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    • 1. 发明申请
    • PROCESS FOR THE CARBONYLATION OF A CONJUGATED DIENE
    • 联合二烯的羰基化方法
    • WO2005082829A1
    • 2005-09-09
    • PCT/EP2005/050790
    • 2005-02-24
    • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.DRENT, EitJAGER, Willem WabePRINGLE, Paul Gerard
    • DRENT, EitJAGER, Willem WabePRINGLE, Paul Gerard
    • C07C67/38
    • C07C67/38C07C69/533
    • A process for the carbonylation of a conjugated diene, comprising reacting the conjugated diene with carbon monoxide and a co-reactant having an active hydrogen atom in the presence of a catalyst system including: (a) a source of palladium; and (b) a bidentate diphosphine ligand of formula (II): R 1 > P 1 -R- P 2 2 R 3 wherein P 1 and p2 represent phosphorus atoms; R 1 represents an optionally substituted divalent organic group linked to the phosphorus atom by two tertiary carbon atoms; and R 2 and R 3 independently represent univalent groups of from 1 to 20 atoms containing a tertiary carbon atom through which each group is linked to the phosphorus atom, or R 2 and R 3 jointly form an optionally substituted divalent organic group containing at least 2 tertiary carbon atoms through which the group is linked to the phosphorus atom; and R represents a divalent bridging group comprising 3 atoms through which P 1 is linearly connected to P 2 ;and (c) a source of an anion.
    • 一种共轭二烯的羰基化方法,包括使共轭二烯与一氧化碳和具有活性氢原子的共反应物在催化剂体系存在下反应,所述催化剂体系包括:(a)钯源; 和(b)式(II)的二齿二膦配体:R 1,P 1 -R 2,P 2,R 2 R 3,其中P 1和P 2表示磷 原子; R 1表示通过两个叔碳原子与磷原子连接的任选取代的二价有机基团; R 2和R 3独立地表示含有每个基团与磷原子连接的叔碳原子的1至20个原子的一价基团,或者R 2和R 3共同形成任选的 含有至少2个叔碳原子的取代的二价有机基团,该基团通过其与磷原子连接; 并且R表示包含3个原子的二价桥连基团,P 1与P 2线性连接;和(c)阴离子源。
    • 2. 发明申请
    • PROCESS FOR PRODUCING OLEFINS
    • 生产油脂的方法
    • WO2008034894A1
    • 2008-03-27
    • PCT/EP2007/060030
    • 2007-09-21
    • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.DRENT, EitVAN GINKEL, RoelofJAGER, Willem Wabe
    • DRENT, EitVAN GINKEL, RoelofJAGER, Willem Wabe
    • C07C1/24C07C29/16B01J31/24
    • C07F9/65683B01J31/2419B01J2231/321B01J2531/845C07C1/24C07C29/16C07C11/02C07C31/125
    • Process for converting an olefin having x carbon atoms into an olefin having x+1 carbon atoms wherein the process comprises the steps of : (i) reacting an olefin having x carbon atoms with carbon monoxide and hydrogen in the presence of a hydrof ormylation catalyst to produce an alcohol having x+1 carbon atoms, and (ii) dehydrating the alcohol produced in step (i) in the presence of a dehydration catalyst to produce an olefin having x+1 carbon atoms characterised in that the the hydrof ormylation catalyst used in step (i) is based on: (a) a source of cobalt, and (b) a ligand selected from: (i) a ligand of general formula (I) : R 1 R 2 P-R 3 (I) wherein R 1 and R 2 are independently a hydrocarbyl group with C 1 -C 12 carbon atoms or together with the phosphorus atom P represent an optionally substituted cyclic group with at least 5 ring atoms; and wherein R 3 is a monovalent radical of general formula: -R 4 -C (O) NR 5 R 6 (II) wherein R 4 is an alkylene group and R 5 and R 6 independently represent an alkyl, cycloalkyl, aryl, alkaryl or heteroaryl group; (ii) a ligand of general formula (III) : R 1 R 2 P-R 4 -C(O)N(R 7 ) -R 8 -N(R 7 ) C(O) -R 4 PR 1 R 2 (III) wherein R 1 , R 2 and R 4 are as defined above, wherein R 7 independently represents an alkyl, cycloalkyl, aryl, alkaryl or heteroaryl group, and wherein R 8 represents an alkylene, cycloalkylene, arylene or alkarylene group; and (iii) a ligand of general formula (IV) : R 1 R 2 P-R 4 -C (O) N- (R 8 ) 2 -NC (O) -R 4 -PR 1 R 2 (IV) wherein R 1 , R 2 , R 4 and R 8 are as defined above; and mixtures thereof.
