CA1147899A - Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 with application of such a titanium component - Google Patents
Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 with application of such a titanium componentInfo
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- CA1147899A CA1147899A CA000348651A CA348651A CA1147899A CA 1147899 A CA1147899 A CA 1147899A CA 000348651 A CA000348651 A CA 000348651A CA 348651 A CA348651 A CA 348651A CA 1147899 A CA1147899 A CA 1147899A
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- titanium
- titanium component
- halide
- aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A B S T R A C T
The invention relates to a catalytic titanium component useful for the polymerization of alkenes-1 and for the copolymerization of alkenes-1 with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a mixture of a magnesium halide and an aluminum halide.
The titanium component according to the invention is charac-terized in that it contains 0.1-10 % by wt. of titanium and the titanium : magnesium : aluminium weight ratio amounts to 1 :(0.5-20) :
(0.05-2.5), while the magnesium : aluminium weight ratio is at least 3 : 1.
With these specific weight ratios, the aluminium halide does not act as an inert filler, but has a very special action, reflected in a particular high activity at good stereospecificity of a catalyst system containing such a titanium component.
The catalytic titanium component according to the invention is mainly of importance for stereospecific polymerization of propylene.
The invention relates to a catalytic titanium component useful for the polymerization of alkenes-1 and for the copolymerization of alkenes-1 with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a mixture of a magnesium halide and an aluminum halide.
The titanium component according to the invention is charac-terized in that it contains 0.1-10 % by wt. of titanium and the titanium : magnesium : aluminium weight ratio amounts to 1 :(0.5-20) :
(0.05-2.5), while the magnesium : aluminium weight ratio is at least 3 : 1.
With these specific weight ratios, the aluminium halide does not act as an inert filler, but has a very special action, reflected in a particular high activity at good stereospecificity of a catalyst system containing such a titanium component.
The catalytic titanium component according to the invention is mainly of importance for stereospecific polymerization of propylene.
Description
~1~78~39 Stamicarbon BY
Inventors Jacobus A. LOONTJENS oi Meerssen Denise I.L. JACOMEN oi Genk (Belgium) CATALYTIC TITANIUM COMPONENT, PROCESS FOR THE MANUFACTUR~ THEREOF, AND
PROCESS FOR THE POLYMERIZATION OF ALKEWES-l WITH APPLICATION OF SUCH A
TITANIUN COMPONENT
The invention relates to a catalytic titanium component useiul ior the polymerization oi alkenes-l and ior the copolymerization oi alkenes-l with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor and a mixture oi a magnesium halide and an aluminium halide as carrier.
A similar titanium component is known i'rom ~he Dutch patent ,~ on ~lav~fth, /~7 application No. 7610267, lald open ior publlc inspectio~, which de~cribe~ a catalyst system for the polymerlzation oi alkenes-l wlth a tltanium component whlch contalns the product oi a reaction between a magneslum halide, a titanlum (IV) compound and an electron donor, and whlch may contaln, ior lnstance, 80 % by wt. or more oi an lnert illler, ior lnstance alumlnlum chlorlde.
Accordlng to thls publlcatlon, the presence of, ior instance, alumlnium chlorlde as ~iller has the drawback that the speciiic surface oi the tltanium component 19 only moderately large, whlle the properties oi' the cataly-t ~ystem are not particularly good.
It ha~ now been iound by the appllcant that an alumlnium hallde in a mlxture wlth a magneslum hallde ln a carrler ior a complex of a halogenated tltanlum compound wlth a Lewls base, wlth very speclilc welght ratlos, does not act as an lnert ~iller, but has a very partlcular ei~eot whlch is reilected in a particularly high activity at good steree~peciiicity oi a ¢atalyst system containing such a titanium component. It is assumed that with these very speciiic weight ratios, a specliic conversion oi the complex tltanium compound, magnesium halide and alumlnlum hallde takes place. Houever, the lnvention is not re~tricted by any theoretloal conslderatlon.
According to the invention, a catalytic titanium component useiul ior the polymerization oi alkenes-l and ior the copolymerization oi alkenes-l with each other or with ethylene contains a halogenated titanlum compound, an electron donor, and a mixture oi a magnesium halide and an aluminium halide as carrier, characterized in that the titanium component contains 0.1-10 % by wt. oi titanium and ;'' ~
., , ~4~899 _~ 2 ln that the tltanlum magneclum alumlnlum welght ratlo amounts to 1 (n 5-20) (0 0S-2~5), ~hlle the magned um alu lnlum welght ratlo a ountfl to at leaat 3 - The tltaniu~ co~ponent according to the lnvention l~proves the S actlvlty oi the poly erlzatlon catalyat, ~lth good stereo~pecl~icity ~lth thl~ catalyat, poly ers can be~obtalned - i'or lnatance, polypropy-lene, polybutylene-l, poly-4-~ethyl pentylene-l or other polyalkylene--l -~lth a very lo~ h~aogen content, a very lo~ tltanlu content, good partlcle size and good particle d ze(dletrlbutlon The poly er thererore h-- good proceoslng propertles and a little corro lve ~or the proceqslng equlp~ eDt. ., Yore ln partlcular, the tltanluo agned u~ alu lnluo ~elght ratlo ln the tltanlu co ponent 1~ 5) (0 2-1), while the tltanlu~ content preSerably a ounta to 2-10 % by wt The magneslum alu lnlu ~elp t ratlo preSerably 18 3 l to 100 1, ~ore ln partlcular 4 l to 20 The halogenated tltanlu co pound uaed ln the anuSacture Or the catalyat co~pon-nt can be any halogenated co pound Or bl-, $rl-, or tetravalont tltanlu , lncludlng coupounda ln ~hlch ao e Or the tltaDlu valeDcl-a havo beeD takeD up by atoua other than halogen ato~a The h logon 1D tho h-logenatod tlta~luo co pound 19 preSerably chlorlne, but ay aloo bo bro lne and/or lodine, ~or ln-tance E~a plea oi halogenated tlt-Dluu co pouDd- are TlC13, TlC14, TlBr4, TlI4, Tl~laobuto~y)2C12, Tl~ph-no~r)Cl3 aDd Tl~o- ethyl phenoxy)C13 TlC14 lo partlcularly aultable For appll¢atloD ln ~ultl-atage poly erlzatlon proceaseo, apocl~llr tho~e ln ~hlch more thaD halS aD hour la normally requlred Sor poly erization 1D the Slrot atage beSore a aecond atage la atarted, lt ia Or apeclal advaDtage lS the halogenated titaniu~ compound uaed 18 tltaniu hallde phenolate oS the Sor~ula TlnXaAb, ln which X repre~ent~
; a halogeD ato and ~ the acld radlcal Or a pheDol, n io a ~hole nu ber o~
at leaot 1, and a aDd b are auch nu~bera that a/D aDd b/n both amount to 1-3, OD the uDderatantlng that ~alb)/D lo equal to 3-4 The rate Or decllne ln the activlty Or the catalyot ayote~ ls then ~ubAtantlally reduced, 80 that ~ultl-otage poly erlzatlon proce-aea, ior lnataDce oo-called block copoly erlzatlonc, 1D whlch 1D a ~lrat otsge, Sor lnataDce, Sor halS an hour propylene, butylene-l, 4-~ethyl pentylene-l or another alkene-l ~lth at leaat 3 carbon ato ~ per ~olecule ls poly-.
~147~ 9 ~erlzed, po~lbly ln the presence oi a d nor quantlty Or ethylene, aiterwhlch ln a ~econd stage another monomer or a mono~er l~ture o~ a dli~erent co posltlon ls poly~erlzed ln the pre~ence oi the polymer - -ior ed ln the ~lr~t ~tage, 80 that blocks dliierlng ln onomer co posl--- 5 tlon ay be present ln one polymer molecule, glve conslderablr hlgher proportlon~ oi such block copoly er - - -The phenolate ay be, ior lnetance, the acld radlcal derlvediro un~ubstltuted phenol or irom a phenol ~n whlch one or-more alky} -groupe or lko~ group~ wlth, ~or ln~tance, 1-~ carbon ato~s per group h-ve been ~ub~tltuted, ior lnstance cresol, etho~y phenol, xylenol, ethyl phonol, propyl phenol, octyl phenol, dlbutyl phenol, cumyl phenol or n-pthol Cre~olate~ and etho~ phenolate~ are partlcularly sultable, ~hlle cro~olate~ oiSer the advantage oi partlcularly hlgh stereospecl-ilcltr oS the cataly~t ~te The benzene nucleus oi the phenolate may lS cont-ln other ~ub~tltuents whlch re non-detrl-ental ln the poly~erl-zatlon reactlon, ~uch ~ one or ore hallde ~ub~tltuents The phenolate eroup ar hare, ior ln~tance, 6 to 18 carbon ato ~, preierably 6-12 ato ~
She hallde phenolate ratlo ln the tltanlum hallde phenolate la preierably irom 1 1 to 3 1 Besldes the tltanlum hallde ph nolate, a phonolate ireo tlt nlu hallde can be u~ed ln the halogena-tod tlt nlu co pound, li ao de~lred Preierably, hallde phenolate oi totraral-nt tlt nlu 1~ u~ed She r-lue oi n 1- o~tly 1, but ay al~o b- 2 or hl p r, e~peclally li a polgphenol-te 18 u~ed ~peclilc exa~ple~ oi tltanlum h-llde phenolate~ to be u~ed ln the ethod ccordlng to the lnrentlon are tltanlum(IV) trlchlorlde onophenol-te, tlt nlu (IV) dlchlorlde dl-phenolate, tltanlum(IV) trlchlorlde ono-p-creaol-te, tltanlu ~III)dlchlorlde mono-o-cresol-te, tltanlum(IV) onochlorlde trl-l-naphthol-te, tltanlum(-IV) trlchlorlde ono-(p-chlorophenol-te), tltanlum(IV) trlbro lde ono-p-cresol-te, tltanlu (I~) trlbro lde nono(x~lenolato-l~o er lxture) and tltanlu~(IV) nolodlde trlanl~ol-te 9u¢h ¢o pound~ can be obtalned, ~or lnstance, through ¢onver~lon oi the relevant tltanlum hallde wlth the stoechlo-etrlc quantlt~ oi the relevant phenol, ln whlch reactlon the relevant 3S h~drogen halide j 1~ llberated, or through double converd on oi a tltanlu h-llde wlth et-l phenol-te, ior ln~tance an lkall--etal phenolate .
