USRE37106E1 - Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene - Google Patents

Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene Download PDF

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USRE37106E1
USRE37106E1 US08/394,538 US39453895A USRE37106E US RE37106 E1 USRE37106 E1 US RE37106E1 US 39453895 A US39453895 A US 39453895A US RE37106 E USRE37106 E US RE37106E
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Karl-Heinz Aleksander Ostoja Starzewski
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2247—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
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    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/02—Addition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
    • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/794—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring
    • C07C49/796—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring polycyclic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the invention relates to a process for the reaction of styrene derivatives with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, styrene derivatives being obtained which are extended with ethylene at the olefinic double bond and in which a double bond remains in the extension chain formed.
  • Such styrene derivatives extended with ethylene are interesting intermediates which, owing to the double bond remaining in the extension chain, are suitable as precursors for graft polymers, for example with methyl methacrylate or maleic anhydride, or polymer-analogous reactions can be carried out using them.
  • the styrene derivative employed according to the invention can moreover carry the substituents mentioned further below, which make possible other reactions or introduce other properties into a polymer.
  • products obtainable according to the invention in which the styrene derivative carries a further vinyl group, i.e. is, for example, divinylbenzene. In this case, mainly only one vinyl group is extended.
  • the extended styrene derivatives formed in the course of this are bifunctional; they carry two olefinic double bonds of different reactivity.
  • the unextended vinyl group can then be utilised in a manner known per se for styrene-analogous homo- or copolymerisations.
  • the polymers produced therefrom furthermore carry their poly(oligo)ethylene side chains from the extension according to the invention bonded via the aromatic compounds and are thus poly(oligo)ethylene-modified. Graft reactions, derivatisations, cross-linkings and other reactions can then be carried out on the double bonds of these side chains.
  • a process for the preparation of styrene derivatives extended at the double bond with ethylene and having a double bond remaining in the extension chain formed has been found, which is characterised in that a styrene derivative is reacted with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20° to 160° C. and an ethylene pressure of 1 to 200 bar.
  • a relatively large number of nickel catalysts which carry a phosphorus-oxygen chelate ligand and which can be employed according to the invention are known to the person skilled in the art.
  • the reaction is carried out in the presence of a nickel catalyst which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ to a nickel(O) compound, with a phosphorus compound of the formula
  • R 4 , R 5 , R 6 , R 7 and R 8 independently of one another denote straight-chain or branched C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 1 -C 20 -alkoxy, C 3 -C 8 -cycloalkyl, C 6 -C 12 -aryl, C 6 -C 12 -aryloxy, C 7 -C 15 -aralkyl or C 7 -C 15 -aralkoxy, where
  • R 7 can additionally denote hydrogen and
  • R 8 can additionally denote hydrogen, acyl or sulphonate
  • nickel catalysts which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ to a nickel(O) compound, with an adduct of a quinoid compound or maleic anhydride and a phosphine of the formula
  • R 4 , R 5 and R 6 have the meaning mentioned.
  • Such phosphorus ylide-nickel compounds can be employed both individually and as a mixture of several of them.
  • R 4 has the meaning of optionally substituted C 6 -C 12 -aryl. Additionally preferentially, in the preparation of the above catalysts from a nickel(O) compound or a compound which can be converted in situ to a nickel(O) compound, a compound of the formula (I) and additionally a compound of the formula
  • R 1 , R 2 and R 3 independently of one another denote straight-chain or branched C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, C 3 -C 8 -cycloalkyl, C 2 -C 20 -alkenyl, di-(C 1 -C 4 -alkyl)amino, C 6 -C 12 -aryl, C 6 -C 12 -aryloxy, C 7 -C 15 -aralkyl or C 7 -C 15 -aralkoxy,
  • X denotes doubly bonded oxygen, the doubly bonded group NR 9 or the doubly bonded group
  • R 9 and R 10 independently of one another denote hydrogen, silyl, acyl, chlorophenyl, nitrophenyl, C 1 -C 6 -alkylphenyl, cyano, phenyl-C 2 -C 6 -alkenyl or R 1 , and
  • n assumes the value zero or one.
  • the reaction is carried out in the presence of a nickel catalyst which is obtained by reaction of a nickel(O) compound with phosphorus compounds of the formulae
  • R 11 , R 12 and R 13 independently of one another denote C 1 -C 8 -alkyl, phenyl or benzyl,
  • R 14 represents hydrogen, C 1 -C 8 -alkyl or phenyl
  • R 15 , R 16 and R 17 independently of one another denote C 1 -C 8 -alkyl or phenyl, where R 17 can additionally denote hydrogen or acyl, and
  • R 20 denotes phenyl or C 1 -C 4 -alkyl
  • a nickel catalyst which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ into a nickel(O) compound, with an adduct of benzoquinone or maleic anhydride and a phosphine of the formula
  • R 15 and R 16 have the meaning mentioned
  • R 20 is preferentially phenyl.
  • 0 to 4 mol of the compound of the formula (III) and 1 to 4 mol of the compound of the formula (I) are employed per mole of nickel(O) compound to prepare the catalyst, preferably about 1 mol of the compound of the formula (III) or (IV) and about 1 mol of the compound of the formula (I) or (V) per mol of the nickel(O) compound.
  • Identical molar ratios apply if a compound of the formula (I) or (V) is replaced by a quinone/phosphine adduct or a maleic anhydride/phosphine adduct of the type described.
  • the temperature for the preparation of the catalyst is 0° to 100° C., preferably 20° to 70° C.
  • the preparation is carried out with the exclusion of oxygen, preferably in a solvent, which must be inert to the reactants, such as benzene, toluene, cyclohexane or n-hexane.
  • the catalyst is usually isolated as a solid by filtering, the solution being concentrated and/or cooled beforehand as required.
  • the catalyst can also be employed directly without isolation, i.e. as a solution or suspension, for the reaction according to the invention.
