DK160100B - Catalyst for (CO) POLYMERIZATION OF ALKENES, CATALYTIC COMPONENT, PROCEDURE FOR PREPARING THE CATALYTIC COMPONENT, AND PROCESS FOR (CO) POLYMERIZATION OF ALKENER - Google Patents
Catalyst for (CO) POLYMERIZATION OF ALKENES, CATALYTIC COMPONENT, PROCEDURE FOR PREPARING THE CATALYTIC COMPONENT, AND PROCESS FOR (CO) POLYMERIZATION OF ALKENER Download PDFInfo
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- DK160100B DK160100B DK322276A DK322276A DK160100B DK 160100 B DK160100 B DK 160100B DK 322276 A DK322276 A DK 322276A DK 322276 A DK322276 A DK 322276A DK 160100 B DK160100 B DK 160100B
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- catalytic component
- formula
- solvent
- polymerization
- alkenes
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- 238000006116 polymerization reaction Methods 0.000 title claims description 26
- 230000003197 catalytic effect Effects 0.000 title claims description 25
- 239000003054 catalyst Substances 0.000 title claims description 17
- 150000001336 alkenes Chemical class 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 9
- 239000002904 solvent Substances 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 3
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 229910017682 MgTi Inorganic materials 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KUGRPPRAQNPSQD-UHFFFAOYSA-N OOOOO Chemical compound OOOOO KUGRPPRAQNPSQD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 hydrocarbon radical Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 101100331550 Antirrhinum majus DICH gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
Description
iin
DK '60100 BDK '60100 B
Tillægspatent til patent nr. 152 507Additional Patent to Patent No. 152,507
Patentskrift nr. 152 507 angår en katalysator til (co)po-lymerisation af alkener, og det ejendommelige ved kataly-5 satoren ifølge hovedpatentet er, at den er fremstillet ved at blande: a) en katalytisk komponent med den almene formel 10 M M'X0 Y.nE, hvori: m 2m M = Mg, Mn og/eller Ca m = et tal mellem 0,5 og 2 15 M' = Ti, V og/eller Zr eller blandinger af disse metaller med Zn, Al, Sn, Fe, Co, Ni, Cr og Mo i en sådan mængde, at atomforholdet mellem nævnte metaller og Ti, V og/eller Zr vil ligge mellem 0,1:1 og 20 2:1,Patent No. 152,507 relates to a catalyst for (co) polymerization of alkenes, and the characteristic of the catalyst of the main patent is that it is prepared by mixing: a) a catalytic component of the general formula 10 M M 'X0 Y.nE, wherein: m 2m M = Mg, Mn and / or Ca m = a number between 0.5 and 2M' = Ti, V and / or Zr or mixtures of these metals with Zn, Al, Sn, Fe, Co, Ni, Cr and Mo in such an amount that the atomic ratio of said metals to Ti, V and / or Zr will be between 0.1: 1 and 2: 1,
X - Cl, Br eller JX - Cl, Br or J
Y = et halogenatom og/eller et radikal, som er valgt 25 blandt -NI^, -OR ogY = a halogen atom and / or a radical selected from -NI 2, -OR and
OISLAND
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-0-C-R (R = carbonhydrid-radikal, især alkyl, aryl, cycloalkyl eller aralkyl) og blandinger der-33 af, hvorved dette radikal er tilstede i en sådan mængde, at man tilfredsstiller valensen af M'; n = et tal fra 0,5 m til 20 m 35 E « en elektron-donorforbindelse udvalgt blandt: 2-O-C-R (R = hydrocarbon radical, especially alkyl, aryl, cycloalkyl or aralkyl) and mixtures thereof-33, whereby this radical is present in such an amount as to satisfy the valence of M '; n = a number from 0.5 m to 20 m 35 E «an electron-donor compound selected from: 2
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a) estere af organiske carboxylsyrer b) alkoholer c) ethere d) aminer 5 e) estere af carbonsyre f) nitriler g) estere af phosphorsyre og phosphorsyrling og pho sphoroxychlorid; med 10 b) en metalorganisk forbindelse af et metal fra gruppe I, II eller III i det periodiske system.a) esters of organic carboxylic acids b) alcohols c) ethers d) amines 5 e) esters of carboxylic acid f) nitriles g) esters of phosphoric acid and phosphoric acid and pho sphor oxychloride; with 10 b) a metal-organic compound of a group I, II or III metal of the periodic table.
Opfindelsen angår en katalysator til (co)polymerisation af alkener, nye katalytiske komponenter til polymerisa-15 tion og copolymerisation af alkener, en fremgangsmåde til fremstilling deraf og anvendelsen af katalysatoren ved (co)polymerisation af alkener.The invention relates to a catalyst for (co) polymerization of alkenes, novel catalytic components for polymerization and copolymerization of alkenes, a process for their preparation and the use of the catalyst in (co) polymerization of alkenes.
