NO149847B - PROCEDURE FOR THE PREPARATION OF POLYMERS OF CONJUGATED DIENS OR COPOLYMERS OF CONJUGATED DIENS EITHER INSIDE OR WITH A VINYLAROMATIC COMPONENT - Google Patents
PROCEDURE FOR THE PREPARATION OF POLYMERS OF CONJUGATED DIENS OR COPOLYMERS OF CONJUGATED DIENS EITHER INSIDE OR WITH A VINYLAROMATIC COMPONENT Download PDFInfo
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- NO149847B NO149847B NO760671A NO760671A NO149847B NO 149847 B NO149847 B NO 149847B NO 760671 A NO760671 A NO 760671A NO 760671 A NO760671 A NO 760671A NO 149847 B NO149847 B NO 149847B
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- compounds
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- copolymers
- polymerization
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- 238000000034 method Methods 0.000 title claims abstract description 10
- 229920001577 copolymer Polymers 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 title abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- -1 vinyl aromatic compounds Chemical class 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- SBMJKCDBJMFHGS-UHFFFAOYSA-L barium(2+);2-nonylphenolate Chemical compound [Ba+2].CCCCCCCCCC1=CC=CC=C1[O-].CCCCCCCCCC1=CC=CC=C1[O-] SBMJKCDBJMFHGS-UHFFFAOYSA-L 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- CFHDAYWWVCSWMD-UHFFFAOYSA-N lithium;2-(diethylamino)ethanolate Chemical compound [Li+].CCN(CC)CC[O-] CFHDAYWWVCSWMD-UHFFFAOYSA-N 0.000 claims 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical class COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Fremgangsmåte for fremstilling av polymerer av konjugerte diener eller kopolymerer av konjugerte diener enten seg imellom eller med en vinylaromatisk komponent.Process for the preparation of polymers of conjugated dienes or copolymers of conjugated dienes either between themselves or with a vinyl aromatic component.
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte ved fremstilling av homopolymerer av konjugerte diener og kopolymerer av konjugerte diener med andre diener eller med vinylaromatiske forbindelser ved polymerisering eller kopolymerisering av monomerene i nærvær av en katalysator. The present invention relates to a method for the production of homopolymers of conjugated dienes and copolymers of conjugated dienes with other dienes or with vinyl aromatic compounds by polymerization or copolymerization of the monomers in the presence of a catalyst.
Fra britisk patent nr. 1.246.914 er det kjent å fremstille i losning polymerer av konjugerte diener og kopolymerer av konjugerte diener, enten seg imellom eller med en vinylaromatisk komponent ved hjelp av organometalliske forbindelser av et jordalkalimetall med formel: M^M-jR-jR^s1^ > hvori representerer kalsium, barium eller strontium, M2 representerer sink eller kadmium, og , I^, R3, R^ representerer en hydrokarbonrest. From British patent no. 1,246,914 it is known to prepare in solution polymers of conjugated dienes and copolymers of conjugated dienes, either among themselves or with a vinyl aromatic component by means of organometallic compounds of an alkaline earth metal with the formula: M^M-jR- jR^s1^ > in which represents calcium, barium or strontium, M2 represents zinc or cadmium, and , I^, R3, R^ represents a hydrocarbon residue.
De oppnådde forbindelser har en meget lav grénseviskositet, The obtained compounds have a very low intrinsic viscosity,
som ligger mellom 0,24 og 0,62. which lies between 0.24 and 0.62.
