Urea (meth)acrylate or urea-urethane (meth)acrylate oligomers, compositions containing same, and uses thereof

Abstract

The present invention relates to a urea (meth)acrylate or urea-urethane (meth)acrylate oligomer comprising at least two urea bonds, in particular at least two sterically hindered urea bonds, at least two (meth)acryloyloxy groups, in particular at least two acryloyloxy groups, and optionally at least one urethane bond, in particular optionally at least two urethane bonds. The present invention also relates to a polymerizable composition comprising at least one oligomer according to the invention and optionally at least one other ethylenically unsaturated compound. A method for producing a crosslinked product comprising a step of crosslinking a polymerizable composition according to the invention also constitutes part of the present invention. A process for producing a three-dimensional object comprising an additive manufacturing step using a polymerizable composition according to the present invention also constitutes part of the present invention. The present invention also relates to a crosslinked product obtained by crosslinking a polymerizable composition according to the present invention or obtained by a process according to the present invention. Finally, the invention relates to the use of an oligomer according to the invention as binder in a polymerizable composition or in a composition for additive manufacturing, and to the use of a polymerizable composition according to the invention for the production of inks, coatings, materials filled with fibrous or particulate reinforcing material (which may be carbon nanotubes or graphite), adhesives, molding materials, ink plates, electrode binders or objects obtainable by additive manufacturing.

Description

[Technical field]

[0001] The present invention relates to urea (meth)acrylates or urea-urethane (meth)acrylate oligomers, to polymerizable compositions containing them and to their use in particular as binders in polymerizable compositions, in particular in ink or coating compositions, materials filled with fibrous or particulate reinforcing materials (which may be carbon nanotubes or graphite), adhesives, moldings, ink plates or electrode binder compositions and in compositions for additive manufacturing, in particular compositions for 3D or 4D printing of objects. [Background technology]

[0002] It is a known method to prepare highly functional urethane acrylates by reacting an amine with an acrylate and adding the resulting aminoacrylate to an isocyanate.

[0003] WO 2007 / 005351 describes liquid compositions of self-photoinitiating multifunctional urethane acrylate oligomers having pendant acrylate and tertiary amine groups incorporated into the polymer backbone obtained by reacting two oligomer molecules containing primary hydroxyl groups with the terminal isocyanate groups of a tertiary N-bis-urethane aminoacrylate oligomer.

[0004] WO 2016 / 170264 describes urethane aminoacrylate-acrylates which have one or more acrylate groups and which contain urethane functions attached to the aminoacrylate groups and are derived from a) a hydroxylated aminoacrylate having one or more acrylate groups and b) a polyisocyanate, where the aminoacrylate a) is the product obtained by addition of a1) an aminoalcohol having a hydroxyl group and a secondary amine group to a2) a multifunctional acrylate, a2) in stoichiometric excess relative to the secondary amine group of the aminoalcohol a1).

[0005] Prior art urethane acrylates are derived from secondary amines, which include the formation of significant amounts of tertiary amines prior to the addition of isocyanates, and the tertiary amine functionality is further useful for catalyzing the desired urethanization reaction. However, tertiary amines have been found to be sensitive to certain types of chemical attack (acids) and to become discolored (yellowing) during UV crosslinking. In addition, the preparation of these urethane acrylates requires long periods of high temperature heating and the use of toxic metal catalysts, such as tin catalysts.

[0006] The present invention therefore seeks to overcome the shortcomings of the prior art urethane acrylates by eliminating the presence of tertiary amines prior to the addition of the isocyanate.To this end, the inventors have changed the nature of the urethane acrylate of the final oligomer to a urea (meth)acrylate or urea-urethane (meth)acrylate. Summary of the Invention

[0007] The solution proposed by the inventors is based on the reaction of isocyanates with secondary amines to form ureas without the need for the presence of a catalyst. More specifically, the proposed solution consists in using compounds that simultaneously contain at least one secondary amine function and at least one (meth)acrylate function. In principle, this synthesis is difficult to control due to the coexistence of secondary amine and (meth)acrylate functions that can react with each other. However, the unique characteristics imposed by the amines make it possible to obtain stable compounds that contain both secondary amine and (meth)acrylate functions without forming tertiary amines: the secondary amines are sterically hindered, i.e. α or β substituted to the amine function, and said steric hindrance of the amines makes it possible to control the kinetics of the reaction between the isocyanate (NCO) function and the secondary amine (NH) function.

[0008] Thus, the urea (meth)acrylate or urea-urethane (meth)acrylate oligomers of the present invention offer the following technical advantages compared to prior art urethane acrylates: - the absence or very low content of tertiary amines leads to very good color stability of the crosslinked oligomers (no coloring, no yellowing); - the overall properties of the oligomers are equal to or better than those of urethane acrylates, but without the by-products associated with the consumption of stabilizers and the more severe thermal synthesis conditions (high purity of the oligomers of the invention); - Improved wear resistance, - Better viscosity / hardness compromise than urethane acrylates; the urea functionality is harder and more viscous than the urethane functionality of urethane acrylates; - the synthesis is simpler, faster, safer and more economical due to the lack of prolonged heating (the reactor can be easily maintained at the desired temperature due to the exothermic nature of the reaction and the temperature being controlled by the rate of addition of the starting materials), whereas the synthesis of certain urethane acrylates requires a temperature increase of up to 130°C; and - It does not require the use of solvents or catalysts, especially metal catalysts such as tin-based catalysts, so it is a more environmentally friendly process, free of toxic compounds. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] A first subject of the present invention therefore relates to specific urea (meth)acrylate or urea-urethane (meth)acrylate oligomers.

[0010] Another subject relates to a polymerizable composition comprising at least one oligomer according to the invention and optionally at least one other ethylenically unsaturated compound.

[0011] Also of interest is a process for producing a crosslinked product comprising the step of crosslinking a polymerizable composition according to the present invention.

[0012] It is also directed to a process for producing a three-dimensional object comprising an additive manufacturing step using a polymerizable composition according to the present invention.

[0013] The present invention then relates to the crosslinked products obtained by crosslinking the polymerizable composition according to the invention or obtained by the process according to the invention.

[0014] Another subject matter relates to the use of an oligomer according to the invention as a binder in a polymerizable composition or in a composition for additive manufacturing, in particular for 3D or 4D printing of objects.

[0015] Finally, the invention relates to the use of a polymerizable composition according to the invention for the manufacture of an ink, a coating, a material filled with fibrous or particulate reinforcing material (which may be carbon nanotubes or graphite), an adhesive, a moulding, an ink plate or an electrode binder composition or a composition for additive manufacturing, in particular a composition for 3D or 4D printing of objects.

[0016] The first subject of the invention is therefore at least two urea bonds, in particular at least two sterically hindered urea bonds, at least two (meth)acryloyloxy groups, in particular at least two acryloyloxy groups, and - optionally at least one urethane bond, in particular optionally at least two urethane bonds The present invention relates to certain urea (meth)acrylate or urea-urethane (meth)acrylate oligomers, including

[0017] For the purposes of the present invention, the term "oligomer" corresponds to a polymer molecule consisting of identical and / or different monomer units, preferably consisting of 2 to 50, more preferably consisting of 2 to 20 identical and / or different monomer units. Oligomers are in particular those molecules which contain at least two functional groups f A and at least one monomer A containing at least two functional groups f B and at least one monomer B containing a functional group f A Is sensual BExamples of oligomers are products obtained by polycondensation (in particular between at least one polyacid and at least one polyol and / or at least one polyamine) or by polyaddition (in particular between at least one polyisocyanate and at least one polyol and / or at least one polyamine).

[0018] For purposes of the present invention, a "sterically hindered urea bond" is a urea bond that contains at least one substituent or ring at the alpha or beta position relative to the attached nitrogen atom.

[0019] For the purposes of the present invention, a (meth)acryloyloxy group corresponds to a (meth)acrylate functionality.

[0020] Preferably, the two (meth)acryloyloxy groups of the oligomer of the invention are terminal (meth)acryloyloxy groups of said oligomer. For the purposes of the present invention, a terminal group is a group at the end of the backbone of the oligomer.

[0021] The oligomer of the invention may comprise at least two sterically hindered urea linkages linked by linker groups, each of which is linked to said linker group by a nitrogen atom that does not bear a hydrogen atom. The sterically hindered urea linkages linked by linker groups may be the same or different, preferably the same.

[0022] For the purposes of the present invention, the sterically hindered urea bond is preferably a bond of the formula *-NR-C(=O)-NH-*, where R is other than H, preferably R is a sterically hindering group and each * symbol represents a point of attachment to a carbon atom.

[0023] In this embodiment, preferably the linker group does not include a urea or urethane linkage.

[0024] The oligomers of the invention are in particular those of the following formula (I): TIFF2025501941000001.tif31170[In the formula, The linker group A is a residue of a polyamine, preferably A does not contain a urea or urethane linkage; R is other than H, preferably R is a sterically hindering group; z is an integer from 2 to 6; TIFF2025501941000002.tif12170 represents the point of attachment to the carbon atom.] The nucleic acid sequence may include at least one fragment corresponding to:

[0025] For the purposes of the present invention, when R is a sterically hindered group, it is preferably a group containing at least one substituent or ring in the α or β position relative to the nitrogen atom to which it is attached. The substituent may in particular be any group other than H, or a ring, for example a group selected from optionally alkoxylated alkyl. The ring may in particular be selected from cycloalkyl, heterocycloalkyl, aryl, or heteroaryl.

[0026] The oligomers of the invention may comprise at least two urea linkages, each of which is the product of an aza-Michael reaction between a primary amine and an α,β-unsaturated carbonyl compound, in particular a) between a sterically hindered primary amine and a (meth)acrylate, or b) Between a primary amine and a maleic acid diester or a fumaric acid diester is directly linked to a group derived from the aza-Michael reaction of

[0027] For the purposes of the present invention, a "primary amine" is a compound that contains at least one primary amine function -NH2 and preferably does not contain any secondary and / or tertiary amine functions.

[0028] For purposes of this invention, a "sterically hindered primary amine" is a primary amine that contains at least one substituent or ring at the alpha or beta position relative to the nitrogen atom of the attached primary amine function.

[0029] For the purposes of the present invention, an "α,β-unsaturated carbonyl compound" is a compound that contains a C═C double bond in the α-β-unsaturated position relative to a carbonyl group, in particular a carboxylic acid, ester, anhydride, ketone, or aldehyde.

[0030] For purposes of this invention, a "maleic or fumaric acid diester" is a diester derived from maleic or fumaric acid.

[0031] The oligomers of the present invention have the following formula (Ia): TIFF2025501941000003.tif37170[In the formula, Z is H or a group containing an ester function -COOY, Y is an alkyl group which may be substituted with one or more (meth)acrylate groups, and preferably Y is a linear or branched C1-C alkyl group which may be substituted with one or more (meth)acrylate groups. 13 is an alkyl group, TIFF2025501941000004.tif12170 represents the point of attachment to the carbon atom.] The fragment may comprise at least two fragments corresponding to:

[0032] In this embodiment, the oligomer of the invention comprises: at least four fragments of formula (Ia), or at least two fragments (Ia) and two urethane bonds, or At least two fragments (Ia) and at least two other sterically hindered urea bonds may include.

