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WO2021144395A1 - Composés d'anhydride d'acide dithiocarbamique carboxylique et compositions de ceux-ci - Google Patents

Composés d'anhydride d'acide dithiocarbamique carboxylique et compositions de ceux-ci Download PDF

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WO2021144395A1
WO2021144395A1 PCT/EP2021/050751 EP2021050751W WO2021144395A1 WO 2021144395 A1 WO2021144395 A1 WO 2021144395A1 EP 2021050751 W EP2021050751 W EP 2021050751W WO 2021144395 A1 WO2021144395 A1 WO 2021144395A1
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group
formula
compound
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alkyl
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Bertrand Schweitzer-Chaput
Paolo Melchiorre
Frank ARROYAVE
Aymeric CHAMPION
Fernando Bravo Lara
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Institut Catala dInvestigacio Quimica ICIQ
Institucio Catalana de Recerca i Estudis Avancats ICREA
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Institut Catala dInvestigacio Quimica ICIQ
Institucio Catalana de Recerca i Estudis Avancats ICREA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the present invention relates to certain carboxylic dithiocarbamic acid anhydride compounds and their use as photoinitiators in living free-radical polymerization reactions.
  • the invention also relates to curable or cross-linkable compositions comprising the carboxylic dithiocarbamic acid anhydride compounds of the invention.
  • Photopolymerization is currently used in industry in a broad range of applications such as coating of materials (for example, wood, metal or plastics), decorative paints for outdoor and indoor, binding with adhesives, advanced manufacturing (for example, 3D printing) and medical applications (for example, light-curable dental resins).
  • materials for example, wood, metal or plastics
  • decorative paints for outdoor and indoor
  • binding with adhesives for example, advanced manufacturing (for example, 3D printing)
  • medical applications for example, light-curable dental resins.
  • irradiation with high-intensity UV light is privileged as it enables using non coloured light absorbing initiation systems and allows for the fast release of free radicals within the resin to be cured or cross-linked together with fast curing times.
  • Safety measures however need to be taken when operating with UV light, as exposure of individuals to UV radiation causes health concerns (for example, vision and tissue damage).
  • irradiation with UV light at high intensity must be avoided to exclude the related health hazards, which causes the polymerization reaction to lose in efficiency.
  • irradiation with visible light would be preferred in order to avoid the above-mentioned health concerns, most photoinitiators operating under visible light are coloured systems, which typically results in a poor control over the aspect of the cured or cross-linked product and does not allow for the production of non-coloured products.
  • the effectiveness of a photoinitiator for polymerization can be measured by several parameters, such as the rate of polymerization, the achievable conversion of monomer, the curing/drying time, the polydispersity index of the formed polymer and the molecular weight of the formed polymer. Different degrees of control over these parameters are desirable depending on the targeted application. Living free-radical polymerization is widely used in industry for the preparation of polymers and polyolefins with a certain control on the degree of polymerization, molecular weight of the polymer and polydispersity index.
  • RAFT polymerization is a useful method to control the length of the polymer while providing a certain degree of homogeneity in polymer chain lengths.
  • RAFT polymerization as reported in Australian patent application AU2009900271 , is a mechanism where the propagation step involves a chain transfer agent that can reversibly and rapidly add to a certain polymer chain, which means that, when carried out under the control of a RAFT agent, the reaction mixture contains polymer chains with similar lengths, which allows for the formation of polymers with a narrow index of polydispersity and allows for carrying out block polymerization reactions in a reliable way.
  • the chain transfer agent for the RAFT control typically results from the addition of the RAFT agent to a growing polymer in the free radical form. Such addition is typically triggered by thermal initiators, such as azoisobutyronitrile (hereinafter, AIBN) and other diazo compounds, or photoinitiators (for example, irradiation with gamma rays or light). Consequently, the use of a RAFT agent typically requires the use of an external initiator.
  • Typical RAFT agents are compounds of formula Z-CS2-R wherein the moiety of formula Z-CS2- acts as chain transfer agent. Typical RAFT agents, as reviewed by Rizzardo and co-workers (Rizzardo E., Moad G., Thang S.H.
  • RAFT Polymerization in Bulk Monomer or in (Organic) Solution in Handbook of RAFT polymerization belong to the family of trithiocarbonates (general formula: Z-S-C(S)-S-R), dithioesters (general formula: Z- C(S)-S-R) or dithiocarbamates (general formula: Z-NR’-C(S)-S-R).
  • RAFT agents are also usually good chain transfer agents for a narrow range of monomers and need to be carefully chosen with account taken of the polymer to be produced.
  • the reported compound is able to absorb light in the visible light range and undergo the initiation of a free radical polymerization (through the generation of a free radical) at a wavelength at which the chain transfer agent responsible for the controlled polymerization decomposes very slowly.
  • This subtle balance allows the prepared compound to undergo both photoinitiation and controlled polymerization.
  • the photolysis of the reported compound leads to the formation of two free radicals, one of which can trigger the polymerization and act as an initiator while the second one bearing a N- carbazole unit (which, therefore, strongly absorbs in the visible light range) recombines to act further as a chain transfer agent.
  • This compound cannot provide discoloration of the polymer concomitantly with a controlled polymerization.
  • Dithiocarbamate compounds are well known in the art as well as their use as chain transfer agent in RAFT polymerization reactions. Much fewer carboxylic dithiocarbamic acid anhydride have, however, been reported and have barely been used in the art as photoinitiators for polymerization (except by Lalevee et al as described above for compound BEC). For instance, Ashirbaev and co-workers described a benzoic dithiocarbamic acid anhydride derived from pyrrolidine as a reaction intermediate in the copper-catalysed coupling reaction of benzoyl chloride with difluorinated organozinc reagents (Ashirbaev, S. et al., J. Org. Chem. 2018, 83, 478). The authors report in particular a compound of formula (XII)
  • carboxylic dithiocarbamic acid anhydride compounds useful as photoinitiators for living free-radical polymerization reactions of olefins, in particular of acrylate-type olefins.
  • the developed carboxylic dithiocarbamic acid anhydride compounds are compounds of formula (I) which are prompt to be cleaved upon irradiation with light (preferably, with visible light) in the free radicals of formulae (II) and (III) according to reaction (1 ) included below:
  • the free radical of formula (II) is suitable for the initiation of a free radical olefin polymerization reaction (by attack of the radical of formula (II) to the double bond of monomer molecule), while the free radical of formula (III) is suitable to act as a chain transfer agent in a controlled living polymerization reaction according to a RAFT mechanism.
  • the specific carboxylic dithiocarbamic acid anhydride group in the compound of formula (I) facilitates that the compounds of formula (I) absorb light in a broad range of the spectrum (300 - 600 nm) and in particular in the visible range of the spectrum, in particular in the 400-500 nm region (blue light), which advantageously allows for the formation of radicals of formulae (II) and (III), even when blue light is used as irradiation system. This advantageously allows avoiding the use of UV light in polymerization applications, hence avoiding the health hazards of UV irradiation.
  • reaction (2) The inventors have also found that the equilibrium of reaction (1) actually competes with a side reaction (2), responsible for deactivation of the initiating system and for the instability upon storage of compounds incorporating a carboxylic dithiocarbamic acid anhydride group by thermal decomposition, see reaction (2) included below:
  • the inventors of the present invention have surprisingly found compounds of formula (I) wherein q and the X, Y, Ri , R and R 3 groups were found to provide improved photoinitiator systems for living polymerization induced by light irradiation and in particular, by visible light irradiation such that the compound of the invention is thermally stable (negligible rate of the reaction (2)) and triggers a living controlled free-radical polymerization when irradiated with light and put in presence of an olefin monomer (polymerization is faster than the photolytic degradation of the compound of formula (I) described in the art).
  • the present invention refers to a compound of formula (I) wherein q is 0 or 1 , when q is 0, Ri is a radical selected from the group consisting of a branched (C 3 -Ci2)alkyl radical attached to the carbonyl group of the compound of formula (I) through a tertiary or quaternary carbon atom; a ring system attached to the carbonyl group of the compound of formula (I) through a quaternary carbon atom and comprising from one to four rings, wherein each ring is saturated, each ring comprises from 3 to 7 members selected from the group consisting of C, CH, CH 2 , NH, O and S, and each ring is optionally substituted at any available position with one or more radical selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acy
  • R 2 and R 3 are each a radical independently selected from the group consisting of (Cr Ci 2 )alkyl group; (C 5 -C2o)heteroaryl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr Cejalkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; and (C 6 - C 2 o)aryl group optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (CrC 6 )alkyloxy, halo, (Cr Cejalkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they
  • the inventors have surprisingly found that the R 2 and R 3 groups in the compound of formula (I) or (XII) of the invention allow for preparing polymers with narrower distribution of molecular weights than with the carboxylic dithiocarbamic acid anhydride initiators known in the state of the art.
  • dithiocarbamate RAFT agents described in the state of the art require large induction periods in visible-light triggered polymerization reactions, it was also surprisingly found that the R 2 and R 3 groups in the compound of formula (I) or (XII) allow for a significant reduction of said induction time.
  • the present invention refers to a process for the preparation of a compound of formula (I) of the present invention.
  • the present invention in a third aspect, refers to the use of a compound of formula (I) or of formula (XII) as defined in the first aspect of the invention as a photoinitiator for polymerization.
  • Such polymerization reaction provides polymer materials that incorporate both radicals of formulae (II) and (III) as end groups of the polymer chain.
  • the present invention refers to a compound of formula (IV) wherein n is an integer of from 1 to 5; each P is a polymeric block consisting of a polymerized product of a composition comprising a monomer having a polymerizable carbon-carbon double bond and wherein q, X, Y, Ri, R and R are as defined in the first aspect of the invention.
  • the compound of formula (IV) incorporates both radicals of formulae (II) and (III) as end groups of the polymer chain.
  • the compound of formula (IV) is advantageously functionalizable at the end of the polymer chain, thanks to the presence of a carbonyl group, via chemical modification of the carbonyl group.
  • the compound of formula (IV) may also further act as a macromolecular chain transfer agent in RAFT processes.
  • the present invention refers to a process for the preparation of a compound of formula (IV) of the present invention.
  • the present invention refers to the use of the compound of formula (IV) of the present invention (and as defined in the fourth aspect of the present invention) as chain transfer agent.
  • the present invention refers to a composition comprising:
  • the present invention refers to a process for the preparation of a cross-linked material comprising the step of irradiating the composition of the seventh aspect of the present invention with light, preferably with blue light, wherein when the composition does not comprise a compound of formula (I) or of formula (XII) according to the present invention, it further comprises a polymerization initiation system.
