CA1219998A - Process for preparing polyolefins - Google Patents
Process for preparing polyolefinsInfo
- Publication number
- CA1219998A CA1219998A CA000442532A CA442532A CA1219998A CA 1219998 A CA1219998 A CA 1219998A CA 000442532 A CA000442532 A CA 000442532A CA 442532 A CA442532 A CA 442532A CA 1219998 A CA1219998 A CA 1219998A
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- CA
- Canada
- Prior art keywords
- component
- compound
- titanium
- vanadium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
Abstract
ABSTRACT
Olefin is polymerized using a catalyst which comprises the combination of:
[I] a solid substance obtained by the reaction of at least the following two components:
(i) a magnesium halide and (ii) a titanium compound and/or a vanadium compound;
[II] a compound represented by the general formula R1mSi(OR2)4-m wherein R1 and R2 are hydrocarbon radicals having 1 to 24 carbon atoms and 0 ? m ? 3;
[III] a compound represented by the general formula R3nAl(OR4)3-n wherein R3 and R4 are hydrocarbon radicals having 1 to 24 carbon atoms and 1 ? n ? 2; and [IV] an organometallic compound, the molar ratio of silicon in said component [II] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 100, the molar ratio of aluminum in said component III to silicon in said component being in the range of 0.01 to 10 and the molar ratio of the metal in said component [IV] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 1,000.
Olefin is polymerized using a catalyst which comprises the combination of:
[I] a solid substance obtained by the reaction of at least the following two components:
(i) a magnesium halide and (ii) a titanium compound and/or a vanadium compound;
[II] a compound represented by the general formula R1mSi(OR2)4-m wherein R1 and R2 are hydrocarbon radicals having 1 to 24 carbon atoms and 0 ? m ? 3;
[III] a compound represented by the general formula R3nAl(OR4)3-n wherein R3 and R4 are hydrocarbon radicals having 1 to 24 carbon atoms and 1 ? n ? 2; and [IV] an organometallic compound, the molar ratio of silicon in said component [II] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 100, the molar ratio of aluminum in said component III to silicon in said component being in the range of 0.01 to 10 and the molar ratio of the metal in said component [IV] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 1,000.
Description
PROCI~SS FOR P~PARING POLYOLEF'INS
~CKG~OUND OF '~ INV~NTION
The present invention relates to a process fo= preparing polyole:~ins using a nove.1 po]ymeri.zation 5 catalyst.
Ileretofore, in tl1e technical field of lhis sort ~ re llas been Icl1owll :EroM Japanese ~atent licatiol1 No.121()5/1964 a catalyst comprisin~ a Iml~Jlles;illln lla:lide ~nd a tral1sitiol1 metal coln~)ound such 1() as a tita~ m conl~oul1c1 supported thereon. Further, a catcll.yst obta.il1ed by the co-pulverization o:E a ma~llesillm l1alide and titanium tetrachloride is known ~rom RelcJian Patent No,742,112.
~lowever, when viewed from the standpoin-t that the catalyst activity is clesired to be as high as possible in the manufacture of polyolefins, the process disclosed in the Japanese Patent Publication No.12105/1964 is stil~ unsatisEactory beca~lse of a low polymerization activity, while the polymerization activity attail1ed in the process oE Belgian Patent 742,112 is fairly hial1, but a further improvement is c1esired.
ln the process disclosed in German Patent No.2137872, the anloul1t o~ a magnesium halide used 2r~ is su~stal1ti.al~y decreased by the co-pulverizat:ion _ thereof with titanium tetraehloride and alumina, but a remarkable i.nerease in aeti.vity per solid, whieh can b~ reeoynized as a (3uideline or produetivity, is not reeoynized, ancl it is desired to develop a catalyst of a h.igl1er acti.vity~
In the manuEacture of polyo1efins, moreover, it .is a1so des:i.rable from -the aspeets o~ productivity ant1 sl~lrry hclndlillc3 that tt-~e bulk dens:ity of the r.es~llt:i.l1cl po].ylTIer be as hi~h as possible. F'rom this I() sLalldL)o.i.nt, the l~rocess d.iselosed in the Japanese t~ltel1t P~lblieat:i.on No.12105/1964 is no-t satisfaetory :in loth the bul)c dens.ity of the resulting polymer al1d polymerization activi-ty, while in the proeess diselosed in the Belgian Patent 742,112, -the polymeri-~5 zation activi-ty is hic3h, but the bulk density of the resulting polymer is low. Thus, in both -the proeesses, a further improvement is desired.
SUMMI~RY OF TIIE: INVl~:NTION
It .is tl~e object oE the present invention to ~)rovide a nove.1 polymeriza-tion eata]yst and a proeess for the holllopot.ymerization or copolymerizatio o~ olefiT1s usin~3 the catalyst, eapable of remedying the above~ el1tiolled drawbaeks, attainin~ a high po.lylllerizati.on activity, affordinc3 polymers wi-th a hiclh bul)c density in higt1 yield and prac-ticing a eontinuous polymeriza-tion extremely easily.
The present inven-tion resides in a process Eor preparing ~olyoleEins by the ho3l10polymerization or copolymerization oE oleEins using a eatalyst whieh comprises the combi31atio1l of:
[I~ a solid substance obtained by the reaction oE at least the Eollowing two co1npo1lents:
(i) a ma(11lesium halide and (ii) a tita~ n compound and/or a vanadil1m 1() con1poln~d;
~II] a compoulld represented by the general formula R~ 5i(0l~2)4 1~ wl1erein R1 and 1~2 are hydrocarbon radicals havinc~ 1 to 24 carton atoms and O ~- m ~ 3;
[III~ a eompound represented by the general formula R3n~l(0R4)3_n wherein R3 and R4 are hydrocarbon radicals havinc~ 1 to 24 carbon atoms and 1 C- n < 2; and [IV3 an organo1netall3c compound, and which catalyst satisfies the cond:it:ions that the mola3- ratio o~ s:i1:icon in tl-1e compo1le11t [II] to titanium ancl/or va11ad:ium in tl-1e component LI~ s1~ould be in the range of 0.1 to 100, the molar ra-tio of aluminum in the compo1le1lt lI:1I~ to silicon in the con1por1ent LII~ sllo-1ld be in the range of 0.01 to 10 and the molar ratio oE t11e n1elal in the componen-t [IV~ to tltanium and/or vanadium in the componen-t ~I~ should be :in the rancle of 0.1 to 1000.
Sir1ce the polymerization catalyst used in the present invention exhibits a very hlgh polymeriza-tion activity, the partial pressure of monomer duringpolymerizatio11 is ~.ow, and because of a hic3h bulk density o.~ the result:i11c3 polymer, the productivity cal-l be :iln~rovecl. Moreover, -the amount of -the catalyst ~ lla~ .ill(J i.n tl1e l^es~ltinc3 polymer a~ter polyme:rization 1() is so sll1al.l thclt the polyole.Ein manu:Eacturing process can d:ispense w:ith the catalyst removing s-tep, which leac1s to silnp].lfication of the polymer trea-ting s-tep, and consequently polyolefins can be prepared very economically.
~ccording to the process of the present invention, the amount of polymer procluced per unit polymerization reactor is large because of a high bulk density of -the resulting polymer.
The present invention is Eurther advantage-_() ol1s in t.hat wl1en viewed from the stancdpoi.nt of particlesi~e of the resLl1tinq polymer, the propor-tion Or coarse par-t:ic1.es ancl that of fine particles below 50 ~Im are small desp:ite oF a high bullc density of the polymer, a~ hat the1~efore not on].y it becomes easy to perfol-ln a Co~ti.lluo~s polymer:i.zation re~ction but also the centriEuclal separati.on i.n the polymer treating step as well as the handling of polymer pa.r-ticles in powder transport become easy.
~ ccorcling -to the present i.nven-ti.on, in addit:ion to the high bulk densi-ty of polyolefins obtained by usin~ the catalyst of the lnvention as previously noted, polyolefins havina a desired melt illdeX can be prepal-ed at a lower hydroqen concentra-tion thall in convelltiollal me-thods, thus permitt,ing E-o.l.ylne.L-.ization to be carried out a-t a relatively ln slllall total pressure, and th.is ~reatly cont:ributes to the .imp.roveme1lt oE ecollomy and productivity.
~ dditi.onally, in -the oleEin pol.ymerlza-tion using -the catalys-t oE -the present invention, the olefin absorbincJ rate does not decrease so much even with lapse of tirne, and therefore the polymerization can be conducted for a long time in a small amount of the catalyst.
Furthermore, polymers prepared by using the catalyst of the present inven-tion i-lave a very 2Q narrow molecular wei~ht d:istributi.on and their he~ane e~traction :is very small, reflectln~ nllnimlzed by-production of low c~rade polymers. There:Eore, for example, in the film grade, -those polymers can afford products of good (luali.ty such as a superior anti-l~locking property.
DESCRIPTION OF PREFERRE:D EMBODIMENTS
~ xamples of the magnesium halide used intlle p:resellt :inventioll include substantially anllydrous maclrles:ium .Eluorlde, magnesium chloride, magnesium brolnide, macJIlesium iodide, and mi.x-tures -thereof, with magnesium chloride being mos-t preEerable.
Exalllyles of the titanium compound and/or vallaclium compoulld used in -the present inven-tion include Il~I.icl~s, all;oxyllal:i.clcs, a]kox,ides and haloc7enated 1() ox.i.(lcs, o.E t.itall iUIll alld/Or ValladiUm . ~S pre:Eerred e,Yllnp.les o.E the -titanium compound there may be men-tione~ tetravalent and trivalent -titallium compounds.
~s tetravalent titanium compounds, those represented by the general Eormula Ti(OR) X3_r are preEerred wherein R i.s an allcyl, aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and r is 0 < r C 4, such as titanium -te-trachloride, titanium tetrabromide, -titar3ium tetraiodide, monomethoxy-tri-chlorotitaniuln, dimethoxydichlorotitanium, trimethoxy-monochlorotitanium, d:ietlloxydi.cllloro-t.itani.um, tetra-metho~y-titalli.uln, mcllloethoxytrj.clllorotita~ m, tri-etlloxymonoch~oroti tal~ m, te-traethoxy~i.talli.um~ mono-i.soyropoxytrich:l.oroti-tanium, diisopropoxydichloro-titanium, triisopror)oxymollochlorotitanium, tetraiso-~ropoxytitanium, monobutoxytrichloroti-tanium, di~utoxy-'clichlorotital~ m, monopelltoxytriclllorotitanium, monophenoxytriehlorotitanium, diphenoxydiehlorotitanium,triphenoxymonoehlorotitanium and -tetraphenoxytitanium.
~s trivalent titanium eompounds there may be used, :Eor exanlple, titanium trihalides ob-tained by redueing titanium tetrahalides such as titanium tetraehloride and titanium tetrabromide with hydrogen, aluminum, ti~an:ium or an orcJal1ollletclllie eompound o~ ~ nletal .selected ~rrom Groups l tl1rougl1 III in tl1e Periodie Table r as we:Ll as trivalent tital1ium eompounds cbta~ ed by rec1ucin~ tet:ravalent alkoxytitanium l1alicles o.E the general :~ormula Ti(OR)SX4_s with an orcJallometallie compound of a metal selected ~rom Groups I througl1 III in the Periodie Table in whieh formula R is an alkyl, aryl or aralkyl group having 1 to 24 earbon atoms, X is a halogen atom and s is 0 ~ s < 4~ Examples oE the vanadium eompound include tetravalent vanadium compounds such as vanadium tetraehloride, vanadiulll tetrabromide, vanaclium tetra-iodide and tetraetl1oxyvanadium; pentavalent vanadium compounds sueh as vanadium oxytriehlori.~le, ethoxy-dichlorovanaclyl, triethoxyvanadyl and trihutoxyvanadyl;
and trivalent vanadium eompounds sueh as vanadi.um tricl1loride and vanadium triethoxide. Tetravalent titanium eompounds are most preferable in the present invention.
