NO780152L - PROCEDURE FOR POLYMERIZATION OF CONNECTIONS WITH CONJUGATED DOUBLE BONDS - Google Patents
PROCEDURE FOR POLYMERIZATION OF CONNECTIONS WITH CONJUGATED DOUBLE BONDSInfo
- Publication number
- NO780152L NO780152L NO780152A NO780152A NO780152L NO 780152 L NO780152 L NO 780152L NO 780152 A NO780152 A NO 780152A NO 780152 A NO780152 A NO 780152A NO 780152 L NO780152 L NO 780152L
- Authority
- NO
- Norway
- Prior art keywords
- polymerization
- millimoles
- double bonds
- stated
- polymer
- Prior art date
Links
- 238000006116 polymerization reaction Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 7
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 7
- 235000021286 stilbenes Nutrition 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 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 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- -1 tetraphenylethylene, 1,1-diphenylethylene Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZNOVTXRBGFNYRX-UHFFFAOYSA-N 2-[[4-[(2-amino-5-methyl-4-oxo-1,6,7,8-tetrahydropteridin-6-yl)methylamino]benzoyl]amino]pentanedioic acid Chemical compound C1NC=2NC(N)=NC(=O)C=2N(C)C1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 ZNOVTXRBGFNYRX-UHFFFAOYSA-N 0.000 description 1
- PHFWUIVYQMKDDL-UHFFFAOYSA-N 2-methylbuta-1,3-diene;penta-1,3-diene Chemical group CC=CC=C.CC(=C)C=C PHFWUIVYQMKDDL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000006583 body weight regulation Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Description
Foreliggende oppfinnelse vedrorer en fremgangsmåte for polymirisering av forbindelser som inneholder minst et system av konjugerte dobbeltbindinger, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at det som katalysator anvendes et katalysatorsystem bestående av produktet fra innvirkningen av et alkalimetall på et substrat med den generelle formel The present invention relates to a method for the polymerization of compounds containing at least one system of conjugated double bonds, and the peculiarity of the method according to the invention is that a catalyst system consisting of the product from the action of an alkali metal on a substrate with the general formula is used as a catalyst
hvor R-p R2, R^og R^_ er valgt blant aryl, aralkyl, alkaryl, idet i tillegg R^eller R^, R^og R^_ også kan være hydrogen eller et alkyl radikal. where R-p R2, R^ and R^_ are chosen from aryl, aralkyl, alkaryl, whereby in addition R^ or R^, R^ and R^_ can also be hydrogen or an alkyl radical.
Fra US patentskrift nr. 3 177 190 er^det kjent å anvende et katalysatorsystem sammensatt av organiske derivater av lithium (lithium-isoprenyl) eller adukter av slike derivater med cyclo-alipatiske eller aromatiske molekyler (f.eks. li-isobutyl, og aduktet dilithiumstilbene-dimethylbutadien) for fremstilling av polymerer med reaktive endegmpper. From US patent no. 3 177 190 it is known to use a catalyst system composed of organic derivatives of lithium (lithium-isoprenyl) or adducts of such derivatives with cyclo-aliphatic or aromatic molecules (e.g. li-isobutyl, and the adduct dilithiumstilbene-dimethylbutadiene) for the production of polymers with reactive end groups.
Det er likeledes kjent (Die Makromolekulare Chemie, 92 (1966), sidene 180-197) at det er mulig å anvende sammensetninger av den type som er omhandlet ovenfor ved polymirisering av noen monovinyl monomerer, som f.eks. acrylnitril, styrene, metyl-metacrylat, som'inneholder elektron-tiltrekkende grupper. It is likewise known (Die Makromolekulare Chemie, 92 (1966), pages 180-197) that it is possible to use compositions of the type referred to above in the polymerization of some monovinyl monomers, such as e.g. acrylonitrile, styrene, methyl methacrylate, which contain electron-withdrawing groups.
Det er nå funnet at det er mulig å polymirisere forbindelser som inneholder minst et system av konjugerte dobbeltbindinger i nærvær av et katalysatorsystem sammensatt av produktet fra innvirkningen av et alkalimetall på organiske substrater som definert ovenfor. Dette forhold er overraskende da det ikke er i samsvar med de forventninger som de ovennevnte publikasjoner skulle tilsi og spesielt ikke i samsvar med den forstnevnte publikasjon hvori alkalimetallet anvendes i form av et alkyl-eller alkiny1-derivat. It has now been found that it is possible to polymerize compounds containing at least one system of conjugated double bonds in the presence of a catalyst system composed of the product of the action of an alkali metal on organic substrates as defined above. This relationship is surprising as it is not in accordance with the expectations that the above-mentioned publications would imply and especially not in accordance with the first-mentioned publication in which the alkali metal is used in the form of an alkyl or alkynyl derivative.
