NO852451L - PROCEDURE FOR POLYMERIZATION OF OLEFINES. - Google Patents
PROCEDURE FOR POLYMERIZATION OF OLEFINES.Info
- Publication number
- NO852451L NO852451L NO852451A NO852451A NO852451L NO 852451 L NO852451 L NO 852451L NO 852451 A NO852451 A NO 852451A NO 852451 A NO852451 A NO 852451A NO 852451 L NO852451 L NO 852451L
- Authority
- NO
- Norway
- Prior art keywords
- titanium
- stated
- compound
- zirconium
- hafnium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 24
- 238000006116 polymerization reaction Methods 0.000 title description 15
- 239000010936 titanium Substances 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- -1 aluminum compound Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 150000002363 hafnium compounds Chemical class 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 239000000725 suspension Substances 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 101000798109 Homo sapiens Melanotransferrin Proteins 0.000 description 4
- 102100032239 Melanotransferrin Human genes 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- ABNGESMFWMTZHX-UHFFFAOYSA-N 1-chlorohexane Chemical compound [CH2]CCCCCCl ABNGESMFWMTZHX-UHFFFAOYSA-N 0.000 description 1
- 241000974482 Aricia saepiolus Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 125000006277 halobenzyl group Chemical group 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Fremgangsmåte for fremstilling av en katalysator på grunnlag titan, magnesium, hafnium eller zirkonium, og bruk av denne ved homopolymerisering av etylen, og kopolymerisering av etylen med C\-olefiner for å oppnå polymerer med bred mole-kyl vektsfordel ing .Process for preparing a catalyst based on titanium, magnesium, hafnium or zirconium, and using it by homopolymerizing ethylene, and copolymerizing ethylene with C 1-6 olefins to obtain broad molecular weight polymers.
Description
Oppfinnelsen vedrører fremgangsmåte for homopolymerisering av etylen eller kopolymerisering av etylen med o(-olefiner,karakterisert vedet katalytisk system med en katalysator på grunnlag av titan, magnesium, zirkonium eller hafnium. Det katalytiske system som er et resultat av kombinasjonen mellom ovennevnte katalysator og ytterligere to forbindelser som er spesifisert i det påfølgende, opptrår meget spesielt og over-raskende hva angår blant annet virkningen, ved dannelsen av homopolymerer med bred molekylvektsfordeling, eller dannelse av kopolymerer som er meget motstandsdyktige overfor påkjenninger fra omgivelsene, en egenskap som kreves for spesielle artikler som for eksempel flasker, i tillegg til andre karakteristika som en så bred molekylvektsfordeling at produktene er spesielt godt egnet for produksjon av folier eller rør, som klarlegges i det påfølgende. The invention relates to a process for the homopolymerization of ethylene or the copolymerization of ethylene with o(-olefins, characterized by a catalytic system with a catalyst based on titanium, magnesium, zirconium or hafnium. The catalytic system which is the result of the combination between the above-mentioned catalyst and two further compounds that are specified in the following behave very particularly and surprisingly with regard to, among other things, the effect, in the formation of homopolymers with a wide molecular weight distribution, or the formation of copolymers that are highly resistant to stresses from the environment, a property that is required for special articles that for example bottles, in addition to other characteristics such as such a wide molecular weight distribution that the products are particularly well suited for the production of foils or tubes, which will be clarified in the following.
Polymeriseringen av etylen ved hjelp av titankatalysatorer er mye beskrevet i patentlitteraturen. I norsk patentansøkning nr. 81.0307 er det gitt en fremgangsmåte for homopolymerisering (eller kopolymerisering) av umettede forbindelser, spesielt etylen og høyere 0(-olefiner, for å oppnå homopolymerer (eller kopolymerer) med bred molekylvektsfordeling (8 <_ Mw/Mn <_12) som betyr at forholdet mellom vektmidlere og antallsmidlere molekylvekt er mellom 8 og 12, og som lett kan formes ved formblåsningsteknikk, men som ikke er spesielt egnet til folier eller rør. I den nevnte fremgangsmåte benyttes som katalysator sammen med en organisk aluminiumforbindelse, en sammensetning med titan trihalogen med følgende formel: The polymerization of ethylene using titanium catalysts is widely described in the patent literature. In Norwegian patent application no. 81.0307, a method is given for the homopolymerization (or copolymerization) of unsaturated compounds, especially ethylene and higher 0(-olefins), in order to obtain homopolymers (or copolymers) with a broad molecular weight distribution (8 <_ Mw/Mn <_12 ) which means that the ratio between weight averages and number average molecular weight is between 8 and 12, and which can be easily shaped by blow molding, but which is not particularly suitable for foils or tubes. In the aforementioned method, a composition is used as a catalyst together with an organic aluminum compound with titanium trihalogen of the following formula:
hvor X representerer et halogenion og m, g, c, M',M'', Y, Y', Y' ' , n, p, s og R har en betydning som angitt i ovennevnte patentansøkning. where X represents a halogen ion and m, g, c, M', M'', Y, Y', Y' ' , n, p, s and R have a meaning as indicated in the above-mentioned patent application.
