Trifunctional photoinitiators
View Patent ↗The Invention relates to novel ketones of formulae (I) and (II) wherein R 1 , R 2 , R 3 and R 4 are, for example, C 1 -C 8 alkyl, R 5 is, for example, hydrogen, A is CI, Br, -0-R 7 , —NR 8 R 9 or —S—R 16 , A′ is —O—, —NH— or —NR 8 —, X and Y are each independently of the other —O—R 10 or —N(R 11 )(R 12 ), n is an integer from 1 to 10, R 6 is, for example, an n-valent radical of linear or branched C 2 -C 20 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —C(CH 3 )(CH 2 —CH 2 —OH)—, —C(CH 2 —CH 2 —OH) 2 —, —N(CH 3 )—, —N(C 2 H 5 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —P(CH 2 —CH 2 —OH)—, —P(O)(CH 2 —CH 2 —OH)—, -0-P(O—CH 2 —CH 2 —OH)—O—, -0-P(O)(0-CH 2 —CH 2 —OH)—O—, —O-cyclohexanediyl-C(CH 3 ) 2 -Cyclohexanediyl-O—, —O-phenylene-C(CH 3 ) 2 -phenylene-O—, —O-phenylene-CH 2 -phenylene-O—, —Si(CH 3 ) 2 —, -0-Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(0-CH 3 )—O—, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, 5-(2-hydroxyethyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl and/or by from one to nine oxygen atoms.
1. A photoinitiator of formula I or II
wherein
R 1 , R 2 , R 3 and R 4 are each independently of the others C 1 -C 8 alkyl; C 1 -C 4 alkyl substituted by OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 8 alkyl), (C 1 -C 4 alkyl)-COO—, benzyl, phenyl or by —N(R 13 )(R 14 );
C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl; or
R 1 and R 2 together and/or R 3 and R 4 together are unbranched or branched C 2 -C 9 alkylene or C 3 -C 6 -oxa- or -aza-alkylene;
R 5 is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl;
A is Cl, Br, —O—R 7 , —NR 8 R 9 or —S—R 16 ;
A′ is —O—, —NH— or —NR 8 —;
X and Y are each independently of the other —O—R 10 or —N(R 11 )(R 12 );
n is an integer from 1 to 10,
R 6 is an n-valent radical of linear or branched C 2 -C 20 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —C(CH 3 )(CH 2 —CH 2 —OH)—, —C(CH 2 —CH 2 —OH) 2 —, —N(CH 3 )—, —N(C 2 H 5 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —O—CO—NH, NH—CO—O—, —P(CH 2 —CH 2 —OH)—, —P(O)(CH 2 —CH 2 —OH)—, —O—P(O—CH 2 —CH 2 —OH)—O—, —O—P(O)(O—CH 2 —CH 2 —OH)—O—, —O-cyclohexanediyl-C(CH 3 ) 2 -cyclohexanediyl-O—, —O-phenylene-C(CH 3 ) 2 -phenylene-O—, —O-phenylene-CH 2 -phenylene-O—, —Si(CH 3 ) 2 —, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(O—CH 3 )—O—, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, 5-(2-hydroxyethyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl and/or by from one to nine oxygen atoms, or
R 6 is an n-valent radical of linear or branched —CO—NH—(C 2 -C 16 alkylene)-(NH—CO) n-1 — or linear or branched —CO—NH—(C 0 -C 9 alkylene)-(NH—CO) n-1 — which may be interrupted by one or two phenylene, methylphenylene, phenylene-O-phenylene, cyclohexanediyl, methylcyclohexanediyl, trimethylcyclohexanediyl, norbornanediyl, [1-3]diazetidine-2,4-dione-1,3-diyl, 3-(6-isocyanatohexyl)-biuret-1,5-diyl or 5-(6-isocyanatohexyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl radical(s), or
R 6 is an n-valent radical of linear or branched —CO-(C 0 -C 12 alkylene)-(CO) n-1 -and the alkylene may be interrupted by oxygen, phenylene, cyclohexanediyl or by norbornanediyl; or
R 6 is an n-valent radical of linear or branched —C 2 -C 50 alkylene the carbon chain of which is interrupted by one to 15 oxygen, and may be subsituted by OH or NH 2 ;