En spesiell fordelaktig utforelsesform av den foreliggende oppfinnelse går ut på at det som alkalimetall anvendes natrium, som ikke er særlig dyrt og lett tilgjengelig i sammenlikning A particularly advantageous embodiment of the present invention involves sodium being used as the alkali metal, which is not particularly expensive and easily available in comparison
med de andre alkalimetal ler, idet den organiske forbindelse velges blant stilben, tetrafenylethylen, 1-1- difenylethylen, with the other alkali metals, the organic compound being chosen from among stilbene, tetraphenylethylene, 1-1-diphenylethylene,
1,1,2- trifenylethylen osv.1,1,2-triphenylethylene etc.
Man kan imidlertid også anvende de andre alkalimetaller og fag-mannen vil ikke ha noen vanskelighet med å velge det katalysator-par som er best egnet. However, the other alkali metals can also be used and the person skilled in the art will have no difficulty in choosing the catalyst pair that is most suitable.
Reaksjonen mellom Na og den organiske forbindelse foregår mellom -78°C og +70°C, foretrukket ved den temperatur fra 0°C til +30°C i polare løsningsmidler og spesielt i THF/methyl-THF, dioxan, dietyl eter, dimethyl eter, dietyleneglycol-diethyl- The reaction between Na and the organic compound takes place between -78°C and +70°C, preferably at the temperature from 0°C to +30°C in polar solvents and especially in THF/methyl-THF, dioxane, diethyl ether, dimethyl ether, diethylene glycol-diethyl-
eter eller hydrocarbon løsningsmidler eller blandinger derav. ether or hydrocarbon solvents or mixtures thereof.
Produktet fra reaksjonen kan anvendes som sådant i polymerisasjonsblandingen, eventuelt sammen med andre løsningsmidler, for å oppnå spesielle virkninger på nrblekylvekten og/eller mikrostrukturen. The product from the reaction can be used as such in the polymerization mixture, possibly together with other solvents, to achieve special effects on the molecular weight and/or the microstructure.
Polymeriseringen gjennomføres foretrukket ved en temperatur mellom -50°C og +100°C under et trykk som kan variere fra atmosfæretrykk til det aktuelle trykk for angjeldende monomer-losningsmiddel-system. The polymerization is preferably carried out at a temperature between -50°C and +100°C under a pressure which can vary from atmospheric pressure to the relevant pressure for the monomer-solvent system in question.
Mer spesielt kan polyir,érisasjonslosningsmiddelet velges blant polare forbindelser og blandingene av alifatiske, cycloalifa tiske eller aromatiske forbindelser med slike polare forbindelser. More particularly, the polymerization solvent can be selected from polar compounds and the mixtures of aliphatic, cycloaliphatic or aromatic compounds with such polar compounds.
De monomerer som kan polymeriseres ved fremgangsmåten i henholdThe monomers that can be polymerized by the method according to
til oppfinnelsen er monomerer som inneholder minst et system av konjugerte dobbeltbindinger, som f.eks. butadien, isopren.-piperylen, en C^-C^-fraksjon og endelig blandinger av monomerer av konjugert diolefintype. to the invention are monomers that contain at least one system of conjugated double bonds, such as e.g. butadiene, isoprene-piperylene, a C^-C^ fraction and finally mixtures of monomers of the conjugated diolefin type.
Sammenlikning med de konvensjonelle polimirisasjonsmetoder ogComparison with the conventional polymerization methods and
mer spesielt ved sammenlikning ved Na-naftalen tillater fremgangsmåten i henhold til den foreliggende oppfinnelse oppnåelse av et antall avgjorte fordeler som f.eks.: a) En forbedret stabilitet av katalysatoren regnet over tid (Na-stilbensysternet er stabilt i noen dogn ved romtemperatur) og more particularly when compared with Na-naphthalene, the method according to the present invention allows the achievement of a number of decided advantages such as: a) An improved stability of the catalyst calculated over time (the Na-stilbene ester is stable for some time at room temperature) and
ved temperaturer opp til 60°C' - 70°C.at temperatures up to 60°C' - 70°C.