Især angår opfindelsen katalysatorer, der udviser en høj 20 aktivitet ved polymerisation af ethylen eller a-alkener eller blandinger af ethylen og α-alkener og/eller dialke-ner eller multialkener.In particular, the invention relates to catalysts which exhibit a high activity in the polymerization of ethylene or α-alkenes or mixtures of ethylene and α-alkenes and / or dialks or multi-alkenes.
Patentskrift nr. 152 507 beskriver som anført katalysa-25 torsystemer, som er velegnede til polymerisation af alkener, bestående af kombinationen af en metalorganisk forbindelse af et metal af gruppe I, II og III af det periodiske system og af et metalkompleks.Patent No. 152,507 discloses, as mentioned, catalyst systems suitable for polymerization of alkenes, consisting of the combination of a metal-organic compound of a group I, II and III metal of the periodic system and of a metal complex.
30 Ansøgeren har nu vist - og dette er opfindelsens formål - at det er muligt i stedet for de ovenfor angivne metalkomplekser at anvende andre dermed analoge metalkomplekser, der i kombination med metalorganiske forbindelser af gruppe I, II og III i det periodiske system tilvejebrin-35 ger katalysatorer til polymerisation af alkener, hvilke udviser en høj katalytisk aktivitet.The applicant has now shown - and this is the object of the invention - that it is possible to use other, instead of the above-mentioned metal complexes, analogous metal complexes which, in combination with metal-organic compounds of groups I, II and III of the periodic system, provide provides catalysts for polymerization of alkenes, which exhibit high catalytic activity.
33
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Katalysatoren ifølge opfindelsen er ejendommelig ved det i den kendetegnende del af krav 1 angivne, og den katalytiske komponent ifølge opfindelsen er ejendommelig ved det i den kendetegnende del af krav 2 angivne.The catalyst according to the invention is characterized by the element of claim 1, and the catalytic component according to the invention is characterized by the element of claim 2.
5 På dette område, der omfatter de ovenfor angivne klasser af elektrondonor-forbindelser, har man nu opnået særligt interessante resultater med alkylestere af alifatiske eller aromatiske syrer, hvori alkyldelen indeholder 1-8 10 carbonatomer, og ethere ROR', hvori R og R’, der er ens eller forskellige, kan være alkyler med 1-8 carbonatomer eller aryler.In this field, comprising the above classes of electron donor compounds, particularly interesting results have now been obtained with alkyl esters of aliphatic or aromatic acids, wherein the alkyl moiety contains 1-8 carbon atoms and ethers ROR 'wherein R and R' which are the same or different may be alkyls having 1-8 carbon atoms or aryls.
Typiske forbindelser af de ovenfor angivne klasser, som 15 har frembragt de bedste resultater, hvad angår aktiviteten af de katalysatorer, der er fremstillet på basis deraf, er følgende: ethylacetat, ethylbenzoat, methanol, ethanol, ethylether 20 og phosphoroxychlorid.Typical compounds of the above classes which have produced the best results in terms of the activity of the catalysts prepared therefrom are the following: ethyl acetate, ethyl benzoate, methanol, ethanol, ethyl ether 20, and phosphorus oxychloride.
De ovenfor angivne komplekser kan fremstilles ved omsætning mellem ækvimolære mængder af forbindelser MgT og TiY ved en temperatur, der ligger mellem stuetemperatur og 25 1 50 0C, især opløsningsmidler E, der fungerer som elek trondonor-forbindelser, og som er isoleret ved krystallisation af det angivne opløsningsmiddel eller ved fordampning af det angivne opløsningsmiddel eller ved bundfældning med et opløsningsmiddel, hvori komplekserne er uop-30 løselige.The above complexes may be prepared by reaction of equimolar amounts of compounds MgT and TiY at a temperature ranging from room temperature to 251 50 ° C, in particular solvents E, which act as electron donor compounds, and are isolated by crystallization of the solvent or by evaporation of the indicated solvent or by precipitation with a solvent in which the complexes are insoluble.
