkyl. The solid product was then dried under vacuum at 50 ° C.
Elementæranalysen udviste følgende resultater:The elemental analysis showed the following results:
Mg = 19,5 g/100 gMg = 19.5 g / 100 g
Al = 4,2 g/100 g ti = 1,95 g/100 gAl = 4.2 g / 100 g ti = 1.95 g / 100 g
Cl = 65,10 g/100 g.Cl = 65.10 g / 100 g.
Overfladearealet var 70 m /g.The surface area was 70 m / g.
(b) ?olymerisation_af_pro2ylen_i_et_opløsningsmiddel 234 mg af det faste produkt (eksempel 4a) blev indført i en 2,5 liter autoklav, der var fremstillet af rustfrit stål, og som indeholdt 1 liter n-heptan og 1,135 g A1(02H^)^ forblandet med 571 mg ethylanisat#(b)? omerization_of_pro2ylene_in_et_ solvent 234 mg of the solid product (Example 4a) was introduced into a 2.5 liter stainless steel autoclave containing 1 liter of n-heptane and 1.135 g of A1 (02H2) ^ premixed. with 571 mg of ethyl anisate #
Polymerisationen blev gennemført ved 60°C under et tryk på 5 kg/cm^ med propylen og hydrogen (1,5f° volumenprocent i gasfasen) i 5 timer.The polymerization was carried out at 60 ° C under a pressure of 5 kg / cm 2 with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours.
trykket blev holdt konstant ved kontinuerlig tilførsel af propy- Ί anthe pressure was kept constant by the continuous supply of propylene
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Ted afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp fremkom der 95 g polymer, hvorved udbyttet er 20.800 g polypropylen/g Ti i 5 timer - med en remanens efter ekstraktion med kogende heptan på 80,5# og en løs massefylde på 0,355 kg/liter.At the end and after removing the solvent by stripping with steam, 95 g of polymer were obtained, yielding 20,800 g of polypropylene / g Ti for 5 hours - with a residual post-extraction with boiling heptane of 80.5 # and a loose density of 0.355 kg / liter.
10 kg propylen sammen med 12,5 g AlCCgH^)^ i 90 ml n-heptan, 7,75 g ethylanisat i 120 ml n-heptan, 1,1 g af det faste produkt (eksempel 4a) i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål og med en volumenkapacitet på 30 liter. Polymerisationstemperaturen blev indstillet på 65°C, og trykket p blev indstillet på 26,5 kg/cm .10 kg of propylene together with 12.5 g of AlCCgH 2) in 90 ml of n-heptane, 7.75 g of ethyl anisate in 120 ml of n-heptane, 1.1 g of the solid product (Example 4a) in 130 ml of n-heptane and 15 NI of hydrogen were introduced into a stainless steel autoclave with a volume capacity of 30 liters. The polymerization temperature was adjusted to 65 ° C and the pressure p was adjusted to 26.5 kg / cm.
Efter 5 timer og efter fjernelse af overskud af propylen fremkom der 1,5 kg polypropylen med en remanens efter ekstraktion med kogende heptan på 81,5$, hvorved udbyttet var 70.000 g polymer/g Ti.After 5 hours and after removal of excess propylene, 1.5 kg of polypropylene with a residual extraction with boiling heptane of $ 81.5 was obtained, yielding 70,000 g of polymer / g of Ti.
Ydermere udviste den polymere følgende egenskaber: - løs massefylde .......................... 0,21 kg/liter - viskositet.............................. 1,5 dl/g - smeltef lydeindeks ....................... 1,34 g/10* 2 1 - bøjningsstivhed ......................... 11.830 kg/cm .In addition, the polymer exhibited the following properties: - loose density .......................... 0.21 kg / liter - viscosity ...... ........................ 1.5 dl / g - melting sound index ................. ...... 1.34 g / 10 * 2 1 - bending stiffness ......................... 11,830 kg / cm.
EKSEMPEL· 5 (a) Fremstilling af komponent B af .katalysatoren 18,12 g Mg(002H^)2 blev blandet med 5,4 g Ti(O-n.C^Hg)^ (titan-tetrabutylat) i 240 ml n-hexan ved ca. 70°C, idet man arbejdede i 45*.EXAMPLE 5 (a) Preparation of Component B of the Catalyst 18.12 g Mg (002 H 2) 2 was mixed with 5.4 g Ti (On.C 2 Hg) 2 (titanium tetrabutylate) in 240 ml of n-hexane. at about. 70 ° C, working at 45 *.
Denne blanding blev tilført med 90 g Al^H^C^ (aluminium-ethyl-dichlorid) i en n-heptan-opløsning i en koncentration på 478 g/liter. Temperaturen blev indstillet på 75°C og holdt på denne værdi i 1 time.This mixture was fed with 90 g of Al 2 H 2 C 2 (aluminum ethyl dichloride) in a n-heptane solution at a concentration of 478 g / liter. The temperature was set at 75 ° C and kept at this value for 1 hour.
