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    • 6. 发明授权
    • Method for producing dialkylphosphinic acids and esters and salts thereof by means of acrylnitriles and use thereof
    • 通过丙烯腈生产二烷基次膦酸及其酯及其盐的方法及其用途
    • US08735477B2
    • 2014-05-27
    • US13127069
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313
    • C08K5/5313C07F9/301C07F9/3211C07F9/4816C07F9/4866C09K21/12
    • The invention relates to a method for producing mono-carboxyfunctionalized dialkylphosphinic acids and esters and salts thereof, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (H) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with compounds of formula (V) to yield mono-functionalized dialkylphosphinic acid derivatives (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivatives (VI) are reacted to yield a mono-carboxyfunctionalized diakylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R1, R2, R3, R4, R5, R6, R7 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl and X and Y are the same or different and stand independently of each for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalyst A is formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides and/or peroxo compounds and/or azo compounds and/or alkali metals and/or alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates, and catalyst C is an acid or a base.
    • 本发明涉及一种用于制备单羧基官能化二烷基次膦酸及其酯和盐的方法,其特征在于a)将次膦酸源(I)与烯烃(Ⅳ)反应,得到烷基膦酸,盐或酯(H) 在催化剂A存在下,将由此得到的烷基膦酸,其盐或酯(II)与式(Ⅴ)化合物反应得到单官能化二烷基次膦酸衍生物(Ⅵ),在催化剂存在下 B和c)由此得到的单官能化二烷基次膦酸衍生物(Ⅵ)在催化剂C存在下反应得到单羧基官能化二烷基次膦酸衍生物(Ⅲ),其中R1,R2,R3,R4,R5, 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,X和Y相同或不同,R 6,R 7相同或不同,彼此独立地相互独立地表示 并独立于H,C1-C18烷基 1,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li ,Na,K和/或质子化的氮碱,并且催化剂A由过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物和至少一种配体组成的催化剂体系形成, 催化剂B由形成过氧化物和/或过氧化合物和/或偶氮化合物和/或碱金属和/或碱土金属,碱金属氢化物,碱土金属氢化物和/或碱金属醇盐和碱土金属醇盐的化合物和催化剂C形成 是酸或碱。
    • 7. 发明授权
    • Method for producing monoamino-functionalised dialkylphosphinite acids esters and salts and use thereof
    • 用于制备单氨基官能化二烷基磷酸酯酯和盐的方法及其用途
    • US08604232B2
    • 2013-12-10
    • US13127105
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C07F9/02C07F9/28
    • C09K21/12C07F9/301C07F9/3211C08K5/5313
    • The invention relates to method for producing mono amino-functionalised dialkylphosphonic acids esters and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, the salt or ester thereof (II), b) the alkylphosphonous acid, the salt or ester thereof (II) produced above is reacted with an allylamine of formula (V) in the presence of a catalyst B to give mono amino-functionalised dialkylphosphinic acid derivatives (III) where, R1, R2, R3, R4, R5, R6, R7, R8, R9 independently=amongst others, H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl and X═H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogen base and Y=a mineral acid, a carboxylic acid, a Lewis acid or organic acid, where n=a whole or fractional number from 0 to 4, catalyst A is a transition metal and/or transition metal compound and/or catalyst system comprising a transition metal and/or a transition metal compound and at least one ligand and catalyst B is compounds forming peroxides and/or peroxide compounds and/or azo compounds.
