NO116930B

NO116930B -

Info

Publication number: NO116930B
Application number: NO15062163A
Authority: NO
Inventors: J Price
Original assignee: Avisun Corp
Priority date: 1961-04-19
Filing date: 1963-10-29
Publication date: 1969-06-09
Also published as: NL302235A; AT286616B; NL122498C; NL125097C; GB1015894A; NL277530A; GB966788A; DE1495052A1; DE1445208B2; CH464532A; AT293721B; DE1445208A1

Description

Fremgangsmåte for polymerisering av 1-alkener. Process for the polymerization of 1-alkenes.

Foreliggende oppfinnelse angår en fremgangsmåte for polymerise- The present invention relates to a method for polymerizing

ring av propylen og hbyere alfa-olefiner ved anvendelse av en katalysator med tre bestanddeler nemlig visse typer titantriklorid, et alkyl-aluminium-dihalogenid eller sesquihalogenid, og et alkoksysilan, av den type som er beskrevet i patent nr. ring of propylene and higher alpha-olefins using a three-component catalyst, namely certain types of titanium trichloride, an alkyl aluminum dihalide or sesquihalide, and an alkoxysilane, of the type described in patent no.

107.61M-. 107.61M-.

Det er kjent at alfa-olefiner kan polymeriseres i nærvær av katalysatorer som omfatter et overgangmetall-halogenid f.eks. titanklorid sammen med et aluminium-alkyl eller -dialkyl-aluminium-monoklorid slik at eiet dannes faste krystallinske polymerér som kan brukes ved fremstilling av formede gjenstander, filmer og fibre. Det har imidlertid ikke vist seg mul-6a bruke et alkyl-aluminium-halogenid. eller -sesquihalogenid som aktiv be-standdel i denne type katalysatorer selv om dir: se forbindelser i er meget mindre kostbare enn de alkyl-aluminiurr "orbindelser soni er brukt tidligere. I U.S. patent nr.2.967.2o sr det således brukt ul kyl-aluminium-;.: i halogenider sammen med titan-halogenider for å oppnå polymer! < ug av propylen og hoyere olefiner til oljeaktige/polymerer, j.-ch ved denne katalysator dannes det ingen faste polymerer. At uerTie katalysator ikke virker er også kjent fro det belgiske patent nr. 605.60<I>+ og U.3. patent 3.081.287. Selv om litt. fart polymer kan oppnås under bruk av aluminium-s-.:;:-.quihal6genid-titantriklorid-katalysator er utbyttene meget små og disse katalysatorer har derfor ingen industriell betyd-ning . It is known that alpha-olefins can be polymerized in the presence of catalysts comprising a transition metal halide, e.g. titanium chloride together with an aluminum-alkyl or -dialkyl-aluminum monochloride so that solid crystalline polymers are formed which can be used in the production of shaped objects, films and fibres. However, mul-6a has not been shown to use an alkyl aluminum halide. or -sesquihalide as an active ingredient in this type of catalyst, even though these compounds are much less expensive than the alkyl-aluminum compounds that have been used previously. aluminium-;.: in halides together with titanium halides to obtain polymer! < ug of propylene and higher olefins to oily/polymers, j.-ch with this catalyst no solid polymers are formed. That uerTie catalyst does not work is also known from Belgian Patent No. 605,60<I>+ and U.S. Patent 3,081,287 Although some speed polymer can be obtained using aluminum-s-.:;:-.quihalogenide-titanium trichloride catalyst the yields are very small and these catalysts therefore have no industrial significance.

Foreliggende oppfinnelse går ut på en.koordinert katalysator hvor det brukes et alkyl-aluminium-diha]ogenid aller --;e -. a- ; i hal - ogenid som organisk metall-bestanddel av katalysatoren, som The present invention is based on a coordinated catalyst where an alkyl-aluminum-di]ogenide is used. a- ; in hal - ogenide as an organometallic component of the catalyst, which

vil polymerisere propylen og hoyere olefiner til faste kry. 1.all-/ ; inske polymerer med utbytter som er av interesse i imhi r, tr i en. will polymerize propylene and higher olefins to solid cry. 1.all-/ ; insic polymers with yields that are of interest in imhi r, tr i en.

I henhold til oppfinne] r.on lias* det vist seg at en katt:.; saior According to invent] r.on lias* it appeared that a cat:.; saior

r. om inneholder visse typer ! ; ;;antriklorid, et alkyl-aiuminium-dihalogenid eller-sesquihalogenid og et alkoksysilan er effekt-ive for polymerisering av propylen, og andre 1-alkener som innr.-. helder så mange som åtte karbonatomer, til faste krystallinsk r--p-.-;.ymerer. Sn form for titantriklorid som kan bruker i honhold til oppfinnelsen er et aktivert aluminium-redusert t.i tuntriklo-rid som brukes med silan og alkyl-aluminium-dihaljd eller r. if contains certain types ! ; ;;antrichloride, an alkyl aluminum dihalide or sesquihalide and an alkoxysilane are effective for the polymerization of propylene, and other 1-alkenes such as inr.-. clear as many as eight carbon atoms, to solid crystalline r--p-.-;.ymers. The form of titanium trichloride which can be used in accordance with the invention is an activated aluminium-reduced titanium trichloride which is used with silane and alkyl aluminum dihalide or