b) Hoyere polymerutbytter med den samme mengde alkalimetall inne-holdt i•initiatoren, idet de andre polimirisasjonsparametre b) Higher polymer yields with the same amount of alkali metal contained in the initiator, as the other polymerization parameters
er uendret (en mol-prosent av katalysator i forhold til noe mer variabel fra 0,1% - 5% er vanligvis tilstrekkelig.) is unchanged (a mole percent of catalyst relative to something more variable from 0.1% - 5% is usually sufficient.)
c) Kortere polymerisasjonstider for å oppnå en fullstendig om-dannelse (fra 10 minutter - 1 time med ellers uendrede c) Shorter polymerization times to achieve a complete transformation (from 10 minutes - 1 hour with otherwise unchanged
parametre.)parameters.)
d) En bredere anvendelighet av ka taly satorsysternet for regulering av molekylvekten (i samsvar med den typen løsningsmiddel som d) A wider applicability of the catalyst array for molecular weight regulation (according to the type of solvent used
anvendes)idet det kan oppnås obligomerer med en molekylvekt fra 500 - 2000 når man arbeider i toluen eller polymerer med en hoyere molekylvekt, således molekylvekt tilsvarende used) as obligomers with a molecular weight from 500 - 2000 can be obtained when working in toluene or polymers with a higher molecular weight, thus molecular weight corresponding
0 h. v i0 h. v i
mJhvis man arbeider i THF (tetra hydromJif working in THF (tetra hydro
t t
x x
furan). Mellomliggende viskositetsverdier oppnås ved å arbeide med blandinger av de to løsningsmidler. furan). Intermediate viscosity values are obtained by working with mixtures of the two solvents.
e) Muligheten for å styre mikrostrukturen i den oppnådde polymer og mer spesielt muligheten til å oppnå hoye innhold av 1,2 - e) The possibility of controlling the microstructure of the obtained polymer and more particularly the possibility of achieving high contents of 1,2 -
ved fremstilling av polybutadien og hoye innhold 3><*>+ - ved fremstilling av polyisoprener." in the production of polybutadiene and high content 3><*>+ - in the production of polyisoprenes."
Vinyl-addisjonsinnholdet kan imidlertid varieres i samsvar med arten av løsningsmiddelet og tilsiktede praktiske anvendelser av polymermaterialet. However, the vinyl addition content may be varied in accordance with the nature of the solvent and intended practical uses of the polymer material.
EKSEMPEL 1EXAMPLE 1
A) Polimirisasjonskatalysa toren fremstilles ved å omsette 10 millimol stilben med en stokiometrisk mengde av Na - sand i 70 ml THF og ved å holde reaksjonsblandingen omrort ved 2.5°C A) The polymerization catalyst is prepared by reacting 10 millimoles of stilbene with a stoichiometric amount of Na - sand in 70 ml of THF and by keeping the reaction mixture stirred at 2.5°C
i 5 timer. Blandingen filtreres og titreres og utbytte i forhold til omsatt Na er 95%. for 5 hours. The mixture is filtered and titrated and the yield in relation to converted Na is 95%.
B) .2 ml av den vannfri løsning i THF (0,2 millimol katalysator) fremstilt som angitt under A) anbringes i en flaske lukket med en .crown-kork etterat flaskene var blitt luftet og spylt med nitrogen ved en temperatur på 25°C. Det tilsettes 18 ml vannfri toluen, flasken lukkes og det inngis 2,8 gr butadien (50 millimol. ) B) .2 ml of the anhydrous solution in THF (0.2 millimole catalyst) prepared as indicated under A) is placed in a bottle closed with a .crown stopper after the bottles had been vented and flushed with nitrogen at a temperature of 25° C. 18 ml of anhydrous toluene are added, the bottle is closed and 2.8 g of butadiene (50 millimoles) are introduced.
Etter 30 minutter behandles polymerisasjonsblandingen med 1/1 losning av vann og metanol i en skjilletrakt og det overliggende væskeskikt gjenvinnes og inndampes til torrhet. After 30 minutes, the polymerization mixture is treated with a 1/1 solution of water and methanol in a separatory funnel and the overlying liquid layer is recovered and evaporated to dryness.