    • 本发明涉及用于制备单氨基官能化二烷基膦酸酯和盐的方法,其特征在于a)在催化剂A存在下,使次膦酸源(I)与烯烃(Ⅳ)反应得到烷基亚磷酸, 其盐或酯(II),b)在催化剂B的存在下,将上述制备的烷基亚膦酸,其盐或酯(II)与式(V)的烯丙胺反应,得到单氨基官能化的二烷基次膦酸衍生物 (III)其中,R1,R2,R3,R4,R5,R6,R7,R8,R9独立地为H,C1-C18烷基,C6-C18芳基,C6-C18芳烷基,C6-C18烷基芳基和X = H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn ,Cu,Ni,Li,Na,K和/或质子化的氮碱,Y =无机酸,羧酸,路易斯酸或有机酸,其中n = 0至4的整数或分数,催化剂A 是过渡金属和/或运输 包含过渡金属和/或过渡金属化合物和至少一种配体和催化剂B的金属化合物和/或催化剂体系是形成过氧化物和/或过氧化物和/或偶氮化合物的化合物。
    • 8. 发明授权
    • Method for producing mono-hydroxyfunctionalized dialkylphosphinic acids and esters and salts thereof by means of acroleins and use thereof
    • 通过丙烯醛及其用途制备单羟基官能化二烷基次膦酸及其酯和盐的方法
    • US08604108B2
    • 2013-12-10
    • US13121903
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313
    • C09K21/12C07F9/301C07F9/3211C07F9/4816C07F9/4866C08K5/5313
    • The invention relates to a method for producing mono-hydroxyfunctionalized dialkylphosphinic acids and esters and salts thereof by means of acroleins, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with compounds of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivatives (IV) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivatives (VI) are reacted to yield a mono-hydroxyfunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R1, R2, R3, R4, R5, R6, R7 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C6-C18 aralkyl, C6-C18 alkylaryl, and X stands for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalyst A and C are formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides and/or peroxo compounds and/or azo compounds and/or alkali metals and/or alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates.
    • 本发明涉及通过丙烯醛生产单羟基官能化二烷基次膦酸及其酯和盐的方法,其特征在于a)将次膦酸源(I)与烯烃(Ⅳ)反应,得到烷基膦酸盐或盐 酯(II),b)由此获得的烷基膦酸,其盐或酯(II)与式(V)化合物反应,得到单官能化二烷基次膦酸衍生物(IV),其中 催化剂B的存在和c)如此获得的单官能化二烷基次膦酸衍生物(VI)在催化剂C存在下反应得到单羟基官能化二烷基次膦酸衍生物(III),其中R1,R2,R3 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18 -C 18芳烷基,C 6 -C 18烷芳基和C 6 -C 18烷基芳基,R 4,R 5,R 6,R 7相同或不同, X代表H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基 k,C6-C18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/或质子化氮 碱,催化剂A和C由过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物和至少一种配体组成的催化剂体系形成,催化剂B由形成 过氧化物和/或过氧化合物和/或偶氮化合物和/或碱金属和/或碱土金属,碱金属氢化物,碱土金属氢化物和/或碱金属醇盐和碱土金属盐。
    • 9. 发明申请
    • Process for Preparing Mono-Carboxy-Functionalized Dialkylphosphinic Acids, Esters and Salts by Means of Alkylene Oxides and Use Thereof
    • 通过氧化亚烷基制备单羧基官能化二烷基膦酸,酯和盐的方法及用途
    • US20110245385A1
    • 2011-10-06
    • US13140126
    • 2009-10-06
    • Michael HillMathias DietzWerner KrauseMartin Sicken
    • Michael HillMathias DietzWerner KrauseMartin Sicken
    • C08K5/5313C07F9/30C07F9/32
    • C09K21/12C07F9/301C07F9/3211C08K5/5313
    • The invention relates to a process for preparing mono-carboxy-functionalized dialkylphosphinic acids, dialkylphosphinic esters and dialkylphosphinic salts by means of alkylene oxides, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to form an alkylphosphonous acid, its salt or ester (II), b) the resultant alkylphosphonous acid, its salt or ester (II) is reacted with alkylene oxides of the formula (V) in the presence of a catalyst B, to give a mono-functionalized dialkylphosphinic acid derivative (VI), and c) the resultant mono-functionalized dialkylphosphinic acid derivative (VI) is reacted in the presence a catalyst C to give the mono-carboxy-functionalized dialkylphosphinic acid derivative (III), where R1,R2,R3,R4,R5, and R6 are identical or different and independently of one another are inter alia H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl or C6-C18-alkylaryl, and X and Y are identical or different and independently of one another are H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogen base, and the catalysts A and C are transition metals and/or transition-metal compounds and/or catalyst systems which are composed of a transition metal and/or a transition-metal compound and at least one ligand, and the catalyst B is a Lewis acid.