.. _ . .. _.. ... . _ ., __ , . .,,.. . .... . . ...... . , . , .. ~, .. .. .... ....... . . . .... .. ... : . .. .... .
._ _ .. . ..
~14~7899 .. . . . .. . ... . . . . .
As electron donor in the tltanium component one or more o~ the compounds used in a know _ anner in similar catalyst systems may be used, i'or instance oxygen-containing electron donors, .. . . . . .............. . .
~uch a# water, alcohol#, phenol#, ketone#, aldehyde-, acld hallde#, -carboxyllc acld#, ester~, ether~ and acld a lde#, or nltrogenou# electron --donor~ auch a~ am onla, a lne#, nltrlle#, i#ocyanate# and nitro compound#
Speciiic exa ple~ oS #ultable electron donor# are alcohols ~ith 1-18 carbon ato # per moleeulo, ior ln~tance metha 1, ethanol, propanol, hoxanol, ~tearyl alcohol, benzyl alcohol, phenyl ethyl alcohol or cu yl alcohol; phenol~ ~ith 6-18 carbon atom# per molecule, Sor lnatance phenol, creaol, xylenol, ethyl phenol, propyl phenol, octyl phonol, dlbutyl phenol, cu yi phenol or naphthol; ketones wlth 3-lS
- carbon ato a per olecule, ior ln~tance acetone, methyl ethyl ketone, methyl l~obutyl ketone, acetophonono or benzophenone; aldehyde# ~lth lS 2-lS c-rbon ato ~ per lecule, ior ln~tance ethanal, propanal, heptanal, benzaldohyde, tolu-ldehyde or naphthaldehyde; acld halldes wlth 2-15 c rbon to a per olecule, ior ln#tance acetyl chlorlde, benzoyl chlo-rlde or toluyI chlorlde; acld a ldea ~lth 2-lS carbon ato # per olecule, ~or lnat nce ior u lde, aceta lde, benz~ lde or tolua lde; amlne# ~lth 20 2-18 c-rbon ato ~ per olecule, ior ln~tanee ~ethyla lne, ethyla lne, dlethyl-slno, trlethyla lne, trlbutyla lne, plperldlne, trlbenzyla~lne, anlllne, pyrldlne, plcollne or ethylene dlamlne; nltrlle~ ulth 2-15 carbon to ~ per ~oleeule, ior ln~tanee aeetonltrlle, benzonltrlle or tolunltrlle; or nltro co pound#, ior lnstance nltrobenzene PreSerence 25 1~ glven to ether# ~lth 2-20 carbon atom# per olecule, rOr ln#tance dl ethyl ether, dlethyl ether, dl-n-butyl ether, dl-l#o-s yl ether, - tetrahydroiuran, nl~ole or dlphenyl ether, and ln partlcular organlc e~ter~ ~nth 2-40, ln partleular 2-18, earbon atom~ per molecule The aeld eo ponent oi the e~ter ~o~tly contaln# 1-~ carbon ato # per mole-cule or 1~ a natural iatty aeld, ~hlle the alcohol co ponent o#tly contalna 1-~ carbon ato # per olecule E~a ple# oi ~ultablo e~ter~ aro methyl ~ormate, cyclohe~yl Sormate, ethyl acetate, vlnyl acetate, amyl acetate, 2-ethyl hesyl acetate, cyclohexyl acetate, ethyl proplonate, amyl proplonate, methyl butyrate, ethyl valerlate, methyl chloroacetate, ethyl dl-chlo~oacetate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, ethyl crotonate, dl-ethyl aleate, ethyl cyclohexane carboxylate, methyl benzoate, ethyl _ . _ _ . _ . .... . .. . . .. .... ... ~ . . ... . _ .. .. . . .. ..... _ _ . _ _ _ _ _ . .. -- _ . .. . .
---^`` 114~399 benzoato, l-butyl benzoate, octyl benzoate, cyolohexyl benzoate, phenyl benzoate, benzyl benzoate, phenyl ethyl benzoats, methyl toluate, ethyl toluate, i-amyl toluate, methyl anisate, ethyl anisate, ~-butyrolactone, C -caprolactone, coumarin, phthalide and ethylene carbonate Particular preierence 18 given to esters derlved i'rom aromatic acids, in particular esters of benzoic acid, substituted or not ~ith alkyl or alkoxy groups Alkyl esterJ ~ith 1-4 carbon atoms per alkyl group, in particular methyl or ethyl eJterJ oi benzoic acid, o- or p-toluene carbosylic acid, p-methosy benzoic acid or phthalic acid, are preferred in particular Le~ides the halogenated titanium compound and the Lewis base, th catalytic tltanium co-ponent according to the invention contains a ixture oi a agneJium halide and an aluminium halide as carrier material Preierably, this carrier iJ at leaJt virtually anhydrous and also virtually i'ree oi ~ gnesium oxide Al~o alu inium oside i9 preferably ~ubJtantially absent The expre~sion~ 'at least virtually anhydrous' and 'at least vlrtually ireo oi' magneJiu oxide' are under~tood to mean here that tha concontratlon oi' ~ater and magne~iu oxide, re~pectively, in the carrier aterial lt ln~ignii'icant, i e a~ regards ~ater at any rate less than 0,2 % by ~t , preierably at mo~t 0 1 % by ~t , and aJ regards magneslum oxld a~ any rato leJ~ than 0 1, prei'erably at most 0 01, mgeq oi' baJe p r g oi carrlor aterlal dotermlned by titratlon ~lth a dllute ~trong acld, Sor ln~tanoe 0 1 N hydrochlorlc acid The c-rrl-r matorlal may i'urther contaln mlnor quantltles oi 0th r ~otal lon~, i'or ln~tance sodium, tin, silicon or germanium The halido lon 1~, in partlcular, bro lde, preierably chlorlde It 1~ re arked that the JapaneJe patent publlcation 54033578 (Der~ent ab~tract 30894 B) deJcribe~ a catalyst ior the polymerlzatlon oi' alkene~-l, ~hlch contaln~ ln the tltanlu- component a mlxture oi an lnorganlc agne~lum co pound and an electron donor-alumlnium halide-complex Such a cataly-t ~ho~ ho~ever only moderate periormance Apparently said complex doe~ not have that partlcular eiiect on the periormance oi the tltanium component that the aluminium hallde does have The carrler materlal may have been manuiactured by any Juitable ~ethod, preierably by grlndlng together oi the magneJlum hallde and the alumlnlum hallde, ior lnstance ln a ball mill, a vlbration mill or a beatermill 11~7~99 ~ he various constituent elements oi the titanium component may be combined in any known manner. Preierably, iir~t a complex oi' the titanium hallde compound and the electron donor is prepared.
The complexes oi the titanium halide compoun~ and the 5 electron donor may be obtained ln any known manner, ior instance by bringlng the components of the complex into contact with each other.
The titanium hallde compound may be applied to the carrier material in any kno~n manner, ior inJtance by simple mixing, preierably by grinding together, ior inJtancelin a ball mill, a~vibration mill or beater mill. The mixing may be done in the co-presence oi an inorganic or organic i'iller, ior inJtance lithium chloride, calcium carbonate, calcium chlorlde, chromium(II)chloride, barium chloride, sodium sulphate, sodium carbonate, titanium dioxide, sodium tetraborate, calcium ortho-phosphate, calcium Julphate, barium carbonate, aluminium sulphate, borium lS trloxide, aluminium oxide, Jilicon oxide, polyethylene, polypropylene or polyJtyrene. The iiller may also have been taken up in the carrier material beiorehand. It is poJaible to iirst iorm a complex oi the titanium halide co pound and the electron donor and apply it to the carrier, or alJo to iirJt apply the non-complexed titanium halide co pound to the carrier and add the electron donor aiterward~, either beSor- or aiter addition oi' the organoaluminium component used in the iini~hed catalyst.
