Photoinitiators and their applications

Details Photoinitiators and their applications Photoinitiators and their applications

2001-10-18

2004-01-06

Seidleck, James J. (Department: 1711)

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

Synthetic resins

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

C522S034000, C522S035000, C522S044000, C522S904000, C522S153000, C522S157000, C522S158000, C522S178000, C522S179000, C522S182000

Reexamination Certificate

active

06673850

ABSTRACT:

The present application refers to photoinitiator compounds comprising addition fragmentation agent (AFA) type chain transfer groups, macrophotoinitiators, which are obtained by the polymerization of monomers in the presence of photoinitiators with said chain transfer groups and the photopolymerization of said macrophotoinitiators to give block copolymers.
In European Patent Application No. 98810501.1, filed May 29, 1998 photoinitiator compounds comprising SH-substitutents as chain transfer agents are disclosed. 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, 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. Some odorless functional copolymers by using AFA type chain transfer agents are disclosed for examples in WO 88/4304, WO 91/7387, WO 91/7440 and U.S. Pat. No. 5,395,903.
In technique, there still exists a need for reactive, easy to prepare, easy to handle and odorless photoinitiator compounds and 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 odorless photoinitiator compounds having chain transfer groups. The compounds comprising chain transfer groups are those of formula Ia or Ib
wherein
n is 1 or 2;
PI is a group of formula IIa, IIb or IIc
PI′ is a group of formula IIIa or IIIb
Ar is phenyl, biphenylyl or benzoylphenyl, each of which is unsubstituted or substituted 1 to 5 times by 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
, —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 formula IV,
or Ar is a group of formula V or VI
Ar
2
is
 each of which is unsubstituted or substituted 1 to 5 times by 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
, —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 formula IV;
or Ar
2
is a group of formula Va or VIa
G is unbranched or branched C
1
-C
7
alkylene;
L and E independently of one another are a direct bond,
13
O—, —S— or —N(R
6
)—, provided that L and E are not both a direct bond simultaneously;
R
1
and R
2
independently of one another are R
7
O—, C
1
-C
8
alkyl, which is unsubstituted or substituted by OH, C
1
-C
4
alkoxy, SR
8
, CN, (C
1
-C
8
alkyl)O(CO)—, (C
1
-C
4
alkyl)—(OC)O— 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, or R
1
and R
2
together are unbranched or branched C
2
-C
9
alkylene, C
3
-C
9
oxaalkylene or C
3
-C
9
azaalkylene, or R
1
and R
2
independently of one another are a radical of formula VII or VIII
p is 0 or 1;
Ar
3
is phenyl, naphthyl, furyl, thienyl or pyridiyl, each of which is unsubstituted or substituted by halogen, SH, OH, C
1
-C
12
alkyl, OH-substituted C
1
-C
4
alkyl, halogen-substituted C
1
-C
4
alkyl, SH-substituted C
1
-C
4
alkyl, N(R
17
)
2
-substituted C
1
-C
4
alkyl, C
1
-C
12
alkoxy-substituted C
1
-C
4
alkyl, (C
1
-C
18
alkyl)O(OC)-substituted C
1
-C
4
alkyl, CH
3
O(CH
2
CH
2
O)
m
CO-substituted C
1
-C
4
alkyl, (C
1
-C
4
alkyl)(OC)O-substituted C
1
-C
4
alkyl, C
1
-C
12
alkoxy, (C
1
-C
18
alkyl)(OC)O-substituted C
1
-C
4
alkoxy, CH
3
O(CH
2
CH
2
O)
m
CO-substituted C
1
-C
4
alkoxy, —(OCH
2
CH
2
)
m
OH, —(OCH
2
CH
2
)
m
OCH
3
, C
1
-C
8
alkylthio, phenoxy, —COO(C
1
-C
18
alkyl), —CO(OCH
2
CH
2
)
m
OCH
3
, phenyl or benzoyl;
m is 1 to 20;
M
1
is —NR
3
R
4
or —OH, or, when R
1
and R
2
are R
7
O—, M
1
is Ar;
M
1
′ is a group
 or, when R
1
and R
2
are R
7
O—, M
1
′ is Ar
2
;
R
1
′ and R
3
′ independently of one another are a direct bond, C
1
-C
12
alkylene, or phenylene;
E
1
is —CH
2
—, —O—, —N(R
6
)— or —S—;
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; phenyl which is 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, optionally interrupted by —O—, —S—, —CO— or —N(R
6
)— and which C
3
-C
7
alkylene is unsubstituted or substituted by OH, SH, C
1
-C
4
alkoxy or —COO(C
1
-C
4
alkyl);
R
6
is hydrogen, C
1
-C
12
alkyl, OH-substituted C
1
-C
12
alkyl, SH-substituted C
1
-C
12
alkyl or HS—(CH
2
)
n
—COO-substituted C
1
-C
12
alkyl; C
2
-C
12
alkyl, which is interrupted by —O—, —NH— or —S—; or R
6
is C
3
-C
5
alkenyl, phenyl-C
1
-C
3
-alkyl, —CH
2
CH
2
CN, C
1
-C
4
alkyl-CO—CH
2
CH
2
—, OH-substituted C
1
-C
4
alkyl-CO—CH
2
CH
2
—, SH-substituted C
1
-C
4
alkyl-CO—CH
2
CH
2
—, C
2
-C
8
alkanoyl, OH-substituted C
2
-C
8
alkanoyl, SH-substituted C
2
-C
8
alkanoyl or benzoyl;
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
, piperidinyl, morpholinyl, 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), —CONH(C
1
-C
4
alkyl), —CON(C
1
-C
4
alkyl)
2
,
 —CO(C
1
-C
4
alkyl) or by
 or R
7
is 2,3-epoxypropyl, —(CH
2
CH
2
O)
n
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 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
, piperidinyl, morpholinyl, 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
 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, optionally interrupted by —O—, —S—, —CO— 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 not a direct bond simultaneously;
R
13
is hydrogen, C
1
-C
8
alkyl or phenyl;
R
14
, R
15
and R
16
independently of one another are hydrogen or C
1
-C
4
alkyl;
R
17
is hydrogen, C
1
-C
8
alkyl or phenyl;
R
19

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