US 9,310,677 B2 · Polymerizable composition comprising an oxime sulfonate as thermal curing agent

Abstract

The present invention relates to a polymerizable composition comprising at least one ethylenically unsaturated, polymerizable compound and at least one oxime sulfonate compound of the formula (I) QAaBbCc where a is 0, 1, 2, 3, 4 or 6, b is 0, 1, 2, 3, 4 or 6, and c is 0, 1, 2, 3, 4 or 6, where the sum of a+b+c is 1, 2, 3, 4 or 6 where (A) is a group (B) is a group (C) is a group where # denotes the point of attachment to Q; X is S or NR14 and Q, R1, R2, R3 and R14 are as defined in claim 1 and in the description. The present invention also relates to the use of the this composition, to novel oxime sulfonates and the use of the oxime sulfonates as thermal curing promoter.

A polymerizable composition comprising

(a) an oxime sulfonate compound of formula I
QAaBbCc (I)
where
a is 0, 1, 2, 3, 4 or 6;
b is 0, 1, 2, 3, 4 or 6;
and
c is 0, 1, 2, 3, 4 or 6;
where the sum of a+b+c is 1, 2, 3, 4 or 6
where
A is a group
B is a group
C is a group
where
# denotes a point of attachment to Q;
X is S, SO2 or NR14;
Q if a is 1, b is 0 and c is 0,
is a radical R1;
or
Q if a is 2, b is 0 and c is 0
is a divalent linker selected from the group consisting of
L-C1-C30-alkylene-L,
L-C2-C30-alkenylene-L, L-C3-C16-cycloalkylene-L, L-heterocycloalkylene-L, L-C6-C20-arylene-L, L-heteroarylene-L, L-C1-C30-alkylene-L2-L,
L-C2-C30-alkenylene-L2-L,
L-C3-C16-cycloalkylene-L1-C3-C16-cycloalkylene-L,
L-C3-C16-cycloalkylene-L1-heterocycloalkylene-L,
L-C3-C16-cycloalkylene-L1-C6-C20-arylene-L
L-C3-C16-cycloalkylene-L1-heteroarylene-L,
L-C6-C20-arylene-L1-C6-C20-arylene-L,
L-C6-C20-arylene-L1-heteroarylene-L,
L-heteroarylene-L1-heteroarylene-L,
L-C3-C16-cycloalkylene-L1-L3-L1-C3-C16-cycloalkylene-L,
L-C3-C16-cycloalkylene-L1-L3-L1-heterocycloalkylene-L,
L-C3-C16-cycloalkylene-L1-L3-L1-C6-C20-arylene-L
L-C3-C16-cycloalkylene-L1-L3-L1-heteroarylene-L,
L-C6-C20-arylene-L1-L3-L1-C6-C20-arylene-L,
L-C6-C20-arylene-L1-L3-L1-heteroarylene-L, and
L-heteroarylene-L1-L3-L1-heteroarylene-L,
where each alkylene and each alkenylene may be interrupted by one or more identical or different nonadjacent groups L4, and may carry one or more identical or different radicals RQa;
where each cycloalkylene and each heterocycloalkylene may be interrupted by one or more CO groups and may carry one or more identical or different radicals RQb,
where each arylene and each heteroarylene may carry one or more identical or different radicals RQc,
where
each L is independently selected from the group consisting of a single bond,
C(S)O, and C(S)NR12;
each L1 is independently selected from the group consisting of a single bond, O, S, NR14, CO, OC(O), C(O)O, C(S)O, OC(S), C(O)NR10, NR10C(O), C(S)NR12, NR12C(S) and NR10SO2;
L2 is C3-C20-cycloalkylene, heterocycloalkylene, C6-C20-arylene or heteroarylene,
where cycloalkylene and heterocycloalkylene may be interrupted by one or more CO and may be substituted by one or more identical or different radicals RL2b,
where arylene and heteroarylene may be substituted by one or more identical or different radicals RL2c, where
each RL2b is independently selected from the group consisting of C1-C12-alkyl, C1-C12-haloalkyl, F, Cl, Br, I, CN, NO2, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11 and phenyl;
RL2c has one of the meanings indicated for RL2b;
L3 is selected from the group consisting of C1-C30-alkylene, C2-C30-alkenylene, C3-C20-cycloalkylene, heterocycloalkylene, C6-C20-arylene and heteroarylene,
where alkylene and alkenylene may be interrupted by one or more identical or different O, S, NR6 or CO and may carry one or more identical or different radicals RL3a,
where cycloalkylene and heterocycloalkylene may be interrupted by one or more CO, and may be substituted by one or more identical or different radicals RL3b,
where arylene and heterarylene may be substituted by one or more identical or different radicals RL3c, where
each RL3a is independently selected from the group consisting of F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, C3-C10-cycloalkyl, heterocyclyl, heteroaryl, phenyl and naphthyl, where the five last-mentioned radicals may be substituted by one or more identical or different radicals R3aa, where