It may be advantageouJ to treat the titanium aomponent with a halogen or an interhalogen compounq~ ior instance bromium, preSerably in the absence oi an inactlve solvent.
The titanium content oi thé iinished titanium component on the carrier noroally amountJ to between 0.1 and 10 % by wt. The electron donor in the titanium component iJ preierably present in a quantity oi, ior inJtance,~l to 5 molecule~ per titanium atom. A typical example oi the co poJition oi the titanium component, although varying in dependence on the conditlon~ oi the catalyst manuiacture, ls: 2-10 % by wt. oi tltanium, 16-25 % by ~t. oi magnesium, 1.5-2.5 % by wt. oi aluminium, 45-64 % bj wt. oi halogen and S-25 % by wt. oi the electron donor.
It is pointed out that aiter combining the titanium halide 3s compound with the metal halide used as carrier, the tetravalent titanium maybe reduced to a lower valency, ior instance to bi- or trivalent titanium, ii ~o deJired, so that the iinished titanium component need not necessarily contain tetravalent titanium.
~147~99 In the iinished poly~erization catalyst, the titanium compound is used in combination ~ith an organometal component derived irom a metal oi one oi the groups I-III oi the Periodic Sy~tem, with a hydrocarbon group bonded direct to the metal Examples are tra~
aluminlum compoundJ, alkyl aluminium alkoxides, alkyl aluminium ; hydrideJ, alkyl alu-lnium halides, dialkyl zinc compounds and dlalkyl magneJiu co poundJ Among th-se, the organoaluminium co pounds are partlcularly sultable Examples oi the organoaluminium co pounds are tr~alkyl or trlalkenyl aluminium compounds, ior instance tilethyl alumlnlum, trlpropyl alumlnlum, trlisobutyl aluminium, triiJoprenyl alu-inlum, trlheYyl alu-inium and trioctyl aluminium;
alkyl aluminiu- co pounds in ~hich a nu-ber oi the aluminium atoms are connected via an osygen or nitrogen atom, ior instance (C2H532AlOAl (C2H5)2, (i-C4Hg)2AlOAl(l-C4Hg)2 or (C2H5)2AINHAl(C2H5); dialkyl alu-iniu hydrideJ Juch as diethyl aluminium hydride or diisobutyl alu inium hydride; dialkyl aluminium halides, in particular a chloride or bro lde, diethyl alu inium chloride and bro lde bolng p rtlcularly ault-ble, ~hlle alJo other dlalkyl alu lnium hallde~ ~lth pr-i'er-bly 1-10 carbon ato J ln the alkyl group, such a~
i'or ln~t~nce dl-n-butyl lu~lnlu chlorlde and ethyl-n-butyl alumlnium chlorlde, c n be u~ed; nd dlalkyl alu~lnlum alkoslde~ or phenoxide~, i'or ln~tanco dlethyl ethosy aluulnluo or dlethyl phenosy alumlnlu~ The trlalkyl alu lnlu~ co pound~ de~erve ~o~t preierence The organooetal compound ay al~o contaln a trlalkyl alu inium co pound a~ ~ell a~ a dlalkyl alu lnluo hallde or a ~lsture oi' a dl-lkyl agnealu coupound and a onoalkyl alu~lnlum dlhallde The alkyl groupa oi' the organoalu lnlu co pound~ preierably contaln 1-10 carbon ato ~ e-ch The alkyl group~ oi' the dlalkyl agne~luu co po w d preiera-bly contaln 1-10 carbon ato~ ew h or are a palmltyl or stearyl group ~anple~ oi' ~ultable dlalkyl uagne~lu~ co pound~ are dlethyl magne~lu , dl-n-butyl agnedu~, dl-n-hesyl uagne~luu and di-n-octyl ~agne~iu~
The onoalkyl aluoinlu~ dlhallde prei'erably 19 a chlorlde or a bro~lde Ethyl alu~lnlu~ dl¢hlorlde or dlbro lde 1~ partlcularly ~ultable, but al~o other onoalkyl alu lnlu dlhalogenlde~ ~lth prei'erably 1-10 carbon ato~J ln the alkyl group ay be u~ed, such ag lsopropyl aluminlum dlchlorlde, n-butyl alu lnlum dlbro ide or n-octyl alumlnlum dlchloride The olar ratio bet~een the dialkyl agnesium compound and the onoalkyl alumlnl _ ~ih-lide may be bet~e-n, ior inst _c-, 0 1 and 1, preierably .
95~
between 0.3 and 0.6. Too high a molar ~atio leads to insuificiently stereospecli'ic catalysts, while insu$ficient catalyst acti~ity results ii it is too low.
The organometal component prei'erably contains a complex of an organic metal compound, in particular a trialkyl aluminium compound, with an ester o$ an oxygen-containing organic acid. Suitable esters are the same esters as may be used in the titanium component, in particular again the esters oi aromatic carboxylic acids. Por brevity's sake, reierence is made to the i'oregoing. Prei'erably, part oi' the organic metal compound, i'or instance 50-80 %, is present in a non-complexed condition.
The Al : Ti atom ratio is generally between 10 and 1000; the molecule-atom ratio oi Lewis base bonded in total in the catalyst to Tl i3 in general between 5 and 500.
_ .. . . .. . .
Thepro¢ess according to the inventlon 19 applied in particular ln the ~tereo~peciSic poly erlzation oi alkenes-l with 3-6 carbon atoms per molecule, ~uch a~ propylene~ butylene-1, 4-methyl pentylene-l and hexylene-l, and in the copolymerizatlon Or theee alkenes-l wlth each other and/or with ethylene. Copolymer~ wlth a random arrangement oi' the varlou~ monomer unit~ a~ well as block copolymer~ can be produced. Ii ethylene i~ taken as a comonomer, it 19 u~ual to lncorporate minor quantltlec oi lt ln the polymer, Sor lnetance at most 30 % by wt., more ln partlcular between 1 and lS % by wt. The~processaccording to the lnventlon 1~ oi lmportance ln partlcular ior manuiacture oi isotactlc polypropylene, random copolymers oi propylene wlth mlnor quantitie~ oi' ethylene, and block copolymer~ oi propylene and ethylene. For the manu-iacture oi block copolymer~, any deslred ~equence oi monomer addltlons may be applled.
The clrcum~tance~ under which the polymerlzatlon reaction wlth the tltanlu component accordlng to the lnventlon 1~ carrled out do not devlate irom tho~e known ln the art. The reaction may be carrled out ln the ga~ pha~e or in the presence oi a dl~persant. The dlspersant may be lnert or al~o a monomer in llquld iorm. Examples oi ~ultable dl~persant~
are allphatlc, cycloaliphatic, aromatlc and mixed aromatic/aliphatlc hydrocarbons wlth 3-8 carbon atoms per molecule, i'or instance propylene, butylene-l, butane, isobutane, n-hexane, n-heptane, cyclohexane, ben-zene, toluene and the xylene~.
. ... ..... - - - ' ,,, .
~147Y~9~
g In the case oi' polymerization in the liquid pha~e, it is preierable ior the concentration oi the titanium component to be set at about 0.001-0.5 mmole, calculated as titanium atom, and the concentration oi the organometal compound at about 0.1-50 mmole, both per litre oi' liquld phase.
The polymerization temperature is normally bet~een 190 and 47~ K, preierably bet~een 310 and 375 K. The pressure may be, ior instance, between 100 and 3000 kPa.
Ii 90 desired, it i9 possible to tegulate the molecular weight oi the poly er during the polymerlzation process ior instance by carrying out the reactlon in the presence oi hydrogen or with any other kno~n molecular weight regulator.
The polymerization reaction may be carried out as a batch process or a~ a continuous process.
The lnvention will now be elucidated by means oi the ~ollowing non-re~trictive esamples and the comparative expertiments.
Example~ and co parative exDeriments EX mDl-- I
A ProParatlon oS the titaniu- co Ponent At 273 K, 6.5 ml oi water-iree ethyl bensoate (E8), dlssolved ln 75 ml oi water-iree ga~oline, i9 added to a ~olutlon oi 5 ml oi TiC14 and 125 ml oi gasollne, iluJhed wlth dry nitrogen. The re~ultant preclpltate Or TlC14.EB ls separated oii by illtratlon and subsequently drled.
At 970 K, commerclally avallable MgC12 1~ dehydrated iurther ln a ilow oi' C0 and C12 ln order to remove the residual content oi H20 and Mg~. 3.0 g oi thlJ MgC12, 0.210 g oi AlC13 and 3.4 g oi TiC14.EB
are ground together ior 17 hourJ ln ~talnless steel ball mlll ln an atmoaphere oi' dry nltrogen.