[0033] For the purposes of the present invention, the following definitions apply: - Alkyl: linear or branched, saturated C1-C 20 , preferably C1 to C 13 , more preferably C1 to C6, and even more preferably C1 to C4 aliphatic hydrocarbon-based groups. 20Alkyl means an alkyl group containing 1 to 20 carbon atoms. The term "branched" means that at least one alkyl group, such as methyl or ethyl, is attached to a linear alkyl chain. Examples of alkyl groups mentioned include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and n-pentyl groups. - alkyl containing at least one heteroatom: alkyl in which at least one carbon atom is replaced by a heteroatom (in particular selected from O, N or S, preferably O). - Cycloalkyl: non-aromatic, saturated or partially unsaturated, cyclic, preferably C to C 10 It is a hydrocarbon-based group and can be monocyclic, bicyclic, or polycyclic. - heterocycloalkyl: a cycloalkyl, where at least one ring atom is a heteroatom, preferably selected from O, N or S. - Aryl: a group containing at least one aromatic ring. Aryl can contain a single aromatic ring or multiple rings, at least one of which is aromatic. Aromatic rings correspond to rings that follow the Hückel rule. Examples of aryl groups are phenyl, biphenyl, naphthyl and anthracenyl. The aryl group of the present invention preferably contains 6 to 12 carbon atoms. Even more preferably, the aryl group of the present invention is a phenyl group. - Heteroaryl: An aryl in which at least one ring atom of the aromatic ring is a heteroatom, preferably selected from O, N or S. - Alkylene: Formula C m H 2m+2 An aliphatic radical derived from an alkane (m=2-50) by removing a hydrogen atom from each attachment point of the radical. The alkylene may be straight or branched. The alkylene may be divalent, trivalent, tetravalent, pentavalent, or hexavalent. - oxyalkylene: alkylene interrupted by at least one oxygen atom, preferably of the formula -Alk'-[O-Alk'] k’’ -, each Alk' is independently alkylene, and k'' ranges from 1 to 50.

[0034] More specifically, the oligomer of the present invention has the following formula (Ib) or (Ic): TIFF2025501941000005.tif71170[In the formula, R is other than H, preferably R is a sterically hindering group; Z is H or a group containing an ester function -COOY, Y is an alkyl group which may be substituted with one or more (meth)acrylate groups, and preferably, Y is a linear or branched C1-C alkyl group which may be substituted with one or more (meth)acrylate groups. 13 is an alkyl group, TIFF2025501941000006.tif12170 represents the point of attachment to the carbon atom.] The fragment may include at least two fragments corresponding to one of:

[0035] In this embodiment, the oligomer of the invention comprises: at least four fragments of formula (Ib), or at least two fragments (Ib) and two urethane bonds, or At least two fragments (Ib) and at least two other sterically hindered urea bonds may include.

[0036] In this embodiment, the oligomer of the invention comprises: at least two fragments (Ic) and at least two urethane bonds, or At least two fragments (Ic) and at least two other sterically hindered urea bonds may include.

[0037] The oligomers of the present invention have the following formula (Id) or (Ie): TIFF2025501941000007.tif82170[In the formula, R is other than H, preferably R is a sterically hindering group; Z is H or a group containing an ester function -COOY, Y is an alkyl group which may be substituted with one or more (meth)acrylate groups, and preferably, Y is a linear or branched C1-C alkyl group which may be substituted with one or more (meth)acrylate groups. 13 is an alkyl group, P is the residue of a polyol, preferably free of urea or urethane linkages, more preferably P is an alkylene having at least one ester function derived from the ring opening of a lactone, such as caprolactone, which may be alkoxylated or esterified; A is a residue of a polyamine, preferably A does not contain a urea or urethane bond; z' is an integer from 2 to 6; z'' is an integer from 2 to 6; TIFF2025501941000008.tif12170 represents the point of attachment to the carbon atom.] The fragment may include a fragment corresponding to one of:

[0038] According to one embodiment, the oligomer of the present invention may be a reaction product of at least one poly(meth)acrylate, at least one sterically hindered primary monoamine, and at least one isocyanate compound, the oligomer being preferably produced by the following sequential steps: (i) an aza-Michael reaction between at least one poly(meth)acrylate and at least one sterically hindered primary monoamine, having a stoichiometric excess of (meth)acryloyloxy groups relative to the primary amine groups, preferably having a ratio of NH2 / (meth)acryloyloxy of less than 0.9, preferably in the range of 0.1-0.8, or 0.2-0.7, or 0.3-0.5; and (ii) reacting the amino-(meth)acrylate mixture obtained in step (i) with at least one isocyanate compound, preferably having a NCO / NH2 ratio of less than 1.05, preferably in the range of 0.6-1.01, or 0.8-1, or 0.9-0.99; The method is obtained by a process including:

[0039] For purposes of this invention, a "poly(meth)acrylate" is a compound that contains at least two (meth)acryloyloxy groups, at least one of which is an acryloyloxy group.

[0040] In this embodiment, the poly(meth)acrylate in step (i) is preferably a compound comprising at least 2, preferably 2 to 6, more preferably 2 to 4 (meth)acryloyloxy groups, at least one of which is an acryloyloxy group.

[0041] For purposes of the present invention, a "primary monoamine" is a compound that contains a single primary amine function, -NH2, and preferably does not contain any secondary and / or tertiary amine functions.

[0042] For purposes of this invention, a "sterically hindered primary monoamine" is a primary monoamine having at least one substituent or ring alpha or beta relative to the nitrogen atom of the attached primary amine function.

[0043] More specifically, in this embodiment, the sterically hindered primary monoamine in step (i) has the following formula (II): TIFF2025501941000009.tif20170[In the formula, R1 and R2 are independently selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or alkyl groups containing at least one heteroatom, or R1 and R2 can form a ring of C4 to C8, preferably C6, optionally containing one or more heteroatoms; R3 is H or an alkyl group, preferably C1-C4, more preferably -CH3; a is equal to 0 or 1] It can be equivalent to.

[0044] Even more specifically, in this embodiment, the sterically hindered primary monoamine in step (i) has the following formula (IIa), (IIb), or (IIc): TIFF2025501941000010.tif72170[In the formula, R'1 and R'2 are each independently preferably a C1-C4, more preferably a C1-C2 alkyl group; Cy is a C4 to C8, preferably a C6 ring; R'3 is H or a methyl group; a is equal to 0 or 1, b and c are each independently an integer ranging from 1 to 50. This corresponds to one of the following:

[0045] Even more specifically, in this embodiment, the sterically hindered primary monoamines in step (i) are selected from the group consisting of 2-aminopentane, 3-aminopentane, 1,2-dimethylpropylamine, 1,3-dimethylbutylamine, 2-aminooctane, isopropylamine, isobutylamine, sec-butylamine, tert-butylamine, tert-octylamine (2-amino-2,4,4-trimethylpentane), 2-ethylhexylamine, (2-methylbutyl)amine, cyclopentylamine, cyclohexylamine, 3,3,5-trimethylcyclohexylamine, cycloheptylamine, benzylamine, polypropylene glycol based polyether monoamines and optionally preferably having a weight average molecular weight M in the range of 200 to 3000 g / mol. w (Jeffamine® M-600, Jeffamine® M-1000, or Jeffamine® M-2005), and mixtures thereof.

[0046] In this embodiment, the isocyanate compound in step (ii) is preferably a compound containing at least one -NCO group.

[0047] More specifically, in this embodiment, the isocyanate compound of step (ii) is polyisocyanates and (meth)acrylates, optionally functionalized with OH or NHR' groups, or - an adduct obtained by reaction of a polyisocyanate with a (meth)acrylate functionalized with an OH or NHR' group, the adduct having a stoichiometric excess of NCO groups relative to the OH or NHR' groups, formed before the reaction with the compound obtained at the end of step (i). may include R' is a group other than H, particularly a sterically hindering group.

[0048] For the purposes of the present invention, with respect to R, when R' is a sterically hindering group, it is preferably a group that contains at least one substituent or ring in the alpha or beta position relative to the nitrogen atom to which it is attached. Preferably, R' is a tert-butyl group.

[0049] Thus, in this embodiment, the polyisocyanate in step (ii) is - reacting alone with mono(meth)acrylates bearing secondary amine functions present in the mixture of amino(meth)acrylates obtained in step (i), leading to the formation of a sterically hindered urea bond during step (ii) by an aza-Michael reaction on the secondary amine, or in the form of a mixture or adduct with a (meth)acrylate functionalized with an OH group during step (i), which leads to the formation of a urethane bond during step (ii), or - during step (i) in the form of a mixture or an adduct with a (meth)acrylate functionalized with a group NHR', which leads to the formation of a sterically hindered urea bond with the group R' during step (ii).

[0050] Even more specifically, in this embodiment, the polyisocyanate in step (ii) is a diisocyanate, and The OH-functionalized (meth)acrylate in step (ii) is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, or the NHR'-functionalized (meth)acrylate in step (ii) is 2-(tert-butylamino)ethyl methacrylate.

[0051] According to another embodiment, the oligomer of the present invention may be a reaction product of at least one mono(meth)acrylate, at least one sterically hindered primary polyamine, and at least one isocyanate compound, which is preferably prepared by the following sequential steps: (i') the formation of a poly(amino ester) by aza-Michael reaction of at least one mono(meth)acrylate with at least one sterically hindered primary polyamine, in particular having an NH2 / double bond ratio in the range of 0.7 to 1.3, preferably 0.9 to 1.1 or 0.95 to 1.05, (ii') optionally adding an acrylate to remove residual primary amine functions; (iii') reacting the poly(amino ester) obtained in step (i') or (ii') with at least one isocyanate compound. wherein the compound is obtained by a process comprising: The isocyanate compound is - polyisocyanates and (meth)acrylates functionalized with OH or NHR' groups, or - an adduct obtained by reaction of a polyisocyanate with a (meth)acrylate functionalized with an OH or NHR' group, the adduct having a stoichiometric excess of NCO groups relative to the OH or NHR' groups, formed before the reaction with the compound obtained at the end of step (i') or (ii'). Including, R' is a group other than H, particularly a sterically hindering group, as defined above.

[0052] For purposes of this invention, a "mono(meth)acrylate" is a compound that contains a single acryloyloxy group and, optionally, one or more methacryloyloxy groups.

[0053] For the purposes of the present invention, a "primary polyamine" is a compound that contains at least two primary amine functions -NH2 and preferably does not contain any secondary and / or tertiary amine functions.

[0054] For purposes of this invention, a "sterically hindered primary polyamine" is a primary polyamine in which each primary amine function is hindered by a substituent or ring that is alpha or beta to the nitrogen atom of the attached primary amine function.