Det er kjent fra Chemical Abstracts, bind 78; 85 514 (1973) It is known from Chemical Abstracts, Volume 78; 85,514 (1973)
og RAPRA nr. 23 738 L (1974) å fremstille i losning og i hydro-karbonmiljo polymerer eller kopolymerer av konjugerte diener og/eller vinylaromatiske komponenter ved hjelp av organometalliske forbindelser av et jordalkalimetall og aluminium. Imid-lertid besidder forbindelsene som oppnåes ved denne fremgangsmåten, i likhet med forbindelsene nevnt ovenfor, en meget lav viskositet og kan ikke besidde de tilstrekkelige elastomere egenskaper som gjor det mulig å bruke dem som hovedbestanddel i de blandinger som tjener til fremstilling av dekk. Videre er denne fabrikasjonsfremgangsmåten uanvendelig industrielt på grunn av polymerisasjonens eller kopolymerisasjonens meget lave reaksjonshastighet. and RAPRA No. 23 738 L (1974) to prepare in solution and in hydrocarbon milieu polymers or copolymers of conjugated dienes and/or vinyl aromatic components by means of organometallic compounds of an alkaline earth metal and aluminium. However, the compounds obtained by this method, like the compounds mentioned above, have a very low viscosity and cannot possess the sufficient elastomeric properties that make it possible to use them as the main component in the mixtures used for the manufacture of tires. Furthermore, this manufacturing method is industrially inapplicable due to the very low reaction rate of the polymerization or copolymerization.
Til slutt er det velkjent at organiske aluminiumforbindelser Finally, it is well known that organic aluminum compounds
i seg selv er i besiddelse av en meget svak katalytisk virk- in itself has a very weak catalytic effect
ning, praktisk talt null, og at de ikke kan betraktes som initiatorer for polymer isasjonen eller kopolymerisasjonen av konjugerte diener. ning, practically zero, and that they cannot be considered as initiators for the polymerization or copolymerization of conjugated dienes.
Foreliggende oppfinnelse gir en ny fremgangsmåte som muliggjør industriell oppnåelse relativt hurtig, og med et godt utbytte av polymerer eller kopolymerer av konjugerte diener og/ eller vinylaromatiske komponenter som besidder en elastisitet som ligner kautsjukens, og som er anvendelige for fremstil- The present invention provides a new method which enables the industrial achievement relatively quickly, and with a good yield of polymers or copolymers of conjugated dienes and/or vinyl aromatic components which possess an elasticity similar to that of rubber, and which are applicable for the production
ling av pneumatiske dekk. ling of pneumatic tires.
Det særpregede ved foreliggende oppfinnelse er at polymeriseringen eller kopolymeriseringen utføres ved en temperatur mellom 50°C The distinctive feature of the present invention is that the polymerization or copolymerization is carried out at a temperature between 50°C
og 120°C og med et katalysatorsystem som er et reaksjonspro- and 120°C and with a catalyst system that is a reaction pro-
dukt av result of
a) en organisk forbindelse av et metall fra gruppe III A a) an organic compound of a metal from group III A
i det periodiske system med den generelle formel in the periodic table with the general formula
hvor Me^ er et alkalimetall, M et metall fra gruppe III A i det periodiske system og R-^ og R2 er en where Me^ is an alkali metal, M a metal from group III A of the periodic table and R-^ and R2 are a
alkyl eller aralkylrest, og alkyl or aralkyl residue, and
b) en eller flere elektronavgivende forbindelser med et eller flere heteroatomer fra gruppen aprotiske forbindelser, b) one or more electron-donating compounds with one or more heteroatoms from the group of aprotic compounds,
polare protiske forbindelser og reaksjonsproduktet av en polar protisk forbindelse med et alkali- eller jordalkalimetall. polar protic compounds and the reaction product of a polar protic compound with an alkali or alkaline earth metal.
Det overraskende ved oppfinnelsen er at reaksjonsproduktet av forbindelsene som betraktet hver for seq ikke er initiatorer for polymerisasjonen eller kopolymerisasjonen av de konjugerte dienene og/eller vinylaromatene, eller som ikke besidder annet enn ekstremt svak initieringsvirkning, gir et katalytisk initieringssystem for polymerisasjonen og kopolymerisasjonen av konjugerte diener og/eller vinylaromatiske komponenter som er industrielt brukbart. The surprising thing about the invention is that the reaction product of the compounds considered each for seq are not initiators for the polymerization or copolymerization of the conjugated dienes and/or vinyl aromatics, or which do not possess anything other than an extremely weak initiation effect, provide a catalytic initiation system for the polymerization and copolymerization of conjugated dienes and/or vinyl aromatic components which are industrially usable.
