CA2005283C - Radiation-sensitive, ethylenically unsaturated, copolymerizable compounds and their preparation - Google Patents

Abstract

Radiation-sensitive, ethylenically unsaturated compounds and a process for their preparation.
The ethylenically unsaturated organic compounds axe of the general formula (see formula I) where R is alkyl, aryl or a radical R1 and R1 is a radical (see formula II) where R2 to R6 are each H, alkyl, OH, OAlkyl, SH, SAlkyl, halogen, N(Alkyl)2 or N(Alkyl)(Aryl) and at least one but not more than three of the radicals R2 to R6 is or are a radical (see formula III) (see formula IV) where X is alkylene, cycloalkylene, oxaalkylene or arylene, Y is H or CH3- and Z is O or NY.
The novel radiation-sensitive ethylenically unsaturated compounds are suitable for the preparation of polymeric radiation-sensitive compounds.

Description

2UU~~~
O.Z. 0050/40443 Radiation-sensitive, ethylenically unsaturated, copolvmerizabie compounds and their preparation The present invention relates to novel radiation sensitive, ethylenically unsaturated phenone derivatives and a process for their preparation.
W-sensitive aceto- and benzophenones are fre-quently added as external initiators to radiation-sensitive polymers (eg. G. Li Bassi, J. Rad. Cur. _14 (1987), 18). In general, however, such procedures are not completely satisfactory since, after the initiator has been mixed with the polymer, problems with the com-patibility, the uniformity of the distributiOrc, the volatility, the odor, the toxicity, the exudation and the migration of the additive are encountered, frequently leading to an undesirable, premature and non-uniform reaction. In the actual exposure process, lower reac-tivity is then observed owing to lower effective initiator concentrations, and a number of troublesome secondary reactions are observed after exposure.
It is known that some of the stated problems can be solved if the radiation-sensitive initiator is copoly-merized with monomers by a conventional process, ie. is incorporated in a polymer chain. The photosensitive in-itiator is linked t~ the base polymer by means of an anchor group, ie. the spacer. The spacer also serves to reduce the influence of the base polymer chain on the photochemical behavior of the initiator.
In principle, therefore; copolymerizable in-itiators have the following structure:
z Initiator Spacer Reactive double bond Scheme I
U.S. Patents 3,214,492, 3,429,852, 3,622,848 and 4,304,895 describe acryloxy- or methacryloxy-substituted aceto- and benzophenone derivatives, for example .. 2005283 - 2 - O.Z. 0050/40443 I . I
' ' o These can be copolymerized with ethylene or other vinyl monomers to give polymers which can be cured by irradia-tion, for example after thermal forming. In the model according to Scheme I, the reactive double bond and the initiator are separated by the carbonyloxy group as a spacer in the case of these radiation-sensitive monomers.
From the photochemical point of view, these compounds are of less interest since the acryloyl substituent st311 has a very pronounced influence on the absorption of the in-itiator fragment at long wavelengths.
A similar situation is also observed in the case of the copolymerizable acetophenone acrylates described in DE-A-35 34 645, o CHj I
i-CH3 ' 0 in which the photoreactivity is reduced by virtue of the fact that the reactive acrylate group is too closely coupled to the carbon atom a to the carbonyl group. The reason for this behavior is that, during the photochemically initiated a cleavage, a further, not very reactive radical is formed in addition to the benzoyl radical.
To avoid substantially reducing the photochemical reactivity of the copolymerizable initiator compared with the parent substance, the reactive double bond must be decoupled mesomerically and inductively from the photo initiator moiety.
In 2-acryloylthioxanthone (Eur. Polym. J. 2~
(1987), 985) . I s I . o - 3 - O.Z. 0050/40443 the separation has not yet been completely achieved. The copolymer with methyl methacrylate is less reactive than 2-hydroxythioxanthone.
In 4-(4'-vinylbenzyloxy)-benzophenone, I
I
described in DE-A-28 18 763, the styrylbenzyloxy radical proves to be a good spacer.
In Uvecryl' P36, a commercial product from UCB, a particularly long spacer consisting of four ethyleneoxy units separates the benzophenone from the acryloxy radical.

I ~ I

This compound, which is described in, for ex-ample, Technical Bulletin 2480/885 (1985) of UCB or in New Polym. Mat. 1 (19 87), 63, can be used in photopoly-mers for coating materials. The synthesis is expensive, and this product has only moderate photochemical reac tivity since the spacer is too long.
The introduction of functional groups into the spacer does not significantly influence the photochemical s behavior of the chromophore if they are separated from one another by an alkyleneoxy group. The benzophenone derivatives of the type I . I . N_ xo I
OH
mentioned in EP-A-279 475 are examples of this.

- 4 - O.Z. 0050/40443 According to the abovementioned prior art, an ether or ester group should therefore form part of the spacer (Scheme II).
Initiator ~0~ ; ~0~ Reactive Io' double bond Scheme II
A novel spacer scheme is obtained by considering the influence and the function of the spacer as a sub-stituent on the photochemically excited aceto- or benzo-phenone fragment. For example, possible spacers are those which, owing to their structure, can have a stabil-izing or destabilizing effect.
In particular, the carbamoyl-substituted benzo-phenones of the type o ' ~N R
Scheme III
constitute an interegting class of substances from this point of view. U.S. Patent 3,322,818 describes allyl- or methallyl-substituted carbamoylbenzophenones. However, they are only suitable as fungicides (cf. Scheme IV).
r Carbamoyl group = 0 o ' ' NH-CNZ H-CHI
Initiator Spacer Double bond Scheme IV
An allyl or methallyl group is unsuitable for - 5 - O.Z. 0050/40443 copolymerizations. These benzoylphenyl allyl carbamates are therefore of no practical importance in the polymer sector.
Novel but photochemically less reactive monomers having an extremely long spacer are described in British Patent 2,100,722.
Finally, DE-A-3 820 463 claims monomers of the type (Scheme V) ~