15 DK 151892 BDK 151892 B
Efter afkøling blev det faste bundfald dekanteret og gentagne gange vasket med n-hexan ved dekantering for at fjerne overskydende aluminium-alkyl. Eet faste produkt blev tørret under vakuum ved 45°C.After cooling, the solid precipitate was decanted and repeatedly washed with n-hexane by decantation to remove excess aluminum alkyl. One solid product was dried under vacuum at 45 ° C.
Elementæranalysen udviste følgende resultater:The elemental analysis showed the following results:
Mg = 12,25 g/100 gMg = 12.25 g / 100 g
Al = 8,0 g/100 gAl = 8.0 g / 100 g
Ti = 3,6 g/100 g 01 = 68,8 g/100 g.Ti = 3.6 g / 100 g 01 = 68.8 g / 100 g.
(b) Polymerisation af propylen i et opløsningsniddel 189 mg af det faste produkt (eksempel 5a) blev indført i en autoklav, der var fremstillet af rustfrit stål, og som havde en kapacitet på 2,5 liter, indeholdende 1 liter n-heptan og 1,135 g AliOgH^)^, forblandet med 447 mg ethylanisat. Polymerisationen gennemførtes ved 60°0, under et tryk på 5 kg/cm2 g med propylen og hydrogen (1,5$ volumenprocent i gasfasen), i 5 timer.(b) Polymerization of propylene in a solvent 189 mg of the solid product (Example 5a) was introduced into a stainless steel autoclave having a capacity of 2.5 liters containing 1 liter of n-heptane and 1.135 g of AliOgH 2), premixed with 447 mg of ethyl anisate. The polymerization was carried out at 60 ° C, under a pressure of 5 kg / cm 2 g with propylene and hydrogen (1.5% v / v in the gas phase), for 5 hours.
Trykket blev holdt konstant ved kontinuerlig tilførsel af propylen.The pressure was kept constant by continuous supply of propylene.
Ved afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp fremkom der 290 g polypropylen med en remanens efter ekstraktion med kogende heptan lig 71$, hvorved udbyttet er 42.600 g polymer/g Ti i 5 timer.At the end and after removing the solvent by stripping with steam, 290 g of polypropylene was obtained with a residue after extraction with boiling heptane equal to $ 71, yielding 42,600 g of polymer / g Ti for 5 hours.
(c) Polymerisation af propylen 4, ggflydendemonomer 10 kg propylen sammen med 12,5 g A1(02H^)^ i 90 ml n-heptan, 6,56 g ethylanisat i 120 ml n-heptan, 790 mg af det faste produkt (eksempel 5a) i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål og med en kapacitet på 30 liter. Polymerisationstemperaturen blev indstillet på 65°0, og trykket blev indstillet på 26,5 kg/cm2.(c) Polymerization of propylene 4, gg flow end monomer 10 kg of propylene together with 12.5 g of Al (O 2 H 2) 2 in 90 ml of n-heptane, 6.56 g of ethyl anisate in 120 ml of n-heptane, 790 mg of the solid product ( Example 5a) in 130 ml of n-heptane and 15 N of hydrogen was introduced into a stainless steel autoclave with a capacity of 30 liters. The polymerization temperature was adjusted to 65 ° 0 and the pressure was adjusted to 26.5 kg / cm 2.
16 DK 151892 B16 DK 151892 B
Efter 5 timer og efter at overskydende propylen var fjernet, fremkom der 3,05 kg polypropylen (udbytte = 107.000 g polymer/g Ti), hvilket udviste en remanens efter ekstraktion med kogende heptan på 74$, en løs massefylde på 0,29 kg/liter, et smeltef lydeindeks p på 2,5 g/10' og en bøjningsstivhed på 8730 kg/cm .After 5 hours and after the excess propylene was removed, 3.05 kg of polypropylene (yield = 107,000 g polymer / g Ti) was obtained, showing a residue after boiling heptane of $ 74, a loose density of 0.29 kg / liter, a melt flow index p of 2.5 g / 10 'and a bending stiffness of 8730 kg / cm.
EKSEMPEL 6 (a) Eremstilling af komponent B af katalysatoren 59,6 g Mg(OCgHjj^ blev blandet med 5,62 g Ti(onC^H^)^ (titan-n-tetrabutylat) i 240 ml n-hexan, idet man arbejdede ved ca. 70°0 i 45 minutter.EXAMPLE 6 (a) Preparation of Component B of the Catalyst 59.6 g of Mg (OCgH₂j ^) was mixed with 5.62 g of Ti (onC₂H ^) (titanium n-tetrabutylate) in 240 ml of n-hexane worked at about 70 ° 0 for 45 minutes.
