Photoinitiators having chain transfer groups polymerized to...

Details Photoinitiators having chain transfer groups polymerized to... Photoinitiators having chain transfer groups polymerized to...

2000-11-27

2002-10-01

Berman, Susan W. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C522S035000, C522S036000, C522S039000, C522S051000, C522S057000, C522S182000, C522S188000, C525S093000, C525S094000

Reexamination Certificate

active

06458864

ABSTRACT:

The present application refers to macrophotoinitiators, which are obtained by the polymerization of photoinitiators with chain transfer groups and the photopolymerization of said macrophotoinitiators to give block copolymers.
Some photoinitiator compounds comprising SH-substituents are known in the art and disclosed for example in U.S. Pat. No. 4,582,862. More SH-substituted photoinitiators with SH-substitution are described in GB-A 2320027. These compounds are not known as chain transfer agents. EP-A 341560 teaches the preparation and use of photoinitiator copolymers. Y. Yagci et al in J. Macromol. Sci. Chem., A28(1), pp. 129-141 (1991) describe the use of azo-benzoin compounds as initiators for the preparation of block-copolymers, by thermally polymerizing the first monomer with the compounds and then polymerizing the second monomer photochemically. In J. of Polym. Sci., Part A, Polymer Chemistry, Vol. 34, 3471-3484 (1996) and FR-A 2715653 R. Popielarz employs compounds having thermal chain transferring moieties and thermal initiating moieties for the preparation of block-copolymers.
In technique there is a need for easy controllable preparation methods for defined block copolymers. By means of photopolymerization with specific macrophotoinitiators such copolymers are obtainable.
Subject of the invention therefore are macrophotoinitiators which are obtained by thermally polymerizing a photoinitiator compound which additionally to the photoinitiating group comprises a chain transfer group.
Photoinitiators comprising chain transfer groups are those of formula I, II, III or IV
wherein
a is an integer 1, 2 or 4;
Ar is phenyl, biphenylyl or benzoylphenyl, each of which is unsubstituted or substituted by 1 to 5 halogen, C
1
-C
12
alkyl, C
3
-C
12
alkenyl, C
5
-C
6
cycloalkyl, phenyl-C
1
-C
3
alkyl, —COOH, —COO(C
1
-C
4
alkyl), —OR
7
, —SH, —SR
8
, —SOR
8
, —SO
2
R
8
, —CN, —SO
2
NH
2
, —SO
2
NH(C
1
-C
4
alkyl), —SO
2
—N(C
1
-C
4
alkyl)
2
, —NR
9
R
10
, —NHCOR
9
, or by a group of the formula V,
or Ar is a group of the formula VI or VII
Ar
1
if a is 1, has the same meanings as Ar;
if a is 2, Ar
1
is a divalent aromatic radical of the formula VIII or VIIIa
if a is 4, Ar
1
is a tetravalent aromatic radical of the formula VIIIb
 each of which is unsubstituted or substituted by 1 to 5 halogen, C
1
-C
12
alkyl, C
3
-C
12
alkenyl, C
5
-C
6
cycloalkyl, phenyl-C