Skulle forbindelsen MgT eller forbindelsen TiY være lidet opløselige i opløsningsmiddel E, ville det være tilrådeligt af gennemføre den ovenfor angivne reaktion i et 35 andet passende elektrondonor-opløsningsmiddel E', for at opnå komplekset MgTiTy.nE, der efter isolation behandles ved en temperatur, der ligger mellem stuetemperatur og 4Should the compound MgT or the compound TiY be insoluble in solvent E, it would be advisable to carry out the above reaction in another suitable electron donor solvent E ', to obtain the complex MgTiTy.nE, which is treated after isolation at a temperature. which is between room temperature and 4
DK 160 00 BDK 160 00 B
150 “C, med et overskud af opløsningsmiddel E, der skifter opløsningsmiddel E'. For at gennemføre et sådant skift er det også muligt at tilsætte et overskud af opløsningsmiddel E til opløsningen af komplekset MgTiTy.nE 5 i opløsningsmiddel E'.150 ° C, with an excess of solvent E changing solvent E '. To effect such a shift, it is also possible to add an excess of solvent E to the solution of the complex MgTiTy.nE 5 in solvent E '.
Det er også muligt at omsætte forbindelserne MgT og TiY i et molært forhold, der afviger fra værdien 1:1 og stadig at opnå katalytiske komponenter, der udviser god aktivi-10 tet. I et sådant tilfælde isolerer man ved krystallisation eller fordampning af opløsningsmidlet eller ved bundfældning med et passende opløsningsmiddel en blanding, der udgøres af det ønskede kompleks (eller af komplekset indeholdende opløsningsmidlet Er) og af et kom-15 pleks, der består af forbindelsen MgT eller TiY og opløsningsmiddel E (eller opløsningsmidlet E').It is also possible to react the compounds MgT and TiY in a molar ratio which deviates from the value of 1: 1 and still obtain catalytic components which exhibit good activity. In such a case, by crystallization or evaporation of the solvent, or by precipitation with a suitable solvent, a mixture is formed of the desired complex (or of the complex containing the solvent Er) and of a complex consisting of the compound MgT or TiY and solvent E (or solvent E ').
Blandt de forbindelser af Ti, der er anvendelige til fremstilling af de ovenfor beskrevne komplekser , kan man 20 anføre følgende:Among the compounds of Ti useful for the preparation of the complexes described above, the following may be stated:
TiCl3, TiCl^, TiOCl2, TiBr^, TiJ4,TiCl 3, TiCl 2, TiOCl 2, TiBr
Cl3TiOCH3, Cl2Ti(OC4Hg )2, Ti(OC4Hg ) ^ Cl^iNCCgHg )2,Cl3TiOCH3, Cl2Ti (OC4Hg) 2, Ti (OC4Hg) ^ Cl ^ iNCCgHg) 2,
ClgTiOCOCgHg, CITiSCgHg, ClgTi-acetylacetonat, 25 Cl3Ti0S02C6H5, ClgTiOCgHg.ClgTiOCOCgHg, CITiSCgHg, ClgTi acetylacetonate, Cl3TiOS02C6H5, ClgTiOCgHg.
Nogle eksempler på metalkomplekser, der ligger inden for den almene formel, som er angivet i det foregående, er følgende: 30Some examples of metal complexes which fall within the general formula given above are the following:
MgTiOCl4.2CH3C00C2H5 MgTiOCl3.4CH3C00C2H5 35 MgTiOCl3.5C2H5OHMgTiOCl4.2CH3C00C2H5 MgTiOCl3.4CH3C00C2H5 35 MgTiOCl3.5C2H5OH
55
MgTiClgOH.2CH3COOC2H5 MgTiCl4(OC2H5)2.CH3COOC2H5 5 MgTi0Cl3.2(n-C3H7)20MgTiClgOH.2CH3COOC2H5 MgTiCl4 (OC2H5) 2.CH3COOC2H5 MgTiOCl3.2 (n-C3H7) 20
MgTiOClg.5P0C13.MgTiOClg.5P0C13.
Metalorganiske forbindelse, der er særligt velegnede til 10 fremstilling af katalysatorerne ifølge opfindelsen, er f.eks.: akc2h5)3 15 A1(C2H5)2C1Metal organic compounds which are particularly suitable for the preparation of the catalysts of the invention are, for example: acc2h5) 3 15 A1 (C2H5) 2C1
Al(i-C4Hg)3 Al(i-C4Hg)2Cl 20 A12*C2H5*3C13 akc2h5)2hAl (i-C4Hg) 3 Al (i-C4Hg) 2Cl 20 A12 * C2H5 * 3C13 akc2h5) 2h
25 Al(i-C4Hg)2HAl (i-C4Hg) 2H
A1(C2H5)2Br (C2H5 > 2A1“0_A1(c2H5)2 30 (C2H5)2A1-N-A1(C2H5)2 C6H5 35 6A1 (C2H5) 2Br (C2H5> 2A1 “0_A1 (c2H5) 2 (C2H5) 2A1-N-A1 (C2H5) 2 C6H5 35 6
ρΛ s 'ΐ ' η λ ο η ry Ui\ : Ο ! υ J DρΛ s 'ΐ' η λ ο η ry Ui \: Ο! υ J D
οο
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(c2h5)2Al-0-S-0Al(C2H5)2(C2H5) 2Al-0-S-0AL (C2H5) 2
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5 ο5 ο
LiAl(i-C4Hg)4 Li-i-C4Hg 10LiAl (i-C4Hg) 4 Li-i-C4Hg 10
Zn(C4Hg)2.Zn (C4Hg) second
Det molære forhold mellem metalorganisk forbindelse og kompelks, der indeholder Ti, er ikke kritisk, og det lig-15 ger fortrinsvis mellem 10 og 100 i tilfælde af (co)poly-merisation af ethylen og a-alkener.The molar ratio of metal-organic compound to complex containing Ti is not critical and it is preferably between 10 and 100 in the case of (co) polymerization of ethylene and α-alkenes.