183 g AlCCgHj^C^ (aluminiumethyl-dichlorid) i opløsning i n-heptan ved en koncentration på 478 g/liter blev tilført til blandingen. Temperaturen blev indstillet på 75°C og holdt på denne værdi i 1 time.183 g of AlCCgH 2 H 2 C (aluminum ethyl dichloride) in solution in n-heptane at a concentration of 478 g / liter was added to the mixture. The temperature was set at 75 ° C and kept at this value for 1 hour.
Efter afkøling dekanterede man det faste bundfald og vaskede det gentagne gange med n-hexan for at fjerne overskydende alu-miniumalkyl. Let faste produkt blev tørret under vakuum ved 45°C. 1 mg af det faste produkt (eksempel 6a) blev indført i en autoklav af rustfrit stål og med en kapacitet på 2,5 liter indeholdende 1 liter n-heptan og 1,135 g A1(C2H^) forblandet med 571 mg ethylanisat.After cooling, the solid precipitate was decanted and washed repeatedly with n-hexane to remove excess aluminum alkyl. Light solid product was dried under vacuum at 45 ° C. 1 mg of the solid product (Example 6a) was introduced into a stainless steel autoclave with a capacity of 2.5 liters containing 1 liter of n-heptane and 1.135 g of A1 (C2H2) premixed with 571 mg of ethyl anisate.
nn
Polymerisationen gennemførtes ved 60°0 under et tryk på 5 kg/cnr med propylen og hydrogen (1,5 volumen-pct. i gasfasen) i 5 timer.The polymerization was carried out at 60 ° 0 under a pressure of 5 kg / cm³ with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours.
Trykket blev holdt konstant ved kontinerulig tilførsel af propylen.The pressure was kept constant by continuous delivery of propylene.
Yed slutningen og efter fjernelse af opløsningsmidlet ved stripping med damp fremkom der 150 g prolypropylen, der havde en remanens efter ekstraktion med kogende heptan på 72,6$ og en løs massefylde på 0,353 kg/liter, hvorved udbyttet er 45.500 g poly-At the end and after removal of the solvent by stripping with steam, 150 g of prolypropylene were obtained which had a residual post-extraction with boiling heptane of $ 72.6 and a loose density of 0.353 kg / liter, yielding 45,500 g of polyethylene.
17 DK 151892 B17 DK 151892 B
mer/g Ti, i 5 timer.more / g Ti, for 5 hours.
(o) Polymerisation af grogylenien flydende monomer 10 kg propylen sammen med 12,5 g Α1(02Η^)^ i 90 ml n-heptan, 8,75 g ethylanisat i 120 ml n-heptan, 1,05 g af det faste produkt (eksempel 6a) i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål og med en kapacitet på 30 liter. Polymerisationstemperaturen blev indstillet på 65 C, og trykket blev indstillet på 26,5 kg/cn/\(o) Polymerization of the grogylene liquid monomer 10 kg of propylene together with 12.5 g of (1 (02Η) in 90 ml of n-heptane, 8.75 g of ethyl anisate in 120 ml of n-heptane, 1.05 g of the solid product (Example 6a) in 130 ml of n-heptane and 15 N of hydrogen was introduced into a stainless steel autoclave with a capacity of 30 liters. The polymerization temperature was adjusted to 65 C and the pressure was adjusted to 26.5 kg / cn /
Efter 5 timers forløb, og efter at overskydende propylen var fjernet, fremkom der 1,13 kg polypropylen, der havde en remanens efter ekstraktion med kogende heptan på 80,5$> hvorved udbyttet er 53.800 g polymer/g Ti.After 5 hours and after the excess propylene was removed, 1.13 kg of polypropylene was obtained, which had a residual extraction with boiling heptane of $ 80.5> yielding 53,800 g polymer / g Ti.
Desuden udviste den polymere følgende egenskaber: - løs massefylde ........................ 0,33 kg/1 - smeltef lydeindeks ..................... 5,1 g/10' - bøjningsstivhed ....................... 11.500 g/cm .In addition, the polymer exhibited the following properties: - loose density ........................ 0.33 kg / 1 - melt flow index ....... .............. 5.1 g / 10 '- bending stiffness ....................... 11,500 g / cm .
EKSEMPEL· 7EXAMPLE · 7
Polymerisation af propylen_i_et_0£lØsningsmddel 328 mg af det faste produkt fremstillet i henhold til eksempel 4 (a) blev indført i en 2,5 liter autoklav, der var fremstillet af rustfrit stål, og som indeholdt 1 liter n-heptan og 1,135 g Α1(02Η^)^ forblandet med 450 mg ethyl-paratoluat.Polymerization of Propylene_I_O_ Solvent 328 mg of the solid product prepared according to Example 4 (a) was introduced into a 2.5 liter stainless steel autoclave containing 1 liter of n-heptane and 1.135 g of (1 ( 02ΗΗ) premixed with 450 mg of ethyl paratoluate.
o 2.o 2.
Polymerisationen gennemførtes ved 60 C under et tryk på 5 kg/cm g med propylen og hydrogen (1,5 volumenprocent i gasfasen) i 5 timer.The polymerization was carried out at 60 ° C under a pressure of 5 kg / cm g with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours.
