Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
  • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/147—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
  • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
  • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
  • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
  • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a urea (meth)acrylate or urea-urethane (meth)acrylate oligomer, to polymerizable compositions comprising, and its uses, in particular as a binder in a polymerizable composition, in particular in an ink composition, a coating composition, a material filled with fibrous or particulate reinforcements which may be carbon nanotubes or graphite, an adhesive composition , molding, ink plate, electrode binder, and in a composition for additive manufacturing, in particular for printing 3D or 4D objects.
• urethane acrylates of high functionality by reacting an amine with an acrylate, then adding the aminoacrylate obtained to an isocyanate.
• WO 2007/005351 describes liquid compositions of self-photoinitiating multifunctional acrylate urethane oligomers having pendant acrylate groups and tertiary amine groups integrated into the polymer backbone, obtained by the reaction of two oligomer molecules comprising primary hydroxyl groups with the terminal isocyanate groups of a tertiary N-bis-urethane aminoacrylate oligomer.
• WO 2016/170264 describes an aminoacrylate-acrylate urethane comprising a urethane function linked to an aminoacrylate group, the latter carrying one or more acrylate groups and deriving from a) a hydroxylated aminoacrylate carrying one or more acrylate groups with b) a polyisocyanate, the aminoacrylate a) being the addition product of a1) an aminoalcohol carrying a hydroxy group and a secondary amine group on a2) a multifunctional acrylate, with a2) being in excess stoichiometric with respect to the secondary amine groups of the aminoalcohol a1).
• the urethane acrylates of the prior art are obtained from secondary amines, which involves the formation of a large quantity of tertiary amine before the addition of the isocyanate, the tertiary amine functions being moreover useful for catalyzing the desired urethanization reaction. It turns out, however, that tertiary amines are sensitive to certain chemical attacks (acids) and become colored (yellowing) during crosslinking under UV. Furthermore, the preparation of these urethane acrylates requires prolonged heating at high temperature and the use of toxic metal catalysts, such as tin-based catalysts.
• the present invention seeks to overcome the drawbacks of the urethane acrylates of the prior art by eliminating the presence of tertiary amines before the addition of isocyanate.
• the inventors have therefore modified the urethane acrylate nature of the final oligomer into urea (meth)acrylate or urea-urethane (meth)acrylate.
• the solution proposed by the inventors is based on the reaction between an isocyanate and a secondary amine to form a urea, without requiring the presence of any catalyst. More particularly, the proposed solution consists in the use of a compound comprising simultaneously at least one secondary amine function and at least one (meth)acrylate function.
• the urea (meth) acrylate or urea-urethane (meth) acrylate oligomer of the invention makes it possible to achieve the following technical advantages compared to urethane acrylates of the prior art: - the absence or the very low content of tertiary amine leading to a very good stability of the color of the oligomer after crosslinking (absence of coloring, no yellowing), - overall properties of the oligomer equivalent or superior to urethane acrylates, but without the presence of secondary products linked to the consumption of stabilizer and to the more severe thermal conditions of synthesis (higher purity of the oligomer of the invention), - resistance to abrasion improved, - better viscosity/hardness compromise than urethane acrylates, the urea function being harder and more viscous than the urethane function of urethane acrylates, - simpler, faster, safer and more economical synthesis, due to the absence prolonged heating (the reactor can simply be maintained at the desired temperature thanks to the
• the first object of the present invention therefore relates first to a specific urea (meth) acrylate or urea-urethane (meth) acrylate oligomer.
• Another object concerned is a polymerizable composition comprising at least one oligomer according to the present invention and optionally at least one other ethylenically unsaturated compound.
• a process for the manufacture of a crosslinked product comprising a step of crosslinking a polymerizable composition according to the invention is also concerned.
• a method for manufacturing a three-dimensional object comprising an additive manufacturing step using a polymerizable composition according to the invention is also concerned.
• a crosslinked product obtained by crosslinking a polymerizable composition according to the invention or obtained by a method according to the invention is concerned.
• Another object 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 printing a 3D or 4D object.
• the present invention relates to the use of a polymerizable composition according to the invention for obtaining an ink, a coating, a material loaded with fibrous or particulate reinforcements which may be nanotubes carbon or graphite, an adhesive, molding, ink plate, electrode binder composition, or a composition for additive manufacturing, in particular for printing 3D or 4D objects.