R3aa has one of the meanings indicated for RL2b;
RL3b has one of the meanings indicated for RL2b;
RL3c has one of the meanings indicated for RL2c;
each L4 is independently selected from the group consisting of O, S, NR6, CO, C(O)O, OC(O), C(O)NR10, NR10C(O), C(S)NR12, NR12C(S), NR10SO2, C3-C20-cycloalkylene, heterocycloalkylene, C6-C20-arylene, and heteroarylene, where cycloalkylene and heterocycloalkylene may be interrupted by one or more CO, and may be substituted by one or more identical or different radicals RL4b,
where arylene and heteroarylene may be substituted by one or more identical or different radicals RL4c, where
RL4b has one of the meanings indicated for RL2b;
and
RL4c has one of the meanings indicated for RL2c;
each RQa is independently selected from the group consisting of F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, C3-C10-cycloalkyl which may be interrupted by one or two CO groups,
heterocyclyl which may be interrupted by one or two CO groups,
heteroaryl, phenyl and naphthyl, where the five last-mentioned radicals may be substituted by one or more identical or different radicals RQaa, where
each RQaa is independently selected from the group consisting of C1-C12-alkyl, C1-C12-haloalkyl, F, Cl, Br, I, CN, NO2, SR4, OR5, NR6R7, COR8, COOR9 and CONR10R11;
each RQb is independently selected from the group consisting of F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, C1-C12-alkyl, C1-C12-haloalkyl, heteroaryl, phenyl and naphthyl, where the three last-mentioned radicals may be substituted by one or more identical or different radicals
RQba, where
RQba has one of the meanings indicated for RQaa;
each RQc is independently selected from the group consisting of C1-C12-alkyl, C1-C12-haloalkyl, F, Cl, Br, I, CN, NO2, SR4, OR5, NR6R7, COR5, COOR5, CONR10R11, phenyl, C3-C10-cycloalkyl and heterocyclyl, where in the two last-mentioned radicals one or two CH2 groups may be replaced by CO;
Q if b is 2, a is 0 and c is 0,
is a divalent linker, which is selected from the group consisting of
L5-C1-C30-alkylene-L5, L5-C2-C30-alkenylene-L5, L5-C3-C16-cycloalkylene-L5, L5-heterocycloalkylene-L5, L5-C6-C20-arylene-L5, L5-heteroarylene-L5,
L5-C1-C30-alkylene-L6-L5, L5-C2-C30-alkenylene-L6-L5,
L5-C3-C16-cycloalkylene-L7-C3-C16-cycloalkylene-L5,
L5-C3-C16-cycloalkylene-L7-heterocycloalkylene-L5,
L5-C3-C16-cycloalkylene-L7-C6-C20-arylene-L5,
L5-C3-C16-cycloalkylene-L7-heteroarylene-L5,
L5-C6-C20-arylene-L7-C6-C20-arylene-L5,
L5-C6-C20-arylene-L7-heteroarylene-L5,
L5-heteroarylene-L7-heteroarylene-L5,
L5-C3-C16-cycloalkylene-L7-L8-L7-C3-C16-cycloalkylene-L5,
L5-C3-C16-cycloalkylene-L7-L8-L7-heterocycloalkylene-L5,
L5-C3-C16-cycloalkylene-L7-L8-L7-C6-C20-arylene-L5,
L5-C3-C16-cycloalkylene-L7-L8-L7-heteroarylene-L5,
L5-C6-C20-arylene-L7-L8-L7-C6-C20-arylene-L5,
L5-C6-C20-arylene-L7-L8-L7-heteroarylene-L5,
L5-heteroarylene-L7-L8-L7-heteroarylene-L5,
where each alkylene and each alkenylene may be interrupted by one or more identical or different groups L9, and may carry one or more identical or different radicals RQa;
where each cycloalkylene and each heterocycloalkylene may be interrupted by one or more CO groups and may carry one or more identical or different radicals RQb,
where each arylene and each heteroarylene may carry one or more identical or different radicals RQc, where
each L5 independently is a single bond, S, O, NR6, CO, C(O)O, OC(O), NR10CO or CONR10;
L6 has one of the meanings indicated for L2;
L7 has one of the meanings indicated for L1;
L8 has one of the meanings indicated for L3;
L9 has one of the meanings indicated for L4;
or
Q if c is 2, a is 0 and b is 0,
is a divalent linker selected from the group consisting of C1-C30-alkylene, C2-C30-alkenylene, C3-C16-cycloalkylene, heterocycloalkylene, C6-C20-arylene, heteroarylene, C1-C30-alkylene-L10, C2-C30-alkenylene-L10,
C3-C16-cycloalkylene-L11-C3-C16-cycloalkylene,
C3-C16-cycloalkylene-L11-heterocycloalkylene,
C3-C16-cycloalkylene-L11-C6-C20-arylene,
C3-C16-cycloalkylene-L11-heteroarylene,
C6-C20-arylene-L11-C6-C20-arylene,
C6-C20-arylene-L11-heteroarylene, heteroarylene-L11-heteroarylene,