De organiske forbindelser av et metall fra gruppe III A som er særlig anvendelig for formålet består av et katalytisk system hvori alkalimetallet er litium, natrium eller kalium. The organic compounds of a metal from group III A which are particularly useful for the purpose consist of a catalytic system in which the alkali metal is lithium, sodium or potassium.
Som eksempler kan det angis folgende forbindelser: As examples, the following compounds can be specified:
Li 0 Al (C2H5)2 og Na 0 Al (C2H5)2- Li 0 Al (C2H5)2 and Na 0 Al (C2H5)2-
Som polare aprotiske komponenter forstås etere og spesielt cykliske etere som tetrahydrofuran, dioksan, likeledes tilsvarende tioetere, tertiære aminer, slik som N, N, N', N'-tetra-metyl-etylen-diamin, aromatiske aminer og særlig pyridin-deri-vater og tilsvarende oksyder, fosforkomponenter som fosfiner og deres oksyder, fosfit-ter, fosforamider og særlig heksametyl-fosfortriamid, ketoner og særlig aceton, nitriller og særlig acetonitril, aldehyder, estere, amider, nitroalifatiske eller aromatiske forbindelser, sulfoksyder og særlig dimetylsulfoksyd, sulfoner, sulfitter. Polar aprotic components are understood to mean ethers and especially cyclic ethers such as tetrahydrofuran, dioxane, likewise corresponding thioethers, tertiary amines, such as N, N, N', N'-tetra-methyl-ethylene-diamine, aromatic amines and especially pyridine-deri- hydrates and corresponding oxides, phosphorus components such as phosphines and their oxides, phosphites, phosphoramides and especially hexamethylphosphoric triamide, ketones and especially acetone, nitriles and especially acetonitrile, aldehydes, esters, amides, nitroaliphatic or aromatic compounds, sulfoxides and especially dimethyl sulfoxide, sulfones , sulfites.
Som polare protiske forbindelser er særlig vann, alkoholer og spesielt metanol, primære eller sekundære aminer, tioler anvendelig. As polar protic compounds water, alcohols and especially methanol, primary or secondary amines, thiols are applicable.
Som reaksjonsprodukter av reaksjonen av polare protiske forbindelser med et alkali- eller jordalkalimetall kommer særlig på tale alkoholater og fenolater av alkali- eller jordalkalimetaller, merkapto eller tiofenolater av alkali- eller jordalkalimetaller, videre forbindelser av eter-alkoholater og amino-alkoholater. The reaction products of the reaction of polar protic compounds with an alkali or alkaline earth metal include alcoholates and phenolates of alkali or alkaline earth metals, mercapto or thiophenolates of alkali or alkaline earth metals, further compounds of ether alcoholates and amino alcoholates.
Denorganiske forbindelser» av et metall fra gruppen III A og den eller de polare forbindelse(r) kan innfores i reaksjonsmiljoet enten separat uavhengig av rekkefølgen^eller i en forutdannet form. Ifolge den andre varianten''preformer" man det katalytiske system som en blanding av forskjellige bestanddeler og tilsetter så blandingen ved en temperatur mellom 20 og 10O°C i lopet av 5 til 60 minutter. The organic compounds" of a metal from group III A and the polar compound(s) can be introduced into the reaction medium either separately, regardless of the order, or in a preformed form. According to the second variant, the catalytic system is "preformed" as a mixture of different components and the mixture is then added at a temperature between 20 and 100°C over the course of 5 to 60 minutes.