-sesquihalogen. Dette aktiverte titantriklorid n ;>'-;finert her som overveiende amorft og kan fremstilles ved kui -Uer stav-maling av titantriklorid kokrystallicert med alum<*>< r. Lrmklor j d og har den empiriske formel 3TiCl^.AlCl^, fremstillet veu redu-sering av titantetraklorid med aluminium, inntil det, bestemt ved rontgendifraksjon har mindre enn ^ 0% krystallinsk struktur i det krystallinske titantriklorid for kule-eller stav-mali r\ r:; r:>. I praksis er krystallmengden i alminnelighet 2o# eller mindre "og fortrinnsvis er den lo% eller mindre. Denne type titaril.ri- -sesquihalogen. This activated titanium trichloride n ;>'-;fined here as predominantly amorphous and can be prepared by kui -Uer rod grinding of titanium trichloride cocrystallized with alum<*>< r. Lrmchlor j d and has the empirical formula 3TiCl^.AlCl^, prepared veu reducing titanium tetrachloride with aluminum until, as determined by X-ray diffraction, it has less than 10% crystalline structure in the crystalline titanium trichloride for ball or rod mali r\ r:; r:>. In practice, the amount of crystals is generally 20% or less, and preferably it is 10% or less. This type of titaril.ri-

i klorid skal heretter omtales som X TiCl,. in chloride shall hereafter be referred to as X TiCl,.

i in

En annen type titantriklorid som kan brukes ved utforelsen av i Another type of titanium trichloride that can be used in the execution of i

foreliggende oppfinnelse er det bunnfall som oppnåes ved-å reagere titantetraklorid med et alkylaluminiumdiklorid. Dette er present invention is the precipitate obtained by reacting titanium tetrachloride with an alkyl aluminum dichloride. This is

en kokrystallinsk forbindelse av titantriklorid og aluminium- a cocrystalline compound of titanium trichloride and aluminium-

klorid med den empiriske formel TiCl^ /TQCl^. Denne type'skal her omtales som ERA TiCl^. chloride with the empirical formula TiCl^ /TQCl^. This type shall be referred to here as ERA TiCl^.

Under utforelsen av polymeriseringer i henhold til foreliggende During the performance of polymerizations according to the present

oppfinnelse blir katalysatoren i alminnelighet opplost eller ! suspendert 1 et inert hydrokarbonopplosningsmiddel, f.eks. hek- invention, the catalyst is generally dissolved or ! suspended in an inert hydrocarbon solvent, e.g. hook-

: san, heptan eller oktan eller blandinger av disse i et egnet reaksjonskar i fravær av -oksygen og fuktighet. Oppldsningsmidl— : san, heptane or octane or mixtures of these in a suitable reaction vessel in the absence of -oxygen and moisture. Solvents—

et med katalysatoren blir så i alminnelighet bragt til en tem- with the catalyst is then generally brought to a temperature

peratur i området 25 - 15o°C, fortrinnsvis 6p - 8o°C og det olefin som skal polymeriseres fores inn i reaksjonkaret. Når I olefinet er en væske ved reaksjontemperaturen, f.eks. 4-metyl-• penten-1, kan atmosfæretrykk brukes, men når olefinet normalt er gassformet, f.eks. propylen eller buten-1 blir det fortrinns- temperature in the range 25 - 15o°C, preferably 6p - 8o°C and the olefin to be polymerized is fed into the reaction vessel. When the olefin is a liquid at the reaction temperature, e.g. 4-methyl-•pentene-1, atmospheric pressure can be used, but when the olefin is normally gaseous, e.g. propylene or butene-1 will be preferred

vis brukt moderat overtrykk, f.eks. fra ca. 1,5 kg/cm p til 35 show used moderate overpressure, e.g. from approx. 1.5 kg/cm p to 35

kg/cm • 2 for å oke den mengde olefin som er opplost i opplbsnings- kg/cm • 2 to increase the amount of olefin dissolved in the solvent

: midlet og derved påskynde reaksjonen..... i i Aluminium- be standdelen i katalysatoren i henhold til oppfinnel- . ; : the agent and thereby speed up the reaction..... in the Aluminum component in the catalyst according to the invention. ;

sen kan væjre hvilket som helst alkyl-aluminium-dihalogenid, f. it can be any alkyl aluminum dihalide, e.g.

i eks. etyl-aluminium-diklorid, propyl-aluminlum-diklorid, butyl-aluminium- liklorid eller de tilsvarende brom- eller jod-analoger, in ex. ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum lichloride or the corresponding bromine or iodine analogues,

eller seaqaihalogenider f.eks. aluminium-etyl-sesquiklorid eller propyl-sesiuiklorid samt alkyl-aluminium-dihalogenider ellar or seaqai halides e.g. aluminum ethyl sesquichloride or propyl sesquichloride as well as alkyl aluminum dihalides or