~. PolYmerlzatlon Into a stalnless steel reactor, ilushed with dry nitrogen and provided with a mochaoical agitator, 1.3 1 oi gasoline, 2.5 ml oi trilsobutyl alu-lnlum (TIEA), 0.25 ml E~ and 0 068 g oi the titanium component prepared as described under IA are introduced. ~y leading in -35 propylene, the pressure is raised to and maintained at 700 kPa. The ,, ,. ,.. . , .. _... . . ... .. .. . . .
~1478~9 temperature i9 raised to and maintained at 333 K. Aiter a polymerization time oi 2 hours, the supply oi propylene i9 stopped, the pressure is let oii and the polymerization suspension is removed irom the reactor. The polymer i~ separated oii by iiltration.
S The polymerization activitg amounts to 870 g oi polypropylene (PP)/
mmole Ti.h; the Joluble polymer content i~ 5.5 %. The average particle diameter (d50) i~ 550 microns.
Comoarative esperi ent A
A. pre~Darstion Or the titanlum comPonent The titanium component iJ prepared analogously to the procedure de~cribed in example IA, except ior the omission oi addition oi AlCl3.
B. Polymerization Poly erization ls carrled out ln a manner analogous to that lS d ~crlb d ln example IB, but now 0.06S g oi the titanium component esnt under point A oi thls comparative experlment is used The polymorlzstlon actlvlty a ount~ to 810 g PP/m~ole Ti.h; the D ~olublo DO1Y er content 1J S.3 ~. The ~ particle diameter oi the Doly-Or (d50) 1J 400 1CrOnJ~
ExamDlo II
A. ProDar~tlon oi the tltanlum component Tho tltanlum co ponent is prepared analogously to the procedure deJcrlbed ln example IA, but no~ 0.270 g oi AlCl3 i9 added.
: ~. Pol~merlzatlon Poly erlzatlon 1~ carried cut in a m nner analogou~ to that doJcrlbed ln esample I~, but no~ 0.070 g oi the titanlum component oi example IIA is used.
The polymerization activity now amounts to 920 g PP/mmole Ti.h; the soluble polymer content is 5.5 %. The average particle dlameter oi the polymer is 575 mlcrons.
1~478~9 ExamPle III
A. Preparation oi the titanlum comPonent The tltanlum component $e prepared analogously to the procedure described ln example IA, but no~ 0.320 g oi AlCl3 i8 added.
S B. Polymerization Polymerlzation i- carried out in the same ~ay as described in exa ple IB, but no~ 0.067 g oi the titanlum ¢omponent oi' example IIIA is u~ed.
The polymerization actlvity amounts to 1080 g PP/mmole Tl.h; tho diseolved polymer content is S.S %. The average particle dia eter i~ 600 micron~.
ExamDle IV
A Pr-Daratlon o~ the tlt-nlum comDonent The tltanlum comyonent i9 prepared analogously to the proce-lS dure deecrlb d ln ex~;mple IA, but n~ 0,370 g oi' AlC13 19 added.
~, PolYmerlzatlon Polymerlzatlon ia oarrled out ln the ~ame way as descrlbed ln eYumple IB, but no~ 0.071 g Or the tltanlum component oi example IVA le used.
Th- poly erlzatlo~ actlvlty a ounte to 1070 g PP/mmole Tl.h;
the dleeolved poly er content le ff.2 %. Tbe average partlcle dla oter le ff50 mlcron-.
~a~Dle V
.
A. PreDaratlon oi the tltanlum co Donent The tltanlu- co ponent le prepared analogouely to the proce-dure deecrlbed ln esa ple IA, but no~ 0.425 g oi AlC13 le added.
B. Poly erlzatlon Polyrerlzatlon le carrled out ln a manner analogoue to that deecrlbed ln esa ple IB, but no~ 0.072 g oi the tltanlum component ol esa ple VA 18 ueed.
The poly~erlzatlon actlvlty amounts to 990 PP/mmole Ti.h; the dlesolved polymer content 1~ 6.4 %. Tbe average particle diameter is ff50 mlcrons.
.. ,, __ . _, . . . .. . . . . .. . . _ . , .
- -: ' '.,' -:' ,, ~ ,.
.. ,.. -., . ~ .
'11~7~gg Comparative experiment B
A. Preparation oi' the titanium component The titanlum component is prepared analogously to the proce-dure described in example IA, but now 0.530 g o~ AlC13 19 ground in.
B. Poly erization ` Polymerlzation is carried out in a manner analogous to that described ln example IB, but no~ 0:74 g oi' the titanium component oi' co parative esperimont B, part A, is usod.
The polymerization activity amounts to 720 g PP/mmole Ti.h;
the dissolved poly~er content is 6.0 %. The average partlcle diameter i~ 675 icro~s.
A graphic representation oi' the polymerization results above iJ ~ho~n in the i'igure annesed hereto, in which the polymerization activity a in g oi PP/m ole Tl.h has been plotted against the aluminium : magneslum ~eight ratio r oi the tltanlum compon~nt.
Co Daratlve ~cDerlmont C
A. Pr-par-tlon oi' tho tltanlum com w nent The tltanlu- component 1J prepued analogously to the procedure de~crlbed ln example IA, but ln stead oi AlCl3 now 2.85 g o~ AlCl3.
.o~hYl bonzoate-complex 1~ uJed.
B. Polvmerlzation Polymerlzation is carrled out in a manner analogou- to that de~crlbed in example IB, but nov 0.069 g oi the tltanium component oi' comparatlve exporimont C, part A, 19 u ed.
The polymerlzatlon activity amounts to 890 g PP/mmole Tl.h;
tho dl~olved polYmor oontent i~ 7.8 %, the average partlcle diameter 1~ 675 mlcrons.
.
Inventors Jacobus A. LOONTJENS oi Meerssen Denise I.L. JACOMEN oi Genk (Belgium) CATALYTIC TITANIUM COMPONENT, PROCESS FOR THE MANUFACTUR~ THEREOF, AND
PROCESS FOR THE POLYMERIZATION OF ALKEWES-l WITH APPLICATION OF SUCH A
TITANIUN COMPONENT
The invention relates to a catalytic titanium component useiul ior the polymerization oi alkenes-l and ior the copolymerization oi alkenes-l with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor and a mixture oi a magnesium halide and an aluminium halide as carrier.
A similar titanium component is known i'rom ~he Dutch patent ,~ on ~lav~fth, /~7 application No. 7610267, lald open ior publlc inspectio~, which de~cribe~ a catalyst system for the polymerlzation oi alkenes-l wlth a tltanium component whlch contalns the product oi a reaction between a magneslum halide, a titanlum (IV) compound and an electron donor, and whlch may contaln, ior lnstance, 80 % by wt. or more oi an lnert illler, ior lnstance alumlnlum chlorlde.
Accordlng to thls publlcatlon, the presence of, ior instance, alumlnium chlorlde as ~iller has the drawback that the speciiic surface oi the tltanium component 19 only moderately large, whlle the properties oi' the cataly-t ~ystem are not particularly good.
It ha~ now been iound by the appllcant that an alumlnium hallde in a mlxture wlth a magneslum hallde ln a carrler ior a complex of a halogenated tltanlum compound wlth a Lewls base, wlth very speclilc welght ratlos, does not act as an lnert ~iller, but has a very partlcular ei~eot whlch is reilected in a particularly high activity at good steree~peciiicity oi a ¢atalyst system containing such a titanium component. It is assumed that with these very speciiic weight ratios, a specliic conversion oi the complex tltanium compound, magnesium halide and alumlnlum hallde takes place. Houever, the lnvention is not re~tricted by any theoretloal conslderatlon.
