Functionalized photoinitiators, derivatives and macromers...

Details Functionalized photoinitiators, derivatives and macromers... Functionalized photoinitiators, derivatives and macromers...

1997-08-11

2001-03-20

Mullis, Jeffrey C. (Department: 1711)

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

Synthetic resins

Processes of preparing a desired or intentional composition...

C523S108000, C351S16000R, C351S16000R, C525S243000

Reexamination Certificate

active

06204306

ABSTRACT:

The present invention relates to &agr;-aminoacetophenones functionalised with organic diisocyanates, which can be used as reactive photoinitiators; to oligomers and polymers to which such functionalised &agr;-aminoacetophenones are bonded; to &agr;-aminoacetophenones having an unsaturated polymerisable side-chain; to dimeric and trimeric photoinitiators; to the use of such photoinitiators; to materials coated with such photoinitiators; and to the use of the functionalised &agr;-aminoacetophenones for modifying surfaces.
Alpha-aminoacetophenones of the structural type (A)
are known, for example, from EP-A-003 002 and are described therein as outstanding photoinitiators for radiation-induced polymerisation of ethylenically unsaturated monomeric, oligomeric or polymeric compounds. Considered to be a disadvantage are the low-molecular-weight fragments produced which emerge from a polymer, for example as a result of migration, and thus may impair its performance properties. In order to avoid that disadvantage and other disadvantages of such monomeric photoinitiators, EP-A-261 941 proposes modifying photoinitiators at the phenyl nucleus in such a way that the photolysis products are securely bonded into the resulting polymer structure. Also mentioned very generally as functional groups for that purpose are isocyanate groups, which are bonded to the phenyl nucleus via a spacer group, for example a linear alkylene group. The preparation of such compounds poses considerable problems of synthesis, however, since, in the reaction of linear diisocyanates with compounds containing hydroxy groups, the formation of diadducts cannot be avoided or even predominates.
There is therefore a need for functional photoinitiators that can be produced easily, that can be obtained in high purity and are distinguished by high reactivity and stability to storage, that can be linked to suitable oligomers or polymers to produce highly effective macromeric photoinitiators, that are suitable for modifying surfaces, especially plastics surfaces, by photo-induced graft polymerisation, and that can also be used for biologically tolerable materials, especially in the biomedical sector. It has been found that that objective can be achieved by using, for the introduction of isocyanate groups, diisocyanates that comprise isocyanate groups of differing reactivity and reacting them with &agr;-aminoacetophenones that carry in the phenyl nucleus suitable functional groups according to formula (II) to form compounds of formula (I), in which reaction the formation of isomers and other by-products is suppressed by a high regioselectivity.
The invention relates to compounds of formula (I)
wherein
X is bivalent —O—, —NH—, —S—, lower alkylene or
Y is a direct bond or —O—(CH
2
)
n
— wherein n is an integer from 1 to 6 and the terminal CH
2
group of which is linked to the adjacent X in formula (I);
R is H, C
1
-C
12
alkyl, C
1
-C
12
alkoxy, C
1
-C
12
alkylNH- or —NR
1A
R
1B
wherein R
1A
is lower alkyl and R
1B
is H or lower alkyl;
R
1
is linear or branched lower alkyl, lower alkenyl or aryl-lower alkyl;
R
2
independently of R
1
has the same definitions as R
1
or is aryl, or
R
1
and R
2
together are —(CH
2
)
m
— wherein m is an integer from 2 to 6;
R
3
and R
4
are each independently of the other linear or branched lower alkyl that may be substituted by C
1
-C
4
alkoxy, or aryl-lower alkyl or lower alkenyl; or
R
3
and R
4
together are —(CH
2
)
z
—Y
1
—(CH
2
)
z
— wherein Y
1
is a direct bond, —O—, —S— or —NR
1B
—, and R
1B
is H or lower alkyl and z is independently of the other an integer from 2 to 4;
R
5
is linear or branched C
3
-C
18
alkylene, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
6
-C
10