  • Nickel(O) compounds which may be mentioned by way of example are Ni(cyclooctadiene) 2 and Ni(allyl) 2 .
  • nickel compounds which can be converted in situ to nickel(O) compounds are: Ni acetylacetonate, Ni octanoate and Ni stearate, which can be reduced with the aid of customary reducing agents, such as borohydride, alumino-hydride, aluminium alkyl or organolithium compounds.
  • alkyl preferably C 1 -C 8 -alkyl, which can be straight-chain or branched are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, the isomeric pentyls, hexyls, octyls, decyls, dodecyls, hexadecyls and eicosyls.
  • Particularly preferred alkyl has 1 to 4C atoms.
  • C 1 -C 20 -alkoxy which can be straight-chain or branched are: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert.-butoxy, the isomeric pentyloxys, hexyloxys, octyloxys, decyloxys, dodecyloxys and eicosyloxys.
  • Preferred alkoxy has 1 to 8C atoms, particularly preferred alkoxy 1 to 4C atoms.
  • C 3 -C 8 -cycloalkyl examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methyl cyclopentyl, methyl cyclohexyl, cycloheptyl, cyclooctyl.
  • C 6 -C 12 -aryl examples include phenyl, naphthyl, biphenylyl. Preferred aryl is phenyl.
  • C 2 -C 20 alkenyl examples include vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, octenyl, decenyl or eicosenyl and their branched isomers.
  • C 6 -C 12 -aryloxy examples include phenoxy, naphthyloxy, biphenyloxy. Phenoxy is preferred.
  • C 7 -C 15 -aralkyl examples include: benzyl, phenylethyl, phenylpropyl, naphthyl-methyl, preferably benzyl.
  • C 7 -C 15 -aralkoxy examples are: benzyloxy, phenylethyloxy, phenyl-propyloxy, naphthyl-methyloxy, preferably benzyloxy.
  • di-(C 1 -C 4 -alkyl)-amino examples include dimethylamino, diethylamino, dipropylamino, methylbutylamino, ethylbutylamino etc.
  • silyl examples include tri-C 1 -C 4 -alkylsilyl, triphenylsilyl or mixed trisubstituted alkylphenyl-silyls, preferably tri-C 1 -C 4 -alkyl-silyls, such as trimethylsilyl, triethylsilyl etc.
  • Acyl is C 1 -C 8 -alkylcarbonyl or C 6 -C 12 -arylcarbonyl which can be substituted in the manner mentioned below, such as acetyl, propionyl, butyryl, C 5 -alkyl-carbonyl, C 8 -alkylcarbonyl, benzoyl, substituted benzoyl or naphthylcarbonyl.
  • Preferred acyl is substituted or unsubstituted C 1 -C 4 -alkyl-carbonyl or benzoyl. Acetyl or benzoyl are particularly preferred.
  • the said substituents can be monosubstituted to trisubstituted, preferably monosubstituted or disubstituted, particularly preferably monosubstituted, by C 1 -C 4 -alkyl, by C 1 -C 4 -alkoxy, by C 6 -C 12 -aryl, or by C 6 -C 12 -aryloxy or nitro, preferably by C 1 -C 4 -alkyl, by C 1 -C 4 -alkoxy, or by phenyl or phenoxy, it being possible in the case of multiple substitution for the substituents to be different from the said enumeration.
  • tolyl for example, is additionally understood as aryl.
  • Suitable quinoid compounds are o- or p-quinoid compounds of the benzene and naphthalene series and also anthraquinones, which can additionally be substituted in the manner described above.
  • p-Benzoquinone, 1,4-naphthoquinone and 9,10-anthraquinone may be mentioned by way of example.
  • the preferred nickel compounds containing phosphorus-oxygen chelate ligands are, according to present knowledge, in agreement with the formula
  • X, n and R 1 to R 8 have the meanings mentioned above.
  • a general structural feature of the nickel catalysts which can be employed according to the invention and which carry a phosphorus-oxygen chelate ligand is the following configuration
  • R 1 , R 2 and R 3 are C 1 -C 8 -alkyl, cyclohexyl, phenyl, tolyl, benzyl, di-(C 1 -C 4 -alkyl)-amino, phenoxy and C 1 -C 4 -alkoxy.
  • R 4 is preferably C 6 -C 12 -aryl, particularly preferably phenyl.
  • R 5 , R 6 , R 7 and R 8 are independently of one another preferably cyclohexyl, phenyl, tolyl, benzyl, vinyl and C 1 -C 4 -alkyl.
  • R 7 is moreover preferably hydrogen or C 1 -C 4 -alkoxy
  • R 8 is moreover preferably hydrogen, acetyl, benzoyl or the sulphonate group.
  • R 9 and R 10 are preferably hydrogen, C 1 -C 8 -alkyl, phenyl, chlorophenyl, nitrophenyl, C 1 -C 6 -alkylphenyl, trimethylsilyl, cyano, C 2 -C 6 -alkenyl and phenyl-C 2 -C 6 -alkenyl.
  • nickel catalysts 0.01 to 100 mmol of nickel catalyst per mol of styrene derivative, preferably 0.1 to 10 mmol of nickel catalyst, particularly preferably 0.2 to 5 mmol of nickel catalyst, are employed for the reaction according to the invention. It is furthermore possible to activate these nickel catalysts by organoaluminium compounds, preferably alkyl- or alkoxy-aluminiu compounds.
  • the process according to the invention is carried out at a temperature of 20° to 160° C., preferably at 30° to 140° C., particularly preferably at 40° to 120° C., very particularly preferably at 50° to 100° C.
  • ethylene pressure 1 to 200 bar, preferably 2 to 50 bar, particularly preferably 3 to 25 bar.
  • R 18 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 7 -acyl, fluorine, chlorine or bromine and
  • R 19 is hydrogen, C 1 -C 4 -alkyl, vinyl or chlorine.