According to the invention, a catalytic titanium component useiul ior the polymerization oi alkenes-l and ior the copolymerization oi alkenes-l with each other or with ethylene contains a halogenated titanlum compound, an electron donor, and a mixture oi a magnesium halide and an aluminium halide as carrier, characterized in that the titanium component contains 0.1-10 % by wt. oi titanium and ;'' ~
., , ~4~899 _~ 2 ln that the tltanlum magneclum alumlnlum welght ratlo amounts to 1 (n 5-20) (0 0S-2~5), ~hlle the magned um alu lnlum welght ratlo a ountfl to at leaat 3 - The tltaniu~ co~ponent according to the lnvention l~proves the S actlvlty oi the poly erlzatlon catalyat, ~lth good stereo~pecl~icity ~lth thl~ catalyat, poly ers can be~obtalned - i'or lnatance, polypropy-lene, polybutylene-l, poly-4-~ethyl pentylene-l or other polyalkylene--l -~lth a very lo~ h~aogen content, a very lo~ tltanlu content, good partlcle size and good particle d ze(dletrlbutlon The poly er thererore h-- good proceoslng propertles and a little corro lve ~or the proceqslng equlp~ eDt. ., Yore ln partlcular, the tltanluo agned u~ alu lnluo ~elght ratlo ln the tltanlu co ponent 1~ 5) (0 2-1), while the tltanlu~ content preSerably a ounta to 2-10 % by wt The magneslum alu lnlu ~elp t ratlo preSerably 18 3 l to 100 1, ~ore ln partlcular 4 l to 20 The halogenated tltanlu co pound uaed ln the anuSacture Or the catalyat co~pon-nt can be any halogenated co pound Or bl-, $rl-, or tetravalont tltanlu , lncludlng coupounda ln ~hlch ao e Or the tltaDlu valeDcl-a havo beeD takeD up by atoua other than halogen ato~a The h logon 1D tho h-logenatod tlta~luo co pound 19 preSerably chlorlne, but ay aloo bo bro lne and/or lodine, ~or ln-tance E~a plea oi halogenated tlt-Dluu co pouDd- are TlC13, TlC14, TlBr4, TlI4, Tl~laobuto~y)2C12, Tl~ph-no~r)Cl3 aDd Tl~o- ethyl phenoxy)C13 TlC14 lo partlcularly aultable For appll¢atloD ln ~ultl-atage poly erlzatlon proceaseo, apocl~llr tho~e ln ~hlch more thaD halS aD hour la normally requlred Sor poly erization 1D the Slrot atage beSore a aecond atage la atarted, lt ia Or apeclal advaDtage lS the halogenated titaniu~ compound uaed 18 tltaniu hallde phenolate oS the Sor~ula TlnXaAb, ln which X repre~ent~
; a halogeD ato and ~ the acld radlcal Or a pheDol, n io a ~hole nu ber o~
at leaot 1, and a aDd b are auch nu~bera that a/D aDd b/n both amount to 1-3, OD the uDderatantlng that ~alb)/D lo equal to 3-4 The rate Or decllne ln the activlty Or the catalyot ayote~ ls then ~ubAtantlally reduced, 80 that ~ultl-otage poly erlzatlon proce-aea, ior lnataDce oo-called block copoly erlzatlonc, 1D whlch 1D a ~lrat otsge, Sor lnataDce, Sor halS an hour propylene, butylene-l, 4-~ethyl pentylene-l or another alkene-l ~lth at leaat 3 carbon ato ~ per ~olecule ls poly-.
~147~ 9 ~erlzed, po~lbly ln the presence oi a d nor quantlty Or ethylene, aiterwhlch ln a ~econd stage another monomer or a mono~er l~ture o~ a dli~erent co posltlon ls poly~erlzed ln the pre~ence oi the polymer - -ior ed ln the ~lr~t ~tage, 80 that blocks dliierlng ln onomer co posl--- 5 tlon ay be present ln one polymer molecule, glve conslderablr hlgher proportlon~ oi such block copoly er - - -The phenolate ay be, ior lnetance, the acld radlcal derlvediro un~ubstltuted phenol or irom a phenol ~n whlch one or-more alky} -groupe or lko~ group~ wlth, ~or ln~tance, 1-~ carbon ato~s per group h-ve been ~ub~tltuted, ior lnstance cresol, etho~y phenol, xylenol, ethyl phonol, propyl phenol, octyl phenol, dlbutyl phenol, cumyl phenol or n-pthol Cre~olate~ and etho~ phenolate~ are partlcularly sultable, ~hlle cro~olate~ oiSer the advantage oi partlcularly hlgh stereospecl-ilcltr oS the cataly~t ~te The benzene nucleus oi the phenolate may lS cont-ln other ~ub~tltuents whlch re non-detrl-ental ln the poly~erl-zatlon reactlon, ~uch ~ one or ore hallde ~ub~tltuents The phenolate eroup ar hare, ior ln~tance, 6 to 18 carbon ato ~, preierably 6-12 ato ~
She hallde phenolate ratlo ln the tltanlum hallde phenolate la preierably irom 1 1 to 3 1 Besldes the tltanlum hallde ph nolate, a phonolate ireo tlt nlu hallde can be u~ed ln the halogena-tod tlt nlu co pound, li ao de~lred Preierably, hallde phenolate oi totraral-nt tlt nlu 1~ u~ed She r-lue oi n 1- o~tly 1, but ay al~o b- 2 or hl p r, e~peclally li a polgphenol-te 18 u~ed ~peclilc exa~ple~ oi tltanlum h-llde phenolate~ to be u~ed ln the ethod ccordlng to the lnrentlon are tltanlum(IV) trlchlorlde onophenol-te, tlt nlu (IV) dlchlorlde dl-phenolate, tltanlum(IV) trlchlorlde ono-p-creaol-te, tltanlu ~III)dlchlorlde mono-o-cresol-te, tltanlum(IV) onochlorlde trl-l-naphthol-te, tltanlum(-IV) trlchlorlde ono-(p-chlorophenol-te), tltanlum(IV) trlbro lde ono-p-cresol-te, tltanlu (I~) trlbro lde nono(x~lenolato-l~o er lxture) and tltanlu~(IV) nolodlde trlanl~ol-te 9u¢h ¢o pound~ can be obtalned, ~or lnstance, through ¢onver~lon oi the relevant tltanlum hallde wlth the stoechlo-etrlc quantlt~ oi the relevant phenol, ln whlch reactlon the relevant 3S h~drogen halide j 1~ llberated, or through double converd on oi a tltanlu h-llde wlth et-l phenol-te, ior ln~tance an lkall--etal phenolate .
.. _ . .. _.. ... . _ ., __ , . .,,.. . .... . . ...... . , . , .. ~, .. .. .... ....... . . . .... .. ... : . .. .... .
._ _ .. . ..
~14~7899 .. . . . .. . ... . . . . .
As electron donor in the tltanium component one or more o~ the compounds used in a know _ anner in similar catalyst systems may be used, i'or instance oxygen-containing electron donors, .. . . . . .............. . .
~uch a# water, alcohol#, phenol#, ketone#, aldehyde-, acld hallde#, -carboxyllc acld#, ester~, ether~ and acld a lde#, or nltrogenou# electron --donor~ auch a~ am onla, a lne#, nltrlle#, i#ocyanate# and nitro compound#
Speciiic exa ple~ oS #ultable electron donor# are alcohols ~ith 1-18 carbon ato # per moleeulo, ior ln~tance metha 1, ethanol, propanol, hoxanol, ~tearyl alcohol, benzyl alcohol, phenyl ethyl alcohol or cu yl alcohol; phenol~ ~ith 6-18 carbon atom# per molecule, Sor lnatance phenol, creaol, xylenol, ethyl phenol, propyl phenol, octyl phonol, dlbutyl phenol, cu yi phenol or naphthol; ketones wlth 3-lS
- carbon ato a per olecule, ior ln~tance acetone, methyl ethyl ketone, methyl l~obutyl ketone, acetophonono or benzophenone; aldehyde# ~lth lS 2-lS c-rbon ato ~ per lecule, ior ln~tance ethanal, propanal, heptanal, benzaldohyde, tolu-ldehyde or naphthaldehyde; acld halldes wlth 2-15 c rbon to a per olecule, ior ln#tance acetyl chlorlde, benzoyl chlo-rlde or toluyI chlorlde; acld a ldea ~lth 2-lS carbon ato # per olecule, ~or lnat nce ior u lde, aceta lde, benz~ lde or tolua lde; amlne# ~lth 20 2-18 c-rbon ato ~ per olecule, ior ln~tanee ~ethyla lne, ethyla lne, dlethyl-slno, trlethyla lne, trlbutyla lne, plperldlne, trlbenzyla~lne, anlllne, pyrldlne, plcollne or ethylene dlamlne; nltrlle~ ulth 2-15 carbon to ~ per ~oleeule, ior ln~tanee aeetonltrlle, benzonltrlle or tolunltrlle; or nltro co pound#, ior lnstance nltrobenzene PreSerence 25 1~ glven to ether# ~lth 2-20 carbon atom# per olecule, rOr ln#tance dl ethyl ether, dlethyl ether, dl-n-butyl ether, dl-l#o-s yl ether, - tetrahydroiuran, nl~ole or dlphenyl ether, and ln partlcular organlc e~ter~ ~nth 2-40, ln partleular 2-18, earbon atom~ per molecule The aeld eo ponent oi the e~ter ~o~tly contaln# 1-~ carbon ato # per mole-cule or 1~ a natural iatty aeld, ~hlle the alcohol co ponent o#tly contalna 1-~ carbon ato # per olecule E~a ple# oi ~ultablo e~ter~ aro methyl ~ormate, cyclohe~yl Sormate, ethyl acetate, vlnyl acetate, amyl acetate, 2-ethyl hesyl acetate, cyclohexyl acetate, ethyl proplonate, amyl proplonate, methyl butyrate, ethyl valerlate, methyl chloroacetate, ethyl dl-chlo~oacetate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, ethyl crotonate, dl-ethyl aleate, ethyl cyclohexane carboxylate, methyl benzoate, ethyl _ . _ _ . _ . .... . .. . . .. .... ... ~ . . ... . _ .. .. . . .. ..... _ _ . _ _ _ _ _ . .. -- _ . .. . .