[0055] More specifically, the sterically hindered primary polyamine of step (i') is represented by the following formulae (IIIa), (IIIb), (IIIc), (IIId), and (IIIe): TIFF2025501941000011.tif182170[In the formula, Cy is a C4-C8, preferably C6, ring, or Cy is -CR4R5-; Cy' is a C4 to C8, preferably C6 ring; R4 is an alkyl group; R5 is H or an alkyl group; R6 is H or an alkyl or alkoxy group; L is a single bond, alkylene, or oxyalkylene; a', a'', d, e and f are each independently equal to 0 or 1; g, g', g'', h, i, j, l, m, and n are each independently an integer ranging from 1 to 50; k is equal to 2 or 4, k' is equal to 0 or 1] This corresponds to one of the following:

[0056] Even more specifically, in this embodiment, the sterically hindered primary polyamine in step (i') is selected from the group consisting of 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-cyclohexanebis(methylamine), 1,8-diamino-p-menthane, o-, m- or p-xylylenediamine, acyclic polyether diamines based on polypropylene glycol, and optionally acyclic polyether diamines having a weight average molecular weight M preferably in the range of 200 to 10,000 g / mol. w and optionally polyethylene glycols or polytetramethylene glycols (Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-2010, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® THF170), polyether triamines based on polypropylene glycols, and optionally polyether triamines based on polypropylene glycols, preferably having a weight average molecular weight M in the range of 300 to 10,000 g / mol. w (Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000), preferably having a weight average molecular weight M in the range of 500 to 5000 g / mol w (Jeffamine® RFD-270), and mixtures thereof.

[0057] During step (i'), the ratio of NH2 / double bond is preferably close to 1. In some cases, the ratio can be less than 1, so as to have residual acrylate in the mixture acting as a reactive diluent.

[0058] More specifically, in this embodiment, The polyisocyanate of step (iii') is a diisocyanate, and The OH-functionalized (meth)acrylate of step (iii') is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, or the NHR'-functionalized (meth)acrylate of step (iii') is 2-(tert-butylamino)ethyl methacrylate.

[0059] According to yet another embodiment, the oligomer of the present invention may be a reaction product of at least one maleic or fumaric acid diester, at least one primary polyamine and at least one isocyanate compound, which is preferably prepared by the following sequential steps: (i'') by aza-Michael reaction of at least one maleic or fumaric acid diester with at least one primary polyamine to form a poly(amino ester), in particular having an NH2 / double bond ratio in the range of 0.7 to 1.3, preferably 0.9 to 1.1 or 0.95 to 1.05, (ii'') reacting the poly(amino ester) obtained in step (i'') with at least one isocyanate compound. wherein the compound is obtained by a process comprising: The isocyanate compound is - polyisocyanates and (meth)acrylates functionalized with OH or NHR' groups, or - an adduct obtained by reaction of a polyisocyanate with a (meth)acrylate functionalized with an OH or NHR' group, the adduct having a stoichiometric excess of NCO groups relative to the OH or NHR' groups, preferably formed before the reaction with the compound obtained at the end of step (i''). Including, R' is a group other than H, particularly a sterically hindering group, as defined above.

[0060] In this embodiment, the primary polyamine is preferably a diamine.

[0061] More specifically, in this embodiment, The polyisocyanate of step (ii'') is a diisocyanate, and The OH-functionalized (meth)acrylate of step (ii'') is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, or the NHR'-functionalized (meth)acrylate of step (ii'') is 2-(tert-butylamino)ethyl methacrylate.

[0062] Advantageously, the oligomer of the invention has the following formula (IV): TIFF2025501941000012.tif29170[In the formula, Each Acr is, independently of the other, a (meth)acryloyloxy group; L1 and L2 are independent of each other, [●] o -P-[OC(=O)-CH2-CH2] r -◆ and P is the residue of a polyol, preferably P is an alkylene which may be alkoxylated or esterified; The symbol ● represents the point of attachment to the Acr group; The symbol ◆ represents the point of attachment to the group U1 or U4, U1 and U4 are independently selected from a urea bond or a urethane bond; U2 and U3 are urea bonds, I is a residue of a polyisocyanate, W is absent or -U1-L2-[Acr] o represents a branch on an oligomer such as A is a residue of a polyamine, X is absent or -U2-I-U1-L2-[Acr] o represents a branch on an oligomer such as each o is independently an integer ranging from 1 to 5; p is an integer from 0 to 50, and when p is equal to 0, at least one of the groups U1 or U4 is a urea bond; Each q is independently an integer from 0 to 4; r is equal to 0 or 1] The product includes at least one product corresponding to:

[0063] When the functionality of the isocyanate compound used to prepare the oligomer of the present invention is less than or equal to 2, W is absent. When the functionality of the isocyanate compound used to prepare the oligomer of the present invention is greater than 2, W represents a branch on the oligomer, preferably W is -U1-L2-[Acr] o It is.

[0064] When the functionality of the amine or (meth)acrylate used to prepare the oligomer of the present invention is less than or equal to 2, X is absent. When the functionality of the amine or (meth)acrylate used to prepare the oligomer of the present invention is greater than 2, X represents a branch on the oligomer, preferably -U2-I-U1-L2-[Acr] o It is.

[0065] More specifically, in formula (IV) of the oligomer of the invention, the (meth)acryloyloxy Acr groups are, independently of each other, of the following formula (V): TIFF2025501941000013.tif26170[In the formula, R7 is H or a methyl group, in particular R7 is H; symbol TIFF2025501941000014.tif4170 represents the point of attachment to group L1 or L2] It is expressed as:

[0066] More specifically, in formula (IV) of the oligomer of the invention, each I is a residue of an aliphatic, cycloaliphatic, or aromatic polyisocyanate, and even more specifically an aliphatic or cycloaliphatic diisocyanate, the cycloaliphatic diisocyanate preferably being a C6-C 18 It is.

[0067] In certain embodiments, in the formula (IV) of the oligomer of the invention, U1 and U4 are each independently of each other a group of the following formula (VI): TIFF2025501941000015.tif23170[in the formula, R8 is a sterically hindering group; symbol TIFF2025501941000016.tif4170 represents the point of attachment to group L1 or L2, symbol TIFF2025501941000017.tif4170 represents the point of attachment to group I] It is a urea bond represented by When p>0, U2 and U3 are each independently represented by the following formula (VII): TIFF2025501941000018.tif23170[In the formula, R9 is a sterically hindering group; symbol TIFF2025501941000019.tif5170 represents the point of attachment to group A, and symbol TIFF2025501941000020.tif4170 represents the point of attachment to group I] It is a urea bond represented by the formula:

[0068] For purposes of this invention, R8 is a sterically hindering group that contains at least one substituent or ring at the alpha or beta position relative to the attached nitrogen atom.

[0069] For purposes of this invention, R9 is a sterically hindering group that contains at least one substituent or ring at the alpha or beta position relative to the attached nitrogen atom.

[0070] In a particular embodiment, in the formulas (VI) and (VII) of the present invention, R8 and R9 are each independently represented by the following formula (VIII): TIFF2025501941000021.tif22170[in the formula, R1, R2, R3 and a are as defined above; The symbol ■ represents the point of attachment to the nitrogen atom. It is a steric hindrance group represented by the following formula:

[0071] More specifically, in the formulae (VI) and (VII) of the present invention, R8 and R9 are each independently represented by the following formulae (VIIIa), (VIIIb), or (VIIIc): TIFF2025501941000022.tif72170[In the formula, R'1, R'2, R'3, Cy, a, b, and c are as defined above; The symbol ■ represents the point of attachment to the nitrogen atom. It is a sterically hindering group represented by one of the following:

[0072] In certain embodiments, in the formula (IV) of the oligomer of the invention, U1 and U4 are independently of each other a group of the following formula (IX): TIFF2025501941000023.tif29170 Symbol TIFF2025501941000024.tif4170 represents the point of attachment to group L1 or L2, symbol TIFF2025501941000025.tif4170 represents the point of attachment to group I] is a urethane bond represented by the formula: p>0, and U2 and U3 are each independently represented by the following formula (X): TIFF2025501941000026.tif23170[in the formula, R 10 is other than H, preferably R 10 is a sterically hindering group, symbol TIFF2025501941000027.tif5170 represents the point of attachment to group A; symbol TIFF2025501941000028.tif4170 represents the point of attachment to group I] It is a urea bond represented by the formula:

[0073] For the purposes of this invention, R 10 is a sterically hindering group that contains at least one substituent or ring at the alpha or beta position relative to the attached nitrogen atom.

[0074] More specifically, in the formula (X) of the present invention, R 10 is one of the groups of formula (VIII), (VIIIa), (VIIIb) or (VIIIc) defined above, or the following formula (XI) or (XII): TIFF2025501941000029.tif41170[In the formula, R 11 is selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and alkyl groups containing at least one heteroatom, polyester, or combinations thereof; R 12 and R 13 are, independently of each other, an alkyl group; symbol TIFF2025501941000030.tif6170 represents the attachment point to the nitrogen atom] is a steric hindrance group selected from the group represented by one of the following:

[0075] In this particular embodiment, when U1 and U4 are each independently a urethane linkage, in formula (IV) of the oligomer of the invention, r, L1, L2, P, and o can be defined as follows: r is equal to 0, L1 and L2 are independent of each other, [●] o -P-◆, P is the residue of a polyol, preferably P is an alkylene which may be alkoxylated or esterified; o is an integer from 1 to 5; The symbol ● represents the point of attachment to the Acr group; The symbol ◆ represents the point of attachment to the U1 or U4 group.

[0076] In this particular embodiment, when U1 and U4 are each independently a urethane bond, in formula (IV) of the oligomer of the invention, A may be the residue of a sterically hindered polyamine, in particular A is a group of formula (XIIIa), (XIIIb), (XIIIc), (XIIId) or (XIIIe): TIFF2025501941000031.tif182170 [In the formula, Cy, Cy', R6, L, a', a'', d, e, f, g, g', g'', h, i, j, k, k', l, m, and n are as defined above; symbol TIFF2025501941000032.tif4170 represents the attachment point to U2 or U3] is selected from one of the following:

[0077] In this particular embodiment, when U1 and U4 are each independently a urethane bond, in formula (IV) of the oligomer of the invention, A may be the residue of a non-sterically hindered polyamine, in particular A is a group of formula (XIVa), (XIVb), (XIVc), (XIVd), (XIVe) or (XIVf): TIFF2025501941000033.tif108170[In the formula, Alk is alkylene optionally substituted with one or more groups independently selected from alkyl and alkenyl; Cy is a ring optionally substituted with one or more groups independently selected from alkyl and alkenyl; R 14 and R 15 are each independently H or an alkyl group, k'' is an integer from 1 to 50; symbol TIFF2025501941000034.tif4170 represents the attachment point to U2 or U3] You can choose from one of the More specifically, A is selected from the group consisting of ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, diethylenetriamine, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, 2-(aminomethyl)-2-methyl-1,3-propanediamine, N-(2-aminoethyl)-N-methylethylenediamine, preferably having a weight average molecular weight M in the range of 200 to 10,000 g / mol. w and preferably containing 20 to 40 carbon atoms, is the residue of a non-sterically hindered polyamine selected from a polyethylene glycol-based polyether diamine (Jeffamine® EDR), a fatty acid dimer-based diamine (Priamine® 1071, Priamine® 1073, T-403® 1074).

