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    Production of co-oligomers of 1,3-dienes and compounds with activated olefinic double bonds
    1.
    发明专利
    Production of co-oligomers of 1,3-dienes and compounds with activated olefinic double bonds 未知

    公开(公告)号：GB1014541A

    公开(公告)日：1965-12-31

    申请号：GB3380362

    申请日：1962-09-04

    Applicant: BASF AG

    Inventor： LAUTENSCHLAGER HANS ,  SCHARF EMIL ,  WITTENBERG DIETMAR ,  MUELLER HERBERT

    IPC: B01J21/02 ,  B01J27/24 ,  B01J31/12 ,  B01J31/16 ,  B01J31/18 ,  B01J31/20 ,  B01J31/22 ,  B01J31/24 ,  C07C2/02 ,  C07C2/04 ,  C07C2/08 ,  C07C2/52 ,  C07C15/44 ,  C07C17/275 ,  C07F15/04

    Abstract: Co-oligomers of 1,3-dienes and compounds containing an olefine group a ,b - to an aromatic group are obtained by reacting the starting materials at 0-250 DEG C. in the presence of a zero-valent compound of iron, cobalt or nickel. The principal products contain a mol. ratio of diene: olefine of 1:2 in the case of aryl olefines and 1:1 in other cases and include the new compounds C6H5-CH = CH-CH2-CR1 = CR11-CH2-CR1 = CR11-CH3 in which R1 and R11 are hydrogen or methyl, obtained from styrene and butadiene, isoprene or dimethylbutadiene. Other diene starting materials include 2-ethylbutadiene, pentadiene-1,3, hexadiene-2,4, cyclohexadiene-1,3, cyclo-octadiene-1,3, 1-vinylcyclohexene-1, 3-methylheptatriene-1,4,6, and octatriene-1,3,6. Aryl olefins may contain benzene, naphthalene or anthracene, and the olefinic substituent, of which there may be a plurality, being vinyl or a - or b -methyl vinyl. The catalyst may be a carbonyl or carbonyl hydride or such a compound in which one or more ligands have been replaced by a trivalent phosphorus, arsenic and/or antimony compound or a nitrile, thioether, or amine including heterocyclic amine compounds or complexes of the metal with an aromatic hydrocarbon and aluminium halide or with an olefin or acetylene. The catalyst may be formed from an ordinary compound and a reducing agent in the presence of an electron donor; the reducing agent may be a metal or hydride or organoderivative thereof and the electron donor may be a tertiary amine, phosphine, phosphine oxide, ester or substituted triamide of phosphorous acid, ester of thiophosphorous acid, arsine, stilbine, bismuth hydrocarbyl ether, ethioether, sulphoxide, sulphone, mercaptan or an olefinic or acetylinic compound. A hydrocarbon halogenohydrocarbon or ether solvent is preferably present during the formation of the catalyst and the subsequent oligomerization. Where an aluminium halide is formed or used in the catalyst preparation a polymerization inhibitor is preferably added or a complexing agent for the halide. The following co-oligomers are exemplified:-styrene, butadiene; styrene: isoprene; ethylvinylbenzene / divinylbenzene : butadiene; a - methylstyrene : butadiene; b -methylstyrene : butadiene; 1 - vinylnaphthalene : butadiene; styrene: 2,3-dimethybutadiene; styrene : 1-vinylcyclohexene-1; and styrene : cyclopentadiene.ALSO:Co-oligomers of 1,3-dienes and compounds containing an olefine group a ,b - to an aromatic (including "aromatic" heterocyclic), ether, thioether, or carboxylic salt, ester, anhydride, amide, N-substituted amide or nitrile group are obtained by reacting the starting materials at 0-250 DEG C. in the presence of a zero-valent compound of iron, cobalt or nickel. The principal products contain a mol ratio of diene; olefine of 1 : 2 in the case of aryl olefines and 1 : 1 in other cases and include the new compounds CH2 = CR1-CR11 = CH-CH2-CH2-COOR in which R1 and R11 are hydrogen or methyl and R is a C1-C12 hydrocarbon group obtained from an acrylic ester and butadiene, isoprene or dimethylbutadiene. Other diene starting materials include 1-methoxybutadiene, 2-ethyl-butadiene, pentadiene - 1,3, hexadiene - 2,4, cyclohexadiene - 1,3, cyclooctadiene - 1,3, 1-vinylcyclohexene - 1, 3 - methylheptatriene-1,4,6, and octatriene - 1,3,6. Aryl olefins may contain halogen, alkoxy, aryloxy, dialkylamino, carbalkoxy, or nitro groups, the aryl group being benzene, naphthalene, anthracene, pyridine or thiophene and the olefinic substituent, of which there may be a plurality, being vinyl or a - or b -methyl vinyl. Suitable alkenyl ethers or thioethers have a saturated or aromatic hydrocarbon group attached to the oxygen or sulphur. The unsaturated carboxylic acid derivative may be derived from maleic, fumaric, 2-hexenoic, crotonic, methacrylic or acrylic acid. The catalyst may be a carbonyl or carbonyl hydride or such a compound in which one or more ligands have been replaced by a trivalent phosphorus, arsenic and/or antimony compound or a nitrile, thioether, or amine (including heterocyclic amine) compounds or complexes of the metal with an aromatic hydrocarbon and aluminium halide or with an olefin or acetylene. The catalyst may be formed from an ordinary compound and a reducing agent in the presence of an electron donor; the reducing agent may be a metal or hydride or organo-derivative thereof and the electron donor may be a tertiary amine, phosphine, phosphine oxide, ester or substituted triamide of phosphorous acid, ester of thiophosphorous acid arsine, stilbine, bismuth hydrocarbyl, ether, thioether, sulphoxide, sulphone, mercaptan or an olefinic or acetylenic compound. A hydrocarbon halogenohydrocarbon or ether solvent is preferably present during the formation of the catalyst and the subsequent oligomerization. Where an aluminium halide is formed or used in the catalyst preparation a polymerization inhibitor is preferably added or a complexing agent for the halide. The following co-oligomers are exemplified: p-methoxystyrene: butadiene; 2,4 - dichlorostyrene: butadiene; vinyl isobutyl ether: butadiene; tert. butyl acrylate: butadiene; ethyl acrylate: isoprene; ethyl acrylate: butadiene; acrylamide: butadiene; acrylonitrile: butadiene; tert. butyl acrylate: 3 - methylheptatriene - 1,3,6; ethyl acrylate: 2,3 - dimethylbutadiene and 2 - vinylpyridine: butadiene.