  • the present invention refers to a cross-linked material obtainable by the process of the eighth aspect of the invention.
  • Figure 1 shows the evolution of the conversion of monomer into polymer (in %, this is the percentage of monomer polymerized with regard to the total monomer added initially) over time (in minutes) for methyl acrylate when put in presence of 0.5 mol% of a compound of formula (la) (black line with a cross marker), (lb) (black line with a triangular marker), (lc) (black line with a diamond-shaped marker) , (Id) (black line with a square marker), (le) (black line with a circular marker), (G) (black dotted line ⁇ , comparative example) and
  • BEC black dotted line - , comparative example
  • irradiated with blue light as measured following the method described in Example 2.
  • the y-axis refers to the % of conversion of monomer into polymer (percentage of monomer polymerized with regard to the total monomer added initially) and the x-axis refers to the time in minutes.
  • Figure 2 shows the evolution of the conversion of monomer into polymer (in %, this is the percentage of monomer polymerized with regard to the total monomer added initially) over time (in minutes) for methyl acrylate when put in presence of 0.5 mol% of a compound of formula (If) (black plain line), (Ig) ( — line), (Ih) ( line) and BEC ( — — line) and irradiated with blue light, as measured following the method described in Example 2.
  • the y-axis refers to the % of conversion of monomer into polymer (percentage of monomer polymerized with regard to the total monomer added initially) and the x-axis refers to the time in minutes.
  • Figure 3 shows the absorbance with regard to the wavelength of light (in nm) of a mixture consisting of methyl acrylate and the compound of formula (Id) in 0.5 mol% amount before (plain line) and after (dashed line) irradiation with blue light (400 mW per cm 2 , 460 nm) during 15 minutes.
  • the y-axis refers to the absorbance of the mixture (arbitrary units), and the x-axis refers to the wavelength in nm.
  • the y-axis refers to the % of conversion of monomer into polymer (percentage of monomer polymerized with regard to the total monomer added initially) and the x-axis refers to the time in minutes.
  • any ranges given include both the lower and the upper end-points of the range. Ranges given, such as temperatures, times, molar ratio and the like, should be considered approximate (this is, with a 5% margin of variation around the indicated points), unless specifically stated.
  • free radical and its plural refer to a molecule bearing an atom with an unpaired valence electron.
  • halo or “halogen” or their plurals refer to a halogen radical or group, they thus refer to fluoro, chloro, bromo or iodo.
  • alkyl and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims.
  • alkyl groups include, but are not limited to: methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, pentyl, and hexyl.
  • branched alkyl and its plural refer to a saturated hydrocarbon group having the number of carbon atoms indicated in the description or in the claims wherein at least one of the carbon atoms is tertiary or quaternary.
  • branched alkyl groups include, but are not limited to, iso-propyl, iso-butyl, tert-butyl, isobutyl, neo-pentyl, 2-methylpentyl and 2-methylhexyl.
  • alkene and its plural refer to a saturated linear or branched hydrocarbon compound having the number of carbon atoms indicated in the description or in the claims and at least one carbon-carbon double bond.
  • tertiary carbon atom and its plural refer to a carbon atom in a saturated hydrocarbon group having three substituents other than hydrogen.
  • quaternary carbon atom and its plural refer to a carbon atom in a saturated hydrocarbon group having four substituents other than hydrogen.
  • alkyloxy and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the formula through an ether group (-0-).
  • alkylamino and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the formula through an amino group (-NH-).
  • acylamido and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims, which is attached to the remainder of the formula through a carbonylamino group (that is, a group of formula G-CONH- wherein G is the saturated linear or branched hydrocarbon group).
  • alkylaminocarbonyl and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims, which is attached to the remainder of the formula through an aminocarbonyl group (that is, a group of formula G-NHCO- where G is the saturated linear or branched hydrocarbon group).
  • alkyloxycarbonyl and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims, which is attached to the remainder of the formula through an oxycarbonyl group (that is, a group of formula G-OCO- where G is the saturated linear or branched hydrocarbon group).
  • acyloxy and its plural refer to a saturated linear or branched hydrocarbon group having the number of carbon atoms indicated in the description or in the claims, which is attached to the remainder of the formula through a carbonyloxy group (that is, a group of formula G-COO- where G is the saturated linear or branched hydrocarbon group).
  • photopolymerization and its derivatives refer to a process initiated thanks to light irradiation and through which a polymer is formed.
  • photoinitiator and its plural refer to a substance which, when submitted to light irradiation, is able to generate reactive species and trigger a chemical transformation, such as a free radical polymerization process.
  • photoiniferter and its plural refer to a substance which, when submitted to light irradiation, is able to generate reactive species suitable for the initiation, transfer and termination of a free radical polymerization carried out under the control of chain transfer agent.
  • Dithiocarbamate compounds are known photoiniferters.
  • a “photoiniferter” is a specific class of “photoinitiators”.
  • RAFT agent and its plural refer to a substance or reagent for free radical polymerization processes controlled through the RAFT mechanism.
  • (C 6 -C2o)aryl and its plural refer to an aromatic hydrocarbon ring system comprising from 1 to 5 6-membered aromatic rings.
  • (C 5 -C2o)heteroaryl and its plural refer to an aromatic ring system comprising from 1 to 6 aromatic rings comprising each 5 or 6 members independently selected from the group consisting of C, CH, N, NH, O and S.
  • a cyclic ring A is said to be “fused” with another cyclic ring B when the rings A and B have two adjacent members in common in their cyclic structure.
  • the term “acrylate” and its plural refer to polymerizable compounds comprising in their molecular formula the triradical of formula
  • the term “methacrylate” and its plural refer to polymerizable compounds comprising in their molecular formula the triradical of formula
  • acrylamide and its plural refer to polymerizable compounds comprising in their molecular formula the triradical of formula
  • chain transfer agent and its plural refer to a substance able to react with a chain carrier by a reaction in which the original chain carrier is deactivated and a new chain carrier is generated.
  • polymer block and its plural refer to the product of the polymerization of a polymerizable mass, such as an olefin compound, such that the formed polymer has a single type of repeating units in its molecular formula.
  • a polymerizable mass such as an olefin compound
  • polymethylacrylate is a polymeric block resulting from the polymerization of methyl acrylate.
  • polyethylene is a polymeric block resulting from the polymerization of ethylene.
  • the present invention refers to a compound of formula (I) as defined above.
  • the compound of formula (I) is one wherein when q is 0, Ri is a radical selected from the group consisting of a branched (C3-Ci 2 )alkyl radical attached to the carbonyl group of the compound of formula (I) through a tertiary or quaternary carbon atom; a ring system attached to the carbonyl group of the compound of formula (I) through a quaternary carbon atom and comprising from one to four rings, wherein each ring is saturated, each ring comprises from 3 to 7 members selected from the group consisting of C, CH, CH 2 , NH, O and S, and each ring is optionally substituted at any available position with one or more radical selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Cr C 6 )acylamido, (Ci-
  • the compound of formula (I) is one wherein q is 1 .
  • the compound of formula (I) is one wherein q is 1 , X and Y are each independently selected form the group consisting of (Ci-C 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C3-C 8 )cycloalkyl ring.
  • the compound of formula (I) is one wherein q is 1 , X and Y are each a methyl group or, alternatively, X and Y together with the carbon atom to which they are attached form a (C3-C 6 )cycloalkyl ring.
  • the compound of formula (I) is one wherein q is 1 , X and Y are each a methyl group.
  • the compound of formula (I) is one wherein q is 1 and Ri is a substituent selected from the group consisting of cyano, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Ci-C 6 )alkylaminocarbonyl, an amidine group and a phenyl group optionally substituted at any available position with one or more substituents selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, (Cr C 6 )alkylcarbonyl, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Ci-C 6 )perfluoroalkyl, halo, nitro, di(Ci-C 6 )alkylamino and cyano.
  • Ri is a substituent selected from the group consisting of cyano, (Ci-C 6
  • the compound of formula (I) is one wherein q is 1 and Ri is a substituent selected from the group consisting of cyano, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Ci-C 6 )alkylaminocarbonyl and a phenyl group.
  • (I) is one wherein q is 1 , X and Y are each independently selected form the group consisting of (Ci-C 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C3-C 8 )cycloalkyl ring; and Ri is a substituent selected from the group consisting of cyano, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Cr
  • C 6 )alkylaminocarbonyl an amidine group and a phenyl group optionally substituted at any available position with one or more substituents selected from the group consisting of (Cr C 6 )alkyl, (Ci-C 6 )alkyloxy, (Ci-C 6 )alkylcarbonyl, (Ci-C 6 )alkyloxycarbonyl, (Cr C 6 )alkylcarbonyloxy, (Ci-C 6 )perfluoroalkyl, halo, nitro, di(Ci-C 6 )alkylamino and cyano; preferably, X and Y are each a methyl group.
  • (I) is one wherein q is 1 , X and Y are each independently selected form the group consisting of (Ci-C 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C3-C 8 )cycloalkyl ring; and Ri is a substituent selected from the group consisting of cyano, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Cr
  • the compound of formula (I) is one wherein q is 0.
  • Ri is a radical selected from the group consisting of a branched (C3-C 8 )alkyl radical attached to the carbonyl group of the compound of formula (I) through a tertiary or quaternary carbon atom; a ring system attached to the carbonyl group of the compound of formula (I) through a quaternary carbon atom and comprising from one to four rings, wherein each ring is saturated, each ring comprises from 3 to 7 members selected from the group consisting of C, CH and CH 2 , and each ring is optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; and
  • Ri is a radical selected from the group consisting of a branched (C3-C 8 )alkyl radical attached to the carbonyl group of the compound of formula (I) through a quaternary carbon atom; a ring system attached to the carbonyl group of the compound of formula (I) through a quaternary carbon atom and comprising from one to four rings, wherein each ring is saturated, each ring comprises from 3 to 7 members selected from the group consisting of C, CH and CH 2 , and each ring is optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl and halo; and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of brom
  • Ri is a radical selected from the group consisting of isopropyl; 1 -methylpropyl; 1 - ethylpropyl; tert-butyl; 1 , 1 -dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 -diethylpropyl; 1- methylcyclohexyl; 1-methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; ad am an ty I; and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of bromo and (CrCi 2 )alkyl, and further optionally, yet preferably, substituted at any available
  • Ri is a radical selected from the group consisting of isopropyl; 1 -methylpropyl; 1 - ethylpropyl; tert-butyl; 1 ,1 -dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 -diethylpropyl; 1- methylcyclohexyl; 1-methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; ad am an ty I; and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a methyl group, and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of (CrC 6 )alkyl, (Cr Cejalkyloxy and halo.