I norsk patentansøkning nr. 82.2580 er det derimot beskrevet en fremgangsmåte for polymerisering og kopolymerisering av 0( - olefiner (inkluderende etylen) også i nærvær av konjugerte diolefiner, og særlig polymerisering av etylen med 1,3-butadien, hvor man benytter et katalytisk system av flere forbindelser, hvor en av forbindelsene inneholder titan og magnesium, men polymerene som oppnås ved et slikt system har snever molekylvektfordeling (3 <_Mw/Mn <_ 5 ) . Norwegian patent application no. 82.2580, on the other hand, describes a method for the polymerization and copolymerization of 0( - olefins (including ethylene) also in the presence of conjugated diolefins, and in particular the polymerization of ethylene with 1,3-butadiene, where a catalytic system is used of several compounds, where one of the compounds contains titanium and magnesium, but the polymers obtained by such a system have a narrow molecular weight distribution (3 <_Mw/Mn <_ 5 ) .
Man har nå funnet at det er mulig å fremstille en katalysator som særlig er passende som katalytisk komponent ved homopolymerisering av etylen, eller kopolymerisering av etylen med o( -olefiner. It has now been found that it is possible to produce a catalyst which is particularly suitable as a catalytic component in homopolymerisation of ethylene, or copolymerisation of ethylene with o(-olefins).
Katalysatoren er fremstilt ved en fremgangsmåte som beskrevet i følgende punkter: a) fordampning av magnesium i vakuum og omsetning av de oppnådde magnesiumdamper med en fireverdig titanforbindelse i The catalyst is produced by a method as described in the following points: a) evaporation of magnesium in a vacuum and reaction of the obtained magnesium vapors with a tetravalent titanium compound in
nærvær av en halogen atomdonorforbindelse og en zirkonium presence of a halogen atom donor compound and a zirconium
og/eller hafniumforbindelse,and/or hafnium compound,
b) varmebehandling av den kalde oppnådde blandingen under tilsetning av alkohol med generell formel ROH, hvor R representerer en lineær forgrenet alifatisk kjede inneholdende fra 1 til 10 karbonatomer, eventuelt substituert med b) heat treatment of the cold mixture obtained while adding alcohol of general formula ROH, where R represents a linear branched aliphatic chain containing from 1 to 10 carbon atoms, optionally substituted with
aromatiske grupper, ogaromatic groups, and
c) varmebehandling av den oppnådde blandingen under tilsetning av minst en organisk aluminiumforbindelse med formel c) heat treatment of the obtained mixture while adding at least one organic aluminum compound of formula
AlR'2_yXy, hvor R<1>representerer et hydrokarbon radi-AlR'2_yXy, where R<1>represents a hydrocarbon radi-
kal, X representerer et halogen og y er et tall fra 0-2, slik at 1 <_halogen/Al <_ 2. cal, X represents a halogen and y is a number from 0-2, so that 1 <_halogen/Al <_ 2.
Fordampningen under a) utføres under trykk fra IO<*>"<*>tilThe evaporation under a) is carried out under pressure from IO<*>"<*>to
-4 o -4 o
10 torr, ved temperatur fra 300 til 600 C. Omsetningen av de oppnådde dampene med titanforbindelsen i nærvær av halogendonoren utføres ved lav temperatur, vanligvis mellom 10 torr, at a temperature from 300 to 600 C. The reaction of the obtained vapors with the titanium compound in the presence of the halogen donor is carried out at a low temperature, usually between
-80 og +20°C. For å holde reaksjonsblandingen i flytende -80 and +20°C. To keep the reaction mixture liquid
tilstand kan det tilsettes et inert hydrokarbon-fortynnings-middel som for eksempel n-heptan eller n-heksan til de av-kjølte reaktantene med temperaturer mellom -100 til +10°C. state, an inert hydrocarbon diluent such as n-heptane or n-hexane can be added to the cooled reactants with temperatures between -100 to +10°C.