C3-C16-cycloalkylene-L11-L12-L11-C3-C16-cycloalkylene,
C3-C16-cycloalkylene-L11-L12-L11-C6-C20-arylene,
C3-C16-cycloalkylene-L11-L12-L11-heterocycloalkylene,
C3-C16-cycloalkylene-L11-L12-L11-heteroarylene,
C6-C20-arylene-L11-L12-L11-C6-C20-arylene,
C6-C20-arylene-L11-L12-L11-heteroarylene, and
heteroarylene-L11-L12-L11-heteroarylene,
where each alkylene and each alkenylene may be interrupted by one or more identical or different groups L13, and may carry one or more identical or different radicals RQa;
where each cycloalkylene and each heterocycloalkylene may be interrupted by one or more CO groups and may carry one or more identical or different radicals RQb,
where each arylene and each heteroarylene may carry one or more identical or different radicals RQc,
where
L10 has one of the meanings indicated for L2
L11 has one of the meanings indicated for L1;
L12 has one the meanings indicated for L3;
L13 has one of the meanings indicated for L4;
or
Q if two of the indices a, b or c are each 1 and the remaining index is 0, the sum of a+b+c being 2,
is a divalent linker selected from the group consisting of C1-C30-alkylene, C2-C30-alkenylene, C3-C16-cycloalkylene, heterocycloalkylene, C6-C20-arylene, heteroarylene, C1-C30-alkylene-L10, C2-C30-alkenylene-L10,
C3-C16-cycloalkylene-L11-C3-C16-cycloalkylene,
C3-C16-cycloalkylene-L11-heterocycloalkylene,
C3-C16-cycloalkylene-L11-C6-C20-arylene,
C3-C16-cycloalkylene-L11-heteroarylene,
C6-C20-arylene-L11-C6-C20-arylene,
C6-C20-arylene-L11-heteroarylene, heteroarylene-L11-heteroarylene,
C3-C16-cycloalkylene-L11-L12-L11-C3-C16-cycloalkylene,
C3-C16-cycloalkylene-L11-C6-C20-arylene,
C3-C16-cycloalkylene-L11-L12-L11-heterocycloalkylene,
C3-C16-cycloalkylene-L11-L12-L11-heteroarylene,
C6-C20-arylene-L11-L12-L11-C6-C20-arylene,
C6-C20-arylene-L11-L12-L11-heteroarylene, and
heteroarylene-L11-L12-L11-heteroarylene,
where each alkylene and each alkenylene may be interrupted by one or more identical or different groups L13, and may carry one or more identical or different radicals RQa;
where each cycloalkylene and each heterocycloalkylene may be interrupted by one or more CO groups and may carry one or more identical or different radicals RQb,
where each arylene and each heteroarylene may carry one or more identical or different radicals RQc,
where
L10 has one of the meanings indicated for L2
L11 has one of the meanings indicated for L1;
L12 has one the meanings indicated for L3;
L13 has one of the meanings indicated for L4;
or
Q if the sum of a+b+c=3,
is a trivalent linker selected from the group consisting of C1-C30-alkanetriyl, C2-C30-alkenetriyl, C3-C16-cycloalkanetriyl, heterocycloalkanetriyl, C6-C20-arenetriyl, heteroarenetriyl, C1-C30-alkanetriyl-L14-L15, C2-C30-alkenetriyl-L14-L15, C1-C30-alkylene-L14-L16, C2-C30-alkenetriyl-L14-L15, C2-C30-alkenylene-L14-L16, C3-C16-cycloalkanetriyl-L14-L11-C3-C16-cycloalkylene, C3-C16-cycloalkanetriyl-L14-L15-C6-C20-arylene, C6-C20-arenetriyl-L14-L11-C6-C20-arylene, and C6-C20-arylene-L14-L15-C3-C16-cycloalkanetriyl
where each alkanetriyl, each alkylene, each alkenetriyl and each alkenylene may be interrupted by one or more identical or different groups L17 and may carry one or more identical or different radicals RQa;
where each cycloalkanetriyl, each cycloalkylene, each heterocycloalkanetriyl and each heterocycloalkylene may be interrupted by one or more CO groups and may carry one or more identical or different radicals RQb,
where each arenetriyl, each arylene, each heteroarenetriyl and each heteroarylene may carry one or more identical or different radicals RQc, where
L14 has one of the meanings indicated for L1;
L15 has one of the meanings indicated for L2;
L16 is C6-C20-arenetriyl, heteroarenetriyl, C3-C20-cycloalkanetriyl or heterocycloalkanetriyl, where cycloalkanetriyl and heterocycloalkanetriyl may be interrupted by one or more CO, and may be substituted by one or more identical or different radicals RL16b,
where arenetriyl and heteroarenetriyl may be substituted by one or more identical or different radicals RL16c, where
RL16b has one of the meanings indicated for RL2b;
RL16c has one of the meanings indicated for RL2c;
L17 has one of the meanings indicated for L4;