-sesquihalDgenider, hvor alkylradikalene inneholder storre an,- -sesquihalogenides, where the alkyl radicals contain larger an,-

tall karbonatomer enn de som er angitt ovenfor. Silan-bestand- number of carbon atoms than those indicated above. Silane Stock

I delen i katalysatoren kan være hvilket som helst alkoksysilan In the part in the catalyst can be any alkoxysilane

! med formelen R^Si hvor minst en, Rer aljkoksy og de ovrige R-er j j hvis det er noen, er hydrokarbonradikajler, f.eks. trimetyl- j etoksysilan, dletyldietoksysllan, tetrlametoksysilan, etylortosi- ; ! with the formula R^Si where at least one, Rer alkyloxy and the other R's j j if there are any, are hydrocarbon radicals, e.g. trimethyl-j ethoxysilane, dletyldiethoxysilane, tetramethoxysilane, ethylorthoxy-;

I likat, eli<t>er trifenyletoksysilan. Molelkyiforholdet mellom alkyl-I aruminivmc|ihalogenid "eller -sesqaifeaicigeriid og titantriklorid i i katalysatoren må være fra o.21 :1 til lo:l x>g er fortrinnsvis | fra 1:1 til k:l. Atomforholdet mellom aluminii silan- j i oksygen, når det brukes et silan med bare ett t to oksygen- ! 1 atomer må ikke være mindre enn y<<:>h da polymeriseringen da er i ganske langsom og heller ikke må forholdet være over ca. 5:1. i In licate, eli<t>er triphenylethoxysilane. The molecular ratio between alkyl-I aluminivmc|ihalide "or -sesqaifeaicigeriide and titanium trichloride in the catalyst must be from o.21 :1 to lo:l x>g is | preferably | from 1:1 to k:l. The atomic ratio between aluminii silane- j i oxygen, when a silane with only one t two oxygen atoms is used, !1 must not be less than y<<:>h as the polymerization is then quite slow and the ratio must not be above about 5:1 either.

Et praktisk arbeidsforhold ligger 1 området mel"" ->m $ :k og ca. I I3:1-A practical working relationship lies in the 1 area mel"" ->m $ :k and approx. I I3:1-

Når det brukes et silan med mere enn to oksygen-atomer ef dét When a silane with more than two oxygen atoms is used ef that

optimale forhold mellom aluminium og oksygen noe annet. Det viser seg at oksygen i overskudd på to ikke lett koordinerer med alkyl-aluminium-halogenidet og kan betraktes som ikke aktivt!. optimum ratio between aluminum and oxygen something else. It turns out that oxygen in excess of two does not easily coordinate with the alkyl aluminum halide and can be considered not active!.

Oppfinnelsen skal nærmere beskrives under henvisning til en rek-; ke eksempler.. The invention shall be described in more detail with reference to a reference; ke examples..

Eksempel I En polymer-flaske bir fylt med 5o ml heptan, 1,72 ml l,o5M Example I A polymer bottle was filled with 50 ml of heptane, 1.72 ml of 1.05M

heptanoppldsning av etylaluminiumdiklorid og o,l6 g trimetyletoksysilan. Flasken ble så lukket og rort i et bad med 72°C heptane solution of ethyl aluminum dichloride and 0.16 g of trimethylethoxysilane. The bottle was then closed and stirred in a bath at 72°C

i 3o minutter. Flasken ble så avkjolt og åpnet og0.126 g'X-titantriklorid ble tilsatt. Atomforholdet mellom aluminium og titan og silanoksygen var 2,o:l,o:l,J. Flasken ble så igjen lukket, satt tilbake i badet med 72°C og katalysatoren ble aldret i lo minutter. Flasken ble så satt under trykk med propylen til o,28 kg/cm^ og dette trykk ble opprettholdt i h timer under roring av innholdet i flasken. Katalysatoraktiviteten ble så stanset ved tilsetning av lo ml metanol og 5°nil heptan. Polymeret ble oppsamlet på et sintret glassrbr og vasket etter tur med loo ml heptan, loo ml isopropanol, og loo ml metanol. Det ble så tbrket i en vakuumoven natten over ved 6o°C..Det faste polypropylen som ble oppnådd vejce 17, '- j g. Resten fra fordampning av de samlede heptan-opplb^ninger veide l,o g. for 3o minutes. The flask was then cooled and opened and 0.126 g of X-titanium trichloride was added. The atomic ratio of aluminum to titanium and silane oxygen was 2.0:1.0:1.J. The bottle was then recapped, returned to the 72°C bath and the catalyst was aged for 10 minutes. The bottle was then pressurized with propylene to 0.28 kg/cm 2 and this pressure was maintained for h hours while stirring the contents of the bottle. The catalyst activity was then stopped by the addition of 10 ml methanol and 50 nil heptane. The polymer was collected on a sintered glass tube and washed in turn with 10 ml of heptane, 10 ml of isopropanol, and 10 ml of methanol. It was then dried in a vacuum oven overnight at 6o°C. The solid polypropylene which was obtained weighed 17.0 g. The residue from evaporation of the combined heptane solutions weighed 1.0 g.