    • 将具有x个碳原子的烯烃转化为具有x + 1个碳原子的烯烃的方法,其中该方法包括以下步骤:(i)在氢化甲酰化催化剂存在下使具有x个碳原子的烯烃与一氧化碳和氢气反应, 产生具有x + 1个碳原子的醇,和(ii)在脱水催化剂存在下使步骤(i)中产生的醇脱水以产生具有x + 1个碳原子的烯烃,其特征在于所用的氢化甲酰化催化剂 步骤(i)基于:(a)钴源,和(b)选自以下的配体:(i)通式(I)的配体:R 1, 其中R 1和R 2独立地是具有C 1〜C的烃基,其中R 1,R 2, C 1 -C 12碳原子或与磷原子一起P表示具有至少5个环原子的任选取代的环状基团; 并且其中R 3是通式的一价基团:-R 4 -S(O)NR 5 R 6, 其中R 4为亚烷基且R 5和R 6独立地代表烷基,环烷基,芳基,烷芳基或 杂芳基; (ii)通式(III)的配体:R 1,R 2,R 4,C(O)N(R) 7(R 7)-R 8 - (R 7)C(O)-R 4 PR 1, 其中R 1,R 2和R 4如上所定义,其中R 1,R 2,R 2, R 7独立地表示烷基,环烷基,芳基,烷芳基或杂芳基,其中R 8表示亚烷基,亚环烷基,亚芳基或亚烷基; 和(iii)通式(IV)的配体:R 1,R 2,R 4,-C(O) SUP> 8)2 -NO(O)-R 4 - PR 1 R 2 - (Ⅳ)其中R 1,R 2,R 4和R 8如上所定义; 及其混合物。
    • 5. 发明申请
    • PROCESS FOR THE CARBONYLATION OF A CONJUGATED DIENE
    • 联合二烯的羰基化方法
    • WO2004103948A1
    • 2004-12-02
    • PCT/EP2004/050794
    • 2004-05-13
    • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.DRENT, EitERNST, RenéJAGER, Willem, Wabe
    • DRENT, EitERNST, RenéJAGER, Willem, Wabe
    • C07C67/38
    • B01J31/04B01J31/24B01J2231/321B01J2531/824C07C67/38C07C231/12C07F9/5027C07F9/657163C07C69/24C07C233/09
    • A process for the carbonylation of a conjugated diene, comprising reacting the conjugated diene with carbon monoxide and a co-reactant having a mobile hydrogen atom in the presence of a catalyst system including: (a) a source of palladium; and (b) a bidentate diphosphine ligand of formula (II): R 1 R 2 > p 1 R 3 m -R-R 4 n -p 2 5 R 6 wherein p 1 and p 2 represent phosphorus atoms; R 1 , R 2 , R 5 , and R 6 independently represent the same or different optionally substituted organic radical containing a tertiary carbon atom through which each radical is linked to the phosphorus atom; R 3 and R 4 independently represent the same or different optionally substituted methylene groups; R represents an organic group comprising the bivalent bridging group C 1 -C 2 through which R is connected to R 3 and R 4 ; m and n independently represent a natural number in the range of from 0 to 4, wherein the rotation about the bond between the carbon atoms C 1 and C 2 of the bridging group is restricted a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C 1 , C 2 and the atom directly bonded to C 1 in the direction of p 1 , and the plane occupied by the three atom sequence C 1 , C 2 and the atom directly bonded to C 2 in the direction of p 2 , is in the range of from 0 to 120°; and (c) a source of an anion.
    • 一种共轭二烯的羰基化方法,包括在催化剂体系存在下使共轭二烯与一氧化碳和具有可移动氢原子的共反应物反应,包括:(a)钯源; 和(b)式(II)的二齿二膦配体:R 1 R 2 p 1 R 3 mRR 4 np 2 R 5 R 6其中p &lt; 1&gt;和p&lt; 2&gt;表示磷原子。 R 1,R 2,R 5和R 6独立地表示相同或不同的含有叔碳原子的任选取代的有机基团,每个基团通过其与磷原子连接; R 3和R 4独立地表示相同或不同的任选取代的亚甲基; R表示包含与R 3和R 4连接的二价桥连基团C 1 -C 2的有机基团; m和n独立地表示0至4范围内的自然数,其中桥接基团的碳原子C 1和C 2之间的键的旋转限制在0的范围内的温度 ℃至250℃,并且其中由C 1,C 2构成的三原子序列占据的平面与在p 1方向上直接键合到C 1的原子之间的二面角,以及 由3原子序列C 1,C 2和直接键合到C 2的原子在p <2>的方向上占据的平面在0至120°的范围内; 和(c)阴离子源。
    • 9. 发明申请
    • PROCESS FOR THE CARBONYLATION OF A CONJUGATED DIENE
    • 联合二烯的羰基化方法
    • WO2006084891A1
    • 2006-08-17
    • PCT/EP2006/050825
    • 2006-02-10
    • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.DRENT, EitERNST, ReneJAGER, Willem, WabeKROM, Cornelia, AlidaNISBET, Timothy, Michael
    • DRENT, EitERNST, ReneJAGER, Willem, WabeKROM, Cornelia, AlidaNISBET, Timothy, Michael
    • C07C51/14C07C57/03C07C57/13
    • C07C51/14C07C57/03
    • A process for the carbonylation of a conjugated diene to an ethylenically unsaturated acid, comprising the steps of (a) contacting a conjugated diene with carbon monoxide and water in the presence of a catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand, to obtain a mixture comprising an ethylenically unsaturated acid and a reversible diene adduct comprising alkenyl ester of the conjugated diene with the ethylenically unsaturated acid; (b) separating the obtained reaction mixture into a gaseous stream comprising unreacted conjugated diene and carbon monoxide, a first liquid product stream comprising at least part of the ethylenically unsaturated acid and the reversible diene adducts, and a second liquid stream comprising the catalyst system in admixture with the ethylenically unsaturated acid; (c) separating the first liquid product stream obtained in step (b) into a stream comprising the ethylenically unsaturated acid and a stream comprising the reversible diene adducts; and (d) recycling the stream comprising the reversible diene adducts to step (a) , or converting the reversible diene adducts back to the conjugated diene and the ethylenically unsaturated acid and recycling the thus obtained conjugated diene to step (a).