Q if the sum of a+b+c=4,
is a tetravalent linker, which is a C1-C30-alkanetetrayl which may be interrupted by one or more identical or different groups L18 and may carry one or more identical or different radicals RQa;
where
L18 has one of the meanings given for L17;
Q if the sum of a+b+c=6
is a hexavalent linker which is a C2-C30-alkanehexayl which may be interrupted by one or more identical or different groups L19 and may carry one or more identical or different radicals RQa;
where
L19 has one of the meanings given for L17;
R1 is C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C20-cycloalkyl, heterocyclyl, C6-C20-aryl, heteroaryl, C1-C20-alkanoyl, C3-C20-cycloalkanoyl, C2-C20-alkenoyl, C6-C20-aroyl, CSNR12R13, C(O)OR9 or CSOR9,
where C1-C20-alkyl, C2-C20-alkenyl and C2-C20-alkynyl may be interrupted by one or more identical or different groups selected —O—, —S—, —N(R6)— and CO, and may carry one or more identical or different radicals R1a,
where C3-C20-cycloalkyl and heterocyclyl may be interrupted by one or more CO groups, and may carry one or more identical or different radicals R1b,
where C6-C20-aryl and heteroaryl may carry one or more identical or different radicals R1c,
where C1-C20-alkanoyl and C2-C20-alkenoyl may carry one or more identical or different radicals R1a,
where C3-C20-cycloalkanoyl may carry one or more identical or different radicals R1b,
where C6-C20-aroyl may carry one or more identical or different radicals R1d,
where
each R1a is independently selected from the group consisting of F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, C3-C20-cycloalkyl which may be interrupted by one or more CO groups, heterocyclyl which may be interrupted by one or more CO groups, heteroaryl and C6-C10-aryl where the four last-mentioned radicals may carry one or more identical or different radicals R1aa,
where
each R1aa is independently selected from the group consisting of C1-C12-alkyl, C1-C12-alkyl which may be interrupted by one or more groups selected from the group consisting of CO, O, S, C(O)O, OC(O), C(O)S and SC(O), C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C2-C12-alkenyl, F, Cl, Br, I, NO2, SR4, OR5, NR6R7, COR8, COOR9 and CONR10R11;
each R1b is independently selected from the group consisting of F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, C1-C12-alkyl, C1-C12-hydroxyalkyl, C1-C12-haloalkyl, C2-C12-alkenyl, heteroaryl and C6-C10-aryl where the two last-mentioned radicals may carry one or more identical or different radicals R1ba, where
R1ba has one of the meanings indicated for R1aa;
each R1C is independently selected from the group consisting of C1-C12-alkyl, C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C2-C12-alkenyl, F, Cl, Br, I, CN, NO2, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, phenyl, heteroaryl, heterocyclyl and C3-C10-cycloalkyl where the two last-mentioned radicals may be interrupted by one or two C═O groups and where phenyl, heteroaryl, heterocyclyl and C3-C10-cycloalkyl may carry one or more identical or different radicals R1ca, where
R1ca has one of the meanings indicated for R1aa;
each R1d is independently selected from the group consisting of C1-C12-alkyl, C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C2-C12-alkenyl, F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR8, COOR9, CONR16R11, C3-C20-cycloalkyl which may be interrupted by one or more CO groups, heterocyclyl which may be interrupted by one or more CO groups, C6-C10-aryl and heteroaryl where the four last-mentioned radicals may carry one or more radicals R1da, where R1da has one of the meanings indicated for R1aa;
or
if b is 2, 3, 4 or 6 and/or c is 2, 3, 4 or 6, two radicals R1 together can be a divalent bridging group having 1 to 20 atoms between the flanking bonds,
or
if b is 2, 3, 4 or 6, at least one group-X—R1 may be bound to a carbon atom or nitrogen atom of Q via a divalent bridging group having 1 to 10 atoms between the flanking bonds,
R2 is hydrogen, SR4, OR5, NR1R14, COR8, SO2R4, COOR9, CONR10R11, SO2NR10R11, PO(OR9)2, CN, C1-C16-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C20-cycloalkyl, heterocyclyl, C6-C20-aryl, heteroaryl, C1-C20-alkanoyl, C2-C20-alkenoyl, C3-C20-cycloalkanoyl, C6-C20-aroyl or a group E,
