DK147620B - METHOD OF PREPARING METAL CHLORIDE MIXTURES CONTAINING TITAN OR VANADIUM TRICHLORIDE - Google Patents
METHOD OF PREPARING METAL CHLORIDE MIXTURES CONTAINING TITAN OR VANADIUM TRICHLORIDE Download PDFInfo
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Description
147620147620
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af metalchloridbiåndinger indeholdende titan- eller vanadiumtrichlorid.The present invention relates to a process for the preparation of metal chloride bonds containing titanium or vanadium trichloride.
Metalchloridblandinger indeholdende titan- eller vanadiumtrichlorid kan benyttes som polymerisationskatalysatorer sammen med organoaluminiumforbindelser. Fremstillingen af titan- og vanadiumchlorider ved reducerende fremgangsmåder er beskrevet i litteraturen. J. Barksdale beskriver i "Titanium,Metal chloride mixtures containing titanium or vanadium trichloride can be used as polymerization catalysts together with organoaluminum compounds. The preparation of titanium and vanadium chlorides by reducing processes is described in the literature. J. Barksdale describes in "Titanium,
Its Occurrence, Chemistry and Technology", New York 1966, s. 148 -155, reduktionen af titantetrachlorid i dampfase med metallisk magnesium. Ved denne fremgangsmåde opnås metallisk titan; der er ikke mulighed for at stoppe reduktionen på metalchloridblandings- 2 147820 trinnet.Its Occurrence, Chemistry and Technology ", New York 1966, pp. 148 -155, the reduction of the titanium tetrachloride in the vapor phase with metallic magnesium. By this method, metallic titanium is obtained; there is no possibility of stopping the reduction of the metal chloride mixture step.
I DE-offentliggørelsesskrift nr. 21 58 956 beskrives fremstillingen af violet titantrichlorid ved elektrokemisk reduktion; man opnår mere eller mindre rent titantrichlorid, der imidlertid ikke er direkte anvendeligt i polymerisationskatalysatorer.DE Publication No. 21 58 956 describes the preparation of violet titanium trichloride by electrochemical reduction; more or less pure titanium trichloride is obtained, however, which is not directly applicable in polymerization catalysts.
Det er også kendt at fremstille titantrichlorider ved reduktion af T1CI4 ved følgende fremgangsmåder: a) Med hydrogen under drastiske betingelser (500°C til 700°C). Det opnåede produkt er på grund af den høje temperatur, der er anvendt, kun lidt virksomt ved polymerisationen af definer, b) med metaller såsom aluminium, antimon og andre ved temperaturer lig med eller højere end 200°C. I dette tilfælde er ikke alle metaller velegnede, da omsætningen for mange metallers vedkommende kun sker i begrænset omfang eller slet ikke finder sted. En sådan ulempe kan ganske vist afhjælpes ved at anvende polære opløsningsmidler, f.eks. dimethylformamid, tetrahydrofuran, dimethoxyheptan, men i sådanne tilfælde er det opnåede titantrichlorid komplekst forbundet med det polære opløsningsmiddel og er ikke af interesse til fremstilling af katalysatorer. Også anvendelsen af flydende amalgam kan afhjælpe nævnte ulempe (US patentskrift nr. 3 658 723), men alle metallerne har meget begrænset opløselighed i kviksølv, således at en sådan fremgangsmåde kræver en stor mængde af dette metal, som kun vanskeligt kan skilles fra titantrichloridet.It is also known to prepare titanium trichlorides by reduction of T1 Cl4 by the following methods: a) With hydrogen under drastic conditions (500 ° C to 700 ° C). The product obtained, due to the high temperature used, is only slightly effective in the polymerization of defines, b) with metals such as aluminum, antimony and others at temperatures equal to or higher than 200 ° C. In this case, not all metals are suitable, since the turnover of many metals is limited or does not take place at all. Admittedly, such a drawback can be remedied by using polar solvents, e.g. dimethylformamide, tetrahydrofuran, dimethoxyheptane, but in such cases the titanium trichloride obtained is complexly associated with the polar solvent and is not of interest in the preparation of catalysts. Also, the use of liquid amalgam can alleviate said disadvantage (U.S. Patent No. 3,658,723), but all of the metals have very limited solubility in mercury, so that such a process requires a large amount of this metal which is difficult to separate from the titanium trichloride.
Desuden er disse produkter ikke særligt aktive ved polymerisation, c) med metalalkyler, en fremgangsmåde der tillader at anvende moderate temperaturer, men som anvender forholdsvis kostbare materialer, som også er yderst reaktionsdygtige og farlige.Furthermore, these products are not particularly active in polymerization, (c) with metal alkyls, a process which allows the use of moderate temperatures, but which uses relatively expensive materials which are also highly reactive and dangerous.
Ved denne fremgangsmåde er det ikke muligt at anvende overgangsmetaller, hvis alkyler ikke er tilstrækkeligt stabile for praktisk anvendelse, d) med carbonylforbindelser af overgangsmetaller med lav valens f.eks. mangancarbonyl således som beskrevet i det danske patent nr. 146.027. Der er herved den fordel, at reduktionen opnås med et metal, der ikke reagerer som et sådant. De således opnåede 3 147620 titanchlorider udviser en god katalysevirkning ved polymerisation af umættede carbonhydrider, enten alene eller i blandinger.In this process it is not possible to use transition metals if the alkyls are not sufficiently stable for practical use; d) with carbonyl compounds of low valence transition metals e.g. manganese carbonyl as described in Danish Patent No. 146,027. Thereby, the advantage is that the reduction is achieved with a metal which does not react as such. The thus obtained titanium chlorides obtained have a good catalysis effect in the polymerization of unsaturated hydrocarbons, either alone or in mixtures.
e) Der kendes endvidere fra U.S. Patentskrift nr.e) Also known from U.S. Patent Specification no.
3.179.601 en fremgangsmåde til fremstilling af en polymerisations-initiator, ved hvilken magnesiumdampe omsættes med titantetra-chloriddampe over et bad af smeltet magnesium. Titantetrachlorid-dampene indføres i reaktionszonen sammen med en inert bæregas, og den resulterende gasstrøm indeholdende reaktionsprodukterne mellem titantetrachlorid - og magnesiumdampene ledes til en køle-og udfældningszone. Der opnås herved et brunt pyrofort, pulverformet reaktionsprodukt indeholdende magnesium, titan og chlor. Den præcise kemiske struktur af dette reaktionsprodukt kendes ikke ifølge patentskriftet.No. 3,179,601 is a process for preparing a polymerization initiator in which magnesium vapors are reacted with titanium tetrachloride vapors over a bath of molten magnesium. The titanium tetrachloride vapors are introduced into the reaction zone together with an inert carrier gas and the resulting gas stream containing the reaction products between the titanium tetrachloride and magnesium vapors is fed to a cooling and precipitation zone. There is thus obtained a brown pyrophoretic powdered reaction product containing magnesium, titanium and chlorine. The exact chemical structure of this reaction product is not known in the patent.