1
-C
3
alkyl, —COOH, —COO(C
1
-C
4
alkyl), —OR
7
, —SH, —SR
8
, —SOR
8
, —SO
2
R
8
, —CN, —SO
2
NH
2
, —SO
2
NH(C
1
-C
4
alkyl), —SO
2
—N(C
1
-C
4
alkyl)
2
, —NR
9
R
10
, —NHCOR
9
, or by a group of the formula V as defined above;
or Ar
2
is a group of the formula VIa or VIIa
X is a direct bond, —O—, —S— or —N(R
6
)—;
Y is hydrogen, C
1
-C
12
alkyl, which is unsubstituted or substituted by 1 to 5 OH, OR
6
, COOR
6
, SH, N(R
6
)
2
, halogen or by a group of the formula Ia
or Y is C
2
-C
20
alkyl, which is interrupted by 1 to 9 —O—, —N(R
6
)—, —S—, —SS—, —X—C(═O)—, —X—C(═S)—, —C(═O)—X—, —X—C(═O)—X—, —C(═S)—X—, or
 wherein the interrupted C
2
-C
20
alkyl is unsubstituted or is substituted by 1 to 5 SH; or Y is benzyl which is unsubstituted or substituted once or twice by —CH
2
SH and said benzyl may further be substituted by 1 to 4 C
1
-C
4
alkyl; or Y is Ar (as defined above), a group
 a heterocyclic 5- to 7-membered aliphatic or aromatic ring, comprising 1 to 4 N, O or/and S-atoms; a 8- to 12-membered bicyclic aliphatic or aromatic ring system, comprising 1 to 6 N, O or/and S-atoms, which mono- or bicyclic rings are unsubstituted or substituted by SH or 1-5 times by a group of the formula Ia; or Y is a group
q is 1 or 2;
r is 1,2 or 3;
p is 0 or 1;
t is 1 to 6;
u is 2 or 3;
M
1
is —NR
3
R
4
or —OH;
R
1
and R
2
independently of one another are C
1
-C
8
alkyl, which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, SH, CN, —COO(C
1
-C
8
alkyl), —OCO(C
1
-C
4
alkyl) or —N(R
3
)(R
4
); or R
1
and R
2
independently of one another are C
3
-C
6
alkenyl, phenyl, chlorophenyl, R
7
—O-phenyl, R
8
—S-phenyl or phenyl-C
1
-C
3
-alkyl, each of which is unsubstituted or substituted by 1 to 5 SH; or R
1
and R
2
together are C
2
-C
9
alkylene, C
3
-C
9
oxaalkylene or C
3
-C
9
azaalkylene, each of which is unsubstituted or substituted by 1 to 5 SH; or R
1
and R
2
independently of one another are a group of the formula IX or X
R
3
is hydrogen, C
1
-C
12
alkyl; C
2
-C
4
alkyl, which is substituted by OH, SH, C
1
-C
4
alkoxy, CN or —COO(C
1
-C
4
alkyl); or R
3
is C
3
-C
5
alkenyl, C
5
-C
12
-cycloalkyl or phenyl-C
1
-C
3
alkyl;
R
4
is C
1
-C
12
alkyl; C
2
-C
4
alkyl, which is substituted by OH, SH, C
1
-C
4
alkoxy, CN or —COO(C
1
-C
4
alkyl); or R
4
is C
3
-C
5
alkenyl, C
5
-C
12
-cycloalkyl, phenyl-C
1
-C
3
alkyl; or phenyl, which unsubstituted or substituted by halogen, C
1
-C
12
alkyl, C
1
-C
4
alkoxy or —COO(C
1
-C
4
alkyl); or R
4
together with R
2
is C
1
-C
7
alkylene, phenyl-C
1
-C
4
alkylene, o-xylylene, 2-butenylene, C
2
-C
3
oxaalkylene or C
2
-C
3
azaalkylene;
or R
3
and R
4
together are C
3
-C
7
alkylene, which can be interrupted by —O—, —S—, —CO— or —N(R
6
)— and which is unsubstituted or substituted by OH, SH, C
1
-C
4
alkoxy or —COO(C
1
-C
4
alkyl);
R
5
is C
1
-C
6