Trykket blev holdt konstant ved kontinuerlig tilførsel af propylen.The pressure was kept constant by continuous supply of propylene.
18 DK 151892 B18 DK 151892 B
Yed afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp, fremkom der 296 g polymer med en remanens efter ekstraktion med kogende heptan på 78,6$, en løs massefylde på G,38 kg/liter og et grænseviskositetstal på 2 dl/g, hvorved udbyttet er 46.300 g polypropylen/g Ti i 5 timer.At the end and after removing the solvent by stripping with steam, 296 g of polymer was obtained with a residual post-extraction with boiling heptane of $ 78.6, a loose density of G, 38 kg / liter and an intrinsic viscosity of 2 dl / g , whereby the yield is 46,300 g of polypropylene / g Ti for 5 hours.
Polymerisation af propylen i en flydende monomer 10 kg propylen sammen med 12,5 g AlCCgH^)^ i 90 ml n-heptan, 6 g ethyl-paratoluat i 120 ml n-heptan, 1,05 g af det faste produkt fremstillet i henhold til eksempel 4 (a) i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål og med en kapacitet på 30 liter. Polymerisationstemperaturen blev indstillet på 65°C og trykket indstillet på 26,5 kg/cm2.Polymerization of propylene in a liquid monomer 10 kg of propylene together with 12.5 g of AlCCgH 3 in 90 ml of n-heptane, 6 g of ethyl paratoluate in 120 ml of n-heptane, 1.05 g of the solid product for example, 4 (a) in 130 ml of n-heptane and 15 N of hydrogen was introduced into a stainless steel autoclave with a capacity of 30 liters. The polymerization temperature was adjusted to 65 ° C and the pressure adjusted to 26.5 kg / cm 2.
Efter 5 timer og efter at overskydende propylen var fjernet, fremkom der 1,9 .kg polypropylen, hvorved udbyttet er 97.500 g poly-mer/g li - med en remanens efter ekstraktion med kogende heptan på 80,5$.After 5 hours and after the excess propylene was removed, 1.9 kg of polypropylene was obtained, yielding 97,500 g of polymer / g of li - with a residue after extraction with boiling heptane of $ 80.5.
Pen polymere havde desuden følgende egenskaber: - løs massefylde ........................... 0,21 kg/liter - grænseviskositetstal....................... 2 dl/g - smeltef lydeindeks .......................... 3,1 g/10’Pen polymers also had the following properties: - loose density ........................... 0.21 kg / liter - intrinsic viscosity ..... .................. 2 dl / g - melting sound index ......................... 3.1 g / 10
OISLAND
- bøjningsstivhed............................ 10.750 g/cm EKSEMPEL 8- bending stiffness ............................ 10,750 g / cm EXAMPLE 8
Polymerisation af propylen i et opløsningsmiddel 240 mg af det faste produkt (fremstillet i henhold til eksempel 4 (a)) blev indført i en autoklav af rustfrit stål og med en kapacitet på 2,5 liter, indeholdende 1 liter n-heptan og 1,135 g Al(iC^H^)^ forblandet med 329 mg ethylanisat.Polymerization of propylene in a solvent 240 mg of the solid product (prepared according to Example 4 (a)) was introduced into a stainless steel autoclave with a capacity of 2.5 liters containing 1 liter of n-heptane and 1.135 g Al (iC + H +) + premixed with 329 mg of ethyl anisate.
Polymerisationen blev gennemført ved 60°0 under et tryk på 5 kg/αη2 med propylen og hydrogen (1,5 volumenprocent i gasfasen) i 5 timer.The polymerization was carried out at 60 ° 0 under a pressure of 5 kg / αη 2 with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours.
19 DK 15189 2 B19 DK 15189 2 B
Trykket blev holdt konstant ved kontinuerlig tilførsel af pro-pylen.The pressure was kept constant by continuous application of the propylene.
Ted afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp, fremkom der 137 g polymer med et udbytte på 29.400 g polypropylen/g Ti i 5 timer, hvorved den polymere udviste en remanens efter ekstraktion i kogende heptan på 72,5$.At the end and after removing the solvent by stripping with steam, 137 g of polymer was obtained with a yield of 29,400 g of polypropylene / g Ti for 5 hours, whereby the polymer exhibited a residue after extraction in boiling heptane of $ 72.5.
Polymerisation af_pro£ylen=iraen_flydende_monomer 10 kg propylen sammen med 12,5 g Al(iC^Hg)^ i 90 ml n-heptan, 4,15 g ethylanisat i 120 ml n-heptan, 1 g af det faste produkt, fremstillet i henhold til eksempel 4 (a) i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål og med en kapacitet på 30 liter.Polymerization of the Propylene = Irene Liquid Monomer 10 kg of propylene together with 12.5 g of Al (iC ^ Hg) ^ in 90 ml of n-heptane, 4.15 g of ethyl anisate in 120 ml of n-heptane, 1 g of the solid product prepared in According to Example 4 (a), 130 ml of n-heptane and 15 N of hydrogen were introduced into a stainless steel autoclave with a capacity of 30 liters.