Eksempel II Example II

eksempel I ble gjentatt bortsett fra at o,'ll g irimetyl-etoksysilan ble brukt i stedet for o,l6 g. Utbyttet av fa si polymer var 11,6 g. Rer var atomforholdet Al:Ti;0 ?,0:1,0:i:0. Example I was repeated except that 0.11 g of irimethylethoxysilane was used instead of 0.16 g. The yield of phase polymer was 11.6 g. 0:in:0.

Eksempel III Example III

I Eksempel LL ble gjentatt bortsett fra at 13,2 g ^-metyl-penten-1 In Example LL was repeated except that 13.2 g of β-methyl-pentene-1

ble satt inn i stedet for propylen. Forholdet Al:Ti:0 var 2,o: was inserted in place of propylene. The ratio Al:Ti:0 was 2.o:

1, o;ljo. Det ble oppnådd 5»1 g fast polyC^-metylpenten-l) og 1, o;ljo. 5.1 g of solid polyC3-methylpentene-1) and

• 3,1 g pentanopploselig polymer. • 3.1 g of pentane-soluble polymer.

I Eksempel IV In Example IV

I0.36 ml 2,52M etyl-aluminium-sesquiklorid ble forbehandlet i en trykkflaske i et bad med 72°C i 30minutter med0^053g trimetyletoksysilan 1 ?o ml heptan og0,07g X-titan-triklorid ble tilsatt. Forholdet Al:Ti:0 var 2,o:l,o:l,o. Flasken ble så 10.36 ml of 2.52 M ethyl aluminum sesquichloride was pretreated in a pressure bottle in a bath at 72°C for 30 minutes with 0.053 g of trimethylethoxysilane, 1.0 ml of heptane and 0.07 g of X-titanium trichloride was added. The Al:Ti:0 ratio was 2.0:1.0:1.0. The bottle was so

1 1 satt under trykk på 2,8 kg/cm 2 propyeln og polymeriseringen ble . 1 1 was put under pressure of 2.8 kg/cm 2 propylene and the polymerization was .

i utfort i h timer ved 72°C. Det resulterende torre hvite pulver- in continuous for h hours at 72°C. The resulting dry white powder

I formede polymer velde lo,6 g. Resten fra fordampning av den I samlede heptanopplosning veide0,8 g. In shaped polymer welde weighed 0.6 g. The residue from evaporation of the combined heptane solution weighed 0.8 g.

i Eksempel V in Example V

i En polymer-flaske ble fylt med lo ml heptan, 1,8 ml o,98M i A polymer bottle was filled with 10 ml heptane, 1.8 ml o.98M

I EtAlGl2i heptan, o,oW65'g etylsilikat ((EtCO^Si) og ror.t ved 72°C i 30minutter. Flasken ble fylt med ekstra ^o ml heptan og en paraffin-pellet som inneholdt0,0636X-titan-triklorid for ; å skaffe en katalysator hvor molrforholdet mellom EtAlCl2og In EtAlGl2i heptane, o.oW65'g ethyl silicate ((EtCO^Si) and stirred at 72°C for 30 minutes. The flask was filled with additional ^o ml of heptane and a paraffin pellet containing 0.0636X titanium trichloride for to obtain a catalyst where the molar ratio between EtAlCl2 and

TiCl, og etylsilikat var<l>f:l:o,5- Etter aldring i lo minutter TiCl, and ethyl silicate were<l>f:l:o.5- After aging for lo minutes

3 .2 3 .2

ble vellingen satt under trykk pa 2,8kg/cm propylen og flaske-innholdet ble holdt ved 72°C i •+ timer under roring.. Det ikke reagerte propylen ble så trukket ut og den avkjblte velling ble fortynnet med lo ml metanol og loo ml heptan. Polymeret ble oppsamlet på et sintret glassrbr, vasket etter tur med loo ml por- the slurry was pressurized to 2.8 kg/cm propylene and the contents of the flask were kept at 72°C for •+ hours with stirring. The unreacted propylene was then drawn off and the cooled slurry was diluted with 10 ml methanol and 100 ml ml of heptane. The polymer was collected on a sintered glass tube, washed in turn with 10 ml por-

sjoner heptan, isopropanol og metanol og tbrket i en vakuumovn natten over ved 6o°C. Utbyttet av fast krystallinsk polypropy- heptane, isopropanol and methanol and dried in a vacuum oven overnight at 6o°C. The yield of solid crystalline polypropylene

len var0.7 g. Resten frs fordampning av de samlede heptanopp-losninger veide0.3 g. len was 0.7 g. The residue after evaporation of the combined heptane solutions weighed 0.3 g.