  • C 2 -C 7 -acyl examples are; acetyl, propionyl, butyryl, benzoyl, preferably benzoyl.
  • R 28 is hydrogen, methyl, ethyl, i-butyl, C 2 -C 7 -acyl, vinyl or chlorine and
  • R 29 is hydrogen, vinyl, methyl or chlorine.
  • styrene or divinylbenzene are employed.
  • the styrene derivatives to be employed according to the invention can be employed both in pure form and as a technical mixture.
  • An important example of this latter case is technical divinylbenzene, which additionally contains ethyl-styrene and; or diethyl-benzene.
  • benzoyl styrenes e.g. 3-benzoyl styrene, can be mentioned.
  • the process according to the invention is Carried out in the liquid phase.
  • the reaction can basically be carried out without co-use of an inert solvent if the styrene derivative is liquid.
  • the process according to the invention is carried out in the presence of an inert solvent.
  • inert solvents are: n-hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, chlorobenzene, acetone, dimethylformamide and other solvents which are not attacked under the reaction conditions, preferably cyclohexane or toluene.
  • the inert solvent is employed in an amount by weight which is 0.1 to 100 times, preferably 0.5 to 20 times, relative to the styrene derivative.
  • the reaction product of the process according to the invention is in general initially a homologous series of extended styrene derivatives in which the extension comprises one molecule of ethylene per molecule of the basic styrene derivative or two or more molecules of ethylene per mol of the basic styrene derivative and in which a double bond remains in the extension chain.
  • the individual components of the styrene-ethylene reaction can be represented by the following formulae:
  • Polyolefins occur as by-products.
  • Such a product mixture can be separated into individual components or into fractions in a manner known to the person skilled in the art, for example by chromatographic separation, fractional distillation or precipitation.
  • the process according to the invention is surprising insofar as using the nickel catalyst to be employed, with which, as is known, ethylene can be polymerised, polyethylene formation in this case now becomes the side reaction. Polystyrene formation is also almost completely suppressed.
  • the homologous series of styrene/ethylene coupling products becomes the principal reaction product, a shift to higher or lower molecular weights taking place according to the methods known for polyethylene molecular weight control.
  • Molecular weights below 10,000 g/mol are preferred, particularly preferably below 1,000 g/mol.
  • the process according to the invention can be carried out, for example, as follows: the solvent is initially introduced into an autoclave. The intended amount of styrene derivative is then added. Ethylene, on its own or mixed with an inert gas, is then pumped into the closed autoclave to the desired reaction pressure, if appropriate taking into account the pressure increase at reaction temperature. The autoclave is then heated to the desired reaction temperature and the nickel catalyst is added as a solid, as a suspension or as a solution. Preferably, a catalyst solution is pumped in simultaneously to the use of ethylene (multi-pulse process). The carrying-out of the polymerising coupling of the styrene is assisted by shaking of the autoclave or by a suitable lifting or stirring device.
  • the ethylene can be replenished at the rate of its consumption during the reaction.
  • the autoclave is cooled, depressurised and opened.
  • the reaction mixture is worked up, for example, by distillation.
  • the optionally co-used inert solvent and the unreacted styrene derivative are separated off first, for example by distillation.
  • the remaining reaction mixture containing the extended styrene derivatives prepared according to the invention can then be separated into individual components or into suitable fractions by fine distillation, by crystallisation or precipitation or by other separating operations. All distillations are advantageously carried out in the presence of customary stabilisers in order to suppress thermal polymerisation.
  • a number of styrene derivatives extended with ethylene, which can be prepared according to the invention and which have a remaining double bond in the extension chain formed, are new.
  • the invention therefore furthermore relates to styrene derivatives extended with ethylene, of the formula
  • R 38 represents C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 7 -acyl, fluorine, chlorine or bromine,
  • R 19 has the above scope of meaning
  • m assumes values of 4 to 104 204, preferably 4 to 34 6 to 64 , particularly preferably 4 to 14 6 to 24,
  • R 48 denotes vinyl, i-butyl or benzoyl
  • R 48 and m have the above scope of meaning, whereby compounds are excepted wherein R 19 and R 29 , respectively, denote hydrogen, R 38 and R 48 , respectively, denote i-butyl or benzoyl, and m assumes the value 4.
  • the new styrene derivatives extended with ethylene of the formulae (XVIII), (XIX), and (XX) also include the mixture of the homologous series formed from them.
  • the new substances mentioned likewise also include the mixture with the technical impurities of the basic styrenes and/or with the homologous reaction products extended with ethylene in the case in which styrene derivatives present in technical purity have been used as starting materials; this case has been illustrated further above for technical divinylbenzene.
  • the crude catalyst thus obtained was dissolved in toluene at 60° C., hexane was added until turbidity persisted and the solution was crystallised in the cold, the crystals were isolated by Schlenk filtration, washed with hexane and dried in vacuo.
  • the amount of toluene mentioned in the following tables, the amount of catalyst mentioned and the amount of styrene derivative mentioned were initially introduced into an autoclave of suitable size. An amount of ethylene was then added under pressure such that the ethylene pressure indicated in the tables was attained at the reaction temperature indicated. During the reaction period indicated in the tables, ethylene was additionally added to maintain the pressure indicated. The yield was determined by weighing the residue after distillative separation of solvent and unreacted styrene derivative. The tables show the results obtained by gas chromatography relating to the percentage distribution of extended styrene derivatives (denoted as “product”) and co-formed ⁇ -olefin (polyethylene by-product).