• the first object of the present invention relates to a specific urea (meth)acrylate or urea-urethane (meth)acrylate oligomer comprising: - at least two urea bonds, in particular at least two 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 term oligomer corresponds to a polymer molecule consisting of identical and/or different monomer units, preferably from 2 to 50, and more preferably from 2 to 20, identical monomer units and/or different.
• An oligomer can in particular be obtained by reaction between at least one monomer A having at least two functions f A and at least one monomer B having at least two functions f B , the functions f A being capable of reacting with the functions fB.
• Examples 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).
• a “congested urea bond” is a urea bond having at least one substituent or one ring in the ⁇ or ⁇ position with respect to the nitrogen atom to which it is bonded.
• a (meth)acryloyloxy group corresponds to a (meth)acrylate function.
• the two (meth)acryloyloxy groups of the oligomer of the invention are terminal (meth)acryloyloxy groups of said oligomer.
• a terminal group is a group at the end of the main chain of the oligomer.
• the oligomer of the invention may comprise at least two hindered urea bonds linked together by a linker group, each hindered urea bond being connected to said linker group by a nitrogen atom not carrying a hydrogen atom.
• Said hindered urea bonds linked together by a linker group can be identical or different, and are preferably identical.
• the linker group preferably does not comprise a urea bond or a urethane bond.
• the oligomer of the invention may in particular comprise at least one fragment corresponding to the following formula (I): in which: the linker group A is the residue of a polyamine, and preferably A does not comprise a urea bond, nor a urethane bond, R is different from H, and preferably R is a hindered group, z is an integer ranging from 2 to 6, and represents a point of attachment to a carbon atom.
• R is a hindered group, it is preferably a group having at least one substituent or one ring in the ⁇ or ⁇ position with respect to the nitrogen atom to which he is linked.
• a substituent can in particular be any group other than H or a cycle, for example a group chosen from optionally alkoxylated alkyl.
• a cycle can in particular be chosen from cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
• the oligomer of the invention may comprise at least two urea bonds, each urea bond being directly bonded to a group originating from an aza-Michael reaction between a primary amine and an ⁇ , ⁇ -unsaturated carbonyl compound, and in particular an aza-Michael reaction between: a) a hindered primary amine and a (meth)acrylate, or b) a primary amine and a maleate or fumarate diester.
• a “primary amine” is a compound having at least one —NH 2 primary amine function, and preferably having no secondary and/or tertiary amine function.
• a “primary hindered amine” is a primary amine having at least one substituent or one ring in the ⁇ or ⁇ position relative to the nitrogen atom of the primary amine function to which it is related.
• a “maleate or fumarate diester” is a diester derived from maleic acid or fumaric acid.
• the oligomer of the invention may comprise at least two fragments corresponding to the following formula (Ia): in which: Z is H or a group comprising an ester function -COOY, Y is an alkyl group, optionally substituted by one or more (meth)acrylate groups, and preferably Y is a linear or branched C 1 alkyl group -C 1 3, optionally substituted by one or more (meth)acrylate groups, and represent points of attachment to a carbon atom.
• Z is H or a group comprising an ester function -COOY
• Y is an alkyl group, optionally substituted by one or more (meth)acrylate groups, and preferably Y is a linear or branched C 1 alkyl group -C 1 3, optionally substituted by one or more (meth)acrylate groups, and represent points of attachment to a carbon atom.
• the oligomer of the invention may comprise: 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 hindered urea linkages.
• - Alkyl a saturated hydrocarbon-based, linear or branched aliphatic group, C 1 -C 20 , preferably C 1 -C 13 , more preferably C 1 -C 6 , and even more preferably C 1 -C 4 .
• a C 1 -C 20 alkyl means an alkyl having 1 to 20 carbon atoms.
• branched means that at least one alkyl group such as a methyl or an ethyl is carried by a linear alkyl chain.
• alkyl group mention may be made, for example, of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl and n-pentyl groups.
• - Alkyl containing at least one heteroatom an alkyl of which at least one carbon atom is replaced by a heteroatom, in particular chosen from O, N or S, preferably O.
• Cycloalkyl a non-aromatic, saturated or partially unsaturated cyclic hydrocarbon group , preferably C 3 -C 10 , which may be monocyclic, bicyclic or polycyclic.
• Heterocycloalkyl a cycloalkyl in which at least one ring atom is a heteroatom, preferably chosen from O, N or S.