eksempel VI example VI

Fremgangsmåten i ekr-empel 7 ble gjentatt, bortsett fra at0,928 The procedure in Example 7 was repeated, except at0.928

g etyl r. i li kat ble i^ukt for n gj r«ol-f orhol mellom Et, Al Cl 0 g ethyl r. in li cat was i^ukt for n gj r«ol-f orhol between Et, Al Cl 0

og i'i Ci^ og etyl:/' -...t pd'-i:L:l. Utbyttet av fast polyj.ro- and i'i Ci^ and ethyl:/' -...t pd'-i:L:l. The yield of solid polyj.ro-

pyleu var 6, 2 iU pyleu was 6.2 iU

L.-k:j empel VII L.-k:j empel VII

Fremgangsmåte:'i eksempel V ble gjentatt, bort.seit fra cl 0,139 Procedure: in example V was repeated, except from cl 0.139

g etylsilikat Mt brukt for å gi et mol-forhold mellom :]t/UCl? g ethyl silicate Mt used to give a molar ratio of :]t/UCl?

og TiCl-j°g etylsilikat på l+:l:l,5. Utbyttet av fast heptan-uoppldselig polypropylen var 13,0g. and TiCl-j°g ethyl silicate of l+:l:l.5. The yield of solid heptane-insoluble polypropylene was 13.0g.

Eksempel VIII Example VIII

Fremgangsmåten i eksempel V ble fulgt, bortsett fra at0,186 g etylsilikat ble brukt. Mol-forholdet mellom.EtAlGl^ig TiCl^og etylsilikat var k:l:2 og utbyttet av fast polypropylen var 7,8 g. The procedure of Example V was followed, except that 0.186 g of ethyl silicate was used. The molar ratio between EtAlGl2 and TiCl2 and ethyl silicate was k:1:2 and the yield of solid polypropylene was 7.8 g.

Eksempel IX Example IX

Fremgangsmåten i eksempel V ble fulgt, bortsett fra at o,232.g The procedure in Example V was followed, except that o.232.g

etylsilikat blir brukt. Mol-forholdet mellom EtAlCl2og TiCl^ethyl silicate is used. The molar ratio between EtAlCl2 and TiCl^

og etylsilikat var ^:1:2,5 og utbyttet av fast polypropylen var , 3,o g. and ethyl silicate was ^:1:2.5 and the yield of solid polypropylene was , 3.o g.

Eksempel X Example X

Fremgangsmåten i eksempel V ble gjentatt, bortsett fra at 1, h ml. o,97M ÉtAlCl2og o,lolf g etylsilikat ble brukt for å gi et mol-"' forhold mellom EtAlCl2og TiCl^og etylsilikat på 3:1:1,1. Utbyttet av fast polypropylen var 8,1 g. The procedure in Example V was repeated, except that 1, h ml. 0.97 M EtAlCl 2 and 0.10lf g ethyl silicate were used to give a molar ratio of EtAlCl 2 to TiCl 2 and ethyl silicate of 3:1:1.1. The yield of solid polypropylene was 8.1 g.

Eksempel XI Example XI

Fremgangsmåten i eksempel V ble fulgt, idet l,o2 g metylsilikat ble sått inn i stedet for etylsilikat. Molforholdet mellom i EtAlCl2og TiCl^og metylsilikat var if:l:l,5. 7-3 heptan-uopploselig polypropylen ble oppnådd. The procedure in Example V was followed, with 1.02 g of methyl silicate being added instead of ethyl silicate. The molar ratio between EtAlCl2 and TiCl2 and methyl silicate was 1:1:1.5. 7-3 heptane-insoluble polypropylene was obtained.

Eksempel XII Example XII

Fremgangsmåten i eksempel V ble fulgt idet0,0993g dlmetyldi-etoksysilan ble satt inn i stedet for etylsilikat. Mol-forholcleS mellom EtAlCl2og TiCl-j°S silan var<l>f:l:l,5-Utbyttet av ; heptan-uopplbselig polypropylen var 6,7 g«i Eksempel XIII : Fremgangsmåten i eksempel V. ble fulgt, idet o,122 g netyltrie- j i toksysilan ble satt isetedet for ety], silikatet. Mol-f orholdet The procedure in Example V was followed in that 0.0993 g of dlmethyldiethoxysilane was inserted in place of ethyl silicate. Mol-forholcleS between EtAlCl2 and TiCl-j°S silane was<l>f:l:l,5-The yield of ; heptane-insoluble polypropylene was 6.7 g in Example XIII: The procedure in Example V was followed, with 0.122 g of netyltriene in toxysilane being added to the ethoxylate, the silicate. The molar ratio