Det angives, at reaktionsproduktet kan initiere polymerisationen af ethylen og propylen. Det angives ikke, hvor stort udbyttet ved polymerisationen er.It is stated that the reaction product can initiate the polymerization of ethylene and propylene. It is not stated how much the yield in the polymerization is.
Ved fremgangsmåden ifølge opfindelsen til fremstilling af metalchloridblandinger indeholdende titan- eller vanadium-t'richlorid benytter man sig ligeledes af en reaktion mellem f.eks. magnesiumdampe og en titanforbindelse.The process of the invention for the preparation of metal chloride mixtures containing titanium or vanadium trichloride also uses a reaction between e.g. magnesium fumes and a titanium compound.
Ved fremgangsmåden fordampes Al, Mg, Cr, Mn eller Fe under et vakuum på 10“1 til 10“® Torr, og de således opnåede dampe omsættes med T1CI4 eller VCI4, og det ejendommelige ifølge opfindelsen er at omsætningen mellem metaldampene og TiCl4 eller VCI4 udføres ved en temperatur mellem -80 og +20°C, eventuelt i nærværelse af en halogendonor.In the process, Al, Mg, Cr, Mn or Fe are evaporated under a vacuum of 10 "1 to 10" ® Torr and the vapors thus obtained are reacted with T1Cl4 or VCI4, and the characteristic of the invention is that the reaction between the metal vapors and TiCl4 or VCI4 is carried out at a temperature between -80 and + 20 ° C, optionally in the presence of a halogen donor.
Gennem fremgangsmåden ifølge opfindelsen bliver det muligt at reducere titantetrachlorid eller vandiumtetrachlorid indtil det trin, hvor der foreligger metalchloridblandinger indeholdende titan- eller vanadiumtrichlorid. Reduktionen sker under milde kontrollerbare temperaturbetingelser. Man opnår på denne måde produkter med godt differentierbare fysiske egenskaber og tilsvarende variable katalytiske aktiviteter. Metalchlorid-blandingerne kan direkte tjene som katalysatorer til polymerisation og copolymerisation af α-olefiner under anvendelse af aluminiumalkyl- forbindelser som co- katalysatorer. Disse fordele ved fremgangsmåden ifølge opfindelsen og de herved opnåede produkter kunne ikke forudses udfra kendskabet til de kendte 4 147620 reduktionsfremgangsmåder.By the process of the invention, it becomes possible to reduce titanium tetrachloride or vanadium tetrachloride to the stage of metal chloride mixtures containing titanium or vanadium trichloride. The reduction occurs under mild controllable temperature conditions. In this way, products with well-differentiable physical properties and corresponding variable catalytic activities are obtained. The metal chloride mixtures can directly serve as catalysts for the polymerization and copolymerization of α-olefins using aluminum alkyl compounds as cocatalysts. These advantages of the process of the invention and the products thus obtained could not be foreseen from the knowledge of the known reduction methods.
Ved fremgangsmåden fordampes Al, Mg, Cr, Mn eller Fe f.eks. ved hjælp af elektriske modstande, elektronstråler, ved induktion samt ved anvendelse af høje frekvenser, laserstråler, elektriske gnister eller spændingsbuer. Fordampningen sker fortrinsvis ved 10”3 til 10“6 Torr ved temperaturer, der varierer alt efter det anvendte metal og sædvanligvis ligger ved 800 - 2500°C, således som beskrevet af P. L. Timms, Angew. Chem., Bd. 14, s. 273 (1975).In the process, Al, Mg, Cr, Mn or Fe are evaporated e.g. by means of electrical resistors, electron beams, by induction and by the use of high frequencies, laser beams, electric sparks or voltage arcs. Evaporation is preferably carried out at 10 "3 to 10" 6 Torr at temperatures which vary according to the metal used and are usually at 800 - 2500 ° C, as described by P. L. Timms, Angew. Chem., Vol. 14, pp. 273 (1975).
Metaldampene omsættes fortrinsvis med T1CI4 eller VCI4 ved -60 til -20°C.The metal vapors are preferably reacted with T1 Cl4 or VCl4 at -60 to -20 ° C.
TiCl4 eller VCI4 kan anvendes til reaktionen enten i ren tilstand eller fortyndet med et inert opløsningsmiddel valgt blandt alifatiske eller aromatiske, mættede eller umættede carbonhydrider og halogenerede carbonhydrider, såsom chlorhexan og fluorbenzen.TiCl4 or VCI4 can be used for the reaction either in the pure state or diluted with an inert solvent selected from aliphatic or aromatic, saturated or unsaturated hydrocarbons and halogenated hydrocarbons such as chlorhexane and fluorobenzene.
Valget af opløsningsmiddlet eller opløsningsmiddelblandingen retter sig efter de anvendte betingelser (størknings- og fordampningstemperaturer under det anvendte tryk).The choice of the solvent or solvent mixture depends on the conditions used (solidification and evaporation temperatures under the pressure used).
De ved fremgangsmåden ifølge opfindelsen opnåede metal-chloridblandinger kan sammen med organoaluminiumforbindelser anvendes som polymerisationskatalysatorer for definer. Et sådant katalysatorsystem er egnet til polymerisation og copolymerisation af ethylen og højere α-olefiner til henholdsvis lavtrykspoly-ethylen (high density) og isotaktisk polypropylen og ligeledes til polymerisation af butadien til 1,4-trans-polybutadien og af isopren til 1,4-cis-polyisopren med særdeles gode udbytter.The metal chloride mixtures obtained by the process according to the invention can be used together with organoaluminum compounds as polymerization catalysts for definers. Such a catalyst system is suitable for polymerization and copolymerization of ethylene and higher α-olefins for low density polyethylene (high density) and isotactic polypropylene respectively, and also for polymerization of butadiene to 1,4-trans-polybutadiene and of isoprene to 1.4 cis-polyisoprene with extremely good yields.