---^`` 114~399 benzoato, l-butyl benzoate, octyl benzoate, cyolohexyl benzoate, phenyl benzoate, benzyl benzoate, phenyl ethyl benzoats, methyl toluate, ethyl toluate, i-amyl toluate, methyl anisate, ethyl anisate, ~-butyrolactone, C -caprolactone, coumarin, phthalide and ethylene carbonate Particular preierence 18 given to esters derlved i'rom aromatic acids, in particular esters of benzoic acid, substituted or not ~ith alkyl or alkoxy groups Alkyl esterJ ~ith 1-4 carbon atoms per alkyl group, in particular methyl or ethyl eJterJ oi benzoic acid, o- or p-toluene carbosylic acid, p-methosy benzoic acid or phthalic acid, are preferred in particular Le~ides the halogenated titanium compound and the Lewis base, th catalytic tltanium co-ponent according to the invention contains a ixture oi a agneJium halide and an aluminium halide as carrier material Preierably, this carrier iJ at leaJt virtually anhydrous and also virtually i'ree oi ~ gnesium oxide Al~o alu inium oside i9 preferably ~ubJtantially absent The expre~sion~ 'at least virtually anhydrous' and 'at least vlrtually ireo oi' magneJiu oxide' are under~tood to mean here that tha concontratlon oi' ~ater and magne~iu oxide, re~pectively, in the carrier aterial lt ln~ignii'icant, i e a~ regards ~ater at any rate less than 0,2 % by ~t , preierably at mo~t 0 1 % by ~t , and aJ regards magneslum oxld a~ any rato leJ~ than 0 1, prei'erably at most 0 01, mgeq oi' baJe p r g oi carrlor aterlal dotermlned by titratlon ~lth a dllute ~trong acld, Sor ln~tanoe 0 1 N hydrochlorlc acid The c-rrl-r matorlal may i'urther contaln mlnor quantltles oi 0th r ~otal lon~, i'or ln~tance sodium, tin, silicon or germanium The halido lon 1~, in partlcular, bro lde, preierably chlorlde It 1~ re arked that the JapaneJe patent publlcation 54033578 (Der~ent ab~tract 30894 B) deJcribe~ a catalyst ior the polymerlzatlon oi' alkene~-l, ~hlch contaln~ ln the tltanlu- component a mlxture oi an lnorganlc agne~lum co pound and an electron donor-alumlnium halide-complex Such a cataly-t ~ho~ ho~ever only moderate periormance Apparently said complex doe~ not have that partlcular eiiect on the periormance oi the tltanium component that the aluminium hallde does have The carrler materlal may have been manuiactured by any Juitable ~ethod, preierably by grlndlng together oi the magneJlum hallde and the alumlnlum hallde, ior lnstance ln a ball mill, a vlbration mill or a beatermill 11~7~99 ~ he various constituent elements oi the titanium component may be combined in any known manner. Preierably, iir~t a complex oi' the titanium hallde compound and the electron donor is prepared.
The complexes oi the titanium halide compoun~ and the 5 electron donor may be obtained ln any known manner, ior instance by bringlng the components of the complex into contact with each other.
The titanium hallde compound may be applied to the carrier material in any kno~n manner, ior inJtance by simple mixing, preierably by grinding together, ior inJtancelin a ball mill, a~vibration mill or beater mill. The mixing may be done in the co-presence oi an inorganic or organic i'iller, ior inJtance lithium chloride, calcium carbonate, calcium chlorlde, chromium(II)chloride, barium chloride, sodium sulphate, sodium carbonate, titanium dioxide, sodium tetraborate, calcium ortho-phosphate, calcium Julphate, barium carbonate, aluminium sulphate, borium lS trloxide, aluminium oxide, Jilicon oxide, polyethylene, polypropylene or polyJtyrene. The iiller may also have been taken up in the carrier material beiorehand. It is poJaible to iirst iorm a complex oi the titanium halide co pound and the electron donor and apply it to the carrier, or alJo to iirJt apply the non-complexed titanium halide co pound to the carrier and add the electron donor aiterward~, either beSor- or aiter addition oi' the organoaluminium component used in the iini~hed catalyst.
It may be advantageouJ to treat the titanium aomponent with a halogen or an interhalogen compounq~ ior instance bromium, preSerably in the absence oi an inactlve solvent.
The titanium content oi thé iinished titanium component on the carrier noroally amountJ to between 0.1 and 10 % by wt. The electron donor in the titanium component iJ preierably present in a quantity oi, ior inJtance,~l to 5 molecule~ per titanium atom. A typical example oi the co poJition oi the titanium component, although varying in dependence on the conditlon~ oi the catalyst manuiacture, ls: 2-10 % by wt. oi tltanium, 16-25 % by ~t. oi magnesium, 1.5-2.5 % by wt. oi aluminium, 45-64 % bj wt. oi halogen and S-25 % by wt. oi the electron donor.
It is pointed out that aiter combining the titanium halide 3s compound with the metal halide used as carrier, the tetravalent titanium maybe reduced to a lower valency, ior instance to bi- or trivalent titanium, ii ~o deJired, so that the iinished titanium component need not necessarily contain tetravalent titanium.
~147~99 In the iinished poly~erization catalyst, the titanium compound is used in combination ~ith an organometal component derived irom a metal oi one oi the groups I-III oi the Periodic Sy~tem, with a hydrocarbon group bonded direct to the metal Examples are tra~
aluminlum compoundJ, alkyl aluminium alkoxides, alkyl aluminium ; hydrideJ, alkyl alu-lnium halides, dialkyl zinc compounds and dlalkyl magneJiu co poundJ Among th-se, the organoaluminium co pounds are partlcularly sultable Examples oi the organoaluminium co pounds are tr~alkyl or trlalkenyl aluminium compounds, ior instance tilethyl alumlnlum, trlpropyl alumlnlum, trlisobutyl aluminium, triiJoprenyl alu-inlum, trlheYyl alu-inium and trioctyl aluminium;
alkyl aluminiu- co pounds in ~hich a nu-ber oi the aluminium atoms are connected via an osygen or nitrogen atom, ior instance (C2H532AlOAl (C2H5)2, (i-C4Hg)2AlOAl(l-C4Hg)2 or (C2H5)2AINHAl(C2H5); dialkyl alu-iniu hydrideJ Juch as diethyl aluminium hydride or diisobutyl alu inium hydride; dialkyl aluminium halides, in particular a chloride or bro lde, diethyl alu inium chloride and bro lde bolng p rtlcularly ault-ble, ~hlle alJo other dlalkyl alu lnium hallde~ ~lth pr-i'er-bly 1-10 carbon ato J ln the alkyl group, such a~
i'or ln~t~nce dl-n-butyl lu~lnlu chlorlde and ethyl-n-butyl alumlnium chlorlde, c n be u~ed; nd dlalkyl alu~lnlum alkoslde~ or phenoxide~, i'or ln~tanco dlethyl ethosy aluulnluo or dlethyl phenosy alumlnlu~ The trlalkyl alu lnlu~ co pound~ de~erve ~o~t preierence The organooetal compound ay al~o contaln a trlalkyl alu inium co pound a~ ~ell a~ a dlalkyl alu lnluo hallde or a ~lsture oi' a dl-lkyl agnealu coupound and a onoalkyl alu~lnlum dlhallde The alkyl groupa oi' the organoalu lnlu co pound~ preierably contaln 1-10 carbon ato ~ e-ch The alkyl group~ oi' the dlalkyl agne~luu co po w d preiera-bly contaln 1-10 carbon ato~ ew h or are a palmltyl or stearyl group ~anple~ oi' ~ultable dlalkyl uagne~lu~ co pound~ are dlethyl magne~lu , dl-n-butyl agnedu~, dl-n-hesyl uagne~luu and di-n-octyl ~agne~iu~
The onoalkyl aluoinlu~ dlhallde prei'erably 19 a chlorlde or a bro~lde Ethyl alu~lnlu~ dl¢hlorlde or dlbro lde 1~ partlcularly ~ultable, but al~o other onoalkyl alu lnlu dlhalogenlde~ ~lth prei'erably 1-10 carbon ato~J ln the alkyl group ay be u~ed, such ag lsopropyl aluminlum dlchlorlde, n-butyl alu lnlum dlbro ide or n-octyl alumlnlum dlchloride The olar ratio bet~een the dialkyl agnesium compound and the onoalkyl alumlnl _ ~ih-lide may be bet~e-n, ior inst _c-, 0 1 and 1, preierably .
95~
between 0.3 and 0.6. Too high a molar ~atio leads to insuificiently stereospecli'ic catalysts, while insu$ficient catalyst acti~ity results ii it is too low.
The organometal component prei'erably contains a complex of an organic metal compound, in particular a trialkyl aluminium compound, with an ester o$ an oxygen-containing organic acid. Suitable esters are the same esters as may be used in the titanium component, in particular again the esters oi aromatic carboxylic acids. Por brevity's sake, reierence is made to the i'oregoing. Prei'erably, part oi' the organic metal compound, i'or instance 50-80 %, is present in a non-complexed condition.