Polymerisationstemperaturen blev indstillet på 65°C, og trykket blev indstillet på 26,5 kg/cm ·The polymerization temperature was adjusted to 65 ° C and the pressure was adjusted to 26.5 kg / cm ·
Efter 5 timers forløb og efter fjernelse af overskydende propylen fremkom der 1,55 kg polypropylen med et udbytte på 79.500 g poly-mer/g Ti, hvilket udviste en remanens efter ekstraktion i kogende heptan på 76 1°% en løs massefylde på 0,3 kg/liter, et grænsevis-After 5 hours and after removal of excess propylene, 1.55 kg of polypropylene was obtained with a yield of 79.500 g of polymer / g Ti, which exhibited a residue after extraction in boiling heptane of 76 1% a loose density of 0. 3 kg / liter, a limit-
OISLAND
kositetstal på 2 dl/g og en bøjningsstivhed på 8.850 kg/cm .a density of 2 dl / g and a flexural stiffness of 8,850 kg / cm.
EKSEMPEL· 9EXAMPLE · 9
Polymerisation af^propylen^i^en^flydende^monomer 10 kg propylen sammen med 12,5 g Al(iC^H^)^ i 90 ml n-heptan, 3,45 g ethylparatoluat i 120 ml n-heptan, 1,06 g af det faste produkt (fremstillet i henhold til eksempel 4 (a)) i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål, og som havde en 30 liter kapacitet.Polymerization of ^ propylene ^ in ^ a ^ liquid ^ monomer 10 kg of propylene together with 12.5 g of Al (iC ^ H ^) ^ in 90 ml of n-heptane, 3.45 g of ethyl paratoluate in 120 ml of n-heptane, 1, 06 g of the solid product (prepared according to Example 4 (a)) in 130 ml of n-heptane and 15 N of hydrogen was introduced into a stainless steel autoclave which had a 30 liter capacity.
Polymerisationstemperaturen blev indstillet på 65°C, og trykket blev indstillet på 26,5 kg/cm .The polymerization temperature was adjusted to 65 ° C and the pressure was adjusted to 26.5 kg / cm.
Efter 5 timer og efter at overskydende propylen var fjernet, frem-After 5 hours and after the excess propylene was removed,
20 DK 151892 BDK 151892 B
kom der 1,4 kg polypropylen med et udbytte på 67.600 g polymer/g li, hvilket udviste en remanens efter ekstraktion med kogende heptan på 80,5$, en løs massefylde på 0,32 kg/liter, et grænse- p viskositetstal på 2 dl/g og en bøjningsstivhed på 10.200 kg/cm .1.4 kg of polypropylene was obtained with a yield of 67,600 g of polymer / g of li, which showed a residual post-extraction with boiling heptane of $ 80.5, a loose density of 0.32 kg / liter, a viscosity limit of 2 dl / g and a flexural stiffness of 10,200 kg / cm.
EKSEMPEL 10 287 mg af det faste produkt fremstillet i henhold til eksempel 6 (a) blev indført i en autoklav, der var af rustfrit stål, og som havde en 2,5 liter kapacitet, indeholdende 1 liter n-heptan og 1,135 g A1(02H5)3 forblandet med 533 mg ethylparatoluat.EXAMPLE 10 287 mg of the solid product prepared according to Example 6 (a) was introduced into a stainless steel autoclave having a 2.5 liter capacity, containing 1 liter of n-heptane and 1.135 g of A1 ( 2H5) 3 premixed with 533 mg of ethyl paratoluate.
Polymerisationen blev gennemført ved 60°0 under et tryk på 5 kg/ cm^ g med propylen og hydrogen (1,5 volumenprocent i gasfasen) i 5 timer.The polymerization was carried out at 60 ° C under a pressure of 5 kg / cm 2 g with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours.
Trykket blev holdt konstant ved kontinuerlig tilførsel af propylen. Ved afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp, fremkom der 180 g polymer med et udbytte på 31.400 g polypropylen/g Ti i 5 timer, hvilket udviste en remanens efter ekstraktion med kogende heptan på 80$ og en løs massefylde på 0,253 kg/liter.The pressure was kept constant by continuous supply of propylene. At the end and after removing the solvent by stripping with steam, 180 g of polymer was obtained with a yield of 31,400 g of polypropylene / g Ti for 5 hours, exhibiting a residual post-extraction with boiling heptane of $ 80 and a loose density of 0.253 kg / liter.