9~
To make the present invention more effective the titanium compound and the vanadium compound are orten used tccJether. In this case it is preferable Lllat the V/Ti mole ratio be in the ranc~e 2/1 -to 0.01/1.
The metl~od o:E obtaining the catalys-t compo-nel1t ¦I~ by reactinq -tlle magnesium halide ~i) with tl~e titanium cornpouncl and/or vanadium compound (ii) in the pl^esel1t ~ vel1tiol1 is not specially limlted.
otl1 (i) al1d (:iL) Incly be reacte~ by contacting toge-lllel- llsual:ly Eor 5 minutes to 20 hours under heating at: a tell1perature o:E 20 to 400 C pre:Eerably 50 to 300C in the presence or absence of an iner-t solvent. ~lterna-tively the reac-tion may be carried out by a co-pulverization treatment. The lat-ter is preferable in the present inventiol1.
q~he inert solvent which may be used in prep3ring tl1e cal-alyst compol1en-t ~I~ is not specially limited. I~drocarbons al1d/or derivatives thereof not inaCtivatil1cJ ~ieJle~ ype catalysts are usua]ly employ-able. E~arnples are various saturate(1 aliphatic hy(7ro-carbol1s aromat:ic hyc1rocarbons cand alicycllc hydro-CarbOllS S~lCh as propane hutal1e pentane hexane l-eptane octane benzel1e to:luene xylene and cyclo-~1e~ane as well as alcohols ether.c. and esters such 'as etllallol, diethyl ether, tetrahyclrofuran, etllyl 9~
acetate and ethyl benzoate.
The apparat:us to be used for the co-plllver:izati.on i-s not specially limi.ted. Usually, a ball mill, a vibration mill, a rod mill or an impact mill is l1sed. Conditions for the co-pu.1.veri.zation such as temperat~lre and ti.lne can be deci.ded easi.ly ~y tl~os~ skilled in the art according to the co-p~llveLization method used. In general, the co-pll1ve~r:iza~.ion .is carried out at a temperature i.n the l0 r(1l1cle oE 0 to 200C, preferably 20 to 100C, :Eor a pe:r.iocl o.E time .in the range of 0.5 to 50 hours, preEerably 1 to 30 hours. Of course, the co-p~l:lv~r.izlnc~ operation should be performed in an inert gas atmosphere, and moisture should be avo.ided.
~s to the reaction ra-tio of the magnesium halide and the titanium compound and/or vanadium compound, it is most preferable -to adjust i-t so that the amount of titanium and/or vanadium contained in the catalyst component [I~ is in the range of 0.5 to 20 20 wt.%. The range of 1 to 10 wt.~ is particularly preEerred in orcler to atta:in a well-balanced activity per titanillm al1d/or val1adium and that per solid.
In preparing the catalyst component [I~ in the present in~entioll, moreover, a member or members ?5 se.lectecl :Erom t.l-le cJroup consisting of compounds of the c3eneral formula Me(OR) X wherein Me is an elelnel1t p z--p L99~ -selected from Groups I -through VIII in the Periodic Table, provided titanium and vanadium are excluded, R .is a l1ydrocar-~on radical having 1 -to 24 carbon atoms, X is a haloc3en atom, z is the valence of Me and p is 0 C p < z, orgal1ic halides, ha]ogenating ac3ents, phosp]loric esters, electron donors and poly-cycl:ic al^omatic coml~o~lnds~ may alc,o pre~elably be llsecl as c0lnl~01lellt (c~) in (lclcli tion to t}le mac3nesium i~al i.de (:i) alld t:lle t.i.l:aniuJn compound al~d/or vanadiuln colllpo~ d (.i-i). The compol1ent (cx) may be u~ed in an allloullt o~ 0.01 to 5 moles, preferably 0.05 to 2 moles, per Illole oE the magnesium halide (i).
Fxamples of compounds of the general formula Me(OR)pXz p which may be used in the present inven-tion include the followincJ compounds: NaOR, Mg(OR)2, Mg(OR)X, Ca(OR)2, Zn(OR)2, Zn(OR)X, Cd(OR)2, ~l(OR)3, A1 (OR) 2X, B (OR) 3, ~ (OR) 2X, Ga (OR) 3, Ge(OR)4, Sn (OR) 4, P(OR)3, Cr (OR) 2~ Mn(OR)2, Fe(OR)2, Fe(OR) 3, Co (OR12 and Ni(OR)2. ~s more concrete preferable examples tl1ere may ~e mentiol1ed the Eollowinc3 compounds:
NaOC 1I NaOC,~119, M9 (OC113) 2 ~ Mc3 (0C21 5) 2 ~ 3 3 7 2 (C2~l5)2' Zl~(oc2llsl2~ Zn(OC2ll5)Cl~ ~l (OC113 ) 3, ~l(oc H5)3~ ~l(OC2lls)2cl, ~l (OC3M7) 3, 4 9 3 6 5 ) 3 ~ B (C2ll5 ) 3 ~ B (OC2~]5 ) 2Cl ~ E' (OC2115) 3, 25P(OC6115)3 and Fe(OC4119)3. Particularly, compounds represented by the cJel1eral :~ormulae Mc) (OR) X2_ , Al~OR) X3 an~ B~OR) X3 are preferred. ~s the substituent R, C1 to C4 alkyl groups and phenyl are preferred.
Or~anic ha].ldes which may be used i.n the 5_ present invelltion are partially ha]o~en-sllbstitllted, saturated or unsaturated alipha-tic and aromati.c llydro-carbons, inclucling mono-, di- and tri-~ubs-tltuted colllpoull(ls. 'l`lle llalo~en may be any of :Eluorine, clllorlne, bromlne and iodine.
amp].es o.E s~ch organic halides :include nlc~thyl.ene ch:Lorlde, cllloro:Form, carbon tetrachloride, bromochlorometllane, dlchlorodifluoromethane, 1-bromo-
~CKG~OUND OF '~ INV~NTION
The present invention relates to a process fo= preparing polyole:~ins using a nove.1 po]ymeri.zation 5 catalyst.
Ileretofore, in tl1e technical field of lhis sort ~ re llas been Icl1owll :EroM Japanese ~atent licatiol1 No.121()5/1964 a catalyst comprisin~ a Iml~Jlles;illln lla:lide ~nd a tral1sitiol1 metal coln~)ound such 1() as a tita~ m conl~oul1c1 supported thereon. Further, a catcll.yst obta.il1ed by the co-pulverization o:E a ma~llesillm l1alide and titanium tetrachloride is known ~rom RelcJian Patent No,742,112.
~lowever, when viewed from the standpoin-t that the catalyst activity is clesired to be as high as possible in the manufacture of polyolefins, the process disclosed in the Japanese Patent Publication No.12105/1964 is stil~ unsatisEactory beca~lse of a low polymerization activity, while the polymerization activity attail1ed in the process oE Belgian Patent 742,112 is fairly hial1, but a further improvement is c1esired.
ln the process disclosed in German Patent No.2137872, the anloul1t o~ a magnesium halide used 2r~ is su~stal1ti.al~y decreased by the co-pulverizat:ion _ thereof with titanium tetraehloride and alumina, but a remarkable i.nerease in aeti.vity per solid, whieh can b~ reeoynized as a (3uideline or produetivity, is not reeoynized, ancl it is desired to develop a catalyst of a h.igl1er acti.vity~
In the manuEacture of polyo1efins, moreover, it .is a1so des:i.rable from -the aspeets o~ productivity ant1 sl~lrry hclndlillc3 that tt-~e bulk dens:ity of the r.es~llt:i.l1cl po].ylTIer be as hi~h as possible. F'rom this I() sLalldL)o.i.nt, the l~rocess d.iselosed in the Japanese t~ltel1t P~lblieat:i.on No.12105/1964 is no-t satisfaetory :in loth the bul)c dens.ity of the resulting polymer al1d polymerization activi-ty, while in the proeess diselosed in the Belgian Patent 742,112, -the polymeri-~5 zation activi-ty is hic3h, but the bulk density of the resulting polymer is low. Thus, in both -the proeesses, a further improvement is desired.
SUMMI~RY OF TIIE: INVl~:NTION
It .is tl~e object oE the present invention to ~)rovide a nove.1 polymeriza-tion eata]yst and a proeess for the holllopot.ymerization or copolymerizatio o~ olefiT1s usin~3 the catalyst, eapable of remedying the above~ el1tiolled drawbaeks, attainin~ a high po.lylllerizati.on activity, affordinc3 polymers wi-th a hiclh bul)c density in higt1 yield and prac-ticing a eontinuous polymeriza-tion extremely easily.
The present inven-tion resides in a process Eor preparing ~olyoleEins by the ho3l10polymerization or copolymerization oE oleEins using a eatalyst whieh comprises the combi31atio1l of:
[I~ a solid substance obtained by the reaction oE at least the Eollowing two co1npo1lents:
(i) a ma(11lesium halide and (ii) a tita~ n compound and/or a vanadil1m 1() con1poln~d;
~II] a compoulld represented by the general formula R~ 5i(0l~2)4 1~ wl1erein R1 and 1~2 are hydrocarbon radicals havinc~ 1 to 24 carton atoms and O ~- m ~ 3;
[III~ a eompound represented by the general formula R3n~l(0R4)3_n wherein R3 and R4 are hydrocarbon radicals havinc~ 1 to 24 carbon atoms and 1 C- n < 2; and [IV3 an organo1netall3c compound, and which catalyst satisfies the cond:it:ions that the mola3- ratio o~ s:i1:icon in tl-1e compo1le11t [II] to titanium ancl/or va11ad:ium in tl-1e component LI~ s1~ould be in the range of 0.1 to 100, the molar ra-tio of aluminum in the compo1le1lt lI:1I~ to silicon in the con1por1ent LII~ sllo-1ld be in the range of 0.01 to 10 and the molar ratio oE t11e n1elal in the componen-t [IV~ to tltanium and/or vanadium in the componen-t ~I~ should be :in the rancle of 0.1 to 1000.
Sir1ce the polymerization catalyst used in the present invention exhibits a very hlgh polymeriza-tion activity, the partial pressure of monomer duringpolymerizatio11 is ~.ow, and because of a hic3h bulk density o.~ the result:i11c3 polymer, the productivity cal-l be :iln~rovecl. Moreover, -the amount of -the catalyst ~ lla~ .ill(J i.n tl1e l^es~ltinc3 polymer a~ter polyme:rization 1() is so sll1al.l thclt the polyole.Ein manu:Eacturing process can d:ispense w:ith the catalyst removing s-tep, which leac1s to silnp].lfication of the polymer trea-ting s-tep, and consequently polyolefins can be prepared very economically.
~ccording to the process of the present invention, the amount of polymer procluced per unit polymerization reactor is large because of a high bulk density of -the resulting polymer.
The present invention is Eurther advantage-_() ol1s in t.hat wl1en viewed from the stancdpoi.nt of particlesi~e of the resLl1tinq polymer, the propor-tion Or coarse par-t:ic1.es ancl that of fine particles below 50 ~Im are small desp:ite oF a high bullc density of the polymer, a~ hat the1~efore not on].y it becomes easy to perfol-ln a Co~ti.lluo~s polymer:i.zation re~ction but also the centriEuclal separati.on i.n the polymer treating step as well as the handling of polymer pa.r-ticles in powder transport become easy.
~ ccorcling -to the present i.nven-ti.on, in addit:ion to the high bulk densi-ty of polyolefins obtained by usin~ the catalyst of the lnvention as previously noted, polyolefins havina a desired melt illdeX can be prepal-ed at a lower hydroqen concentra-tion thall in convelltiollal me-thods, thus permitt,ing E-o.l.ylne.L-.ization to be carried out a-t a relatively ln slllall total pressure, and th.is ~reatly cont:ributes to the .imp.roveme1lt oE ecollomy and productivity.