Som nævnt kan omsætningen mellem metaldampene og T1CI4 eller VCI4 udføres i nærværelse af en halogendonor. Det bliver herved muligt at opnå et produkt, der sammen med en ©rganøaåuminium-. forbindelse giver særligt gode. resultater ved polymerisation af α-olefiner, især af ethylen som sådant eller i blanding med en eller flere af dettes højere homologe, under opnåelse af høje udbytter. Mere specielt opnås et sådant produkt ved fordampning af magnesium eller en legering heraf og efterfølgende kondensation af dampene i et inert fortyndingsmiddel indeholdende T1CI4 og halogendonoren.As mentioned, the reaction between the metal vapors and T1Cl4 or VCI4 can be carried out in the presence of a halogen donor. In this way it becomes possible to obtain a product which, together with an © rganoa aluminum. connection provides particularly good. results in polymerization of α-olefins, especially of ethylene as such or in admixture with one or more of its higher homologues, to obtain high yields. More particularly, such a product is obtained by evaporation of magnesium or an alloy thereof and subsequent condensation of the vapors in an inert diluent containing T1Cl4 and the halogen donor.
Ved anvendelsen kan den ved fremgangsmåden ifølge opfindelsen opnåede metalchloridblanding benyttes således som den er fremstillet sammen med organoaluminiumforbindelsen ved 5 147620 opslemningspolymerisation af f.eks. ethylen uden efterfølgende adskillelser/ filtreringer eller elueringer. Den kan også anvendes efter at den er blevet dispergeret på en inert bærer, der endog ved polymerisation af ethylen i gasfasen kan være selve poly-olefinen, hvorved tilstedeværelsen af et carbonhydridholdigt dispergeringsmiddel kan ungås. Justering af molekylvægten med hydrogen indenfor et bredt molekylvægtsområde (MFI (smelteindeks) 0.1 til MFI 15) bevirker ikke tab i udbyttet af polymer.In use, the metal chloride mixture obtained by the process according to the invention can be used as prepared together with the organoaluminum compound by slurry polymerization of e.g. ethylene without subsequent separations / filtrations or elutions. It can also be used after it has been dispersed on an inert carrier which, even by polymerization of ethylene in the gas phase, may be the polyolefin itself, thereby avoiding the presence of a hydrocarbon containing dispersant. Adjusting the molecular weight with hydrogen within a wide molecular weight range (MFI (melt index) 0.1 to MFI 15) does not cause a loss in polymer yield.
Fremgangsmåden ifølge opfindelsen belyses nærmere gennem nedenstående eksempler.The process according to the invention is further illustrated by the following examples.
Eksempel 1Example 1
Fremstilling af blandingen TiCl3, AICI3.Preparation of the mixture TiCl3, AICl3.
Der anvendes en rotationskolbe, i hvis midte der er anbragt en wolframtråd, der er forbundet med en elektrisk kraftkilde. Under kolben er anbragt et afkølingsbad horisontalt.A rotary flask is used in the center of which is a tungsten wire connected to an electric power source. A cooling bath is placed horizontally under the flask.
I toppen af apparatet er der arrangementer for nitrogentilledning og vakuum. Inden i den spiralformet opvundne wolframtråd er anbragt 160 mg ren aluminium i flageform. Kolben fyldes under nitrogen med 250 ml vand frit decan, der indeholder TiCl^ i en mængde svarende til 30% af opløsningsmidlet. Den roterende kolbe afkøles med et bad, der har en temperatur på -40°C, hvorefter vakuum sættes på ved hjælp af en diffusianspumpe, indtil der nås 10 ^ Torr. Når disse betingelser er opnået, opvarmes tråden indtil metallet er fordampet. Det fordampede metal reagerer straks med TiCl^, hvorved der fremkommer et meget fint mørkebrunt bundfald.At the top of the apparatus are arrangements for nitrogen conduction and vacuum. 160 mg of pure aluminum in flake form is placed inside the helically wound tungsten wire. The flask is charged under nitrogen with 250 ml of water free decane containing TiCl 2 in an amount equal to 30% of the solvent. The rotary flask is cooled with a bath having a temperature of -40 ° C, after which vacuum is applied by means of a diffusion pump until 10 ^ Torr is reached. When these conditions are achieved, the wire is heated until the metal has evaporated. The vaporized metal immediately reacts with TiCl 2, resulting in a very fine dark brown precipitate.
Efter at fordampningen er tilendebragt, sættes kolben atter under tryk, og den bringes op til stuetemperatur ved at tilføre nitrogen, hvorefter opslæmningen bringes op på 150°C i 3 timer. Efter filtrering og tørring analyseres det således opnåede violette produkt: A1C13.3 TiCl3 Ti% Al% Cl%After evaporation is complete, the flask is re-pressurized and brought to room temperature by adding nitrogen, after which the slurry is brought to 150 ° C for 3 hours. After filtration and drying, the violet product thus obtained is analyzed: AlCl3.3 TiCl3 Ti% Al% Cl%
Beregnet 24,12 4,52 71,36Calcd 24.12 4.52 71.36
Fundet 24,01 4,90 69,80 6 147620Found 24.01 4.90 69.80 6 147620
Eksempel 2Example 2
Der anvendes det samme apparat og den samme fremgangsmåde som i eksempel 1. Der tilsættes 190 mg metallisk rent Mg i trådform og 250 ml octan, der indeholder 2% TiCl.. Efter at der o -4 4 er afkølet til -60 C og et vakuum på 10 Torr er opnået, påbegyndes fordampningen af metallet, og den tager 5 minutter. Man iagttager dannelsen af et fint brunviolet bundfald. Kolben bringes atter på stuetemperatur og normalt tryk. En prøve bringes op på 125°C i 4 timer, hvorefter opslæmningen filtreres, og det violette bundfald vaskes med n-heptan indtil TiCl^ fuldstændig er fjernet. Herefter analyseres det faste produkt efter at det er tørret i vakuum (2 g): MgCl2.2 TiCl3The same apparatus and procedure are used as in Example 1. 190 mg of metallic pure Mg in wire form and 250 ml of octane containing 2% TiCl are added. After o-4 has cooled to -60 ° C and a a vacuum of 10 Torr is obtained, the evaporation of the metal begins and it takes 5 minutes. The formation of a fine brown-violet precipitate is observed. The flask is brought back to room temperature and normal pressure. A sample is brought to 125 ° C for 4 hours, after which the slurry is filtered and the violet precipitate is washed with n-heptane until TiCl 2 is completely removed. The solid product is then analyzed after drying in vacuo (2 g): MgCl2.2 TiCl3
Ti% Mg% Cl%Ti% Mg% Cl%
Beregnet 23,76 5,94 70,28Calculated 23.76 5.94 70.28
Fundet 22,97 5,8 67,1Found 22.97 5.8 67.1
De to prøver, den ubehandlede og den behandlede, har når de analyseresmed røntgenstråler γ-struktur.The two samples, the untreated and the treated, have γ-structure when analyzed with X-rays.