[0078] For purposes of this invention, an alkenyl is an alkyl containing at least one carbon-carbon double bond.

[0079] In one embodiment, when U1 and U4 are each independently a urea or urethane linkage, in formula (IV) of the oligomer of the invention, r, L1, L2, P, and o can be defined as follows: r is equal to 1, L1 and L2 are independent of each other, [●] o -POC(=O)-CH2-CH2-◆ P is the residue of a polyol, preferably P is an alkylene which may be alkoxylated or esterified; The symbol ● represents the point of attachment to the Acr group; The symbol ◆ represents the point of attachment to the group U1 or U4.

[0080] In this particular embodiment, in the formula (IV) of the oligomer of the invention, when U1 and U4 are each independently a urea or urethane linkage, A can be the residue of a sterically hindered polyamine resulting from the aza-Michael reaction of a polyacrylate with a sterically hindered primary monoamine, having a stoichiometric excess of acryloyloxy groups relative to the primary amine groups, more specifically A can be the residue of the following formula (XV): TIFF2025501941000035.tif23170[in the formula, P is the residue of a polyol, preferably P is an alkylene which may be alkoxylated or esterified; q is equal to 0, 1, 2, or 3; X is absent or X is -OC(=O)-CH2-CH2-U2-I-U1-CH2-CH2-C(=O)-O-P'-[Acr] o and U1, U2, I, Acr, and o are as defined above; P' is the residue of a polyol, preferably P' is an alkylene which may be alkoxylated or esterified; symbol TIFF2025501941000036.tif4170 represents the attachment point to U2 or U3] is equivalent to.

[0081] For the purposes of this invention, a polyacrylate is a compound that contains at least two acryloyloxy groups.

[0082] Preferably, in formula (IV) of the oligomer of the invention, P and P' are each independently ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1, 4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecane diol, tricyclodecane dimethanol, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, preferably with a weight average molecular weight M in the range of 200 to 10,000 g / mol w and preferably having a weight average molecular weight M in the range of 200 to 10,000 g / mol. w Polypropylene glycol having a weight average molecular weight M preferably in the range of 200 to 10,000 g / mol w Polytetramethylene glycol having a weight average molecular weight M preferably in the range of 200 to 10,000 g / mol wpoly(ethylene glycol-co-propylene glycol), alditols (i.e., erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, or iditol), dianhydrohexitols (i.e., isosorbide, isomannide, or isoidide), tris(2-hydroxyethyl)isocyanurate, preferably having a weight average molecular weight M in the range of 200 to 10,000 g / mol. w Polybutadiene polyols having a weight average molecular weight M preferably in the range of 200 to 10,000 g / mol w and preferably a polyester polyol having a weight average molecular weight M in the range of 200 to 10,000 g / mol. w and preferably a polyether polyol having a weight average molecular weight M in the range of 200 to 10,000 g / mol. w and preferably a polyorganosiloxane polyol having a weight average molecular weight M in the range of 200 to 10,000 g / mol. w and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, and derivatives obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) initiated with any of the above polyols.

[0083] Another subject of the invention relates to a polymerizable composition comprising at least one oligomer defined according to the invention and optionally at least one other ethylenically unsaturated compound.

[0084] For the purposes of the present invention, "ethylenically unsaturated compound" refers to a compound that contains a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. The polymerizable carbon-carbon double bond is generally within the group selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and corresponding combinations, preferably selected from acrylates, methacrylates, and vinyls, more preferably selected from acrylates and methacrylates. Carbon-carbon double bonds of phenyl rings are not considered to be polymerizable carbon-carbon double bonds.

[0085] In one embodiment, the ethylenically unsaturated compound can be selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and corresponding mixtures. In particular, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized monomer.

[0086] The total amount of ethylenically unsaturated compounds in the polymerizable composition may be 0 to 90% by weight, in particular 5 to 85% by weight, more particularly 10 to 80% by weight, relative to the total weight of the composition. In particular, the polymerizable composition may contain 0 to 60% by weight, or 5 to 60% by weight, or 10 to 60% by weight, or 15 to 60% by weight, or 20 to 60% by weight, relative to the weight of the composition. In a variant, the polymerizable composition may contain 50 to 80% by weight, or 55 to 80% by weight, or 60 to 80% by weight, relative to the weight of the composition.

[0087] As used herein, the term "(meth)acrylate-functionalized monomer" refers to a monomer containing at least one (meth)acryloyloxy group, particularly an acryloyloxy group. The term "(meth)acrylate-functionalized oligomer" refers to an oligomer containing a (meth)acryloyloxy group, particularly an acryloyloxy group. The term "(meth)acryloyloxy group" includes acryloyloxy groups (-O-CO-CH=CH2) and methacryloyloxy groups (-O-CO-C(CH3)=CH2).

[0088] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate functionalized monomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate functionalized monomers.

[0089] The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, specifically from 100 to 550 g / mol, and more specifically from 200 to 500 g / mol.

[0090] The (meth)acrylate functionalized monomer may contain 1 to 6 (meth)acryloyloxy groups, especially 1 to 4 (meth)acryloyloxy groups.

[0091] The (meth)acrylate-functionalized monomer may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized monomer may comprise a mixture of (meth)acrylate-functionalized monomers containing a single acryloyloxy or methacryloyloxy group per molecular weight (referred to herein as "mono(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized monomers containing two or more, preferably two or three, acryloyloxy and / or methacryloyloxy groups per molecular weight.

[0092] In one embodiment, the (meth)acrylate functionalized monomer comprises a mono(meth)acrylate functionalized monomer, which can advantageously function as a reactive diluent to reduce the viscosity of the polymerizable composition of the present invention.

[0093] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohols may be linear, branched, or alicyclic and may be mono-, di-, or polyalcohols, provided that a single hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (e.g., phenols, including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (e.g., benzyl alcohol); oligomeric and polymeric glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) fatty alcohols (the fatty alcohols may be linear, branched, or alicyclic and may be mono-, di-, or polyalcohols, provided that only one hydroxyl group of the alkoxylated fatty alcohol is esterified with (meth)acrylic acid); mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (e.g., alkoxylated phenols); caprolactone mono(meth)acrylate; and the like.

[0094] The following compounds are specific of the mono(meth)acrylate functionalized monomers suitable for use in the polymerizable compositions of the present invention: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate. acrylate;Tridecyl(meth)acrylate;Tetradecyl(meth)acrylate;Hexadecyl(meth)acrylate;2-Hydroxyethyl(meth)acrylate;2-Hydroxypropyl(meth)acrylate and 3-Hydroxypropyl(meth)acrylate;2-Methoxyethyl(meth)acrylate;2-Ethoxyethyl(meth)acrylate;2-Ethoxypropyl(meth)acrylate and 3-Ethoxypropyl(meth)acrylate;Tetrahydrofurfuryl(meth)acrylate;Alkoxy Silated tetrahydrofurfuryl (meth)acrylate;2-(2-ethoxyethoxy)ethyl (meth)acrylate;Cyclohexyl (meth)acrylate;Glycidyl (meth)acrylate;Isodecyl (meth)acrylate;Lauryl (meth)acrylate;2-Phenoxyethyl (meth)acrylate;Alkoxylated phenol (meth)acrylate;Alkoxylated nonylphenol (meth)acrylate;Cyclic trimethylolpropane formal (meth)acrylate;Isobornyl (meth)acrylate acrylate;tricyclodecane methanol (meth)acrylate;tert-butyl cyclohexanol (meth)acrylate;trimethylcyclohexanol (meth)acrylate;diethylene glycol monomethyl ether (meth)acrylate;diethylene glycol monobutyl ether (meth)acrylate;triethylene glycol monoethyl ether (meth)acrylate;ethoxylated lauryl (meth)acrylate;methoxypolyethylene glycol (meth)acrylate;hydroxyethylbutyl urethane (meth)acrylate;3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate;and corresponding combinations.

[0095] In one embodiment, the (meth)acrylate functionalized monomer may include a (meth)acrylate functionalized monomer that includes two or more (meth)acryloyloxy groups per molecular weight.

[0096] Examples of suitable (meth)acrylate-functionalized monomers containing two or more (meth)acryloyloxy-type groups per molecular weight include acrylate and methacrylate esters of polyols (organic compounds containing two or more, e.g., 2 to 6, hydroxyl groups per molecular weight). Specific examples of suitable polyols are as defined above for P and P'. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acryloyloxy-type functional groups per molecular weight.

[0097] Examples of (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy groups per molecular weight include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-Butanediol di(meth)acrylate;1,4-Butanediol di(meth)acrylate;1,5-Pentanediol di(meth)acrylate;1,6-Hexanediol di(meth)acrylate;1,8-Octanediol di(meth)acrylate;1,9-Nonanediol di(meth)acrylate;1,10-Decanediol di(meth)acrylate;1,12-Dodecanediol di (Meth)acrylates;Neopentyl glycol di(meth)acrylate;2-Methyl-2,4-pentanediol di(meth)acrylate;Polybutadiene di(meth)acrylate;Cyclohexane-1,4-dimethanol di(meth)acrylate;Tricyclodecane dimethanol di(meth)acrylate;Metal di(meth)acrylates;Modified metal di(meth)acrylates;Glycerol di(meth)acrylate;Glycerol Tri(meth)acrylate;Trimethylolethane tri(meth)acrylate;Trimethylolethane di(meth)acrylate;Trimethylolpropane tri(meth)acrylate;Trimethylolpropane di(meth)acrylate;Pentaerythritol di(meth)acrylate;Pentaerythritol tri(meth)acrylate;Pentaerythritol tetra(meth)acrylate;Bis(trimethylolpropane)di(meth)acrylate;Bis(trimethylolpropane)tri(meth)acrylate;Mention may be made of bis(trimethylolpropane)tetra(meth)acrylate, sorbitol penta(meth)acrylate; di(pentaerythritol)tetra(meth)acrylate; di(pentaerythritol)penta(meth)acrylate; di(pentaerythritol)hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and their alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives; and mixtures thereof;

[0098] The polymerizable composition of the present invention may comprise 0 to 90% by weight, in particular 5% to 85% by weight, more particularly 10% to 80% by weight of (meth)acrylate functionalized monomer, relative to the weight of the composition. In particular, the polymerizable composition may comprise 0 to 60% by weight, or 5% to 60% by weight, or 10% to 60% by weight, or 15% to 60% by weight, or 20% to 60% by weight of (meth)acrylate functionalized monomer, relative to the weight of the composition. As a variant, the polymerizable composition may comprise 50% to 80% by weight, or 55% to 80% by weight, or 60% to 80% by weight of (meth)acrylate functionalized monomer, relative to the weight of the composition.

[0099] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized oligomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized oligomers.

[0100] (Meth)acrylate-functionalized oligomers can be selected to enhance, among other attributes, the flexibility, strength, and / or modulus of cured polymers prepared using the polymerizable compositions of the present invention.