    Improvements in the production of triaryl phosphines
    4.
    发明专利
    Improvements in the production of triaryl phosphines 未知

    公开(公告)号：GB918359A

    公开(公告)日：1963-02-13

    申请号：GB2969861

    申请日：1961-08-17

    Applicant: BASF AG

    Inventor： LAUTENSCHLAGER HANS ,  WITTENBERG DIETMAR

    IPC: C07F9/50

    Abstract: Triaryl phosphines are prepared by mixing an aryl halide with activated aluminium, stirring the mixture for about 1 to 100 hours at an elevated temperature, if desired in the presence of an inert solvent, until the bulk of the aluminium is dissolved and reacting the resultant product with a halide of trivalent phosphorus at a temperature between 100 and 300 DEG C., if desired after distilling off the solvent. The aluminium may be activated by intimately mixing with small amounts of a halogen, hydrogen halide, a metal halide, a non-metal halide or an organo-metallic compound. The phosphorus halide may be organic or inorganic. The product, which consists essentially of a mixture of aluminium halide and a triaryl phosphine-aluminium halide adduct may be worked up by hydrolysis and extraction or by adding a complex former for the aluminium halide, e.g. an alkali metal halide, a t-amine or POCl3, and distilling. Triphenyl phosphine is prepared in examples.