  • Type Amount derivative bar ml g % % 2 NiPh(Ph 2 PCHCMeO) 1 mmol 0.1 mol 10 80 not 60 40 (Pr i 3 PCHPh) p-methyl- deter- styrene mined 3 NiPh(Ph 2 PCHCMeO 1 mmol 0.1 mol 10 80 not 50 50 (Pr i 3 PCHPh) 3,4-dichloro- deter- styrene mined 4 Ni(COD) 2 4 mmol 1 mol 5 500 35 71 29 Ph 3 PCHCPhO o-chlorostyrene Ph 3 PO 5 Ni(COD) 2 4 mmol 3 mol 5 500 220 74 26 Ph 3 PCHCPhO styrene Ph 3 PO

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Abstract

The title compounds can be prepared by reaction of a styrene derivative with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20° to 160° C. and an ethylene pressure of 1 to 200 bar. Styrene derivatives extended with ethylene, of the formula
Figure USRE037106-20010320-C00001
in which
R19 denotes hydrogen, C1-C4-alkyl, vinyl or chlorine and
R38 denotes C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, flourine, chlorine or bromine and
m assumes values of 4-104,
with the exception of compounds wherein R19 denotes hydrogen and R38 denotes i-butyl or benzoyl, and m assumes the value 4, are new.

Description

This application is a continuation of application Ser. No. 08/145,377, filed Oct. 29, 1993, now abandoned, which is a division of Ser. No. 08/084,379, filed Jun. 29, 1993, which is an allowed reissue 34,706 of Ser. No. 07/704,751, filed May 23, 1991, now U.S. Pat. No. 5,180,872.
BACKGROUND OF THE INVENTION
The invention relates to a process for the reaction of styrene derivatives with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, styrene derivatives being obtained which are extended with ethylene at the olefinic double bond and in which a double bond remains in the extension chain formed.
Such styrene derivatives extended with ethylene are interesting intermediates which, owing to the double bond remaining in the extension chain, are suitable as precursors for graft polymers, for example with methyl methacrylate or maleic anhydride, or polymer-analogous reactions can be carried out using them. The styrene derivative employed according to the invention can moreover carry the substituents mentioned further below, which make possible other reactions or introduce other properties into a polymer. Of particular interest are products obtainable according to the invention in which the styrene derivative carries a further vinyl group, i.e. is, for example, divinylbenzene. In this case, mainly only one vinyl group is extended. The extended styrene derivatives formed in the course of this are bifunctional; they carry two olefinic double bonds of different reactivity. The unextended vinyl group can then be utilised in a manner known per se for styrene-analogous homo- or copolymerisations. The polymers produced therefrom furthermore carry their poly(oligo)ethylene side chains from the extension according to the invention bonded via the aromatic compounds and are thus poly(oligo)ethylene-modified. Graft reactions, derivatisations, cross-linkings and other reactions can then be carried out on the double bonds of these side chains.
SUMMARY OF THE INVENTION
A process for the preparation of styrene derivatives extended at the double bond with ethylene and having a double bond remaining in the extension chain formed has been found, which is characterised in that a styrene derivative is reacted with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20° to 160° C. and an ethylene pressure of 1 to 200 bar.
DETAILED DESCRIPTION OF THE INVENTION
A relatively large number of nickel catalysts which carry a phosphorus-oxygen chelate ligand and which can be employed according to the invention are known to the person skilled in the art.
Preferentially, the reaction is carried out in the presence of a nickel catalyst which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ to a nickel(O) compound, with a phosphorus compound of the formula
Figure USRE037106-20010320-C00002
in which
R4, R5, R6, R7 and R8 independently of one another denote straight-chain or branched C1-C20-alkyl, C2-C20-alkenyl, C1-C20-alkoxy, C3-C8-cycloalkyl, C6-C12-aryl, C6-C12-aryloxy, C7-C15-aralkyl or C7-C15-aralkoxy, where
R7 can additionally denote hydrogen and
R8 can additionally denote hydrogen, acyl or sulphonate
or nickel catalysts which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ to a nickel(O) compound, with an adduct of a quinoid compound or maleic anhydride and a phosphine of the formula
Figure USRE037106-20010320-C00003
in which
R4, R5 and R6 have the meaning mentioned.
Such phosphorus ylide-nickel compounds can be employed both individually and as a mixture of several of them.
Preferentially, R4 has the meaning of optionally substituted C6-C12-aryl. Additionally preferentially, in the preparation of the above catalysts from a nickel(O) compound or a compound which can be converted in situ to a nickel(O) compound, a compound of the formula (I) and additionally a compound of the formula
Figure USRE037106-20010320-C00004
are used as starting compounds, in which
R1, R2 and R3 independently of one another denote straight-chain or branched C1-C20-alkyl, C1-C20-alkoxy, C3-C8-cycloalkyl, C2-C20-alkenyl, di-(C1-C4-alkyl)amino, C6-C12-aryl, C6-C12-aryloxy, C7-C15-aralkyl or C7-C15-aralkoxy,
X denotes doubly bonded oxygen, the doubly bonded group NR9 or the doubly bonded group
Figure USRE037106-20010320-C00005
 R9 and R10 independently of one another denote hydrogen, silyl, acyl, chlorophenyl, nitrophenyl, C1-C6-alkylphenyl, cyano, phenyl-C2-C6-alkenyl or R1, and
n assumes the value zero or one.
In the preparation of the above catalysts, starting from a nickel(O) compound, or a compound which can be converted in situ to a nickel(O) compound, and an adduct of a quinoid compound or maleic anhydride and a compound of the formula (II), it is additionally still preferred to start from a compound of the formula (III).
Particularly preferentially, the reaction is carried out in the presence of a nickel catalyst which is obtained by reaction of a nickel(O) compound with phosphorus compounds of the formulae
Figure USRE037106-20010320-C00006
in which
R11, R12 and R13 independently of one another denote C1-C8-alkyl, phenyl or benzyl,
R14 represents hydrogen, C1-C8-alkyl or phenyl,
R15, R16 and R17 independently of one another denote C1-C8-alkyl or phenyl, where R17 can additionally denote hydrogen or acyl, and
R20 denotes phenyl or C1-C4-alkyl,
or a nickel catalyst which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ into a nickel(O) compound, with an adduct of benzoquinone or maleic anhydride and a phosphine of the formula
Figure USRE037106-20010320-C00007
in which
R15 and R16 have the meaning mentioned,
and a compound of the formula (IV).