~ dditi.onally, in -the oleEin pol.ymerlza-tion using -the catalys-t oE -the present invention, the olefin absorbincJ rate does not decrease so much even with lapse of tirne, and therefore the polymerization can be conducted for a long time in a small amount of the catalyst.
Furthermore, polymers prepared by using the catalyst of the present inven-tion i-lave a very 2Q narrow molecular wei~ht d:istributi.on and their he~ane e~traction :is very small, reflectln~ nllnimlzed by-production of low c~rade polymers. There:Eore, for example, in the film grade, -those polymers can afford products of good (luali.ty such as a superior anti-l~locking property.
DESCRIPTION OF PREFERRE:D EMBODIMENTS
~ xamples of the magnesium halide used intlle p:resellt :inventioll include substantially anllydrous maclrles:ium .Eluorlde, magnesium chloride, magnesium brolnide, macJIlesium iodide, and mi.x-tures -thereof, with magnesium chloride being mos-t preEerable.
Exalllyles of the titanium compound and/or vallaclium compoulld used in -the present inven-tion include Il~I.icl~s, all;oxyllal:i.clcs, a]kox,ides and haloc7enated 1() ox.i.(lcs, o.E t.itall iUIll alld/Or ValladiUm . ~S pre:Eerred e,Yllnp.les o.E the -titanium compound there may be men-tione~ tetravalent and trivalent -titallium compounds.
~s tetravalent titanium compounds, those represented by the general Eormula Ti(OR) X3_r are preEerred wherein R i.s an allcyl, aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and r is 0 < r C 4, such as titanium -te-trachloride, titanium tetrabromide, -titar3ium tetraiodide, monomethoxy-tri-chlorotitaniuln, dimethoxydichlorotitanium, trimethoxy-monochlorotitanium, d:ietlloxydi.cllloro-t.itani.um, tetra-metho~y-titalli.uln, mcllloethoxytrj.clllorotita~ m, tri-etlloxymonoch~oroti tal~ m, te-traethoxy~i.talli.um~ mono-i.soyropoxytrich:l.oroti-tanium, diisopropoxydichloro-titanium, triisopror)oxymollochlorotitanium, tetraiso-~ropoxytitanium, monobutoxytrichloroti-tanium, di~utoxy-'clichlorotital~ m, monopelltoxytriclllorotitanium, monophenoxytriehlorotitanium, diphenoxydiehlorotitanium,triphenoxymonoehlorotitanium and -tetraphenoxytitanium.
~s trivalent titanium eompounds there may be used, :Eor exanlple, titanium trihalides ob-tained by redueing titanium tetrahalides such as titanium tetraehloride and titanium tetrabromide with hydrogen, aluminum, ti~an:ium or an orcJal1ollletclllie eompound o~ ~ nletal .selected ~rrom Groups l tl1rougl1 III in tl1e Periodie Table r as we:Ll as trivalent tital1ium eompounds cbta~ ed by rec1ucin~ tet:ravalent alkoxytitanium l1alicles o.E the general :~ormula Ti(OR)SX4_s with an orcJallometallie compound of a metal selected ~rom Groups I througl1 III in the Periodie Table in whieh formula R is an alkyl, aryl or aralkyl group having 1 to 24 earbon atoms, X is a halogen atom and s is 0 ~ s < 4~ Examples oE the vanadium eompound include tetravalent vanadium compounds such as vanadium tetraehloride, vanadiulll tetrabromide, vanaclium tetra-iodide and tetraetl1oxyvanadium; pentavalent vanadium compounds sueh as vanadium oxytriehlori.~le, ethoxy-dichlorovanaclyl, triethoxyvanadyl and trihutoxyvanadyl;
and trivalent vanadium eompounds sueh as vanadi.um tricl1loride and vanadium triethoxide. Tetravalent titanium eompounds are most preferable in the present invention.
9~
To make the present invention more effective the titanium compound and the vanadium compound are orten used tccJether. In this case it is preferable Lllat the V/Ti mole ratio be in the ranc~e 2/1 -to 0.01/1.
The metl~od o:E obtaining the catalys-t compo-nel1t ¦I~ by reactinq -tlle magnesium halide ~i) with tl~e titanium cornpouncl and/or vanadium compound (ii) in the pl^esel1t ~ vel1tiol1 is not specially limlted.
otl1 (i) al1d (:iL) Incly be reacte~ by contacting toge-lllel- llsual:ly Eor 5 minutes to 20 hours under heating at: a tell1perature o:E 20 to 400 C pre:Eerably 50 to 300C in the presence or absence of an iner-t solvent. ~lterna-tively the reac-tion may be carried out by a co-pulverization treatment. The lat-ter is preferable in the present inventiol1.
q~he inert solvent which may be used in prep3ring tl1e cal-alyst compol1en-t ~I~ is not specially limited. I~drocarbons al1d/or derivatives thereof not inaCtivatil1cJ ~ieJle~ ype catalysts are usua]ly employ-able. E~arnples are various saturate(1 aliphatic hy(7ro-carbol1s aromat:ic hyc1rocarbons cand alicycllc hydro-CarbOllS S~lCh as propane hutal1e pentane hexane l-eptane octane benzel1e to:luene xylene and cyclo-~1e~ane as well as alcohols ether.c. and esters such 'as etllallol, diethyl ether, tetrahyclrofuran, etllyl 9~
acetate and ethyl benzoate.
The apparat:us to be used for the co-plllver:izati.on i-s not specially limi.ted. Usually, a ball mill, a vibration mill, a rod mill or an impact mill is l1sed. Conditions for the co-pu.1.veri.zation such as temperat~lre and ti.lne can be deci.ded easi.ly ~y tl~os~ skilled in the art according to the co-p~llveLization method used. In general, the co-pll1ve~r:iza~.ion .is carried out at a temperature i.n the l0 r(1l1cle oE 0 to 200C, preferably 20 to 100C, :Eor a pe:r.iocl o.E time .in the range of 0.5 to 50 hours, preEerably 1 to 30 hours. Of course, the co-p~l:lv~r.izlnc~ operation should be performed in an inert gas atmosphere, and moisture should be avo.ided.
~s to the reaction ra-tio of the magnesium halide and the titanium compound and/or vanadium compound, it is most preferable -to adjust i-t so that the amount of titanium and/or vanadium contained in the catalyst component [I~ is in the range of 0.5 to 20 20 wt.%. The range of 1 to 10 wt.~ is particularly preEerred in orcler to atta:in a well-balanced activity per titanillm al1d/or val1adium and that per solid.
In preparing the catalyst component [I~ in the present in~entioll, moreover, a member or members ?5 se.lectecl :Erom t.l-le cJroup consisting of compounds of the c3eneral formula Me(OR) X wherein Me is an elelnel1t p z--p L99~ -selected from Groups I -through VIII in the Periodic Table, provided titanium and vanadium are excluded, R .is a l1ydrocar-~on radical having 1 -to 24 carbon atoms, X is a haloc3en atom, z is the valence of Me and p is 0 C p < z, orgal1ic halides, ha]ogenating ac3ents, phosp]loric esters, electron donors and poly-cycl:ic al^omatic coml~o~lnds~ may alc,o pre~elably be llsecl as c0lnl~01lellt (c~) in (lclcli tion to t}le mac3nesium i~al i.de (:i) alld t:lle t.i.l:aniuJn compound al~d/or vanadiuln colllpo~ d (.i-i). The compol1ent (cx) may be u~ed in an allloullt o~ 0.01 to 5 moles, preferably 0.05 to 2 moles, per Illole oE the magnesium halide (i).
Fxamples of compounds of the general formula Me(OR)pXz p which may be used in the present inven-tion include the followincJ compounds: NaOR, Mg(OR)2, Mg(OR)X, Ca(OR)2, Zn(OR)2, Zn(OR)X, Cd(OR)2, ~l(OR)3, A1 (OR) 2X, B (OR) 3, ~ (OR) 2X, Ga (OR) 3, Ge(OR)4, Sn (OR) 4, P(OR)3, Cr (OR) 2~ Mn(OR)2, Fe(OR)2, Fe(OR) 3, Co (OR12 and Ni(OR)2. ~s more concrete preferable examples tl1ere may ~e mentiol1ed the Eollowinc3 compounds:
NaOC 1I NaOC,~119, M9 (OC113) 2 ~ Mc3 (0C21 5) 2 ~ 3 3 7 2 (C2~l5)2' Zl~(oc2llsl2~ Zn(OC2ll5)Cl~ ~l (OC113 ) 3, ~l(oc H5)3~ ~l(OC2lls)2cl, ~l (OC3M7) 3, 4 9 3 6 5 ) 3 ~ B (C2ll5 ) 3 ~ B (OC2~]5 ) 2Cl ~ E' (OC2115) 3, 25P(OC6115)3 and Fe(OC4119)3. Particularly, compounds represented by the cJel1eral :~ormulae Mc) (OR) X2_ , Al~OR) X3 an~ B~OR) X3 are preferred. ~s the substituent R, C1 to C4 alkyl groups and phenyl are preferred.
Or~anic ha].ldes which may be used i.n the 5_ present invelltion are partially ha]o~en-sllbstitllted, saturated or unsaturated alipha-tic and aromati.c llydro-carbons, inclucling mono-, di- and tri-~ubs-tltuted colllpoull(ls. 'l`lle llalo~en may be any of :Eluorine, clllorlne, bromlne and iodine.
amp].es o.E s~ch organic halides :include nlc~thyl.ene ch:Lorlde, cllloro:Form, carbon tetrachloride, bromochlorometllane, dlchlorodifluoromethane, 1-bromo-
2-chloroel:llane, chloroethane, 1,2-dibromo-l,1-~ichloroethalle, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloro-1,1,2,2-tetraEluoroe-thane, hexachloroethalle, pentachloroethane, 1,1,1,2--tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,1,1-trlchloroethane, 1,1,2-trichloroe-thane, 1-chloropropane, 2-chloropropane, 1,2-dich:Loropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1,1,1,2,2,3,3-heptacllloropropane, 1 r -1 ~ 2,2,3,3-hexachloropropane, octachloropropane, l,1,2-trichloropropane, 1-chlorobutane, 2-clllorobutalle, 1-chloro-2--methylpropane, 2-chloro-2-methylpropane, 1,2-dichlorobutane, 1,3-dich1orobutane, :'5 1,4-dichlorobutane, 2,2^dicll1Orobutalle, 1-chlorodecane, vinyl ch]orlde, I,1-dichloroethylene, 1,2-dichloroethylene, tetrachloroethylene, 3-ch].oro-1-propene, 1,~-dichloropropene, chloroprene, oleyl chl.or:ide, chlorobenzene, chloronaph-thalene, benzyl chlori.cl~, ben~ylidene ch.]oride, chloroethylbenzene, styrene dichlori.de and ~-chlorocumene.
Examp]es c~f i1alocIenating a~erIts W}l;.C}l may be used in the ~resent invention include halides oE nonme~als such a~ sulfur chloride, PCl3, PCl5 and SiCl4, as wel~ s oxyhalides of no~ etals s~Ic:I
'~5 I'OCl3, COC1.2, NOCl2, SOCl2 and S02C12.
I() Phosp11oric esters which may be used in the present invention are compounds represen-ted by OR
the cJeneral Eormula P - OR wherein R, which may be Il \
O 01~
alike or diEferent, is a hydrocarbon radical havinq 1 to 29 carbon atoms. Examples of such compounds are triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl pl1osphate, trixylyl phosphate and c1iphenylxylenyl phosphate.
~xamples o:E electron donors which may be 2n ~Ised in the present invention are alcohols, ethers, ketones, aldehycles, organic acids, organic acid esters, acid halides, acicl amic1es, amines and nitriles.