! mellom StAlCl2og TiCl^c)g silan var Utbyt;et av heptan-uopplbselig polypropylen var 8,9 g. i ! between StAlCl2 and TiCl^c)g silane was The yield of heptane-insoluble polypropylene was 8.9 g. in

j EHsempei XIV i Fremgangsmåten i eksempel V ble gjentatt, idet0,<1>+ g trifenyletoksysilan ble satt inn i stedet for etylsilikat. llol-forhold-j et mellom EtAlCl2og TiCl^ og silan var i+: 1:3 . ^,6 heptan- j EHsempei XIV i The procedure in Example V was repeated, with 0.<1>+ g of triphenylethoxysilane being inserted instead of ethyl silicate. llol ratio-j et between EtAlCl2 and TiCl^ and silane was i+: 1:3 . ^.6 heptane-

uoppløselig polypropylen,ble oppnådd. i insoluble polypropylene, was obtained. in

Eksempel XV Example XV

En polymer-flaske ble fylt med lo ml heptan, 1,<1>+3 ml o,95<*>+- etyl-aluminiumsesquiklorid i heptan og o,o539 g etylsilikat og rdrt ved 25° C i 3o minutter. Flasken ble fylt med ytterligere l+o ml heptan og0,063 g X TiCl . Etter aldring i lo minutter ved 72°C A polymer bottle was filled with 10 ml of heptane, 1.<1>+3 ml of o.95<*>+- ethyl aluminum sesquichloride in heptane and o.o539 g of ethyl silicate and rotated at 25° C. for 30 minutes. The flask was charged with an additional 1+0 ml of heptane and 0.063 g of X TiCl . After aging for 10 minutes at 72°C

3 p 3 p.m

ble flasken satt under propylentrykk på 2,8 kg/cm og polymeriseringen ble utfort i k timer. Trykket ble så avlastet og poly-propylenet ble gjenvunnet slik som beskrevet i eksempel V. Utbyttet var m,3 g heptan-uoppldselig polymer. the bottle was placed under a propylene pressure of 2.8 kg/cm and the polymerization was carried out for k hours. The pressure was then relieved and the polypropylene was recovered as described in Example V. The yield was m.3 g of heptane-insoluble polymer.

Eksempel XVI Example XVI

En lagervelling av ER TiCl^ble fremstillet ved å fylle 8,5 ml heptan og 8,5 ml 9,68M etyl-aluminium-diklorid i en trykkflaske som inneholdt en teflonbelagt magnetisk rbrer. Flasken ble lukket med en kronekork som inneholdt en neoprenforing og anbragt i et bad ved lo°C. I opplbsningen ble det fort inn ^,6 A stock slurry of ER TiCl2 was prepared by filling 8.5 mL of heptane and 8.5 mL of 9.68 M ethyl aluminum dichloride into a pressure bottle containing a Teflon-coated magnetic probe. The bottle was closed with a crown cap containing a neoprene liner and placed in a bath at 10°C. In the opening, it quickly became ^.6

ml 9,o511 TiCl^. Etter ca. 5 minutter begynte det å danne seg et rbdt bunnfall av TiCl^.AlCl^. Flasken ble fjernet fra bedet etter ytterligere 5 minutter og rbrt ved romtemperatur i en time. Den ble så anbragt i et bad med loo°C i 16 timer. Etter '• '••lingen ble vellingen fortynnet med heptan slik at en 2 ml a..>.i;]uel ville inneholde et millimol TiCl^.AlCl^og et millimol ikke reagert etylaluminiumdiklorid. ml 9.0511 TiCl^. After approx. 5 minutes, a rbdt precipitate of TiCl^.AlCl^ began to form. The flask was removed from the bed after another 5 minutes and stirred at room temperature for one hour. It was then placed in a bath at 10°C for 16 hours. After the mixing, the slurry was diluted with heptane so that a 2 ml a..>.i;]uel would contain one millimole of TiCl^.AlCl^ and one millimole of unreacted ethyl aluminum dichloride.

\- m aliquot ,v denne velling ble så anbragt i en trykkflaske sann-en med Io ml heksan og0,357 millimol etylsilikat. Vellingen ble aldret under rbring i 3°minutter ved /2°C i h timer. A m aliquot of this slurry was then placed in a pressure bottle filled with 10 ml of hexane and 0.357 millimoles of ethyl silicate. The curd was aged under stirring for 3 minutes at 2°C for 1 hour.

Vei. enden av denne tid ble produktet opparbeidet slik som be-sirevet ovenfor, lo,35 g heksan-uopplbselig polypropylen ble oppnåad. Road. at the end of this time, the product was worked up as described above, so that 35 g of hexane-insoluble polypropylene was obtained.

hksempol XVII hksempol XVII

/ikr--;* : XVI ule 1" n'. « <■. j(;r.! et millimol ! r' -■. ■. ■tyl et ok sysilan i: i " r;i-tt i stedet - f -. ■..lyisili.kat. lo,25 g hek san-uopplbselig polypropylen ble op-id. /ikr--;* : XVI ule 1" n'. « <■. j(;r.! a millimole ! r' -■. ■. ■tyl et ok sysilan i: i " r;i-tt instead - f -. ■..lyisili.cat. lo,25 g hek san-insoluble polypropylene was op-id.