where C1-C16-alkyl, C2-C20-alkenyl and C2-C20-alkynyl may be interrupted by one or more identical or different groups selected from —O—, —S—, —N(R6)— and CO, and may carry one or more identical or different radicals R2a,
where C3-C20-cycloalkyl and heterocyclyl may be interrupted by one or more CO groups, and may carry one or more identical or different radicals R2b,
where C6-C20-aryl and heteroaryl may carry one or more identical or different radicals R2c,
where C1-C20-alkanoyl and C2-C20-alkenoyl may carry one or more identical or different radicals R2a,
where C3-C20-cycloalkanoyl may carry one or more identical or different radicals R2b,
where C6-C20-aroyl may carry one or more identical or different radicals Red,
where
each R2a is independently selected from the group consisting of F, Cl, Br, I, CN, SR4, OR5, NR6R7, COR5, COOR5, CONR10R11, C3-C20-cycloalkyl which may be interrupted by one or more CO groups, heterocyclyl which may be interrupted by one or more CO groups, heteroaryl and C6-C10-aryl where the four last-mentioned radicals may carry one or more identical or different radicals R2aa,
where
each R2aa is independently selected from the group consisting of C1-C12-alkyl, C1-C12-alkyl which may be interrupted by one or more groups selected from the group consisting of CO, O, S, C(O)O, OC(O), C(O)S and SC(O), C1-C12-haloalkyl, C1-C12-hydroxyalkyl, C2-C12-alkenyl, phenyl, F, Cl, Br, I, CN, NO2, SR4, OR5, NR6R7, COR5, COOR5 and CONR10R11;
R2b has one of the meanings indicated for R1b;
R2c has one of the meanings indicated for R1c;
R2d has one of the meanings indicated for R1d;
E is selected from the group consisting of
where
# is a point of attachment to a remainder of the molecule;
d is 0, 1, 2, 3 or 4;
e is 0, 1, or 2;
f is 0, 1, or 2;
g is 0, 1, 2, 3 or 4;
R2e has one of the meanings indicated for R2c;
R2f is C1-C20-alkylene-COO−, C2-C20-alkenylene-COO−, C2-C20-alkynylene-COO−, C3-C20-cycloalkylene-COO−, heterocycloalkylene-COO−, C6-C20-arylene-COO−, heteroarylene-COO−, alkylene-S(O2)O−, C2-C20-alkenylene-S(O2)O−, C2-C20-alkynylene-S(O2)O−, C3-C20-cycloalkylene-S(O2)O−, heterocycloalkylene-S(O2)O−, C6-C20-arylene-S(O2)O−, heteroarylene-S(O2)O−, C1-C20-alkylene-OS(O2)O−, C2-C20-alkenylene-OS(O2)O−, C2-C20-alkynylene-OS(O2)O−, C3-C20-cycloalkylene-OS(O2)O−, heterocycloalkylene-OS(O2)O−, C6-C20-arylene-OS(O2)O− or heteroarylene-OS(O2)O−
where each alkylene, each alkenyle and each alkynyle may be interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(R6)— and CO, and may carry one or more identical or different radicals R2a,
where each cycloalkylene and each heterocycloalkylene may be interrupted by one or two groups CO and may carry one or more identical or different radicals R2b,
where each arylene and each heteroarylene may carry one or more radicals R2c,
An− is Cl−, Br−, I−, SCN−, BF4−, PF6−, ClO4−, SbF6−, AsF6, C1-C20-alkyl-COO−, C1-C20-alkyl-S(O)2O−, C1-C20-alkyl-OS(O)2O−, C6-C20-aryl-COO−, C6-C20-aryl-S(O)2O− or C6-C20-aryl-OS(O)2O−, where the aryl moiety of the three last-mentioned radicals may be substituted by 1, 2, 3 or 4 identical or different
or
—R2 together with —X—R1 may be X—(C1-C20-alkylene)-Y, X—(C2-C20-alkenylene)-Y, X—(C3-C20-cycloalkylene)-Y, X-(heterocycloalkylene)-Y, X-(o-phenylene)-Y, X-(o-xylylene)-Y, X-(o-phenylene-C1-C12-alkylene)-Y, X—(C1-C12-alkylene-o-phenylene)-Y, X—(O—C1-C20-alkylene)-Y, X—(S—C1-C20-alkylene)-Y or X—(N(R6)—C1-C20-alkylene)-Y, Y being attached to the oxime carbon atom carrying X
where each alkylene and alkenylene may comprise one or more identical or different groups selected from the group consisting of O, S, NR6 and CO and may be substituted by one or more radicals R2g,
where cycloalkylene and heterocycloalkylene may be interrupted by one or more groups CO and may be optionally substituted by one or more identical or different radicals R2h,
where each phenylene and the phenylene moiety of o-xylylene may be substituted by one or more identical or different radicals R2h,
where
Y is O, S, NR14, CO, SC(O), OC(O), C(O)O, NR10C(O), C(O)NR10, NR10SO2 or a single bond;