Man kan benytte de to bestanddelene i det katalytiske systemet You can use the two components in the catalytic system
i variable forhold, men det er å foretrekke å bruke dem i molarforhold til den eller de polare forbindelsene i den organiske forbindelsen av metallet fra gruppe III A som in variable proportions, but it is preferable to use them in molar proportions to the polar compound(s) in the organic compound of the group III A metal which
liggermellom 0,01 og 100. For en gitt konsentrasjon av den organiske forbindelsen av metallet fra gruppe III A kan en modifi-kasjon av størrelsen av det molare forholdet samtidig påvirke viskositeten og mikrostrukturen av det dannete produkt, like- lies between 0.01 and 100. For a given concentration of the organic compound of the metal from group III A, a modification of the magnitude of the molar ratio can simultaneously affect the viscosity and microstructure of the product formed, as well
des reaksjonshastigheten av polymerisasjonen og kopolymerisasjonen. Som organiske forbindelser av et metall fra gruppe III A bruker man fortrinnsvis organo-aluminium-forbindelser, både på grunn av deres fremstillingsmessige fordeler og på grunn av deres lette kommersielle tilgjengelighet. des the reaction rate of the polymerization and copolymerization. As organic compounds of a metal from group III A, organo-aluminum compounds are preferably used, both because of their manufacturing advantages and because of their easy commercial availability.
Polymerisasjons- eller kopolymerisasjonsreaksjonen utfores i et inert løsningsmiddel som f.eks..enten kan være et alifatisk eller alicyklisk hydrokarbon som pentan, heksan, heptan, iso-oktan, cykloheksan eller et aromatisk hydrokarbon som benzen, toluen, xylen, etc.. The polymerization or copolymerization reaction is carried out in an inert solvent which, for example, can either be an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, iso-octane, cyclohexane or an aromatic hydrocarbon such as benzene, toluene, xylene, etc..
Man gjennomfører generelt reaksjonen ved.en temperatur mellom The reaction is generally carried out at a temperature between
50 og 120°C, fortrinnsvis mellom 80 og 100°C under et trykk 50 and 120°C, preferably between 80 and 100°C under pressure
som tilsvarer reaktantenes damptrykk. Fremgangsmåten ifolge oppfinnelsen kan gjennomføres satsvis eller kontinuerlig. which corresponds to the vapor pressure of the reactants. The method according to the invention can be carried out in batches or continuously.
Fremgangsmåten muliggjør ikke bare å oppnå hoye utbytter av makromolekulare forbindelser pr. vektenhet a/katalysator- The method not only makes it possible to achieve high yields of macromolecular compounds per weight unit a/catalyst-
systemet, men tillater likeledes samtidig å regulere den onskede størrelse av molekylvekten av de fremstilte polymerer eller kopolymerer. system, but also allows at the same time to regulate the desired size of the molecular weight of the produced polymers or copolymers.
Videre tillater fremgangsmåten å oppnå polymerer og kopolymerer som kan gi anledning til, i lopet av reaksjonen, og ved podningsreaksjoner med alle mulige reaktanter, å reagere med de eksisterende polymerer. Furthermore, the method allows polymers and copolymers to be obtained which can give rise, in the course of the reaction, and by grafting reactions with all possible reactants, to react with the existing polymers.
Som representative eksempler "på konjugerte diener som er egnet for polymerisasjonen og kopolymerisasjonen kan angis: butadien 1,3, isopren, 2,3 dimetyl-butadien 1,3, pentadien 1,3, etyl- As representative examples "of conjugated dienes suitable for the polymerization and copolymerization can be stated: butadiene 1,3, isoprene, 2,3 dimethyl-butadiene 1,3, pentadiene 1,3, ethyl-
2 butadien. 2 butadiene.
99
Som eksempler på representative vinylaromatiske forbindelser kan angis styren, ortho, meta, para-metyl-styren, di- og poly-metylstyren, para-tertiær butylstyren, vinylnaftalener, metoksy-styrener, halogenstyrener, divinylbenzen. As examples of representative vinyl aromatic compounds, styrene, ortho, meta, para-methylstyrene, di- and polymethylstyrene, para-tertiary butylstyrene, vinylnaphthalenes, methoxystyrenes, halostyrenes, divinylbenzene can be given.