arylene, or unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
7
-C
18
aralkylene, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
13
-C
24
-arylenealkylenearylene, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
3
-C
8
-cycloalkylene, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
3
-C
8
cycloalkyl-ene-C
y
H
2y
— or unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted —C
y
H
2y
-(C
3
-C
8
-cycloalkylene)-C
y
H
2y
—, wherein y is an integer from 1 to 6; and
D is an isocyanato group.
One preferred definition of X is —O—, —NH— or —S—. Another preferred definition of X is lower alkylene. More preferably, X is —O— or —S— and especially —O—.
In a preferred definition of Y, the index n is 1 to 5, more preferably 2 to 4, and most preferably 2 or 3, so that Y is, for example, ethyleneoxy or propyleneoxy. In another preferred definition, Y is a direct bond, X then preferably containing at least one hetero atom.
The group R contains as alkyl, alkoxy, alkylNH- or —NR
1A
R
1B
preferably from 1 to 6 and especially from 1 to 4 carbon atoms. Some examples are methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy, propoxy, butoxy, N,N-dimethylamino and N-methylamino. Most preferably, R is H. A preferred definition of —NR
1A
R
1B
is N,N-dimethylamino, N-methylamino, N-methyl-N-ethylamino, N-ethylamino, N,N-diethylamino, N-isopropylamino or N,N-diisopropylamino.
R
1
is preferably allyl, benzyl or linear C
1
-C
4
alkyl, for example methyl or ethyl.
R
2
has preferably the same definitions as R
1
and is more preferably linear lower alkyl having from 1 to 4 carbon atoms and especially 1 or 2 carbon atoms. R
2
as aryl may be, for example, naphthyl or especially phenyl that is unsubstituted or substituted by lower alkyl or lower alkoxy. When R
1
and R
2
together are —(CH
2
)
m
—, m is preferably 4 or 5 and especially 5.
R
3
is preferably linear lower alkyl having from 1 to 4 carbon atoms, benzyl or allyl, and more preferably methyl or ethyl.
R
4
is preferably linear lower alkyl having from 1 to 4 carbon atoms and more preferably methyl or ethyl.
When R
3
and R
4
together are —(CH
2
)
z
—Y
1
—(CH
2
)
z
—, Y
1
is preferably a direct bond, —O— or —N(CH
3
)— and most preferably —O—; z is preferably 2 or 3 and especially 2.
R
5
is preferably linear or branched C
3
-C
18
alkylene, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
-alkoxy-substituted C
6
-C
10
arylene, unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
13
-C
24
arylenealkylenearylene or unsubstituted or C
1
-C
4
alkyl- or C
1
-C
4
alkoxy-substituted C
3
-C
8
cycloalkylene, and preferably linear or branched C
3
-C
11
alkylene, unsubstituted or C
1
-C
2
alkyl- or C
1
-C
2
alkoxy-substituted C
6
-C
10
arylene, unsubstituted or C
1
-C
2
-alkyl- or C
1
-C
2
alkoxy-substituted C
13
-C
24
arylenealkyleneazylene or unsubstituted or C
1
-C
2
alkyl- or C
1
-C
2
alkoxy-substituted C
3
-C
8
cycloalkylene.
Some examples of linear C
3
-C
18
alkylene are 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 1,14-tetradecylene and 1,18-octadecylene.
Some examples of branched C
3
-C
18
alkylene are 2,2-dimethyl-1,4-butylene, 2,2-dimethyl-1,5-pentylene, 2,2,3- or 2,2,4-trimethyl-1,5-pentylene, 2,2-dimethyl-1,6-hexylene, 2,2,3- or 2,2,4- or 2,2,5-trimethyl-1,6-hexylene, 2,2-dimethyl-1,7-heptylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6-trimethyl-1,7-heptylene, 2,2-dimethyl-1,8-octylene, 2,2,3- or 2,2,4- or 2,2,5- or 2,2,6- or 2,2,7-trimethyl-1,8-octylene.
When R
5
is arylene, it is preferably naphthylene and especially phenylene. When the arylene is substituted, one substituent is preferably in the ortho-position with respect to an isocyanate group. Examples of substituted arylene are 1-methyl-2,4-phenylene, 1,5-di-methyl-2,4-phenylene, 1-methoxy-2,4-phenylene and 1-methyl-2,7-naphthylene.
R
5
as aralkylene is preferably naphthylalkylene and especially phenylalkylene. The alkylene group in aralkylene contains preferably from 1 to 12, especially from 1 to 6, and more especially from 1 to 4 carbon atoms. Most preferably, the alkylene group in aralkylene is methylene or ethylene. Some examples are 1,3- or 1,4-benzylene, naphth-

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