R20 is preferentially phenyl.
0 to 4 mol of the compound of the formula (III) and 1 to 4 mol of the compound of the formula (I) are employed per mole of nickel(O) compound to prepare the catalyst, preferably about 1 mol of the compound of the formula (III) or (IV) and about 1 mol of the compound of the formula (I) or (V) per mol of the nickel(O) compound. Identical molar ratios apply if a compound of the formula (I) or (V) is replaced by a quinone/phosphine adduct or a maleic anhydride/phosphine adduct of the type described.
The temperature for the preparation of the catalyst is 0° to 100° C., preferably 20° to 70° C. The preparation is carried out with the exclusion of oxygen, preferably in a solvent, which must be inert to the reactants, such as benzene, toluene, cyclohexane or n-hexane. After its preparation, the catalyst is usually isolated as a solid by filtering, the solution being concentrated and/or cooled beforehand as required. However, the catalyst can also be employed directly without isolation, i.e. as a solution or suspension, for the reaction according to the invention.
Nickel(O) compounds which may be mentioned by way of example are Ni(cyclooctadiene)2 and Ni(allyl)2. Examples of nickel compounds which can be converted in situ to nickel(O) compounds are: Ni acetylacetonate, Ni octanoate and Ni stearate, which can be reduced with the aid of customary reducing agents, such as borohydride, alumino-hydride, aluminium alkyl or organolithium compounds.
Examples of alkyl, preferably C1-C8-alkyl, which can be straight-chain or branched are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, the isomeric pentyls, hexyls, octyls, decyls, dodecyls, hexadecyls and eicosyls. Particularly preferred alkyl has 1 to 4C atoms.
Examples of C1-C20-alkoxy which can be straight-chain or branched are: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert.-butoxy, the isomeric pentyloxys, hexyloxys, octyloxys, decyloxys, dodecyloxys and eicosyloxys. Preferred alkoxy has 1 to 8C atoms, particularly preferred alkoxy 1 to 4C atoms.
Examples of C3-C8-cycloalkyl are: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methyl cyclopentyl, methyl cyclohexyl, cycloheptyl, cyclooctyl.
Examples of C6-C12-aryl are: phenyl, naphthyl, biphenylyl. Preferred aryl is phenyl.
Examples of C2-C20 alkenyl are: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, octenyl, decenyl or eicosenyl and their branched isomers.
Examples of C6-C12-aryloxy are: phenoxy, naphthyloxy, biphenyloxy. Phenoxy is preferred.
Examples of C7-C15-aralkyl are: benzyl, phenylethyl, phenylpropyl, naphthyl-methyl, preferably benzyl.
Examples of C7-C15-aralkoxy are: benzyloxy, phenylethyloxy, phenyl-propyloxy, naphthyl-methyloxy, preferably benzyloxy.
Examples of di-(C1-C4-alkyl)-amino are: dimethylamino, diethylamino, dipropylamino, methylbutylamino, ethylbutylamino etc.
Examples of silyl are tri-C1-C4-alkylsilyl, triphenylsilyl or mixed trisubstituted alkylphenyl-silyls, preferably tri-C1-C4-alkyl-silyls, such as trimethylsilyl, triethylsilyl etc.
Acyl is C1-C8-alkylcarbonyl or C6-C12-arylcarbonyl which can be substituted in the manner mentioned below, such as acetyl, propionyl, butyryl, C5-alkyl-carbonyl, C8-alkylcarbonyl, benzoyl, substituted benzoyl or naphthylcarbonyl. Preferred acyl is substituted or unsubstituted C1-C4-alkyl-carbonyl or benzoyl. Acetyl or benzoyl are particularly preferred.
The said substituents can be monosubstituted to trisubstituted, preferably monosubstituted or disubstituted, particularly preferably monosubstituted, by C1-C4-alkyl, by C1-C4-alkoxy, by C6-C12-aryl, or by C6-C12-aryloxy or nitro, preferably by C1-C4-alkyl, by C1-C4-alkoxy, or by phenyl or phenoxy, it being possible in the case of multiple substitution for the substituents to be different from the said enumeration. In this sense, tolyl, for example, is additionally understood as aryl.
Suitable quinoid compounds are o- or p-quinoid compounds of the benzene and naphthalene series and also anthraquinones, which can additionally be substituted in the manner described above. p-Benzoquinone, 1,4-naphthoquinone and 9,10-anthraquinone may be mentioned by way of example.
The preferred nickel compounds containing phosphorus-oxygen chelate ligands are, according to present knowledge, in agreement with the formula
Figure USRE037106-20010320-C00008
in which
X, n and R1 to R8 have the meanings mentioned above.
In the case in which a compound of the formula (I) is replaced, for example, by a maleic anhydride/phosphine adduct of the type described, the formula (VII) becomes the formula below
Figure USRE037106-20010320-C00009
A general structural feature of the nickel catalysts which can be employed according to the invention and which carry a phosphorus-oxygen chelate ligand is the following configuration
Figure USRE037106-20010320-C00010
Preferred radicals R1, R2 and R3 are C1-C8-alkyl, cyclohexyl, phenyl, tolyl, benzyl, di-(C1-C4-alkyl)-amino, phenoxy and C1-C4-alkoxy.
R4 is preferably C6-C12-aryl, particularly preferably phenyl.
R5, R6, R7 and R8 are independently of one another preferably cyclohexyl, phenyl, tolyl, benzyl, vinyl and C1-C4-alkyl.
R7 is moreover preferably hydrogen or C1-C4-alkoxy, R8 is moreover preferably hydrogen, acetyl, benzoyl or the sulphonate group.