each R2g is independently selected from the group consisting of F, Cl, Br, I, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, heteroaryl and C6-C10-aryl where the two-last-mentioned radicals may carry one or more radicals R2ga, where R2ga is phenoxy or has one of the meanings indicated for R1aa;
each R2h is independently selected from the group consisting of F, Cl, Br, I, SR4, OR5, NR6R7, COR8, COOR9, CONR10R11, C1-C12-alkyl, C1-C12-haloalkyl, heteroaryl and C6-C10-aryl where the two last-mentioned radicals may carry one or more radicals R2ha, where R2ha has one of the meanings indicated for R1aa;
or if X is S, —R2 together with —S—R1 may be S—C(S)—NR12—C(O) or S—C(═NOR15)—C(O)—NR12—C(O), where R15 is hydrogen or phenylsulfonyl where the phenyl moiety may be substituted by C1-C4-alkyl or C1-C4-alkoxy;
or
if a is 2, 3, 4 or 6 and/or c is 2, 3, 4 or 6, two radicals R2 together may be a divalent bridging group having 1 to 20 atoms between flanking bonds;
R3 is C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C20-cycloalkyl, heterocyclyl, C6-C20-aryl or heteroaryl,
where C1-C20-alkyl, C2-C20-alkenyl and C2-C20-alkynyl may be interrupted by one or more identical or different groups selected from —O—, —S—, —N(R6)— and CO, and may carry one or more identical or different radicals R3a,
where C3-C20-cycloalkyl and heterocyclyl may be interrupted by one or more CO groups, and may carry one or more identical or different radicals R3b,
where C6-C20-aryl and heteroaryl may carry one or more identical or radicals R3c,
where
R3a has one of the meanings indicated for R2a;
R3b has one of the meanings indicated for R1b;
R3c has one of the meanings indicated for R1c;
or
—X—R1 and R3 may together form a divalent radical selected from the group consisting of
X—(C1-C20-alkylene)-Z, X—(C2-C20-alkenylene)-Z, X—(C3-C20-cycloalkylene)-Z, X-(heterocycloalkylene)-Z, X-(o-phenylene)-Z,
X-(o-xylylene)-Z, X—(C0-C12-alkylene-heteroarylene-C0-C12-alkylene)-Z;
X-(o-phenylene-C1-C12-alkylene)-Z,
X—(C1-C12-alkylene-o-phenylene)-Z and S—C(S)—NR12—C(O),
where Z is attached to the sulfur atom of the sulfonate group, where each alkylene and each alkenylene may be interrupted by one or more identical or different groups selected from the group consisting of O, S, NR6 and CO, and may be substituted by one or more radicals R3g,
where each cycloalkylene and each heterocycloalkylene may be interrupted by one or more groups CO and may be optionally substituted by one or more identical or different radicals R3h,
where each phenylene and the phenylene moiety of o-xylylene may be substituted by one or more identical or different radicals R3h, where
R3g has one of the meanings indicated for R2g;
R3h has one of the meanings indicated for R2h;
and
Z is O, S, NR14, CO, OC(O), SC(O), C(O)O, NR10C(O), C(O)NR10, NR10 (SO2) or a single bond;
each R4 is independently selected from the group consisting of hydrogen, C1-C20-alkyl, C2-C12-alkenyl,
C3-C10-cycloalkyl, heterocyclyl, where the two last-mentioned radicals may be interrupted by one or more C═O groups,
C1-C20-alkyl which is interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(C1-C8-alkyl)- and CO, and may carry one or more identical or different radicals R4a,
C2-C12-alkenyl which is interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, and —N(C1-C8-alkyl)-,
—(CH2CH2O)mH, with m being 1-20,
—(CH2CH2O)n(CO)—(C1-C8-alkyl), with n being 1-20,
C2-C8-alkanoyl, C3-C6-alkenoyl, where the two-last mentioned radicals may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, OH and C1-C6-alkoxy,
benzoyl which may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, C1-C6-alkyl, OH and C1-C6-alkoxy,
phenyl and naphthyl, where the two last-mentioned radicals may be substituted by one or more identical or different radicals R4c,
wherein phenyl or naphthyl may form a 5- or 6-membered ring with the phenyl ring to which the SR4 is attached via a single bond, C1-C4-alkylene, O, S, NR6 or CO,
where
each R4a is independently selected from the group consisting of F, Cl, Br, I, C3-C10-cycloalkyl, heterocyclyl, phenyl, OH, SH, CN, C3-C6-alkenoxy, OCH2CH2CN, OCH2CH2(CO)O(C1-C8-alkyl), O(CO)—(C1-C8-alkyl), O(CO)-phenyl, (CO)OH and (CO)O(C1-C8-alkyl);