Initiator NH-Scheme V
which are particularly reactive and conveniently obtain-able from hydroxyaromatics and (meth)acryloylalkyl iso-cyanates. The necessary isocyanates, for example ~O~NCO ( I EM ) or ~O~O~NCO (IOPM) are, however, very toxic and expensive to prepare.
It is an object of the present invention to pro vide radiation-sensitive, ethylenically unsaturated phenone derivatives, for example acetophenone, benzo phenone or thioxanthone derivatives, which are readily obtainable and contain a spacer optimally tailored to the phatoinitiator moiety.
A number of aceto- and benzophenone carbonates are known for various obligations.
In the total synthesis of griseofulvin (A.C. Day et al., J. Chem. Soc. 1 61, 4067), the compound H3C0 OCHj 0~~
H jC ~ I H H;C ~ I ~CH;
CI

- 6 - O.Z. 0050/40443 is used as an intermediate. Further examples of pharmacologically interesting carbonates of the above mentioned type are described in J. Chem. Soc. C 1969, 1721; ibid 1970, 392; Tetrahedron Lett. 1979, 4363, and Dutch Patent 7,008,636.
According to Japanese Preliminary Published Applications 54-002323 and 57-181001, the halogenated benzophenone carbonates Cl 0 ct ~ I ~ I ~o-Atkyt ci act as herbicides.
If, on the other hand, at least one OH group is introduced ortho to C=0 in the parent benzophenone structure, a substance belonging to the UV stabilizer class is obtained. As is evident in the Example below, chromophores I ~ ~_~ N ~ I

(cf. U.S. Patents 3,981,822, 4,115,348 and 4,174,321) or a further structural element having UV-absorbing proper ties, as described in USSR Patents 352,883 and 491,661 or Japanese Preliminary Published Applications 58-159460 and 61-130 362, are frequently attached to the benzophenone via the carbonate group.
Finally, the noncopolymerizable benzil dimethyl ketals I
C-OR

Alky l - 7 - O.Z. 0050/40443 and the benzoin monomethyl ethers C-H

Alkyl-0~0 mentioned in Japanese Preliminary Published Application 61-228007 are claimed for photopolymerization.
- Thus, only alkyl- and aryl-substituted aceto- and benzophenone carbonates which do not contain a functional group which permits copolymerization have been disclosed to date.
It is an object of the present invention to pro-vide copolymerizable phenone derivatives of the type R

Scheme VI
We have found that this object is achieved by ethylenically unsaturated copolymerizable, radiation-sensitive organic compounds of the general formula (I) R_~~_R 1 - ( I ) where R is straight-chain alkyl of 1 to 4 carbon atoms, prefer-ably methyl, ethyl or n-propyl, branched, unsubstituted or substituted alkyl of 3 or 4 carbon atoms, such as isopropyl,sec-hydroxyisopropyl,sec-dimethylaminopropyl, sec-morpholinopropyl or tert-butyl, aryl, eg. phenyl, tolyl or naphthyl, or a radical R1, and R1 is a radical R6 ~ ~ R4 RS

.. 2005283 - O.Z. 0050/40443 where R2 to Re are identical or different and are each H, alkyl of 1 to 4 carbon atoms, eg. methyl, ethyl, n-propyl, isopropyl or tert-butyl, phenyl, OH, OCH3, OCZHS, SH, SCH3, SCZHS, F, C1, Br, CN, COOH, COOAlkyl where alkyl is 1 to 17 carbon atoms, COOAryl, CF3, N(Alkyl)z, N ( Alkyl ) ( Aryl ) , N ( Aryl ) z, N~ ( Alkyl ) 3Ae, N~H ( Alkyl ) zAe where alkyl is of 1 to 4 carbon atoms and Ae is the anion of an acid, eg. Cle, S042e, P043e, acetates, BFde, CF3S03 , SbFfi , AsFfi or PFfi, and at least one but not more than three of the radicals Rz to R6 is a radical -o- ~-o-x-z-II j-cH z or -o- j"'o x z-~N cH z 0 ov o where X is a divalent, unsubstituted or substituted alkylene radical -(CHz)m-, a radical R
I
-C-R~~ m where m is from 1 to 10 and R' and R " are identical or different and are each aryl, eg. phenyl, C1-C4-alkyl, H, COOH, COOCH3 or COOC2H5, a perfluorinated alkylene radical (-CFz)m where m is 1 to 10, preferably a perfluoroethylene radical, an oxaalkylene radical Qf the type - ( CHz ) n-O- ( CHz ) p- where n and p are each from 1 to 5, preferably n and p are each 2, ie. -CZH~-O-CZH,-, a perfluorinated oxaalkylene radical of the type - (CFz ) ~,-O- ( CFz ) p- where_ n and p are each 1 to 5, for example tetrafluoroethylene, or a polyoxaalkylene radical which may be perfluorinated and has 2 to 20 s oxygen atoms which are bonded to one another via at least one -CHz-, -CFz- or -CHz-CH ( CH3 ) - group, or are each an alkylene radical of the type - ( CHz ) m O-CO-O- ( CHz ) n-. -( CHz ) n-O-CO-NH- ( CHz ) m- ~
- ( CHz ) n-~-CO-O- ( CHz ) m i - ( CHz ) m-CO-O- ( CHz ) n- Or - ( CHz ) m 0 3 0 CO- ( CHz ) n- where m and n are each from 1 to 10 , a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, eg. methyl, ethyl, n propyl or isopropyl, OH, OCH3, OC2H5, SH, SCH3, SC2H5, C1, F, N(Alkyl)2 or N(CH3)C6H5 in the o-, m- and/or p-position, or a cycloalkylene radical of 5 to 10 carbon atoms, eg.
cyclohexylene or cyclooctylene, or a (bis)methylene-cycloalkylene radical of 6 to 12 carbon atoms, Y is H, alkyl of 1 to 6 carbon atoms or phenyl, Z is 0 or NY
or, if R is aryl, one of the radicals R2 or R6 may be a sulfur atom by means of which the aryl radical R is bonded in the ortho-position with R1 and gives, for example, a thioxanthonyl radical.
The present invention also proposes an ethylenically unsaturated copolymerizable, radiation-sensitive organic compound of the formula (I) O