~ s alcoI1ols there may be used, for example, ~tIIose haviIlcJ 1 -to 18 carboIl atoms SUCll as methyl aleohol, ethyl aleohol, n-propyl aleohol, isopropyl aleohol, allyl aleohol, n-bu-tyl aleohol, isobutyl aleoilol, see-butyl aleohol, t-butyl alcohol, n-amyl aleohol, n-hexyl aleohol, eyelohexyl aleohol, deeyl alcohol, lauryl alcohol, myristyl alcohol, ce-tyl alcohol, stearyl aleohol, oleyl aleohol, benzyl aleohol, na~ tllyl aleohol, phenol and eresol.
~ s ethers there may be used, Eor example, tI1OSe 11~Vil1C~ 2 to 20 earbon atoms sueh as climetllyl l~ etller, d.;etllyl ethcr, dibutyl ether, isoamy:L ether, an.isole, phenetole, diphenyl ether, phenylallyl ether and benzofuran.
~ s ketones there may be used, for example, those having 3 to 18 earbon atoms such as aee-tone, methyl ethyl ketone, methyl isobutyl ketone, me-thyl phenyl ke-tone, ethyl phenyl ketone and diphenyl ketone.
~ s aldellydes there may be used, for example, those havin~ 2 to 15 carbon a-toms such as acetaldehyde, propinaldehyde, oetylaldehyde, benzaldehyde and naplltllaldehyde.
~ s or~ani.e acids tllere may be used, for example, those havinc~ 1 to 29 earbon atoms such as formie, aeetie, propionie, bu-tyrie, valeric, pivalic, caproic, eaprylic, stearic, oxalic, malonic, succinic, adipiel methaeryli.c, berlzoic, toluic, anisic, oleic, `linolei.c and lino.l.~llie acids.
_ 13 ~L2~9g~ ' ~ s organic esters there may be used, for example, those having 2 to 30 carbon atoms such as metllyl :Eormate,-methyl acetate, ethyl acetate, propyl acetate, octyl acetate, e-thyl propionate, methyl butyrate, ethyl va]cl-ate, methyl methacry]ate, met}lyl benzoate, ethyl benzoate, propyl benzoate, octyl len7.0ate, phelly:l bel~zoate, benzyl ben7.0ate, butyl etl~o.~ybenzoate, methyl toluylate, ethyl. toluylate, e~ yl. e~l~yll~en~oa~e~ met}lyl. salitylate, phellyl sality-1~) la~:e, Inetlly:l napllthoate, etllyl napllthoate and ethyl all.isate~
~ s ac:i.d hal:i.des there may be used, forexamp:le, those having 2 to 15 carbon a-toms such as acetyl chloride,benzoyl chloride, -toluoyl chloride 15 and anisoyl chloride.
As acid amides there may be used, for example, acetamide, benzoylamide and toluoylamide.
~ s amines there may be used, for example, methylamine, ethylamille, diethylamine, tributylamine, piperidine, tribenzy:lam:ine, aniline, pyridine, picoline and tetrametllylened:iamil-~e.
~ s nitril.es there may be used, Lor e~ample, acetonitrile, bell7.0nitrile and tolunitrile.
E~amp].es of polycyclic aromatic compoullds '5 whi.ch may be used in the present invention inc~.ude napllthalene, pheJlanthrene, triphenylene, chrysene,
Examp]es c~f i1alocIenating a~erIts W}l;.C}l may be used in the ~resent invention include halides oE nonme~als such a~ sulfur chloride, PCl3, PCl5 and SiCl4, as wel~ s oxyhalides of no~ etals s~Ic:I
'~5 I'OCl3, COC1.2, NOCl2, SOCl2 and S02C12.
I() Phosp11oric esters which may be used in the present invention are compounds represen-ted by OR
the cJeneral Eormula P - OR wherein R, which may be Il \
O 01~
alike or diEferent, is a hydrocarbon radical havinq 1 to 29 carbon atoms. Examples of such compounds are triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl pl1osphate, trixylyl phosphate and c1iphenylxylenyl phosphate.
~xamples o:E electron donors which may be 2n ~Ised in the present invention are alcohols, ethers, ketones, aldehycles, organic acids, organic acid esters, acid halides, acicl amic1es, amines and nitriles.
~ s alcoI1ols there may be used, for example, ~tIIose haviIlcJ 1 -to 18 carboIl atoms SUCll as methyl aleohol, ethyl aleohol, n-propyl aleohol, isopropyl aleohol, allyl aleohol, n-bu-tyl aleohol, isobutyl aleoilol, see-butyl aleohol, t-butyl alcohol, n-amyl aleohol, n-hexyl aleohol, eyelohexyl aleohol, deeyl alcohol, lauryl alcohol, myristyl alcohol, ce-tyl alcohol, stearyl aleohol, oleyl aleohol, benzyl aleohol, na~ tllyl aleohol, phenol and eresol.
~ s ethers there may be used, Eor example, tI1OSe 11~Vil1C~ 2 to 20 earbon atoms sueh as climetllyl l~ etller, d.;etllyl ethcr, dibutyl ether, isoamy:L ether, an.isole, phenetole, diphenyl ether, phenylallyl ether and benzofuran.
~ s ketones there may be used, for example, those having 3 to 18 earbon atoms such as aee-tone, methyl ethyl ketone, methyl isobutyl ketone, me-thyl phenyl ke-tone, ethyl phenyl ketone and diphenyl ketone.
~ s aldellydes there may be used, for example, those havin~ 2 to 15 carbon a-toms such as acetaldehyde, propinaldehyde, oetylaldehyde, benzaldehyde and naplltllaldehyde.
~ s or~ani.e acids tllere may be used, for example, those havinc~ 1 to 29 earbon atoms such as formie, aeetie, propionie, bu-tyrie, valeric, pivalic, caproic, eaprylic, stearic, oxalic, malonic, succinic, adipiel methaeryli.c, berlzoic, toluic, anisic, oleic, `linolei.c and lino.l.~llie acids.
_ 13 ~L2~9g~ ' ~ s organic esters there may be used, for example, those having 2 to 30 carbon atoms such as metllyl :Eormate,-methyl acetate, ethyl acetate, propyl acetate, octyl acetate, e-thyl propionate, methyl butyrate, ethyl va]cl-ate, methyl methacry]ate, met}lyl benzoate, ethyl benzoate, propyl benzoate, octyl len7.0ate, phelly:l bel~zoate, benzyl ben7.0ate, butyl etl~o.~ybenzoate, methyl toluylate, ethyl. toluylate, e~ yl. e~l~yll~en~oa~e~ met}lyl. salitylate, phellyl sality-1~) la~:e, Inetlly:l napllthoate, etllyl napllthoate and ethyl all.isate~
~ s ac:i.d hal:i.des there may be used, forexamp:le, those having 2 to 15 carbon a-toms such as acetyl chloride,benzoyl chloride, -toluoyl chloride 15 and anisoyl chloride.
As acid amides there may be used, for example, acetamide, benzoylamide and toluoylamide.
~ s amines there may be used, for example, methylamine, ethylamille, diethylamine, tributylamine, piperidine, tribenzy:lam:ine, aniline, pyridine, picoline and tetrametllylened:iamil-~e.
~ s nitril.es there may be used, Lor e~ample, acetonitrile, bell7.0nitrile and tolunitrile.
E~amp].es of polycyclic aromatic compoullds '5 whi.ch may be used in the present invention inc~.ude napllthalene, pheJlanthrene, triphenylene, chrysene,
3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene, tetraphene, 1,2,3,4-dibenzan-thracene, per)taphene, 3,4-benzopentaphene, tethracene, 1,2-benzotethracer1e, hexaphene, heptaphene, diphenyl, '~Luorene, biphenyler1e, perylene, coronene, bisantene, ovalene, pyrene and perinapl1thene, as well as halogen-al1d a]kyl-substituted derivatives thereof Tl1e catalyst component ~I~ thus obtained may be su~portec1 on al1 oxide of a metal selected from ~,roups XI through IV in the Periodic Table. This mode oE use is also pre~erable in the present invention.
In t]liS case, not only o~ides oE Group II-IV metals eacl~ alone bu-t also double oxides of these metals, as well as mixtures thereoE, are employable Examples of such metal oxides are M~O, CaO, ZnO, BaO, SiO2, 2' 23~ MgO-~l2O3, SiO2-~l2O3, MgO-SiO
MgO CaO-Al2O3 and ~l2O3 CaO. Par-ticularly preferred 2' ~l23~ SiO2-~l2O3 and MgO-A12o The method of supporting -the catalyst component ~I~ on an oxide of a Group II-IV metal in the Periodic l~a~le is nol: specially limited, but ~s a preferred exarnple t}lel^e may be mentioned a method wherein the components (i) and (ii), and the component (~) if required, are allowed to react under h~at-in~, 2~ for example in an etller compound as solvent in the presence of the said me-tal oxide and then the liquid ~19~
phase portion is removed.
Examples o:E the compound of the general fo.rlrlu.1.a R1mSi(~l~ )4 m used in the present invention include monornethyl trimethoxy silane, monome-thyl triethoxy silane, monolnethyl tri-n-buto~y silane, monomethyl tri-sec-butoxy silane, monornethyl tr:iisopropoxy silane, monomethyl tripen-toxy silane r monolrlet:l1yl t.rioctoxy s:ilane, monometl1yl tristearoxy si.lal~o, nlor1olnetllyl tr:iphenoxy silane, dime~l1yl c1lmetl1oxy 1~ s:i.1.ane, d.im~thyl diethoxy silane, dimethyl diisopropoxy silane, c1imethyl diphenoxy silane, trime-thyl monomethoxy s:ik~l1e, trLmethyl molloethoxy silane, trime-thyl mono-isopropo~y silane, trimethyl monophenoxy silane, monoethyl trimethoxy silane, monoe-thyl triethoxy silane, monoethyl triisopropoxy silane, monoe-thyl triphenoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diethyl diphenoxy silane, triethyl monomethoxy silane, triethyl monoethoxy silane, -trie-thyl monop}lenoxy silane, monoi.sopropyl tr.i.methoxy silane, mono-n-butyl trimethoxy silane, mono-n-butyl triethoxy silane, mono-sec-butyl -triethoxy silane, monophenyl tr.ietl1o~y si.lal1e~ di.pl1enyl diethoxy silal1e, tetra-ethoxy silalle and te-traisopropoxy si].ane.
If tl1e amount of the compound of the ~JeneLa:l.
formula R1mSi(OR )4 m used in the present invention is too large or too small, its effect oE addition cannot _ ~6 be expec-ted. Usually, its amount is in the range of 0.1 to 100 moles, preferably 0.3 to 2n moles, per mole o:E the ti-tanium ~ompound and/or vànadium compound .in the catalyst component ~
~s examp1es o:E the compo~ d o:E the general formula R3 ~l~OR )3_ used in -tl1e present invention, mention may be ma~e o:E the :Eol.lowin~: dimethylaluminum monoethc),Y.icle, dim(?thylaluminum monoisopropoxide, cl:imc?t.lly:l.a,l~lmillunl mollo-ll-l)ul:oxide, dimetllylalumillum In sec-bu ~:oxide, climetllylaluminum monophenoxlde, diethyl-a~ lin~lm mollolnethoxide, diethylalumlnum monoethoxide, diethylaluminum monoisopropoxide, diethylaluminum mol1o~ butoxide, diethylaluminum sec-butoxide, diethylaluminum monophenoxide, diethylaluminum mono-octoxide, diethylaluminum monos-tearyloxide, diisobutyl-aluminum monoethoxide, methylaluminum dimethoxide, methylaluminum diethoxide, e-thylaluminum dlmethoxide, ethylaluminum die-thoxide, ethylaluminum diisopropoxi.de, ethylaluminum di-n-butoxide, ethylaluminum phenoxide, isobutylaluminum dimetl1oxide and isobutylaluminum d:iethoxlcle.
~ s to the amount of -the coml~ouncl o:~ the ~eneral :Eormula R41l~l(OR4)3 used in the present invention, both a too 1.ar~e amount and a too small amoul1t would not be e:Efective. Its amoul1t i.s in .the ran~e oE 0.01 to 10 moles, preferably 0.05 to 2 ~Z~
moles, per mole of the silicon compound in the catalyst coml~onent [II~.
