Photoactivatable nitrogen-containing bases based on...

Details Photoactivatable nitrogen-containing bases based on... Photoactivatable nitrogen-containing bases based on...

2001-06-13

2002-06-25

Sanders, Kriellion A. (Department: 1714)

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

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C544S253000, C544S255000, C544S279000, C544S282000, C548S453000, C528S054000, C528S407000

Reexamination Certificate

active

06410628

ABSTRACT:

The invention relates to &agr;-amino ketones which can be converted photochemically into amidine derivatives, to a process for their preparation and to a process for the photochemical preparation of the amidine derivatives. Further subjects of the invention are base-polymerizable or crosslinkable compositions comprising these &agr;-amino ketones, a method of implementing photochemically induced, base-catalysed reactions, and the use of the &agr;-amino ketones as photoinitiators for base-catalysed reactions.
The photolytic cleavage of specific &agr;-amino ketones into free radicals and the photopolymerization of olefinically unsaturated monomers or oligomers which this initiates have long been known and are described, for example, in U.S. Pat. No. 5,077,402.
In addition to free-radically polymerizable oligomers or monomers, base-catalysable systems have been disclosed in particular for photolithographic processes. These systems require a photoinitiator which on exposure to light releases a base. D. R. MacKean et al., Polym. Mater. Sci. Eng. (1992), 66, 237-238 report, for example, on the photostructuring of polyimide using specific carbamates as photoinitiators.
It has now surprisingly been found that certain &agr;-amino ketones which comprise a structural unit of the formula (I)
release an amidine group on exposure to visible or UV light. This amidine group is sufficiently basic to initiate a large number of base-catalysable reactions, especially polymerization reactions. The compounds are of high sensitivity and through the choice of the substituent R
1
the absorption spectrum can be varied within a wide range.
The compounds make it possible to prepare so-called one-pot systems with base-catalysable oligomers or monomers having an extremely long storage life. A polymerization reaction, for example, is initiated only after exposure to light. The systems can be formulated with little or no solvent, since the compounds can be dissolved in the monomers or oligomers without being affected. The active catalyst is formed only after exposure to light. These systems can be employed for numerous purposes, such as for finishes, coatings, moulding compounds or photolithographic reproductions.
The invention provides organic compounds having a molecular weight of less than 1000, comprising at least one structural unit of the formula (I)
in which R
1
is an aromatic or heteroaromatic radical capable of absorbing light in the wavelength range from 200 to 650 nm and in doing so brings about cleavage of the adjacent carbon-nitrogen bond. The structural unit of the formula (I) features a divalent and monovalent nitrogen atom and a divalent and monovalent carbon atom, the nitrogen atoms being in &bgr; position relative to one another.
By aromatic or heteroaromatic radicals R
1
are meant those which conform to the Hückel 4n+2 rule.
The absorption maximum can be varied within a wide range through the choice of the aromatic or heteroaromatic radical R
1
, and so the photosensitivity of the compounds can be shifted from the UV into the daylight region.
Preference is given to organic compounds in which the structural unit of the formula (I) comprises compounds of the formula (II)
in which
R
1
is an aromatic or heteroaromatic radical which is capable of absorbing light in the wavelength range from 200 to 650 nm and in doing so brings about cleavage of the adjacent carbon-nitrogen bond;
R
2
and R
3
independently of one another are hydrogen, C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl or phenyl and, if R
2
is hydrogen or C
1
-C
18
alkyl, R
3
is additionally a group —CO—R
14
in which R
14
is C
1
-C
18
alkyl or phenyl; or R
1
and R
3
, together with the carbonyl group and the C atom to which R
3
is attached, form a benzocyclopentanone radical;
R
5
is C
1
-C
18
alkyl or NR
15
R
16
;
R
4
, R
6
, R
7
, R
15
and R
16
independently of one another are hydrogen or C
1
-C
18
alkyl; or
R
4
and R
6
together form a C
2
-C
12
alkylene bridge or
R
5
and R
7
together, independently of R
4
and R
6
, form a C
2
-C
12
alkylene bridge or, if R
5
is NR
15
R
16
, R
16
and R
7
together form a C
2
-C
12
alkylene bridge.
Alkyl in the various radicals having up to 18 carbon atoms is a branched or unbranched radical such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. Preference is given to alkyl having 1 to 12, especially 1 to 6 carbon atoms.
Alkenyl having 3 to 18 carbon atoms is a branched or unbranched radical such as propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having 3 to 12, especially 3 to 6 carbon atoms.
Alkynyl having 3 to 18 carbon atoms is a branched or unbranched radical such as propynyl (—CH
2
—CH≡CH), 2-butynyl, 3-butynyl, n-2-octynyl, or n-2-octadecynyl. Preference is given to alkynyl having 3 to 12, especially 3 to 6 carbon atoms.
The C
2
-C
2
alkylene bridge is ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene.
R
1
is preferably an aromatic radical which is unsubstituted or substituted one or more times by C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, NR
8
R
9
, N
3
, OH, CN, OR
10
, SR
10
, C(O)R
11
, C(O)OR
12
or halogen and is selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thiathrenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, &bgr;-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl, fluorenyl or phenoxazinyl, or R
1
is a radial of the formulae A, B or C
in which
R
8
, R
9
, R
10
, R
11
and R
12
are hydrogen or C
1
-C
18
alkyl;
R
13
is C
1
-C
18
alkyl, C
2
-C
18
alkenyl, C
2
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, NR
8
R
9
, OH, CN, OR
10
, SR
10
, C(O)R
11
, C(O)OR
12
or halogen; and n is 0 or a number 1, 2 or 3.
Examples of C
1
-C
18
alkyl, C
3
-C
18
alkenyl and C
3
-C
18
alkynyl have already been indicated above.
Halogen is fluorine, chlorine, bromine or iodine.
Examples of C
1
-C
18
haloalkyl are fully or partly halogenated C
1
-C
18
alkyl. The halogen (halo) here is F, Cl, Br, or I. Examples are the positional isomers of mono- to decafluoropentyl, mono- to octafluorobutyl, mono- to hexafluoropropyl, mono- to tetrafluoroethyl and mono- and difluoromethyl and also the corresponding chloro, bromo and iodo compounds. Preference is given to the perfluorinated alkyl radicals. Examples of these are perfluoropentyl, perfluorobutyl, perfluoropropyl, perfluoroethyl and, in particular, trifluoromethyl.
Examples of the NR
8
R
9
amino group are the respective monoalkyl or dialkylamino groups such as methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, octadecylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, di-n-butylamino, di-isobutylamino, dipentylamino, dihexylamino or dioctadecylamino. Further dialkylamino groups are those in which the two radicals independently of one another are branched or unbranched, for example methylethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, m

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