Katalysatoren ifølge opfindelsen udnyttes ved (co)polymerisationen af alkener, især ethylen, propylen, buten-1 og 20 4-methylpenten-l, i henhold til konventionel teknik, dvs. i en væskefase, i nærværelse eller i fravær af et indifferent opløsningsmiddel eller i gasfase. Man kan med fordel anvende et alifatisk eller cycloalifatisk carbonhy-drid, såsom f.eks. hexan, heptan eller cyclohexan.The catalyst of the invention is utilized in (co) the polymerization of alkenes, especially ethylene, propylene, butene-1 and 4-methylpenten-1, according to conventional techniques, i.e. in a liquid phase, in the presence or absence of an inert solvent or in the gas phase. An aliphatic or cycloaliphatic hydrocarbon such as e.g. hexane, heptane or cyclohexane.
2525
Temperaturen af (co)polymerisationen kan ligge mellem -80 og 200 °C, fortrinsvis mellem 50 og 100 °C, idet der arbejdes under atmosfærisk tryk eller under undertryk. Under (co)polymerisationen reguleres molekylvægten i hen-30 hold til kendte metoder, ved f.eks. at arbejde i nærværelse af alkylhalogenider, metalorganiske forbindelser af Zn eller Ca, eller hydrogen.The temperature of the (co) polymerization may be between -80 and 200 ° C, preferably between 50 and 100 ° C, operating under atmospheric pressure or under pressure. During (co) polymerization, the molecular weight is controlled according to known methods, e.g. to work in the presence of alkyl halides, metal-organic compounds of Zn or Ca, or hydrogen.
De følgende eksempler angives for bedre at illustrere den 35 foreliggende opfindelse.The following examples are set forth to better illustrate the present invention.
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EKSEMPEL 1 2,02 g (50,1 mmol) MgO blev i en nitrogenatmosfære suspenderet i 160 ml vandfrit ethylacetat. 5,57 ml (50,1 5 mmol) TiCl^ blev tilsat dråbevis, og hele massen blev omsat i 3 timer ved 40 °C. På denne måde opnåede man en gul opløsning.Example 1 2.02 g (50.1 mmol) of MgO was suspended in a nitrogen atmosphere in 160 ml of anhydrous ethyl acetate. 5.57 ml (50.1 5 mmol) of TiCl ^ was added dropwise and the whole mass was reacted for 3 hours at 40 ° C. In this way a yellow solution was obtained.
Reaktionsproduktet blev isoleret ved fordampning af op-10 løsningsmidlet, og det resulterende gule pulver udviste ved analyse en sammensætning svarende til formlen MgTiOCl^.2CHgC00C2Hg. Den ethylenpolymerisationsprøve, som blev gennemført under anvendelse af et sådant kompleks som katalytisk bestanddel, er angivet i tabellen 15 (forsøg I).The reaction product was isolated by evaporation of the solvent and the resulting yellow powder showed by analysis a composition similar to the formula MgTiOCl 2 .2CHgC00C2Hg. The ethylene polymerization test conducted using such a complex as catalytic component is given in Table 15 (Experiment I).
EKSEMPEL 2 1,75 g (11,3 mmol) TiCl^HR blev i en nitrogenatmosfære 20 opløst i 250 ml vandfrit ethylacetat ved 60 °C.EXAMPLE 2 1.75 g (11.3 mmol) of TiCl 3 HR was dissolved in a nitrogen atmosphere 20 in 250 ml of anhydrous ethyl acetate at 60 ° C.