  • a radical selected from the
  • Ri is a radical selected from the group consisting of isopropyl; 1 -methylpropyl, 1 - ethylpropyl, tert-butyl, 1 ,1 -dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1 -diethylpropyl, 1- methylcyclohexyl, 1-methylcyclopentyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl.
  • Ri is a radical selected from the group consisting of tert-butyl, 1 ,1 -dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1 -diethylpropyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl.
  • q is 0 and Ri is a radical selected from the group consisting of adamantyl and 2,4,6- trimethylphenyl.
  • Ri is as defined in any of the embodiments described above, R 2 and R are each a radical independently selected from the group consisting of (CrCi 2 )alkyl group; (C 5 -C 20 )heteroaryl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Cr C 6 )acylamido, (CrC 6 )acyloxy and nitro; and (C 6 -C2o)aryl group optionally substituted at any available position with one or more radicals selected from the group consisting of (Cr C 6 )alkyl, (CrC 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (
  • Ri is as defined in any of the embodiments described above
  • R 2 and R 3 are each a radical independently selected from the group consisting of (CrCi 2 )alkyl group; (C 5 -C 20 )heteroaryl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Cr C 6 )acylamido, (CrC 6 )acyloxy and nitro; and (C 6 -C 2 o)aryl group optionally substituted at any available position with one or more radicals selected from the group consisting of (Cr C 6 )alkyl, (CrC 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido
  • R 2 and R 3 are each a radical independently selected from the group consisting of (Ci-C 6 )alkyl group and a phenyl group optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Cr C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, S and O, wherein the ring is optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Cr C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, and S, wherein the ring is optionally fused with one or two phenyl groups optionally substituted at any available position with one or more radicals selected
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Cr C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring selected from the group consisting of pyrrolidine, piperazine, morpholine, thiomorpholine, oxazolidine, thioxazolidine and piperidine, wherein said ring is further optionally fused with one or two radicals selected from the group consisting of (Ci-C 6 )alky
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of methyl and methoxy; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring selected from the group consisting of pyrrolidine, piperazine, morpholine, thiomorpholine, oxazolidine, thioxazolidine and piperidine, wherein said ring is further optionally fused with one or two phenyl groups.
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl, ethyl, 4-methylphenyl and 4-methoxyphenyl; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic cyclic ring system selected from the group consisting of pyrrolidine and phenothiazine.
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of bromo and (CrCi 2 )alkyl, and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of bromo and (CrCi 2 )alkyl, and further optional
  • R 2 and R 3 are each a radical independently selected from the group consisting of (Cr Cejalkyl group; and a phenyl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, S and O, wherein the ring is optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr C 6 )alkyloxy, halo, (C
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of bromo and (Ci-Ci 2 )alkyl, and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of bromo and (Ci-Ci 2 )alkyl, and
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyloxy, halo, (Cr Cejalkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, and S, wherein the ring is optionally fused with one or two phenyl groups optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (CrC 6
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of bromo and (Ci-Ci )alkyl, and further optionally, yet preferably, substituted at any available position with a radical
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of bromo and (CrCi 2 )alkyl, and further optionally, yet preferably, substituted at any available position with a radical
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a radical selected from the group consisting of bromo and (Ci-Ci )alkyl, and further optionally, yet preferably, substituted at any available position with a radical
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a methyl group and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyl, (CrC 6 )alkyl, (CrC 6 )
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a methyl group and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyl, (Ci-C 6 )alkyl, (Ci-
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a methyl group and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyl, (Ci-C 6 )alkyl, (Ci-
  • Ri is a radical selected from the group consisting of isopropyl; 1- methylpropyl; 1 -ethylpropyl; tert-butyl; 1 ,1-dimethylpropyl; 1 -methyl- 1-ethylpropyl; 1 ,1 - diethylpropyl; 1-methylcyclohexyl; 1 -methylcyclopentyl; bicyclo[2.2.1]heptyl; bicyclo[2.2.2]octyl; adamantyl and a phenyl group substituted at one or both carbon atoms adjacent to the carbon atom of the phenyl group that is attached to the carbonyl group of the compound of formula (I) with a methyl group and further optionally, yet preferably, substituted at any available position with a radical selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyl, (CrC 6 )alkyl, (CrC 6 )
  • Ri is a radical selected from the group consisting of tert-butyl, 1 ,1- dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1-diethylpropyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl; and R 2 and R 3 are each a radical independently selected from the group consisting of (CrC 6 )alkyl group; and a phenyl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (CrC 6 )alkyloxy, halo, (Cr Cejalkylamino, (Ci-C 6 )acylamido, (CrC 6 )
  • Ri is a radical selected from the group consisting of tert-butyl, 1 ,1- dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1-diethylpropyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl; and R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Cr C 6 )alkylamino, (Ci-C 6 )acylamido, (
  • Ri is a radical selected from the group consisting of tert-butyl, 1 ,1- dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1-diethylpropyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl; and R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Ci-C 6 )alkyloxy, halo, (Cr C 6 )alkylamino, (Ci-C 6 )acylamido, (
  • Ri is a radical selected from the group consisting of tert-butyl, 1 ,1- dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1-diethylpropyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl; and R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of methyl and methoxy; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring selected from the group consist
  • Ri is a radical selected from the group consisting of tert-butyl, 1 ,1- dimethylpropyl, 1 -methyl-1 -ethylpropyl, 1 ,1-diethylpropyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl; and R 2 and R 3 are each a radical independently selected from the group consisting of methyl, ethyl, 4- methylphenyl and 4-methoxyphenyl; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic cyclic ring system selected from the group consisting of pyrrolidine and phenothiazine.
  • Ri is a radical selected from the group consisting of adamantyl and 2,4,6- trimethylphenyl
  • R 2 and R 3 are each a radical independently selected from the group consisting of (CrC 6 )alkyl group and a phenyl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr C 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, S and O,
  • Ri is a radical selected from the group consisting of adamantyl and 2,4,6- trimethylphenyl
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr C 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, and S
  • Ri is a radical selected from the group consisting of adamantyl and 2,4,6- trimethylphenyl
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr C 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring of 5 to 6 members selected from the group consisting of C, CH, CH 2 , NH, N, and S
  • Ri is a radical selected from the group consisting of adamantyl and 2,4,6- trimethylphenyl
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr C 6 )alkyloxy, halo, (Ci-C 6 )alkylamino, (Ci-C 6 )acylamido, (CrC 6 )acyloxy and nitro;or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring selected from the group consisting of pyrrolidine, piperazine, morpholine, thiomorpho
  • Ri is a radical selected from the group consisting of adamantyl and 2,4,6- trimethylphenyl
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of methyl and methoxy;or; alternatively, R and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic ring system consisting of a cyclic ring selected from the group consisting of pyrrolidine, piperazine, morpholine, thiomorpholine, oxazolidine, thioxazolidine and piperidine, wherein said ring is further optionally fused with one or two phenyl groups.
  • Ri is a radical selected from the group consisting of adamantyl and 2,4,6-trimethylphenyl; andR 2 and R 3 are each a radical independently selected from the group consisting of methyl, ethyl, 4-methylphenyl and 4-methoxyphenyl; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic cyclic ring system selected from the group consisting of pyrrolidine and phenothiazine.
  • the compound of formula (I) of the present invention is selected from the group consisting of the compounds of formulae (la), (lb), (lc), (Id), (le), (If), (Ig) and (Ih) [105]
  • the compound of formula (I) is the compound of formula (la) wherein q is 0, Ri is 2,4,6-trimethylphenyl and each of R2 and R3 is ethyl.
  • the compound of formula (I) is the compound of formula (lb) wherein q is 0, Ri is 2,4,6- trimethylphenyl and wherein R 2 and R3 form a pyrrolidine ring with the nitrogen atom to which they are attached.
  • the compound of formula (I) is the compound of formula (lc) wherein q is 0, Ri is 2,4,6- trimethylphenyl, R 2 is phenyl and R 3 is methyl.
  • the compound of formula (I) is the compound of formula (Id) wherein q is 0, Ri is adamantyl and wherein R 2 and R 3 form a pyrrolidine ring with the nitrogen atom to which they are attached.
  • the compound of formula (I) is the compound of formula (le) wherein q is 0, Ri is adamantyl and each of R 2 and R 3 is ethyl.
  • the compound of formula (I) is the compound of formula (If) wherein q is 0, Ri is 2,4,6-trimethylphenyl and each of R 2 and R3 is phenyl.
  • the compound of formula (I) is the compound of formula (Ig) wherein q is 0, Ri is 2,4,6-trimethylphenyl and wherein R 2 and R3 form a phenothiazine ring with the nitrogen atom to which they are attached.
  • the compound of formula (I) is the compound of formula (Ih) wherein q is 0, Ri is 2,4,6-trimethylphenyl, R 2 is 4- methoxyphenyl and R 3 is 4-methylphenyl.
  • q is 1
  • X and Y are each (Ci-C 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C 3 -C 8 )cycloalkyl ring (preferably, X and Y are each a methyl group)
  • Ri is a substituent selected from the group consisting of cyano, (CrC6)alkyloxycarbonyl, (Ci-C6)alkylcarbonyloxy, (Ci-C6)alkylaminocarbonyl and a phenyl group
  • R 2 and R3 are each a radical independently selected from the group consisting of (CrC6)alkyl group and a phenyl group optionally substituted at any available position with one or more radicals selected from the group consisting of (CrC 6 )alkyl, (Cr C 6 )alkyloxy, halo, (
  • q is 1
  • X and Y are each (CrC 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C3-C 8 )cycloalkyl ring (preferably, X and Y are each a methyl group)
  • Ri is a substituent selected from the group consisting of cyano, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Ci-C 6 )alkylaminocarbonyl and a phenyl group
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of (Ci-C 6 )alkyl, (Cr C 6 )
  • q is 1
  • X and Y are each (Ci-C 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C 3 -C 8 )cycloalkyl ring (preferably, X and Y are each a methyl group)
  • Ri is a substituent selected from the group consisting of cyano, (CrC 6 )alkyloxycarbonyl, (CrC 6 )alkylcarbonyloxy, (Ci-C 6 )alkylaminocarbonyl and a phenyl group
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl; ethyl; propyl; butyl and phenyl optionally substituted at any available position with one or more radicals selected from the group consisting of methyl and methoxy; or; alternatively, R 2 and R 3 ,
  • q is 1
  • X and Y are each (CrC 6 )alkyl or, alternatively, X and Y together with the carbon atom to which they are attached form a (C 3 -C 8 )cycloalkyl ring (preferably, X and Y are each a methyl group)
  • Ri is a substituent selected from the group consisting of cyano, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylcarbonyloxy, (Ci-C 6 )alkylaminocarbonyl and a phenyl group
  • R 2 and R 3 are each a radical independently selected from the group consisting of methyl, ethyl, 4-methylphenyl and 4-methoxyphenyl; or; alternatively, R 2 and R 3 , together with the nitrogen atom to which they are attached form a non-aromatic cyclic ring system
  • R 2 and R 3 are such that none or one of the carbon atoms of R 2 and R 3 that are attached to the nitrogen atom in the compound of formula (I) is member of an aromatic group. While such compounds of formula (I) absorb light in the visible range of the spectrum (this is, between 400 and 800 nm), the products of photolytic degradation of these compounds do not absorb in the visible light range of the spectrum. This advantageously allows differentiating with the human eye polymerized products (uncoloured) over non-polymerized products (coloured composition).