R 7 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 12 alkyl, R 21 , C 2 -C 18 acyl, —CO—NH—C 1 -C 12 alkyl, C 2 -C 20 hydroxyalkyl, C 2 -C 20 methoxyalkyl, 3-(C 1 -C 18 alkoxy)-2-hydroxy-propyl, 3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-propyl, 2,3-dihydroxy-propyl or linear or branched C 2 -C 21 hydroxyalkyl or (C 1 -C 4 alkoxy)-C 2 -C 21 alkyl the carbon chain of which is interrupted by from one to nine oxygen atoms;
R 8 and R 9 are each independently of the other hydrogen, C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
when R 9 =H or methyl, R 8 is also C 2 -C 50 alkyl substituted by one or more of the groups methyl, ethyl, OH, NH 2 , and is interrupted by one or more oxygen, —NH—, cyclohexanediyl, norbornanediyl or phenylene, or
R 8 and R 9 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 10 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 8 alkyl, C 3 -C 6 alkenyl or benzyl,
R 11 and R 12 are each independently of the other C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
R 11 and R 12 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 13 and R 14 are each independently of the other hydrogen, C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
R 13 and R 14 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 15 is hydrogen, C 1 -C 4 alkyl, allyl, benzyl, C 1 -C 4 hydroxyalkyl, —CH 2 CH 2 —COO(C 1 -C 4 alkyl) or —CH 2 CH 2 CN;
R 16 is C 1 -C 18 alkyl, hydroxyethyl, 2,3-dihydroxypropyl, cyclohexyl, benzyl, phenyl, C 1 -C 12 alkylphenyl, —CH 2 —COO(C 1 -C 18 alkyl), —CH 2 CH 2 —COO(C 1 -C 18 alkyl) or —CH(CH 3 )—COO(C 1 -C 18 alkyl);
R 17 and R 18 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, —O—Si(CH 3 )(R 19 )—, —O—Si(CH 3 )(R 20 )— and form chains;
R 19 and R 20 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, and extend chains and, when R 19 and R 20 are linked into a ring, —(R 19 )—(R 20 )— is the bridge —O—;
R 21 is, independently of formula I, a radical of formula
p is an integer from 2 to 12, it being possible for the carbon chain of the alkylene to be interrupted by from one to three oxygen atoms.
2. A photoinitiator according to claim 1 of formula III or IV
wherein
R 1 , R 2 , R 3 and R 4 are each independently of the others C 1 -C 8 alkyl, C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl, or
R 1 and R 2 together and/or R 3 and R 4 together are unbranched or branched C 2 -C 9 alkylene;
R 5 is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl;
n is an integer from 1 to 10; and
R 6 is an n-valent radical of linear or branched C 2 -C 20 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —C(CH 3 )(CH 2 —CH 2 —OH)—, —C(CH 2 —CH 2 —OH) 2 —, —N(CH 3 )—, —N(C 2 H 5 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —P(CH 2 —CH 2 —OH)—, —P(O)(CH 2 —CH 2 —OH)—, —O—P(O—CH 2 —CH 2 —OH)—O—, —O—P(O)(O—CH 2 —CH 2 —OH)—O—, —O-cyclohexanediyl-C(CH 3 ) 2 -cyclohexanediyl-O—, —O-phenylene-C(CH 3 ) 2 -phenylene-O—, —O-phenylene-CH 2 -phenylene-O—, —Si(CH 3 ) 2 —, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(O—CH 3 )—O—, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, 5-(2-hydroxyethyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl and/or by from one to nine oxygen atoms, or
R 6 is an n-valent radical of linear or branched —CO—NH—(C 2 -C 9 alkylene)—(NH—CO) n-1 — or linear or branched —CO—NH—(C 0 -C 9 alkylene)-(NH—CO) n-1 — which may be interrupted by one or two phenylene, methylphenylene, phenylene-O-phenylene, cyclohexanediyl, methylcyclohexanediyl, trimethylcyclohexanediyl, norbornanediyl, [1-3]diazetidine-2,4-dione-1,3-diyl, 5-(6-isocyanatohexyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl or 3-(6-isocyanatohexyl)-biuret-1,5-diyl radical(s), or