• Aryl a group containing at least one aromatic ring.
• An aryl can contain a single aromatic ring or several rings of which at least one is aromatic.
• An aromatic cycle corresponds to a cycle respecting Hückel's rule. Examples of aryl groups are phenyl, biphenyl, naphthyl and anthracenyl.
• the aryl groups of the invention preferably comprise from 6 to 12 carbon atoms. Even more preferably, the aryl group of the invention is a phenyl group.
• - Heteroaryl an aryl in which at least one ring atom of the aromatic ring is a heteroatom, preferably chosen from O, N or S.
• An alkylene can be linear or branched.
• An alkylene can be divalent, trivalent, tetravalent, pentavalent or hexavalent.
• oligomer of the invention may comprise at least two fragments corresponding to one of the following formulas (Ib) or (Ic):
• the oligomer of the invention may comprise: 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 hindered urea linkages.
• the oligomer of the invention may comprise: at least two fragments (Ic) and at least two urethane bonds, or at least two fragments (Ic) and at least two other hindered urea bonds.
• the oligomer of the invention may comprise a fragment corresponding to one of the following formulas (Id) or (Ie): in which: R is different from H, and preferably R is a hindered group, Z is H or a group comprising an ester function -COOY; Y is an alkyl group, optionally substituted by one or more (meth)acrylate groups, and preferably Y is a linear or branched, C 1 -C 13 alkyl group, optionally substituted by one or more (meth)acrylate groups, P is the residue of a polyol, preferably not comprising a urea bond or a urethane bond, and more preferably P is an optionally alkoxylated or esterified alkylene, for example by at least one ester
• the oligomer of the invention may be the reaction product between at least one poly(meth)acrylate, at least one hindered primary monoamine and at least one isocyanate compound, the oligomer being of preferably obtained by a process comprising the following successive steps: (i) aza-Michael reaction between at least one poly(meth)acrylate and at least one hindered primary monoamine with a stoichiometric excess of (meth)acryloyloxy groups relative to the primary amine groups, preferably with an NH 2 /(meth )acryloyloxy less than 0.9, preferably ranging from 0.1 to 0.8, or from 0.2 to 0.7, or from 0.3 to 0.5, and (ii) reaction of the mixture of amino -(meth)acrylates obtained in step (i) with at least one isocyanate compound, preferably with an NCO/NH 2 ratio of less than 1.05, preferably ranging from 0.6 to 1.01, or from 0 .8 to 1,
• a “poly(meth)acrylate” is a compound having at least 2 (meth)acryloyloxy groups and at least one of the (meth)acryloyloxy groups is an acryloyloxy group.
• the poly(meth)acrylate of step (i) is preferably a compound having at least 2, preferably 2 to 6, and more preferably 2 to 4, (meth)acryloyloxy groups and wherein at least one of the (meth)acryloyloxy groups is an acryloyloxy group.
• a “primary monoamine” is a compound having a single primary amine function —NH 2 , and preferably having no secondary and/or tertiary amine function.
• a “hindered primary monoamine” is a primary monoamine having at least one substituent or one ring in the ⁇ or ⁇ position relative to the nitrogen atom of the primary amine function to which it is related. More particularly, in this embodiment, the hindered primary monoamine of step (i) may correspond to the following formula (II): in which: R 1 and R 2 are, independently of each other, chosen from the groups alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or alkyl containing at least one heteroatom, or R 1 and R 2 can form a C 4 -C 8 ring, preferably in C 6 , optionally comprising one or more heteroatoms, R3 is H or an alkyl group, preferably C 1 -C 4 , and more preferably -CH 3 , a is equal to 0 or 1.
• the hindered primary monoamine of step (i) corresponds to one of the following formulas (IIa), (IIb) or (IIc): in which: R'1 and R'2 are, independently of each other, alkyl groups, preferably C 1 -C 4 , and more preferably C 1 -C 2 , Cy is a C 4 -C 8 , preferably C 6 , R'3 is H or a methyl group, a is equal to 0 or 1, b and c are, independently of each other, integers ranging from 1 to 50 [0045]
• the hindered primary monoamine of step (i) is chosen from: 2-aminopentane, 3-aminopentane, 1,2-dimethylpropylamine, 1,3-dimethylbutylamine , 2-aminooctane, iso-propylamine, iso-butylamine, sec-butylamine, tert-butyl
• the isocyanate compound of step (ii) is preferably a compound having at least one -NCO group. More particularly, in this embodiment, the isocyanate compound of step (ii) may comprise: - a polyisocyanate, and optionally a (meth)acrylate functionalized with an OH or NHR' group, or - an adduct obtained by reaction between a polyisocyanate and a (meth)acrylate functionalized by an OH or NHR' group with a stoichiometric excess of NCO groups relative to the OH or NHR' groups, said adduct being formed before reaction with the compound obtained from step (i), R' being a group different from H, and in particular a hindered group.