  • the compound of formula (I) of the present invention is selected from the group consisting of the compounds of formulae (la), (lb), (lc), (Id) and (le). It is also further preferred that none of the carbon atoms of R 2 and R 3 that are attached to the nitrogen atom in the compound of formula (I) are members of an aromatic group.
  • the compound of formula (I) of the present invention is selected from the group consisting of the compounds of formulae (la), (lb), (Id) and (le).
  • the compound of formula (I) of the present invention is selected from the group consisting of the compounds of formulae (lb), (Id) and (le).
  • R 2 and R 3 are such that at least one of the two carbon atoms of R 2 and R 3 that are attached to the nitrogen atom in the compound of formula (I) are members of an aromatic group.
  • R 2 and R 3 are such that both carbon atoms of R 2 and R 3 that are attached to the nitrogen atom in the compound of formula (I) are members of an aromatic group.
  • Such compounds were advantageously and surprisingly found to provide polymers with a narrow distribution of molecular weight, that is, a low polydispersity index (PDI), when used as photoinitiators, and more particularly, as photoiniferters, for the bulk polymerization of methyl acrylate.
  • PDI polydispersity index
  • the first aspect of the present invention relates to a compound of formula (I) that is selected from the group consisting of the compounds of formulae (If), (Ig), and (Ih).
  • the compound of formula (I) of the present invention is a compound of formula (If).
  • the compounds of the present invention solve the technical problems present in the state of the art and mentioned above, as they are effective initiators of living free-radical polymerization triggered by irradiation with light, more preferably, visible light.
  • the invention also provides a process for the preparation of a compound of formula (I) of the present invention, such process comprising the steps of:
  • step (ii) contacting the product obtained in step (i) with a compound of formula Ri(CXY) q COCI or a compound of formula Ri(CXY) q COOCORi, wherein q, X, Y and Ri are as defined in any of the embodiments defined above; and
  • Suitable bases to carry out step (i) are known in the state of the art and are, preferably, selected from the group consisting of salts of alkali metal hydroxides or (Ci-C 6 )alkyloxides (such as NaOH, KOH, LiOH, CsOH, NaOEt, KOEt and KOtert-Bu).
  • Step (ii) is preferably carried out under anhydrous conditions and in the presence of an aprotic anhydrous solvent.
  • the compounds of formula (I) or of formula (XII) as defined above are useful as photoinitiators for polymerization. Therefore, said third aspect of the present invention refers to the use of a compound of formula (I) or of formula (XII) as defined above as a photoinitiator for polymerization.
  • the polymerization is a living free-radical polymerization reaction, more preferably a RAFT-polymerization reaction.
  • the third aspect of the present invention refers to the use of a compound of formula (I) or of formula (XII) as defined above as a photoiniferter for polymerization.
  • the third aspect of the invention refers to the use of a compound of formula (I) as defined in any of the embodiments mentioned above or of a compound of formula (XII) as defined above in the first aspect of the present invention as photoinitiator for a polymerization that is carried out under irradiation of light having a wavelength of from 300 nm to 600 nm.
  • the use in this third aspect of the present invention is as photoinitiator for a polymerization that is carried out under irradiation of light having a wavelength of from 300 nm to 500 nm, more preferably, of from 350 nm to 500 nm, more preferably, of from 365 nm to 430 nm.
  • the polymerization is carried out under irradiation of a light source selected from the group consisting of a LED (light-emitting diode) emitting at 365 nm, a LED emitting at 405 nm, a LED emitting at 415 nm, a LED emitting at 430 nm, a LED emitting at 450 nm, a LED emitting at 460 nm, a Hg lamp or combinations thereof.
  • the use in this third aspect of the present invention is as photoinitiator for a polymerization that is carried out under irradiation of a LED emitting at 460 nm. This is advantageous as it allows avoiding the use of UV light, which can be damaging for tissues of an exposed user.
  • the third aspect of the present invention refers to the use of a compound of formula (I) or of formula (XII) as defined above (as defined in any of the embodiments of the first aspect of the present invention) as photoinitiator for a polymerization that is carried out under irradiation of visible light.
  • the compounds of formula (I) or of formula (XII) as defined above allow for the production of a polymer according to a RAFT mechanism, as described in the state of the art. The polymerization, thus, takes place under the control of a chain transfer agent.
  • each P is a polymeric block comprising from 2 to 1000 repeating monomer units, more preferably from 10 to 1000 repeating monomer units. More preferably, each P is a polymeric block comprising from 10 to 500 repeating monomer units, more preferably, each P is a polymeric block comprising from 10 to 200 repeating monomer units, even more preferably, each P is a polymeric block comprising from 10 to 100 repeating monomer units.
  • each P is a polymeric block consisting of a polymerized product of a monomeric composition comprising a monomer selected from any suitable monomer for photopolymerization comprising a carbon-carbon double bond known in the state of the art; more preferably a monomer selected from the group consisting of (C 2 -C 6 )alkene, acrylates, methacrylates, acrylamides, styrenes, cyanoacrylates, vinyl ethers, vinyl esters, terpenes or combinations thereof; more preferably a monomer selected from the group consisting of acrylates, methacrylates, acrylamides, cyanoacrylates or combinations thereof; more preferably a monomer selected from the group consisting of acrylates, methacrylates or combinations thereof.
  • each P is a polymeric block consisting of a polymerized product of a monomeric composition comprising a monomer selected from the group consisting of acrylates.
  • each P is a polymeric block consisting of a polymerized product of methyl acrylate.
  • the compound of formula (IV) is a compound of formula (IV ' ) as described above wherein n is 1 .
  • the compound of formula (IV’) is preferably one wherein RT, R 2 ’, R 3 ’ and R 4 ’ are each independently selected from the group consisiting of hydrogen, (Ci-C 6 )alkyl, (Cr C 6 )alkyloxy, (Ci-C 6 )alkyloxycarbonyl, (Ci-C 6 )alkylaminocarbonyl, cyano and (C 6 -C 2 o)aryl; and wherein more preferably, at least two of Ri’, R 2 ’, R ’ and R 4 ’ are hydrogen.
  • the compound of formula (IV’) is more preferably one wherein Ri’, R 2 ’, R 3 ’ and R 4 ’ are each independently selected from the group consisiting of hydrogen, methyl, (CrC 6 )alkyloxy, methyloxycarbonyl, butyloxycarbonyl, dimethylaminocarbonyl, cyano and phenyl; and wherein more preferably, Ri’ and R 2 ’ are hydrogen.
  • the compound of formula (IV’) is even more preferably one wherein R 3 ’ is methyloxycarbonyl, and Ri’, R’ 2 and R 4 ’ are hydrogen.
  • n’ is an integer of from 2 to 1000; preferably of from 10 to 1000; more preferably, of from 10 to 500; even more preferably, of from 10 to 200 and even more preferably, of from 10 to 100.
  • the compound of formula (IV) is a compound of formula (IVa) or (IVb) wherein I is an integer comprised of from 2 to 1000.
  • the value of I may be controlled by adjusting the molar ratio of compound of formula (I) or of formula (XII) as defined above to monomer to 1 : 1 in the mixture comprising (preferably, consisting of) the monomer and the compound of formula (I) or of formula (XII) as defined above.
  • I is from 10 to 1000; more preferably, I is from 10 to 500; more preferably, I is from 10 to 200; even more preferably, I is comprised of from 10 to 100.
  • the compounds of formulae (IVa) and (IVb) are compounds of formula (IV) wherein n is equal to 1 and P is a polymeric block resulting from the polymerization of methyl acrylate and containing I repeating units.
  • the compound of formula (IVa) is also a compound of formula (IV’) wherein n’ is I, R’i, R and R’ 4 are hydrogen; R’ is methyloxycarbonyl; R 2 and R 3 form a pyrrolidine ring with the nitrogen atom to which they are attached, q is 0 and Ri is 2,4,6-trimethylphenyl.
  • the compound of formula (IVb) is also a compound of formula (IV’) wherein n’ is I, R’ I , R’ 2 and R’ are hydrogen; R’ 3 is methyloxycarbonyl; R 2 and R 3 are each a phenyl group, q is 0 and Ri is 2,4,6- trimethylphenyl.
  • R 2 and R 3 are such that at least one, preferably both, of the two carbon atoms of R 2 and R 3 that are attached to the nitrogen atom in the compound of formula (IV) are members of an aromatic group, such as phenyl optionally substituted as defined above.
  • a process for the preparation of a compound of formula (IV) of the present invention is also part of the present invention, as a fifth aspect thereof.
  • Such process comprises the step of (i) irradiating with light a mixture comprising (preferably, consisting of) a compound of formula (I) or of formula (XII) as defined above and a monomer having a polymerizable carbon-carbon double bond wherein the molar ratio of the compound of formula (I) or of formula (XII) as defined above to the monomer is preferably from 1 :1000 to 1 :10; and, when n is higher than 1 in the compound of formula (IV) of the present invention, the process further comprises step (ii) of contacting the product of step (i) with a monomer having a polymerizable carbon-carbon double bond in the presence of a suitable initiation system.
  • the molar ratio of the compound of formula (I) or of formula (XII) as defined above to the monomer is from 1 :500 to 1 :10; more preferably from 1 :200 to 1 :10.
  • step (i) is carried out under irradiation of light having a wavelength of from 300 nm to 600 nm, more preferably of from 350 nm to 500 nm, more preferably of from 365 nm to 430 nm.