0,46 g (11,3 mmol) MgO blev tilsat efterhånden. Man omsatte ved 60 °C i 20 timer, hvorved der fremkom en sort opløsning, som derpå fordampedes til tørhed. Det resulte-25 rende sorte pulver afslørede ved analyse en sammensætning svarende til formlen MgTiOClg. 4CHCOOC2H,-. Den ethylenpolymerisationsprøve, som blev gennemført under anvendelse af et sådant kompleks som katalytisk komponent, er angivet i tabellen (prøve II).Gradually, 0.46 g (11.3 mmol) of MgO was added. The reaction was carried out at 60 ° C for 20 hours to give a black solution, which was then evaporated to dryness. The resulting black powder revealed by analysis a composition similar to the formula MgTiOClg. 4CHCOOC2H, -. The ethylene polymerization test performed using such a complex as catalytic component is given in the table (Sample II).
30 EKSEMPEL 3 1,85 g (12 mmol) TiCl^ blev i en nitrogenatmosfære opløst i 180 ml vandfrit ethylalkohol ved 60 °C. Derpå tilsattes 35 0,484 g (12 mmol) MgO dertil. Der omsattes ved 60 °C i 8 timer, hvorved der fremkom en brun opløsning og et pulver, der forelå i suspension, og som også var brunt. Den- 8EXAMPLE 3 1.85 g (12 mmol) of TiCl ^ was dissolved in a nitrogen atmosphere in 180 ml of anhydrous ethyl alcohol at 60 ° C. Then 0.484 g (12 mmol) of MgO was added thereto. Reacted at 60 ° C for 8 hours to give a brown solution and a powder which was in suspension, which was also brown. Den- 8
DK ΊόΠίοΟ BDK ΊόΠίοΟ B
ne suspension blev fordampet til tørhed, og det resulterende brune pulver afslørede ved analyse en sammensætning svarende til formlen MgTiOCl^. 5C2HgOH. Det ethylenpoly-merisationsforsøg, som udførtes ved anvendelse af et 5 sådant kompleks som katalytisk bestanddel, er angivet i tabellen (prøve III).The suspension was evaporated to dryness and the resulting brown powder revealed by analysis a composition similar to the formula MgTiOCl 2. 5C2HgOH. The ethylene polymerization experiment performed using such a complex as catalytic component is given in the table (Sample III).
EKSEMPEL 4 10 1,88 g (24,4 mmol) HO-Mg-Cl blev i en nitrogenatmosfære delvist opløst i 160 ml vandfrit ethylacetat ved 60 °C.EXAMPLE 4 1.88 g (24.4 mmol) of HO-Mg-Cl were partially dissolved in a nitrogen atmosphere in 160 ml of anhydrous ethyl acetate at 60 ° C.
2,68 ml (24,4 mmol) TiCl^ blev tilsat dråbevis, og hele blandingen blev omsat i 3 timer og 30 minutter: den re-15 suiterende gule opløsning blev derpå fordampet til tørhed. Der fremkom således et gult pulver, der ved analyse udviste en sammensætning svarende til formlen MgTiCl,-0H. 20Η200002Η5-. Den ethylenpolymerisationsprøve, som gennemførtes ved anvendelsen af et sådant kompleks 20 som katalytisk komponent, er angivet i tabellem (prøve IV).2.68 ml (24.4 mmol) of TiCl 3 was added dropwise and the whole mixture was reacted for 3 hours and 30 minutes: the resulting yellow solution was then evaporated to dryness. There was thus obtained a yellow powder which showed, by analysis, a composition similar to the formula MgTiCl, -0H. 20Η200002Η5-. The ethylene polymerization test performed using such a complex 20 as catalytic component is given in Table (Sample IV).
EKSEMPEL 5 25 l,68g(14,7 mmol) Mg(0C2H5)2 blev i en nitrogenatmosfære suspenderet i 100 ml vandfrit ethylacetat ved 60 °C.EXAMPLE 5 25 l, 68g (14.7 mmol) of Mg (OC2H5) 2 were suspended in a nitrogen atmosphere in 100 ml of anhydrous ethyl acetate at 60 ° C.
En opløsning af 2,73 g (14,7 mmol) Cl^TiOCHg i 50 ml ethylacetat blev tilsat dråbevis til en sådan opløsning.A solution of 2.73 g (14.7 mmol) of Cl 2 TiOCHg in 50 ml of ethyl acetate was added dropwise to such a solution.
30 Der blev omsat ved 60 °C i 4 timer, hvorved der fremkom en farveløs opløsning. Reaktionsproduktet blev isoleret ved fordampning af opløsningsmidlet, og det resulterende hvide pulver afslørede ved analyse en sammensætning svarende til formlen MgTiiO^HgJ^OCHgjClg.CHgCOOC^Hj-.30 was reacted at 60 ° C for 4 hours to give a colorless solution. The reaction product was isolated by evaporation of the solvent and the resulting white powder revealed by analysis a composition similar to the formula MgTiiO ^ HgJ ^ OCHgjClg.CHgCOOC ^ H
Den ethylenpolymerisationsprøve, som blev gennemført under anvendelse af et sådant kompleks som katalysator- 35 9 DK unions komponent, er angivet i tabellen (forsøg V).The ethylene polymerization test conducted using such a complex as the catalyst component of DK 9 is given in the table (Experiment V).