    Production of liquid oligomers of 1, 3-dienes
    5.
    发明专利
    Production of liquid oligomers of 1, 3-dienes 未知

    公开(公告)号：GB892759A

    公开(公告)日：1962-03-28

    申请号：GB4369860

    申请日：1960-12-20

    Applicant: BASF AG

    Inventor： WITTENBERG DIETMAR ,  MUELLER HERBERT

    IPC: C07C2/46

    Abstract: A catalyst for the polymerization of 1, 3-dienes to oligomers, consists of (1) a titanium compound, (2) an organo-aluminium halide and (3) a metal of Group 1a, 2a, 2b, 3a or 3b, of the periodic system, an alkali or alkaline earth metal salt, an amine, ether, thioether and/or an organic phosphine. The titanium compound (1) may be a tetra-alkylate or -cycloalkylate, a tri- or tetrahalide and ester halide or organo halide. The ogano-aluminium halide has the formula A12RnX6-n where R is aliphatic or aromatic, X is halogen and n is 1-5 and may be previously complexed with component (3) where this is a complexing agent. The salts of alkali or alkaline earth metals are preferably the halides, hydrides and C1-C4 carboxylates. Where an organic compound is used as component (3) this preferably contains aliphatic, cycloaliphatic, araliphatic, or aromatic hydrocarbon radicals or the functional group may be part of a heterocyclic ring; other substituents may be present, e.g. carbonyl, carboxyl, cyano, carboalkoxy and aromatic halogen. Many suitable components (3) are specified. The mol. ratio of (1): (2): (3) may be 1 : 2 : 1, e.g. 1 : 3-10: 1,5-50. Solvents may be used, e.g. hydrocarbons and halohydrocarbons and the catalyst may be "developed" by mixing all components in a ball mill or vibratory mill in the solvent or by mixing two components in the solvent and then adding the third. If a suspension is obtained this may be filtered and the solution used as catalyst. The catalyst may be destroyed at the end of the reaction by adding a small amount of water or an alcohol or a large amount of acetone.ALSO:The polymerization of 1,3-dienes to oligomers, principally cyclic polyolefins, is effected in the presence of (1) a titanium compound, (2) an organo-aluminium halide and (3) a metal of Group 1a, 2a, 2b, 3a or 3b, of the Periodic System, an alkali or alkaline earth metal salt, an amine, ether, thioether and/or an organic phosphine. Specified dienes are butadiene which yields cyclooctadiene and cyclodecatriene, isoprene, 2,3-dimethylbutadiene and cyclohexadiene and may be used in admixture with inert substances. The titanium compound (1) may be a tetra-alkylate or -cycloalkylate, a tri- or tetrahalide and ester halide or organic halide. The organo-aluminium halide has the formula Al2RnX6-n where R is aliphatic or aromatic, X is halogen and n is 1-5 and may be previously complexed with component (3) where this is a complexing agent. The salts of alkali or alkaline earth metals are preferably the halides, hydrides and C1-C4 carboxylates. Where an organic compound is used as component (3) this preferably contains aliphatic, cycloaliphatic, araliphatic, or aromatic hydrocarbon radicals or the functional group may be part of the heterocyclic ring; other substituents may be present, e.g. carbonyl, carboxyl, cyano, carboalkoxy and aromatic halogen. Many suitable components (3) are specified. The mol ratio of (1) : (2) : (3) may be 1 : \sF 2 : \sF 1, e.g. 1 : 3-10 : 1.5-50. Solvents may be used, e.g. hydrocarbons and halohydrocarbons and the catalyst may be "developed" by mixing all components in a ball mill or vibratory mill in the solvent or by mixing two components in the solvent and then adding the third. If a suspension is obtained this may be filtered and the solution used as catalyst. Suitable conditions are - 10 DEG C. to 150 DEG C. and reduced pressure to 10 atmospheres, normal pressure being preferred. The catalyst may be destroyed at the end of the reaction by adding a small amount of water or an alcohol or a large amount of acetone.