.. ksempel XVIII .. example XVIII

d.;> per-:-.jon •..•• • roue bunnfall som ble dannet ved reaksjonen mel i on. TiC.'L- tyialunini umdiklorid ble gjenvunnet fra vellingen ved filtrering under en nitrogenatmosfære, opparbeidet flere ganger med heksan for å fjerne ikke reagert etylaluminiumdi- d.;> per-:-.ion •..•• • roue precipitate which was formed by the reaction mel in on. TiC.'L- tyialunini um dichloride was recovered from the slurry by filtration under a nitrogen atmosphere, worked up several times with hexane to remove unreacted ethyl aluminum di-

klorid og så tbrket natten over. Det tbrré pulver ble så kule-j malt i 66 timer med keramiske kuler for å gi et ERA titantri- j { I klorid. o,l* millimol av dette material ble suspendert i loo ml !' i I heksan i en trykkflaske sammen med tilstrekkelig etylaluminium-j diklorid og dimetyldietoksysilan til å gi et mol-forhold mellom ! I etylaluminiumdlklorld og ERA titantriklorid og dimetyletoksysi- ! | lan på i*:l:l,5. Flasken ble så satt under propylentrykk på lf,8 i i i p o ' kg/cm og polymeriseringen ble utfort ved 72 C i k timer. Etter! opparbeidelse av reaksjonsproduktene ble det oppnådd 5>35g heksan-uopplbselig polypropylen. Ved kontrollforsbk med samme ! i katalysatornivå brukt på ikke malt pulver (ER TiCl^) og AA TiCl^ j ble det oppnådd hehv. 3,2o pg 3>85 g heksan-uopplbselig poly- IIpropylen. I i ■ ' i I de foregående eksempler ble forsbkene utfort med glassutstyr ' ' ." ■ •0'i som begrenset, arbeidstrykket til 2,8 kg/cm , noe som ligger | godt underdet trykk som ville bli anvendt i industrielle anlegg.; i En ytterligere rekke forsbk ble derfor gjort med trykkutstyr i i i stor laboratoriemålestokkjunder vanlig industrielle arbeidsfor- i chloride and then dried overnight. The tbrre powder was then ball-j ground for 66 hours with ceramic balls to give an ERA titanium tri-j { I chloride. o,l* millimoles of this material was suspended in loo ml !' i I hexane in a pressure bottle together with sufficient ethylaluminum-j dichloride and dimethyldiethoxysilane to give a molar ratio of ! In ethyl aluminum dlchlorld and ERA titanium trichloride and dimethylethoxy- ! | lan on i*:l:l,5. The bottle was then placed under a propylene pressure of 1,8 kg/cm and the polymerization was carried out at 72°C for k hours. After! processing of the reaction products, 5>35 g of hexane-insoluble polypropylene were obtained. In the case of control tests with the same ! in catalyst level used on unground powder (ER TiCl^) and AA TiCl^ j it was obtained respectively. 3.2o pg 3>85 g hexane-insoluble polypropylene. In i ■ ' i In the previous examples, the tests were carried out with glass equipment ' ' ." ■ •0'i as limited, the working pressure to 2.8 kg/cm , which is | well below the pressure that would be used in industrial plants.; i A further series of experiments was therefore carried out with pressure equipment in a large laboratory scale and ordinary industrial working conditions.

hold for temperatur og trykk for å bestemme om det kunne oppnås i industrielle utbytter med disse katalysatorer. Industrielle j , ! utbytter blir uttrykt i kg polymer frembragt pr. liter opplbs- \ ningsmiddel pr. time og for å betraktes som industriell verdi-! full må en katalysator frembringe minst0,03kg polymer pr. li- j hold for temperature and pressure to determine if it could be achieved in industrial yields with these catalysts. Industrial j , ! yields are expressed in kg of polymer produced per liters of solvent per hour and to be considered industrial value-! full, a catalyst must produce at least 0.03 kg of polymer per li-j

■ter pr. time når det arbeides med et titantriklorid-nivå i nær- j ' i : 1 ■ter per hour when working with a titanium trichloride level in the vicinity of j ' i : 1

I heten av o,l g pr. loo ml opplbsningsmiddel og fortrinnsvis merei I enn 0,05 kg. Ved lavere mengder er enten kapitalinvesteringen In the heat of o,l g per loo ml of solvent and preferably more than 0.05 kg. At lower amounts, either the capital investment is

pr. kg produkt så stor at arbeidet ikke er av industriell inter-<:>, '• esse eller det må brukes alt .for store mengder katalysator. Re-. per kg of product so large that the work is not of industrial interest, or excessive amounts of catalyst must be used. Re-.

sultater av disse ytterligere forsbk er gitt i fblgende tabell. results of these further trials are given in the following table.