Produktene som oppnås ved fremstillingsprosessen som benytter seg av det katalytiske systemet ifolge oppfinnelsen,besidder videre en stor fordeling av molekylvekten og et hoyt grenseviskositets-tall, d.v.s. tilstrekkelig til at produktene blir brukbare til å danne hovedkomponenten i blandingene som tjener til fremstil-lig av pneumatiske dekk, åens mikrostrukturen kan være ekstremt variable. Som folge av dette kan 1,4-trans-bindingene være mellom 20 og 90 % og 1,2-bindingene kan ligge mellom 1 og 60 %. Videre er disse produktene meget velegnet for mekanisk bearbeidelse med verktoy. The products obtained by the manufacturing process which uses the catalytic system according to the invention, further possess a large distribution of the molecular weight and a high limit viscosity number, i.e. sufficient for the products to become usable to form the main component of the mixtures used for the production of pneumatic tires, the river's microstructure can be extremely variable. As a result, the 1,4-trans bonds can be between 20 and 90% and the 1,2-bonds can be between 1 and 60%. Furthermore, these products are very suitable for mechanical processing with tools.
Oppfinnelsen vil fullstendig belyses ved hjelp av de påfolgende eksempler som beskriver gjennom illustrasjon de spesielle modi-fikasjoner som settes i verk. I alle eksemplene bestemmes de foreliggende viskositetene ved 25°C i en losning på 1 g/liter i toluen, konsentrasjonene er uttrykt i mikromol pr. 100 g monomerer og polymerisasjonsreaksjonene eller kopolymerisa-sjonsreaksjonene er stoppet når omsetningsgraden har nådd 80% ved tilsetning av metanol i formålstjenlige mengder (1 %). Prosentdelene trans 1,4 og 1,2 er uttrykt på basis av poly-butadienandelen slik at prosentandelen styren er uttrykt på grunnlag av den totale mengden av oppnådd polymer. The invention will be fully illustrated with the help of the following examples which describe through illustration the special modifications that are implemented. In all the examples, the present viscosities are determined at 25°C in a solution of 1 g/liter in toluene, the concentrations are expressed in micromoles per 100 g of monomers and the polymerization reactions or copolymerization reactions are stopped when the degree of conversion has reached 80% by adding methanol in suitable amounts (1%). The percentages trans 1.4 and 1.2 are expressed on the basis of the poly-butadiene proportion so that the percentage of styrene is expressed on the basis of the total amount of polymer obtained.
EKSEMPEL EXAMPLE
Man gjennomførte 3 forsøk. I en Steinie-flaske på 250 ml under trykk med renset nitrogen, innførte man 100 ml heptan som løsningsmiddel og 13,6 g butadien. Man tilførte derpå det katalytiske systemet som bestod av Li 0 AMC-jH^),, og barium-nonylfenolat. Flasken ble plassert i et termostatbad på 80°C hvor den ble omrørt. Polymerisasjonsreaksjonen ble stoppet når omsetningsgraden hadde nådd 60%. Ved slutten av reaksjonen gjenvant man polybutadien ved en vanlig fremgangsmåte. Resultatene er oppført i tabell I nedenunder: 3 trials were carried out. Into a 250 ml Steinie flask under pressure with purified nitrogen, 100 ml of heptane as solvent and 13.6 g of butadiene were introduced. The catalytic system which consisted of Li 0 AMC-jH^), and barium nonylphenolate was then added. The bottle was placed in a thermostatic bath at 80°C where it was stirred. The polymerization reaction was stopped when the degree of conversion had reached 60%. At the end of the reaction, polybutadiene was recovered by a conventional method. The results are listed in Table I below:
Under samme betingelser forte bruken av Li O Al(C2H5)2 alene ikke til noe spor av polymer, selv etter 48 timers reaksjon. Under the same conditions, the use of Li O Al(C2H5)2 alone did not lead to any trace of polymer, even after 48 hours of reaction.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7506239A FR2302311A1 (en) | 1975-02-27 | 1975-02-27 | PROCESS FOR PREPARING DIENE POLYMERS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO760671L NO760671L (en) | 1976-08-30 |
| NO149847B true NO149847B (en) | 1984-03-26 |
| NO149847C NO149847C (en) | 1984-07-04 |
Family
ID=9151865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO760671A NO149847C (en) | 1975-02-27 | 1976-02-27 | PROCEDURE FOR THE PREPARATION OF POLYMERS OF CONJUGATED DIENS OR COPOLYMERS OF CONJUGATED DIENS EITHER INSIDE OR WITH A VINYLAROMATIC COMPONENT |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS602323B2 (en) |
| AR (1) | AR218220A1 (en) |
| AT (1) | AT346580B (en) |
| BE (1) | BE838825A (en) |
| BR (1) | BR7601266A (en) |
| CA (1) | CA1052948A (en) |
| CH (1) | CH610339A5 (en) |
| DE (1) | DE2607721A1 (en) |
| EG (1) | EG12520A (en) |
| FI (1) | FI62107C (en) |
| FR (1) | FR2302311A1 (en) |
| GB (1) | GB1531085A (en) |
| IE (1) | IE42880B1 (en) |
| IT (1) | IT1062199B (en) |
| LU (1) | LU74429A1 (en) |
| NL (1) | NL164870C (en) |
| NO (1) | NO149847C (en) |
| RO (1) | RO69312A (en) |
| SE (2) | SE7602502L (en) |
| ZA (1) | ZA761198B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6026406B2 (en) * | 1978-09-13 | 1985-06-24 | 旭化成株式会社 | Method for producing conjugated diene polymer |
| US4297240A (en) | 1980-02-25 | 1981-10-27 | The General Tire & Rubber Company | Solution polymerization |
| US4302568A (en) | 1980-02-25 | 1981-11-24 | The General Tire & Rubber Co. | Solution polymerization |
| FR2480289A1 (en) * | 1980-04-09 | 1981-10-16 | Michelin & Cie | PROCESS FOR THE PREPARATION OF POLYMERS OF CONJUGATED DIENES OR COPOLYMERS OF CONJUGATED DIENES EITHER THEREWITH OR WITH A COMPOUND |
| FR2480290A1 (en) * | 1980-04-09 | 1981-10-16 | Michelin & Cie | PROCESS FOR THE PREPARATION OF POLYMERS OF CONJUGATED DIENES OR COPOLYMERS OF CONJUGATED DIENES EITHER THEREWITH OR WITH A VINYLAROMATIC COMPOUND |
| FR2567135B1 (en) * | 1984-07-03 | 1989-01-13 | Asahi Chemical Ind | POLYMER OR COPOLYMER OF BUTADIENE AND PROCESS FOR PREPARATION |
| US4933401A (en) * | 1988-02-26 | 1990-06-12 | Japan Synthetic Rubber Co., Ltd. | Catalyst composition for polymerization of conjugated diene and process for producing conjugated diene polymer |
| FR2722503A1 (en) | 1994-07-15 | 1996-01-19 | Michelin & Cie | FUNCTIONAL DIENE POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN ELASTOMERIC SILICA-FILLED COMPOSITIONS FOR USE IN TIRE ENVELOPES |
| FR2722505B1 (en) | 1994-07-15 | 1996-09-27 | Michelin & Cie | SILICA-FILLED ELASTOMERIC COMPOSITIONS FOR USE IN TIRE TIRES |