Varmebehandlingen under b) utføres ved temperaturer fra 50 til 100°C i løpet av 60 til 180 minutter under omrøring. The heat treatment under b) is carried out at temperatures from 50 to 100°C during 60 to 180 minutes with stirring.
Den organiske aluminiumforbindelsen tilsettes under c) i ovennevnte form eller som en hydrokarbonoppløsning, der den fore-trukkede forbindelse er A^Et^Cl^. The organic aluminum compound is added under c) in the above-mentioned form or as a hydrocarbon solution, where the preferred compound is A^Et^Cl^.
Varmebehandlingen under c) utføres ved temperaturer fra 80 til 100°C under omrøring. Følgende molare forhold benyttes: The heat treatment under c) is carried out at temperatures from 80 to 100°C with stirring. The following molar ratios are used:
Zirkonium- eller hafniumforbindelsen som også kan tilsettes under b), er utvalgt blant halogenidene og alkoksydene, og zirkonium-tetraalkoksyd, zirkonium-tetraklorid, hafnium-tetraklorid er særlig anvendt. The zirconium or hafnium compound which can also be added under b), is selected from among the halides and alkoxides, and zirconium tetraalkoxide, zirconium tetrachloride, hafnium tetrachloride are particularly used.
Alkoholen med generell formel ROH kan være en primær, sekundær eller tærtiær alkohol, hvor R representerer en alifatisk, lineær eller forgrenet kjede, med 1 til 10 karbonatomer, eventuelt substituert med aromatiske grupper, men butylalkohol, amylalkohol, isoamylalkohol og benzylalkohol er særlig anvendt. The alcohol with general formula ROH can be a primary, secondary or tertiary alcohol, where R represents an aliphatic, linear or branched chain, with 1 to 10 carbon atoms, optionally substituted with aromatic groups, but butyl alcohol, amyl alcohol, isoamyl alcohol and benzyl alcohol are particularly used.
Som halogendonor kan organiske halogenider anvendes, særlig dem som er uttrykt ved formelen C H„ ,. X , hvor X As a halogen donor, organic halides can be used, especially those expressed by the formula C H„ ,. X , where X
1m 2m+2-x x'1m 2m+2-x x'
representerer Cl eller Br, m representerer et tall fra 1 til 18, og x representerer et tall fra 1 til 4, men i dette til- represents Cl or Br, m represents a number from 1 to 18, and x represents a number from 1 to 4, but in this to-
felle kan halogenidene også utgjøres av den ovennevnte for-tynningsoppløsning, eller uorganiske halogenider av elementer med en høyere valenstilstand og som kan forekomme i minst to oksydas jonstilstander, som SnCl4, SbCl,- , P0C13, VC14>trap, the halides can also be made up of the above-mentioned dilution solution, or inorganic halides of elements with a higher valence state and which can occur in at least two oxidation states, such as SnCl4, SbCl,- , P0C13, VC14>
Når det gjelder titanforbindelsen, kan denne velges blant en rekke forbindelser, for eksempel trihalogenider og tetrahalo-genider av titan, titantetraalkoksyder og halogenalkoksyder, titantetrabenzyl og halogenbenzylderivater, titantetraallyl og halogenallyler, titanamider og amidhalogenider, titanchelater o.s.v. Anvendelse av slike forbindelser viser seg å være særlig effektiv i katalytiske systemer ved homopolymerisering av etylen eller kopolymerisering av etylen med Oi -olefiner. As for the titanium compound, this can be selected from a number of compounds, for example trihalides and tetrahalides of titanium, titanium tetraalkoxides and halogenalkoxides, titanium tetrabenzyl and halobenzyl derivatives, titanium tetraallyl and halogenallyls, titanium amides and amide halides, titanium chelates, etc. Use of such compounds proves to be particularly effective in catalytic systems by homopolymerization of ethylene or copolymerization of ethylene with Oi -olefins.