, I denne tabell henviser ER(S)TiCl^til den velling som ble opp- , In this table, ER(S)TiCl^ refers to the slurry that was

nådd ved å reagere etylaluminiumdiklorid med titantetraklorid i et mol-forhold på 2:1 og ERA TiCl^henviser til ER TiCly .gom er skilt ut fra vellingen, tbrket,-og aktivert ved maling,i en Schutz-O' Neill vibrerings-kulemblle .i en tid på 2 timer. TES reached by reacting ethylaluminum dichloride with titanium tetrachloride in a molar ratio of 2:1 and ERA TiCl^refers to ER TiCly .gom is separated from the slurry, tbrked,-and activated by grinding, in a Schutz-O' Neill vibrating ball mill .in a time of 2 hours. TEST

betyr trimetyletoksysilan og ES betyr etylortosilikat• /time/ liter angir mengden av polymer uopplbselig i kokende pentan, frembragt pr. time av reaksjontiden yv. liter opplbsningsmiddel. means trimethylethoxysilane and ES means ethyl orthosilicate • /hour/ liter indicates the amount of polymer insoluble in boiling pentane, produced per hour of the reaction time yv. liter of solvent.

Katalysator-forhol-et er mol-forholi et mellom ikke reagert etyl-aluminium;.. i kloriu og ti tan triklori^ og sili. sium-forbind el se. Katalysatornivaet er gram titantriklorid pr. loo ml o<p>pldsnings-miduel basert pfi den samlede vekt av titan-triklorid-aluminiumklorid-masse som ble brukt, og Ikke vekten av titantriklorid-komponenten i. massen. The catalyst ratio is molar ratio between unreacted ethyl aluminum;... in chloride and titanium trichlori^ and silicon. sium-connect el se. The catalyst level is grams of titanium trichloride per loo ml of processing medium based on the total weight of titanium trichloride aluminum chloride mass used, and not the weight of the titanium trichloride component in the mass.

Den fremgangsmåte som ble brukt var a fylle en autoklav meu et volum p;':. h , 5 liter og omrUrer mod 5oo ml heksan og oppvarme den til 72°.., under ni trogen trykk. Katalysatoren ble r. A tilsatt og vasket inn roen ytterligere 2oo rui heksan og det saml ed9 innhold i autoklaven ble bragt opp til 72°. under avtrekk av nitrogen til0,035kg/cm<*>". I alle fall unntagen forsak I hvor det ikke ble brukt hydrogen, ble 22 vektueler hydrogen pr. million reg-net på-heksanet satt under trykk i reaktoren. Autoklaven ble så satt under trykk med propylen ti.l det angitte trykk og polymeriseringen ble utfort i en tid som var lang nok til' .r> for-bruke 300ml propylen i tillogg til den mengde som trengtes for opprinnelig a sette reaktoren under trykk. Reaksjonen ble sa' stanset ved tilsetning av 600ml metanol og reaksjonsproduktene ble opparbeidet for å gjenvinne det pentan-uopplobuLLge polypropylen som var dannet vevi reaksjonen. The method used was to fill an autoclave with a volume p;':. h , 5 liters and stir against 5oo ml of hexane and heat it to 72°.., under nine true pressure. The catalyst was then added and a further 200 ml of hexane was washed in, and the total contents of the autoclave were brought up to 72°. under extraction of nitrogen to 0.035 kg/cm<*>". In all cases, except for case I where no hydrogen was used, 22 vectuelles of hydrogen per million calculated on the hexane were pressurized in the reactor. The autoclave was then set under pressure with propylene to the indicated pressure and the polymerization was carried out for a time long enough to consume 300 ml of propylene in addition to the amount needed to initially pressurize the reactor. The reaction was stopped by the addition of 600 ml of methanol and the reaction products were worked up to recover the pentane-insoluble polypropylene which had been formed by the reaction.

Claims

Process for the polymerization of 1-alkenes with 3-8 carbon atoms, preferably propylene, according to patent no. 107,614, for the production of solid crystalline polymers, in the presence of a catalyst which is formed by mixing in an inert hydrocarbon solvent aluminum alkyl- dihalides or aluminum

alkylsesquihalides with an activated titanium trichloride and an alkoxysilane of the general formula R-^F^RgR^Si in which R-^ is an alkoxy radical and R2»R3 and R^ are alkoxy radicals and/or hydrocarbon radicals, and where the molar ratio between alkylaluminum compound and titanium trichloride is from 0.2:1 to 10:1 and the molar ratio between the alkyl aluminum compounds and active silane oxygen is from 5:4 to 5:1, characterized by the use of a titanium trichloride produced by 1) ball or stick grinding of crystalline titanium trichloride which is co-crystallized with aluminum chloride and of the empirical formula STiClg-AlClg which is prepared by reducing titanium tetrachloride with aluminum until, as determined by X-ray diffraction, it has less than 30% of the original crystal structure of the spherical or rod crystalline titanium trichloride -the paint, or by 2) precipitation of a co-crystalline compound of titanium trichloride and aluminum chloride with the empirical formula TiCl^.AlCl^ obtained by reaction a v titanium tetrachloride with an alkyl aluminum dichloride, or by 3) activation of the TiCl^-AlCl^ mentioned under 2) using the method mentioned under 1).