| FR2744127A1 (en) | 1996-01-26 | 1997-08-01 | Michelin & Cie | RUBBER COMPOSITION BASED ON A DIENE POLYMER HAVING A SILANOL FUNCTION AND COMPRISING AN ORGANOSILANE DERIVATIVE |
| US6018007A (en) | 1997-09-22 | 2000-01-25 | Bridgestone Corporation | Synthesis of 1,4-trans-polybutadiene using a lanthanide organic acid salt catalyst |
| FR2951186B1 (en) | 2009-10-12 | 2012-01-06 | Michelin Soc Tech | RUBBER COMPOSITION BASED ON GLYCEROL AND A FUNCTIONALIZED ELASTOMER AND TIRE TREAD FOR PNEUMATIC |
| FR2992649B1 (en) | 2012-07-02 | 2015-06-19 | Michelin & Cie | PROCESS FOR CONTINUOUS SYNTHESIS OF DIENE ELASTOMER |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3716495A (en) * | 1970-09-02 | 1973-02-13 | Phillips Petroleum Co | Polymerization initiator composition and use thereof |
-
1975
- 1975-02-27 FR FR7506239A patent/FR2302311A1/en active Granted
-
1976
- 1976-02-20 NL NL7601763.A patent/NL164870C/en not_active IP Right Cessation
- 1976-02-23 BE BE164535A patent/BE838825A/en not_active IP Right Cessation
- 1976-02-25 LU LU74429A patent/LU74429A1/xx unknown
- 1976-02-25 DE DE19762607721 patent/DE2607721A1/en not_active Ceased
- 1976-02-26 CA CA246,639A patent/CA1052948A/en not_active Expired
- 1976-02-26 RO RO7684923A patent/RO69312A/en unknown
- 1976-02-26 GB GB7677/76A patent/GB1531085A/en not_active Expired
- 1976-02-26 SE SE7602502D patent/SE7602502L/en not_active Application Discontinuation
- 1976-02-26 IT IT67445/76A patent/IT1062199B/en active
- 1976-02-26 SE SE7602502A patent/SE417521B/en not_active IP Right Cessation
- 1976-02-27 IE IE395/76A patent/IE42880B1/en unknown
- 1976-02-27 FI FI760518A patent/FI62107C/en not_active IP Right Cessation
- 1976-02-27 CH CH247076A patent/CH610339A5/en not_active IP Right Cessation
- 1976-02-27 AT AT146576A patent/AT346580B/en not_active IP Right Cessation
- 1976-02-27 NO NO760671A patent/NO149847C/en unknown
- 1976-02-27 BR BR7601266A patent/BR7601266A/en unknown
- 1976-02-27 AR AR262411A patent/AR218220A1/en active
- 1976-02-27 ZA ZA761198A patent/ZA761198B/en unknown
- 1976-02-27 JP JP51020214A patent/JPS602323B2/en not_active Expired
- 1976-02-28 EG EG117/76A patent/EG12520A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FI760518A (en) | 1976-08-28 |
| SE7602502L (en) | 1976-08-30 |
| FR2302311B1 (en) | 1979-08-17 |
| NL164870C (en) | 1981-02-16 |
| FR2302311A1 (en) | 1976-09-24 |
| GB1531085A (en) | 1978-11-01 |
| CA1052948A (en) | 1979-04-17 |
| IE42880B1 (en) | 1980-11-05 |
| IT1062199B (en) | 1983-07-28 |
| DE2607721A1 (en) | 1976-09-09 |
| ZA761198B (en) | 1977-02-23 |
| NL164870B (en) | 1980-09-15 |
| AR218220A1 (en) | 1980-05-30 |
| ATA146576A (en) | 1978-03-15 |
| EG12520A (en) | 1979-09-30 |
| SE417521B (en) | 1981-03-23 |
| JPS51115590A (en) | 1976-10-12 |
| FI62107B (en) | 1982-07-30 |
| IE42880L (en) | 1976-08-27 |
| NO149847C (en) | 1984-07-04 |
| CH610339A5 (en) | 1979-04-12 |
| AT346580B (en) | 1978-11-10 |
| BR7601266A (en) | 1976-09-14 |
| RO69312A (en) | 1980-05-15 |
| FI62107C (en) | 1982-11-10 |
| BE838825A (en) | 1976-08-23 |
| NL7601763A (en) | 1976-08-31 |
| LU74429A1 (en) | 1977-01-07 |
| JPS602323B2 (en) | 1985-01-21 |
| AU1143976A (en) | 1977-09-01 |
| NO760671L (en) | 1976-08-30 |
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