Det oppnås 2,8 gram (utbyttet =* 100%) av en polymer med vajske-konsistens (molykylvekt 800) med fblgende mikrostruktur:1,2- : 81+. 7% ; 1,<>>+- : 15.3% 1,^-cis : 0% 2.8 grams (yield =* 100%) of a polymer with a waxy consistency (molecular weight 800) with the following microstructure are obtained: 1,2- : 81+. 7%; 1,<>>+- : 15.3% 1,^-cis : 0%
EKSEMPEL 2EXAMPLE 2
I en flaske utstyrt med crown-kork som var blitt utluftet og spylt med nitrogen anbringes 2 ml av en losning av katalysator i THF (0,2 millimol katalysator) fremstilt som i Eksempel IA. Into a bottle fitted with a crown cap which had been vented and flushed with nitrogen is placed 2 ml of a solution of catalyst in THF (0.2 millimole of catalyst) prepared as in Example IA.
Det tilsettes 2 ml THF og 16 ml toluen, flasken lukkes og det injiseres 2,8 gram butadien (50 millimol). Etter 30 minutter behandles polymerisasjonsblandingen med en 1/1 losning av metanol og vann i en skilletrakt og toluenskiktet gjenvinnes og inndampes til torrhet. 2 ml of THF and 16 ml of toluene are added, the bottle is closed and 2.8 grams of butadiene (50 millimoles) are injected. After 30 minutes, the polymerization mixture is treated with a 1/1 solution of methanol and water in a separatory funnel and the toluene layer is recovered and evaporated to dryness.
Det oppnåg 2,8 gram (utbytte = 100%) av en polymer med en [^ 1 ^ = 0.26 og folgende mikrostruktur: toluen 1,2- : 85% l,<*>f- : 15% 1,^-cis : 0%. 2.8 grams (yield = 100%) of a polymer with a [^ 1 ^ = 0.26 and the following microstructure were obtained: toluene 1,2- : 85% l,<*>f- : 15% 1,^-cis : 0%.
EKSEMPEL 3EXAMPLE 3
En polymerisasjonsreaktor som tidligere var blitt utluftetA polymerization reactor that had previously been vented
og spylt med nitrogen skylles ved -40°C med 2 millimol (beregnet Na-innhold) av en løsning sammensatt av produktet oppnådd ved innvirkning og reaksjon i 4 timer ved -40°C av Na på stilben i THF. THF tilsettes inntil et totalt volum and flushed with nitrogen is flushed at -40°C with 2 millimoles (calculated Na content) of a solution composed of the product obtained by the action and reaction for 4 hours at -40°C of Na on stilbene in THF. THF is added up to a total volume
på 20 ml og det tilsettes 2,8 gram butadien (50 millimol). of 20 ml and 2.8 grams of butadiene (50 millimoles) are added.
Etter to timer behandles polymerisasjonsblandingen medAfter two hours, the polymerization mixture is treated with
CH^OHog det oppnås en polymer med en 9^7<30>°c1#10gCH^OHAnd a polymer with a 9^7<30>°c1#10g is obtained
L / J ToluenL / J Toluene
følgende mikrostruktur:following microstructure:
1,2 : 87% ; 1,4-cis : 0% ; 1,4-trans = 13% 1.2: 87%; 1,4-cis: 0%; 1,4-trans = 13%
Utbyttet av fast polymer er 80%.The yield of solid polymer is 80%.
EKSEMPEL 4EXAMPLE 4
En luftet polymerisasjonsflaske som var spylt med nitrogen og utstyrt med en crown-kork fylles med en temperatur på 25°C med 0,2 millimol av produktet fra innvirkningen av Na på stilben, fremstilt som i eksempel 1 (A). An aerated polymerization bottle flushed with nitrogen and fitted with a crown cap is filled at a temperature of 25°C with 0.2 millimoles of the product from the action of Na on stilbene, prepared as in Example 1 (A).
Det tilsettes 18 ml toluen og 5 ml isopren (50 millimol). Flasken lukkes og omrøring foretas. Etter 2 timer gjennom-føres koagulering av polymeren med metanol. 18 ml of toluene and 5 ml of isoprene (50 millimoles) are added. The bottle is closed and stirring is carried out. After 2 hours, coagulation of the polymer is carried out with methanol.
