Acyl- and bisacylphosphine derivatives

A process for the preparation of an acyl- or bisacylphosphine derivative of the formula (I)

• where
• R1, R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R2 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
• Y is O, S, NR3, N—OR3or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• FG is a leaving group having the structure —F, —Cl, —I, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)Cl, —O(SO2)R5, —O(CO)Cl, —O(NO)OR5 or, in the case where Z≠S, —SR5,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups,
• from a substance of the formula (II)
• where
• X is hydrogen or a cation,
• which comprises reacting substance (II) with at least one agent which converts the —OX group into an —FG group.

A method of photoinitiation comprising photoinitiating a potopolymerizable compositions with an acyl- or bisacylphosphine derivative of the formula (I)

• where
• R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
• R2, R5 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R2 is furthermore C1-C18-alkoxy is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocylic radicals, or is R1—(C═Y)—,
• Y is O, S, NR3, N—OR3 or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.

A method of photoinitiation comprising photoinitiating a potopolymerizable compositions with an acyl- or bisacylphosphine derivative of the formula (I)

• where
• R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
• R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
• Y is O, S, NR3, N—OR3 or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, and
• FG is defined as follows:
• FG —Br, —(NR3)—NR4R9, —(NR3)—OR9 or —SR3 (for Z=S), and
• R9 is hydrogen or C1- to C4-alkyl.

A photoinitiator mixture comprising at least one acyl- or bisacyiphosphine derivative of the formula (I)

• where
• R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
• R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
• Y is O, S, NR3, N—OR3 or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.

A radiation-curable composition comprising at least one acyl- or bisacyiphosphine derivative of the formula (I)

• where
• R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
• R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
• Y is O, S, NR3, N—OR3 or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.

A radiation-curable composition obtainable by reaction of at least one acyl- or bisacylphosphine derivative of the formula (I)

• where
• R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
• R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
• Y is O, S, NR3, N—OR3 or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups,
• with a compound containing free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups.

An acyl- or bisacyiphosphine derivative of the formula (I)

• where
• R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
• R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• Y is O, S, NR3, N—OR3 or N—NR3R4,
• Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
• R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
• R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
• R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
• R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, and
• R2 is ethoxy.