Eksempel 3Example 3
Man anvender det samme apparatur og den samme fremgangsmåde som i eksempel 2, idet man anvender en koncentration af TiCl^ i n-octan på 14%.The same apparatus and procedure are used as in Example 2, using a concentration of TiCl 2 in n-octane of 14%.
Der opnås et brunviolet produkt, der filtreres, vaskes med n-heptan indtil TiCl4 er forsvundet, hvorefter der atter opslæmmes i n-heptan og analyseres. Analysen giver Mg^Ti^ .84C14*A brown-violet product is obtained, which is filtered, washed with n-heptane until TiCl4 has disappeared, then resuspended in n-heptane and analyzed. The analysis gives Mg
Eksempel 4Example 4
Der anvendes det samme apparatur og den samme fremgangsmåde som beskrevet i eksempel 1. Der tilsættes 0,240 g metallisk magnesium i trådform og 300 ml n-octan, der indeholder 0,07% TiCl^ og 12% n-chlorhexan son halogendonor. Efter afkøling til -60°C tilvejebringes et vakuum o -4 pa 10 Torr og magnesiumet fordampes i løbet af 7 minutter. Herved dannes et fast, lyst brunt produkt, der opsamles på et filter, vaskes med n-heptan og holdes ved 100°C i opløsningsmidlet i 2 timer. Analysen viser følgende molsammensætning: Mg„ .Ti. Cl_ D.The same apparatus and method as described in Example 1. is used. 0.240 g of metallic magnesium in wire form and 300 ml of n-octane containing 0.07% TiCl 2 and 12% n-chlorohexane halogen donor are added. After cooling to -60 ° C, a vacuum is obtained o -4 pa 10 Torr and the magnesium is evaporated over 7 minutes. This produces a solid, light brown product which is collected on a filter, washed with n-heptane and kept at 100 ° C in the solvent for 2 hours. The analysis shows the following mole composition: Mg „.Ti. Cl_ D.
3 · J. X / · o 7 1476203 · J. X / · o 7 147620
Eksempel 5Example 5
Der anvendes det samme apparat og fremgangsmåde som beskrevet i eksempel 1.The same apparatus and method as described in Example 1 are used.
I kolben indføres 0,180 g metallisk Mn i flageform og 250 ml octan, der indeholder 2% TiCl.. Efter afkøling til -60°C og efter at et -4 4 vakuum på 10 Torr er opnået, påbegyndes fordampningen af metallet, der er fuldendt i løbet af 3 minutter. Der observeres en dannelse af et brunviolet bundfald. Kolben bringes tilbage til stuetenper atur og normalt tryk, hvorefter suspensionen filtreres, vaskes med n-hexan indtil TiCl4 er forsvundet fuldstændig, hvorefter produktet tørres 1 vakuum og analyseres.Into the flask are introduced 0.180 g of metallic Mn in flake form and 250 ml of octane containing 2% TiCl. After cooling to -60 ° C and after obtaining a -4 4 vacuum of 10 Torr, the complete evaporation of the metal is started. in 3 minutes. A formation of a brown-purple precipitate is observed. The flask is returned to room temperature and normal pressure, after which the suspension is filtered, washed with n-hexane until TiCl 4 is completely disappeared, then the product is dried in vacuo and analyzed.
Analysen giver: 2 TiCl3.MnCl2 Ti% Cl% Mn%The analysis gives: 2 TiCl3.MnCl2 Ti% Cl% Mn%
Beregnet 22,0 65,30 12,63Calculated 22.0 65.30 12.63
Fundet 22,0 63,4 14,4Found 22.0 63.4 14.4
Eksempel 6Example 6
Der anvendes det samme apparatur og fremgangsmåde som beskrevet i eksempel 1. Der tilsættes 0,25 g metallisk Fe i form af spåner og 250 ml vandfrit n-octan, der indeholder 5% TiCl.. Efter afkøling til-50°C og —3 ’ efter at et vakuum på 10 Torr er nået, påbegyndes fordampningen af metallet, der tager 5 minutter. Der observeres dannelse af et fast rødbrunt produkt, der opsamles på et filter, vaskes med vandfrit hexan og tørres i vakuum. Herved opnås 1,87 g af et produkt, der har følgende analyse:The same apparatus and method as described in Example 1. are used. 0.25 g of metallic Fe in the form of chips and 250 ml of anhydrous n-octane containing 5% TiCl are added. After cooling to -50 ° C and -3 'After reaching a vacuum of 10 Torr, the 5 minute evaporation of the metal begins. Formation of a solid reddish brown product which is collected on a filter is observed, washed with anhydrous hexane and dried in vacuo. This gives 1.87 g of a product having the following analysis:
FeCl2.2 TiCl3 Ti% Fe% Cl%FeCl2.2 TiCl3 Ti% Fe% Cl%
Beregnet 21,99 12,89 65,19Calculated 21.99 12.89 65.19
Fundet 21,73 12,70 66,90Found 21.73 12.70 66.90
Eksempel 7Example 7
Der anvendes det samme apparatur og den samme fremgangsmåde som beskrevet i eksempel 1. I kolben indføres 0,120 g magnesiumtråd og 250 ml n-octan, der indeholder 3 ml VCl.. Efter afkøling til -60°C og opnåelse af et vakuum på 10 Torr påbegyndes fordampningen af metallet, der tager 5 minutter. Der observeres dannelsen af et fast mørkebrunt produkt, der vaskes med n-heptan for at fjerne overskydende VCl^, hvorefter der genopslæmmes i n-heptan. Analysen giver 8 147620The same apparatus and procedure as described in Example 1 are used. Into the flask are introduced 0.120 g of magnesium wire and 250 ml of n-octane containing 3 ml of VCl. After cooling to -60 ° C and obtaining a vacuum of 10 Torr the evaporation of the metal, which takes 5 minutes, begins. The formation of a solid dark brown product which is washed with n-heptane is observed to remove excess VCl3, and then resuspended in n-heptane. The analysis gives 8 147620
Eksempel 8Example 8
Man anvender det samme apparatur og den samme fremgangsmåde som beskrevet i eksempel 1. I kolben indføres 1 g metallisk chrcm i form af klumper og 250 ml n-heptan, der indeholder 10 ml TiCl^. Efter afkøling til -80°C og efter-at et vakuum pa^lO-4 Torr er nået/ påbegyndes fordampningen af metallet, der tager 20 minutter for at vare fuldendt.The same apparatus and method as described in Example 1 are used. Into the flask are introduced 1 g of metallic chromium in the form of chunks and 250 ml of n-heptane containing 10 ml of TiCl 2. After cooling to -80 ° C and after reaching a vacuum of O10-4 Torr, evaporation of the metal takes 20 minutes to complete.