R 6 is an n-valent radical of linear or branched —CO—(C 0 -C 12 alkylene)-(CO) n-1 — and the alkylene may be interrupted by oxygen, phenylene, cyclohexanediyl or by norbornanediyl;
R 7 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 12 alkyl, R 21 , C 2 -C 18 acyl, —CO—NH—C 1 -C 12 alkyl, C 2 -C 20 hydroxyalkyl, C 2 -C 20 methoxyalkyl, 3-(C 1 -C 18 alkoxy)-2-hydroxy-propyl, 3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-propyl, 2,3-dihydroxypropyl or linear or branched C 2 -C 21 hydroxyalkyl or (C 1 -C 4 alkoxy)-C 2 -C 21 alkyl the carbon chain of which is interrupted by from one to nine oxygen atoms;
R 10 is hydrogen, —Si(C 1 -C 6 alkyl)(CH 3 ) 2 , C 1 -C 8 alkyl, C 3 -C 6 alkenyl or benzyl;
R 17 and R 18 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, —O—Si(CH 3 )(R 19 )—, —O—Si(CH 3 )(R 20 )— and form chains;
R 19 and R 20 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, and extend chains and, when R 19 and R 20 are linked into a ring, —(R 19 )—(R 20 )— is the bridge —O—;
R 21 is, independently of formula III, a radical of the formula
p is an integer from 2 to 12, it being possible for the carbon chain of the alkylene to be interrupted by from one to three oxygen atoms.
3. A photoinitiator according to claim 1 of formula V
wherein
R 7 is hydrogen, —Si(CH 3 ) 3 , C 1 -C 8 alkyl, bis[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-methyl, C 2 -C 18 acyl, —CO—NH—C 1 -C 8 alkyl, C 2 -C 20 hydroxyalkyl, C 2 -C 20 methoxyalkyl or C 2 -C 20 hydroxyalkyl the carbon chain of which is interrupted by from one to nine oxygen atoms.
4. A photoinitiator according to claim 1 of the formula B
5. A photoinitiator according to claim 1 of formula
6. A photoinitiator according to claim 1 of formula VI, VII or VIII
wherein
n is an integer from 1 to 4, and
R 6 is an n-valent radical of linear or branched C 2 -C 16 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(CH 2 —CH 2 —OH) 2 —, —C(CH 3 )(CH 2 —CH 2 —OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —N(CH 3 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —Si(CH 3 ) 2 —, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(O—CH 3 )—O—, 5-(2-hydroxyethyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl and/or by from one to six oxygen atoms, or
R 6 is an n-valent radical of linear or branched —CO—NH—(C 2 -C 16 alkylene)-(NH—CO) n-1 — or linear or branched —CO—NH—(C 0 -C 9 alkylene)-(NH—CO) n-1 — which may be interrupted by one or two phenylene, methylphenylene, phenylene-O-phenylene, cyclohexanediyl, methylcyclohexanediyl, trimethylcyclohexanediyl, norbornanediyl, [1-3]diazetidine-2,4-dione-1,3-diyl, 5-(6-isocyanatohexyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl or 3-(6-isocyanatohexyl)-biuret-1,5-diyl radical(s),
R 17 and R 18 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, —O—Si(CH 3 )(R 19 )—, —O—Si(CH 3 )(R 20 )— and form chains,
R 19 and R 20 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, and extend chains and, when R 19 and R 20 are linked into a ring, —(R 19 )—(R 20 )— is the bridge —O—, and
p is an integer from 2 to 12, it being possible for the carbon chain of the alkylene to be interrupted by from one to three oxygen atoms.