~ s e~amp:les of -the organomet~]lic compound used in -the present invention, there may be mentioned orcJanometallic compoullds of Group I-IV me-tals in the Periodic Table knowll as a component of Ziegler type cacalysts, but orcJanoaluMillum compounds and or~anozil~c compounds are particularly preferred, ror e~alllr):le, or~anoal~lmillum compounds of the c~eneral 1() ~o~ e ~3~1, R2~1X, RAlX2 and R3A12X3 wllerei~l R, which may be alike or different, is an alkyl or aryl cJroup having 1 to 20 carbon atoms and X is a halogen atoln, and organoz:inc compounds of the general formula R2Z wherein R, which may be alike or different, is an alkyl group having 1 to 20 carbon atoms, such as triethylaluminum, triisopropylaluminum, triisobutyl-aluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethy]aluminum chloride, diiso-propylaluminum chloride, et~lylaluminum sesquichloride, diethylzillc, and mixtures thereof. TocJether with tilese or~anometallic compounds there may be used orgallocarboxylic acid esters such as ethyl benzoate, ethyl toluylate and ethyl anlsate. The or~anometallic 2r compoulld may be used in an amount of 0.1 to 1,000 moles per mole of the titanium compound and/or vanadium compound in the catalyst component [I~.
The olefin polymerization using the catalyst oE the present -invention may be carried out by slurry po1ylnerizat:io1l, solution polymerization or vapor phase polyl1lerization. Particularly, slurry polymerization and vapor phase polymerization are preferred. The polymerlzatioll reaction is carried ou-t ln the same way as in t1ie co~1vent;o3lal olefin polymerl2atlo1l reaCtiOIl USillg a Zie~ler type ca-talyst. ~'hat is, the -10 reactiot1 :is perEormed in a substan-tially oxygen- and wal:er-~1^ee conditior1 and in the presence or absence o~ ~n inert hydrocarbon. Olefin polymerizing condi-tions involve temperatures in the range of 20 to 120DC, pre~erably 50 to 100C, and pressures in the range of atmospheric pressure to 70 kg/cm2, preferably 2 to 60 kg/cm2. Adjustment of the molecular weight can be made to some extent by changing polymerization condi-tions such as the polymerization -temperature and the catalyst mole ratio, but the addition of hydrogen 2n into the polymerization sys-tem is more effective for this purpose. Of course, usin~ the catalyst of the present invention, two or more mu:Lti-staae polymeriza-tion reactiorls l1aving different polymerization condi-tions sucll as differer1t hydrogen concer1trations and different polylnerization temperatures can be performed ~i~ho~1t any trol~le.
~ 19 The process of the present invention is applicable to the polymerization of all olefins that are polymerizable with a Ziegler type catalys-t. Parti-cularly, ~-oleEins having 2 to 12 carbon atoms are preferred. For example, the process of the presellt invention is suitable for the homopolymerization of such ~-olefins as ethylene, propylene, butene-1, hexene-1, 4-methylI)elltene-1 and octene--1, the copolymer-ization oE etl-ylene/propylene, ethy]elle/butelle-1, 10 etllylc!ne/l-~exene-l, ethylene/4-metllylpentene~1, etllylene/octene-1 and propylene/butene-1, as well as the copolymerization oE ethylene and other -two or more ~-oleEins.
Copolymerization with dienes Eor the modifica-tion of polyolefins is also preferable. As dienesthere may be used, for example, bu-tadiene, 1,4-hexadiene, ethylidene norbornene and dicyclopentadiene.
The following examples are given to fur-ther illustrate -the present inven-tion, bu-t i-t ls to be understood -that the invention is not llmited thereto.
Example 1 (a) Preparation of Solid Ca-talyst Componen-t rI~
10 g. o~ a comlllercially availab]e anhydrous magnesiu]n chloride, 2.3 g. of aluminum triethoxide `and 2.5 g, of titanium tetrachloride were placed in a stainless steel pot having a con-tent volume of 400 ml. and containing 25 stainless s-teel balls each 1/2 inch .in diameter, and ball-milled for 16 hours at room telnperature in a nitrogen a-tmosphere, to obtain a solid catalyst component LI~ COI1taining - 41 mg of titanium per yram -thereof.
(b) Polymeriza-tion ~ 2-liter stainless steel autoclave equipped Wit]1 al~ duction stirrer was puryed wlth nitroyen 1() and tl1en cl1aryed w:it.h l,000 ml. oE hexane, then 1 Inlllol. o.~ trietl1ylaluminum, 0.05 mmol. of diethyl c1:ieti-loxy silane, 0.01 mmol. of diethylaluminum mono-ethoxide and 10 mg. of the above solid catalyst com-ponent LI} were added and t~le tempera-ture was raised -l5 to 90C under stirring. Wi-th -the vapor pressure of hexane, the system was pressurized to 2 ky/cm2-G.
Then, hydrogen was introduced up to a total pressure of 4.8 kg/cm2-G and -then ethylene was in-troduced up to a tota] pressure of 10 k.g/cm G. In this state, polymerization was allowed to star-t, which was continued for 1 hour while mail1taining the internal pressure of the autoclave at 10 kg/cm G. Thereaf-ter, the polymer slurry w~s transferred in-to a beaker and hexane was removed under reduced pressure to obtain 175 g. o.E a ~5 white polyethylene having a melt index o:E 1.1 and a bulk density of 0.38. Cataly-tic acti.vi-ty was 82,100g.polyethylene/g.Ti-hr-C21l4 pressure, 3,370g.polyethylene/g.solld~hr C2H4 pressure.
F.R.-value of the polyethylene thus obtained was 7.5. The molecular wei~ht distribu-tion was extremely narrow as compared with the following Comparative Example 1.
* F.R. value represents the extent of molecular weight distribution and is ca:Lculated as Eollows:
I n F.R. = melt index at 10 kg. load/
mel-t index at 2.16 kg. load The melt index was measured according to ASTM D-1238.
Comparative Example 1 Polymerization o: ethylene was carried out in the same way as in Example 1 excep-t that the diethylaluminum monoethoxide was not used, to ob-tain 140 g. of a white polyethylene having a bulk density of 0.33 and a melt index of 1Ø Catalytic activity was 65~700g.polyet11ylene/g.Ti~hr C2ll4 pressure, 2,700g.polyethylel1e/g.solid-hr-C2~l4 pressure. The F.R. value of the polyethylene was 8Ø
ample 2 Polymerization of ethylene was carried out in the same way as in Example 1 excep-t that 0.05 mmol. oE monoethyl triethoxy silane was used in place oE the diethyl diethoxy silane and -that the amount oE th~ d:iethylaluminum monoethoxide was changed to 0.02 mrnol. As a result, there was obtained 163 g.
of a white polyethylene having a melt index of 0.9 atld a bulk density oE 0.41. Cataly-tic activity was 76,500g.polyethylelle/g.Ti hr C2ll4 pressure, 3,130~.polyeilly]elle/~.solld hr C2l-l4 pressure.
The l;'.R. value oE the polyethylene thus obtailled was 7.4. 'l'he molecular weigh-t distribu-tion was extremely narrow as compared with -the following Comparative Flxample 2.
Comparative ~xample 2 Polymeriza-tion of e-thylene was carried out in the same way as in Example 2 except tlla-t the diethylaluminum monoethoxide was not used. As a result, there was obtained 121 g. of a white poly-e-thylelle havillg a mel-t index of 1.1 and a bulk density of 0.32. Cataly-tic activ:ity was 5~,800g.polyethylene/
.II`i-hr C2]14 pressure, 2,330g.polyethylene/g.solid hr C2ll4 pressure. The F.R. value oE -the polyethylene was 8.1.
E'~alllple 3 Polymeriza-tion of ethylene was carried ou-t in the same way as in Example 1 excep-t that 0.1 mmol.
of diphenyl diethoxy silane and 0.02 mmol. of ethyl-alulninum diphenoxide were used in place of the die-thyl c1ietl1oxy sllane and diethylaluminum monoeti1oxide, respectively. ~s a result, there was obtained 181 g.
of a white polyethylene having a melt index of 1.3 and a bulk density o:E 0.39~ Ca-talytic activity was ~,900~.polyethylene/~.Ti-}1r C2H4 pressure, 3,430g.
~olye~l1ylene/~solid~l1r C2~l4 pressure. The F.R.
I() va~ale ~E thc polyethylene was 7.5. The molecular wei(lllt clistribut:iol1 was extremely narrow as compared ~it-i1 the following Compara~ive ~ample 3.
Comparative Example 3 Polymerization of ethylene was carried out in the same way as ïn Example 3 except -that the ethyl-aluminum diphenoxide was no-t used. As a result, there was obtained 133 ~. of a white polyethylene having a melt inde~ of 1.0 and a bulk densi-ty of 0.33. Catalytic activity ~-~Jas 62,400g.polyethylene/g Ti-hr-C2l~4 pressllre, 2,560g.polyethylene/g.solid hr C2ll4 pressure. The F.R. value oE the polyethylene was ~Ø
E.~ample 4 (a) Preparation of Solid Catalys-t Component [I~
_ 24 10 g. of a commercially available magnesium chloride and 4.2 ~. of aluminum triethoxide were placed in a stainless steel po-t having a content vo1ume oE 400 ml. ancl containing 25 stainless steel ~ci-lls each 1~2 inch in diallleter, and ball-milled for 16 hours at room temperature in a ni-trogen atmos-phere to ob-tain a reac-tion product. Then, a -three-necked f:lask equipl~ed with a stirrer and a reflux condel1ser was purc~ed with nitrogen and thel1 charged -lO witl1 5 ~J. of the a~ove reaction product and 5 g. of silica (/~52, a product o~ Fuji-Davlson) which had ~)eell calcined at ~00C. ~ en, 100 ml. of -tetrahydro-Euran was aclded and reaction was allowed -to take p]ace at G0C Eor 2 hours. Thereafter, -tetrahydrofuran was removed by drying at 120C under reduced pressure.
Then, 50 ~IIl. of hexane was added, and after s-tirring, 1.1 ml. of titanium te-trachloride was added and reac-tion was allowed to take place for 2 hours under reflux of hexane to give a solid powder (~) containing 40 mg. of titanium ~er gram thereof.
The solid powder (A) was added into 50 ml. of hexane, then 1 ml. of tetraethoxy silane was added and reaction was allowed -to take place for 2 hours undel- reElux of hexane -to obtain a solid catalyst component ~
~99~
(b) Polymeriza-tion 2-liter stainless steel autoclave equipped ~i.th an inductlon stirrer was purged wi-th nitrogen and then charged with 1,000 ml. oE hexane, -then 1 mrn^~l. of -triethylal.uminum, 0.05 mmol. of dimethyl diethoxy silane, 0.01 mmol. of diethylaluminum mono-ethoxide and 10 mg. of the above solid catalyst compo-ne1lt ~I~ were added and the temperature was raised to 90C und~r stirring. ~ith the vapor pressure 1() o~ hexclne, the syste1ll was pressurized -to 2 kg/cm -G.
, hydrogen was introduced up to a total pressure oE ~.8 kg/cm2-G and then ethylene was introduced up to a total pressure oE 10 kg/cm2 G. In this state, ~olymerization was allowed to start, which was continued Eor 1 hour while maintaining the internal pressure o the autoclave at 10 kg/cm2 G. Thereafter, the polymer slurry was transEerred into a beaker and hexane was removed under reduced pressure to give 60 g. of a white polyethylene having a melt index of 0.7 and a bulk density of 0.42. Catalytic activity was 28,800cJ.polyethyleile/~.Ti-hr C21~4 pressure, 1,150g.polyet11ylene/c~.solid ilr-C2114 pressure. The F.R. value of t11e polye-thylene was 7.4. The molecular wei~ht distribution was extremely narrow as compared with the following Comparative Example 4. Further, the polymer particles proved to be superior in fluidity and have an average particle diameter of 730~m.