R9 and R10 are preferably hydrogen, C1-C8-alkyl, phenyl, chlorophenyl, nitrophenyl, C1-C6-alkylphenyl, trimethylsilyl, cyano, C2-C6-alkenyl and phenyl-C2-C6-alkenyl.
0.01 to 100 mmol of nickel catalyst per mol of styrene derivative, preferably 0.1 to 10 mmol of nickel catalyst, particularly preferably 0.2 to 5 mmol of nickel catalyst, are employed for the reaction according to the invention. It is furthermore possible to activate these nickel catalysts by organoaluminium compounds, preferably alkyl- or alkoxy-aluminiu compounds.
The process according to the invention is carried out at a temperature of 20° to 160° C., preferably at 30° to 140° C., particularly preferably at 40° to 120° C., very particularly preferably at 50° to 100° C.
It is carried out at an ethylene pressure of 1 to 200 bar, preferably 2 to 50 bar, particularly preferably 3 to 25 bar.
According to the invention, a styrene derivative of the formula
Figure USRE037106-20010320-C00011
is employed in which
R18 is hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, fluorine, chlorine or bromine and
R19 is hydrogen, C1-C4-alkyl, vinyl or chlorine.
Examples of C2-C7-acyl are; acetyl, propionyl, butyryl, benzoyl, preferably benzoyl.
Preferentially, styrene derivatives of the formula
Figure USRE037106-20010320-C00012
are employed in which
R28 is hydrogen, methyl, ethyl, i-butyl, C2-C7-acyl, vinyl or chlorine and
R29 is hydrogen, vinyl, methyl or chlorine.
Particularly preferentially, styrene or divinylbenzene are employed.
The styrene derivatives to be employed according to the invention can be employed both in pure form and as a technical mixture. An important example of this latter case is technical divinylbenzene, which additionally contains ethyl-styrene and; or diethyl-benzene. Further benzoyl styrenes, e.g. 3-benzoyl styrene, can be mentioned.
The process according to the invention is Carried out in the liquid phase. In this case, the reaction can basically be carried out without co-use of an inert solvent if the styrene derivative is liquid.
In many cases, the process according to the invention is carried out in the presence of an inert solvent. Suitable examples of such inert solvents are: n-hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, chlorobenzene, acetone, dimethylformamide and other solvents which are not attacked under the reaction conditions, preferably cyclohexane or toluene.
The inert solvent is employed in an amount by weight which is 0.1 to 100 times, preferably 0.5 to 20 times, relative to the styrene derivative.
The reaction product of the process according to the invention is in general initially a homologous series of extended styrene derivatives in which the extension comprises one molecule of ethylene per molecule of the basic styrene derivative or two or more molecules of ethylene per mol of the basic styrene derivative and in which a double bond remains in the extension chain. The individual components of the styrene-ethylene reaction can be represented by the following formulae:
Figure USRE037106-20010320-C00013
Formula (XIa) in this connection represents the case styrene/ethylene =1:1, formula (XIb) represents the case styrene/ethylene =1:2, and formula (XIc) represents the general case styrene/ethylene =1:1 +n, where n principally assumes values from 0 (zero) to 100, in particular 0 to 30, very particularly 0-10.
As a result of isomerisation reactions, homologous series of isomeric products are also formed in the process according to the invention, which appear to be in agreement with the following formulae:
Figure USRE037106-20010320-C00014
Figure USRE037106-20010320-C00015
With olefinically unsaturated compounds, owing to the cis-trans isomerism known to the person skilled in the art, the corresponding cis isomers always also occur in addition to the above compounds of the formulae (XI) to (XVII) (XVI) represented as trans isomers.
In the formulae (XI a-c), (XII a and b) and (XIII) to (XVII), the bending points and end points of the bent line (=extension chain) denote, in a manner familiar to the person skilled in the art, C atoms which have the necessary number of H atoms. As a result, for example, the following detailed notation results for the formulae (XIa) and (XIII)
Figure USRE037106-20010320-C00016
In the formulae (XI) to (XVII), the ring substitution as in formula (IX) or (X) has been left out for the sake of clarity.
The whole of the process product of the process according to the invention having a double bond remaining in the branched or unbranched extension chain can thus be represented by the formula
Figure USRE037106-20010320-C00017
in which the index m assumes the value of the above index n+4 2n+4 and R18 and R19 have the above scope of meaning.
In the manner shown above, this is in general the mixture of the homologues coming under the formula (XVII).
Polyolefins occur as by-products.
Such a product mixture can be separated into individual components or into fractions in a manner known to the person skilled in the art, for example by chromatographic separation, fractional distillation or precipitation.
The process according to the invention is surprising insofar as using the nickel catalyst to be employed, with which, as is known, ethylene can be polymerised, polyethylene formation in this case now becomes the side reaction. Polystyrene formation is also almost completely suppressed. The homologous series of styrene/ethylene coupling products becomes the principal reaction product, a shift to higher or lower molecular weights taking place according to the methods known for polyethylene molecular weight control. Molecular weights below 10,000 g/mol are preferred, particularly preferably below 1,000 g/mol.
The following procedures, for example, are suitable for the process according to the invention:
a) initial introduction of the solid, suspended or dissolved catalyst (or its components) and addition of the monomers simultaneously or successively at the desired temperature;
b) initial introduction of the monomers and injection of the catalyst solution or suspension (or its components) at the desired temperature, if appropriate with subsequent heating;
c) continuous metering of the catalyst solution (or its components) and the monomers under prestated desired polymerisation conditions (pressure, temperature).