where R is aryl or a radical R1 and R1 is a radical R~
R R~
Rs where R2 and R6 are identical or different and each of the radicals can be H or one of the radicals 9a -0-C-0-X-Z-C-C=CH2 or to Y
-O-;I-0-X-Z-CH=CH2 , R3 to R5 are identical or different and each is H, alkyl of 1 to 4 carbon atoms, phenyl, OCH3, OC2H5, F, C1, Br, CN, COOAlkyl where alkyl is 1 to 17 carbon atoms, COOAryl, CF3, N (Alkyl) 2, N (Alkyl) - (Aryl) , N (Aryl) 2, I~(Alkyl) 3A0 or N~H(Alkyl)2 A~ where alkyl is of 1 to 4 carbon atoms, and A~
is the anion of an acid, and one of the radicals -0-C-O-X-Z-C-C=CH2 or [o to r -0-il-0-X-Z-CH=CH2 where at least one of the radicals R2 to R6 is a radical -O-C-0-X-Z-C-C=CH2 or il [l I

-0-li-0-X-Z-CH=CH2 O
where A ~~

r 9b X is a divalent, unsubstituted or substituted alkylene radical -CH2)m or R' -C-R"
r . m where m is from 1 to 10 and R' and R" are identical or different and each is H or alkyl, an oxaalkylene radical -(CH2)n-0-(CH2)p- where n and p are each from 1 to 5, or a polyoxaalkylene radical having 2 to 20 oxygen atoms which are bonded to one another via at least one -CH2- or -CH2- CH(CH3)-group, or a radical -(CH2)m-0-CO-0 (CH2)n-, -(CH2)n-NH-CO-0-(CH2)~ , -(CH2)m-CO-0-(CH2)n or - (CH2 ) m 0-CO- (CH2 ) n- where m and n are each from 1 to 10, an unsubstituted or substituted cycloalkylene radical of 5 to 10 carbon atoms, a (bis)methylenecycloalkylene radical of 6 to 12 carbon atoms or an unsubstituted or substituted o-, m- or p-phenylene radical, Y is H, alkyl of 1 to 6 carbon atoms or phenyl and Z is 0.
Surprisingly, the novel compounds have particularly high photochemical reactivity in the short wavelength to relatively long wavelength W range from 254 to 400 nm and a good shelf like.
It is a further object of the present invention to provide a process for the preparation of novel radiation-sensitive acetophenone, benzophenone and thioxanthone carbonates containing at least one terminal acrylate or methacrylate group.
.A

~~ ~p0 5283 The synthesis of aryl carbonates without a copolymerizable terminal group is known (Japanese Preliminary Published Applications 59-001 438 and 59-170 033). A good overview is given in: a) Houben-Weyl, Methoden der Organische Chemie, Vol 8, pages 75, 101-107, Thieme-Verlag 1952, b) Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 4, pages 758-771, John Wiley 1978, and c) Ullmann's Encyclopedia of Industrial Chemistry, Vol. A5, pages 197-202, Verlag Chemie 1986.
The most important preparation process for carbonates is the reaction of carbonic ester chlorides with alcohols.
Theprocedure is described in detail in Houben-Weyl, Vol. 8 (see above), German Patent 1,080,546 and J. Org. Chem. 26 (1961), 5119. The carbonic esters are formed in good to very good yields if the alcohol and the chlorocarbonic esters are reacted with one another in t .. ,.
L

- 10 - O.Z. 0050/40443 a molar ratio of 1 . 1 in the absence of a solvent or in excess alcohol as a solvent. Where the alcohol or the phenol and/or the chlorocarbonic ester are present as solids, aprotic solvents, eg. dichloromethane, dichloro-ethane, acetonitrile, toluene, xylene, etc. are used.
There are in principle two routes for the syn-thesis of the compounds stated in claim 1 (Scheme VII):

- 11 - O.Z. 0050/40443 a~
z of x i I O~ U
O ~O
i i O O
O
\_/
Z
O
Z
\ / N
+ N
O
N
O
v \ /
\ U
N