7. A photoinitiator according to claim 1 of formula IX
wherein
R 8 and R 9 are each independently of the other hydrogen, C 1 -C 12 alkyl, C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
when R 9 =H or methyl, R 8 is also C 2 -C 50 alkyl substituted by one or more of the groups methyl, ethyl, OH or NH 2 , and is interrupted by one or more oxygen, —NH—, cyclohexanediyl, norbornanediyl or phenylene, or
R 8 and R 9 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—.
8. A photoinitiator according to claim 1 of formula X
wherein
n is an integer from 1 to 4, and
R 6 is an n-valent radical of linear or branched C 2 -C 16 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(CH 2 —CH 2 —OH) 2 —, —C(CH 3 )(CH 2 —CH 2 —OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —N(CH 3 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —O—CO—NH, NH—CO—O—, —Si(CH 3 ) 2 —, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(O—CH 3 )—O—, 5-(2-hydroxyethyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl and/or by from one to six oxygen atoms, or
R 6 is an n-valent radical of linear or branched —C 2 -C 50 alkylene the carbon chain of which is interrupted by one to 15 oxygen, and may be subsituted by OH or NH 2 ; and
R 8 is hydrogen, C 1 -C 4 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl.
9. A composition consisting of
(A) at least one ethylenically unsaturated compound,
(B) a photoinitiator of formula I or II according to claim 1 ,
(C) optionally, further additives and
(D) optionally, further photoinitiators and coinitiators.
10. A composition according to claim 9 , wherein the compound (A) is a resin containing free OH groups, free isocyanate groups or free carboxy groups and the photoinitiator (B) is bonded to the resin.
11. A composition according to claim 10 which is a surface coating for food packaging materials.
12. A process for the production of a scratch-resistant durable surface, wherein a composition according to claim 9 is applied to a support; and curing is carried out either solely by means of irradiation with electromagnetic radiation having a wavelength of from 200 nm into the IR range, or by irradiation with electromagnetic radiation and prior, simultaneous and/or subsequent application of heat.
13. A composition according to claim 9 which is a pigmented or non-pigmented surface coating, overprint coating, powder coating, printing ink, inkjet ink, gel coat, composite material or a glass fibre coating.
14. A process for the preparation of a compound of formula I or II, comprising the following steps:
a) reaction of diphenylmethane with an acid halide of formula R 1 R 2 CH—COHal and, optionally, further reaction with an acid halide of formula R 3 R 4 CH—COHal in the presence of a Friedel-Crafts catalyst, whereupon an isomeric mixture of formula A is obtained,
b) halogenation of the isomeric mixture of formula A, followed by bromination and hydrolysis, whereupon an isomeric mixture of formula B is obtained,
c) optionally, selective substitution of the benzylic hydroxy group in the resulting isomeric mixture of formula B by reaction
with an alcohol in the presence of an acid as catalyst for the preparation of an ether,
with a carboxylic acid for the preparation of an ester,
with an isocyanate for the preparation of a urethane,
with a diol, dicarboxylic acid or diisocyanate for the preparation of a bridged compound,
with a diisocyanate together with a diol or a diamine or
with a siloxane for the preparation of a silicone derivative,
d) optionally, reaction of the alpha-hydroxy group in the resulting isomeric mixture of formula B and
e) optionally, separation of the isomers,
where the compounds of formula I and II are
wherein
R 1 , R 2 , R 3 and R 4 are each independently of the others C 1 -C 8 alkyl; C 1 -C 4 alkyl substituted by OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 8 alkyl), (C 1 -C 4 alkyl)-COO—, benzyl, phenyl or by —N(R 13 )(R 14 );
C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl; or