Compara~.ive Example 4 Polymeriæation of ethylene was carried ou~ in ti1e salne ~ay as in Example 4 except that the diethylalumil1um monoet]-loxide was nQt used. ~s a result, there was obtained 48 g. of polye-tl1ylene having a melt ill(]eX of ().9 and a bulk density of 0.3~. Catalytic activity was 23,100g.po1yethylene/g.
'l'i~hr.C2Tl4 pressure, 920g.polyethylene/g.solid-hr-C2H~
l~ pres:~lre. 'I`hc F.~. value o~ the polyeth~lene was . 1 .
~ample 5 (a) Preparation of Solid Catalyst Component ~I~
10 g. of a commercially available anhydrous magnesium chloride, 2.0 g. of -titanium tetraisopropoxide and 1.7 g. of isopropyl chloride were placed in a stainless steel pot having a content volume of 400 ml. and containinc3 25 stainless steel ba]ls each 1/2 inch in diameter, and ball-milled for 16 hours at 2n room temperature in a nitrogen atrnosphere, to give a solid ca-talyst component [I] containing 25 mg.
of titanium per gram thereof.
(b) Polyme1^ization A 2-liter stainless steel autoclave equipped with an induction stirrer was purged wlth nitrogen ancl then charged with 1,000 lnl. of hexane, then 1 mlnol. oE trie~hylaluminum, 0.1 mmol. o~ diphenyl diethoxy silane, 0.05 mmol. of diethylaluminum mono-etl1oxide and 10 Ing. of t-lle above solid catalyst component ~I~ were adcled and the temperature was raised to 90C under stirring. With the vapor pressure oC hexane, the system was pressurized to 2 kg/cm2-G.
'l`l1e~ ydl-oclel1 was :introduced up to a total pressure l() Or 4.8 Icg/cm2-G and then ethylel1e was introduced up to a tota:l pressure of 10 kg/cm2 G. In -this s-tate, ~olymerization was allowed to start, which was con-tinued for 1 hour while maintaining -the -total pressure at 10 kg/cm G. Thereafter, -the polymer slurry was transferred in-to a beaker and hexane was removed under reduced pressure to afford 44 g. of a white polyethylene having a melt index of 1.1 and a bulk density of 0.38 Catalytic activity was 33,700g.
polyethylene/g.Ti-hr-C2ll4 pressure, 850g.polyethylene/g.
solid-hr-C2ll4 pressure. The F.R. value was 7.6 and thus the molecular weigi1-t distribution was narrow.
Comparative ~xample 5 Polymeriza-tion of ethylene was carried out in the same way as in ~xample 5 except that the diethylaluminum monoethoxide was not used. As a result, there was obtained 3S g. of polyethylene having a me1t index of 0.9 and a bul]c densi-ty of 0.31. Catalytic activi-ty was 26,800g.polye-thylene/g.
Ti.hr.C2ll4 pr~ssure, 670~.polyethylene/g.solid-hr-C2H~
pressure. rl`he ~'.R. value was 8.2.
Example 6 ~ vapor-pl1ase polymerization was carried out Usil1g the solid catalys-t componen-t LI~ obtained ill L;:~alllple 1. ~s the vapor-phase polymerization I n aE~parcltus there was used a stainless steel autoclave, ancl a loop was Eormed by a blower, a flow control clev:ice and a dry cyclone. The temperature of -the autoclave was adjusted by passing warm water through its jacket.
Into the autoclave adjus-ted to 80C were fed the solid catalys-t component ~I~ obtained in Example 1, diethyl die-thoxy silane, diethylaluminum monoethoxide and triethylaluminum at rat-s of 50 mq/hr, 0.25 mmol/hr, 0.05 mmol/hr and 5 mmol/hr, respectively. Further, hydrogen and ethylene were introduced while making an adjustment so as to ~ive a hydro~en/ethylene mol ra-tio of 0.45 in the vapor phase in the autoclave. ~t -the same time, the intra-system ~ases were circulated by means of the blower to maintain -the total pressure at 10 k~/cm G.
_ 29 Polymerization was carried out under these conditions to give polyethylene having a bulk density of 0.36 and a melt index of 0.9. Ca-talytic acitivyt was 38~,000g.polyethylene/g.Ti. The F.R. value was 7.6.
Example 7 (a) Preparation of Solid Catalyst Component rI~
6.5 g. of a commercially available anhydrous ma~nesium chloride, 1.5 g. of boron -triethoxide and 1.5 g. o;E titanium te-trachloride were placed in a st~inless steel pot having a content volume of 400 ml. and con-taining 25 stainless steel ball each 1/2 inch in diameter, and ball-milled for 16 hours at room temperature in a ni-trogen atmosphere, to obtain a solid catalyst component LI~ containing 40 mg.
of titanium per gram thereof.
(b) Polymeriza-tion Polymerization of ethylene was carried out in the same way as in Example 1 except that 10 mg.
of the solid catalyst component tI~ prepared just ahove was used.
As a result, there was obtained 166 g.
of a white polye-thylene having a melt index of 1.3 and a bulk density of 0.30. Cataly-tic activity was 79,800g.polye-thylene/g.Ti-hr C2H4 pressure, 3,190g.
polyethylene/g.solid hr-C2H4 pressure. The F.R.
3~ _ value of the polyethylene was 7.6.
Example 8 The ball mill pot of the same type described :In ~Yample 7 was charyed with 10 g. of a commercially available anhydrous magnesium chloride, 2.2 g. of magnesium diethoxide and 2.3 g. of titanium -tetra-chloride. The admixture was ball-milled for 16 hours at room tempera-ture in a nitrogen atmosphere to obtain a solid catalyst component ~I~ containing 40 mg.
oE titanlum per gram thereof.
Polymeriza-tion of ethylene was carried out in the same way as in Example 1 except that 10 mg.
of the solid catalyst component ~I~ prepared just above was used.
As a result, there was obtained 88.4 g.
of a white polyethylene having a mel-t index of 0.95 and a bulk density of 0.28. Catalytic activity was 42t500g.polyethylene/g.Ti-hr-C2H4 pressure, 1,700g.
polyethylene/g.solid hr C2H4 pressure. The F.R.
value of the polyethylene was 7.6.
_ 31
In t]liS case, not only o~ides oE Group II-IV metals eacl~ alone bu-t also double oxides of these metals, as well as mixtures thereoE, are employable Examples of such metal oxides are M~O, CaO, ZnO, BaO, SiO2, 2' 23~ MgO-~l2O3, SiO2-~l2O3, MgO-SiO
MgO CaO-Al2O3 and ~l2O3 CaO. Par-ticularly preferred 2' ~l23~ SiO2-~l2O3 and MgO-A12o The method of supporting -the catalyst component ~I~ on an oxide of a Group II-IV metal in the Periodic l~a~le is nol: specially limited, but ~s a preferred exarnple t}lel^e may be mentioned a method wherein the components (i) and (ii), and the component (~) if required, are allowed to react under h~at-in~, 2~ for example in an etller compound as solvent in the presence of the said me-tal oxide and then the liquid ~19~
phase portion is removed.
Examples o:E the compound of the general fo.rlrlu.1.a R1mSi(~l~ )4 m used in the present invention include monornethyl trimethoxy silane, monome-thyl triethoxy silane, monolnethyl tri-n-buto~y silane, monomethyl tri-sec-butoxy silane, monornethyl tr:iisopropoxy silane, monomethyl tripen-toxy silane r monolrlet:l1yl t.rioctoxy s:ilane, monometl1yl tristearoxy si.lal~o, nlor1olnetllyl tr:iphenoxy silane, dime~l1yl c1lmetl1oxy 1~ s:i.1.ane, d.im~thyl diethoxy silane, dimethyl diisopropoxy silane, c1imethyl diphenoxy silane, trime-thyl monomethoxy s:ik~l1e, trLmethyl molloethoxy silane, trime-thyl mono-isopropo~y silane, trimethyl monophenoxy silane, monoethyl trimethoxy silane, monoe-thyl triethoxy silane, monoethyl triisopropoxy silane, monoe-thyl triphenoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diethyl diphenoxy silane, triethyl monomethoxy silane, triethyl monoethoxy silane, -trie-thyl monop}lenoxy silane, monoi.sopropyl tr.i.methoxy silane, mono-n-butyl trimethoxy silane, mono-n-butyl triethoxy silane, mono-sec-butyl -triethoxy silane, monophenyl tr.ietl1o~y si.lal1e~ di.pl1enyl diethoxy silal1e, tetra-ethoxy silalle and te-traisopropoxy si].ane.
If tl1e amount of the compound of the ~JeneLa:l.
formula R1mSi(OR )4 m used in the present invention is too large or too small, its effect oE addition cannot _ ~6 be expec-ted. Usually, its amount is in the range of 0.1 to 100 moles, preferably 0.3 to 2n moles, per mole o:E the ti-tanium ~ompound and/or vànadium compound .in the catalyst component ~
~s examp1es o:E the compo~ d o:E the general formula R3 ~l~OR )3_ used in -tl1e present invention, mention may be ma~e o:E the :Eol.lowin~: dimethylaluminum monoethc),Y.icle, dim(?thylaluminum monoisopropoxide, cl:imc?t.lly:l.a,l~lmillunl mollo-ll-l)ul:oxide, dimetllylalumillum In sec-bu ~:oxide, climetllylaluminum monophenoxlde, diethyl-a~ lin~lm mollolnethoxide, diethylalumlnum monoethoxide, diethylaluminum monoisopropoxide, diethylaluminum mol1o~ butoxide, diethylaluminum sec-butoxide, diethylaluminum monophenoxide, diethylaluminum mono-octoxide, diethylaluminum monos-tearyloxide, diisobutyl-aluminum monoethoxide, methylaluminum dimethoxide, methylaluminum diethoxide, e-thylaluminum dlmethoxide, ethylaluminum die-thoxide, ethylaluminum diisopropoxi.de, ethylaluminum di-n-butoxide, ethylaluminum phenoxide, isobutylaluminum dimetl1oxide and isobutylaluminum d:iethoxlcle.
~ s to the amount of -the coml~ouncl o:~ the ~eneral :Eormula R41l~l(OR4)3 used in the present invention, both a too 1.ar~e amount and a too small amoul1t would not be e:Efective. Its amoul1t i.s in .the ran~e oE 0.01 to 10 moles, preferably 0.05 to 2 ~Z~
moles, per mole of the silicon compound in the catalyst coml~onent [II~.
~ s e~amp:les of -the organomet~]lic compound used in -the present invention, there may be mentioned orcJanometallic compoullds of Group I-IV me-tals in the Periodic Table knowll as a component of Ziegler type cacalysts, but orcJanoaluMillum compounds and or~anozil~c compounds are particularly preferred, ror e~alllr):le, or~anoal~lmillum compounds of the c~eneral 1() ~o~ e ~3~1, R2~1X, RAlX2 and R3A12X3 wllerei~l R, which may be alike or different, is an alkyl or aryl cJroup having 1 to 20 carbon atoms and X is a halogen atoln, and organoz:inc compounds of the general formula R2Z wherein R, which may be alike or different, is an alkyl group having 1 to 20 carbon atoms, such as triethylaluminum, triisopropylaluminum, triisobutyl-aluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethy]aluminum chloride, diiso-propylaluminum chloride, et~lylaluminum sesquichloride, diethylzillc, and mixtures thereof. TocJether with tilese or~anometallic compounds there may be used orgallocarboxylic acid esters such as ethyl benzoate, ethyl toluylate and ethyl anlsate. The or~anometallic 2r compoulld may be used in an amount of 0.1 to 1,000 moles per mole of the titanium compound and/or vanadium compound in the catalyst component [I~.