    Production of diene polymers
    9.
    发明专利
    Production of diene polymers 未知

    公开(公告)号：GB1070207A

    公开(公告)日：1967-06-01

    申请号：GB3528564

    申请日：1964-08-28

    Applicant: BASF AG

    Inventor： MUELLER HERBERT ,  WITTENBERG DIETMAR

    IPC: C08F36/04

    Abstract: A 1,3-diene is polymerized in the presence of a catalyst comprising (A) a compound containing nickel in zerovalent form, and (B) a fluorine compound of boron, and in the absence of any organometallic compound of a metal of Groups IA, IIA and IIIA. The nickel compound may contain one to four ligands consisting of carbon monoxide, triarylphosphines, triaryl arsines, triaryl stilbines, esters of phosphoric acid with alkanols having 1 to 10 carbon atoms, cycloalkanols and phenols having up to ten carbon atoms, alkyl isonitriles, aryl isonitriles, pyridine, dipyridyl, o-phenanthroline nitriles of mono- and di-carboxylic acids which are ethylenically unsaturated in the alphabeta position and which have three to five carbon atoms, aldehydes ethylenically unsaturated in the alpha-beta position and having three to five carbon atoms, aromatic hydrocarbons having one benzene ring, and linear branched and cyclic ethylenically unsaturated hydrocarbons having one to four carbon to carbon double bonds and two to fifteen carbon atoms. Specified dienes are butadiene, isoprene, 2,3-dimethylbutadiene, 2-ethylbutadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene and vinylcyclohexene-1-up to 40% of comonomers, e.g. styrene, alpha-methyl styrene, vinyltoluene, and/or linar aliphatic triene, e.g. hexatriene-1,3,5, or 3-methylheptatriene, 1,3,5- or octatriene-1,3,6 may also be present. Boron fluoride or an addition complex of boron fluoride are specified boron compounds while aluminium halides may additionally be present. Polymerization may take place in solution, batchwise or continuously. The products may be oily or elastomeric products having almost exclusively 1,4-structure, the fraction having cis, 1,4-structure preponderating are obtained.ALSO:A catalyst composition for polymerising 1,3-dienes comprises (A) a compound containing zerovalent nickel and (B) a fluorine compound of boron - no organometallic compound of metals of groups IA, IIA, or IIIA being present. The nickel compound may contain one to four ligands consisting of carbon monoxide, triaryl phosphines, arsines, and stilbines, esters of phosphoric acid with alkanols of 1-10 carbon atoms cycloalkanols and phenols having up to 10 carbon atoms, alkyl and aryl isonitriles, pyridine, dipyridyl, o-phenanthroline, nitriles of mono and di carboxlic acids which are ethylenically unsaturated in the alpha-beta position and have three to five carbon atoms, aldehydes ethylenically unsaturated in the alpha-beta position and having three to five carbon atoms, aromatic hydrocarbons having one benzene ring and linear, branched and cyclic ethylenically unsaturated hydrocarbons having one to four carbon to carbon double bonds and two to fifteen carbon atoms. Lists are given. Examples use triphenylphosphine nickel tricarbonyl, nickel tetracarbonyl, nickel-(o)benzene, nickel(o)-cyclododecatriene (1,5,9) and nickel-bis-acrylonitrile. Boron fluoride or an addition complex of boron fluoride are specified boron compounds while aluminium halides may additionally be present.