- 12 - O.Z. 0050/40443 The hydroxyacetophenones and hydroxybenzophenones required as starting materials can be prepared by known processes. For example, 4-hydroxybenzophenone is ob-tained in a yield of about 90% by Friedel-Crafts acyla-tion of phenol with benzoyl chloride in nitrobenzene in the presence of A1C13 or TiCl4 (Houben-Weyl 7/2a, page 186) or in the form of a pure isomer by oxidation of 4-hydroxydiphenylmethane with 5,6-dichloro-2,3-dicyano-p-benzoquinone (Houben-Weyl 7/2a, page 681).
- The syntheses of the amino-substituted benzo-phenones, eg. 2-benzyl-2-(dimethylamino)-1-(4-hydroxy-phenyl)-butan-1-one or 1-(4-hydroxyphenyl)-2-mE~~yl-2-morpholinopropan-1-one, are described in EP-A-284 561 and EP-A-117 233.
2-Hydroxythioxanthone can be prepared from thio-salicylic acid and phenol by the process described in British Patents 2,108,487 (1981) and 2,108,979 (1982).
The aromatic chloroformates (cf. J. Prakt. Chem.
(1971), 331, ibid 17 (1975), 62, 73 and 81) of the general formula (IIIb) can be prepared in good yields from a substituted phenol, -eg. 4-chloro-5'-fluoro-2'-hydroxybenzophenone, 4-chloro-4'-hydroxybenzophenone, 2,4-dihydroxybenzophenone,4,4'-dihydroxybenzophenone,4-fluoro-4'-hydroxybenzophenone, 2-hydroxybenzophenone, 4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxythioxanthone, 3-hydroxythioxanthone or 4-hydroxyphenyl 2-hydroxyprop-2-yl ketone (German Laid-Open Application DOS 3,534,645), by phosgenation with phosgene by standard processes known from the literature, cf. for example Houben-Weyl, Method-en der Organischen Chemie, Vol. 8, Thieme-Verlag 1952, trichloromethyl chloroformate (diphosgene), J. Prakt.
Chem. ~ (1930), 210, ibid ~ (1930), 233, Chem. Abstr.
81766, J. Org. Chem. ,~Q (1985), 715, J. Org. Chem. 41 (1976), 2070, Angew. Chem. ~ (197?), 267, crystalline triphosgene, Angew. Chem. ~ (1987), 922, N,N'-carbonyl diimidazole or N,N'-carbonyldi-s-triazole (Fieser _1 . ~. 200283 - 13 - O.Z. 0050/40443 {1967), 116).
Merck Kontakte 1 1 (1), 14-18, gives information about the use of alternative methods of phosgenation, for example reaction with chlorocarbonic esters.
The hydroxyalkylene (meth)acrylates and hydroxy-alkylene {meth)acrylamides are formed by acylation or esterification of suitable a, ~-alkanediols or amino-alcohols, for example 1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, ethanolamine, p-hydraxyaniline or diols such as poly-tetrahydrofuran, polyethylene oxide, or polypr~rylene oxide, with acyl chlorides, esters or anhydrides of acrylic and methacrylic acid. The transesterification reaction is of particular interest. For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl meth-acrylate, ethyl methacrylate, propyl methacrylate,~n-butyl methacrylate and tert-butyl methacrylate are used for transesterification. Methyl methacrylate is of par-ticular interest. When the process is carried out in practice, the acrylate or methacrylate can be used in less than the stoichiometric amount or, preferably, in excess. In general, from 1 to 1.5 times the molar amount, based on the diol, of the acrylate or meth-acrylate are used; an excess of from 1.5 to 5 times the amount should be avoided in particular in order to keep the amount of diacrylate to a minimum. In addition, the reaction mixture may contain solvents, eg. benzene, tolu-ene, xylene, chlorobenzene, dioxane, cyclohexane, n-heptane, n-octane, n-nonane or n-decane. The reaction is preferably carried out in the absence of solvents.
In general, a catalyst conventionally employed for transesterifications is used in the transesterifica-tion stage. Examples of suitable catalysts are alkali metal alcoholates, such as sodium methylate, ethylate or propylate, lithium methylate and, preferably, compounds of titanium, tin and zirconium. Examples are titanium - 14 - O.Z. 0050/40443 tetramethylate, tetraethylate, tetrapropylate and tetra-butylate, dibutyltin oxide, dibutyltin dilaurate, di-methoxydibutyltin and zirconium pentane-2,4-dionate.
The amounts of catalyst are frequently from 0.0005 to 0.5, preferably from 0.001 to 0.02, mole of catalyst per mole of diol. The transesterification is generally carried out at from 50 to 150°C, preferably from 80 to 120°C, with boiling of the reaction mixture, if necessary the alkanol liberated during the transesterification being distilled off from the reaction mixture together with some of the acrylate or methacrylate, as an azeotropic mixture.
After the transesterification reaction has been carried out, the excess acrylates or methacrylates and any solvent can be separated off from the reaction mix ture, for example, by distillation, preferably under reduced pressure. If desired, the monohydroxyalkylene (meth)acrylate obtained can be purified, for example by distillation under reduced pressure, by extraction or by crystallization. However, it is also possible for the reaction product of the transesterification stage to be fed to the next stage of the process without further purification or, if necessary, after removal of the catalyst or of its salt by hydrolysis and filtration.
In carrying out the acylation with (meth)acrylic anhydride, the educts are preferably used in stoichio-metric amounts. The reaction is carried out in general at from 80 to 140°C, preferably from 90 to 110°C. Par-ticularly suitable catalysts are acids, in particular conccentrated sulfuric acid, which are used in amounts of from 0.1 to 2 mol %. After the catalyst and (meth)-acrylic acid have been separated off, for example by neutralization with an aqueous base, eg. sodium carbonate solution or dilute sodium hydroxide solution, the crude product can be used in the next stage without further purification, if necessary after drying, for example with sodium sulfate or magnesium sulfate.