EKSEMPEL 6 5 3,6 g (33 mmol) Mg(OC2H,-)2 blev i en nitrogenatmosfære suspenderet i 200 ml vandfrit ethylacetat ved 60 °C, og 3,6 ml (33 mmol) TiCl^ blev dråbevis tilsat dertil. Der blev omsat ved 60 °C i 4 timer, hvorved der fremkom en lysebrun opløsning.EXAMPLE 6 3.6 g (33 mmol) of Mg (OC 2 H 2 - 2) was suspended in a nitrogen atmosphere in 200 ml of anhydrous ethyl acetate at 60 ° C and 3.6 ml (33 mmol) of TiCl 2 was added dropwise thereto. It was reacted at 60 ° C for 4 hours to give a light brown solution.
1010
Reaktionsproduktet blev isoleret ved fordampning af opløsningsmidlet, og det resulterende brune pulver udviste ved analyse en sammensætning svarende til formlen MgTiCl^O^Hg^.CH^COOC^Hg. Den ethylenpolymerisations-15 prøve, der blev gennemført under anvendelse af et sådant kompleks som katalysatorkomponent, er angivet i tabellen (forsøg VI).The reaction product was isolated by evaporation of the solvent and the resulting brown powder showed by analysis a composition similar to the formula MgTiCl 2 O 2 Hg 2 .CH 2 COOC 2 Hg. The ethylene polymerization test performed using such a complex as a catalyst component is given in the table (Experiment VI).
EKSEMPEL 7 20 0,5 g af komplekset MgTiOCl^. COOC2Hg fremstillet i henhold til eksempel 2 blev tilsat til 20 ml vandfrit dipropylether; hele blandingen blev omsat ved 60 °C i 8 timer, og herved fremkom der er sort opløsning.EXAMPLE 7 0.5 g of the MgTiOCl complex. COOC 2 Hg prepared according to Example 2 was added to 20 ml of anhydrous dipropyl ether; the whole mixture was reacted at 60 ° C for 8 hours to give a black solution.
2525
Skiftereaktionen blev afsluttet ved fordampning af CHgC00C2Ht-, idet det resulterende produkt derpå blev isoleret ved fordampning af dipropylether. På denne måde opnåede man et sort pulver, der ved analyse afslørede en 30 sammensætning svarende til formlen MgTiOCl^·2(n-C^H^)20.The switching reaction was terminated by evaporation of CHgC00C2Ht-, the resulting product being then isolated by evaporation of dipropyl ether. In this way, a black powder was obtained which revealed by analysis a composition similar to the formula MgTiOCl 2 · 2 (n-C 2 H 2) 20.
Den ethylenpolymerisationsprøve, som blev gennemført ved at anvende et sådant kompleks som katalysatorbestanddel, er angivet i tabellen (forsøg VII).The ethylene polymerization test conducted using such a complex as a catalyst component is given in the table (Experiment VII).
35 10 EKSEMPEL 8 1,2 g af komplekset MgTiOClg. 40^00002^, fremstillet i henhold til eksempel 2, blev tilsat til 20 ml phosphor-5 oxychlorid; hele blandingen blev omsat ved 60 °C i 8 timer, hvorved der fremkom en grøn opløsning.EXAMPLE 8 1.2 g of the MgTiOClg complex. 40%, prepared according to Example 2, was added to 20 ml of phosphorus oxychloride; the whole mixture was reacted at 60 ° C for 8 hours to give a green solution.
Skiftereaktionen blev afsluttet ved fordampning af CHgCOOC^Hg, og produktet blev efterhånden isoleret ved 10 fordampning af phosphoroxychlorid.The switching reaction was terminated by evaporation of CH 2 COOC 3 Hg and the product was eventually isolated by evaporation of phosphorus oxychloride.
Der fremkom et lysebrunt pulver, der ved analyse afslørede en sammensætning svarende til formlen MgTiOClg.5P0Clg.A light brown powder was obtained which revealed by analysis a composition similar to the formula MgTiOClg.5 POClg.
15 Den ethylenpolymerisationsprøve, som blev gennemført under anvendelse af et sådant kompleks som katalytisk komponent, er angivet i tabellen (forsøg VIII).The ethylene polymerization test conducted using such complex as catalytic component is given in the table (Experiment VIII).