10 kg propylen sammen med 12,5 g A1(C2H^)3 i 90 ml n-heptan, 6,45 g ethylparatoluat i 120 ml n-heptan, 1 g af det faste produkt fremstillet i henhold til eksempel 6 (a), i 130 ml n-heptan og 15 NI hydrogen blev indført i en autoklav, der var af rustfrit stål, og som havde en kapacitet på 30 liter.10 kg of propylene together with 12.5 g of Al (C 2 H 2) 3 in 90 ml of n-heptane, 6.45 g of ethyl paratoluate in 120 ml of n-heptane, 1 g of the solid product prepared according to Example 6 (a), in 130 ml of n-heptane and 15 N of hydrogen were introduced into a stainless steel autoclave with a capacity of 30 liters.
Polymerisationstemperaturen blev indstillet på 65°0, og trykket blev indstillet på 26,5 kg/cm^.The polymerization temperature was adjusted to 65 ° 0 and the pressure was adjusted to 26.5 kg / cm 2.
Efter 5 timer og efter at overskydende propylen var fjernet, fremkom der 1,3 kg polypropylen med et udbytte på 65.000 g polymer/g Ti, hvilket udviste en remanens efter ekstraktion med kogendeAfter 5 hours and after the excess propylene was removed, 1.3 kg of polypropylene was obtained with a yield of 65,000 g polymer / g Ti, which showed a residue after extraction with boiling.
21 DK 151892 B21 DK 151892 B
heptan på 84$, en løs massefylde på 0,27 kg/liter, et grænsevisko sitetstal lig 2,4 dl/g, smelteflydeindeks på 3,2 g/10* og en bøjnings stivhed på 13.520 kg/cm .heptane of $ 84, a loose density of 0.27 kg / liter, an intrinsic viscosity of 2.4 dl / g, melt flow index of 3.2 g / 10 * and a flexural stiffness of 13,520 kg / cm.
-EKSEMPEL 11EXAMPLE 11
Polymerisatio^a^^ro^ylen^i^ogløsningsmiddel 204 mg af det faste produkt fremstillet i henhold til eksempel 6 (a) hlev indført i en 2,5 liter autoklav af rustfrit stål indeholdende 1 liter n-heptan og 1,135 g ΑΐίΐΟ^Η^)^ forblandet med 215 mg ethylparatoluat.Polymerisation of aqueous and solvent 204 mg of the solid product prepared according to Example 6 (a) was introduced into a 2.5 liter stainless steel autoclave containing 1 liter of n-heptane and 1.135 g of ΐΟίΐΟ ^ ) ^) ^ Premixed with 215 mg of ethyl paratoluate.
Polymerisationen blev gennemført ved 60°C og under et tryk på 5 kg/cm med propylen og hydrogen (1,5 volumenprocent i gasfasen) i 5 timer. Trykket blev holdt konstant ved kontinuerlig tilførsel af propylen.The polymerization was carried out at 60 ° C and under a pressure of 5 kg / cm with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours. The pressure was kept constant by continuous supply of propylene.
Ved afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp fremkom der 196 g polymer med et udbytte på 19.400 g polypropylen/g Ti i 5 timer, hvilket udviste en remanens efter ekstraktion i kogende heptan på 69,5$.At the end and after removing the solvent by stripping with steam, 196 g of polymer was obtained with a yield of 19,400 g of polypropylene / g of Ti for 5 hours, showing a residue after extraction in boiling heptane of $ 69.5.
Polymerisation af propylen i en flydende monomer 10 kg propylen sammen med 12,5 g Al(iC^Hg)^ i 90 ml n-heptan, 3,45 g ethylparatoluat i 120 ml n-heptan, 1,04 g af det faste produkt fremstillet i henhold til eksempel 6 (a) i 90 ml n-heptan og 15 NI hydrogen blev indført i en autoklav af rustfrit stål og med en 30 liter kapacitet. Polymerisationstemperaturen blev indstil- n let på 65°0, og trykket blev indstillet på 26,5 kg/cm ·Polymerization of propylene in a liquid monomer 10 kg of propylene together with 12.5 g of Al (1C 3 Hg) 2 in 90 ml of n-heptane, 3.45 g of ethyl paratoluate in 120 ml of n-heptane, 1.04 g of the solid product prepared according to Example 6 (a) in 90 ml of n-heptane and 15 N of hydrogen was introduced into a stainless steel autoclave and with a 30 liter capacity. The polymerization temperature was set slightly to 65 ° 0 and the pressure was adjusted to 26.5 kg / cm ·
Efter 5 timer og efter at overskydende propylen var fjernet, fremkom der 1,15 kg polypropylen med et udbytte på 55.300 g poly-mer/g Ti, hvilket udviste en remanens efter ekstraktion i kogende heptan på 76,5$, en løs massefylde på 0,30 kg/liter, et grænseviskositetstal på 1,8 dl/g, et smelteflydeindeks på 4 g/10* og en bøjningsstivhed på 10.460 kg/cm .After 5 hours and after removing the excess propylene, 1.15 kg of polypropylene was obtained with a yield of 55,300 g of polymer / g Ti, which exhibited a residual post-extraction in boiling heptane of $ 76.5, a loose density of 0.30 kg / liter, an intrinsic viscosity of 1.8 dl / g, a melt flow index of 4 g / 10 * and a flexural stiffness of 10,460 kg / cm.