. M 2005283 - 15 - O.Z. 0050/40443 To prevent premature polymerization of the a,8-monoolefinically unsaturated reactants, a conventional stabilizer is preferably added to the reaction mixture.
Examples of suitable stabilizers are hydroquinone, hydro-quinone monomethyl ether, 2,6-di-tert-butyl-4-methyl-phenol, para-nitrosophenol and/or phenothiazine. Fur-thermore, it has proven extremely advantageous to pass oxygen or air through the reaction mixture during the acylation.
The hydroxyalkyl or hydroxyalkylene monovinyl ether are obtainable in good yields by the process des-cribed in Liebigs Ann. Chem. 601 (1956), 81.
The following (meth)acrylates, (meth)acrylamides and hydroxyalkyl vinyl ethers which can be used according to the invention may be mentioned by way of example:
~NHw/~OH

~NH~OH

iH;
~N~OH

iH3 ~N~OH

~Ow/~OH
'I0 ~O~OH

~Ow/~/OH

- 16 - O.Z. 0050/40443 ~O~OH

~O~OH

~O~OH

~Ow/~0 H

~O~O~O~pH

O~NH~OH

~NHJCpH

~NH ~ - ~ H
I'0 II N i_v H
'' 0 p-( }-OH

~0-C H 2-~-C H 2-OH

- 17 - O.Z. 0050/40443 ~0-CHZ-~CHZ-OH

OH

off cf. also CA 86, 107063a o (Deposited Doc. 1974, o VINITI 2066-74) ~N-~-OH

~O~OH
~O~O~OH
~0-~--OH
~0-CHZ-~-CHZ-OH
For the reaction of the hydroxyacetophenones, hydroxybenzophenones or hydroxythioxanthones, the corres ponding ~-(meth)acryloyloxyalkyl chloroformates are generally required. These can be prepared conveniently and in good yields by processes known from the litera ture, as described in , for example, Eur. Polym. J. 14 a (1978), 205; J. Polym. Sci. Polym. Symp. ,~~ (1979), 41;
Bull. Soc. Chim. Belg. ~ (1984), 159.
Surprisingly, we have found that the novel aceto-phenone, benzophenone and thioxanthone derivatives are obtainable readily and in very good yield by the routes A and B shown in Scheme VII. This is unexpected particularly in view of the reactivity and bifunctionality of the (meth)acrylate or vinyl ether - 18 - O.Z. 0050/40443 component, since many different reaction products are possible. Routes A and B differ in particular from the variant described in DE-A-3 820 463, in which isocyanates which are toxic and dif f icult to obtain are used under neutral conditions.
Routes A and B are more economical, more effi-cient and, because of the bifunctionality of the starting materials, novel compared with the prior art (cf. Houben-Weyl, Vol. 8, pages 75, 101-107).
The present invention furthermore relates to a process for the preparation of compounds of the general formula (I), wherein a compound of the formula (IIa) or (IIb) I I
I I
B~C~O-x-Z-il-i=CHZ or B~C~O-X-Z-CH=CHz (IIa) (IIb) where X, Y and Z have the abovementioned meanings and B is one of the groups tosylate, alkoxy of 1 to 5 carbon atoms, halogen, eg. C1 or Br, chlorocarbonyl, imidazolyl, pyrazolyl or an ammonium, pyridinium, phosphonium or sulfonium cation, preferably, for example, 2-(acryloyloxy)-ethyl _ or 2-(methacryloyloxy)-ethyl chlorocarbonate, 2-(methacryloyloxy)-ethyl chloroglyoxylate or 2-(meth)acryloyloxyethyl methyl carbonate, is reacted with a compound of the general formula (IIIa) R~-CI I ~ R9 ( rIIa) R12 ~ R10 where R' is straight-chain alkyl of 1 to 4 carbon atoms, branched, unsubstituted or substituted alkyl of 3 or 4 carbon atoms, aryl or a radical R1 and - 19 - O.Z. 0050/40443 Re to R12 are identical or different and are each H, alkyl of 1 to 4 carbon atoms, phenyl, OH, OCH3, OCZHS, SH, SCH3, SC2H5, F, C1, Br, CN, COOH, COOAlkyl where alkyl is of 1 to 17 carbon atoms, COOAryl, CF3, N(Alkyl)2, N(Alkyl)-( Aryl ) , N ( Aryl ) 2, N~ ( Alkyl ) 3Ae or N~Fi ( Alkyl ) zAe where alkyl is of 1 to 4 carbon atoms, and Ae is the anion of an acid, eg. Cle S0,''~, PO,~, acetates, BF; , CF3S03 , AsFs , SbFs , PFs etc . , or one of the radicals R8 or R12 is a sulfur atom by means of which the aryl radical is bonded in the ortho-position with R', with the proviso that at least one of the radicals RB to R12 is hydroxyl, in an equimolar ratio (if necessary with up to 20% excess) or, depending on the number of hydroxyl groups in the radicals R° to R12, in two or three times the equimolar ratio, in the presence or absence of an inert solvent or solvent mix-ture and of a basic catalyst, at from 0 to 100°C under anhydrous conditions (route B).
The present invention furthermore relates to a process for the preparation of compounds of the general formula (I), wherein a compound of the formula (IVa) or (IVb) H0-X-Z-C-C=CH2 Or HO-X-Z-CH=CH2 (IVs) _ (IVb) where X, Y and Z have the meanings stated in claim l, prefer-ably the (meth)acrylates, methacrylamides or hydroxyalkyl vinyl ethers stated above by way of example, is reacted with a compound of the general formula (IIIb) .z R~-C I ~ R9 ( IIIb) R12 ~ R10 where R' is straight-chain alkyl of 1 to 4 carbon atoms, pref-erably methyl, ethyl or n-propyl, branched, unsubstituted - 20 - O.Z. 0050/40443 or substituted alkyl of 3 or 4 carbon atoms, such as iso-propyl, hydroxyisopropyl, dimethylaminopropyl, morpholinopropyl or tert-butyl, or aryl, eg. phenyl, tolyl or naphthyl, preferably phenyl, and Re to R12 are identical or different and are each H, alkyl of 1 to 4 carbon atoms, eg. methyl, ethyl, n-propyl, iso-propyl or tert-butyl, phenyl, OH, OCH3, OCZHS, SH, SCH3, SCZHS, F, Cl, Br, CN, COOH, COOAlkyl where alkyl is of 1 to 17 carbon atoms, COOAryl, CF3, N(Alkyl)2, N(Alkyl)-(Aryl), N(Aryl)2, N~(Alkyl)3Ae, or N~I(Alkyl)2Ae where alkyl is of 1 to 4 carbon atoms, and Ae is the anion of an acid, eg. Cle, SO~~, P04~, acetates, BF4 , CF3S03 , Asi~'B'~; SbFs , PFB , etc . , or one of the radicals RB or R12 may be a sulfur atom by means of which the aryl radical is bonded in the ortho-position with R', with the proviso that at least one of the radicals RB to RlZ is a group of the type B-CO-O, where B has the meanings stated in formulae (IIa) and (IIb), for example o~C 1 ' ~ ss ~ ' o~ct 0 iH3 _ 0 ~ I i-CH;
C1 ' OH