  • step (i) is carried out under irradiation of a light source selected from the group consisting of a LED emitting at 365 nm, a LED emitting at 405 nm, a LED emitting at 415 nm, a LED emitting at 430 nm, a LED emitting at 450 nm, a LED emitting at 460 nm, a Hg lamp or combinations thereof; more preferably, step (i) is carried out under irradiation of a blue LED emitting at 460 nm.
  • a light source selected from the group consisting of a LED emitting at 365 nm, a LED emitting at 405 nm, a LED emitting at 415 nm, a LED emitting at 430 nm, a LED emitting at 450 nm, a LED emitting at 460 nm, a Hg lamp or combinations thereof; more preferably, step (i) is carried out under irradiation of a blue LED emit
  • the present invention refers to the use of the compound of formula (IV) of the present invention (and as defined in the fourth aspect of the present invention) as chain transfer agent.
  • the compound of formula (IV) of the present invention is used as chain transfer agent in a polymerization reaction, more preferably, in a living free-radical polymerization reaction, even more preferably in a RAFT polymerization reaction.
  • the use of the compound of formula (IV) of the present invention as chain transfer agent may further require the presence of an initiating system suitable to generate a radical of formula (III) (as explained above) allowing for the propagation of the polymerization reaction in a controlled manner.
  • an initiating system suitable to generate a radical of formula (III) (as explained above) allowing for the propagation of the polymerization reaction in a controlled manner.
  • Such initiating systems are known in the art and may be thermal, chemical or photochemical.
  • a suitable photochemical initiating system is, for instance, irradiation with light, such as UV light.
  • a suitable chemical initiating system is, for instance, azoisobutyronitrile (AIBN).
  • the seventh aspect of the present invention refers to a composition comprising:
  • the seventh aspect of the present invention refers to a composition comprising a compound of formula (I) or of formula (XII) as defined above; and at least one of: a) a monomer comprising in its molecular formula at least one carbon-carbon double bond, and b) an oligomer comprising in its molecular formula at least one carbon-carbon double bond.
  • the seventh aspect of the present invention refers to a composition comprising a compound of formula (IV) of the present invention; and at least one of: a) a monomer comprising in its molecular formula at least one carbon-carbon double bond, and b) an oligomer comprising in its molecular formula at least one carbon-carbon double bond.
  • the seventh aspect of the present invention refers to a composition comprising a compound of formula (IV) of the present invention and at least a monomer comprising in its molecular formula at least one carbon-carbon double bond.
  • the seventh aspect of the present invention refers to a composition comprising both a compound of formula (I) or of formula (XII) as defined above and a compound of formula (IV) of the present invention; and at least one of: a) a monomer comprising in its molecular formula at least one carbon-carbon double bond, and b) an oligomer comprising in its molecular formula at least one carbon-carbon double bond.
  • the seventh aspect of the present invention refers to a composition comprising both a compound of formula (I) or of formula (XII) as defined above and a compound of formula (IV) of the present invention; and at least a monomer comprising in its molecular formula at least one carbon-carbon double bond.
  • the seventh aspect of the present invention refers to a composition comprising a compound of formula (I) or of formula (XII) as defined above; and at least a monomer comprising in its molecular formula at least one carbon-carbon double bond.
  • the seventh aspect of the present invention refers to a composition comprising at least a compound of formula (I) that is selected from the compounds of formulae (la), (lb), (lc), (Id), (le), (If) and (Ig).
  • the seventh aspect of the present invention refers to a composition comprising at least a compound of formula (I) that is selected from the compounds of formulae (lb) and (Id).
  • Suitable monomers comprising in their molecular formula at least one carbon- carbon double bond are known in the state of the art and will become apparent to the skilled person upon reduction of the invention to practice.
  • the monomer comprising in its molecular formula at least one carbon-carbon double bond is selected from the group consisting of (C - C 6 )alkene, acrylates, methacrylates, acrylamides, styrenes, cyanoacrylates, vinyl ethers, vinyl esters, terpenes or combinations thereof; more preferably the monomer is selected from the group consisting of acrylates, methacrylates, acrylamides, cyanoacrylates or combinations thereof; more preferably the monomer is selected from the group consisting of acrylates, methacrylates or combinations thereof.
  • the composition of the seventh aspect comprises one or more monofunctional monomers, one or more bifunctional monomers, one or more trifunctional monomers, one or more tetrafunctional monomers or a mixture of at least two thereof.
  • a monofunctional monomer is a monomer comprising one polymerizable carbon- carbon double bond.
  • a bifunctional monomer is a monomer comprising two polymerizable carbon-carbon double bonds.
  • a trifunctional monomer is a monomer comprising three polymerizable carbon-carbon double bonds.
  • a tetrafunctional monomer is a monomer comprising four polymerizable carbon-carbon double bonds.
  • Suitable monofunctional monomers are known in the art and may be selected from the group consisting of N-vinyl-s-caprolactam, N-vinyl formamide, N-vinyl pyrrolidone, N- vinyl-N-methylacetamide, b-carboxyethyl acrylate, octyl acrylate, decyl acrylate, oxyethylated phenol acrylate, 2-phenoxyethyl acrylate, tertiobutyl cyclohexanol acrylate (TBCHA), 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA), (Ci 6 -Ci 8 )alkyl acrylate, tetrahydrofurfuryl acrylate (THFA), lauryl acrylate, (C12-C14) acrylate, 2-phenoxyethyl acrylate (2-PEA), isodecyl acrylate (IDA), ethoxyl acryl
  • Suitable bifunctional monomers are known in the art and may be selected from the group consisting of dipropylene glycol diacrylate, 1 ,6-hexanediol diacrylate, neopentyl glycol propoxylate, diacrylate, tripropylene glycol diacrylate, tricyclodecanediol diacrylate, bisphenol A ethoxylate diacrylate, 1 ,6-hexanediol diacrylate (HDDA), polyethylene glycol (200) diacrylate (PEG200DA), tetraethylene glycol diacrylate (TTEGDA), triethylene glycol diacrylate (TIEGDA), tripropylene glycol diacrylate (TPGDA), polybutadiene diacrylate (PBDDA), 3-methyl 1 ,5-pentanediol diacrylate (MPDA), polyethylene glycol (400) diacrylate (PEG400DA), ethoxylated-3-bisphenol A diacrylate (BPA3EODA), dipropylene
  • Suitable trifunctional monomers are known in the art and may be selected from the group consisting of propoxylated glycerol triacrylate, trimethylolpropane ethoxy triacrylate, trimethylolpropane triacrylate (TMPTA), tris(2-hydroxyethyl) isocyanurate triacrylate (THEICTA), pentaerythritol triacrylate (PETIA), ethoxylated-3-trimethylolpropane triacrylate (TMP3EOTA), propoxylated-3-trimethylolpropane triacrylate (TMP3POTA), ethoxylated-6-trimethylolpropane triacrylate (TMP6EOTA), ethoxylated-9- trimethylolpropane triacrylate (TMP9EOTA), propoxylated-3-glyceryl triacrylate (GPTA), ethoxylated-15-trimethylolpropane triacrylate (TMP15EOTA), trimethylolpropane
  • Suitable tetrafunctional monomers are known in the art and may be selected from the group consisting of pentaerythritol tri-tetraacrylate, acrylated dipentaerythritol, ditrimethyolpropane tetraacrylate, ethoxylated 4 pentaerythritol tetraacrylate (PETTA), di- trimethylolpropane tetraacrylate (Di TMPTTA) and ethoxylated-4-pentaerythritol tetraacrylate (P(4EO)TTA).
  • the composition of the seventh aspect of the invention comprises a monomer selected from the group consisting of methyl acrylate, methyl methacrylate, butyl acrylate, pentaerythritol tetraacrylate, isodecyl acrylate, dipropylene glycol diacrylate, tricyclodecanedimethanol diacrylate, trimethylolpropane triacrylate, 1 ,6- hexanediol diacrylate, diacrylate of 1 ,10-decanediol, triethylene glycol dimethacrylate, 2- [[(butylamino)carbonyl]oxy]ethyl acrylate and mixtures thereof.
  • a composition according to the seventh aspect of the invention may comprise any chemically compatible combination of the compound of formula (I) or of formula (XII) and/or of formula (IV) with one or more of the monofunctional, bifunctional, trifunctional or tetrafunctional monomers described above.
  • Suitable oligomers comprising in their molecular formula at least one carbon- carbon double bond are known in the state of the art and will become apparent to the skilled person upon reduction of the invention to practice.
  • the oligomer comprising in its molecular formula at least one carbon-carbon double bond is an oligomer selected from the group consisting of the oligomers of (C -C 6 )alkene, oligomers of acrylates, oligomers of methacrylates, oligomers of acrylamides, oligomers of styrenes, oligomers of cyanoacrylates, oligomers of vinyl ethers, oligomers of vinyl esters, oligomers of terpenes or combinations thereof.
  • an oligomer comprises from 2 to 100 monomer units.
  • polyester (meth)acrylate polyester multi-(meth)acrylate, urethane (meth)acrylate, urethane multi-(meth)acrylate, epoxy (meth)acrylate, epoxy multi- (meth)acrylate, silicone (meth)acrylate, silicone multi-(meth)acrylate, amino (meth)acrylate, amino multi-(meth)acrylate, mercapto (meth)acrylate and mercapto multi- (meth)acrylate.
  • the composition of the the seventh aspect of the invention comprises an oligomer selected from the group consisting of an oligomer of an aliphatic polyester ether urethane acrylate, an aliphatic urethane hexaacrylate oligomer, an aliphatic urethane diacrylate, an aliphatic urethane acrylate oligomer, ethoxylated (4) bisphenol A dimethacrylate, urethane dimethacrylate, ethoxylated bisphenol A diacrylate and a mixture thereof.
  • a composition according to the seventh aspect of the invention may thus comprise any chemically compatible combination of the compound of formula (I) or of formula (XII) and/or of formula (IV) with one or more of the oligomers described above.
  • composition according to the seventh aspect of the invention may thus comprise any chemically compatible combination of the compound of formula (I) or of formula (XII) and/or of formula (IV) with one or more of the monofunctional, bifunctional, trifunctional or tetrafunctional monomers described above and further comprising one or more of the oligomers described above.
  • the oligomer may in a preferred embodiment be an aliphatic urethane acrylate. Such a composition is particularly useful for coating applications.
  • the oligomer may in a preferred embodiment be a diepoxyde methacrylate. Such a composition is particularly useful for dental resin applications.
  • the oligomer may in a preferred embodiment be an epoxyde diacrylate. Such a composition is particularly useful for 3D printing applications.
