Novel trifunctional photoinitiators

IPC classes for russian patent Novel trifunctional photoinitiators (RU 2348652):

G03F7/031 -

G03F7/029 -

C08F2/50 - MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS (production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation, C10G0050000000; fermentation or enzyme-using processes to synthesise a desired chemical compound or composition or to separate optical isomers from a racemic mixture C12P; graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics or fibrous goods made from such materials D06M0014000000)

C08F2/46 - MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS (production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation, C10G0050000000; fermentation or enzyme-using processes to synthesise a desired chemical compound or composition or to separate optical isomers from a racemic mixture C12P; graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics or fibrous goods made from such materials D06M0014000000)

C07C49/84 - Ketones; Ketenes; Dimeric ketenes; Ketonic chelates

C07C49/83 - polycyclic

C07C49/813 -

C07C49/784 -

C07C45/71 - being hydroxy groups

C07C45/64 - by introduction of functional groups containing oxygen only in singly bound form

C07C45/63 - by introduction of halogen; by substitution of halogen atoms by other halogen atoms

C07C45/46 - Friedel-Crafts reactions

C07C271/20 - to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups

C07C269/02 - from isocyanates with formation of carbamate groups

C07C225/22 - having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton

C07C225/16 - and containing six-membered aromatic rings

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Polymerisation techniques / 2346010

FIELD: chemistry.

SUBSTANCE: invention concerns new photoinitiators, method of their obtainment, compositions hardening with irradiation, and application of those compositions in coating preparation. Invention claims photoinitiators of formulae I , where R₁, R₂, R₃ and R₄ are independently C₁-C₈alkyl or benzyl; or R₁ and R₂ together and/or R₃ andR₄ together are cyclohexyl; R₅ is hydrogen; A is OH, Br, -O-C₁-C₁₂alkyl, -O-R₇, where R₇ is linear or forked C₂-C₂₁hydroxyalkyl carbon chain interrupted by 1 to 9 oxygen atoms; or -NR₈R₉, where R₈ and R₉ are independently C₁-C₂₁alkyl or C₂-C₄alkyl substituted by one or more OH groups; A' is -O-; X and Y are independently -OH or -N(CH₃)₂; n is 2; R₆ is linear or forked divalent -CO-NH-(C₂-C₁₆alkylene)-(NH-CO)- radical or linear or forked -CO-NH-(C₀-C₉alkylene)-(NH-CO)- which can be interrupted by phenylene, or linear or forked divalent -C₂-C₅₀alkylene radical with carbon chain interrupted by 1 to 15 oxygen atoms.

EFFECT: efficient method of obtaining new organic photoinitiators.

11 cl, 20 cx

The text descriptions are given in facsimile form.

1. Photoinitiator formula I or II

in which

R₁, R₂, R₃and R₄independently of one another denote With₁-C₈alkyl or benzyl, or

R₁and R₂together and/or R₃and R₄together represent cyclohexyl;

R₅denotes hydrogen;

And IT denotes, Br, -O-C₁-C₁₂alkyl, -O-R₇where R₇- linear or branched C₂-C₂₁hydroxyalkyl carbon chain, which is interrupted by from 1 to 9 atoms of oxygen; or

And refers to-NR₈R₉where R₈and R₉independently of one another denote With₁-C₁₂alkyl or C₂-C₄alkyl, substituted by one or more groups;

A' represents-O-;

X and Y independently of one another denote-IT or-N(CH₃)₂;

n = 2;

R₆denotes a linear or branched divalently radical-CO-NH-(C₂-C₁₆alkylen)-(NH-CO)- or a linear or branched - CO-NH-(C₀-C₉alkylen)-(NH-CO)-, which can be interrupted by phenylene,

R₆, denotes a linear or branched divalently radical-C₂-C₅₀alkylen, the carbon chain of which is interrupted by from 1 to 15 oxygen atoms.

2. Photoinitiator according to claim 1 of formula V

in which

R₇denotes hydrogen, C₁-C₁₂alkyl or C₂-C₂₀hydroxyalkyl carbon chain, which is interrupted by from 1 to 9 atoms of oxygen.