Man har funnet at det er mulig å danne etylenpolymerer eller kopolymerer ved at polymeriseringen foregår i nærvær av et system bestående av et aluminiumderivat med formel AlRpX^ p, hvor R representerer en hydrikarbonrest, X representerer et halogen og p et tall fra 1 - 3, og med en katalysator av zirkonium eller hafnium som beskrevet over. It has been found that it is possible to form ethylene polymers or copolymers by the polymerization taking place in the presence of a system consisting of an aluminum derivative with the formula AlRpX^ p, where R represents a hydrocarbon residue, X represents a halogen and p a number from 1 - 3, and with a catalyst of zirconium or hafnium as described above.
De foretrukne 0( -olefinene som kopolymeriseres med etylen er 1-buten, propen, 1-heksen, 1-okten. Ovennevnte komponent kan direkte benyttes i polymeriseringen som den er oppnådd ved den ovenfor omhandlede fremstillingsmetode, uten filtrering eller separering. Polymeriseringen utføres i nærvær av en hydro-karbonoppløsning som kan være lik fortynningsmiddelet som benyttes ved dannelsen av titanderivater, ved temperaturer fra 20 til 200°C og ved trykk fra 1 til 60 atmosfærer. The preferred 0( -olefins which are copolymerized with ethylene are 1-butene, propene, 1-hexene, 1-octene. The above-mentioned component can be directly used in the polymerization as it is obtained by the above-mentioned preparation method, without filtration or separation. The polymerization is carried out in presence of a hydrocarbon solution which may be similar to the diluent used in the formation of titanium derivatives, at temperatures from 20 to 200°C and at pressures from 1 to 60 atmospheres.
Alternativt kan polymeriseringen utføres ved at monomeren eller monomerene tilføres i gassform direkte på katalysatoren. Det oppnås stort utbytte av etylenpolymerer og kopolymerer, med bred molekylvektsfordeling, noe som kommer frem fra Mw/Mn-verdiene oppnådd ved gelfiltreringskromatografi (G.F.K.) som lå i området 12 til 20. Alternatively, the polymerization can be carried out by supplying the monomer or monomers in gaseous form directly onto the catalyst. A large yield of ethylene polymers and copolymers is obtained, with a wide molecular weight distribution, which is evident from the Mw/Mn values obtained by gel filtration chromatography (G.F.K.) which were in the range 12 to 20.
Slike polymerer er passende for ekstruderings- og formblås-ningsteknikker, særlig ved folieproduksjon. Such polymers are suitable for extrusion and blow molding techniques, particularly in foil production.
Takket være deres motstandsdyktighet og påkjenninger fra omgivelsene, passer produktene særlig til belegg i vaskemiddel-beholdere og store beholdere. Thanks to their resistance and environmental stresses, the products are particularly suitable for coating detergent containers and large containers.
Eksempel 1.Example 1.
Fremstilling av en katalysatorkomponent.Preparation of a catalyst component.
Første trinn i fremstillingen utføres i en roterende kolbe med en spiralformet wolframtråd i midten for er forbundet med et elektrisk element. The first step in the production is carried out in a rotating flask with a spiral tungsten wire in the middle which is connected to an electrical element.
Til kolben tilføres 500 cm<3>vannfri heptan, 0,60 cm<3>Add 500 cm<3> of anhydrous heptane, 0.60 cm<3> to the flask
(5,4 mmol) TiCl4, 6 g (25,7 mmol) ZrCl4og 25 cm<3>(5.4 mmol) TiCl4, 6 g (25.7 mmol) ZrCl4 and 25 cm<3>
(237 mmol) klorbutan i en nitrogenatmosfære.(237 mmol) of chlorobutane in a nitrogen atmosphere.
Rundt wolframspiralen tvinnes 3 g Mg-tråd (125 mgatom.er). Kolben nedkjøles til -70°C og anbringes til vakuum ved 10 -2 torr og spiralen oppvarmes for å fordampe magnesiumet. 3 g of Mg wire (125 mgatoms) are twisted around the tungsten spiral. The flask is cooled to -70°C and placed under vacuum at 10 -2 torr and the coil is heated to evaporate the magnesium.
Etter 20 minutter, tilføres nitrogen til kolben og i andre trinn av fremstillingen tilføres 7,43 cm<3>isoamylalkohol til den kalde suspensjonen under omrøring. Kolben bringes tilbake til romtemperatur og reaksjonsblandingen oppvarmes ved koke-feuhkt<s>temperatur i to timer. Resultatet er en brunfarget sus-pens jon. After 20 minutes, nitrogen is added to the flask and in the second step of the preparation, 7.43 cm<3>isoamyl alcohol is added to the cold suspension with stirring. The flask is returned to room temperature and the reaction mixture is heated at boiling-humid<s>temperature for two hours. The result is a brown colored suspension.