R 1 and R 2 together and/or R 3 and R 4 together are unbranched or branched C 2 -C 9 alkylene or C 3 -C 6 -oxa- or -aza-alkylene;
R 5 is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl;
A is Cl, Br, —O—R 7 —NR 8 R 9 or —S—R 16 ;
A′ is —O—, —NH— or —NR 8 —;
X and Y are each independently of the other —O—R 10 or —N(R 11 )(R 12 );
n is an integer from 1 to 10;
R 6 is an n-valent radical of linear or branched C 2 -C 20 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —C(CH 3 )(CH 2 —CH 2 OH)—, —C(CH 2 —CH 2 —OH) 2 —, —N(CH 3 )—, —N(C 2 H 5 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —O—CO—NH, NH—CO—O—, —P(CH 2 —CH 2 —OH)—, —P(O)(CH 2 —CH 2 —OH)—, —O—P(O—CH 2 —CH 2 —OH)—O—, —O—P(O)(O—CH 2 —CH 2 —OH)—O—. —O-cyclohexanediyl-C(CH 3 ) 2 -cyclohexanediyl-O—. —O-phenylene-C(CH 3 ) 2 -phenylene-O—, —O-phenylene-CH 2 -phenylene-O—, —Si(CH 3 ) 2 —, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(O—CH 3 )—O—, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, 5-(2-hydroxyethyl)-1,3,5triazinane-2,4,6-trione-1,3-diyl and/or by from one to nine oxygen atoms, or
R 6 is an n-valent radical of linear or branched —CO—NH—(C 2 -C 16 alkylene)-(NH—CO) n-1 — or linear or branched —CO—NH—(C 0 -C 9 alkylene)-(NH—CO) n-1 — which may be interrupted by one or two phenylene, methylphenylene, phenylene-O-phenylene, cyclohexanediyl, methylcyclohexanediyl, trimethylcyclohexanediyl, norbornanediyl, [1-3]diazetidine-2,4-dione-1,3-diyl, 3-(6-isocyanatohexyl)-biuret-1,5-diyl or 5-(6-isocyanatohexyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl radical(s), or
R 6 is an n-valent radical of linear or branched —CO—(C 0 -C 12 alkylene)-(CO) n-1 — and the alkylene may be interrupted by oxygen, phenylene, cyclohexanediyl or by norbornanediyl; or
R 6 is an n-valent radical of linear or branched —C 2 -C 50 alkylene the carbon chain of which is interrupted by one to 15 oxygen, and may be subsituted by OH or NH 2 ;
R 7 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 12 alkyl, R 21 , C 2 -C 18 acyl, —CO—NH—C 1 -C 12 alkyl, C 2 -C 20 hydroxyalkyl, C 2 -C 20 methoxyalkyl, 3-(C 1 -C 18 alkoxy)-2-hydroxy-propyl, 3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-propyl, 2,3-dihydroxy-propyl or linear or branched C 2 -C 21 hydroxyalkyl or (C 1 -C 4 alkoxy)-C 2 -C 2 ,alkyl the carbon chain of which is interrupted by from one to nine oxygen atoms;
R 8 and R 9 are each independently of the other hydrogen, C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
when R 9 =H or methyl, R 8 is also C 2 -C 50 alkyl substituted by one or more of the groups methyl, ethyl, OH, NH 2 , and is interrupted by one or more oxygen, —NH—, cyclohexanediyl, norbornanediyl or phenylene, or
R 8 and R 9 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 10 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 8 alkyl, C 3 -C 6 alkenyl or benzyl,
R 11 and R 12 , are each independently of the other C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
R 11 and R 12 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 13 and R 14 are each independently of the other hydrogen, C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
R 13 and R 14 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 15 is hydrogen, C 1 -C 4 alkyl, allyl, benzyl, C 1 -C 4 hydroxyalkyl, —CH 2 CH 2 —COO(C 1 -C 4 alkyl) or —CH 2 CH 2 CN;
R 16 is C 1 -C 18 alkyl, hydroxyethyl, 2,3-dihydroxypropyl, cyclohexyl, benzyl, phenyl, C 1 -C 12 alkylphenyl, —CH 2 —COO(C 1 -C 18 alkyl), —CH 2 CH 2 —COO(C 1 -C 18 alkyl) or —CH(CH 3 )—COO(C 1 -C 18 alkyl);
R 17 and R 18 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, —O—Si(CH 3 )(R 19 )—, —O—Si(CH 3 )(R 20 )— and form chains;
R 19 and R 20 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 9 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, and extend chains and, when R 19 and R 20 are linked into a ring, —(R 19 )—(R 20 )— is the bridge —O—;
R 21 is independently of formula I, a radical of the formula
p is an integer from 2 to 12, it being possible for the carbon chain of the alkylene to be interrupted by from one to three oxygen atoms.