• R' when R' is a hindered group, it is preferably a group having at least one substituent or a cycle in the ⁇ or ⁇ position with respect to the nitrogen atom to which it is attached.
• R' is a tert-butyl group.
• the polyisocyanate of step (ii) can: - either be alone, and react with a mono(meth)acrylate having a secondary amine function present in the mixture of amino-( meth)acrylates obtained in step (i), and lead to the formation of hindered urea bonds by aza-Michael reaction on the secondary amine during step (ii), - either be in a mixture or in the form of adduct with a (meth)acrylate functionalized by an OH group during step (i), and lead to the formation of urethane bonds during step (ii), - either be in a mixture or in the form of an adduct with a (meth)acrylate functionalized by an NHR' group during step (i), and lead to the formation of urea bonds hindered with an R' group during step (ii).
• the polyisocyanate of step (ii) is a diisocyanate
• the (meth)acrylate functionalized by an OH group of step (ii) is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate
• the (meth)acrylate functionalized with an NHR' group of step (ii) is 2-(tert-butylamino)ethyl methacrylate.
• the oligomer of the invention may be the reaction product between at least one mono(meth)acrylate, at least one hindered primary polyamine and at least one isocyanate compound, the oligomer being preferably obtained by a process comprising the following successive steps: (i′) aza-Michael reaction between at least one mono(meth)acrylate and at least one hindered primary polyamine to form a poly(amino-ester), in particular with a NH 2 /double bond ratio ranging from 0.7 to 1.3, preferably from 0.9 to 1.1, or from 0.95 to 1.05, (ii') optional addition of an acrylate to eliminate the residual primary amine functions, (iii') reaction of the poly(amino-ester) obtained in step (i') or (ii') with at least one isocyanate compound, and in which the isocyanate compound comprises: - a polyisocyanate and a (meth)acrylate functionalized with an OH or NHR
• a “mono(meth)acrylate” is a compound having a single acryloyloxy group, and optionally one or more methacryloyloxy groups.
• a “primary polyamine” is a compound having at least two —NH 2 primary amine functions, and preferably having no secondary and/or tertiary amine function.
• a “primary hindered polyamine” is a primary polyamine in which each primary amine function is hindered by a substituent or a ring in the ⁇ or ⁇ position relative to the nitrogen atom of the primary amine function to which it is linked. More particularly, the hindered primary polyamine of step (i′) corresponds to one of the following formulas (IIIa), (IIIb), (IIIc), (IIId), (IIIe):
• Cy is a C 4 -C 8 , preferably C 6 , ring, or Cy is -CR 4 R 5 -
• Cy' is a C 4 -C 8 , preferably C 6
• R 4 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
• a', a'', d, e and f are , independently of each other, equal to 0 or 1
• g, g', g'', h, i, j, l, m and n are, independently of each other, integers ranging from 1 to 50
• k is equal to 2 or 4
• k' is equal to 0 or 1.
• the hindered primary polyamine of step (i') is chosen from: 5-amino-1 ,3,3- trimethylcyclohexanemethylamine (isophorone diamine), 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-xylylene diamine, a non-cyclic polyether diamine based on polypropylene glycol and optionally polyethylene glycol or polytetrametylene glycol preferably having a molecular weight by weight M w ranging from 200 to 10,000 g.mol -1 (Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000
• the NH 2 /double bond ratio is preferably close to 1. It may in some cases be less than 1 to have residual acrylate in the mixture which plays the role of reactive diluent. More particularly, in this embodiment: the polyisocyanate of step (iii') is a diisocyanate, and the (meth)acrylate functionalized by an OH group of step (iii') is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, or the (meth)acrylate functionalized with an NHR' group of step (iii') is 2-(tert-butylamino)ethyl methacrylate.