The Al : Ti atom ratio is generally between 10 and 1000; the molecule-atom ratio oi Lewis base bonded in total in the catalyst to Tl i3 in general between 5 and 500.
_ .. . . .. . .
Thepro¢ess according to the inventlon 19 applied in particular ln the ~tereo~peciSic poly erlzation oi alkenes-l with 3-6 carbon atoms per molecule, ~uch a~ propylene~ butylene-1, 4-methyl pentylene-l and hexylene-l, and in the copolymerizatlon Or theee alkenes-l wlth each other and/or with ethylene. Copolymer~ wlth a random arrangement oi' the varlou~ monomer unit~ a~ well as block copolymer~ can be produced. Ii ethylene i~ taken as a comonomer, it 19 u~ual to lncorporate minor quantltlec oi lt ln the polymer, Sor lnetance at most 30 % by wt., more ln partlcular between 1 and lS % by wt. The~processaccording to the lnventlon 1~ oi lmportance ln partlcular ior manuiacture oi isotactlc polypropylene, random copolymers oi propylene wlth mlnor quantitie~ oi' ethylene, and block copolymer~ oi propylene and ethylene. For the manu-iacture oi block copolymer~, any deslred ~equence oi monomer addltlons may be applled.
The clrcum~tance~ under which the polymerlzatlon reaction wlth the tltanlu component accordlng to the lnventlon 1~ carrled out do not devlate irom tho~e known ln the art. The reaction may be carrled out ln the ga~ pha~e or in the presence oi a dl~persant. The dlspersant may be lnert or al~o a monomer in llquld iorm. Examples oi ~ultable dl~persant~
are allphatlc, cycloaliphatic, aromatlc and mixed aromatic/aliphatlc hydrocarbons wlth 3-8 carbon atoms per molecule, i'or instance propylene, butylene-l, butane, isobutane, n-hexane, n-heptane, cyclohexane, ben-zene, toluene and the xylene~.
. ... ..... - - - ' ,,, .
~147Y~9~
g In the case oi' polymerization in the liquid pha~e, it is preierable ior the concentration oi the titanium component to be set at about 0.001-0.5 mmole, calculated as titanium atom, and the concentration oi the organometal compound at about 0.1-50 mmole, both per litre oi' liquld phase.
The polymerization temperature is normally bet~een 190 and 47~ K, preierably bet~een 310 and 375 K. The pressure may be, ior instance, between 100 and 3000 kPa.
Ii 90 desired, it i9 possible to tegulate the molecular weight oi the poly er during the polymerlzation process ior instance by carrying out the reactlon in the presence oi hydrogen or with any other kno~n molecular weight regulator.
The polymerization reaction may be carried out as a batch process or a~ a continuous process.
The lnvention will now be elucidated by means oi the ~ollowing non-re~trictive esamples and the comparative expertiments.
Example~ and co parative exDeriments EX mDl-- I
A ProParatlon oS the titaniu- co Ponent At 273 K, 6.5 ml oi water-iree ethyl bensoate (E8), dlssolved ln 75 ml oi water-iree ga~oline, i9 added to a ~olutlon oi 5 ml oi TiC14 and 125 ml oi gasollne, iluJhed wlth dry nitrogen. The re~ultant preclpltate Or TlC14.EB ls separated oii by illtratlon and subsequently drled.
At 970 K, commerclally avallable MgC12 1~ dehydrated iurther ln a ilow oi' C0 and C12 ln order to remove the residual content oi H20 and Mg~. 3.0 g oi thlJ MgC12, 0.210 g oi AlC13 and 3.4 g oi TiC14.EB
are ground together ior 17 hourJ ln ~talnless steel ball mlll ln an atmoaphere oi' dry nltrogen.
~. PolYmerlzatlon Into a stalnless steel reactor, ilushed with dry nitrogen and provided with a mochaoical agitator, 1.3 1 oi gasoline, 2.5 ml oi trilsobutyl alu-lnlum (TIEA), 0.25 ml E~ and 0 068 g oi the titanium component prepared as described under IA are introduced. ~y leading in -35 propylene, the pressure is raised to and maintained at 700 kPa. The ,, ,. ,.. . , .. _... . . ... .. .. . . .
~1478~9 temperature i9 raised to and maintained at 333 K. Aiter a polymerization time oi 2 hours, the supply oi propylene i9 stopped, the pressure is let oii and the polymerization suspension is removed irom the reactor. The polymer i~ separated oii by iiltration.
S The polymerization activitg amounts to 870 g oi polypropylene (PP)/
mmole Ti.h; the Joluble polymer content i~ 5.5 %. The average particle diameter (d50) i~ 550 microns.
Comoarative esperi ent A
A. pre~Darstion Or the titanlum comPonent The titanium component iJ prepared analogously to the procedure de~cribed in example IA, except ior the omission oi addition oi AlCl3.
B. Polymerization Poly erization ls carrled out ln a manner analogous to that lS d ~crlb d ln example IB, but now 0.06S g oi the titanium component esnt under point A oi thls comparative experlment is used The polymorlzstlon actlvlty a ount~ to 810 g PP/m~ole Ti.h; the D ~olublo DO1Y er content 1J S.3 ~. The ~ particle diameter oi the Doly-Or (d50) 1J 400 1CrOnJ~
ExamDlo II
A. ProDar~tlon oi the tltanlum component Tho tltanlum co ponent is prepared analogously to the procedure deJcrlbed ln example IA, but no~ 0.270 g oi AlCl3 i9 added.
: ~. Pol~merlzatlon Poly erlzatlon 1~ carried cut in a m nner analogou~ to that doJcrlbed ln esample I~, but no~ 0.070 g oi the titanlum component oi example IIA is used.
The polymerization activity now amounts to 920 g PP/mmole Ti.h; the soluble polymer content is 5.5 %. The average particle dlameter oi the polymer is 575 mlcrons.
1~478~9 ExamPle III
A. Preparation oi the titanlum comPonent The tltanlum component $e prepared analogously to the procedure described ln example IA, but no~ 0.320 g oi AlCl3 i8 added.
S B. Polymerization Polymerlzation i- carried out in the same ~ay as described in exa ple IB, but no~ 0.067 g oi the titanlum ¢omponent oi' example IIIA is u~ed.
The polymerization actlvity amounts to 1080 g PP/mmole Tl.h; tho diseolved polymer content is S.S %. The average particle dia eter i~ 600 micron~.
ExamDle IV
A Pr-Daratlon o~ the tlt-nlum comDonent The tltanlum comyonent i9 prepared analogously to the proce-lS dure deecrlb d ln ex~;mple IA, but n~ 0,370 g oi' AlC13 19 added.
~, PolYmerlzatlon Polymerlzatlon ia oarrled out ln the ~ame way as descrlbed ln eYumple IB, but no~ 0.071 g Or the tltanlum component oi example IVA le used.
Th- poly erlzatlo~ actlvlty a ounte to 1070 g PP/mmole Tl.h;
the dleeolved poly er content le ff.2 %. Tbe average partlcle dla oter le ff50 mlcron-.
~a~Dle V
.
A. PreDaratlon oi the tltanlum co Donent The tltanlu- co ponent le prepared analogouely to the proce-dure deecrlbed ln esa ple IA, but no~ 0.425 g oi AlC13 le added.
B. Poly erlzatlon Polyrerlzatlon le carrled out ln a manner analogoue to that deecrlbed ln esa ple IB, but no~ 0.072 g oi the tltanlum component ol esa ple VA 18 ueed.
The poly~erlzatlon actlvlty amounts to 990 PP/mmole Ti.h; the dlesolved polymer content 1~ 6.4 %. Tbe average particle diameter is ff50 mlcrons.
.. ,, __ . _, . . . .. . . . . .. . . _ . , .
- -: ' '.,' -:' ,, ~ ,.
.. ,.. -., . ~ .
'11~7~gg Comparative experiment B
A. Preparation oi' the titanium component The titanlum component is prepared analogously to the proce-dure described in example IA, but now 0.530 g o~ AlC13 19 ground in.
B. Poly erization ` Polymerlzation is carried out in a manner analogous to that described ln example IB, but no~ 0:74 g oi' the titanium component oi' co parative esperimont B, part A, is usod.
The polymerization activity amounts to 720 g PP/mmole Ti.h;
the dissolved poly~er content is 6.0 %. The average partlcle diameter i~ 675 icro~s.
A graphic representation oi' the polymerization results above iJ ~ho~n in the i'igure annesed hereto, in which the polymerization activity a in g oi PP/m ole Tl.h has been plotted against the aluminium : magneslum ~eight ratio r oi the tltanlum compon~nt.
Co Daratlve ~cDerlmont C
A. Pr-par-tlon oi' tho tltanlum com w nent The tltanlu- component 1J prepued analogously to the procedure de~crlbed ln example IA, but ln stead oi AlCl3 now 2.85 g o~ AlCl3.