CY130°C Det oppnås 2,9 gram polymer (utbytte = 85%) med en 'J =CY130°C 2.9 grams of polymer are obtained (yield = 85%) with a 'J =
Jtoluen 0.12 og følgende mikrostruktur: 3,4 - : 85% 1,2 - : 15% Jtoluene 0.12 and the following microstructure: 3,4 - : 85% 1,2 - : 15%
EKSEMPEL 5EXAMPLE 5
En luftet polymerisasjonsflaske som var spylt med nitrogenAn aerated polymerization bottle that had been purged with nitrogen
og forsynt med crown-kork fylles ved en temperatur på 2 5°Cand fitted with a crown cork is filled at a temperature of 25°C
med 30 milligram (0,2 millimol i forhold til Na) av innvirkningsproduktet av Na på stilben (1 : 1) i dioxan. Det tilsettes 10 ml dietylenglykol-dimetyleter og injiseres with 30 milligrams (0.2 millimoles relative to Na) of the reaction product of Na on stilbene (1:1) in dioxane. 10 ml of diethylene glycol dimethyl ether is added and injected
2,8 gram butadien.2.8 grams of butadiene.
Etter 15 minutter koaguleres polymeren med metanol._ Det oppnås 2,8 gram polymer (utbytte 100%) med 3 0®C oppnås 2,8 gram polymer (utbytte = 100%) med en _ ^6/» J toluen 0,5 og følgende mikrostruktur: 2,2- : 85% ; 1,4-trans : 15% After 15 minutes, the polymer is coagulated with methanol._ 2.8 grams of polymer are obtained (yield 100%) with 3 0®C 2.8 grams of polymer are obtained (yield = 100%) with a _ ^6/» J toluene 0.5 and the following microstructure: 2,2- : 85% ; 1,4-trans : 15%
EKSEMPEL 6EXAMPLE 6
A) Adduktet av Na-tetrafenyletylen fremstilles ved å omsette 10 millimol tetrafenyletylen med støkiometriske mengder av Na-sand i 80 ml vannfritt THF og det omrøres ved 25°C i fire timer. Oppløsningen filtreres og titreres og utbyttet i forhold til omsatt Na er 94%. Det bemerkes spesielt at reaksjonen kan gjennomføres også ved -78°C ved utbytter som er sammenliknbare med de ovenstående og med samme reaksjonstider. B) Et millimol katalysatorløsning fremstilt som under A) anbringes i en flaske med en crown-kork med et totalt volum på 20 ml THF. Flasken lukkes og 2,8 gram butadien (50 millimol) innføres deri ved injeksjon. Etter 2 timer koaguleres polymerisasjonsblandingen med metanol. Det oppnås 2,8 polybutadien (utbytte = 100%) med ^7 30°C = 0,9 og følgende mikrostruktur:1" Jtoluen 1,2 = 90% ; 1,4-trans : 10% ; 1,4-cis : 0% A) The adduct of Na-tetraphenylethylene is prepared by reacting 10 millimoles of tetraphenylethylene with stoichiometric amounts of Na-sand in 80 ml of anhydrous THF and it is stirred at 25°C for four hours. The solution is filtered and titrated and the yield in relation to converted Na is 94%. It is particularly noted that the reaction can also be carried out at -78°C with yields comparable to those above and with the same reaction times. B) A millimolar catalyst solution prepared as under A) is placed in a bottle with a crown cap with a total volume of 20 ml of THF. The bottle is closed and 2.8 grams of butadiene (50 millimoles) are introduced into it by injection. After 2 hours, the polymerization mixture is coagulated with methanol. 2,8 polybutadiene (yield = 100%) is obtained with ^7 30°C = 0.9 and the following microstructure:1" Jtoluene 1,2 = 90% ; 1,4-trans : 10% ; 1,4-cis : 0%
EKSEMPEL 7EXAMPLE 7
Ved å anvende en høy-vakuum-teknikk fremstilles Na-stilben katalysatoren i en reaktor ved å omsette in situ 18 milligram Na (0,75 millimol) og 64 milligram stilben (0,35 millimol) Using a high-vacuum technique, the Na-stilbene catalyst is prepared in a reactor by reacting in situ 18 milligrams of Na (0.75 millimoles) and 64 milligrams of stilbene (0.35 millimoles)
i 60 milliliter THF i en time ved en temperatur på 25°C.in 60 milliliters of THF for one hour at a temperature of 25°C.