Der observeres dannelse af et fast grønligt produkt, der opsamles på et filter og vaskes med heptan for at fjerne overskydende Ticl^. Herefter opslæmmes atter i heptan. Analysen giver:Formation of a solid green product is observed, which is collected on a filter and washed with heptane to remove excess Ticl 2. Then it is suspended in heptane again. The analysis gives:
CrCl3.3 TiCl3 Ti% Cr% Cl%CrCl3.3 TiCl3 Ti% Cr% Cl%
Beregnet 23,19 8,37 68,44Calcd 23.19 8.37 68.44
Fundet 23,40 8,20 67,60Found 23.40 8.20 67.60
Eksempel 9Example 9
Fremstilling af en katalysator med et forhold Mg/Ti højere end 0,5.Preparation of a catalyst having a ratio Mg / Ti higher than 0.5.
Der anvendes det samme apparat som beskrevet i eksempel 1. wolframspiralen tilføres 800 mg Mg· i nåleform. 500 ml kolben tilføres under nitrogen 130 ml vandfrit og udluftet n-heptan, 20 ml 1-chlor-hexan scm halogendonor lig med 146 itmol og 0,15 ml TiCl4 svarende til 1,35 mol.The same apparatus as described in Example 1. The tungsten coil is applied to 800 mg of Mg · in needle form. To the nitrogen flask, add 500 ml of the flask to 130 ml of anhydrous and vented n-heptane, 20 ml of 1-chlorohexane scm halogen donor equal to 146 itmol and 0.15 ml TiCl4 corresponding to 1.35 mol.
’ Λ'Λ
Kolben afkøles til -70°C, og der påføres et vakuum på lo” Torr, hvorefter spiralen opvarmes, således at metallet fordamper. Der dannes et meget fint gråbrunt bundfald. Efter at fordampningen er tilendebragt (ca. 15 minutter) indføres nitrogen i apparatet, og kolben bringes tilbage til stuetemperatur, hvorefter man stopper omrøringen. Analyse for opslæmningen gav følgende molforhold:The flask is cooled to -70 ° C and a vacuum is applied to lO ”Torr, after which the coil is heated so that the metal evaporates. A very fine gray-brown precipitate is formed. After evaporation is complete (about 15 minutes), nitrogen is introduced into the apparatus and the flask is brought back to room temperature, after which the stirring is stopped. Analysis for the slurry gave the following mole ratios:
Mg til Ti = 24 ; Cl til Ti = 45.Mg to Ti = 24; Cl to Ti = 45.
Polymerisation.Polymerization.
En 5-liter autoklav, der har en ankeromrører, fyldes med 2 liter vandfrit og udluftet n-heptan, 4 mmol Al(iso Bu)3 og en mængde katalysator, der er fremstillet ifølge dette eksempel, svarende til 0,01 mg-atom elementært titan. Temperaturen hæves til 85°C, hvorefter der tilføres 5 kg/cm hydrogen og 3,5 kg/cm ethylen. Der tilføres ethylen kontinuert, således at det totale tryk holdes konstant i 1 time. Herved opnås 350 g polyethylen, der har MFI = 9,8 g/10 min. og d = 0,9690 g pr. cm . Den specifikke aktivitet er 20φ00 g polymer pr. gram titan pr. time og pr. atmosfære ethylen.A 5-liter autoclave having an anchor stirrer is charged with 2 liters of anhydrous and vented n-heptane, 4 mmol Al (iso Bu) 3 and an amount of catalyst prepared according to this example corresponding to 0.01 mg atom elemental titanium. The temperature is raised to 85 ° C, after which 5 kg / cm of hydrogen and 3.5 kg / cm of ethylene are added. Ethylene is added continuously so that the total pressure is kept constant for 1 hour. This yields 350 g of polyethylene having MFI = 9.8 g / 10 min. and d = 0.9690 g per cm. The specific activity is 20φ00 g polymer per grams of titanium per per hour and per hour. atmosphere ethylene.
9 1476209 147620
Eksempel 10Example 10
Man benytter syntesemetoden ifølge eksempel 9, idet man anvender bromhexan som halogendpnor Der opnås en opslæmning, der har følgende analyse:The synthesis method of Example 9 is used, using bromohexane as a halogen tailor. A slurry is obtained which has the following analysis:
Mg til Ti forhold =16,5; (Br + Cl) til Ti forhold =33.Mg to Ti ratio = 16.5; (Br + Cl) to Ten ratio = 33.
Ved polymerisationen af ethylen under de i eksempel 17 anvendte betin~ gelser opnåedes der 165 g polymer, der havde en MFI= 4,18 g/10 min. svarende til en specifik aktivitet på 98.000 g pr. gram Ti pr. time og pr. atmosfære ethylen.In the polymerization of ethylene under the conditions used in Example 17, 165 g of polymer having an MFI = 4.18 g / 10 min were obtained. corresponding to a specific activity of 98,000 g / ml. grams of Ti per hour and per hour. atmosphere ethylene.
Eksempel 11Example 11
Med samme fremgangsmåde som i eksempel 9 og de samme reaktanter fremstilledes adskillige katalysatorer, der havde forskellige Mg til Ti forhold, og hvis aktiviteter ved polymerisationen af ethylen undersøgtes ved de samme betingelser som i eksempel 9. Resultaterne er angivet i tabel 1.By the same procedure as in Example 9 and the same reactants, several catalysts having different Mg to Ti ratios were prepared and whose activities in the polymerization of ethylene were investigated under the same conditions as in Example 9. The results are given in Table 1.