[0101] The (meth)acrylate functionalized oligomer may contain 1 to 18 (meth)acryloyloxy groups, particularly 2 to 6 (meth)acryloyloxy groups, and more particularly 2 to 6 acryloyloxy groups.

[0102] The (meth)acrylate functionalized oligomer may have a number average molecular weight of 600 g / mol or more, particularly 800 to 15,000 g / mol, and more particularly 1000 to 5000 g / mol.

[0103] In particular, the (meth)acrylate-functionalized oligomer may be selected from the group consisting of (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers", or "carbamate (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (sometimes referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (sometimes referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (sometimes referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate-functionalized polycarbonate oligomers (sometimes referred to as "polycarbonate (meth)acrylate oligomers"), and (meth)acrylate-functionalized polyester oligomers (sometimes referred to as "polyester (meth)acrylate oligomers"), and corresponding mixtures.

[0104] Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic acid or methacrylic acid, or the corresponding synthetic mixtures or equivalents, with hydroxy-terminated polyester polyols. The reaction process can be carried out such that all, or essentially all, of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. The polyester polyols can be prepared by polycondensation reaction of polyhydroxy-functionalized components, especially diols, with poly(carboxylic acid)-functionalized compounds, especially dicarboxylic acids and anhydrides. The polyhydroxy-functionalized and poly(carboxylic acid)-functionalized components can each have a linear, branched, alicyclic, or aromatic structure and can be used individually or in mixtures.

[0105] Examples of suitable epoxy (meth)acrylates include reaction products of acrylic acid or methacrylic acid or corresponding mixtures with epoxy resins (polyglycidyl ethers or esters). Epoxy resins include, in particular, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecalc. carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-Hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols obtained by addition of one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl ethers of long-chain aliphatic dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by addition of alkylene oxides to these compounds, glycidyl ethers of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, etc.,

[0106] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic acid or methacrylic acid or the corresponding mixtures or synthetic equivalents with a polyetherol, which is a polyether polyol (e.g., polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxyl groups. Polyetherols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with starter molecules. Suitable starter molecules include water, polyhydroxy-functionalized materials, polyester polyols, and amines.

[0107] Polyurethane (meth)acrylate oligomers (sometimes referred to as "urethane (meth)acrylate oligomers") suitable for use in the polymerizable compositions of the present invention include urethanes based on aliphatic, cycloaliphatic, and / or aromatic polyester polyols and polyether polyols, and aliphatic, cycloaliphatic, and / or aromatic polyester diisocyanates and polyether diisocyanates capped with terminal (meth)acrylate groups. Suitable polyurethane (meth)acrylate oligomers include, for example, diacrylate and tetraacrylate oligomers of aliphatic polyester-based urethanes, diacrylate and tetraacrylate oligomers of aliphatic polyether-based urethanes, and diacrylate and tetraacrylate oligomers of aliphatic polyester / polyether-based urethanes.

[0108] Polyurethane (meth)acrylate oligomers can be prepared by reacting an aliphatic, cycloaliphatic, or aromatic polyisocyanate (e.g., diisocyanate, triisocyanate) with a polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyorganosiloxane polyol (e.g., polydimethylsiloxane polyol), or polydiene polyol (e.g., polybutadiene polyol) terminated with OH groups, or a corresponding combination, to form an isocyanate-functionalized oligomer, which is reacted with a hydroxy-functionalized (meth)acrylate, such as hydroxyethyl acrylate or hydroxyethyl methacrylate, to obtain terminal (meth)acrylate groups. For example, polyurethane (meth)acrylate oligomers can contain two, three, four, or more (meth)acrylate functional groups per molecular weight. As known in the prior art, other addition sequences can also be carried out to prepare polyurethane (meth)acrylates. For example, a hydroxy-functionalized (meth)acrylate can be first reacted with a polyisocyanate to give an isocyanate-functionalized (meth)acrylate, which can then be reacted with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane polyol, or polybutadiene polyol, or a corresponding combination. In yet another embodiment, a polyisocyanate can be first reacted with a polyol (including any of the aforementioned polyol types) to give an isocyanate-functionalized polyol, which can then be reacted with a hydroxy-functionalized (meth)acrylate to give a polyurethane (meth)acrylate. Alternatively, all components can be combined and reacted simultaneously.

[0109] Suitable acrylic (meth)acrylate oligomers (sometimes referred to in the art as "acrylic oligomers") include oligomers that can be described as materials that include an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups, which can be terminal to the oligomer or pendant to the acrylic backbone. The acrylic backbone can be a homopolymer, random copolymer, or block copolymer made up of repeating units of acrylic-type monomers. The acrylic monomers can be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. Acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art, such as, for example, oligomerizing monomers at least some of which are functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomeric intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functionality.

[0110] The polymerizable composition of the present invention may comprise 0 to 90% by weight, in particular 5 to 85% by weight, more particularly 10 to 80% by weight of (meth)acrylate functionalized oligomer, relative to the weight of the composition. In particular, the polymerizable composition may comprise 0 to 60% by weight, or 5 to 60% by weight, or 10 to 60% by weight, or 15 to 60% by weight, or 20 to 60% by weight of (meth)acrylate functionalized oligomer, relative to the weight of the composition. As a variant, the polymerizable composition may comprise 50 to 80% by weight, or 55 to 80% by weight, or 60 to 80% by weight of (meth)acrylate functionalized oligomer, relative to the weight of the composition.

[0111] The polymerizable compositions of the present invention may also advantageously comprise a free radical or ionic polymerization initiator, more particularly a photoinitiator or a peroxide.

[0112] The photoinitiator can be a free radical photoinitiator, particularly a free radical photoinitiator with Norrish Type I activity and / or Norrish Type II activity, more particularly a free radical photoinitiator with Norrish Type I activity.

[0113] Non-limiting types of free radical photoinitiators suitable for use in the polymerizable compositions of the present invention include, for example, benzoins, benzoin ethers, acetophenones, α-hydroxyacetophenones, benzils, benzil ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoylformates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinones, corresponding polymer derivatives, and corresponding mixtures.

[0114] Examples of suitable free radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzyanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzil, benzoin, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-Phenylbenzoin, Michler's ketone, acetophenones, such as 2,2-dialkoxybenzophenones and 1-hydroxyphenyl ketones, benzophenone, 4,4'-bis(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzyl ketone, α-hydroxyketo keto), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzil dimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-hydroxy-2-methyl-1-phenylpropanone, oligomeric α-hydroxyketones, benzoylphosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisoin, anthraquinone Quinones, anthraquinone-2-sulfonic acid sodium salt monohydrate, (benzene)tricarbonylchromium, benzil, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl phenyl ketone 50 / 50 mixture, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzyl, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone 50 / 50 mixtures, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methyl benzoylformate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyliron(II) hexafluorophosphate, 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one, and the corresponding combinations. ,

[0115] In particular, the photoinitiator may be a benzophenone (e.g., SpeedCure® BP, SpeedCure® 7005, SpeedCure® 7006), a thioxanthone (e.g., SpeedCure® 7010, SpeedCure® ITX), an α-hydroxyacetophenone (e.g., SpeedCure® 73), an acylphosphine oxide (e.g., SpeedCure® BPO, SpeedCure® TPO, SpeedCure® TPO-L). Preferably, the photoinitiator is an α-hydroxyacetophenone or an acylphosphine oxide.

[0116] The polymerizable composition of the invention may in particular comprise from 0 to 20% by weight, in particular from 0.1% to 15% by weight, more particularly from 1% to 10% by weight, of a photoinitiator, relative to the weight of the composition.

[0117] In addition, the polymerizable composition of the present invention may contain other additives selected from antioxidants, light stabilizers, light absorbers, polymerization inhibitors, defoamers, antistatic agents, leveling agents, dispersants (wetting agents, surfactants), slip agents, adhesion promoters, lubricants, pigments, fillers, chain transfer agents, rheological agents (thixotropic agents, thickeners), matting agents, opacifiers, impact resistance agents, waxes.

[0118] Preferably, the polymerizable composition of the invention is an ink, a coating (in particular a protective coating, an electrically insulating coating, a decorative coating or a coating responsive to an external stimuli), a material filled with fibrous or particulate reinforcement (which may be carbon nanotubes or graphite) (in particular a putty, a chemical dowel, an artificial stone, a dental filling material or a composite), an adhesive, a molding, a composition for an ink plate or an electrode binder composition or a composition for additive manufacturing, in particular for 3D or 4D printing of objects.

[0119] For the purposes of this invention, an ink plate is a flexible photopolymer plate intended for transferring ink to a substrate to be printed in rotary letterpress or flexographic printing.

[0120] Additive manufacturing, also known as 3D printing, consists of creating (volumetric / three-dimensional) objects (called voxels, analogous to pixels in traditional 2D printing) point-by-point from a digital model that contains properties related to the shape of the object to be produced (a mesh of points or surfaces) and, optionally, parameters of the material used, or by selectively modifying the properties of a soft medium at these points, for example by solidification (polymerization) from a container of liquid resin, or by agglomeration / sintering / melting / resolidification from a powder bed, or by selectively depositing material at various points on a surface (also known as a layer, generally flat), either continuously (by extrusion) or discontinuously (by inkjet), and surface-by-surface. The surface can be replenished top-to-bottom or from the center outwards, generally starting from a printing support, sometimes with the unmodified material itself as the support. The general principles of 3D printing are defined in the ISO / ASTM standard 52900:2015. Printing of 4D objects can be defined as printing a 3D object that can be deformed over time. 4D printing is therefore a process in which a 3D printed object can modify its own structure and change shape under an impulse of external energy such as temperature, light, or other environmental stimuli.

[0121] Another subject of the invention relates to a process for producing a crosslinked product comprising a step of crosslinking a polymerizable composition defined according to the invention, in particular by exposing said composition to radiation, more particularly ultraviolet, near-ultraviolet, visible, infrared or near-infrared radiation, or to an electron beam.

[0122] More specifically, the process of the invention is directed to the manufacture of crosslinked products chosen from inks, coatings (in particular protective, electrically insulating, decorative or coatings responsive to an external stimuli), materials filled with fibrous or particulate reinforcement (which may be carbon nanotubes or graphite) (in particular putties, chemical dowels, artificial stones, dental fillings or composites), adhesives, molding materials, ink plates, electrode binders or objects obtained by additive manufacturing, in particular objects obtained by 3D or 4D printing.

[0123] Another object of the invention relates to a process for producing a three-dimensional object comprising an additive manufacturing step, in particular a sequential or layer-by-layer printing step, using a polymerizable composition as defined according to the invention.

[0124] The crosslinked products obtained by crosslinking the polymerizable compositions defined according to the invention or obtained by the process defined according to the invention also form part of the invention.

[0125] The crosslinked product of the invention is advantageously an ink, a coating (in particular a protective coating, an electrically insulating coating, a decorative coating or a coating responsive to an external stimuli), a material filled with fibrous or particulate reinforcement (which may be carbon nanotubes or graphite) (in particular a putty, a chemical dowel, an artificial stone, a dental filling or a composite), an adhesive, a molding material, an ink plate, an electrode binder or an object obtained by additive manufacturing, in particular an object obtained by 3D or 4D printing.