each R4c is independently selected from the group consisting of F, Cl, Br, I, C1-C12-alkyl, C1-C12-haloalkyl, C1-C12-alkoxy, phenyl-C1-C3-alkoxy, phenoxy, C1-C12-alkylsulfanyl, phenylsulfanyl, —(CO)O(C1-C8-alkyl), (CO)N(C1-C8-alkyl)2 and phenyl;
each R5 is independently selected from the group consisting of hydrogen, C1-C20-alkyl, C2-C12-alkenyl,
C3-C10-cycloalkyl, heterocyclyl, where the two last-mentioned radicals may be interrupted by one or two C═O groups,
C1-C20-alkyl which may be interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(C1-C8-alkyl)- and CO, and may carry one or more identical or different radicals R5a,
C2-C12-alkenyl which is interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, and —N(C1-C8-alkyl)-,
—(CH2CH2O)mH, with m being 1-20,
—(CH2CH2O)n(CO)—(C1-C8-alkyl), with n being 1-20,
C2-C8-alkanoyl, C3-C6-alkenoyl, where the two-last mentioned radicals may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, OH and C1-C6-alkoxy,
C2-C8-alkanoyl, which is interrupted by one or more identical or different groups selected from —O— and —S— and may be substituted by one or more identical or different radicals selected from the group consisting of hydroxyaminylene (═N—OH), F, Cl, Br, I, OH and C1-C6-alkoxy,
benzoyl which may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, C1-C6-alkyl, OH and C1-C6-alkoxy,
phenyl and naphthyl, where the two last-mentioned radicals may be substituted by one or more identical or different radicals R5C,
wherein phenyl or naphthyl may form a 5- or 6-membered ring with the phenyl ring to which the OR5 is attached via a single bond, C1-C4-alkylene, O, S, NR6 or CO,
where
R5a has one of the meanings indicated for R4a;
R5c has one of the meanings indicated for R4c;
R6, R10and R12 are each independently selected from the group consisting of hydrogen,
OR5, C2-C12-alkenyl,
C3-C10-cycloalkyl, heterocyclyl, where the two last-mentioned radicals may be interrupted by one or two C═O groups,
C1-C20-alkyl which may be interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(C1-C8-alkyl)- and CO, and may carry one or more identical or different radicals R6a,
C2-C12-alkenyl which is interrupted by one or more identical or different groups selected from —O—, —S—, and —N(C1-C8-alkyl)-,
—(CH2CH2O)oH, with o being 1-20,
—(CH2CH2O)p(CO)—(C1-C8-alkyl), with p being 1-20,
C2-C8-alkanoyl, C3-C6-alkenoyl, where the two-last mentioned radicals may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, OH and C1-C6-alkoxy,
benzoyl which may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, C1-C6-alkyl, —OH and C1-C6-alkoxy,
phenyl and naphthyl, where the two last-mentioned radicals may be substituted by one or more identical or different radicals R6c,
where
R6a has one of the meanings indicated for R4a;
R6c has one of the meanings indicated for R4c;
or
two radicals R6 together may be a divalent bridging group having 1 to 20 atoms between flanking bonds;
or
two radicals R10 together may be a divalent bridging group having 1 to 20 atoms between flanking bonds;
or
two radicals R12 together may be a divalent bridging group having 1 to 20 atoms between flanking bonds;
R7, R11 and R13 are each independently selected from the group consisting of OR5, C1-C20-alkyl, C2-C12-alkenyl,
C3-C10-cycloalkyl, heterocyclyl, where in the two last-mentioned radicals one or two CH2 groups may be replaced by a C═O group,
C1-C20-alkyl which may be interrupted by one or more identical or different groups selected from —O—, —S—, —N(C1-C8-alkyl)- and CO, and may carry one or more identical or different radicals R7a,
C2-C12-alkenyl which is interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, and —N(C1-C8-alkyl)-,
—(CH2CH2O)qH, with q being 1-20,
—(CH2CH2O)r(CO)—(C1-C8-alkyl), with r being 1-20,
C2-C8-alkanoyl, C3-C6-alkenoyl, where the two-last mentioned radicals may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, OH and C1-C6-alkoxy,
benzoyl which may be substituted by one or more identical or different radicals selected from the group consisting of F, Cl, Br, I, C1-C6-alkyl, OH and C1-C6-alkoxy,
phenyl and naphthyl, where the two last-mentioned radicals may be substituted by one or more identical or different radicals R7c,
where
R7a has one of the meanings indicated for R4a;
R7c has one of the meanings indicated for R4c;