_Tabel 1__Table 1_
Mg Specif. aktivitet i MFI Tilsynela- MFI21Mg Specif. activity in MFI Apparently- MFI21
Ti g polym. pr. g kat. . dende vægt- — pr. time og pr. atm.C^H^ ' fylde g/cirr* x2.1 5.0 47.000 16,0 0,25 22 9.0 57.000 6,8 0,23 34 13.4 90.000 11,4 0,22 35 16.5 95.000 11,3 0,24 28 22,7 125.000 10,3 0,22 36 25.0 200.000 9,8 0,24 23 35.0 280.000 10,1 0,20 35 147620 ίοTen g of polym. per. g cat. . the same weight - per hour and per hour. atm.C ^ H ^ 'g / cirr * x2.1 5.0 47,000 16.0 0.25 22 9.0 57,000 6.8 0.23 34 13.4 90,000 11.4 0.22 35 16.5 95,000 11.3 0.24 28 22.7 125.000 10.3 0.22 36 25.0 200.000 9.8 0.24 23 35.0 280.000 10.1 0.20 35 147620 ίο
Eksempel 12Example 12
Der anvendes et apparat som det i eksempel 1 beskrevne.An apparatus such as that described in Example 1 is used.
I wolframtråden anbringes 1,096 g ren metallisk magnesiumtråd, 3 medens 1 liters kolben fyldes med 130 cm vandfrit ligroin, der inrlptolrlPT· l mmol TiCl^ sammen med 66,7 mæl SnCl4 som halogendonor. Magnesiumet fordampes fuldstændig i løbet af 40 minutter i et vakuum på 0,09 Torr, idet kolben holdes i rotation ved -60°C til -70°C. Kolben bringes op på stuetemperatur og normalt tryk, og omrøringen fortsættes i ca.Into the tungsten wire are placed 1,096 g of pure metallic magnesium wire, while the 1 liter flask is filled with 130 cm of anhydrous ligroin, which contains inolptolr1PT · 1 mmol TiCl4 together with 66.7 flour SnCl4 as a halogen donor. The magnesium is completely evaporated over 40 minutes in a vacuum of 0.09 Torr, keeping the flask in rotation at -60 ° C to -70 ° C. The flask is brought to room temperature and normal pressure and stirring is continued for approx.
1 time. I løbet af denne tid forandres opslæmningens farve fra mørk brun til gråhvid. Der udføres filtrering på en. porøst G3 filtermembran, derefter vaskes med vandfrit heptan, og den faste rest genopslæmmes i heptan.1 hour. During this time, the color of the slurry changes from dark brown to grayish white. Filtering is performed on one. porous G3 filter membrane, then washed with anhydrous heptane and the solid residue resuspended in heptane.
Analyse af opslæmningen giver følgende resultater:Analysis of the slurry gives the following results:
Ti = 5,77 mmol pr. liter; Mg.= 181 mmol pr. liter Sn = 170 mmol pr. liter ; Cl = 731 mmol pr. liter.Ti = 5.77 mmol per l; Mg. = 181 mmol. liter of Sn = 170 mmol per liter. liter; Cl = 731 mmol per liter.
Eksempel 13 I wolframtråden anbringes 1,0 g ren magnesiumtråd. Kolben fyldes i den angivne rækkefølge med 130 ml vandfrit toluen og 1 mmol TiCl^, hvilket giver opløsningen et gult skær. Herefter tilsættes ved -78°C 2 mmol diethylphthalat dråbevis. Opløsningen går fra gul til lys grøn. Derefter tilsættes 66,7 innol vandfrit SnCl^san halogendonor, hvilket giver et gult-orange skær. En olieagtig orange substans falder til bunds på kolbens bund. Magnesium fordampes i 40 minutter i vakuum på 0,06 Torr, idet man holder kolben i rotation ved -78°C. Herefter bringes kolben tilbage til stuetemperatur og normalt tryk, og der omrøres i ca. 1 time. I løbet af denne tid går opslæmningen fra mørk brun til gul. Opslæmningen opsamles på et filter, vaskes med vandfrit heptan og genopslæmmes i heptan.Example 13 In the tungsten wire, 1.0 g of pure magnesium wire is placed. Fill the flask in the order indicated with 130 ml of anhydrous toluene and 1 mmol of TiCl 2, giving the solution a yellowish tinge. Then, at -78 ° C, 2 mmol diethyl phthalate is added dropwise. The solution goes from yellow to light green. Then 66.7 inches of anhydrous SnCl 2 san halogen donor is added to give a yellow-orange shade. An oily orange substance settles to the bottom of the flask. Magnesium is evaporated for 40 minutes in a vacuum of 0.06 Torr, keeping the flask in rotation at -78 ° C. The flask is then brought back to room temperature and normal pressure and stirred for approx. 1 hour. During this time, the slurry goes from dark brown to yellow. The slurry is collected on a filter, washed with anhydrous heptane and resuspended in heptane.
Analyse af opslæmningen giver følgende resultater:Analysis of the slurry gives the following results:
Ti = 7,74 mmol pr. liter ; Mg = 235 mmol pr. liter Sn = 190 mmol pr. liter ; Cl = 897 mmol pr. liter.Ti = 7.74 mmol per liter; Mg = 235 mmol. liter Sn = 190 mmol per liter. liter; Cl = 897 mmol per liter.
11 14762011 147620
Eksempel 14 I wolframtråden anbringes 809,5 mg ren magnesiumtråd, medens kolben tilføres 100 ml vandfrit toluen og 1 mmol TiCl4, hvilket bibringer opløsningen en gul farve. Herefter tilsættes ved stuetemperatur og under omrøring 2 mmol diethylphthalat. Opløsningen antager et lyst grønt skær. Yderligere tilsættes 43,3 mmol SnCl^nBut som halogen-donor, hvilket bibringer opløsningen et gult-orange skær, hvorefter en · olieagtig substans falder til bunds på kolbens bund. Magnesium fordampes i 40 minutter i et vakuum på 0,07 Torr, idet man holder kolben i rotation ved -78°C. Kolben bringes tilbage til stuetempratur og normalt tryk, og omrøringen fortsættes i ca. 2 timer ved stuetemperatur. Opløsningen går fra mørk brun til lys grå i løbet af denne tid. Filtrering, vask med vandfrit heptan og genopslæmning i heptan udføres.Example 14 In the tungsten wire 809.5 mg of pure magnesium wire is placed, while the flask is charged with 100 ml of anhydrous toluene and 1 mmol of TiCl4, which gives the solution a yellow color. Then, at room temperature and with stirring, 2 mmol diethyl phthalate is added. The solution assumes a bright green shade. In addition, 43.3 mmol of SnCl3 nBut is added as a halogen donor, giving the solution a yellow-orange shade, after which an oily substance settles to the bottom of the flask. Magnesium is evaporated for 40 minutes in a vacuum of 0.07 Torr, keeping the flask in rotation at -78 ° C. The flask is brought back to room temperature and normal pressure and stirring is continued for approx. 2 hours at room temperature. The solution goes from dark brown to light gray during this time. Filtration, washing with anhydrous heptane and resuspending in heptane are performed.