    Production of oligomers of 1,3-dienes
    10.
    发明专利
    Production of oligomers of 1,3-dienes 未知

    公开(公告)号：GB987423A

    公开(公告)日：1965-03-31

    申请号：GB2500962

    申请日：1962-06-29

    Applicant: BASF AG

    Inventor： LAUTENSCHLAGER HANS ,  SCHARF EMIL ,  WITTENBERG DIETMAR ,  MUELLER HERBERT

    IPC: C07C2/46 ,  C07C2/52

    Abstract: Oligomers of 1,3-dienes, particularly cyclic olefins, are obtained in the presence of a catalyst containing titanium, chromium, iron or nickel which has been activated prior to the reaction with an olefinic, polyolefinic or acetylenic compound. The catalyst may comprise a chromium halide and an organo-aluminium compound (Specification 849,236), chromium oxide, an acid chloride, amide or anhydride and an organo-aluminium compound (Specification 878,650), a titanium compound and an organo-aluminium compound (Specifications 848,951, 867,017, 860,377 and 892,759), a titanium compound or ferric halide, a metal of Group Ia, IIa, IIb, IIIb, IVa, IVb, Vb or VIIb and a halide of an element of Group IIb, IIIa, IVa or Va, the presence of aluminium or an aluminium halide being essential (Specifications 878,120 and 907,698), and a nickel compound, an organo-metallic compound or metallic hydride and a phosphine or phosphite (Belgian Specification 598,363). The activating compound may be a hydrocarbon or contain inert groups such as ether, carboxylic ester, nitrile, carboxylic amide, amine, imine, epoxy, aldehyde, ketone or sulphide groups, many being specified, but the preferred compound is the diene to be oligomerized. This is preferably butadiene; also specified are isoprene, 2,3-dimethylbutadiene, 2-ethylbutadiene, pentadiene-1,3 hexadiene - 2,4,3 - methyl - heptatriene-1,4,6 and octatriene-1,3,6. The activating compound is used in an amount to give a molar ratio to the titanium, chromium, iron or nickel of at least 1:1 and preferably in sufficient excess to form a solvent; alternatively an extraneous solvent, particularly a hydrocarbon or ether, is added. The activator may be added to the formed catalyst or the catalyst may be formed in the presence of the activator. Solid constituents of the formed catalyst may be removed if desired. Oligomerization is effected at - 50 DEG to 150 DEG C. and preferably under pressure if the diene is gaseous. Specification 935,716 also is referred to.ALSO:Oligomers of 1,3-dienes, particularly cyclic olefins, are obtained in the presence of a catalyst containing titanium, chromium, iron or nickel which has been activated prior to the reaction with an olefinic, polyolefinic or acetylenic compound. The catalyst may comprise a chromium halide and an organo-aluminium compound (Specification 849,236), chromium oxide, an acid chloride, amide or anhydride and an organo-aluminium compound (Specification 878,650), a titanium compound and an organo-aluminium compound (Specifications 848,951, 867,017, 860,377 and 892,759), a titanium compound or ferric halide, a metal of Group IA, IIA, IIB, IIIB, IVA, IVB, VB or VIIB and a halide of an element of Group IIB, IIIA, IVA or VA, the presence of aluminium or an aluminium halide being essential (Specifications 878,120 and 907,698), and a nickel compound, an organo-metallic compound or metallic hydride and a phosphine or phosphite (Belgian Specification 598,363). The activating compound may be a hydrocarbon or contain inert groups such as ether, carboxylic ester, nitrile, carboxylic amide, amine, imine, epoxy, aldehyde, ketone or sulphide groups, many being specified, but the preferred compound is the diene to be oligomerized. This is preferably butadiene; also specified are isoprene, 2,3-dimethylbutadiene; 2-ethylbutadiene, pentadiene-1,3, hexadiene-2,4, 3-methyl-heptatriene-1,4,6 and octatriene-1,3,6. The activating compound is used in an amount to give a molar ratio to the titanium, chromium, iron or nickel of at least 1:1 and preferably in sufficient excess to form a solvent; alternatively an extraneous solvent, particularly a hydrocarbon or ether, is added. The activator may be added to the formed catalyst or the catalyst may be formed in the presence of the activator. Solid constituents of the formed catalyst may be removed if desired. Oligomerization is effected at -50 DEG C. to 150 DEG C. and preferably under pressure if the diene is gaseous. Specification 935,716 also is referred to.

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