• the oligomer of the invention may be the reaction product between at least one maleate or fumarate diester, at least one primary polyamine and at least one isocyanate compound, the oligomer being preferably obtained by a process comprising the following successive steps: (i'') aza-Michael reaction between at least one maleate or fumarate diester and at least one primary polyamine to form a poly(amino-ester), in particular with an NH 2 / double bond ranging from 0.7 to 1.3, preferably from 0.9 to 1.1, or from 0.95 to 1.05, (ii'') reaction of the poly(amino-ester) obtained at step (i'') with at least one isocyanate compound, and in which the isocyanate compound comprises: - a polyisocyanate and a (meth)acrylate functionalized by an OH or NHR' group, or - an adduct obtained by reaction between a polyisocyanate and a (meth)acryl
• the primary polyamine is preferably a diamine. More particularly, in this embodiment: the polyisocyanate of step (ii'') is a diisocyanate, and the (meth)acrylate functionalized by an OH group of step (ii'') is 2 - hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, or the (meth)acrylate functionalized with an NHR' group from step (ii'') is 2-(tert-butylamino)ethyl methacrylate.
• W is absent.
• W represents a branch on the oligomer, and preferably W is -U 1 -L 2 -[Acr] o .
• X is absent.
• X represents a branch on the oligomer, and preferably X is - U 2 -IU 1 - L 2 -[Acr]o.
• formula (IV) of the oligomer of the invention the (meth)acryloyloxy Acr groups are, independently of each other, represented by the following formula (V): in which: R 7 is H or a methyl group, and in particular R 7 is H, the symbol represents the point of attachment to the L 1 or L 2 group.
• each I is the residue of an aliphatic, cycloaliphatic or aromatic polyisocyanate, and even more particularly an aliphatic or cycloaliphatic diisocyanate, said cycloaliphatic diisocyanate being preferably C 6 -C 18 .
• U 1 and U 4 are, independently of each other, a urea bond represented by formula (VI ) next : where: R 8 is a crowded group, the symbol represents the point of attachment to group L 1 or L 2 , the symbol represents the point of attachment to group I, and when p > 0, U 2 and U 3 are , independently of one another, a urea bond represented by the following formula (VII): in which: R 9 is a hindered group, the symbol represents the point of attachment to group A, and the symbol represents the point of attachment to group I.
• R8 is a hindered group having at least one substituent or ring in the ⁇ or ⁇ position relative to the nitrogen atom to which it is bonded.
• R9 is a hindered group having at least one substituent or one ring in the ⁇ or ⁇ position relative to the nitrogen atom to which it is bonded.
• R 8 and R 9 are, independently of each other, a hindered group represented by formula (VIII ) next : in which: R 1 , R 2 , R 3 and a are as defined previously, the symbol ⁇ represents the point of attachment to the nitrogen atom.
• R8 and R9 are, independently of each other, a hindered group represented by one of formulas (VIIIa ), (VIIIb) or (VIIIc) as follows: in which: R′ 1 , R′ 2 , R′ 3 , Cy, a, b and c are as defined previously, the symbol ⁇ represents the point of attachment to the nitrogen atom.
• U 1 and U 4 are, independently of each other, a urethane bond represented by formula (IX ) next : the symbol ⁇ represents the point of attachment to group L 1 or L 2 , the symbol ⁇ represents the point of attachment to group I, p > 0 and U 2 and U 3 are, independently of each other, a urea bond represented by the following formula (X): in which: R 10 is different from H, and preferably R 10 is a hindered group, the symbol represents the point of attachment to group A, the symbol represents the point of attachment to group I.
• R 10 is a hindered group having at least one substituent or one ring in the ⁇ or ⁇ position with respect to the nitrogen atom to which it is bonded. More particularly, in formula (X) of the invention, R 10 is a hindered group chosen from one of the groups of formulas (VIII), (VIIIa), (VIIIb) or (VIIIc) as defined above, or a group represented by one of the following formulas (XI) or (XII):
• R 11 is selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkyl containing at least one heteroatom, polyester, or combinations thereof
• R 12 and R 13 are independently one of the other, an alkyl group, and the symbol represents the point of attachment to the nitrogen atom.
• r, L 1 , L 2 , P and o can be as defined below: r is equal to 0, L 1 and L 2 are, independently of each other, [ ⁇ ]oP- ⁇ , P is the residue d a polyol, and preferably P is an optionally alkoxylated or esterified alkylene, o is an integer ranging from 1 to 5, the symbol ⁇ represents a point of attachment to an Acr group, the symbol ⁇ represents the point of attachment to group U 1 or U 4 .