Analyse af opslæmningen giver følgende resultater:Analysis of the slurry gives the following results:
Ti = 7,18 mmol pr. liter ; Mg = 66 mmol pr. literTi = 7.18 mmol per liter; Mg = 66 mmol. liter
Sn = 80 mmol pr. liter ; Cl = 349 mmol pr. liter.Sn = 80 mmol per liter; Cl = 349 mmol per liter.
Eksempel 15 970 mg ren magnesiumtråd anbringes på wolframen. Kolben, der indeholder 100 ml vandfrit heptan og 1 mmol TiCl4, tilsættes ved stuetemperatur og vmrfer omrøring 60 mmol SbClj- som halogendonor, destilleret.Example 15 970 mg of pure magnesium wire is applied to the tungsten. The flask containing 100 ml of anhydrous heptane and 1 mmol TiCl4 is added at room temperature and stirred 60 mmol SbCl 2 as halogen donor, distilled.
Opløsningen forbliver klar. Fordampning af magnesium bevirker at suspensionen bliver gulbrun. Herefter dannes et hvidt pulver, der langsomt bliver mørkere, og som går over i gråt og endelig i sort.Filtrering vask med vandfrit heptan og genopslæmning i dette opløsningsmiddel udføres. Analyse af opslæmningen giver følgende resultater:The solution remains clear. Evaporation of magnesium causes the suspension to turn yellowish brown. Then a white powder is formed which slowly darkens and turns to gray and finally to black. Filtration washing with anhydrous heptane and resuspending in this solvent is carried out. Analysis of the slurry gives the following results:
Ti = 4,60 mmol pr. liter ; Mg = 226 mmol pr. literTi = 4.60 mmol per liter; Mg = 226 mmol. liter
Sb = 95 mmol pr. liter ; Cl = 1,058 mmol pr. literSb = 95 mmol. liter; Cl = 1.058 mmol. liter
Eksempel le På wolframtråden anbringes 831,8 mg ren magnesiumtråd. Til kolben, der indeholder 100 ml vandfrit n-heptan, sættes ved stuetemperatur og under omrøring 51,3 mmol destilleret POCl^ son halogendonor og lrarol TiCl4· Der dannes et gult bundfald. Magnesiumen fordampes, idet kolben holdes ved -78°C. Suspensionen er gulbrun. Kolben bringes tilbage til stuetemperatur og normalt tryk, og omrøringen fortsættes 3,2 147620 i 2 timer ved stuetemperatur. Herved bliver suspensionen svagt gul. Filtrering, vask med n-heptan og genop s laamning i dette opløsningsmiddel udføres.EXAMPLE 1 On the tungsten wire, 831.8 mg of pure magnesium wire is placed. To the flask containing 100 ml of anhydrous n-heptane is added at room temperature and with stirring 51.3 mmol distilled POClcone halogen donor and lrarole TiCl4 · A yellow precipitate is formed. The magnesium is evaporated keeping the flask at -78 ° C. The suspension is yellowish brown. The flask is brought back to room temperature and normal pressure and stirring is continued for 2 hours at room temperature. This causes the suspension to turn slightly yellow. Filtration, washing with n-heptane and resuspending in this solvent is performed.
Analyse af opslæmningen giver følgende resultater:Analysis of the slurry gives the following results:
Ti = 9,62 mmol pr. liter ; Mg = 126 mmol pr. liter P - 390 mmol pr. liter ; Cl = 655 mmol pr. liter.Ti = 9.62 mmol per liter; Mg = 126 mmol. liter of P - 390 mmol per liter. liter; Cl = 655 mmol per liter.
Forsøg med ethylenpdLymerisation med katalysatorblandinger fremstillet som i eksemplerne 12 til 16 udførtes som beskrevet i eksempel 9 med en polymerisationstid på 2 timer og med et hydrogen- 2 2 tryk på 5 kg pr. cm og et ethylentryk på 5 kg pr. cm . De opnåede resultater er anført i tabel 2.Experiments with ethylene polymerization with catalyst mixtures prepared as in Examples 12 to 16 were carried out as described in Example 9 with a polymerization time of 2 hours and with a hydrogen pressure of 5 kg per liter. and an ethylene pressure of 5 kg per cm. The results obtained are listed in Table 2.