  • the seventh aspect of the present invention refers to a composition
  • a composition comprising a compound of formula (I) or of formula (XII) as defined above; and a polymerizable compound selected from the group consisting of (C -C 6 )alkene, acrylates, methacrylates, acrylamides, styrenes, cyanoacrylates, vinyl ethers, vinyl esters, terpenes, oligomers thereof or combinations thereof.
  • the polymerizable compound is selected from the group consisting of acrylates, methacrylates, acrylamides, cyanoacrylates or combinations thereof; more particularly the polymerizable compound is selected from the group consisting of acrylates, methacrylates or combinations thereof.
  • the seventh aspect of the present invention refers to a composition
  • a composition comprising a compound of formula (IV) of the present invention; and a polymerizable compound selected from the group consisting of (C2-C 6 )alkene, acrylates, methacrylates, acrylamides, styrenes, cyanoacrylates, vinyl ethers, vinyl esters, terpenes, oligomers thereof or combinations thereof.
  • the polymerizable compound is selected from the group consisting of acrylates, methacrylates, acrylamides, cyanoacrylates or combinations thereof; more preferably the polymerizable compound is selected from the group consisting of acrylates, methacrylates or combinations thereof.
  • the seventh aspect of the present invention refers to a composition
  • a composition comprising both a compound of formula (I) or of formula (XII) as defined above and a compound of formula (IV) of the present invention; and a polymerizable compound selected from the group consisting of (C -C 6 )alkene, acrylates, methacrylates, acrylamides, styrenes, cyanoacrylates, vinyl ethers, vinyl esters, terpenes, oligomers thereof or combinations thereof.
  • the polymerizable compound is selected from the group consisting of acrylates, methacrylates, acrylamides, cyanoacrylates or combinations thereof; more preferably the polymerizable compound is selected from the group consisting of acrylates, methacrylates or combinations thereof.
  • the seventh aspect of the present invention refers to a composition
  • a composition comprising a compound of formula (I) or of formula (XII) as defined above and/or a compound of formula (IV) of the present invention; and a polymerizable compound selected from the group consisting of acrylates, oligomers thereof or combinations thereof.
  • the seventh aspect of the present invention refers to a composition
  • a composition comprising a compound of formula (I) or of formula (XII) as defined above and/or a compound of formula (IV) of the present invention; and a polymerizable compound selected from the group consisting of methyl acrylate, oligomers thereof or combinations thereof.
  • the composition of the seventh aspect of the present invention when the composition of the seventh aspect of the present invention does not comprise a compound of formula (I) or of formula (XII) as defined above, the composition of the seventh aspect further comprises a polymerization initiation system.
  • Suitable polymerization initiation systems in particular for the initiation of free-radical polymerization, are known in the state of the art and may be selected, for instance, from the group consisting of phosphine oxides, metal oxides, hydroxyketones, benzophenones, azoisobutyronitrile (AIBN) or combinations thereof.
  • a suitable polymerization initiation system may be irradiation with light, in particular with UV light.
  • composition of the seventh aspect of the invention may further comprise additional components which may be selected from the group consisting of synergists for preventing oxygen from inhibiting the curing of the composition, dyes or pigments for providing a colour to the composition, flame-retarding agents, matting agents, UV blocking agents, UV stabilizers, fillers, adhesion promoters, defoaming agents, rheology modifiers and mixtures thereof. More preferably, the composition of the seventh aspect of the invention, further comprises at least one synergist, even more preferably one or two synergists, still more preferably, one synergist. The presence of the synergist, surprisingly, provides for a reduction in the initiation time of the polymerization reaction and provides a faster curing process.
  • Suitable synergists for preventing oxygen from inhibiting the curing of the composition are known in the art. Suitable synergists may thus be selected from the group consisting of amines, thiols, phosphines, phosphites, organometallic compounds, boranes, silanes and dienes.
  • Amine synergists are known in the art and comprise aliphatic or aromatic primary, secondary or tertiary amines.
  • An amine synergist may in particular be selected from the group consisting of dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, 3-dimethylamino neopentyl (meth)acrylate, ethyl-3-dimethylamino (meth)acrylate, N-(meth)acrylate-N’-methyl piperazine, N,N-dimethyldodecylamine, N,N- dimethylamino-propylamine, N,N-dimethyltoluidine, triphenylamine, diethylamine, N,N- diethyl-aminoethanol, N,N-dimethylamino propanol, N,N-dimethylamino-propanamine, ethyldi
  • Thiol synergists are known in the art and comprise aliphatic and aromatic thiols.
  • a thiol synergist may in particular be selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), (3- mercaptopropyl)methyldimethoxysilane, methyl thioglycolate, (3- mercaptopropyl)trimethoxysilane, m-carborane-9-thiol, cyclohexanethiol, 2-, 3-, 10- mercaptopinane, ethylene glycol bis(3-mercaptopropionate), thiosalicylic acid, 4- mercaptobenzoic, triphenylmethanethiol, 7-mercapto-4-methylcoumarin, 2,2 - (ethylenedioxy)diethanethiol, 2-mercaptoimi
  • Suitable phosphine synergists are known in the art and may be selected from the group consisting of triphenylphosphine, 4-(diphenylphosphino)styrene, trioctyl phosphine, 2-(diphenylphosphino)benzoic acid, 4-(dimethylamino)phenyldiphenylphosphine, 1 ,5- bis(diphenylphosphino)pentane, 1 ,4-bis(diphenylphosphino)butane, 1 ,3- bis(diphenylphosphino)propane.
  • Suitable phosphite synergists are known in the art and may be selected from the group consisting of 3,9-Bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9- diphosphaspiro[5.5]undecane, dioleyl hydrogen phosphite, poly(dipropyleneglycol) phenyl phosphite, triphenyl phosphite, tris(tridecyl) phosphite, tributylphosphite, 2-propenoic acid, trianhydride with phosphonic acid nitrilotri-2, 1 -ethanediyl ester, tetraphenyl dipropyleneglycol diphosphate.
  • Suitable organometallic compounds synergists may be selected from zinc 2- ethylexanoate, tri-butylstannane, stannous 2-ethylhexanoate, zirconium(IV) propoxide, bis(cyclopentadienyl)dimethyl zirconium(IV), tetrakis(dimethylamido) zirconium(IV), and tetrakis(triethanolaminato)-zirconium(IV).
  • Suitable diene synergists may be selected from 1 ,3-bis[(3-methyl-2-buten-1- yl)oxy]propan-2-ol, 1 ,1-diethoxy-3-methyl-2-butene, prenyl acetate, geranyl acetate, di(3- methyl-2-enyl)ether, prenyl ethyl ether, 1 -[(tetrahydro-2h-pyran-2-yl)oxy]-3-methyl-2- butene, vinyl-beta-ionol, 1-methoxycyclohexa-1 ,4-diene, terpinyl methyl ether and citronellyl acetate.
  • Suitable borane synergists may be selected from borane, borane triphenylphosphine complex, borane morpholine complex, catecholborane, bis(pinacolato)diboron and bis(catecholato)diborane.
  • Suitable borate synergists may be selected from tri(Ci-C 6 )alkyl borate, tritetradecyl borate, triisopropyl borate, trio-tolyl borate, tritetradecyl borate, trimethylene borate, tri-i- propylborate and tri-o-phenylene bis-borate.
  • Suitable silane synergists may be selected from tris(trimethyl silyl) silane, triethylsilane, dimethylphenylsilane, oligomeric silane.
  • synergists such as aldehydes, ethers and iodonium salts are known in the art and may be comprised in the composition of the seventh aspect of the invention.
  • Such synergists include propylene ether, thioether, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethyleneglycoldiacrylate, benzaldehyde, 1 - dodecanal, 3,7-dimethyl-2,6-octadienal, 2,6-dimethyl-5-heptenal, anthraldehyde and bis(4-methylphenyl)iodonium hexafluorophosphate.
  • the composition of the seventh aspect of the invention further comprises a synergist selected from the group consisting of N-methyl diethanolamine, N-phenylglycine, pentaerythritol tetrakis(3-mercaptopropionate), (2- dimethylaminoethyl) methacrylate, 1-adamantanethiol, ethyl 4-dimethylaminobenzoate, trimethylborate, triphenylphosphine, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) and mixtures thereof.
  • a synergist selected from the group consisting of N-methyl diethanolamine, N-phenylglycine, pentaerythritol tetrakis(3-mercaptopropionate), (2- dimethylaminoethyl) methacrylate, 1-adamantanethiol, ethyl 4-dimethylaminobenzoate, trimethyl
  • the composition of the seventh aspect of the invention further comprises a synergist that is pentaerythritol tetrakis(3- mercaptopropionate).
  • a synergist that is pentaerythritol tetrakis(3- mercaptopropionate).
  • composition of the seventh aspect of the invention further comprises a synergist
  • said synergist is preferably present in an amount from 0.1% to 10% in weight of the composition.
  • said synergist is more preferably present in an amount from 0.1% to 6% in weight of the composition.
  • said synergist is even more preferably present in an amount from 1% to 5% in weight of the composition.
  • Suitable UV blocking agents are known in the art and comprise UV absorbing compounds. Suitable UV blocking agents may in particular be selected from the group consisting of avobenzone, 2,5-bis(5-tert-butylbenzoxazol-2-yl)thiophene, disodium 4,4’- bis(2-sulfonatostyryl)biphenyl, benzenepropanoic acid, 2,3,6,7-tetrahydro-9-methyl- 1 H,5H-inolizino(9,1 -gh)coumarin, Martius yellow, morin hydrate, nitrofurazone, 2- nitrophenylphenylsulfide, 5,12-naphthacenequinone, octocrylene, phenazine, 1 ,4-bis-(2- (5-henyloxazolyl))-benzene, quinoline yellow, 3,3’,4’,5,6-pentahydroxyflavone, salicylaldehy
  • Suitable UV stabilizers are known in the art and may in particular be selected from the group consisting of substituted 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-2H- benzotriazoles, 2-(2-hydroxyphenyl)-4,6-phenyl-1 ,3,5-triazines, benzylidenemalonates, and oxalanilides, o-hydroxyphenyltriazenes, o-hydroxybenzotriazoles, oxanilides, 2, 2, 6, 6- tetramethylpiperidine, N-2,2,6,6-pentamethylhydroxypiperidinyl diester of 4- methoxyphenylmethylenemalonic acid.
  • Suitable fillers are known in the art and may in particular be inert fillers selected from the group consisting of calcium carbonate, aluminum silicates, magnesium silicate minerals, silicon dioxide, barium sulfate, polystyrene latex and aramid fibers. Suitable fillers may alternatively be fillers for paint applications, such as silica, talc, sand, glass beads, carbonate powder, alumina hydrate powder, steel powder, aluminum powder, polymer particles, titanium oxide, alumina or polymer particle impact modifier.