Det innføres 2,4 gram butadien (45 millimol) og polymeriseringen bringes til å foregå i løpet av 30 minutter. Blandingen avkjøles til -78°C og det tilsettes 2,2 gram styren (21 millimol). Oppløsningen for stå ved romtemperatur i 10 timer. Blandingen koaguleres fra metanol og 4,3 gram polymer oppnås (Utbytter 100% råpolymer). 2.4 grams of butadiene (45 millimoles) are introduced and the polymerization is brought to take place within 30 minutes. The mixture is cooled to -78°C and 2.2 grams of styrene (21 millimoles) are added. The solution to stand at room temperature for 10 hours. The mixture is coagulated from methanol and 4.3 grams of polymer are obtained (Yield 100% crude polymer).
Det gjennomføres ekstraksjon i 24 timer med aceton. Det oppnås en polymer som inneholder 30% styren, uttrykt i millimol. Extraction is carried out for 24 hours with acetone. A polymer containing 30% styrene, expressed in millimoles, is obtained.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT19385/77A IT1076233B (en) | 1977-01-18 | 1977-01-18 | PROCEDURE FOR THE POLYMERIZATION OF COMPOUNDS HAVING A SYSTEM OF DOUBLE CONJUGATE LINKS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO780152L true NO780152L (en) | 1978-07-19 |
Family
ID=11157237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO780152A NO780152L (en) | 1977-01-18 | 1978-01-16 | PROCEDURE FOR POLYMERIZATION OF CONNECTIONS WITH CONJUGATED DOUBLE BONDS |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5390390A (en) |
| AT (1) | AT359284B (en) |
| BE (1) | BE863038A (en) |
| CA (1) | CA1121100A (en) |
| DE (1) | DE2802044A1 (en) |
| DK (1) | DK24178A (en) |
| ES (1) | ES466392A1 (en) |
| FR (1) | FR2377423A1 (en) |
| GB (1) | GB1591066A (en) |
| IE (1) | IE46141B1 (en) |
| IT (1) | IT1076233B (en) |
| NL (1) | NL7800623A (en) |
| NO (1) | NO780152L (en) |
| SE (1) | SE7800505L (en) |
| ZA (1) | ZA7826B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3932178A1 (en) * | 1989-09-27 | 1991-04-04 | Savalica Bulgaro | Lock for bicycle front wheel - has holder on front wheel fork with rotary swivelling holding lever engaging bicycle frame |
-
1977
- 1977-01-18 IT IT19385/77A patent/IT1076233B/en active
-
1978
- 1978-01-04 ZA ZA00780026A patent/ZA7826B/en unknown
- 1978-01-13 AT AT25978A patent/AT359284B/en not_active IP Right Cessation
- 1978-01-16 SE SE7800505A patent/SE7800505L/en unknown
- 1978-01-16 FR FR7801119A patent/FR2377423A1/en active Granted
- 1978-01-16 NO NO780152A patent/NO780152L/en unknown
- 1978-01-17 GB GB1861/78A patent/GB1591066A/en not_active Expired
- 1978-01-17 DK DK24178A patent/DK24178A/en not_active Application Discontinuation
- 1978-01-17 CA CA000295139A patent/CA1121100A/en not_active Expired
- 1978-01-17 ES ES466392A patent/ES466392A1/en not_active Expired
- 1978-01-18 IE IE113/78A patent/IE46141B1/en unknown
- 1978-01-18 DE DE19782802044 patent/DE2802044A1/en not_active Withdrawn
- 1978-01-18 NL NL7800623A patent/NL7800623A/en not_active Application Discontinuation
- 1978-01-18 JP JP342178A patent/JPS5390390A/en active Pending
- 1978-01-18 BE BE184421A patent/BE863038A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE863038A (en) | 1978-07-18 |
| IT1076233B (en) | 1985-04-27 |
| CA1121100A (en) | 1982-03-30 |
| ES466392A1 (en) | 1978-10-01 |
| DK24178A (en) | 1978-07-19 |
| FR2377423A1 (en) | 1978-08-11 |
| ATA25978A (en) | 1980-03-15 |
| JPS5390390A (en) | 1978-08-09 |
| DE2802044A1 (en) | 1978-07-20 |
| FR2377423B1 (en) | 1980-09-12 |
| SE7800505L (en) | 1978-07-19 |
| GB1591066A (en) | 1981-06-10 |
| NL7800623A (en) | 1978-07-20 |
| AT359284B (en) | 1980-10-27 |
| ZA7826B (en) | 1978-11-29 |
| IE780113L (en) | 1978-07-18 |
| IE46141B1 (en) | 1983-03-09 |
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