I tredje fremstillingstrinn tilføres 108 mmol A^Et^Cl^In the third production step, 108 mmol of A^Et^Cl^ are added
til ovennevnte oppnådde suspensjon, og hele reaksjonsblandingen oppvarmes til kokepunktstemperatur i tre timer. Fargen på suspensjonen- blir grønnblå. to the suspension obtained above, and the entire reaction mixture is heated to boiling temperature for three hours. The color of the suspension- becomes greenish-blue.
Den oppnådde katalysator vaskes med heptan og har følgende sammensetning etter tørking: Ti = 1,55 % The obtained catalyst is washed with heptane and has the following composition after drying: Ti = 1.55%
Mg = 14,65 % Mg = 14.65%
Zr = 14,34 % Zr = 14.34%
Cl = 6 9,4 % Cl = 6 9.4%
Eksempel 2.Example 2.
Polymerisering.Polymerization.
Til en 5 liters autoklav, fri for luft og fuktighet og med en magnetisk rører, tilføres 2 liter vannfri og luftfri n.heptan og 8 mmol Al (isobutan)^. Temperaturen økes til 80°C og til autoklaven tilføres i følgende rekkefølge: 5,6 bar U^, 8 g 1-buten, katalysatorsuspensjon fremstilt ifølge Eksempel 1 med sammensetning 0,0212 mgatom titan, og etylen inntil et totaltrykk på 9,4 bar er oppnådd. Tilførselen av etylen til autoklaven fortsetter i to timer, mens trykket holdes kon-stant. Etter to timer stoppes reaksjonen og autoklaven luftes. Oppnådd mengde polymer er 359 g tilsvarende 355.000 g pr. g titan. Produktet har følgende egenskaper: 2 liters of anhydrous and air-free n.heptane and 8 mmol Al (isobutane)^ are added to a 5 liter autoclave, free from air and moisture and with a magnetic stirrer. The temperature is increased to 80°C and the autoclave is fed in the following order: 5.6 bar U^, 8 g 1-butene, catalyst suspension prepared according to Example 1 with composition 0.0212 mgatom titanium, and ethylene up to a total pressure of 9.4 bar has been achieved. The supply of ethylene to the autoclave continues for two hours, while the pressure is kept constant. After two hours, the reaction is stopped and the autoclave vented. The amount of polymer achieved is 359 g, corresponding to 355,000 g per g titanium. The product has the following properties:
- smelteindeks ved belastning 2,16 kg (MFI2 -^g<AS>TM- melt index at load 2.16 kg (MFI2 -^g<AS>TM
Standard 1238/E) = 0,35 g/10 minutter.Standard 1238/E) = 0.35 g/10 minutes.
- skjærfølsomhet (S.S., MFI21 g/MFI2 lg) =<1>01.- shear sensitivity (S.S., MFI21 g/MFI2 lg) =<1>01.
- tetthet (d, ASTM Standard D 1505) = 0,9548 kg/dm3 .- density (d, ASTM Standard D 1505) = 0.9548 kg/dm3 .
- skjærhastighet ( Y , ASTM Standard D 1703) = 1000 s<-1>.- shear rate ( Y , ASTM Standard D 1703) = 1000 s<-1>.
- motstand mot påkjenning fra omgivelsene (ESC, ASTM Standard - resistance to stress from the environment (ESC, ASTM Standard
D 1693) = 220 timer. D 1693) = 220 hours.
- Mw/"Mn = 14,5 (G.F.K. )- Mw/"Mn = 14.5 (G.F.K. )
Eksempel 3.Example 3.
Fremstilling av en katalysatorkomponent.Preparation of a catalyst component.