22 DK 151892 B22 DK 151892 B
EKSEMPEL· 12EXAMPLE · 12
Polymerisation af propylen_i_et opløsningsmiddel 246 mg af det faste produkt fremstillet i henhold til eksempel 6 (a) blev indført i en 2,5 liter autoklav af rustfrit stål og indeholdende 1 liter n-heptan og 1,135 g AlCCgH^)^ forhlandet med 329 mg ethylanisat.Polymerization of Propylene Solvent 246 mg of the solid product prepared according to Example 6 (a) was introduced into a 2.5 liter stainless steel autoclave containing 1 liter of n-heptane and 1.135 g of AlCCgH 2) premixed with 329 mg of ethyl anisate .
Polymerisationen hlev gennemført ved 60°0 under et tryk på 5 kg/cm med propylen og hydrogen (1,5 volumenprocent i gasfasen) i 5 timer.The polymerization was carried out at 60 ° 0 under a pressure of 5 kg / cm with propylene and hydrogen (1.5% by volume in the gas phase) for 5 hours.
Ved afslutningen og efter at have fjernet opløsningsmidlet ved stripping med damp fremkom der 200 g polymer med et udbytte på 41.700 g polypropylen/g Ti i 5 timer, hvilket udviste en remanens efter ekstraktion i kogende heptan lig med 71,5$.At the end and after removing the solvent by stripping with steam, 200 g of polymer was obtained with a yield of 41,700 g of polypropylene / g Ti for 5 hours, which showed a residue after extraction in boiling heptane equal to $ 71.5.
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IT23396/75A IT1038179B (en) | 1975-05-16 | 1975-05-16 | PROCEDURE FOR POLYMERIZATION OF ALPHA OLEFINS WITH AT LEAST THREEATONS OF CARBON |
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IT1078995B (en) * | 1977-05-24 | 1985-05-08 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
JPS54135886A (en) * | 1978-04-14 | 1979-10-22 | Sumitomo Chem Co Ltd | Preparation of ethylenic copolymer |
NO155245C (en) * | 1978-07-24 | 1987-03-04 | Phillips Petroleum Co | PROCEDURE FOR THE PREPARATION OF A POLYMERIZATION CATALYST AND APPLICATION OF THE ALKENE POLYMERIZATION CATALYST. |
US4277370A (en) | 1979-02-15 | 1981-07-07 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
US4324690A (en) | 1979-02-15 | 1982-04-13 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
US4347157A (en) | 1979-04-25 | 1982-08-31 | Sumitomo Chemical Company, Limited | Catalysts for the polymerization of olefins |
US4363746A (en) | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
US4394291A (en) * | 1981-03-04 | 1983-07-19 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
AT377625B (en) * | 1981-06-29 | 1985-04-10 | Georges A Cournoyer | DEVICE FOR TEACHING MUSIC SCREENS AND INTERVALS |
JPS58189206A (en) * | 1982-04-30 | 1983-11-04 | Chisso Corp | Catalytic component for alpha-olefin polymerization |
US4529715A (en) * | 1983-10-17 | 1985-07-16 | The Dow Chemical Company | Catalyst prepared from organomagnesium compound, carbon dioxide, reducing aluminum source, transition metal compound and zinc compound |
US4544647A (en) * | 1982-07-29 | 1985-10-01 | The Dow Chemical Company | Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound |
US4426316A (en) | 1982-09-10 | 1984-01-17 | The Dow Chemical Company | Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound |
US4604374A (en) * | 1982-09-20 | 1986-08-05 | The Dow Chemical Company | Catalyst prepared from organomagnesium compound, epihalohydrin reducing halide source and transition metal compound |
US4605715A (en) * | 1982-09-20 | 1986-08-12 | The Dow Chemical Company | Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, epihalohydrin reducing halide source and transition metal compound |
US4456547A (en) * | 1982-10-21 | 1984-06-26 | Fuentes Jr Ricardo | Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and complex formed from admixture of a transition metal compound and an organozinc compound |
US4661465A (en) * | 1985-10-31 | 1987-04-28 | The Dow Chemical Company | Method for preparing transition metal component of Ziegler-Natta catalysts |
US5045612A (en) * | 1990-04-18 | 1991-09-03 | The Dow Chemical Company | Catalyst and process for polymerizing olefins |