0 ~ C-CH;
C1~0 ' I ~C1 0 ~ I CHg C1 ' CHj - 21 - O.Z. 0050/40443 o iH3 0 ~ C-CH 3 C 1 ~0 ~ I N
Ca~
0 iH3 0 ~ C-CH g C1~ ~ I ON~H C10 H
OI~CH3 0 N~
0 ~ C~3 Clue C t ~0 ~ I /
I

/ I / ~ o Cl 0 O~C 1 I

I \ I Cl a Cl ~ ~ C1 I ~ I 0 - 22 - O.Z. 0050/40443 0 O~C l Cl 0 ~ ~ 0 C 1 ~0 ~ I ~ I O~C 1 HO ~ I ~ I 0~C l 0 O~C 1 I OCHg in an equimolar ratio (if necessary in an excess of up to 10-30%) or, depending on the number of B-CO-0 groups in the radicals Re to R12, in two or three times the equi-molar ratio, in the absence of moisture and in the presence or absence of an inert solvent or solvent mix-ture and of a basic catalyst, at from 0 to 100°C, prefer-ably from 20 to 50°C (route A).
Regarding the preparation process, the following may be stated specifically.
The chloroformates used in the reaction react readily with nucleophiles, including water. In the reac-tion, it is therefore essential to exclude moisture by using dried nonnucleophilic solvents, eg. acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, tolu-ene, xylene, chlorobenzene, ethyl acetate, chloroform, etc., and if necessary to maintain an inert gas atmos-phere, for example nitrogen, argon or carbon dioxide.
As a rule, a solution or suspension of the hydroxy compound in an inert solvent, which may be omit ted if the compound is a liquid at the reaction temperature, is initially taken at from 0 to 100°C, . 2005283 - 23 - O.Z. 0050/40443 preferably from 10 to 50°C, in the presence of a basic, nonnucleophilic amine, preferably triethylamine, 4-dimethylaminopyridine, imidazole, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, polyvinylpyridine, N,N'-dimethylpropyleneurea, N,N'-dimethylethyleneurea, etc. The chloroformyl compound, if necessary dissolved in an inert solvent, eg. dichloro-methane, dichloroethane, acetonitrile, toluene, chloro-benzene, xylene, etc., is then added dropwise while stir-ring in the abovementioned temperature range. This pro-cedure is particularly suitable for relativelg large batches.
After stirring has been carried out for from 1 to 48, preferably from 1 to 20, hours at from 10 to 40°C, filtration, washing and drying are carried out by stan-dard methods and the product is isolated after recrystal-lization, distillation or extraction.
The acetophenones, benzophenones and thioxan thones into which functional groups have been introduced according to the invention are suitable as photo initiators, which are polymerizable or copolymerizable with unsaturated compounds, for radiation-curable com positions. _ Surprisingly, we have found that, from a certain spacer length upward, the photoinitiators provided with the carbonate group are more reactive after photochemical excitation than the derivatives described in, for ex-ample, DE-A-37 38 567. In contrast to the carbamoyl derivatives described in DE-A-38 20 463, the carbonates in the irradiated polymer do not tend to yellow and are completely odorless and universally applicable since they are readily compatible with many binders and binder systems.
For all compounds stated in the Examples below, the structure was confinaed in some cases by independent syntheses and in all cases by correct 1H-NMR, IR and mass - 24 - O.Z. 0050/40443 spectra and by conforming elemental analyses.