or
R6 and R7 together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered nitrogen heterocycle which may have a further heteroatom or heteroatomic group selected from the group consisting of CO, O, S and N(C1-C8-alkyl) as a ring member and which may carry 1, 2, 3 or 4 C1-C4-alkyl;
or
R10 and R11 together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered nitrogen heterocycle which may have a further heteroatom or heteroatomic group selected from the group consisting of CO, O, S and N(C1-C8-alkyl) as a ring member and which may carry 1, 2, 3 or 4 C1-C1-alkyl;
or
R12 and R13 together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered nitrogen heterocycle which may have a further heteroatom or heteroatomic group selected from the group consisting of CO, O, S and N(C1-C8-alkyl) as a ring member and which may carry 1, 2, 3 or 4 C1-C4-alkyl;
each R8 is independently selected from the group consisting of hydrogen, C1-C20-alkyl, C2-C12-alkenyl,
C3-C10-cycloalkyl, heterocyclyl, where the two last-mentioned radicals may be interrupted by one or more C═O groups,
C1-C20-alkyl which may be interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(C1-C8-alkyl)- and CO, and may carry one or more identical or different radicals R8a,
C2-C12-alkenyl which is interrupted by one or more identical or different groups selected from —O—, —S—, and —N(C1-C8-alkyl)-,
—(CH2CH2O)sH, with s being 1-20,
—(CH2CH2O)t(CO)—(C1-C8-alkyl), with t being 1-20,
C6-C20-aryl and heteroaryl, where the two last-mentioned radicals may be substituted by one or more identical or different radicals R8c,
where
R8a has one of the meanings indicated for R4a;
R8c has one of the meanings indicated for R4c;
each R9 is independently selected from the group consisting of hydrogen, C1-C20-alkyl, C2-C12-alkenyl,
C3-C10-cycloalkyl, heterocyclyl, where the two last-mentioned radicals may be interrupted by one or more C═O groups,
C1-C20-alkyl which may be interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(C1-C8-alkyl)- and CO, and may carry one or more identical or different radicals R9a,
C2-C12-alkenyl which is interrupted by one or more identical or different groups selected from —O—, —S—, and —N(C1-C8-alkyl)-,
—(CH2CH2O)uH, with u being 1-20,
—(CH2CH2O)v(CO)—(C1-C8-alkyl), with v being 1-20,
phenyl and naphthyl, where the two last-mentioned radicals may be substituted by one or more identical or different radicals R9c,
where
R9a has one of the meanings indicated for R4a;
R9c has one of the meanings indicated for R4c;
R14 is C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C20-cycloalkyl, heterocyclyl, C6-C20-aryl, heteroaryl, C1-C20-alkanoyl, C2-C20-alkenoyl, C3-C20-cycloalkanoyl, C6-C20-aroyl, CSNR12R13 or CSOR9,
where C1-C20-alkyl, C2-C20-alkenyl and C2-C20-alkynyl may be interrupted by one or more identical or different groups selected from the group consisting of —O—, —S—, —N(R6)— and CO and may carry one or more identical or different radicals R14a,
where C3-C20-cycloalkyl and heterocyclyl may be interrupted by one or more CO groups and may carry one or more identical or different radicals R14b,
where C6-C20-aryl, heteroaryl may carry one or more identical or different radicals R14c,
where C1-C20-alkanoyl, C2-C20-alkenoyl may carry one or more identical or different radicals R14a,
where C3-C20-cycloalkanoyl may carry one or more identical or different radicals R14b,
where C6-C20-aroyl may carry one or more identical or different radicals R14d,
where
R14a has one of the meanings indicated for R2a,
R14b has one of the meanings indicated for R1b,
R14c has one of the meanings indicated for R1c;
R14d has one of the meanings indicated for R1d;
or
R1 together with R14 may be a divalent bridging group having 1 to 20 atoms between flanking bonds;
or two radicals R14 together may be a divalent bridging group having 1 to 20 atoms between flanking bonds, and
(b) an ethylenically unsaturated, polymerizable compound.

342 more elements

Polymerizable composition comprising an oxime sulfonate as thermal curing agent

Life of this patent

Polymerizable composition comprising an oxime sulfonate as thermal curing agent

Life of this patent

Abstract

Claims40