Ethylenpolymerisation 20Ethylene Polymerization 20
En passende mængde af et af de katalytiske komplekser, der er fremstillet i de foregående eksempler, og 1000 ml afluftet vandfrit afsvovlet n-heptan blev sammen med 1 eller 2 ml Al(i-C^Hgi en nitrogenatmosfære indført i 25 en autoklav, der er af rustfrit stål, som har en kapacitet på 3 liter, og som er forsynet med en ankerrører og opvarmet til den ønskede temperatur. Hydrogen og ethylen ved de i forvejen fastsatte, partielle tryk blev tilsat dertil, og det totale tryk blev holdt konstant gennem 30 hele polymerisationen ved kontinuerlig tilførsel af ethylen.An appropriate amount of one of the catalytic complexes prepared in the foregoing examples and 1000 ml of deaerated anhydrous desulfurized n-heptane was introduced, together with 1 or 2 ml of Al (1C 2 Hg, a nitrogen atmosphere, in an autoclave which is of stainless steel, having a capacity of 3 liters, fitted with an anchor stirrer and heated to the desired temperature, hydrogen and ethylene at the predetermined partial pressures were added thereto and the total pressure was kept constant throughout 30 the polymerization by continuous supply of ethylene.
Efter 4 timers reaktion blev polymerisationen afbrudt, der blev filtreret, og den resulterende polymer blev tør-35 ret. Den polymeres logaritmiske viskositetstal nin blev bestemt i tetrahydronaphthalen ved 135 °C, under anvendelse af koncentrationer af 0,25 g polymer i 100 ml 11 rvS ' ' ^ ί Λ λ r->After 4 hours of reaction, the polymerization was discontinued, filtered and the resulting polymer dried. The logarithmic viscosity number of the polymer was determined in the tetrahydronaphthalene at 135 ° C using concentrations of 0.25 g polymer in 100 ml of 11 rvS
ϋί\ : · ' , ' U Dϋί \: · ',' U D
opløsningsmiddel. Udbyttet udtrykkes i g fremstillet polymer pr. g Ti.solvent. The yield is expressed in grams of polymer produced per gram. g Ti.
Driftsbetingelserne og resultaterne af de forskellige 5 forsøg er angivet i den følgende tabel.The operating conditions and results of the various 5 experiments are given in the following table.
10 15 20 25 30 35 O) O)10 15 20 25 30 35 O) O)
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A cO H CH H OH CH CH H CHA cO H CH H OH CH CH H CH
i -μ O X ooooo o o oi -µ O X ooooo o o o
PDDlE'-CHvOCH'tf H IS iHPDDlE'-CHvOCH'tf H IS iH
A Ό Μ Ί N (O N 00 H 03 ffi +> Ό p Φ Η Æ "ί "i 'i "Η1 'Φ ^ ^ X > P__ a in o in in o in o in EU co o σ' oo o co o cnA Ό Μ Ί N (ON 00 H 03 ffi +> Ό p Φ Η Æ "ί" i 'i "Η1' Φ ^^ X> P__ a in o in in o in o in EU co o σ 'oo o co o cn
C dl° pH pH pHC dl pH pH pH pH
0 B0 B
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pH 'ΦρΗρΗρΗρΗΗ pHpH rHpH 'ΦρΗρΗρΗρΗΗ pHpH rH
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pHpH
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•Η 'tf CH O' O CO pH O' O• Η 'tf CH O' O CO pH O 'O
Eh v k ^ ^ k i* h in HOOOpHpH OH pH - 0f> pH pH pH pH pH pH pH ΙΠ co X Di Ό O IS IS O »tf IS O' Φ E oh in 'ψ pH in in *tf -«tf pH-- a ε o * in oo oo X in in a pH a to a a ch o oEh vk ^^ ki * h in HOOOpHpH OH pH - 0f> pH pH pH pH pH pH pH ΙΠ co X Di Ό O IS IS O »tf IS O 'Φ E oh in' ψ pH in in * tf -« tf pH - a ε o * in oo oo X in a pH a to aa ch oo
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p φ oo oo æ æ w a o o φ a a a μ o oh oh o o a >i OOOcH^inom chap φ oo oo æ æ w a o o φ a a μ o oh oh o o a> i OOOcH ^ within cha
Eh ch ^tf in · in a O a am • · · a a ch w ch o *tf 00 00 O OHO <tf O 00 OH 00Eh ch ^ tf in · in a O a am • · · a a ch w ch o * tf 00 00 O OHO <tf O 00 OH 00
HHpH mOOpHOHapHHHpH mOOpHOHapH
OOOHOOOOOOO OOOOwOOOO COOOOOHOOOOOOO OOOOwOOOO COO
