Photoactivatable bases containing nitrogen

Details Photoactivatable bases containing nitrogen Photoactivatable bases containing nitrogen

2001-02-16

2002-12-03

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...

C522S028000, C522S049000, C522S050000, C522S053000, C522S056000, C522S057000, C522S062000, C522S063000, C522S065000, C522S120000, C522S121000, C522S126000, C522S129000, C522S148000, C522S167000, C522S170000, C522S174000

Reexamination Certificate

active

06489374

ABSTRACT:

The invention relates to &agr;-ammonium alkenes, iminium alkenes and amidinium alkenes in the form of their tetraaryl- or triaryl-alkylborate salts, to a process for the preparation thereof, as well as to the photochemical cleavage thereof to form amines, imines or amidines and to the use thereof in systems crosslinkable by base catalysis or in hybrid systems (compositions crosslinkable or polymerisable both by free radicals and by base catalysis).
&agr;-Ammonium alkene salts, especially 2-arylallylammonium salts, have already been described, for example in U.S. Pat. No. 3,539,632, J. Org. Chem. 52 (16) (1987), 3683 and in J. Am. Chem. Soc. 101 (11) (1979), 3097.
In addition to oligomers or monomers that are polymerisable by free radicals, systems catalysable by bases have also become known, especially for photolithographic procedures. Such systems require a photoinitiator which during irradiation splits off a base. R. MacKean et al., Polym. Mater. Sci. Eng. (1992), 66, 237-238, report, for example, on the photostructuring of polyimide, in which specific carbamates are used as photoinitiators.
The photolytic generation of bases and photopolymerisation reactions using those bases are also described, use being made of various types of photolabile compounds, e.g. carbamates (Cameron et al., U.S. Pat. No. 5,545,509 and references quoted therein; Cameron and Frechet, J. Am. Chem. Soc. (1991) 113, 4303), &agr;-keto-carbamates (Cameron et al., J. Am. Chem. Soc. (1996) 118, 12925), O-acyloximes (Tsunooka et al., J. Polymer Sci.: Part A: Polymer Chem. (1994), 32, 2177), formamides (Nishikubo et al., Polym. J. (1993) 25, 421; idem, J. Polymer Sci.: Part A: Polymer Chem. (1993), 31, 3013) and co-amine complexes (C. Kutal et al. J. Electrochem. Soc. (1987), 134, 2280).
It has now surprisingly been found that certain &agr;-ammonium alkenes, iminium alkenes and amidinium alkenes in the form of their tetraaryl- or triaryl-alkylborate salts split off an amine, imine or amidine group during irradiation with visible light or UV light. Those groups are sufficiently basic to trigger a plurality of base-catalysable reactions, especially polymerisation reactions. The compounds have a high level of sensitivity and their absorption spectrum can be varied within a wide range according to the substitution pattern chosen.
The compounds enable the preparation of so-called one-pot systems using base-catalysable oligomers or monomers, which have an extraordinarily high level of storage stability. For example polymerisation is not triggered until after irradiation. The systems can be formulated without or substantially without the use of solvents, since the compounds can be dissolved in the monomers or oligomers without any effect. The active catalyst is produced only after irradiation. Such systems can be used for a large number of purposes, for example for finishes, coatings, moulding materials or photolithographic images.
The invention relates to compounds of formula (I)
m is 1 or 2 and corresponds to the number of positive charges of the cation;
R
1
is 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, thianthrenyl, 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, those radicals being unsubstituted or mono- or poly-substituted by C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, NR
6
R
7
, N
3
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or by halogen, or R
1
is a radical of formula A or B
R
2
, R
3
and R
4
are each independently of the others hydrogen, C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl or phenyl or, independently of one another, R
2
and R
3
and/or R
4
and R
3
form a C
2
-C
12
alkylene bridge; or R
2
, R
3
, R
4
, together with the nitrogen atom to which they are bonded, form a phosphazene base of the type P
1
, P
2
, P
4
or a group of the structural formula (a), (b), (c), (d), (e), (f) or (g)
k and l are each independently of the other a number from 2 to 12;
R
5
, R
6
, R
7
, R
8
, R
9
and R
10
are each independently of the others hydrogen or C
1
-C
18
alkyl;
R
11
is C
1
-C
18
alkyl, C
2
-C
18
alkenyl, C
2
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, NR
6
R
7
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or halogen, and
n is 0 or a number 1, 2 or 3;
R
12
, R
13
and R
14
are phenyl or another aromatic hydrocarbon, those radicals being unsubstituted or mono- or poly-substituted by C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
1
C
18
haloalkyl, NO
2
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or by halogen;
R
15
is C
1
-C
18
alkyl, phenyl or another aromatic hydrocarbon, the phenyl and aromatic hydrocarbon radicals being unsubstituted or mono- or poly-substituted by C
1
-C
18
alkyl, C
3
C
18
alkenyl, C
3
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or by halogen, or R
15
is radical
and
X is C
1
-C
20
alkylene, C
2
-C
20
alkylene interrupted by —O—, —S— or NR
8
, or X is
By appropriate selection of the aromatic or heteroaromatic radical R
1
and of the borate anion, the absorption maximum can be varied within a wide range and thus the photosensitivity of the compounds can be shifted from UV into the daylight range.
Alkyl in the various radicals having up to 18 carbon atoms is a branched or unbranched radical, for example 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 or octadecyl. Preference is given to alkyl having from 1 to 12 or from 1 to 8 carbon atoms, especially from 1 to 6 or from 1 to 4 carbon atoms.
Alkenyl having from 3 to 18 carbon atoms is a branched or unbranched radical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having from 3 to 12 carbon atoms, especially from 3 to 6 carbon atoms. Alkynyl having from 3 to 18 carbon atoms is a branched or unbranched radical, for example propynyl (—CH
2
—C≡CH ), 2-butynyl, 3-butynyl, n-2-octynyl or n-2-octadecynyl. Preference is given to alkynyl having from 3 to 12 carbon atoms, especially from 3 to 6 carbon atoms.
The C
2
-C
12
alkylene bridge is ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene.
Halogen is fluorine, chlorine, bromine or iodine.
Examples of C
1
-C
18
haloalkyl are wholly or partially halogenated C
1
-C
18
alkyl. Examples include the position isomers of mono- to deca-fluoropentyl, mono- to octa-fluorobutyl, mono- to hexa-fluoropropyl, mono- to tetra-fluoroethyl and mono- and di-fluoromethyl, as well as the corresponding chlorine, bromine and iodine compounds. Preference is given to the. perfluorinated alkyl radicals. Examples include perfluoropentyl, perfluorobutyl, perfluoropropyl, perfluoroethyl and especially trifluoromethyl.
Examples of the NR
6
R
7
amino groups are the respective monoalkyl- or dialkyl-amino groups, such as methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, octadecylamino, dimethylamino, diethylamio, dipropylamino, diisopropylamino, di-n-butylamino, diisobut

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