    • 本发明涉及一种通过烯化氧制备单羧基官能化二烷基次膦酸,二烷基次膦酸酯和二烷基次膦酸盐的方法,其特征在于a)一种次膦酸源(I)与烯烃(Ⅳ)在 形成烷基亚磷酸,其盐或酯(II)的催化剂A,b)在催化剂B存在下,使得到的烷基亚磷酸,其盐或酯(II)与式(V)的烯化氧反应, 得到单官能化二烷基次膦酸衍生物(Ⅵ),和c)所得到的单官能化二烷基次膦酸衍生物(Ⅵ)在催化剂C存在下反应,得到单羧基官能化二烷基次膦酸衍生物(Ⅲ) 其中R 1,R 2,R 3,R 4,R 5和R 6相同或不同并且彼此独立地尤其是H,C 1 -C 18 - 烷基,C 6 -C 18 - 芳基,C 6 -C 18 - 芳烷基或C 6 -C 18烷基芳基 ,X和Y相同或不同,独立 一个是H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn ,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/或质子化的氮碱,催化剂A和C是组成的过渡金属和/或过渡金属化合物和/或催化剂体系 的过渡金属和/或过渡金属化合物和至少一种配体,催化剂B是路易斯酸。
    • 10. 发明申请
    • Method for Producing Mono-Hydroxyfunctionalized Dialkylphosphinic Acids and Esters and Salts Thereof By Means of Acroleins and Use Thereof
    • 通过丙烯醛及其用途生产单羟基官能化二烷基次膦酸及其酯及其盐的方法
    • US20110224339A1
    • 2011-09-15
    • US13121903
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313C07F9/30C07F9/32
    • C09K21/12C07F9/301C07F9/3211C07F9/4816C07F9/4866C08K5/5313
    • The invention relates to a method for producing mono-hydroxyfunctionalized dialkylphosphinic acids and esters and salts thereof by means of acroleins, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with compounds of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivatives (IV) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivatives (VI) are reacted to yield a mono-hydroxyfunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R1, R2, R3, R4, R5, R6, R7 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C6-C18 aralkyl, C6-C18 alkylaryl, and X stands for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalyst A and C are formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides and/or peroxo compounds and/or azo compounds and/or alkali metals and/or alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates.
    • 本发明涉及通过丙烯醛生产单羟基官能化二烷基次膦酸及其酯和盐的方法,其特征在于a)将次膦酸源(I)与烯烃(Ⅳ)反应,得到烷基膦酸盐或盐 酯(II),b)由此获得的烷基膦酸,其盐或酯(II)与式(V)化合物反应,得到单官能化二烷基次膦酸衍生物(IV),其中 催化剂B的存在和c)如此获得的单官能化二烷基次膦酸衍生物(VI)在催化剂C存在下反应得到单羟基官能化二烷基次膦酸衍生物(III),其中R1,R2,R3 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18 -C 18芳烷基,C 6 -C 18烷芳基和C 6 -C 18烷基芳基,R 4,R 5,R 6,R 7相同或不同, X代表H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基 k,C6-C18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/或质子化氮 碱,催化剂A和C由过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物和至少一种配体组成的催化剂体系形成,催化剂B由形成 过氧化物和/或过氧化合物和/或偶氮化合物和/或碱金属和/或碱土金属,碱金属氢化物,碱土金属氢化物和/或碱金属醇盐和碱土金属盐。