Tabel 2Table 2
Katalysator Specifik aktivitet i MFI21 MFI21 Tilsynela-fra eksempel g polym.'pr. g Ti pc.time min_ — dende vaegt^ og pr. atmosf. y/ * 2,1 fylde g/cm 12 34.700 5,00 36 0,30 13 32.500 5,70 31 ikke bestemt 14 13.000 2,90 32 ikke bestemt 15 34.000 6,98 27 0,20 16 8.300 4,32 31 ikke bestemtCatalyst Specific activity in MFI21 MFI21 Seen from Example g polym. g Ten pc.time min_ - the same weight ^ and per. atmosphere. y / * 2.1 fullness g / cm 12 34,700 5.00 36 0.30 13 32,500 5.70 31 not determined 14 13,000 2.90 32 not determined 15 34,000 6.98 27 0.20 16 8,300 4.32 31 not decided
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DK458580A DK156481C (en) | 1976-01-30 | 1980-10-29 | TITANIC CATALYST AND USE OF THIS COMBINED WITH AN ALUMINUM ORGANIC COMPOUND FOR POLYMERIZATION OF ALFA OLEFINES |
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IT1974876A IT1054583B (en) | 1976-01-30 | 1976-01-30 | Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst |
IT2525776A IT1065073B (en) | 1976-07-13 | 1976-07-13 | Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst |
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IT1080687B (en) * | 1977-06-30 | 1985-05-16 | Snam Progetti | TRIALHYGEN TITANIUM-BASED CHEMICAL COMPOSITIONS, PROCEDURE FOR THEIR PREPARATION AND USE |
IT1081277B (en) * | 1977-06-30 | 1985-05-16 | Snam Progetti | CHEMICAL COMPOSITIONS BASED ON TRIALHYGEN TITANIUM PROCEDURE FOR THEIR PREPARATION AND USE |
IT1113421B (en) * | 1979-03-07 | 1986-01-20 | Anic Spa | METHOD FOR THE REDUCTION OF METALLIC ALCOXIDS AND USE OF THE COMPOUNDS SO OBTAINED |
IT1130243B (en) * | 1980-02-01 | 1986-06-11 | Anic Spa | CHEMICAL COMPOSITION BASED ON TRIALHYGEN TITANIUM, METHOD FOR ITS PREPARATION AND PROCESS OF POLYMERIZATION OR COPOLYMERISATION OF UNSATURATED COMPOUNDS USING THE SAME |
IT1137631B (en) * | 1981-07-29 | 1986-09-10 | Anic Spa | PROCEDURE FOR HIGH YIELD POLYMERIZATION AND COPOLYMERIZATION OF HYDRAULICALLY UNSATURATED COMPOUNDS AND MEDIA SUITABLE FOR SOCPO |
IT1210855B (en) * | 1982-02-12 | 1989-09-29 | Assoreni Ora Enichem Polimeri | LINEAR STRUCTURE ETHYLENE POLYMERS AND PROCESSES FOR THEIR PREPARATION. |
FR3033565B1 (en) * | 2015-03-09 | 2017-03-24 | Centre Nat Rech Scient | IRON PRECATALYST AND USE THEREOF IN THE POLYMERIZATION OF OLEFINS |
RU2707362C1 (en) * | 2019-04-05 | 2019-11-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of producing titanium trichloride |
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US3109822A (en) * | 1963-11-05 | catalyst composition | ||
DE1302122C2 (en) * | 1954-12-03 | 1979-09-13 | Montecatini Edison S.pA, Mailand (Italien); Ziegler, Karl, Dr.Dr.eh, 4330 Mülheim | METHOD FOR MANUFACTURING LINEAR HEAD-TAIL POLYPROPYLENE OR -POL-ALPHA- BUTYLENE |
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AT218733B (en) * | 1957-05-28 | 1961-12-27 | Titan Gmbh | Process for the production of a new, homogeneous, anhydrous aluminum-titanium-chlorine compound |
DE1168876B (en) * | 1962-04-28 | 1964-04-30 | Basf Ag | Process for the preparation of a complex compound of titanium trichloride and aluminum chloride |
DE1268598B (en) * | 1964-03-04 | 1968-05-22 | Rexall Drug Chemical | Process for the preparation of a catalyst for the polymerization of alpha-olefins |
DE1229050B (en) * | 1965-01-13 | 1966-11-24 | Basf Ag | Process for the preparation of a catalyst component which is particularly active in the polymerization of propylene using Ziegler catalysts |
GB1299862A (en) | 1969-01-23 | 1972-12-13 | Shell Int Research | Improvements in or relating to the catalytic polymerisation of olefins |
IT941979B (en) | 1970-12-04 | 1973-03-10 | Naphtachimie Sa | MAGNESIUM-BASED CATALYSTS APPLICABLE TO THE POLYMERIZATION OF OLEFINS |
BE785673A (en) | 1971-06-30 | 1973-01-02 | Naphtachimie Sa | POLYMERIZATION CATALYZERS OF OLEFINS PREPARED FROM DECOMPOSED ORGANOMAGNESIANS |
DE2158956A1 (en) * | 1971-11-27 | 1973-05-30 | Basf Ag | Prepn of violet titanium trichloride - by plasma chemical conversion of titanium tetrachloride |
BE794323A (en) | 1972-01-20 | 1973-07-19 | Naphtachimie Sa | PROCESS FOR THE MANUFACTURE OF ATACTIC POLYOLEFIN WAXES |
IT998599B (en) | 1972-09-18 | 1976-02-20 | Naphtachimie Sa | PROCEDURE OF POLYMERIZATION OF OLEFINS USING PRE ACTIVATED CATALYSTS |
GB1467051A (en) * | 1974-01-03 | 1977-03-16 | Shell Int Research | Process for the production of polyolefins and catalyst therefor |
JPS5724361B2 (en) | 1974-03-27 | 1982-05-24 | ||
IL46858A (en) | 1974-04-17 | 1979-01-31 | Snam Progetti | Process for the polymerization of alpha-olefins,catalyst employed in said process and method for the preparation thereof |
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- 1977-01-25 DK DK30877A patent/DK147620C/en not_active IP Right Cessation
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- 1977-01-26 EG EG51/77A patent/EG13429A/en active
- 1977-01-27 NO NO770274A patent/NO150208C/en unknown
- 1977-01-27 AR AR266342A patent/AR217821A1/en active
- 1977-01-27 GB GB3437/77A patent/GB1576431A/en not_active Expired
- 1977-01-27 FR FR7702334A patent/FR2345467A1/en active Granted
- 1977-01-28 SU SU772446350A patent/SU1056905A3/en active
- 1977-01-28 MX MX167866A patent/MX142961A/en unknown
- 1977-01-28 IE IE189/77A patent/IE45018B1/en not_active IP Right Cessation
- 1977-01-28 LU LU76666A patent/LU76666A1/xx unknown
- 1977-01-28 DE DE2703604A patent/DE2703604C3/en not_active Expired
- 1977-01-28 CH CH108477A patent/CH628597A5/en not_active IP Right Cessation
- 1977-01-28 PH PH19393A patent/PH15890A/en unknown
- 1977-01-28 DD DD7700197143A patent/DD130130A5/en unknown
- 1977-01-28 DE DE2759512A patent/DE2759512C2/en not_active Expired
- 1977-01-28 ES ES455759A patent/ES455759A1/en not_active Expired
- 1977-01-28 DD DD77205331A patent/DD138218A5/en unknown
- 1977-01-28 JP JP52007909A patent/JPS6050806B2/en not_active Expired
- 1977-01-28 PT PT66123A patent/PT66123B/en unknown
- 1977-01-29 IN IN133/CAL/77A patent/IN145866B/en unknown
- 1977-01-31 NL NLAANVRAGE7701005,A patent/NL172329C/en not_active IP Right Cessation
- 1977-06-14 FR FR7718179A patent/FR2345212A1/en active Granted
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1981
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1982
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- 1982-07-29 YU YU1658/82A patent/YU44359B/en unknown
- 1982-12-30 MY MY212/82A patent/MY8200212A/en unknown
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