[0126] A final object of the present invention is the use of the polymerizable composition defined according to the invention for the manufacture of an ink, a coating (in particular a protective, electrically insulating, decorative or coating responsive to an external stimuli), a material filled with fibrous or particulate reinforcement (which may be carbon nanotubes or graphite) (in particular a putty, chemical dowel, artificial stone, dental filling material or composite), an adhesive, a molding material, an ink plate, an electrode binder or an object obtained by additive manufacturing, in particular an object obtained by 3D or 4D printing.

[0127] The present invention also relates to the use of an oligomer as defined according to the invention as a binder in a polymerizable composition.

[0128] Finally, a last subject of the invention relates to the use of an oligomer as defined according to the invention in a composition for additive manufacturing, in particular in a composition for 3D or 4D printing of objects.

[0129] In addition to the provisions mentioned above, the present invention also includes other provisions that will become apparent from the following further description of the synthesis examples of the oligomers according to the invention and the evaluation of the application properties of the compositions containing them. EXAMPLES

[0130] Measurement method: In this patent application, the following measurement methods were used:

[0131] Brookfield Viscosity Measurement: Measured at 25°C using a Brookfield DVII+ Viscometer with an S34 cylindrical spindle according to ISO Standard 2555.

[0132] The temperature was kept constant during the Brookfield viscosity measurements using a water circulating temperature control system.

[0133] Measurement of Noory kinematic viscosity: The Noory kinematic viscosity corresponds to the transit time of a steel ball subjected to gravity through the liquid to be characterized, according to the standard AFNOR XP T51-213, which specifies among other things the shape of the container, the diameter of the ball (2 mm) and the distance travelled by the ball (104 mm). Under these conditions, the kinematic viscosity is proportional to the transit time of the ball, with a transit time of 1 second corresponding to a viscosity of 0.1 Pa.s.

[0134] Reactivity: The compositions were applied filmographically to a thickness of 12 μm on a contrast card (Penopac Chart Form 1B® Leneta) and then photopolymerized by exposure to a 120 W Fusion mercury lamp (Heraeus). This measurement gives the number of passes required under the lamp at a minimum speed (5 m / min) to obtain a touch-dry film.

[0135] Persoz hardness: conforms to NF EN ISO standard 1522.

[0136] The Persaud hardness was measured after applying a 100 μm thick composition to a glass plate using a filmograph, followed by photopolymerization by exposure to a 120 W Fusion mercury lamp (Heraeus). The exposure time was controlled by multiplying the number of passes by the speed of a conveyor that transported the substrate under the lamp at a speed of 8 m / min. The measurements represent the time (in seconds) until the oscillation of a pendulum in contact with a glass plate coated with the composition (change in amplitude from 12° to 4°) decays after 24 hours in a conditioned room at 23° C. and 50% relative humidity.

[0137] Pencil hardness: The composition was applied as a 100 μm film on a glass plate and then photopolymerized by exposure to a 120 W Fusion mercury lamp (Heraeus). This test allows the evaluation of the resistance of the coating to surface scratches. According to ASTM standard D3363:1992, after 24 hours in a conditioned room at a temperature of 23° C. and a relative humidity of 50%, a low hardness pencil (grades 6H to 6B) held in place by a support was moved over the test film. The hardness of the film is determined by the first pencil hardness grade that does not scratch the surface.

[0138] Flexibility: The composition is applied as a 100 μm film onto a 25 / 10 mm thick smooth steel plate (D-46® Q-Panel) and then photopolymerized by exposure to a 120 W Fusion mercury lamp (Heraeus) at a speed of 8 m / min. The coated plate is bent on a cylindrical mandrel according to ISO standard 1519. The result is the value (in mm) of the smallest radius of curvature that the coating can be subjected to without cracking or peeling off from the support.

[0139] Chemical resistance: The composition is applied as a 12 μm film on a glass plate and then photopolymerized by exposure to a 120 W Fusion mercury lamp (Heraeus) at a speed of 8 m / min. The coating is then rubbed with a 500 g weight attached to a cotton wick soaked in acetone, which is rubbed back and forth over the coating to be tested. The result is the time (expressed in seconds) until the film peels off and / or disaggregates from the support, measured using a Taber® 5750 Linear Abrasion Meter.

[0140] APHA Colors: Conforms to ISO standard 6271:2015. In this test, the platinum-cobalt scale can be used to evaluate color, and the term "Pt-Co color" is synonymous with the terms "Hazen color" and "APHA color."

[0141] Additive Manufacturing: 3D objects were printed using compositions D, E, F, G, and H of Example 15 (Table 7) based on the printable object files shown in Figures 1 to 3. The prints were produced on a Photon model 3D printer (LCD printer from Anycubic). The printing program used is shown in Table 1 below, with the adhesive layer being the layer in contact with the platform. The parts obtained after printing were subjected to post-baking under a Phoseon 12 W / cm2 LED lamp at 395 nm with a conveyor bench, at a speed of 5 m / min, with 10 passes. TIFF2025501941000037.tif23170

[0142] Tensile test (elongation, breaking stress): According to the printable object file shown in FIG. 1, the elongation and breaking stress of the printed object are measured using a tensile test according to ISO standard 527-5A:1993 at appropriate tensile speeds for rigid materials (2 mm / min) and flexible materials (500 mm / min).

[0143] Tear strength: The tear strength is measured on the printed object according to the printable object file of FIG. 3, in accordance with standard D624 type C, 2012, at a pulling speed of 500 mm / min.

[0144] Shore Hardness: The Shore hardness was measured using a Shore A type durometer in accordance with ISO standard 868:2003 on the printed object according to the printable object file in Figure 1. The measurement was taken after 5 seconds of contact between the measuring tip and the sample.

[0145] Glass transition temperature (tangent alpha Tα): The glass transition temperature was determined by dynamic mechanical analysis (DMA). The measurements of the storage modulus (G') and loss modulus (G") were carried out on a Rheometric Scientific RDA III instrument controlled by RSI Orchestrator software, applying a rectangular torsional stress to specimens with dimensions of 80*10*4mm (the usable length between the jaws is adjustable between 1.5 and 4cm, this value is taken into account in the calculation of the elastic modulus in the software), printed according to the printable object file in Figure 2, with a temperature ramp rate of 3°C / min from -40°C to 180°C, a typical deformation degree of 0.05%, and a stress frequency of 1Hz. The specimens were first conditioned at a temperature of 23°C ± 2°C and a relative humidity of 50% ± 10% for at least 24 hours. The storage modulus values ​​were reported at different temperatures, in particular at 25°C and 150°C. The ratio G'' / G' is called the loss modulus or tangent delta (tan delta). Tg corresponds to the temperature (Tα) at ​​which the value of this tangent is maximum.

[0146] Isocyanate value (I NCO ) decision: The isocyanate value was determined by acid-base back titration of excess dibutylamine on the isocyanate functions under the following conditions: The exact weight p in grams of the sample (approximately 1 gram) was dissolved in approximately 10 mL of toluene. After complete dissolution, 15 mL of a dibutylamine solution with a titer of 0.15 N was added (solution of 20 g of dibutylamine in 1000 mL of toluene: 20 g / L) and then reacted for 15 minutes at room temperature. Then 100 mL of isopropanol was added. The excess of dibutylamine was analyzed with an aqueous hydrochloric acid solution with a standard titer N (Eq / l) of 0.1 N. The equivalence point was detected with a combination electrode (LiCl Metrohm standard 6.0222.100) connected to an automatic burette (Metrohm "716 DMS Titrino" automatic titrator) delivering the equivalent volume VE expressed in mL. A blank test (15 mL of dibutylamine solution supplemented with 10 mL of toluene and then 100 mL of isopropanol) was also performed using the equivalent volume VB expressed in mL. The isocyanate value (I NCO ) was calculated as follows: I NCO(mgKOH / g)=(VE-VB)*N*56.1 / p.

[0147] Amine value (I Amine ) decision: The amine value was measured by direct acid-base titration under the following conditions: The exact sample weight p (in grams) was dissolved in 40 mL of acetic acid. The basicity of the sample was determined using a solution of perchloric acid in acetic acid with a standard titer N (in Eq / l) of 0.1 N. The equivalence point was detected with a glass electrode (filled with a 1 mol / L solution of lithium perchlorate in acetic acid) connected to an automatic burette (Metrohm "716 DMS Titrino" automatic titrator) delivering the equivalent volume VE expressed in mL. The amine value (I) was calculated using the following equation: Amine ) was calculated as follows: I Amine (mgKOH / g)=VE*N*56.1 / p.

[0148] Products and starting materials: The products and starting materials used in the following examples are as follows: CN981: Aliphatic urethane diacrylate oligomer with a weight average molecular weight of 2200 g / mol (Arkema); IPGA: (2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylate monomer obtained by transesterification of isopropylidene glycerol (Augeo SL 191) (Solvay) with methyl acrylate (Arkema) in an acrylate / alcohol molar ratio of 2:3, catalyzed by zirconium acetylacetonate (Zr(AcAc)4) (Sachem); SR238: 1,6-hexanediol diacrylate (HDDA) monomer with a molecular weight of 226 g / mol (Arkema); SR355: bis(trimethylolpropane)tetraacrylate monomer with molecular weight of 466 g / mol (Arkema); SR595: 1,10-decanediol diacrylate monomer with a molecular weight of 282 g / mol (Arkema); SR256: 2-(2-ethoxyethoxy)ethyl acrylate monomer with a molecular weight of 188 g / mol (Arkema); SR444D: Pentaerythrityl triacrylate monomer with molecular weight of 298 g / mol (Arkema); SR789: Tricyclodecane methanol acrylate monomer with a molecular weight of 220 g / mol (Arkema); - HQME: Hydroquinone methyl ether (Sigma-Aldrich); - BHT: Butylated Hydroxy Toluene (Sigma-Aldrich); - triphenyl phosphite (Sigma-Aldrich), - PTZ: phenothiazine (Sigma-Aldrich); - sec-butylamine (Sigma-Aldrich), - NMEA: N-methylethanolamine (Sigma-Aldrich), 4,4'-methylenebis(cyclohexylamine) (Sigma-Aldrich), - HDI: Hexamethylene diisocyanate (Sigma-Aldrich), IPDI: isophorone diisocyanate sold under the name Desmodur® I (Covestro); - DEM: Diethyl maleate (Sigma-Aldrich); - Jeffamine® ED-600: polyether diamine (Huntsman); - TPO-L: ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, a photoinitiator sold under the trade name SpeedCure® TPO-L (Lambson); - SpeedCure® 73: 2-hydroxy-2-methyl-1-phenylpropanone, a photoinitiator sold under the trade name SpeedCure® 73 (Lambson).