  • Suitable fillers may alternatively be fillers for dental resin applications such as lanthanum oxide, aluminum oxide, bismuth(lll) oxide, cobalt(ll, III) oxide, zinc oxide, tungsten(VI) oxide, zirconium(IV) oxide, boron nitride, potassium hexafluorotitanate or barium zirconate, hydroxyapatite, strontium carbonate, aluminum metaphosphate, lithium phosphate, sodium hexafluorosilicate, terbium(lll) nitrate pentahydrate, zinc hexafluorosilicate hydrate, potassium hexafluoroantimonate, erbium(lll) nitrate pentahydrate, praseodymium(lll) nitrate hexahydrate or iron(lll) oxide nanopowder, calcium phosphate, europium(lll) oxide or bismuth(lll) oxide.
  • dental resin applications such as lanthanum oxide, aluminum oxide
  • Suitable fillers may alternatively be active fillers such as a thickening attapulgite clay, a pyrogenic silicon dioxide powder, pentabromobenzyl acrylate, tribromoneopentyl (meth)acrylate, phosphorous and silicon containing oligomers, matting agent such as silicon dioxide, corrosion protecter such as zinc metal pigment, biocide as zinc oxide or cuprous oxide.
  • active fillers such as a thickening attapulgite clay, a pyrogenic silicon dioxide powder, pentabromobenzyl acrylate, tribromoneopentyl (meth)acrylate, phosphorous and silicon containing oligomers, matting agent such as silicon dioxide, corrosion protecter such as zinc metal pigment, biocide as zinc oxide or cuprous oxide.
  • Suitable adhesion promoters are known in the art and may in particular be selected from the group consisting of thiol, 1 ,6-hexanedioldiacrylate, acrylic acid derivative, acidic (meth)acrylate and chlorine-acid-base promoter. Monomers having afunctional group may also be used to promote adhesion.
  • Suitable defoaming agents are known in the art and may in particular be selected from the group consisting of mineral oil, waxes, hydrocarbons, fluorinated and/or silicated- polymer and fatty acid esters.
  • Suitable rheology modifiers are known in the art and may in particular be selected from the group consisting of fatty acid, silicon, clay derivatives, wax emulsion, polyurethane thickener and mixtures thereof.
  • Suitable inorganic pigments include, among others, white rutile Ti0 , white zinc oxide, yellow iron oxide, chrome yellow, monoarylide yellows, bismuth vanadate yellow, carbon black, red iron oxide, ferric ammonium ferrocyanide blue and acetylene black.
  • Suitable additive dyes include, among others, irgazin red, inkjet magenta, heliogen blue, inkjet yellow, special black, benzimidazolone orange, isoindoline yellow, diarylide yellows, toluidine red, copper phthalocyanine blue, halogenating copper and phthalocyanine green.
  • composition of the seventh aspect of the invention further comprises titanium dioxide as an inorganic pigment.
  • a composition according to the seventh aspect of the invention may thus comprise any chemically compatible combination of the compound of formula (I) or of formula (XII) and/or of formula (IV) with one or more of the monofunctional, bifunctional, trifunctional or tetrafunctional monomers described above and further comprising one or more of the oligomers described above and one or more of the synergists, dyes, pigments, UV filters, UV stabilizers and fillers described above.
  • the seventh aspect of the invention relates to a composition
  • a composition comprising a compound of formula (lb) or of formula (Id), pentaerythritol tetraacrylate as a monomer, and, optionally at least one synergist selected from the group consisting of N-methyl diethanolamine, N-phenylglycine, pentaerythritol tetrakis(3- mercaptopropionate), (2-dimethylaminoethyl) methacrylate, 1 -adamantanethiol, ethyl 4- dimethylaminobenzoate, trimethylborate, triphenylphosphine, and phenylbis(2,4,6- trimethylbenzoyl)phosphine oxide (BAPO).
  • synergist selected from the group consisting of N-methyl diethanolamine, N-phenylglycine, pentaerythritol tetrakis(3- mercaptoprop
  • the compound of formula (lb) is preferably in an amount of 0.6% in weight. In such preferred embodiments, the compound of formula (Id) is preferably in an amount of 1 .2% in weight. In such preferred embodiments, the synergist is preferably in an amount of from 0.1% to 6% in weight.
  • the seventh aspect of the present invention refers to a composition as defined above wherein the molar ratio of the polymerizable mass consisting of monomers and/or the oligomers to the initiating system consisting of the compounds of formula (I) or of formula (XII) as defined above and/or formula (IV) of the present invention is from 10000:1 to 10:1 ; preferably, it is from 1000:1 to 10:1.
  • the seventh aspect of the present invention refers to a composition as defined above wherein the weight ratio of the polymerizable mass consisting of monomers and/or the oligomers to the initiating system consisting of the compounds of formula (I) or of formula (XII) as defined above and/or formula (IV) as defined above is from 10000:1 to 10:1 ; preferably, it is from 1000:1 to 10:1 ; more preferably it is from 1000:1 to 20:1.
  • the composition of the seventh aspect of the invention may preferably be a composition suitable for coating applications.
  • Such a composition preferably comprises an oligomer selected from the group consisting of an oligomer of an aliphatic polyester ether urethane acrylate, an aliphatic urethane hexaacrylate oligomer, an aliphatic urethane diacrylate, and an aliphatic urethane acrylate oligomer.
  • Said oligomer is preferably comprised in the composition in the range of 20% to 60% in weight; preferably of from 30% to 50% in weight.
  • composition further preferably comprises a first monomer selected from the group consisting of pentaerythritol tetraacrylate, isodecyl acrylate, dipropylene glycol diacrylate, tricyclodecanedimethanol diacrylate, and tricyclodecanedimethanol diacrylate.
  • Said first monomer is preferably comprised in the composition in the range of 10% to 70% in weight; preferably of from 20% to 65% in weight.
  • Such composition further optionally comprises a second monomer selected from the group consisting of 1 ,6- hexanediol diacrylate, trimethylolpropane triacrylate and 1 ,10-decanediol diacrylate.
  • Said second monomer being comprised in the composition in the range of 0% to 50% in weight; preferably of from 0% to 40% in weight.
  • composition of the seventh aspect of the invention may thus be a composition suitable for coating applications comprising an oligomer of an aliphatic polyester ether urethane acrylate in an amount of from 40% to 60% in weight, pentaerythritol tetraacrylate in an amount of from 25% to 35% in weight and 1 ,6-hexanediol diacrylate in an amount of from 15% to 25% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • Said composition further preferably comprises a synergist as defined above.
  • composition of the seventh aspect of the invention may also be a composition suitable for coating applications comprising an oligomer of an aliphatic polyester ether urethane acrylate in an amount of from 20% to 40% in weight, dipropylene glycol diacrylate in an amount of from 60% to 70% in weight and 1 ,6-hexanediol diacrylate in an amount of from 5% to 15% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • Said composition further preferably comprises a synergist as defined above.
  • composition of the seventh aspect of the invention may also be a composition suitable for coating applications comprising an aliphatic urethane hexaacrylate oligomer in an amount of from 30% to 50% in weight, isodecyl acrylate in an amount of from 15% to 35% in weight and trimethylolpropane triacrylate in an amount of from 30% to 50% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • Said composition further preferably comprises a synergist as defined above.
  • composition of the seventh aspect of the invention may also be a composition suitable for coating applications comprising an aliphatic polyester based urethane diacrylate oligomer in an amount of from 30% to 50% in weight and tricyclodecanedimethanol diacrylate in an amount of from 40% to 60% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • Said composition further preferably comprises a synergist as defined above.
  • composition of the seventh aspect of the invention may also be a composition suitable for coating applications comprising an aliphatic urethane acrylate oligomer in an amount of from 30% to 50% in weight, tricyclodecanedimethanol diacrylate in an amount of from 20% to 40% in weight and 1 ,10-decanediol diacrylate in an amount of from 10% to 30% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • Said composition further preferably comprises a synergist as defined above.
  • the composition of the seventh aspect of the invention may also be a composition suitable for coating applications comprising an aliphatic urethane acrylate oligomer in an amount of 42% in weight, tricyclodecanedimethanol diacrylate in an amount of 25% in weight, 1 ,10-decanediol diacrylate in an amount of 17% in weight, a compound of formula (Id) in an amount of 3% in weight, rutile titanium dioxide in an amount of 10% in weight and (2-Dimethylaminoethyl) methacrylate in an amount of 3% in weight.
  • Such a composition is suitable as tack-free white paint for coating metal substrates.
  • the composition of the seventh aspect of the invention may also preferably be a composition suitable for dental resin applications.
  • a composition preferably comprises an oligomer selected from the group consisting of ethoxylated (4) bisphenol A dimethacrylate and urethane dimethacrylate, preferably in an amount of from 60% to 80% in weight.
  • Such composition preferably further comprises triethylene glycol dimethacrylate, preferably in an amount of from 20% to 40% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • the composition of the seventh aspect of the invention may also preferably be a composition suitable for 3D printing applications.
  • a composition preferably comprises ethoxylated (4) bisphenol A dimethacrylate in an amount of from 60% to 80% in weight and 1 ,10-decanediol diacrylate in an amount of from 20% to 40% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • composition of the seventh aspect of the invention may thus be a composition suitable for 3D printing applications comprising ethoxylated (4) bisphenol A dimethacrylate in an amount of from 40% to 60% in weight, 2-[[(butylamino)carbonyl]oxy]ethyl acrylate in an amount of from 10% to 30% in weight and pentaerythritol tetraacrylate in an amount of from 20% to 40% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • composition of the seventh aspect of the invention may also be a composition suitable for 3D printing applications comprising ethoxylated (4) bisphenol A dimethacrylate in an amount of from 30% to 50% in weight, dipropylene glycol diacrylate in an amount of from 20% to 40% in weight, and 2-[[(butylamino)carbonyl]oxy]ethyl acrylate in an amount of from 20% to 40% in weight.
  • Said composition further preferably comprises a compound of formula (I) or of formula (XII) and/or of formula (IV) in an amount of from 0.1% to 5% in weight.
  • the present invention refers to a process for the preparation of a cross-linked material comprising the step of irradiating the composition as defined in any of the embodiments of the seventh aspect of the present invention with light, preferably with blue light.
  • composition of the seventh aspect of the present invention when the composition of the seventh aspect of the present invention does not comprise a compound of formula (I) or of formula (XII) as defined above, said composition further comprises a polymerization initiation system.