15. A process for the preparation of compound I or II, comprising the following steps:
a) reaction of diphenylmethane with an acid halide of formula R 1 R 2 CH—COHal and, optionally, further reaction with an acid halide of formula R 3 R 4 CH—COHal in the presence of a Friedel-Crafts catalyst, whereupon an isomeric mixture of formula A is obtained,
b) halogenation of the isomeric mixture of formula A, followed by bromination, aminolysis of the benzylic bromide, and hydrolysis of the tertiary halides, whereupon an isomeric mixture of formula C is obtained,
c) optionally, when R 8 or R 9 in the isomeric mixture of formula C possess a primary hydroxy group, selective substitution of the primary hydroxy group by reaction
with a carboxylic acid for the preparation of an ester,
with an isocyanate for the preparation of a urethane,
with a dicarboxylic acid or diisocyanate for the preparation of a bridged compound or
with a siloxane for the preparation of a silicone derivative and
d) optionally, separation of the isomers,
where the compounds of formula I and II are
wherein
R 1 , R 2 , R 3 and R 4 are each independently of the others C 1 -C 8 alkyl; C 1 -C 4 alkyl substituted by OH,
C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 8 alkyl), (C 1 -C 4 alkyl)-COO—, benzyl, phenyl or by —N(R 13 )(R 14 );
C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 —(C 1 -C 4 alkyl) or phenyl; or
R 1 and R 2 together and/or R 3 and R 4 together are unbranched or branched C 2 -C 9 alkylene or C 3 -C 6 -oxa- or -aza-alkylene;
R 5 is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 alkenyl, benzyl, —CH 2 —C 6 H 4 -(C 1 -C 4 alkyl) or phenyl;
A is Cl, Br, —O—R 7 —NR 8 R 9 or —S—R 16 ;
A′ is —O—, —NH— or —NR 8 —;
X and Y are each independently of the other —O—R 10 or —N(R 11 )(R 12 );
n is an integer from 1 to 10;
R 6 is an n-valent radical of linear or branched C 2 C 20 alkyl the carbon chain of which may be interrupted by cyclohexanediyl, phenylene, —CH(OH)—, —C(C 2 H 5 )(CH 2 —CH 2 —OH)—, —C(CH 3 )(CH 2 —CH 2 —OH)—, —C(CH 2 —CH 2 —OH) 2 —, —N(CH 3 )—, —N(C 2 H 5 )—, —N(CH 2 —CH 2 —OH)—, —CO—O—, —O—CO—, —O—CO—NH, NH—CO—O—, —P(CH 2 —CH—OH)—, —P(O)(CH 2 —CH 2 —OH)—, —O—P(O—CH 2 —CH 2 —OH)—O—, —O—P(O)(O—CH 2 —CH 2 —OH)—O—, —O-cyclohexanediyl-C(CH 3 ) 2 -cyclohexanediyl-O—, —O-phenylene-C(CH 3 ) 2 -phenylene-O—, —O-phenylene-CH 2 -phenylene-O—, —Si(CH 3 ) 2 —, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 )(O—CH 3 )—O—, —Si(CH 3 )(R 17 )—O—Si(CH 3 )(R 18 )—, 5-(2-hydroxyethyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl and/or by from one to nine oxygen atoms, or
R 6 is an n-valent radical of linear or branched —CO—NH—(C 2 -C 16 alkylene)-(NH—CO) n-1 — or linear or branched —CO—NH—(C 0 -C 9 alkylene)-(NH—CO) n-1 — which may be interrupted by one or two phenylene, methylphenylene, phenylene-O-phenylene, cyclohexanediyl, methylcyclohexanediyl, trimethylcyclohexanediyl, norbornanediyl, [1-3]diazetidine-2,4-dione-1,3-diyl, 3-(6-isocyanatohexyl)-biuret-1,5-diyl or 5-(6-isocyanatohexyl)-[1,3,5]triazinane-2,4,6-trione-1,3-diyl radical(s), or