The process according to the invention can be carried out, for example, as follows: the solvent is initially introduced into an autoclave. The intended amount of styrene derivative is then added. Ethylene, on its own or mixed with an inert gas, is then pumped into the closed autoclave to the desired reaction pressure, if appropriate taking into account the pressure increase at reaction temperature. The autoclave is then heated to the desired reaction temperature and the nickel catalyst is added as a solid, as a suspension or as a solution. Preferably, a catalyst solution is pumped in simultaneously to the use of ethylene (multi-pulse process). The carrying-out of the polymerising coupling of the styrene is assisted by shaking of the autoclave or by a suitable lifting or stirring device. The ethylene can be replenished at the rate of its consumption during the reaction. After completion of the reaction, the autoclave is cooled, depressurised and opened. The reaction mixture is worked up, for example, by distillation. In this case, the optionally co-used inert solvent and the unreacted styrene derivative are separated off first, for example by distillation. The remaining reaction mixture containing the extended styrene derivatives prepared according to the invention can then be separated into individual components or into suitable fractions by fine distillation, by crystallisation or precipitation or by other separating operations. All distillations are advantageously carried out in the presence of customary stabilisers in order to suppress thermal polymerisation.
A number of styrene derivatives extended with ethylene, which can be prepared according to the invention and which have a remaining double bond in the extension chain formed, are new.
The invention therefore furthermore relates to styrene derivatives extended with ethylene, of the formula
Figure USRE037106-20010320-C00018
in which
R38 represents C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, fluorine, chlorine or bromine,
R19 has the above scope of meaning and
m assumes values of 4 to 104 204, preferably 4 to 34 6 to 64, particularly preferably 4 to 14 6 to 24,
preferably those of the formula
Figure USRE037106-20010320-C00019
in which
R48 denotes vinyl, i-butyl or benzoyl and
R29 and m have the above scope of meaning,
particularly preferably those of the formula
Figure USRE037106-20010320-C00020
in which R48 and m have the above scope of meaning, whereby compounds are excepted wherein R19 and R29, respectively, denote hydrogen, R38 and R48, respectively, denote i-butyl or benzoyl, and m assumes the value 4.
This means in the case of formula (XX) that m assumes values of 6 to 104 204, preferably 6 to 34 64, particularly preferable 6 to 14 preferably 6 to 24, taking into account that the difference in the lower limit of m (6 instead of 4) makes just one ethylene (C2) unit.
Of course, the new styrene derivatives extended with ethylene, of the formulae (XVIII), (XIX), and (XX) also include the mixture of the homologous series formed from them.
The new substances mentioned likewise also include the mixture with the technical impurities of the basic styrenes and/or with the homologous reaction products extended with ethylene in the case in which styrene derivatives present in technical purity have been used as starting materials; this case has been illustrated further above for technical divinylbenzene.
EXAMPLE 1 Catalyst preparation [NiPh(Ph2PCHCMeO)(Pri 3PCHPh)]
40 mmol of bis-cyclooctadiene-nickel(O) in 250 ml of dry argon-saturated toluene were mixed under argon with 40 mmol of acetylmethylene-triphenylphosphorane and 40 mmol of triisopropyl-phosphinebenzylidene. The mixture was heated to 60° C. for about 3 hours with intensive stirring. The dark brown reaction mixture was filtered under argon and the filtrate was concentrated to dryness in vacuo. The crude catalyst thus obtained was dissolved in toluene at 60° C., hexane was added until turbidity persisted and the solution was crystallised in the cold, the crystals were isolated by Schlenk filtration, washed with hexane and dried in vacuo.
EXAMPLES 2-10 General experimental procedure
The amount of toluene mentioned in the following tables, the amount of catalyst mentioned and the amount of styrene derivative mentioned were initially introduced into an autoclave of suitable size. An amount of ethylene was then added under pressure such that the ethylene pressure indicated in the tables was attained at the reaction temperature indicated. During the reaction period indicated in the tables, ethylene was additionally added to maintain the pressure indicated. The yield was determined by weighing the residue after distillative separation of solvent and unreacted styrene derivative. The tables show the results obtained by gas chromatography relating to the percentage distribution of extended styrene derivatives (denoted as “product”) and co-formed α-olefin (polyethylene by-product).
TABLE 1
(Examples 2 to 5)
Reaction of styrene derivatives in toluene with ethylene at a temperature of 80-90° C. in a
2-hour reaction
Catalyst Styrene Ethylene Toluene Yield Product α-olefin
No. Type Amount derivative bar ml g % %
2 NiPh(Ph2PCHCMeO) 1 mmol 0.1 mol 10 80 not 60 40
(Pri 3PCHPh) p-methyl- deter-
styrene mined
3 NiPh(Ph2PCHCMeO 1 mmol 0.1 mol 10 80 not 50 50
(Pri 3PCHPh) 3,4-dichloro- deter-
styrene mined
4 Ni(COD)2 4 mmol 1 mol 5 500  35 71 29
Ph3PCHCPhO o-chlorostyrene
Ph3PO
5 Ni(COD)2 4 mmol 3 mol 5 500 220 74 26
Ph3PCHCPhO styrene
Ph3PO
TABLE 2
(Examples 6 and 7)
Reaction of divinylbenzene (DVB, freshly distilled, 390 g in each case) in toluene (1,000 ml in
each case) with ethylene in a 2-hour reaction; catalyst metering by multi-pulse
Catalyst Ethylene Temp. Yield Product α-olefin
No. Type Amount bar ° C. g % %
6 Ni(COD)2 4 mmol in 2.5 90 173 89 11
Ph3PCHCPhO situ in
Ph3PO 150 ml toluene
7 NiPh(Ph2PCHCPhO) 4 mmol 5.0 50 278 85 15
(Ph3P) isolated in
150 ml toluene
for the catalyst:
COD = cyclooctadiene;
Ph = phenyl;
Me = methyl