US5114897A (en) * | 1990-04-18 | 1992-05-19 | The Dow Chemical Company | Catalyst and process for polymerizing olefins |
US6001939A (en) * | 1994-09-22 | 1999-12-14 | Solvay Polyolefins Europe-Belgium | Process for the polymerization of olefins |
BE1008702A3 (en) * | 1994-09-22 | 1996-07-02 | Solvay | Process for olefin polymerization. |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2093306A6 (en) * | 1970-06-09 | 1972-01-28 | Solvay | ADVANCED CATALYSTS AND PROCESS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF OLEFINS |
DK125599B (en) * | 1969-01-24 | 1973-03-12 | Solvay | Process for the polymerization and copolymerization of α-olefins and catalyst for use in the process. |
GB1387888A (en) * | 1971-06-25 | 1975-03-19 | Montedison Spa | Olefin polymerization |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL164867C (en) * | 1971-03-11 | 1981-02-16 | Stamicarbon | METHOD FOR POLYMERIZING ALFA OLEGINS. |
BE791676A (en) * | 1971-12-08 | 1973-05-21 | Solvay | Process for the polymerization of olefins |
LU65587A1 (en) * | 1972-06-22 | 1973-12-27 | ||
IT969340B (en) * | 1972-09-13 | 1974-03-30 | Montedison Spa | CATALYSTS FOR POLYMERIZATION OF POLYMER OLEFINS IN SPHERICAL FORM |
-
1975
- 1975-05-16 IT IT23396/75A patent/IT1038179B/en active
-
1976
- 1976-04-11 TR TR19114A patent/TR19114A/en unknown
- 1976-05-10 DK DK206276A patent/DK151892C/en active
- 1976-05-10 NO NO761597A patent/NO150763C/en unknown
- 1976-05-10 SE SE7605272A patent/SE7605272L/en unknown
- 1976-05-10 RO RO86062A patent/RO85498B/en unknown
- 1976-05-10 NL NL7604972A patent/NL7604972A/en not_active Application Discontinuation
- 1976-05-11 GB GB32907/78A patent/GB1539175A/en not_active Expired
- 1976-05-11 FR FR7614146A patent/FR2311032A1/en active Granted
- 1976-05-11 CA CA252,281A patent/CA1068446A/en not_active Expired
- 1976-05-11 GB GB19291/76A patent/GB1538472A/en not_active Expired
- 1976-05-12 IN IN834/CAL/76A patent/IN146040B/en unknown
- 1976-05-12 DE DE19762620886 patent/DE2620886A1/en not_active Withdrawn
- 1976-05-13 JP JP51053910A patent/JPS51139887A/en active Granted
- 1976-05-13 AT AT350576A patent/AT348252B/en not_active IP Right Cessation
- 1976-05-14 HU HU76MO960A patent/HU174358B/en not_active IP Right Cessation
- 1976-05-14 ZA ZA762881A patent/ZA762881B/en unknown
- 1976-05-14 BR BR7603044A patent/BR7603044A/en unknown
- 1976-05-14 BE BE167022A patent/BE841823A/en not_active IP Right Cessation
- 1976-05-15 PL PL1976189597A patent/PL105364B1/en unknown
-
1980
- 1980-03-04 SE SE8001655A patent/SE434515B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK125599B (en) * | 1969-01-24 | 1973-03-12 | Solvay | Process for the polymerization and copolymerization of α-olefins and catalyst for use in the process. |
FR2093306A6 (en) * | 1970-06-09 | 1972-01-28 | Solvay | ADVANCED CATALYSTS AND PROCESS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF OLEFINS |
GB1387888A (en) * | 1971-06-25 | 1975-03-19 | Montedison Spa | Olefin polymerization |
Also Published As
Publication number | Publication date |
---|---|
IN146040B (en) | 1978-02-10 |
NO150763B (en) | 1984-09-03 |
CA1068446A (en) | 1979-12-18 |
IT1038179B (en) | 1979-11-20 |
DK206276A (en) | 1976-11-17 |
JPS5614682B2 (en) | 1981-04-06 |
TR19114A (en) | 1978-05-25 |
ZA762881B (en) | 1977-04-27 |
FR2311032B1 (en) | 1980-07-18 |
DK151892C (en) | 1988-07-18 |
BR7603044A (en) | 1977-05-31 |
DE2620886A1 (en) | 1976-11-25 |
FR2311032A1 (en) | 1976-12-10 |
BE841823A (en) | 1976-11-16 |
AU1392176A (en) | 1977-11-17 |
SE7605272L (en) | 1976-11-17 |
NL7604972A (en) | 1976-11-18 |
ATA350576A (en) | 1978-06-15 |
RO85498B (en) | 1984-11-30 |
RO85498A (en) | 1984-11-25 |
SE434515B (en) | 1984-07-30 |
GB1538472A (en) | 1979-01-17 |
SE8001655L (en) | 1980-03-04 |
PL105364B1 (en) | 1979-10-31 |
NO150763C (en) | 1984-12-12 |
HU174358B (en) | 1979-12-28 |
JPS51139887A (en) | 1976-12-02 |
GB1539175A (en) | 1979-01-31 |
NO761597L (en) | 1976-11-17 |
AT348252B (en) | 1979-02-12 |
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