R 6 is an n-valent radical of linear or branched —CO—(C 0 -C 12 alkylene)-(CO) n-1 — and the alkylene may be interrupted by oxygen, phenylene, cyclohexanediyl or by norbornanediyl; or
R 6 is an n-valent radical of linear or branched —C 2 -C 50 alkylene the carbon chain of which is interrupted by one to 15 oxygen, and may be subsituted by OH or NH 2 ;
R 7 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 12 alkyl, R 21 , C 2 -C 18 acyl, —CO—NH—C 1 -C 12 alkyl, C 2 -C 20 hydroxyalkyl, C 2 -C 20 methoxyalkyl, 3-(C 1 -C 18 alkoxy)-2-hydroxy-propyl, 3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-propyl, 2,3-dihydroxy-propyl or linear or branched C 2 -C 21 , hydroxyalkyl or (C 1 -C 4 alkoxy)-C 2 -C 21 alkyl the carbon chain of which is interrupted by from one to nine oxygen atoms,
R 8 and R 9 are each independently of the other hydrogen, C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
when R 9 =H or methyl, R 8 is also C 2 -C 50 alkyl substituted by one or more of the groups methyl, ethyl, OH, NH 2 , and is interrupted by one or more oxygen, —NH—, cyclohexanediyl, norbornanediyl or phenylene, or
R 8 and R 9 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 10 is hydrogen, —Si(C 1 -C 6 alkyl) 3 , C 1 -C 8 alkyl, C 3 -C 6 alkenyl or-benzyl,
R 11 and R 12 , are each independently of the other C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
R 11 and R 12 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 13 and R 14 are each independently of the other hydrogen, C 1 -C 12 alkyl; C 2 -C 4 alkyl substituted by one or more of the groups OH, C 1 -C 4 alkoxy, —CN, —COO(C 1 -C 4 alkyl); C 3 -C 5 alkenyl, cyclohexyl or C 7 -C 9 phenylalkyl, or
R 13 and R 14 together are unbranched or branched C 3 -C 9 alkylene which may be interrupted by —O— or by —N(R 15 )—;
R 15 is hydrogen, C 1 -C 4 alkyl, allyl, benzyl, C 1 -C 4 hydroxyalkyl, —CH 2 CH 2 —COO(C 1 -C 4 alkyl) or —CH 2 CH 2 CN;
R 16 is C 1 -C 18 alkyl, hydroxyethyl, 2,3-dihydroxypropyl, cyclohexyl, benzyl, phenyl, C 1 -C 12 alkylphenyl, —CH 2 —COO(C 1 -C 18 alkyl), —CH 2 CH 2 —COO(C 1 -C 10 alkyl) or —CH(CH 3 )—COO(C 1 -C 18 alkyl);
R 17 and R 18 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, —O—Si(CH 3 )(R 19 )—, —O—Si(CH 3 )(R 20 )— and form chains;
R 19 and R 20 are each independently of the other a monovalent radical methyl, —O—Si(CH 3 ) 3 , —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 3 , —O—Si(CH 3 )[—(CH 2 ) p —OH]—O—Si(CH 3 ) or a bivalent radical —O—Si(CH 3 ) 2 —, —O—Si(CH 3 )[—(CH 2 ) p —OH]—, and extend chains and, when R 19 and R 20 are linked into a ring, —(R 19 )—(R 20 )— is the bridge —O—;
R 21 is, independently of formula I, a radical of the formula
p is an integer from 2 to 12, it being possible for the carbon chain of the alkylene to be interrupted by from one to three oxygen atoms.