The olefin polymerization using the catalyst oE the present -invention may be carried out by slurry po1ylnerizat:io1l, solution polymerization or vapor phase polyl1lerization. Particularly, slurry polymerization and vapor phase polymerization are preferred. The polymerlzatioll reaction is carried ou-t ln the same way as in t1ie co~1vent;o3lal olefin polymerl2atlo1l reaCtiOIl USillg a Zie~ler type ca-talyst. ~'hat is, the -10 reactiot1 :is perEormed in a substan-tially oxygen- and wal:er-~1^ee conditior1 and in the presence or absence o~ ~n inert hydrocarbon. Olefin polymerizing condi-tions involve temperatures in the range of 20 to 120DC, pre~erably 50 to 100C, and pressures in the range of atmospheric pressure to 70 kg/cm2, preferably 2 to 60 kg/cm2. Adjustment of the molecular weight can be made to some extent by changing polymerization condi-tions such as the polymerization -temperature and the catalyst mole ratio, but the addition of hydrogen 2n into the polymerization sys-tem is more effective for this purpose. Of course, usin~ the catalyst of the present invention, two or more mu:Lti-staae polymeriza-tion reactiorls l1aving different polymerization condi-tions sucll as differer1t hydrogen concer1trations and different polylnerization temperatures can be performed ~i~ho~1t any trol~le.
~ 19 The process of the present invention is applicable to the polymerization of all olefins that are polymerizable with a Ziegler type catalys-t. Parti-cularly, ~-oleEins having 2 to 12 carbon atoms are preferred. For example, the process of the presellt invention is suitable for the homopolymerization of such ~-olefins as ethylene, propylene, butene-1, hexene-1, 4-methylI)elltene-1 and octene--1, the copolymer-ization oE etl-ylene/propylene, ethy]elle/butelle-1, 10 etllylc!ne/l-~exene-l, ethylene/4-metllylpentene~1, etllylene/octene-1 and propylene/butene-1, as well as the copolymerization oE ethylene and other -two or more ~-oleEins.
Copolymerization with dienes Eor the modifica-tion of polyolefins is also preferable. As dienesthere may be used, for example, bu-tadiene, 1,4-hexadiene, ethylidene norbornene and dicyclopentadiene.
The following examples are given to fur-ther illustrate -the present inven-tion, bu-t i-t ls to be understood -that the invention is not llmited thereto.
Example 1 (a) Preparation of Solid Ca-talyst Componen-t rI~
10 g. o~ a comlllercially availab]e anhydrous magnesiu]n chloride, 2.3 g. of aluminum triethoxide `and 2.5 g, of titanium tetrachloride were placed in a stainless steel pot having a con-tent volume of 400 ml. and containing 25 stainless s-teel balls each 1/2 inch .in diameter, and ball-milled for 16 hours at room telnperature in a nitrogen a-tmosphere, to obtain a solid catalyst component LI~ COI1taining - 41 mg of titanium per yram -thereof.
(b) Polymeriza-tion ~ 2-liter stainless steel autoclave equipped Wit]1 al~ duction stirrer was puryed wlth nitroyen 1() and tl1en cl1aryed w:it.h l,000 ml. oE hexane, then 1 Inlllol. o.~ trietl1ylaluminum, 0.05 mmol. of diethyl c1:ieti-loxy silane, 0.01 mmol. of diethylaluminum mono-ethoxide and 10 mg. of the above solid catalyst com-ponent LI} were added and t~le tempera-ture was raised -l5 to 90C under stirring. Wi-th -the vapor pressure of hexane, the system was pressurized to 2 ky/cm2-G.
Then, hydrogen was introduced up to a total pressure of 4.8 kg/cm2-G and -then ethylene was in-troduced up to a tota] pressure of 10 k.g/cm G. In this state, polymerization was allowed to star-t, which was continued for 1 hour while mail1taining the internal pressure of the autoclave at 10 kg/cm G. Thereaf-ter, the polymer slurry w~s transferred in-to a beaker and hexane was removed under reduced pressure to obtain 175 g. o.E a ~5 white polyethylene having a melt index o:E 1.1 and a bulk density of 0.38. Cataly-tic acti.vi-ty was 82,100g.polyethylene/g.Ti-hr-C21l4 pressure, 3,370g.polyethylene/g.solld~hr C2H4 pressure.
F.R.-value of the polyethylene thus obtained was 7.5. The molecular wei~ht distribu-tion was extremely narrow as compared with the following Comparative Example 1.
* F.R. value represents the extent of molecular weight distribution and is ca:Lculated as Eollows:
I n F.R. = melt index at 10 kg. load/
mel-t index at 2.16 kg. load The melt index was measured according to ASTM D-1238.
Comparative Example 1 Polymerization o: ethylene was carried out in the same way as in Example 1 excep-t that the diethylaluminum monoethoxide was not used, to ob-tain 140 g. of a white polyethylene having a bulk density of 0.33 and a melt index of 1Ø Catalytic activity was 65~700g.polyet11ylene/g.Ti~hr C2ll4 pressure, 2,700g.polyethylel1e/g.solid-hr-C2~l4 pressure. The F.R. value of the polyethylene was 8Ø
ample 2 Polymerization of ethylene was carried out in the same way as in Example 1 excep-t that 0.05 mmol. oE monoethyl triethoxy silane was used in place oE the diethyl diethoxy silane and -that the amount oE th~ d:iethylaluminum monoethoxide was changed to 0.02 mrnol. As a result, there was obtained 163 g.
of a white polyethylene having a melt index of 0.9 atld a bulk density oE 0.41. Cataly-tic activity was 76,500g.polyethylelle/g.Ti hr C2ll4 pressure, 3,130~.polyeilly]elle/~.solld hr C2l-l4 pressure.
The l;'.R. value oE the polyethylene thus obtailled was 7.4. 'l'he molecular weigh-t distribu-tion was extremely narrow as compared with -the following Comparative Flxample 2.
Comparative ~xample 2 Polymeriza-tion of e-thylene was carried out in the same way as in Example 2 except tlla-t the diethylaluminum monoethoxide was not used. As a result, there was obtained 121 g. of a white poly-e-thylelle havillg a mel-t index of 1.1 and a bulk density of 0.32. Cataly-tic activ:ity was 5~,800g.polyethylene/
.II`i-hr C2]14 pressure, 2,330g.polyethylene/g.solid hr C2ll4 pressure. The F.R. value oE -the polyethylene was 8.1.
E'~alllple 3 Polymeriza-tion of ethylene was carried ou-t in the same way as in Example 1 excep-t that 0.1 mmol.
of diphenyl diethoxy silane and 0.02 mmol. of ethyl-alulninum diphenoxide were used in place of the die-thyl c1ietl1oxy sllane and diethylaluminum monoeti1oxide, respectively. ~s a result, there was obtained 181 g.
of a white polyethylene having a melt index of 1.3 and a bulk density o:E 0.39~ Ca-talytic activity was ~,900~.polyethylene/~.Ti-}1r C2H4 pressure, 3,430g.
~olye~l1ylene/~solid~l1r C2~l4 pressure. The F.R.
I() va~ale ~E thc polyethylene was 7.5. The molecular wei(lllt clistribut:iol1 was extremely narrow as compared ~it-i1 the following Compara~ive ~ample 3.
Comparative Example 3 Polymerization of ethylene was carried out in the same way as ïn Example 3 except -that the ethyl-aluminum diphenoxide was no-t used. As a result, there was obtained 133 ~. of a white polyethylene having a melt inde~ of 1.0 and a bulk densi-ty of 0.33. Catalytic activity ~-~Jas 62,400g.polyethylene/g Ti-hr-C2l~4 pressllre, 2,560g.polyethylene/g.solid hr C2ll4 pressure. The F.R. value oE the polyethylene was ~Ø
E.~ample 4 (a) Preparation of Solid Catalys-t Component [I~
_ 24 10 g. of a commercially available magnesium chloride and 4.2 ~. of aluminum triethoxide were placed in a stainless steel po-t having a content vo1ume oE 400 ml. ancl containing 25 stainless steel ~ci-lls each 1~2 inch in diallleter, and ball-milled for 16 hours at room temperature in a ni-trogen atmos-phere to ob-tain a reac-tion product. Then, a -three-necked f:lask equipl~ed with a stirrer and a reflux condel1ser was purc~ed with nitrogen and thel1 charged -lO witl1 5 ~J. of the a~ove reaction product and 5 g. of silica (/~52, a product o~ Fuji-Davlson) which had ~)eell calcined at ~00C. ~ en, 100 ml. of -tetrahydro-Euran was aclded and reaction was allowed -to take p]ace at G0C Eor 2 hours. Thereafter, -tetrahydrofuran was removed by drying at 120C under reduced pressure.
Then, 50 ~IIl. of hexane was added, and after s-tirring, 1.1 ml. of titanium te-trachloride was added and reac-tion was allowed to take place for 2 hours under reflux of hexane to give a solid powder (~) containing 40 mg. of titanium ~er gram thereof.
The solid powder (A) was added into 50 ml. of hexane, then 1 ml. of tetraethoxy silane was added and reaction was allowed -to take place for 2 hours undel- reElux of hexane -to obtain a solid catalyst component ~
~99~
(b) Polymeriza-tion 2-liter stainless steel autoclave equipped ~i.th an inductlon stirrer was purged wi-th nitrogen and then charged with 1,000 ml. oE hexane, -then 1 mrn^~l. of -triethylal.uminum, 0.05 mmol. of dimethyl diethoxy silane, 0.01 mmol. of diethylaluminum mono-ethoxide and 10 mg. of the above solid catalyst compo-ne1lt ~I~ were added and the temperature was raised to 90C und~r stirring. ~ith the vapor pressure 1() o~ hexclne, the syste1ll was pressurized -to 2 kg/cm -G.
, hydrogen was introduced up to a total pressure oE ~.8 kg/cm2-G and then ethylene was introduced up to a total pressure oE 10 kg/cm2 G. In this state, ~olymerization was allowed to start, which was continued Eor 1 hour while maintaining the internal pressure o the autoclave at 10 kg/cm2 G. Thereafter, the polymer slurry was transEerred into a beaker and hexane was removed under reduced pressure to give 60 g. of a white polyethylene having a melt index of 0.7 and a bulk density of 0.42. Catalytic activity was 28,800cJ.polyethyleile/~.Ti-hr C21~4 pressure, 1,150g.polyet11ylene/c~.solid ilr-C2114 pressure. The F.R. value of t11e polye-thylene was 7.4. The molecular wei~ht distribution was extremely narrow as compared with the following Comparative Example 4. Further, the polymer particles proved to be superior in fluidity and have an average particle diameter of 730~m.
Compara~.ive Example 4 Polymeriæation of ethylene was carried ou~ in ti1e salne ~ay as in Example 4 except that the diethylalumil1um monoet]-loxide was nQt used. ~s a result, there was obtained 48 g. of polye-tl1ylene having a melt ill(]eX of ().9 and a bulk density of 0.3~. Catalytic activity was 23,100g.po1yethylene/g.
'l'i~hr.C2Tl4 pressure, 920g.polyethylene/g.solid-hr-C2H~
l~ pres:~lre. 'I`hc F.~. value o~ the polyeth~lene was . 1 .
~ample 5 (a) Preparation of Solid Catalyst Component ~I~
10 g. of a commercially available anhydrous magnesium chloride, 2.0 g. of -titanium tetraisopropoxide and 1.7 g. of isopropyl chloride were placed in a stainless steel pot having a content volume of 400 ml. and containinc3 25 stainless steel ba]ls each 1/2 inch in diameter, and ball-milled for 16 hours at 2n room temperature in a nitrogen atrnosphere, to give a solid ca-talyst component [I] containing 25 mg.
of titanium per gram thereof.