• A can be the residue of a hindered polyamine, and in particular A is chosen from one of the following groups of formulas (XIIIa), (XIIIb), (XIIIc), (XIIId) or (XIIIe):
• A can be the residue of an unhindered polyamine, and in particular A can be chosen from one of the following groups of formulas (XIVa), (XIVb), (XIVc), (XIVd), (XIVe) or (XIVf): in which: Alk is an alkylene, optionally substituted by one or more groups independently chosen from alkyl and alkenyl groups, Cy is a cycle, optionally substituted by one or more groups independently chosen from alkyl and alkenyl groups, R 14 and R 15 are, independently of each other, H or an alkyl group, k'' is an integer ranging from 1 to 50, the symbol ⁇ represents the point of attachment to U 2 or U 3 , and more particularly A is the residue of an unhindered polyamine chosen from: ethylenediamine, 1,3-diaminopropane, 1,4-d
• an alkenyl is an alkyl comprising at least one carbon-carbon double bond.
• a polyacrylate is a compound having at least 2 acryloyloxy groups.
• P and P' are, independently of each other, the residue of a polyol chosen from: 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-
• Another object of the present invention relates to a polymerizable composition
• a polymerizable composition comprising at least one oligomer as defined according to the present invention and optionally at least one other ethylenically unsaturated compound.
• an “ethylenically unsaturated compound” means a compound which comprises 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.
• a polymerizable carbon–carbon double bond is generally included in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, preferably selected from acrylate , methacrylate and vinyl, more preferably selected from acrylate and methacrylate.
• the carbon–carbon double bonds of a phenyl ring are not considered polymerizable carbon–carbon double bonds.
• the ethylenically unsaturated compound can be chosen from a monomer functionalized by (meth)acrylate, an oligomer functionalized by (meth)acrylate and corresponding mixtures.
• the ethylenically unsaturated compound comprises a monomer functionalized by (meth)acrylate.
• the total amount of ethylenically unsaturated compound in the polymerizable composition can be 0 to 90%, in particular 5 to 85%, more particularly 10 to 80%, by weight based on the weight of the composition.
• the polymerizable composition may comprise 0 to 60%, or 5 to 60% or 10 to 60% or 15 to 60% or 20 to 60% by weight of ethylenically compound unsaturated based on the weight of the composition.
• the polymerizable composition may comprise 50-80%, or 55-80% or 60-80%, by weight of ethylenically unsaturated compound based on the weight of the composition.
• (meth)acrylate-functionalized monomer means a monomer comprising at least one (meth)acryloyloxy group, in particular an acryloyloxy group.
• (meth)acrylate functionalized oligomer means an oligomer comprising a (meth)acryloyloxy group, in particular an acryloyloxy group.
• the ethylenically unsaturated compound comprises a monomer functionalized by (meth)acrylate.
• the ethylenically unsaturated compound can comprise a mixture of monomers functionalized by (meth)acrylate.
• the monomer functionalized with (meth)acrylate can have a molecular weight of less than 600 g/mol, in particular from 100 to 550 g/mol, more particularly from 200 to 500 g/mol.
• the monomer functionalized by (meth)acrylate can have 1 to 6 (meth)acryloyloxy groups, in particular 1 to 4 (meth)acryloyloxy groups.
• the monomer functionalized by (meth)acrylate can comprise a mixture of monomers functionalized by (meth)acrylate having different functionalities.
• the (meth)acrylate-functionalized monomer can comprise a mixture of a (meth)acrylate-functionalized monomer containing a single acryloyloxy or methacryloyloxy group per molecule (referred to herein as "mono(meth)acrylate-functionalized compounds") and a (meth)acrylate functionalized monomer containing 2 or more, preferably 2 or 3, acryloyloxy and/or methacryloyloxy groups per molecule.
• the (meth)acrylate functionalized monomer comprises a mono(meth)acrylate functionalized monomer.
• the monomer functionalized with mono(meth)acrylate can advantageously function as a reactive diluent and reduce the viscosity of the polymerizable composition of the invention.
• suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohol may be straight chain, branched or alicyclic).