Fremstillingen av katalysatoren utføres som omtalt iThe production of the catalyst is carried out as described in
Eksempel 1. Til kolben tilføres 300 cm<3>vannfri heptan,Example 1. Add 300 cm<3> of anhydrous heptane to the flask,
0,6 cm<3>TiCl4(5,4 mmol), 6 g ZrCl4(25,7 mmol) og 26 cm<3>1-klorheksan (790 mmol) i en nitrogenatmosfære. Rundt wolframspiralen tvinnes 2,45 g magnesiumtråd (100 mgatomer), 0.6 cm<3>TiCl4(5.4 mmol), 6 g ZrCl4(25.7 mmol) and 26 cm<3>1-chlorohexane (790 mmol) in a nitrogen atmosphere. 2.45 g of magnesium wire (100 mg atoms) are twisted around the tungsten spiral,
og fordampningen utføres som i Eksempel 1.and the evaporation is carried out as in Example 1.
7,5 cm<3>butylalkohol tilsettes den kalde suspensjonen under omrøring. I tredje separasjonstrinn tilsettes 100 mmol A^Et^Cl^ til suspensjonen som oppvarmes i tre timer. Produktet vaskes med heptan, og etter tørking finner man følgende sammensetning: Ti = 1, 78 % 7.5 cm<3>butyl alcohol is added to the cold suspension while stirring. In the third separation step, 100 mmol of A^Et^Cl^ are added to the suspension, which is heated for three hours. The product is washed with heptane, and after drying the following composition is found: Ti = 1.78%
Mg = 13,36 % Mg = 13.36%
Zr = 16 , 38 % Zr = 16.38%
Cl = 6 8,15 % Cl = 6 8.15%
Eksempel 4.Example 4.
Polymerisering.Polymerization.
Utstyr og fremgangsmåte er som beskrevet i Eksempel 2.Equipment and procedure are as described in Example 2.
Ved 80°C tilføres 5,6 bar H2, 6 g 1-buten, og en katalysatorsuspensjon fremstilt som i Eksempel 3 inneholdende 0,02 mgatom titan og etylen opp til et totaltrykk på 9,4 bar. Etter polymerisering i to timer, oppnås 320 g polymer tilsvarende 333.000 g pr. g titan. Produktet har følgende egenskaper: MFI2 16 = 0,16 g/10 min'At 80°C, 5.6 bar of H2, 6 g of 1-butene, and a catalyst suspension prepared as in Example 3 containing 0.02 mg of titanium and ethylene are added up to a total pressure of 9.4 bar. After polymerization for two hours, 320 g of polymer corresponding to 333,000 g per g titanium. The product has the following properties: MFI2 16 = 0.16 g/10 min'
S.S = 95S.S = 95
d = 0 , 9565 kg/dm<3>d = 0 , 9565 kg/dm<3>
V 850 s"<1>V 850 s"<1>
rc rc
ESC = 500 timerESC = 500 hours
Mw/Mn = 16Mw/Mn = 16
Eksempel 5.Example 5.
Polymerisering.Polymerization.
Polymeriseringen utføres som i Eksempel 4, med unntagelse av komonomeren som i dette tilfelle er propen i en mengde på 5 g. Det oppnådde produkt, 360 g, har følgende egenskaper: The polymerization is carried out as in Example 4, with the exception of the comonomer, which in this case is propene in an amount of 5 g. The product obtained, 360 g, has the following properties:
MFI2 g = 0,32 g/10 min.MFI2 g = 0.32 g/10 min.
S.S.'= 105 S.S.'= 105
d = 0,95 72 kg/dm<3>d = 0.95 72 kg/dm<3>
yc 1800 s<-1>yc 1800 s<-1>
ESC = 100 timerESC = 100 hours
Mw/Mn = 13,5Mw/Mn = 13.5
Eksempel 6.Example 6.
Fremstilling av en katalytisk komponent.Preparation of a catalytic component.
Fremstillingen av katalysatoren utføres ved at 300 cm<3>vannfri heptan, 0,48 cm<3>TiCl4(4,3 mmol), 3,2 cm<3>klorbutan (30 mmol) tilføres en kolbe i en nitrogenatmosfære. 0,6 g magnesiumtråd (25 mgatom) er tvunnet rundt wolframspiralen og fordampes som i Eksempel 1. Den kalde suspensjonen tilsettes 4,6 g HfCl^(14,4 mmol) og 5,2 cm<3>n.butanol (57,6 mmol) under omrøring. I tredje trinn av fremstillingen tilsettes 42,5 mmol AJ^Et^Cl^ og suspensjonen oppvarmes til kokepunktstemperatur i tre timer. The preparation of the catalyst is carried out by adding 300 cm<3>anhydrous heptane, 0.48 cm<3>TiCl4 (4.3 mmol), 3.2 cm<3>chlorobutane (30 mmol) to a flask in a nitrogen atmosphere. 0.6 g of magnesium wire (25 mg atoms) is twisted around the tungsten spiral and evaporated as in Example 1. To the cold suspension is added 4.6 g of HfCl^ (14.4 mmol) and 5.2 cm<3>n.butanol (57, 6 mmol) with stirring. In the third step of the preparation, 42.5 mmol of AJ^Et^Cl^ are added and the suspension is heated to the boiling point temperature for three hours.