.o~hYl bonzoate-complex 1~ uJed.
B. Polvmerlzation Polymerlzation is carrled out in a manner analogou- to that de~crlbed in example IB, but nov 0.069 g oi the tltanium component oi' comparatlve exporimont C, part A, 19 u ed.
The polymerlzatlon activity amounts to 890 g PP/mmole Tl.h;
tho dl~olved polYmor oontent i~ 7.8 %, the average partlcle diameter 1~ 675 mlcrons.
.
Claims (18)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. Catalytic titanium component useful for the polymerization of alkenes-1 and for the copolymerization of alkenes-1 with each other or with ethylene, which titanium component contains a halogenated titanium compound, an electron donor, and a mixture of a magnesium halide and an aluminium hal-ide as carrier, characterized in that the titanium component contains 0.1-10% by wt. of titanium and in that the titanium : magnesium : aluminium weight ratio amounts to 1 : (0.5-20) : (0.05-2.5), while the magnesium :
aluminium weight ratio is at least 3 : l. - 2. Titanium component according to claim l, characterized in that the titanium : magnesium : aluminium weight ratio amounts to l : (l-5) : (0.2-l).
- 3. Titanium component according to claim 1 or 2, characterized in that the titanium content amounts to 2-10% by wt.
- 4. Titanium component according to claim 1 or 2, characterized in that the magnesium : aluminium weight ratio amounts to 4 : 1 to 20 : 1.
- 5. Titanium component according to claim 1 or 2, characterized in that the halogenated titanium compound is TiCl4.
- 6. Titanium component according to claim 1, characterized in that the halogenated titanium compound is a titanium halide phenolate of the formula TinXaAb, in which X represents a halogen atom and A the acid radical of a phenol, n is a whole number of at least 1, and a and b are such numbers that a/n and b/n both are 1-3, on the understanding that (a+b)/n is equal to 3-4.
- 7. Titanium component according to claim 6, characterized in that the titanium halide phenolate is a titanium(IV) trichloride monophenolate.
- 8. Titanium component according to claim 1, 2 or 6, characterized in that the electron donor is an ether with 2-20 carbon atoms per molecule.
- 9. Titanium component according to claim 1, characterized in that the electron donor is an ester the acid component of which contains 1-9 carbon atoms per molecule, or is a natural fatty acid, while the alcohol component contains 1-6 carbon atoms per molecule.
- 10. Titanium component according to claim 9, characterized in that the ester is derived from an aromatic acid.
- 11. Titanium component according to claim 10, characterized in that the ester is an alkyl ester with 1-4 carbon atoms per alkyl group of benzoic acid, o- or p-toluene carboxylic acid, p-methoxy benzoic acid or phthalic acid.
- 12. Titanium component according to claim 1, 2 or 6, characterized in that the mixture of a magnesium halide and an aluminium halide is at least virtually anhydrous and also at least virtually free of magnesium oxide.
- 13. Titanium component according to claim 1, 2 or 6, characterized in that the carrier material used is a mixture of magnesium chloride and alumin-ium chloride.
- 14. Titanium component according to claim 1, 2 or 6, characterized in that the carrier material is obtained by grinding together of a magnesium halide and an aluminium halide.
- 15. Process for the preparation of a catalytic titanium component use-ful for the polymerization of alkenes-l and for the copolymerization of alkenes-l with each other or with ethylene, which titanium component con-tains a halogenated titanium compound, an electron donor and a mixture of a magnesium halide and an aluminium halide, characterized in that a magnesium halide and an aluminium halide in a weight ratio, calculated as magnesium :
aluminium, of 3 : 1 to 400 : 1 are ground together in the absence of an elec-tron donor, and the ground product is further manufactured into the finished titanium component. - 16. Process according to claim 15, characterized in that the titanium component is manufactured by first forming a complex of the titanium halide component and the electron donor, and grinding this complex together with the mixture of a magnesium halide and an aluminium halide to be used as carrier.
- 17. Process for the polymerization of alkenes-l and for the copolymeri-zation of alkenes-l with each other or with ethylene, with application of a catalyst system consisting of a titanium component containing a halogenated titanium compound, an electron donor and a mixture of a magnesium halide and an aluminium halide, and an organometal component derived from a metal of one of the groups I-III of the Periodic System of the Elements, characterized in that a titanium component according to claim 1 is used.
- 18. Process according to claim 17, characterized in that the organo-metal component contains a complex of an organic metal compound with an ester of an oxygen-containing organic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7902536 | 1979-04-01 | ||
| NL7902536 | 1979-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1147899A true CA1147899A (en) | 1983-06-07 |
Family
ID=19832902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000348651A Expired CA1147899A (en) | 1979-04-01 | 1980-03-28 | Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 with application of such a titanium component |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS55160003A (en) |
| AT (1) | AT368527B (en) |
| BE (1) | BE882544A (en) |
| BR (1) | BR8001973A (en) |
| CA (1) | CA1147899A (en) |
| DE (1) | DE3012276A1 (en) |
| ES (1) | ES490141A0 (en) |
| FR (1) | FR2453184B1 (en) |
| GB (1) | GB2047718B (en) |
| IT (1) | IT1143083B (en) |
| PT (1) | PT71040A (en) |
| SE (1) | SE8002498L (en) |
| ZA (1) | ZA801725B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4425257A (en) * | 1980-05-02 | 1984-01-10 | Phillips Petroleum Company | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
| US4618661A (en) * | 1980-05-02 | 1986-10-21 | Phillips Petroleum Company | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
| FR2529207A1 (en) | 1982-06-24 | 1983-12-30 | Bp Chimie Sa | PROCESS FOR THE PREPARATION OF CATALYST SUPPORTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS AND SUPPORTS OBTAINED |
| NL8500521A (en) * | 1985-02-23 | 1986-09-16 | Stamicarbon | METHOD FOR PREPARING A FIXED CATALYTIC TITAN COMPONENT AND METHOD FOR POLYMERIZING OLEFINS-1 USING SUCH A TITAN COMPONENT |
| ES8609375A1 (en) * | 1985-07-23 | 1986-07-16 | Empresa Nac Petroleo | Improvements in a procedure for polymerisation and copolymerisation of ethylene at high pressures and temperatures. |
| US4948770A (en) * | 1987-06-29 | 1990-08-14 | Shell Oil Company | Method for crystallizing magnesium chloride and method for using in a catalyst composition |
| JPH05292040A (en) | 1992-04-08 | 1993-11-05 | Hitachi Ltd | Method for constructing optical transmission system |
| JP4885818B2 (en) * | 2007-10-01 | 2012-02-29 | ヤンマー株式会社 | engine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175171A (en) * | 1976-08-02 | 1979-11-20 | Mitsui Toatsu Chemicals, Inc. | Catalyst for polymerizing α-olefins |
| DE2831829A1 (en) * | 1978-07-20 | 1980-01-31 | Basf Ag | METHOD FOR PRODUCING A COMPONENT FOR POLYMERIZATION CATALYSTS |
-
1980
- 1980-03-24 ZA ZA00801725A patent/ZA801725B/en unknown
- 1980-03-26 GB GB8010222A patent/GB2047718B/en not_active Expired
- 1980-03-28 CA CA000348651A patent/CA1147899A/en not_active Expired
- 1980-03-29 DE DE19803012276 patent/DE3012276A1/en not_active Ceased
- 1980-03-31 BR BR8001973A patent/BR8001973A/en unknown
- 1980-03-31 AT AT0172780A patent/AT368527B/en not_active IP Right Cessation
- 1980-03-31 ES ES490141A patent/ES490141A0/en active Granted
- 1980-03-31 BE BE0/200044A patent/BE882544A/en not_active IP Right Cessation
- 1980-03-31 FR FR8007200A patent/FR2453184B1/en not_active Expired
- 1980-03-31 PT PT71040A patent/PT71040A/en unknown
- 1980-04-01 JP JP4274880A patent/JPS55160003A/en active Pending
- 1980-04-01 SE SE8002498A patent/SE8002498L/en not_active Application Discontinuation
- 1980-04-01 IT IT48314/80A patent/IT1143083B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| ES8101086A1 (en) | 1980-12-01 |
| ZA801725B (en) | 1981-03-25 |
| SE8002498L (en) | 1980-10-02 |
| ATA172780A (en) | 1982-02-15 |
| GB2047718B (en) | 1983-08-24 |
| IT8048314A0 (en) | 1980-04-01 |
| ES490141A0 (en) | 1980-12-01 |
| AT368527B (en) | 1982-10-25 |
| JPS55160003A (en) | 1980-12-12 |
| BR8001973A (en) | 1980-11-25 |
| GB2047718A (en) | 1980-12-03 |
| PT71040A (en) | 1980-04-01 |
| BE882544A (en) | 1980-09-30 |
| IT1143083B (en) | 1986-10-22 |
| FR2453184A1 (en) | 1980-10-31 |
| DE3012276A1 (en) | 1980-10-09 |
| FR2453184B1 (en) | 1985-09-06 |
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