    • 一种将共轭二烯羰基化成烯属不饱和酸的方法,包括以下步骤:(a)在包括钯源,阴离子源和/或其盐的催化剂体系存在下使共轭二烯与一氧化碳和水接触, 二次膦配体,以获得包含烯键式不饱和酸和包含共轭二烯烯基酯与烯键式不饱和酸的可逆二烯加合物的混合物; (b)将获得的反应混合物分离成包含未反应的共轭二烯和一氧化碳的气流,包含至少部分烯键式不饱和酸和可逆二烯加合物的第一液体产物流和包含催化剂体系的第二液体流 与烯属不饱和酸的混合物; (c)将步骤(b)中获得的第一液体产物流分离成包含烯属不饱和酸的物流和包含可逆二烯加成物的物流; 和(d)将包含可逆二烯加合物的料流再循环到步骤(a)中,或将可逆二烯加合物转化回共轭二烯和烯属不饱和酸,并将由此得到的共轭二烯再循环到步骤(a)。
    • 10. 发明申请
    • PROCESS FOR THE CARBONYLATION OF A CONJUGATED DIENE TO A DICARBOXYLIC ACID
    • 将二羧酸与二羧酸共轭化合物的方法
    • WO2006084893A1
    • 2006-08-17
    • PCT/EP2006/050829
    • 2006-02-10
    • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.DRENT, EitERNST, ReneJAGER, Willem, WabeKROM, Cornelia, AlidaNISBET, Timothy, Michael
    • DRENT, EitERNST, ReneJAGER, Willem, WabeKROM, Cornelia, AlidaNISBET, Timothy, Michael
    • C07C51/14C07C55/14
    • C07C51/14C07C55/14
    • A process for the carbonylation of a conjugated diene to a dicarboxylic acid, comprising the steps of (a) contacting a conjugated diene with carbon monoxide and water in the presence of a catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand, to obtain a mixture comprising an ethylenically unsaturated acid and reversible diene adducts; (b) separating the obtained reaction mixture into a gaseous stream comprising unreacted conjugated diene and carbon monoxide, a first normally liquid stream comprising at least part of the ethylenically unsaturated acid and the reversible diene adducts, and a second normally liquid stream comprising the catalyst system in admixture with the ethylenically unsaturated acid; (c) recycling the second liquid stream obtained in step (b) to step (a) ; (d) separating the first liquid product stream obtained in step (b) into a stream comprising the ethylenically unsaturated acid and a stream comprising the reversible diene adducts; and (e) contacting the stream comprising the ethylenically unsaturated acid obtained in step (d) with carbon monoxide and water in the presence of a second catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand.
    • 一种将共轭二烯羰基化成二羧酸的方法,包括以下步骤:(a)在包括钯源,阴离子源和阴离子的催化剂体系的存在下使共轭二烯与一氧化碳和水接触 二次膦配体,以获得包含烯属不饱和酸和可逆二烯加成物的混合物; (b)将获得的反应混合物分离成包含未反应的共轭二烯和一氧化碳的气流,包含至少部分烯属不饱和酸和可逆二烯加合物的第一常规液体流,以及包含催化剂体系的第二常规液流 与烯属不饱和酸的混合物; (c)将步骤(b)中获得的第二液体流循环到步骤(a); (d)将步骤(b)中获得的第一液体产物流分离成包含烯属不饱和酸的物流和包含可逆二烯加成物的物流; 和(e)在包括钯源,阴离子源和二齿膦配体的第二催化剂体系的存在下,将包含步骤(d)中获得的烯属不饱和酸的物流与一氧化碳和水接触。