[0149] Example 1: Preparation of urea (meth)acrylate oligomers according to the present invention HDDA SR238 (75.00 g) and HQME (0.120 g) were placed in a reactor equipped with a reflux column, two dropping funnels, a thermometer, and a tilted paddle stirrer at 23° C. sec-Butylamine (19.64 g) was introduced through the dropping funnel over 5 min. The reactor was heated to 80° C. over 30 min and then maintained at this temperature for 2 h. The reactor was then cooled to 40° C. Proton NMR analysis showed that the sec-butylamine was completely consumed and no tertiary amine was present. IPDI (28.00 g) was added through the second dropping funnel over 1 h. During the introduction, the exotherm was controlled with an ice-water bath to keep the temperature below 50° C. The temperature was maintained at 50° C. for 15 min.

[0150] Examples 2-8: Preparation of urea (meth)acrylate oligomers according to the present invention The same protocol as in Example 1 was repeated, varying the proportions and nature of the acrylates, amines, and isocyanates as shown in Table 2 below. TIFF2025501941000038.tif133170

[0151] Example 9: Preparation of urethane aminoacrylate-acrylate oligomers according to WO 2016 / 170264 (comparative example) HDDA SR238 (75.00 g), HQME (0.100 g), BHT (0.050 g), triphenyl phosphite (0.100 g), and PTZ (0.020 g) were placed in a reactor equipped with a reflux column, two dropping funnels, a thermometer, and a tilted paddle stirrer at 23° C. NMEA (17.80 g) was introduced through the dropping funnel over 30 minutes. The reactor was heated to 50° C. over 30 minutes and then maintained at this temperature for 2 hours. IPDI (21.95 g) was added through the second dropping funnel over 1 hour. The temperature was then increased to 100° C. and maintained at this temperature for 3 hours.

[0152] Example 10: Preparation of urea (meth)acrylate oligomers according to the present invention HDDA SR238 (75.00 g) and HQME (0.120 g) were charged at 23° C. to a reactor equipped with a reflux column, two dropping funnels, a thermometer, and a tilted paddle stirrer. sec-Butylamine (17.33 g) was introduced through the dropping funnel over 5 min. The reactor was heated to 55° C. over 10 min, then to 75° C. and maintained at this temperature for 1 h. The reactor was then cooled to 40° C. IPDI (21.95 g) was added through the second dropping funnel over 1 h. During the introduction, the exotherm was controlled with an ice-water bath to keep the temperature below 50° C. The temperature was maintained at 50° C. for 15 min.

[0153] Examples 11-13: Preparation of urea (meth)acrylate oligomers according to the present invention The same protocol as in Example 10 was repeated, varying the proportions and nature of the amines and isocyanates as shown in Table 3 below. TIFF2025501941000039.tif71170

[0154] The molar amount of isocyanate functionality introduced was constant for all examples in Table 3, so that they were strictly comparable. These examples could therefore be compared in terms of color, viscosity and hardness after coating a film of a mixture consisting of 9.90 g of the exemplified oligomer composition and 0.10 g of photoinitiator TPO-L. The results obtained are summarized in Table 4 below. TIFF2025501941000040.tif66170

[0155] The results shown in Table 4 indicate that: The oligomers of the invention are much less colored than those of the prior art (reference examples). Examples 10 and 11 show that, when R1 and R2 are identical, the compromise between viscosity (desirably as low as possible) and Persod hardness (desirably as high as possible) is at least comparable to that of the reference. Example 11 shows that, without the presence of rings, it is possible to obtain mechanical properties comparable to those of the reference. Comparison of Examples 9 and 11 proves that the urea functionality present in the oligomers of the invention is preferred over urethane functionality at comparable concentrations. Due to the absence of side reactions, the invention offers the possibility of synthesizing oligomers with an isocyanate / amine R2 ratio close to 1, which is not possible in the reference examples. In this case, examples 12 and 13 show that the compromise between viscosity and Persod hardness is very clearly in favor of the oligomers according to the invention.

[0156] Example 14: Preparation of intermediates containing secondary diamines 2-(2-Ethoxyethoxy)ethyl acrylate SR256 (60.00 g) and HQME (0.100 g) were placed in a reactor equipped with a reflux column, two dropping funnels, a thermometer, and an inclined paddle stirrer at 23° C. 4,4'-methylenebis(cyclohexylamine) (33.51 g) was introduced through the dropping funnel over 5 minutes. The reactor was heated at 90° C. for 3 hours. The reactor was then cooled to 65° C. and then HDDA (20.00 g) was introduced through the other dropping funnel over 5 minutes. The reactor was then maintained at 65° C. for 1 hour and then cooled to room temperature.

[0157] Example 15: Preparation of HDI-Pentaerythrityl Triacrylate Adduct Intermediate HDI (29.66 g), BHT (0.050 g), and HQME (0.050 g) were introduced at 23° C. into a reactor equipped with a reflux column, a dropping funnel, a thermometer, and an inclined paddle stirrer. Pentaerythrityl triacrylate SR444D (91.69 g) was introduced through the dropping funnel over 20 min. The reactor was heated to 80° C. until an isocyanate value of 82 mg KOH / g was obtained. After cooling to room temperature, the intermediate was stored for 30 min (but never for more than 24 h). During this time, the isocyanate value remained stable: I NCO =80.4mgKOH / g.

[0158] Example 16: Preparation of urea-urethane (meth)acrylate oligomers according to the present invention 50.00 g of the intermediate containing secondary diamine prepared in Example 14 and BHT (0.100 g) were placed in a reactor equipped with a reflux column, a dropping funnel, a thermometer, and an inclined paddle stirrer at 23° C. The reactor was heated at 50° C. until the BHT was completely dissolved. 96.54 g of the HDI-pentaerythrityl triacrylate adduct intermediate prepared in Example 15 was introduced through the dropping funnel over 30 minutes. The reactor was heated to 80° C. and maintained at this temperature for 2 hours, then cooled. The isocyanate value I of the resulting oligomer was 1.06 g. NCO and amine value I Amine We measured: I NCO = 0 mg KOH / g, I Amine =2.7mgKOH / g.

[0159] Example 17: Preparation of urea-urethane (meth)acrylate oligomers according to the present invention While sparging with dry nitrogen at a flow rate of 20 mL / min, DEM (28.21 g) was introduced into a reactor equipped with a reflux column, two dropping funnels, a thermometer, and a tilted paddle stirrer at 23° C. Amine number I AmineJeffamine® ED-600, with a measured isocyanate value of 179.0 mg KOH / g (50.16 g), was introduced through the dropping funnel over 30 minutes. The reactor was heated at 100° C. for 7 hours and then cooled to 65° C. The nitrogen sparge was then replaced with an air sparge at a flow rate of 20 mL / min. HDDA (30.00 g) was then added and the temperature was maintained at 65° C. for 1 hour. The reactor was cooled to 50° C. Then HQME (0.100 g) was added. 110.00 g of the HDI-pentaerythrityl triacrylate adduct intermediate prepared in Example 15 was added through a second dropping funnel over 45 minutes. The temperature was increased to 80° C. and maintained at 80° C. for 3 hours. The isocyanate value I of the resulting oligomer was 1.00 g. NCO and amine value I Amine We measured: I NCO = 0 mg KOH / g, I Amine =2.4mgKOH / g.

[0160] Example 18: Preparation and evaluation of polymerizable compositions based on urea (meth)acrylate oligomers according to the present invention Compositions were prepared from the urea (meth)acrylate oligomers of Examples 1, 2, and 3 of the present invention. The oligomers were preheated to 65° C., and then the photoinitiator was introduced and dissolved while stirring manually. The mixture was then allowed to return to room temperature (25° C.). The compositions are shown in Table 5 below (amounts are given in grams). TIFF2025501941000041.tif84170

[0161] The application properties of the films obtained after photopolymerization using compositions A, B, and C were evaluated and are summarized in Table 6 below: TIFF2025501941000042.tif39170

[0162] The application properties of the films obtained from compositions A, B, and C are varied: a compromise between good film formation and good performance (for the film obtained from composition A), flexibility (for the film obtained from composition B), good hardness and chemical resistance (for the film obtained from composition C).

[0163] Example 19: Preparation and evaluation of polymerizable compositions based on urea (meth)acrylate oligomers according to the invention and comparative compositions. Compositions were prepared from the urea (meth)acrylate oligomers of the oligomer examples 4, 5, and 6 of the present invention, and the comparative oligomer. The oligomers were preheated to 65° C., and then the photoinitiator was introduced and dissolved while stirring manually. The mixture was then allowed to return to room temperature (25° C.). The compositions are shown in Table 7 below (amounts are given in grams). TIFF2025501941000043.tif101170

[0164] Additive Manufacturing: Following the aforementioned protocol, 3D objects were printed using the compositions described in the Examples from the printable object files shown in Figures 1-3. All oligomer-based compositions of the present invention were demonstrated to be usable for additive manufacturing.

[0165] The application properties of the objects obtained after photopolymerization from compositions D, E, F, G and H were also evaluated and are summarized in Table 8 below. TIFF2025501941000044.tif135170

[0166] The application results show that the oligomers of the present invention provide properties that are the same or better than those obtained with conventional urethane acrylates (see Examples E and F) without the drawbacks associated with the preparation of urethane acrylates, i.e., the absence of metal residues (especially tin) from the catalysis of the alcohol-isocyanate reaction.

[0167] The final properties of the crosslinked product can be easily tuned by adjusting the ratios of acrylate, amine, and isocyanate to obtain the desired final properties (see Examples G and H).

Claims

1. an oligomer, at least two urea bonds, in particular at least two sterically hindered urea bonds, at least two (meth)acryloyloxy groups, in particular at least two acryloyloxy groups, and optionally at least one urethane bond, in particular optionally at least two urethane bonds An oligomer comprising:

2. The oligomer comprises at least two sterically hindered urea linkages linked together by a linker group, each sterically hindered urea linkage being linked to said linker group by a nitrogen atom that has no hydrogen atoms, and in particular the oligomer has the following formula (I): [In the formula, A is a residue of a polyamine, and preferably A does not contain a urea or urethane bond; R is other than H, preferably R is a sterically hindering group; z is an integer from 2 to 6, represents the point of attachment to the carbon atom] 2. The oligomer of claim 1, comprising at least one fragment corresponding to:

3. at least two urea bonds, each urea bond being capable of reacting with a primary amine and an α,β-unsaturated carbonyl compound via an aza-Michael reaction, in particular a) between a sterically hindered primary amine and a (meth)acrylate, or b) between a primary amine and a maleic acid diester or a fumaric acid diester 2. The oligomer according to claim 1, wherein the group is directly linked to a group derived from the aza-Michael reaction of

4. The following formula (Ia): [In the formula, Z is H or a group containing an ester function -COOY, Y is an alkyl group optionally substituted with one or more (meth)acrylate groups; represents the point of attachment to the carbon atom] and at least two fragments corresponding to In particular, the oligomer has the following formula (Ib) or (Ic): [In the formula, R is other than H, preferably R is a sterically hindering group; Z is H or a group containing an ester function -COOY, Y is an alkyl group optionally substituted with one or more (meth)acrylate groups; represents the point of attachment to the carbon atom] 2. The oligomer of claim 1, comprising at least two fragments corresponding to one of:

5. The following formula (Id) or (Ie): [In the formula, R is other than H, preferably R is a sterically hindering group; Z is H or a group containing an ester function -COOY, Y is an alkyl group optionally substituted with one or more (meth)acrylate groups; P is a residue of a polyol, preferably free of urea or urethane bonds, and preferably P is an alkylene which may be alkoxylated or esterified; A is a residue of a polyamine, and preferably A does not contain a urea or urethane bond; z' is an integer from 2 to 6, z" is an integer from 2 to 6, represents the point of attachment to the carbon atom] 2. The oligomer of claim 1, comprising a fragment corresponding to one of:

6. The oligomer is preferably a reaction product of at least one poly(meth)acrylate, at least one sterically hindered primary monoamine, and at least one isocyanate compound, the reaction product being obtained by the following sequential steps: (i) an aza-Michael reaction between at least one poly(meth)acrylate and at least one sterically hindered primary monoamine, having a stoichiometric excess of (meth)acryloyloxy groups relative to primary amine groups, preferably less than 0.9, preferably in the range of 0.1 to 0.8, or 0.2 to 0.7, or 0.3 to 0.5 NH ２ / (meth)acryloyloxy ratio, and (ii) reacting the amino-(meth)acrylate mixture obtained in step (i) with at least one isocyanate compound to obtain an NCO / NH ratio of preferably less than 1.05, preferably in the range of 0.6 to 1.01, or 0.8 to 1, or 0.9 to 0.99; ２ The reaction has a ratio of 2. The oligomer according to claim 1, characterized in that it is obtained by a process comprising:

7. The sterically hindered primary monoamine has the following formula (II): [In the formula, R １ and R ２ are each independently selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or an alkyl group containing at least one heteroatom, or R １ and R ２ optionally containing one or more heteroatoms, C ４ ~C ８ , preferably C ６ capable of forming a ring, R ３ is H or an alkyl group, preferably C １ ~C ４ , more preferably —CH ３ and a is equal to 0 or 1. Corresponding to, In particular, the sterically hindered primary monoamine is of the following formula (IIa), (IIb), or (IIc): [In the formula, R' １ and R' ２ are, independently of one another, preferably C １ ~C ４ , more preferably C １ ~C ２ is an alkyl group, Cy is C ４ ~C ８ and preferably C ６ It is a ring, R' ３ is H or a methyl group, a is equal to 0 or 1, b and c are each independently an integer ranging from 1 to 50. corresponds to one of More particularly, the sterically hindered primary monoamines are selected from the group consisting of 2-aminopentane, 3-aminopentane, 1,2-dimethylpropylamine, 1,3-dimethylbutylamine, 2-aminooctane, isopropylamine, isobutylamine, sec-butylamine, tert-butylamine, tert-octylamine (2-amino-2,4,4-trimethylpentane), 2-ethylhexylamine, (2-methylbutyl)amine, cyclopentylamine, cyclohexylamine, 3,3,5-trimethylcyclohexylamine, cycloheptylamine, benzylamine, polypropylene glycol-based polyether monoamines, and optionally polyether monoamines having a weight average molecular weight M preferably in the range of 200 to 3000 g / mol. ｗ ethylene glycol having a carboxylic acid group (Jeffamine® M-600, Jeffamine® M-1000, or Jeffamine® M-2005), and mixtures thereof. The oligomer according to claim 6 .

8. The oligomer is a reaction product between at least one mono(meth)acrylate, at least one sterically hindered primary polyamine, and at least one isocyanate compound, the oligomer preferably being prepared by the following sequential steps: (i') by aza-Michael reaction between at least one mono(meth)acrylate and at least one sterically hindered primary polyamine, in particular in the range of 0.7 to 1.3, preferably 0.9 to 1.1, or 0.95 to 1.05, of NH ２ forming a poly(amino ester) having a ratio of 1:1 to 1:1; (ii') optionally adding an acrylate to eliminate residual primary amine functionality; (iii') reacting the poly(amino ester) obtained in step (i') or (ii') with at least one isocyanate compound. wherein: The isocyanate compound is polyisocyanates and (meth)acrylates functionalized with OH or NHR' groups, or adducts obtained by reaction of polyisocyanates with (meth)acrylates functionalized with OH or NHR′ groups, which have a stoichiometric excess of NCO groups relative to the OH or NHR′ groups; Including, R' is a group other than H, especially a sterically hindering group; Preferably, the polyisocyanate is a diisocyanate, the OH-functionalized (meth)acrylate is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and the NHR′-functionalized (meth)acrylate is 2-(tert-butylamino)ethyl methacrylate. The oligomer according to claim 1 , characterized in that

9. The oligomer is preferably a reaction product between at least one maleic or fumaric acid diester, at least one primary polyamine, and at least one isocyanate compound, the oligomer preferably being prepared by the following sequential steps: (i") by aza-Michael reaction between at least one maleic or fumaric acid diester and at least one primary polyamine, in particular to produce NH ２ forming a poly(amino ester) having a ratio of 1:1 to 1:1; (ii") reacting the poly(amino ester) obtained in step (i") with at least one isocyanate compound. wherein: The isocyanate compound is polyisocyanates and (meth)acrylates functionalized with OH or NHR′ groups, or adducts obtained by reaction of polyisocyanates with (meth)acrylates functionalized with OH or NHR′ groups, which have a stoichiometric excess of NCO groups relative to the OH or NHR′ groups; Including, R' is a group other than H, especially a sterically hindering group; Preferably, the polyisocyanate is a diisocyanate, the OH-functionalized (meth)acrylate is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and the NHR′-functionalized (meth)acrylate is 2-(tert-butylamino)ethyl methacrylate. The oligomer according to claim 1 , characterized in that

10. The following formula (IV): [In the formula, each Acr is independently a (meth)acryloyloxy group; L １ and L ２ are independent of each other, [●] ｏ -P-[OC(=O)-CH ２ -CH ２ ] ｒ -◆ and P is the residue of a polyol, preferably P is an alkylene which may be alkoxylated or esterified; The symbol ● represents the point of attachment to the Acr group; The symbol ◆ represents the base U １ or U ４ represents the point of attachment to U １ and U ４ are independently selected from a urea bond or a urethane bond; U ２ and U ３ is a urea bond, I is the residue of a polyisocyanate, W is absent or represents a branch on the oligomer; A is the residue of a polyamine, X is absent or represents a branch on the oligomer; each o is independently an integer ranging from 1 to 5; p is an integer from 0 to 50, and when p is equal to 0, the group U １ or U ４ at least one of which is a urea bond, each q is independently an integer from 0 to 4; r is equal to 0 or 1.

2. The oligomer of claim 1, comprising at least one product corresponding to:

11. 11. The oligomer according to claim 10, characterized in that each I is the residue of an aliphatic, cycloaliphatic, or aromatic polyisocyanate, in particular an aliphatic or cycloaliphatic diisocyanate.

12. U １ and U ４ are each independently of one another represented by the following formula (VI): [In the formula, R ８ is a sterically hindering group, symbol is a group L １ or L ２ represents the point of attachment to symbol represents the point of attachment to group I. It is a urea bond represented by When p>0, U ２ and U ３ are each independently of one another represented by the following formula (VII): [In the formula, R ９ is a sterically hindering group, symbol represents the point of attachment to group A, symbol represents the point of attachment to group I. The oligomer according to claim 10, wherein the urea bond is represented by the following formula:

13. R ８ and R ９ are each independently of one another represented by the following formula (VIII): [In the formula, R １ and R ２ are each independently selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or an alkyl group containing at least one heteroatom, or R １ and R ２ optionally containing one or more heteroatoms, C ４ ~C ８ , preferably C ６ capable of forming a ring, R ３ is H or an alkyl group, preferably C １ ~C ４ , more preferably —CH ３ and a is equal to 0 or 1; The symbol ■ represents the point of attachment to the nitrogen atom. is a sterically hindered group represented by Especially R ８ and R ９ are each independently of one another represented by the following formula (VIIIa), (VIIIb), or (VIIIc): [In the formula, R' １ and R' ２ are, independently of one another, preferably C １ ~C ４ , more preferably C １ ~C ２ is an alkyl group, Cy is C ４ ~C ８ and preferably C ６ It is a ring, R' ３ is H or a methyl group, a is equal to 0 or 1, b and c are each independently an integer ranging from 1 to 50; The symbol ■ represents the point of attachment to the nitrogen atom.

13. The oligomer according to claim 12, wherein the steric hindrance group is one of the following:

14. U １ and U ４ are each independently of one another represented by the following formula (IX): It is a urea bond represented by symbol is a group L 1 or L 2 represents the point of attachment to symbol represents the point of attachment to group I, p>0, and U 2 and U 3 are each independently of one another represented by the following formula (X): [In the formula, R １０ is other than H, preferably R １０ is a sterically hindering group, symbol represents the point of attachment to group A, symbol represents the point of attachment to group I. The oligomer according to claim 10, wherein the urea bond is represented by the following formula:

15. R １０ is one of the groups of formula (VIII), (VIIIa), (VIIIb) or (VIIIc) as defined in claim 13, or the following formula (XI) or (XII): [In the formula, R １１ is selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and alkyl groups containing at least one heteroatom, polyester, or combinations thereof; R １２ and R １３ are, independently of each other, an alkyl group, symbol represents the point of attachment to the nitrogen atom] 15. The oligomer of claim 14, wherein the steric hindrance group is selected from the group represented by one of the following:

16. A is the residue of a sterically hindered polyamine resulting from the aza-Michael reaction between a polyacrylate and a sterically hindered primary monoamine, and has a stoichiometric excess of acryloyloxy groups relative to the primary amine groups, and in particular A is represented by the following formula (XV): [In the formula, P is the residue of a polyol, preferably P is an alkylene which may be alkoxylated or esterified; q is equal to 0, 1, 2, or 3; X is absent or X is —O—C(═O)—CH ２ -CH ２ -U ２ -I-U １ -CH ２ -CH ２ -C(=O)-O-P'-[Acr] ｏ and U １ , U ２ , I, Acr, and o are as defined in claim 10; P' is the residue of a polyol, preferably P' is an alkylene which may be alkoxylated or esterified; symbol is U ２ or U ３ represents the point of attachment to 13. The oligomer according to claim 12, characterized in that it corresponds to

17. A polymerizable composition, characterized in that it comprises at least one oligomer according to claim 1 and optionally at least one other ethylenically unsaturated compound, in particular a (meth)acrylate-functionalized monomer.

18. 18. A method for producing a crosslinked product, characterized in that it comprises a step of crosslinking the polymerizable composition according to claim 17, in particular by exposing said composition to radiation, more particularly ultraviolet, near-ultraviolet, visible, infrared or near-infrared radiation, or an electron beam.

19. 18. A method for producing a three-dimensional object comprising an additive manufacturing step, in particular a continuous or layer-by-layer printing step, using a polymerizable composition according to claim 17.

20. 19. A crosslinked product obtained by crosslinking the polymerizable composition of claim 17 or by the method of claim 18.

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