  • the polymerization initiation system is as defined above.
  • the irradiation is carried out with light having a wavelength of from 300 nm to 600 nm, more preferably, of from 300 nm to 500 nm, even more preferably, of from 350 nm to 500 nm, even more preferably, of from 365 nm to 430 nm.
  • the irradiation is carried out using a light source selected from the group consisting of a LED emitting at 365 nm, a LED emitting at 405 nm, a LED emitting at 415 nm, a LED emitting at 430 nm, a LED emitting at 450 nm, a LED emitting at 460 nm, a Hg lamp or combinations thereof.
  • a light source selected from the group consisting of a LED emitting at 365 nm, a LED emitting at 405 nm, a LED emitting at 415 nm, a LED emitting at 430 nm, a LED emitting at 450 nm, a LED emitting at 460 nm, a Hg lamp or combinations thereof.
  • irradiation is carried out using blue light, more preferably, a blue LED emitting at 460 nm.
  • composition when it does not comprise a compound of formula (I) or of formula (XII) as defined above, it further comprises a polymerization initiation system that is selected from the group consisting of phosphine oxides, metal oxides, hydroxyketones, benzophenones, 1 ,1 '-azobis(cyclohexanecarbonitrile) (ACHN), azoisobutyronitrile (AIBN) or combinations thereof.
  • a polymerization initiation system that is selected from the group consisting of phosphine oxides, metal oxides, hydroxyketones, benzophenones, 1 ,1 '-azobis(cyclohexanecarbonitrile) (ACHN), azoisobutyronitrile (AIBN) or combinations thereof.
  • composition when it does not comprise a compound of formula (I) or of formula (XII) as defined above, it further comprises a polymerization initiation system consisting of irradiation with UV light.
  • the eighth aspect of the present invention refers to a process as defined above that is carried out under irradiation of light having an intensity of irradiation of at least 100 mW per cm 2 , preferably of at least 200 mW per cm 2 , even more preferably of 400 mW per cm 2 .
  • the eighth aspect of the present invention refers to a process as defined above that is carried out under irradiation of light having an intensity of irradiation of from 100 to 1000 mW per cm 2 , preferably of from 200 to 1000 mW per cm 2 and even more preferably of 400 mW per cm 2 .
  • the eighth aspect of the present invention refers to a process as defined above wherein the conversion of the one or more monomer comprising at least one carbon-carbon double bond and/or the one or more oligomer comprising at least one carbon-carbon double bond is higher than 61%, more preferably, higher than 70%, more preferably, higher than 80%, more preferably, higher than 85%, even more preferably, higher than 90%.
  • the eighth aspect of the present invention refers to a process as defined above wherein the polydispersity index of the prepared cross-linked material is from 1 to 3, more preferably, from 1 to 2.6, more preferably, from 1 to 2, even more preferably, from 1 to 1 .5.
  • the ninth aspect of the invention refers to a cross-linked material obtainable by means of the process of the eighth aspect of the invention.
  • the cross-linked material of the ninth aspect is obtainable by means of the process as defined in any embodiment of the eighth aspect of the invention using a composition as defined in any embodiment of the seventh aspect of the invention.
  • Example 1a Diethylcarbamothioic 2,4,6-trimethylbenzoic thioanhydride (la).
  • diethylcarbamothioic 2,4,6-trimethylbenzoic thioanhydride (compound of formula la) was effectively obtained in this example.
  • Example 1d Adamantane-1 -carboxylic pyrrolidine-1 -carbothioic thioanhydride (Id).
  • the mixture was washed with 2% (w/w) HNaC0 (1 time), water (250 mL, 1 time), and brine (1 time), and then dried through anhydrous Na S0 .
  • the solvent was totally removed by rotary evaporation, and the resulting solid was placed under high vacuum.
  • the solid was dispersed in diethyl ether, stirred for 5 minutes, then the solvent was partially removed almost to dryness and then pentanes were added, the mixture was sonicated and stirred, and the solid collected by filtration.
  • the product was placed under high vacuum to obtain a pale yellow solid, 247 mg, 69.1% yield.
  • Example 1f 2,4,6-trimethylbenzoic diphenylcarbamothioic thioanhydride (If).
  • Example 1g 2,4,6-trimethylbenzoic 10H-phenothiazine-10-carbothioic thioanhydride (Ig) [226] To an oven dried vial, containing argon and equipped with a stir bar and a septum, tert-BuOK (68 mg, 0.602 mmol, 1.1 eq) was mixed with anhydrous THF (5 ml_). The mixture was cooled in an ice/water bath ( ⁇ 5 e C), and then, 10H-phenothiazine (109 mg, 0.547 mmol, 1 eq) was added while stirring.
  • Example 1 h (4-methoxyphenyl)(p-tolyl)carbamothioic 2,4,6-trimethylbenzoic thioanhydride (Ih).
  • the LEDs (light-emitting diode) used for irradiation were equipped with a heat sink and a focusing lens that allowed irradiating from about 3 cm of distance, minimizing the vial or quartz cell heating, and focusing the light thoroughly onto the reaction mixture; the irradiating light bean was set up for approximately 90 e , and assuring that the entire sample was irradiated.
  • samples for Gel Permeation Chromatography (GPC) and NMR were taken by dissolving the entire polymer in the vials or quartz cells using DCCI (deuterated chloroform) or THF; the deuterated chloroform solvent was removed in vacuum for the GPC samples.
  • Molecular weight determination was carried out using a GPC (Agilent) equipped with a PSS SDV Analytical Linear M column, and refractive index detector (RID). The column temperature was set to 30 e C. Calibration curve was done using narrow dispersity index polystyrene standards. THF was employed as mobile phase, with a flow of 1.00 mL/min and 20 m ⁇ of injection volume.
  • Table 1 shows the following properties of the resulting polymer after 15 minutes of irradiation: the observed conversion of methyl acrylate as measured by 1 H NMR or NIR according to the methods described above, molecular weight, polydispersity index (PDI) and degree of polymerization (X n ) as measured by GPC and NMR.
  • Figure 3 shows the UV-Vis absorption spectra of the reaction mixture before irradiation with light (plain line) and after 15 minutes of irradiation with light (dashed line) when the compound of formula (Id) was used as initiator.
  • Table 1 Summary of the results obtained in example 2-1 for the polymerization.
  • a Entries related to compound (G) and BEC represent comparative studies. * Target degree of polymerization according to RAFT mechanism: 200.
  • b After 60 minutes of irradiation
  • the photopolymerization of methyl acrylate is more efficient in the sense that it reaches a higher conversion of monomer when a carboxylic dithiocarbamic acid anhydride compound bearing a Ri group suitable for stabilizing the acyl radical of formula (II) generated in reaction (1) through steric hindrance (explained above), as is the case with the compounds of formula (I) or (XII) as defined above, is used as a photoinitiator.
  • the results of Table 1 also show that the compounds of formula (I) act as a chain transfer agent, through the radical of formula (III) generated in reaction (1) (explained above), since the produced polymer has a degree of polymerization in accordance with such polymerization mechanism.
  • the combination of q, Ri, R 2 and R 3 in the compounds of the invention is responsible for an improved control over the molecular weight of the formed polymer combined with an acceptable achieved conversion of monomer to polymer.
  • a conversion above 70% within the 15 minutes of irradiation is considered acceptable, while a conversion of 85% or more is considered a good result.
  • the results of Table 2 show that the compounds of the invention allow obtaining higher degrees of conversion of monomer, together with an improved index of polydispersity, with respect to the carboxylic dithiocarbamic acid anhydride compounds described in the art.
  • the results of Table 2 also show that the compounds of formula (I) act as a chain transfer agent, since the produced polymer has a degree of polymerization in accordance with such polymerization mechanism.
  • the molecular weight distribution of the formed polymer is particularly narrow when R 2 and R 3 are such that both carbon atoms of R 2 and R 3 that are attached to the nitrogen atom in the compound of formula (I) are members of an aromatic group.
  • Table 3 shows that the compounds of formula (I) or (XII) allow reaching high conversions of monomer with different sources of light emitting in the UV-Visible range after only one minute of irradiation.
  • Table 3 shows that the compounds of formula (I) or (XII) are particularly useful photoiniferters when the polymerizable composition consisting of a compound of formula (I) or (XII) and methyl acrylate is irradiated with light having a wavelength comprised of from 350 nm to 500 nm.
  • Preferred wavelengths of irradiation are those ranging from 365 to 430 nm.
  • Example 3 Bulk polymerization of methyl acrylate under discontinuous irradiation
  • Polymethylacrylate was prepared from a polymerizable composition consisting of the compound of formula (lb) and methyl acrylate in a molar ratio of 1 to 400, using set-up 2 explained above and irradiation of blue light (460 nm, 400 mW per cm 2 ). Irradiation was stopped after 67 seconds and resumed after 364 seconds (counted from the time of first irradiation). Irradiation was further stopped after 434 seconds and resumed after 734 seconds (counted from the time of first irradiation).
  • Figure 4 shows the evolution of the conversion of methyl acrylate over time (in minutes) during this experiment.
  • the progress of the polymerization can advantageously be controlled by controlling the irradiation with light.
  • Example 3 shows that light can be used to control the progress of the polymerization process.
  • Table 4 discloses the results obtained with compounds (IVa) and (IVb) in terms of molecular weight, polydispersity and degree of polymerization, as measured by GPC, at different time points of the polymerization.
  • induction time corresponds to the time required for polymerization to start
  • rate of conversion Rc expressed in percentage per second - that is the percentage of monomer that has been converted during one second
  • maximal conversion achieved corresponds to the monomer conversion achieved at the end of the curing process, expressed as the percentage related to the ratio of the amount of converted monomer at the end of the reaction over the amount of monomer engaged.
  • composition according to the seventh aspect comprises a synergist compound, as this allows reducing the induction period and provide a faster curing process.

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  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne certains composés d'anhydride d'acide dithiocarbamique carboxylique et leur utilisation en tant que photo-initiateurs dans des réactions de polymérisation de radicaux libres vivants. L'invention concerne également des compositions durcissables ou réticulables comprenant les composés d'anhydride d'acide dithiocarbamique carboxylique de l'invention.
PCT/EP2021/050751 2020-01-15 2021-01-15 Composés d'anhydride d'acide dithiocarbamique carboxylique et compositions de ceux-ci Ceased WO2021144395A1 (fr)

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CN113880974A (zh) * 2021-10-21 2022-01-04 天津理工大学 一种基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液及其制备方法及应用

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