4-Chloroformylbenzophenone A total of 3.4 kg of phosgene were passed in the course of 5 hours into a solution of 4 kg of 4-hydroxy-benzophenone and 190 g of benzyltrimethylammonium chloride in 11.4 kg of o-xylene. During this time, the internal temperature was increased from 95 to 120°C.
After the end of the introduction of phosgene, stirring was continued for 30 minutes at 115°C. Working up was carried out by expelling the excess phosgene with nitrogen. The salt (catalyst) precipitated toward the end of the reaction was filtered off and the solvent was distilled off. 4.9 kg (93%) of yellowish 4-chloroformylbenzophenone of melting point 67-72°C were obtained. This crude product containing 12.69% of C1-(theoretical value 13.60%) was used directly for the subsequent reactions, without further purification.
The following chloroformyl compounds were prepar-ed by a method similar to that stated in Example 1:

2-Chloroformylthioxanthone (C1: calculated -12.19%; found = 12.03%) was obtained in 79% yield from 2-hydroxythioxanthone.-3-Chloroformylthioxanthone was obtainable in 63%
yield from 3-hydroxythioxanthone- (C1: calculated -12.19%; found = 11.22%).
s EXAMPLE 4 4-Chloroformylphenyl 2-hydroxyprop-2-yl ketone was obtained as a crude product (C1: calculated -14.61%; found = 13.07%) in 75% yield from 4-hydroxyphenyl 2-hydroxyprop-2-yl ketone.

Phosgenation of 1-(4-hydroxyphenyl)-2-methyl-2-morpholinopropan-1-one first gave the hydrochloride, which could be converted into the free amine after the - 25 - O.Z. 0050/40443 careful addition of 1,5-diazabicyclo[4.3.0]non-5-ene;
yield: 62% (C1: calculated = 11.37%; found = 11.21%).

4,4'-Benzoylphenyl ethyl carbonate 1.3 kg of 4-chloroformylbenzophenone in 2.2 kg of tetrahydrofuran were added dropwise at room temperature to a solution of 0.25 kg of ethanol and 0.53 kg of tri-ethylamine in 1.33 kg of tetrahydrofuran. The mixture was refluxed for 1 hour, cooled to 25-30°C and then stirred into 20 kg of ice water. The aqueous phase was extracted three times with dichloromethane and the organic phase was dried over sodium sulfate and evaporated down under reduced pressure. The residue was recrystallized from methanol. 1.05 kg (78%) of pale crystals of melting point 121-122°C were obtained.
The 4,4'-benzoylphenyl ethyl carbonate was iden-tical to authentic material (Can. J. Chem. 5~C (1978), 1031).

The asymmetric carbonates below were prepared by a method similar to that stated in Example 6.
No . Compound yield [ % ~

7 \ I \ I 0 83 0~OCH3 8- I I ~ 58 0 0~OCH3 9 I ' I 0 65 0~OCH3 10 0 ~ I ~ I 0 67 H 3C ~ ~ CH;

- 26 - O.Z. 0050/40443 No . Compound Yield [ % ]
0 iH3 0 ~ C-CH; 75 H3C0~0 ~ I OH

12 0 ~ I i-CH; 69 HgC z0~ ~ OH
0 iH;
13 ~ I i-CH; 52 OH

14 0 ~ CH; $$
H;C0~0 ~ I CH;
0 CH;
15 0 ~ I i-CH; 73 H;CO~ ~ N

16 ~ I ~ I O~OCH; 72 S

17 ~ I ~ I O~OCZHg 77 S

18 ~ I ~ I 0 70 S ~ O~CZHg - 27 - O.Z. 0050/40443 a, ~-Acryloylbutylene 4,4'-benzoylphenyl carbonate 13.0 kg of 4-chloroformylbenzophenone in 22 kg of toluene were added dropwise at from 25 to 30°C to a solution of 7.2 kg of butanediol monoacrylate and 5.3 kg of triethylamine in 17 kg of toluene. The mixture was stirred for 2 hours at room temperature and then washed in succession with water, with sodium bicarbonate solu-tion and then with water. The organic phase was dried over~sodium sulfate and evaporated down under reduced pressure from a water pump. 17.9 kg (97%) of a yellow-ish, viscous liquid, which was found to be pure hry thin-layer chromatography were isolated.

0.91 kg of 2-hydroxythioxanthone was suspended in a solution of 0.5 kg of triethylamine and 4.3 kg of toluene, and a solution of 0.81 kg of 2-chloroformyl ethyl methacrylate in 1.7 kg of toluene was slowly added dropwise to this mixture at from 20 to 24°C. After the addition of 0.002 kg of phenothiazine, stirring was carried out for 18 hours at room temperature. The or-ganic phase was then washed with water, with sodium bi-carbonate solution and again with water, dried over sodium sulfate and evaporated down under reduced pressure from a water pump, and the residue was recrystallized from isopropanol.
0 . 97 kg ( 63% ) of yellow crystals of melting point 72-76°C was obtained.

' The following compounds were synthesized by methods similar to those described in detail in Examples 19 and 20s 20U~~83 28 - O.Z. 0050/40443 No . Compound Yield [ ~ ]

0~0~0 22 ~ ~ 0 94 I II
0~0~0 23 I \ I 0 0 95 0~0~0 24 I \ I 0 0 49 0~0~0 H3i 0 25 H3C-C ~ 0 64 OH ~ I D~~

H; i 0 26 H gC-C ~ 0 71 OH ~ I 0~0 H3i 0 27 H3C N ~ I 76 28 I \ I 0~~~ 58 5~/ 00 - 29 - O.Z. 0050/40443 No . Compound Yield [ $ ]