Product = Total amount of the extended styrene derivative obtained
TABLE 3
(Examples 8 to 10)
Reaction of divinylbenzene (DVB, freshly distilled, 390 g in each case)
in toluene (1,000 ml in each case) with ethylene at 90° C. in a
2-hour reaction with 4 mmol of Ni(COD)2/Ph3PCHCPhO/Ph3PNSiMe3
as an in situ catalyst in 150 ml of toluene, catalyst metering: multi-pulse
Ethylene Yield Product α-olefin
No. bar g % %
 8 10 320 70 30
 9 5 345 83 17
10 2.5 110 91 9

Claims (14)

What is claimed is:
1. A process for the preparation of styrene derivatives extended at the double bond with ethylene and having a double bond remaining in the extension chain formed, according to the formula
Figure USRE037106-20010320-C00021
in which
R19 denotes hydrogen, C1-C4-alkylvinyl or chlorine,
R38 denotes C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, fluorine chlorine or bromine, and
m has a value of 4 to 104,
with the exception of compounds wherein R19 is hydrogen and R38 is isobutyl or benzyl and m has the value 4, wherein a styrene derivative is reacted with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20 to 160° C. and an ethylene pressure of 1 to 200 bar, wherein the nickel catalyst is obtained by reaction of a nickel (O) compound, or a compound which can be converted in situ to a nickel (O) compound, with a phosphorus compound of the formula
Figure USRE037106-20010320-C00022
in which
R4, R5, R6, R7 and R8 independently of one another denote straight-chain or branched C1-C20-alkyl, C2-C20-alkenyl, C1-C20-alkoxy, C3-C8-cycloalkyl, C6-C12-aryl, C6-C12-aryloxy, C7-C15-aralkyl or C7-C15-aralkoxy, where
R7 can additionally denote hydrogen and
R8 can additionally denote hydrogen, acyl or sulphonate,
or a nickel catalyst which can be prepared by reaction of a nickel (O) compound, or a compound which can be converted in situ to a nickel (O) compound, with an adduct of a quinoid compound or maleic anhydride and a phosphine of the formula
Figure USRE037106-20010320-C00023
in which
R4, R5 and R6 have the meaning mentioned.
2. The process of claim 1, wherein for the preparation of the nickel catalyst from a nickel(O) compound or a compound which can be converted in situ into a nickel(O) compound, and from a compound of the formula (I) or from an adduct of a quinoid compound or maleic anhydride and a compound of the formula (II), a compound of the formula
Figure USRE037106-20010320-C00024
in additionally used as a starting material in which
R1, R2 and R3 independently of one another denote straight-chain or branched C1-C20-alkyl, C1-C20-alkoxy, C3-C8-cycloalkyl, C2-C20-alkenyl, di-(C1-C4-alkyl)amino, C6-C12-aryl, C6-C12-aryloxy, C7-C15-aralkyl or C7-C15-aralkoxy,
X denotes doubly bonded oxygen, the doubly bonded group NR9 or the doubly bonded group
Figure USRE037106-20010320-C00025
R9 and R10 independently of one another denote hydrogen, silyl, acyl, chlorophenyl, nitrophenyl, C1-C6-alkylphenyl, cyano, phenyl-C2-C6-alkenyl or R1, and
n assumes the value zero or one.
3. The process of claim 3, wherein the reaction is carried out in the presence of a nickel catalyst which is obtained by reaction of a nickel(O) compound, or a compound which can be converted into a nickel(O) compound in situ, with phosphorus compounds of the formulae
Figure USRE037106-20010320-C00026
in which
R11, R12 and R13 independently of one another denote C1-C8-alkyl, phenyl or benzyl,
R14 represents hydrogen, C1-C8-alkyl or phenyl,
R15, R16 and R17 independently of one another denote C1-C8-alkyl or phenyl, where R17 can additionally denote hydrogen or acyl, and
R20 denotes phenyl or C1-C4-alkyl,
or a nickel catalyst which can be prepared by reaction of a nickel(O) compound, or a compound which can be converted in situ into a nickel(O) compound, with an adduct of benzoquinone or maleic anhydride and a phosphine of the formula
Figure USRE037106-20010320-C00027
in which
R15 and R16 have the meaning mentioned,
and a compound of the formula (IV).
4. The process of claim 1, wherein 0.01 to 100 mmol of nickel catalyst are employed per mol of styrene derivative.
5. The process of claim 5, wherein 0.1 to 10 mmol of nickel catalyst are employed per mol of styrene derivative.
6. The process of claim 6, wherein 0.2 to 5 mmol of nickel catalyst are employed per mol of styrene derivative.
7. The process of claim 1, wherein a styrene derivative of the formula
Figure USRE037106-20010320-C00028
is employed in which
R18 is hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, fluorine, chlorine or bromine and
R19 is hydrogen, C1-C4-alkyl, vinyl or chlorine.
8. The process of claim 8, wherein a styrene derivative of the formula
Figure USRE037106-20010320-C00029
is employed in which
R28 is hydrogen, methyl, ethyl, i-butyl, C2-C7-acyl, vinyl or chlorine and
R29 is hydrogen, vinyl, methyl or chlorine.
9. The process of claim 1, which is carried out at a temperature of 30° to 160° C.
10. The process of claim 9, which is carried out at a temperature of 40° to 120° C.
11. The process of claim 10, which is carried out at a temperature of 50° to 100° C.
12. A styrene derivative extended with ethylene and having a double bond remaining in the extension formed, of the formula
Figure USRE037106-20010320-C00030
in which
R 48 is i-butyl or benzoyl, and
m is an even number from 6 to 204.
13. A styrene derivative extended with ethylene and having a double bond remaining in the extension formed, of the formula
Figure USRE037106-20010320-C00031
in which
R 48 is vinyl, and
Figure USRE037106-20010320-C00032
14. A derivative according to claim 12, wherein m is up to 64.
US08/394,538 1990-06-06 1995-02-22 Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene Expired - Lifetime USRE37106E1 (en)

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US07/704,751 US5180872A (en) 1990-06-06 1991-05-23 Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene
US08/084,379 USRE34706E (en) 1990-06-06 1993-06-29 Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene
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