Η -Η -p| -H -H 00 -H CO -H a ·Η ΕιΕιΕηΕιΕηΒ&ηΒΕιΟ^ a Dl Di Dl a O DlO DICH Dl __s s s s s - s - s - sΗ -Η -p | -H -H 00 -H CO -H a · Η ΕιΕιΕηΕιΕηΒ & ηΒΕιΟ ^ a Dl Di Dl a O DlO DICH Dl __s s s s s s - s - s - s
J I Η Η H > > H H HJ I Η Η H>> H H H
H iH Dl HHH > Η HH iH Dl HHH> Η H
POS· H > HPOS · H> H
< A 10 > E-< ---<A 10> E- <---
Claims (15)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2558875 | 1975-07-21 | ||
| IT25588/75A IT1049565B (en) | 1975-07-21 | 1975-07-21 | CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
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| Publication Number | Publication Date |
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| DK322276A DK322276A (en) | 1977-01-22 |
| DK160100B true DK160100B (en) | 1991-01-28 |
| DK160100C DK160100C (en) | 1991-06-24 |
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| DK322276A DK160100C (en) | 1975-07-21 | 1976-07-16 | Catalyst for (CO) POLYMERIZATION OF ALKENES, CATALYTIC COMPONENT, PROCEDURE FOR PREPARING THE CATALYTIC COMPONENT, AND PROCESS FOR (CO) POLYMERIZATION OF ALKENER |
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| JP (1) | JPS5213492A (en) |
| AT (1) | AT345548B (en) |
| AU (1) | AU503230B2 (en) |
| BE (1) | BE844314R (en) |
| BR (1) | BR7604711A (en) |
| CA (1) | CA1091643A (en) |
| DE (1) | DE2632591A1 (en) |
| DK (1) | DK160100C (en) |
| ES (1) | ES449957A2 (en) |
| FR (1) | FR2318879A2 (en) |
| GB (1) | GB1509648A (en) |
| IT (1) | IT1049565B (en) |
| MX (1) | MX146820A (en) |
| NL (1) | NL191517C (en) |
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| US5021595A (en) * | 1990-03-02 | 1991-06-04 | Exxon Chemical Patents Inc. | Transition metal catalyst composition for olefin polymerization |
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| JPS5242157B2 (en) * | 1972-12-29 | 1977-10-22 | ||
| US3859231A (en) * | 1972-10-13 | 1975-01-07 | Gulf Research Development Co | Simplified process for manufacture of catalyst component |
| US3917575A (en) * | 1972-11-11 | 1975-11-04 | Nippon Oil Co Ltd | Process for production of polyolefins |
-
1975
- 1975-07-21 IT IT25588/75A patent/IT1049565B/en active
-
1976
- 1976-07-16 DK DK322276A patent/DK160100C/en not_active IP Right Cessation
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- 1976-07-19 AT AT531076A patent/AT345548B/en not_active IP Right Cessation
- 1976-07-19 FR FR7621978A patent/FR2318879A2/en active Granted
- 1976-07-19 GB GB29951/76A patent/GB1509648A/en not_active Expired
- 1976-07-19 CA CA257,259A patent/CA1091643A/en not_active Expired
- 1976-07-20 DE DE19762632591 patent/DE2632591A1/en active Granted
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Also Published As
| Publication number | Publication date |
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| ATA531076A (en) | 1978-01-15 |
| CA1091643A (en) | 1980-12-16 |
| DE2632591C2 (en) | 1991-09-19 |
| AU503230B2 (en) | 1979-08-30 |
| NL7607910A (en) | 1977-01-25 |
| JPS636562B2 (en) | 1988-02-10 |
| DK160100C (en) | 1991-06-24 |
| MX146820A (en) | 1982-08-25 |
| NL191517C (en) | 1995-08-21 |
| AT345548B (en) | 1978-09-25 |
| DK322276A (en) | 1977-01-22 |
| ZA764321B (en) | 1977-07-27 |
| SE437161B (en) | 1985-02-11 |
| GB1509648A (en) | 1978-05-04 |
| ES449957A2 (en) | 1978-04-01 |
| FR2318879A2 (en) | 1977-02-18 |
| SE7608134L (en) | 1977-01-22 |
| IT1049565B (en) | 1981-02-10 |
| AU1609876A (en) | 1978-01-26 |
| JPS5213492A (en) | 1977-02-01 |
| BR7604711A (en) | 1977-08-02 |
| NL191517B (en) | 1995-04-18 |
| FR2318879B2 (en) | 1980-09-26 |
| BE844314R (en) | 1977-01-20 |
| DE2632591A1 (en) | 1977-02-10 |
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