3. Photoinitiator according to claim 1 of the formula

4. Photoinitiator according to claim 1 of formula VI

in which

n = 2 and

R₆denotes a linear or branched divalently radical-CO-NH-(C₂-C₁₆alkylen)-(NH-CO)- or a linear or branched-CO-NH-(C₀-C₉alkylen)-(NH-CO)-, which can be interrupted by phenylene, or

R₆denotes a linear or branched divalently radical-C₂-C₅₀alkylen, the carbon chain of which is interrupted by from 1 to 15 oxygen atoms.

5. Photoinitiator according to claim 1 of formula IX

in which

R₈and R₉independently of one another denote With₁-C₁₂alkyl or C₂-C₄alkyl, substituted by one or more groups.

6. The method of obtaining the compounds I or II, in which R₁, R₂, R₃and R₄independently of one another denote With₁-C₈alkyl or benzyl, or

R₁and R₂together and/or R₃and R₄together represent cyclohexyl;

R₅denotes hydrogen;

And IT denotes, Br, -O-C₁-C₁₂alkyl, -O-R₇where R₇- linear or branched C₂-C₂₁hydroxyalkyl carbon chain which p is harivamsa from 1 to 9 atoms of oxygen;

A' represents-O-;

X and Y represent-HE;

n = 2;

R₆denotes a linear or branched divalently radical-CO-NH-(C₂-C₁₆alkylen)-(NH-CO)- or a linear or branched-CO-NH-(C₀-C₉alkylen)-(NH-CO)-, which can be interrupted by phenylene, or R₆denotes a linear or branched divalently radical-C₂-C₅₀alkylen, the carbon chain of which is interrupted by from 1 to 15 oxygen atoms,

includes the following stages:

a) reaction difenilmetana with galogenangidridy acid of formula R₁R₂CH-COHal and optional subsequent reaction with galogenangidridy acid of formula R₃R₄SN-COHal in the presence of a catalyst of the Friedel -, resulting receive a mixture of isomers of the formula

in which R₁, R₂, R₃and R₄independently of one another denote C₁-C₈alkyl or benzyl, or

R₁and R₂together and/or R₃and R₄together represent cyclohexyl;

b) halogenoalkane mixture of isomers of the formula And subsequent bromirovanii and hydrolysis, resulting receive a mixture of isomers of the formula

in which R₁, R₂, R₃and R₄independent the one from another denote C ₁-C₈alkyl or benzyl, or

R₁and R₂together and/or R₃and R₄together represent cyclohexyl;

C) optional selective substitution of benzyl hydroxy-group in the resulting mixture of isomers of the formula In the reaction with alcohol in the presence of an acid as catalyst to obtain a simple ester,

with a carboxylic acid to obtain a complex ether,

with diola or diisocyanate to obtain a bridge connection.

7. The method of obtaining connection IX

includes the following stages:

in which R₁, R₂, R₃and R₄independently of one another denote C₁-C₈alkyl;

b) halogenoalkane mixture of isomers of the formula And subsequent bromirovanii, aminolysis of benzylbromide and hydrolysis of tertiary halides, resulting receive a mixture of isomers of the formula

in which

Rsub> 8and R₉independently of one another denote hydrogen, C₁-C₁₂alkyl or C₂-C₄alkyl, substituted by one or more groups.

8. Curing radiation, the composition comprising

(A) at least one ethyleneamine connection

(B) photoinitiator formulas I, II, V, VI, IX according to claims 1-5,

9. The composition of claim 8 in which the compound (A) is a resin containing free group HE free isocyanate groups or free carboxyl groups, and photoinitiator (In) associated with the resin.

10. The use of a composition of claim 8 in the manufacture of pigmented and non-pigmented coatings for surfaces that can be applied on images coatings, powder coatings, printing inks, inks for inkjet printing, gel coats, composites or coatings for optical fibers.

11. The use of a composition according to claim 9 as a coating for surfaces of packaging materials for food products.