(b) Polyme1^ization A 2-liter stainless steel autoclave equipped with an induction stirrer was purged wlth nitrogen ancl then charged with 1,000 lnl. of hexane, then 1 mlnol. oE trie~hylaluminum, 0.1 mmol. o~ diphenyl diethoxy silane, 0.05 mmol. of diethylaluminum mono-etl1oxide and 10 Ing. of t-lle above solid catalyst component ~I~ were adcled and the temperature was raised to 90C under stirring. With the vapor pressure oC hexane, the system was pressurized to 2 kg/cm2-G.
'l`l1e~ ydl-oclel1 was :introduced up to a total pressure l() Or 4.8 Icg/cm2-G and then ethylel1e was introduced up to a tota:l pressure of 10 kg/cm2 G. In -this s-tate, ~olymerization was allowed to start, which was con-tinued for 1 hour while maintaining -the -total pressure at 10 kg/cm G. Thereafter, -the polymer slurry was transferred in-to a beaker and hexane was removed under reduced pressure to afford 44 g. of a white polyethylene having a melt index of 1.1 and a bulk density of 0.38 Catalytic activity was 33,700g.
polyethylene/g.Ti-hr-C2ll4 pressure, 850g.polyethylene/g.
solid-hr-C2ll4 pressure. The F.R. value was 7.6 and thus the molecular weigi1-t distribution was narrow.
Comparative ~xample 5 Polymeriza-tion of ethylene was carried out in the same way as in ~xample 5 except that the diethylaluminum monoethoxide was not used. As a result, there was obtained 3S g. of polyethylene having a me1t index of 0.9 and a bul]c densi-ty of 0.31. Catalytic activi-ty was 26,800g.polye-thylene/g.
Ti.hr.C2ll4 pr~ssure, 670~.polyethylene/g.solid-hr-C2H~
pressure. rl`he ~'.R. value was 8.2.
Example 6 ~ vapor-pl1ase polymerization was carried out Usil1g the solid catalys-t componen-t LI~ obtained ill L;:~alllple 1. ~s the vapor-phase polymerization I n aE~parcltus there was used a stainless steel autoclave, ancl a loop was Eormed by a blower, a flow control clev:ice and a dry cyclone. The temperature of -the autoclave was adjusted by passing warm water through its jacket.
Into the autoclave adjus-ted to 80C were fed the solid catalys-t component ~I~ obtained in Example 1, diethyl die-thoxy silane, diethylaluminum monoethoxide and triethylaluminum at rat-s of 50 mq/hr, 0.25 mmol/hr, 0.05 mmol/hr and 5 mmol/hr, respectively. Further, hydrogen and ethylene were introduced while making an adjustment so as to ~ive a hydro~en/ethylene mol ra-tio of 0.45 in the vapor phase in the autoclave. ~t -the same time, the intra-system ~ases were circulated by means of the blower to maintain -the total pressure at 10 k~/cm G.
_ 29 Polymerization was carried out under these conditions to give polyethylene having a bulk density of 0.36 and a melt index of 0.9. Ca-talytic acitivyt was 38~,000g.polyethylene/g.Ti. The F.R. value was 7.6.
Example 7 (a) Preparation of Solid Catalyst Component rI~
6.5 g. of a commercially available anhydrous ma~nesium chloride, 1.5 g. of boron -triethoxide and 1.5 g. o;E titanium te-trachloride were placed in a st~inless steel pot having a content volume of 400 ml. and con-taining 25 stainless steel ball each 1/2 inch in diameter, and ball-milled for 16 hours at room temperature in a ni-trogen atmosphere, to obtain a solid catalyst component LI~ containing 40 mg.
of titanium per gram thereof.
(b) Polymeriza-tion Polymerization of ethylene was carried out in the same way as in Example 1 except that 10 mg.
of the solid catalyst component tI~ prepared just ahove was used.
As a result, there was obtained 166 g.
of a white polye-thylene having a melt index of 1.3 and a bulk density of 0.30. Cataly-tic activity was 79,800g.polye-thylene/g.Ti-hr C2H4 pressure, 3,190g.
polyethylene/g.solid hr-C2H4 pressure. The F.R.
3~ _ value of the polyethylene was 7.6.
Example 8 The ball mill pot of the same type described :In ~Yample 7 was charyed with 10 g. of a commercially available anhydrous magnesium chloride, 2.2 g. of magnesium diethoxide and 2.3 g. of titanium -tetra-chloride. The admixture was ball-milled for 16 hours at room tempera-ture in a nitrogen atmosphere to obtain a solid catalyst component ~I~ containing 40 mg.
oE titanlum per gram thereof.
Polymeriza-tion of ethylene was carried out in the same way as in Example 1 except that 10 mg.
of the solid catalyst component ~I~ prepared just above was used.
As a result, there was obtained 88.4 g.
of a white polyethylene having a mel-t index of 0.95 and a bulk density of 0.28. Catalytic activity was 42t500g.polyethylene/g.Ti-hr-C2H4 pressure, 1,700g.
polyethylene/g.solid hr C2H4 pressure. The F.R.
value of the polyethylene was 7.6.
_ 31
Claims (13)
1. A process for preparing a polyolefin, character-ised by polymerizing at least one olefin by using a catalyst, said catalyst comprising the combination of:
[I] a solid substance obtained by the reaction of at least the following two components:
(i) a magnesium halide and (ii) a titanium compound and/or a vanadium compound;
[II] a compound represented by the general formula R1mSi(OR2)4-m wherein R1 and R2 are hydrocarbon radicals having 1 to 24 carbon atoms and 0 ? m ? 3;
[III] a compound represented by the general formula R3nAl(OR4)3-n wherein R3 and R4 are hydrocarbon radicals having 1 to 24 carbon atoms and 1 ? n ? 2; and [IV] an organometallic compound, the molar ratio of silicon in said component [II] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 100, the molar ratio of aluminum in said component [III] to silicon in said component [II]
being in the range of 0.01 to 10 and the molar ratio of the metal in said component [IV] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 1,000.
[I] a solid substance obtained by the reaction of at least the following two components:
(i) a magnesium halide and (ii) a titanium compound and/or a vanadium compound;
[II] a compound represented by the general formula R1mSi(OR2)4-m wherein R1 and R2 are hydrocarbon radicals having 1 to 24 carbon atoms and 0 ? m ? 3;
[III] a compound represented by the general formula R3nAl(OR4)3-n wherein R3 and R4 are hydrocarbon radicals having 1 to 24 carbon atoms and 1 ? n ? 2; and [IV] an organometallic compound, the molar ratio of silicon in said component [II] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 100, the molar ratio of aluminum in said component [III] to silicon in said component [II]
being in the range of 0.01 to 10 and the molar ratio of the metal in said component [IV] to titanium and/or vanadium in said component [I] being in the range of 0.1 to 1,000.
2. The process of claim 1, wherein said catayst component [I] comprises a said substance obtained by the reaction of said component (i), said component (ii) and one or more further components (.alpha.) selected from the group consisting of compound of the general formula Me(OR)pXz-p wherein Me is a element selected from Group I through VIII in the Periodic Table, provided titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, z is the valence of Me and p is 0 < p ? z.
3. The process of claim 1, wherein said catalyst component [I] comprises a said substance obtained by the reaction of said component (i), said component (ii) and one or more further components (.alpha.) selected from the group consisting of organic halides and halogenating agents.
4. The process of claim 1, wherein said catalyst component [I] comprises a said substance obtained by the reaction of said component (i), said component (ii) and one or more further components (.alpha.) selected from the group consisting of phosphoric esters.
5. The process of claim 1, wherein said catalyst component [I] comprises a said substance obtained by the reaction of said component (i), said component (ii) and one or more further components (.alpha.) selected from the group consisting of electron donors.
6. The process of claim 1, wherein said catalyst component [I] comprises a said substance obtained by the reaction of said component (i), said component (ii) and one or more further components (.alpha.) selected from the group consisting of polycyclic aromatic compounds.
7. The process of claim 2, wherein said component (.alpha.) represented by the general formula Me(OR)pXx-p is selected from the group consisting of Al(OR)pX3-p, B(OR)pX3-p and Mg(OR)pX2-p.
8. The process of claim 1, wherein said catalyst component [I] is supported on an oxide of a metal selected from Group II through IV in the Periodic Table.
9. The process of claim 1, wherein said magnesium halide is a substantially anhydrous magnesium halide.
10. The process of claim 1, wherein said titanium compound and/or vanadium compound are (or is) selected from halides, alkoxyhalides, alkoxides and halogenated oxides of titanium and/or vanadium.
11. The process of claim 1, wherein said organometallic compound is an organoaluminum compound or an organozinc compound.
12. The process of claim 1, wherein said olefin is an .alpha.-olefin having 2 to 12 carbon atoms.
13. The process of claim 1, wherein the polymerization reaction is carried out at a temperature in the range of 20°C to 120°C and at a pressure in the range of atmospheric pressure to 70 kg/cm2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22692282A JPS59120602A (en) | 1982-12-27 | 1982-12-27 | Production of polyolefin |
| JP226922/1982 | 1982-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1219998A true CA1219998A (en) | 1987-03-31 |
Family
ID=16852699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000442532A Expired CA1219998A (en) | 1982-12-27 | 1983-12-05 | Process for preparing polyolefins |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS59120602A (en) |
| CA (1) | CA1219998A (en) |
| DE (1) | DE3346798A1 (en) |
| FR (1) | FR2541291B1 (en) |
| GB (1) | GB2135681B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06104681B2 (en) * | 1983-05-11 | 1994-12-21 | 三井石油化学工業株式会社 | Method for producing rubbery ethylene copolymer |
| KR940010330B1 (en) * | 1986-06-17 | 1994-10-22 | 아모코 코포레이션 | Alpha-olefin polymerization catalyst system including an advatageous modifier component |
| CA2089970A1 (en) * | 1992-03-04 | 1993-09-05 | Edwar S. Shamshoum | Catalyst formulation and polymerization processes |
| EP1264847A1 (en) * | 2001-06-06 | 2002-12-11 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Alpha-olefin polymerisation process |
| WO2009027266A1 (en) * | 2007-08-29 | 2009-03-05 | Basell Poliolefine Italia S.R.L. | Catalyst for the polymerization of olefins |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2126250C3 (en) * | 1971-05-26 | 1980-06-12 | Wacker-Chemie Gmbh, 8000 Muenchen | Process for the production of polyethylene or modified polyethylene with a narrow molecular weight distribution |
| DE3027885A1 (en) * | 1979-07-24 | 1981-02-12 | Mitsubishi Petrochemical Co | POLYMERIZATION OF ETHYLENE |
| JPS5695909A (en) * | 1979-12-28 | 1981-08-03 | Nippon Oil Co Ltd | Preparation of polyolefin |
| IT1209255B (en) * | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| JPS57182304A (en) * | 1981-05-07 | 1982-11-10 | Nippon Oil Co Ltd | Production of polyolefin |
| JPS5811509A (en) * | 1981-07-11 | 1983-01-22 | Nippon Oil Co Ltd | Preparation of polyolefin |
| DE3231582C2 (en) * | 1981-08-25 | 1993-10-14 | Nippon Oil Co Ltd | Process for the production of polyolefins |
-
1982
- 1982-12-27 JP JP22692282A patent/JPS59120602A/en active Granted
-
1983
- 1983-12-05 CA CA000442532A patent/CA1219998A/en not_active Expired
- 1983-12-21 GB GB08334098A patent/GB2135681B/en not_active Expired
- 1983-12-23 DE DE19833346798 patent/DE3346798A1/en not_active Withdrawn
- 1983-12-27 FR FR8320877A patent/FR2541291B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2135681B (en) | 1986-05-08 |
| JPS59120602A (en) | 1984-07-12 |
| DE3346798A1 (en) | 1984-08-02 |
| FR2541291B1 (en) | 1988-05-13 |
| GB8334098D0 (en) | 1984-02-01 |
| GB2135681A (en) | 1984-09-05 |
| JPH0149282B2 (en) | 1989-10-24 |
| FR2541291A1 (en) | 1984-08-24 |
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