Produktet vaskes med heptan og har følgende sammensetning etter tørking: The product is washed with heptane and has the following composition after drying:
Ti = 2,7 %Ten = 2.7%
Mg = 7,6 6 % Mg = 7.6 6%
Hf = 34,2 % Hf = 34.2%
Cl = 55,3 % Cl = 55.3%
Eksempel 7.Example 7.
Polymerisering.Polymerization.
Utstyr og fremgangsmåte som beskrevet i Eksempel 2 er benyttet. 6 bar H^, 6 g 1-buten, en mengde katalysatorsuspensjon fremstilt som beskrevet i Eksempel 6 tilsvarende 0,0374 mgatom titan, og etylen opp til et totaltrykk på Equipment and method as described in Example 2 is used. 6 bar H 2 , 6 g 1-butene, an amount of catalyst suspension prepared as described in Example 6 corresponding to 0.0374 mgatom titanium, and ethylene up to a total pressure of
9,4 bar tilføres.9.4 bar is supplied.
Etter at polymeriseringen har pågått i to timer, har man oppnådd 206 g polymer som tilsvarer et utbytte på 115.000 g pr. g titan. Produktet har følgende egenskaper: MFI216= 0,21 g/10 min- After the polymerization has continued for two hours, 206 g of polymer have been obtained, which corresponds to a yield of 115,000 g per g titanium. The product has the following properties: MFI216= 0.21 g/10 min-
S.S = 145 S.S = 145
d = 0, 95 79 kg/dm<3>d = 0.95 79 kg/dm<3>
Y c = 750 s<_1>Y c = 750 s<_1>
ESC = 500 timerESC = 500 hours
Mw/Mn = 15. Mw/Mn = 15.
Claims (16)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21559/84A IT1176299B (en) | 1984-06-22 | 1984-06-22 | METHOD FOR THE PREPARATION OF A ZIRCONIUM OR AFHNIUM CATALYST AND PROCESS OF POLYMERIZATION OR COPOLYMERIZATION OF UNSATURATE COMPOUNDS USING THE SAME |
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| Publication Number | Publication Date |
|---|---|
| NO852451L true NO852451L (en) | 1985-12-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO852451A NO852451L (en) | 1984-06-22 | 1985-06-18 | PROCEDURE FOR POLYMERIZATION OF OLEFINES. |
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|---|---|
| JP (1) | JPS6114202A (en) |
| BE (1) | BE902730A (en) |
| DE (1) | DE3522295A1 (en) |
| DK (1) | DK279185A (en) |
| ES (1) | ES8609372A1 (en) |
| FR (1) | FR2566412A1 (en) |
| GB (1) | GB2160535A (en) |
| GR (1) | GR851522B (en) |
| IL (1) | IL75590A0 (en) |
| IT (1) | IT1176299B (en) |
| LU (1) | LU85968A1 (en) |
| NL (1) | NL8501815A (en) |
| NO (1) | NO852451L (en) |
| PL (1) | PL254120A1 (en) |
| PT (1) | PT80685B (en) |
| RO (1) | RO92339B (en) |
| SE (1) | SE8503033L (en) |
| ZA (1) | ZA854595B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015511A (en) * | 1988-05-12 | 1991-05-14 | The Dow Chemical Company | Linear low density ethylene interpolymers for injection molding |
| JP2740922B2 (en) * | 1989-11-21 | 1998-04-15 | 石原産業株式会社 | Method for producing metal magnetic powder for magnetic recording material |
| IT1311978B1 (en) * | 1999-03-25 | 2002-03-22 | Polimeri Europa Srl | BIMETALLIC CATALYST FOR THE (CO) POLYMERIZATION OF ALPHA-OLEFINS. |
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| GB1464451A (en) * | 1973-09-08 | 1977-02-16 | Chubu Chem Inc | Solid catalytic complexes and their use in olefin polymerization |