alkylene, xylylene, cyclohexylene, each of which is unsubstituted or substituted by 1 to 5 SH; or R
5
is a direct bond;
R
6
is hydrogen; C
1
-C
12
alkyl, which is unsubstituted or substituted by OH, SH or HS—(CH
2
)
q
—(CO)O—; C
2
-C
12
alkyl, which is interrupted by —O—, —NH— or —S—; or R
6
is C
3
-C
5
alkenyl, phenyl, phenyl-C
1
-C
3
-alkyl, CH
2
CH
2
CN; C
1
-C
4
alkyl-CO—CH
2
CH
2
— which is unsubstituted or substituted by OH or SH; C
2
-C
8
alkanoyl which is unsubstituted or substituted by OH or SH; or R
6
is benzoyl;
Z is a divalent radical of the formula
 —N(R
17
)—, —N(R
17
)—R
18
—N(R
17
)—;
G is C
1
-C
7
alkylene;
L and E independently of one another are a direct bond, —O—, —S— or —N(R
6
)—, provided that L and E are not both a direct bond simultaneously;
M is O, S or N(R
6
);
R
7
is hydrogen, C
1
-C
12
alkyl, C
3
-C
12
-alkenyl, cyclohexyl, hydroxycyclohexyl; C
1
-C
4
alkyl, which is mono- or polysubstituted by Cl, Br, CN, SH, —N(C
1
-C
4
alkyl)
2
, piperidino, morpholino, OH, C
1
-C
4
alkoxy, —OCH
2
CH
2
CN, —OCH
2
CH
2
COO(C
1
-C
4
alkyl), —OOCR
19
, —COOH, —COO(C
1
-C
8
alkyl), —CONH(C
1
-C
4
alkyl), —CON(C
1
-C
4
alkyl)
2
,
—CO(C
1
-C
4
alkyl) or
 or R
7
is 2,3-epoxypropyl, —(CH
2
CH
2
O)
m
H; phenyl which is unsubstituted or substituted by halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or —COO(C
1
-C
4
alkyl); or R
7
is phenyl-C
1
-C
3
alkyl, tetrahydropyranyl, tetrahydrofuranyl, —COOR
19
, —COO(C
1
-C
8
alkyl), —CONH(C
1
-C
4
alkyl), —CON(C
1
-C
8
alkyl)
2
, —Si(R
20
)(R
21
)
2
, or —SO
2
R
22
;
R
8
is C
1
-C
12
alkyl, C
3
-C
12
alkenyl, cyclohexyl, hydroxycyclohexyl; C
1
-C
4
alkyl, which is mono- or polysubtituted by Cl, Br, CN, SH, —N(C
1
-C
4
alkyl)
2
, piperidino, morpholino, OH, C
1
-C
4
alkoxy, —OCH
2
CH
2
CN, —OCH
2
CH
2
COO(C
1
-C
4
alkyl), —O(CO)R
19
, —COOH, —COO(C
1
-C
8
alkyl), —CON(C
1
-C
4
alkyl)
2
,
 —CO(C
1
-C
4
alkyl, or benzoyl; or R
8
is 2,3-epoxypropyl, phenyl-C
1
-C
3
alkyl, phenyl-C
1
-C
3
hydroxyalkyl; phenyl which is unsubstituted or mono- or poly-substituted by halogen, SH, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or —COO(C
1
-C
4
alkyl); or R
8
is 2-benzothiazyl, 2-benzimidazolyl, —CH
2
CH
2
—O—CH
2
CH
2
—SH or —CH
2
CH
2
—S—CH
2
CH
2
—SH;
R
9
and R
10
independently of one another are hydrogen, C
1
-C
12
alkyl; C
2
-C
4
alkyl, which is substituted by OH, SH, C
1
-C
4
alkoxy, CN or —COO(C
1
-C
4
alkyl); or R
9
and R
10
independently of one another are C
3
-C
5
alkenyl, cyclohexyl, phenyl-C
1
-C
3
alkyl; phenyl which is unsubstituted or mono- or poly-substituted by C
1
-C
12
alkyl or halogen; or R
9
and R
10
together are C
2
-C
7
alkylene which can be interrupted by —O—, —S— or —N(R
6
)—;
R
11
and R
12
independently of one another are a direct bond, —CH
2
—, —CH
2
CH
2
—, —O—, —S—, —CO— or —N(R
6
)—; provided that R
11
and R
12
are

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