H
29 ~ I ~ I ~ ~ I N
0 0 ~ 0 30 I \ I 0 0 97 O~O~N H

31 I \ I 0 42 32 I \ I 0 0 88 0~0~0~0 33 ~ ~ a 0 79 I 0~0~0 34 ~ ~ 0 82 I
s - 30 - O.Z. 0050/40443 Use of the acetophenone, benzophenone and thioxanthone derivatives as photoinitiators From 0.1 to 0.3 g of the photoinitiator to be tested, together with from 0.2 to 0.3 g of an amine and, if required, a sensitizer, are dissolved in a model polymer consisting of 62% by weight of a bifunctional epoxyacrylate (acrylate derived from bisphenol glycidyl ether), 35% by weight of hexanediol acrylate and 3% by weight of butanol (viscosity adjustment, film formation) and the solution is stirred for 1 hour. During this time, the measuring cell is prepared. It consists of two highly transparent NaCl windows separated by two films, each of which is 25 ~m thick. The polymer sample to be measured is now applied to one of the films and covered with the other, and the stack is clamped with the NaCl windows in a metal frame in such a way that a film about 10-30 ~m thick forms between the films.
This sandwich is exposed to a very high pressure mercury lamp (HBO 200 W) at a distance of 51 cm, inter ference filters furthermore permitting the selection of only one particular wavelength (eg. 330, 365 or 404 nm).
Before exposure, an IR spectrum of. the sample sandwich is recorded (t - 0) and this procedure is repeated after exposure for 5 seconds. In the case of a good photoinitiator, the intensity of the bands assigned to the acrylate groups has decreased substantially while those of the aromatic internal standard remain unchanged.
A number characteristic of the photoinitiator can be cal-culated from this for each band.
This evaluation is carried out for the three most intense acrylate bands and the values are added to give the initiator characteristic. This characteristic is purely a relative number and is from 1 to 15. The better the initiation of the polymerization by an initiator, the higher is its characteristic.
The characteristics correlate with the parameters 31 - O.Z. 0050/40443 typical of photopolymers, such as pencil hardness and Konig pendulum hardness.
The following values were found:

- 32 - O.Z. 0050/40443 U

.,i N
H

O
O

O .r r~ r-' co w c~
U

-1 ~t1 C 07 C~ N
fd s H
U

v a v x N

H

N ~ v i r-~

U

O

O

_~, T~ V
O Z Z
O V V
O O
O ~ '"
V
\ / \ / ~ ~ _ ~ \ / \ /
s V-O O O O
\ / \ / \ / \ /
s '~' O
f~7 ?r - 33 - O.Z. 0050/40443 U
N
.,i O N ,~ o _ b U ~ ~n ~p ,n ..~ cd +~ ~
~.~1 rt!
H U
H
O i i , N
i~
N
O
Z ~ n, en U
U ~ U U
O_ ~ O U O \ / \ /
O U-U
O
\ /
U \ /
V ~~ \ /
O O
CL O\
\ / ~O
/Z O
v z o s \ / /
Q~ ~ cr c~ ~ ~r, .~ ~ a s a ~ O
W ?.

- 34 - O.Z. 0050/40443 U

N

O O

b U ~ ~ rv s _ . , +~ Sa .r - r o~
-_ H U

C

N

y,.r N

N

N , U
i i ,~ ~

U

N

O
O ' O O
O
O
'd O O O O
O
U
s \ / \ / \ / \ /
O O O O
V C~
\ / \ / \ /
Z
? ? ? ?
~C O
W ?, .~ 200283 - 35 - O.Z. 0050/40443 U
.rl N
S-~ H
O O
b ~ ~ ~1 i b ~ ~? °' O~
H U
v C

O C

N

w ~ x H

cn r a U
d1 p, u~
~C O
wz - 36 - O.Z. 0050/40443 Legend to Examples:
41 : According to DE-A-35 34 645 42 : Obtainable in good yields from Darocut 2959 and isocyanatoethyl methacrylate 43 : Obtainable from Darocur 2959 and 2-chloroformyl-ethyl methacrylate in 79% yield 44 : Obtainablefrom2-benzyl-2-dimethylamino-1-[4-(2-hydroxyethyloxy)-phenyl]-butan-1-one and 2-chlorofonaylethyl methacrylate in 84% yield Examples 35 to 44 are Comparative Examples.

Claims (2)

1. An ethylenically unsaturated copolymerizable, radiation-sensitive organic compound of the formula (I) where R is aryl or a radical R1 and R1 is a radical where R2 and R6 are identical or different and each of the radicals can be H or one of the radicals R3 to R5 are identical or different and each is H, alkyl of 1 to 4 carbon atoms, phenyl, OCH3, OC2H5, F, C1, Br, CN, COOAlkyl where alkyl is 1 to 17 carbon atoms, COOAryl, CF3, N (Alkyl) 2, N (Alkyl) - (Aryl), N(Aryl) 2, N~(Alkyl)3A~ or N~H(Alkyl)2 A~ where alkyl is of 1 to 4 carbon atoms, and A~
is the anion of an acid, and one of the radicals where at least one of the radicals R2 to R6 is a radical where X is a divalent, unsubstituted or substituted alkylene radical -CH2)m-or where m is from 1 to 10 and R' and R" are identical or different and each is H or alkyl, an oxaalkylene radical -(CH2)n-O-(CH2)p- where n and p are each from 1 to 5, or a polyoxaalkylene radical having 2 to 20 oxygen atoms which are bonded to one another via at least one -CH2- or -CH2- CH(CH3)-group, or a radical -(CH2)m-O-CO-O-(CH2)n-, -(CH2)n-NH-CO-O-(CH2)m-, -(CH2)m-CO-O-(CH2)n or -(CH2)m-O-CO-(CH2)n- where m and n are each from 1 to 10, an unsubstituted or substituted cycloallkylene radical of 5 to carbon atoms, a (bis)methylenecycloalkylene radical of 6 to 12 carbon atoms or an unsubstituted or substituted o-, m-or p-phenylene radical, Y is H, alkyl of 1 to 6 carbon atoms or phenyl and Z is O.

2. The compound of the formula