| JPS5146387A (en) * | 1974-10-18 | 1976-04-20 | Yozo Kondo | Horiorefuinno seizohoho |
| GB1578745A (en) * | 1976-05-24 | 1980-11-12 | Bp Chem Int Ltd | Polymerisation catalyst component |
| IT1130243B (en) * | 1980-02-01 | 1986-06-11 | Anic Spa | CHEMICAL COMPOSITION BASED ON TRIALHYGEN TITANIUM, METHOD FOR ITS PREPARATION AND PROCESS OF POLYMERIZATION OR COPOLYMERISATION OF UNSATURATED COMPOUNDS USING THE SAME |
| US4396747A (en) * | 1981-05-22 | 1983-08-02 | Phillips Petroleum Company | Zirconium-titanium catalyzed olefin polymerization |
| IT1137631B (en) * | 1981-07-29 | 1986-09-10 | Anic Spa | PROCEDURE FOR HIGH YIELD POLYMERIZATION AND COPOLYMERIZATION OF HYDRAULICALLY UNSATURATED COMPOUNDS AND MEDIA SUITABLE FOR SOCPO |
| IT1210855B (en) * | 1982-02-12 | 1989-09-29 | Assoreni Ora Enichem Polimeri | LINEAR STRUCTURE ETHYLENE POLYMERS AND PROCESSES FOR THEIR PREPARATION. |
-
1984
- 1984-06-22 IT IT21559/84A patent/IT1176299B/en active
-
1985
- 1985-06-18 NO NO852451A patent/NO852451L/en unknown
- 1985-06-18 ZA ZA854595A patent/ZA854595B/en unknown
- 1985-06-18 SE SE8503033A patent/SE8503033L/en not_active Application Discontinuation
- 1985-06-19 GB GB08515470A patent/GB2160535A/en not_active Withdrawn
- 1985-06-20 IL IL75590A patent/IL75590A0/en unknown
- 1985-06-20 LU LU85968A patent/LU85968A1/en unknown
- 1985-06-20 DK DK279185A patent/DK279185A/en not_active Application Discontinuation
- 1985-06-21 JP JP60134440A patent/JPS6114202A/en active Pending
- 1985-06-21 PL PL25412085A patent/PL254120A1/en unknown
- 1985-06-21 GR GR851522A patent/GR851522B/el unknown
- 1985-06-21 DE DE19853522295 patent/DE3522295A1/en not_active Ceased
- 1985-06-21 RO RO119262A patent/RO92339B/en unknown
- 1985-06-21 FR FR8509510A patent/FR2566412A1/en not_active Withdrawn
- 1985-06-21 BE BE0/215248A patent/BE902730A/en not_active IP Right Cessation
- 1985-06-21 PT PT80685A patent/PT80685B/en unknown
- 1985-06-21 ES ES544981A patent/ES8609372A1/en not_active Expired
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Also Published As
| Publication number | Publication date |
|---|---|
| SE8503033L (en) | 1985-12-23 |
| GR851522B (en) | 1985-11-25 |
| DK279185D0 (en) | 1985-06-20 |
| DK279185A (en) | 1985-12-23 |
| GB2160535A (en) | 1985-12-24 |
| JPS6114202A (en) | 1986-01-22 |
| ZA854595B (en) | 1986-02-26 |
| IT8421559A0 (en) | 1984-06-22 |
| DE3522295A1 (en) | 1985-12-19 |
| IT8421559A1 (en) | 1985-12-22 |
| IT1176299B (en) | 1987-08-18 |
| ES544981A0 (en) | 1986-07-16 |
| ES8609372A1 (en) | 1986-07-16 |
| GB8515470D0 (en) | 1985-07-24 |
| BE902730A (en) | 1985-12-23 |
| PL254120A1 (en) | 1986-05-20 |
| PT80685A (en) | 1985-07-01 |
| FR2566412A1 (en) | 1985-12-27 |
| IL75590A0 (en) | 1985-10-31 |
| SE8503033D0 (en) | 1985-06-18 |
| RO92339A (en) | 1987-08-31 |
| LU85968A1 (en) | 1986-01-24 |
| NL8501815A (en) | 1986-01-16 |
| PT80685B (en) | 1987-03-31 |
| RO92339B (en) | 1987-09-01 |
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