• a monoalcohol, a dialcohol or a polyalcohol provided that only one hydroxyl group is esterified by a (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomeric and polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, a polyethylene glycol, and a 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) aliphatic alcohols (the aliphatic alcohol may be straight chain, branched or alicyclic and
• the following compounds are specific examples of 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; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; (meth)acrylate of 2– hydroxypropyl and 3–hydroxy
• the (meth)acrylate-functionalized monomer may comprise a (meth)acrylate-functionalized monomer containing two or more (meth)acryloyloxy groups per molecule.
• suitable (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy type groups per molecule include acrylate and methacrylate esters of polyols (organic compounds containing two or more hydroxyl groups per molecule , e.g. 2 to 6). Specific examples of suitable polyols are as previously defined for P and P'.
• Such polyols can be fully or partially esterified (with a (meth)acrylic acid, a (meth)acrylic anhydride, a (meth)acryloyl chloride or the like), provided that they contain at least two functional groups of type ( meth)acryloyloxy per molecule.
• Examples of (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy groups per molecule may 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-butanedio
• the polymerizable composition of the invention can comprise 0 to 90%, in particular 5 to 85%, more particularly 10 to 80%, by weight of monomer functionalized by (meth)acrylate on the basis of the weight of the composition.
• the polymerizable composition can comprise 0 to 60%, or 5 to 60% or 10 to 60% or 15 to 60% or 20 to 60% by weight of monomer functionalized by (meth)acrylate based on the weight of the composition.
• the The polymerizable composition may comprise 50 to 80%, or 55 to 80%, or 60 to 80%, by weight of (meth)acrylate functionalized monomer based on the weight of the composition.
• the ethylenically unsaturated compound comprises an oligomer functionalized by (meth)acrylate.
• the ethylenically unsaturated compound can comprise a mixture of oligomers functionalized by (meth)acrylate.
• the (meth)acrylate-functionalized oligomer can be selected to increase the flexibility, strength and/or modulus, among other attributes, of a cured polymer prepared using the polymerizable composition of the present invention.
• the oligomer functionalized by (meth)acrylate can have 1 to 18 (meth)acryloyloxy groups, in particular 2 to 6 (meth)acryloyloxy groups, more particularly 2 to 6 acryloyloxy groups.
• the (meth)acrylate-functionalized oligomer may have a number-average molecular weight greater than or equal to 600 g/mol, in particular 800 to 15,000 g/mol, more particularly 1,000 to 5,000 g/mol.
• the oligomers functionalized by (meth)acrylate can be chosen from the group consisting of urethane oligomers functionalized by (meth)acrylate (sometimes also called “oligomers of (meth)acrylate of urethane” “oligomers polyurethane (meth)acrylate” or “carbamate (meth)acrylate oligomers”), (meth)acrylate functionalized epoxy oligomers (sometimes also referred to as "epoxy (meth)acrylate oligomers”), (meth)acrylate functionalized polyether oligomers (sometimes also referred to as "polyether (meth)acrylate oligomers”), (meth)acrylate functionalized polydiene oligomers (sometimes also referred to as "polydiene (
• Exemplary polyester (meth)acrylate oligomers include reaction products of acrylic or methacrylic acid or mixtures or synthetic equivalents thereof with hydroxyl-terminated polyester polyols.
• the reaction process can be conducted such that all, or substantially all, of the hydroxyl groups of the polyester polyol have been (meth)acrylated, particularly in cases where the polyester polyol is difunctional.
• Polyester polyols can be prepared by polycondensation reactions of polyhydroxyl functionalized components (particularly diols) and poly(carboxylic acid) functionalized compounds (particularly dicarboxylic acids and anhydrides).
• the polyhydroxyl functionalized and poly(carboxylic acid) functionalized components can each have linear, branched, cycloaliphatic or aromatic structures and can be used individually or as mixtures.
• suitable epoxy (meth)acrylates include reaction products of acrylic or methacrylic acid or mixtures thereof with an epoxy resin (ether or polyglycidyl ester).
• the epoxy resin may, in particular, be chosen from 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 novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol diglycidyl ether hydrogenated S, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis (3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(
• Suitable polyether (meth)acrylate oligomers include, but are not limited to, condensation reaction products of acrylic or methacrylic acid or mixtures or synthetic equivalents thereof with polyetherols which are polyether polyols (such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol).
• polyetherols can be linear or branched substances containing ether linkages and terminal hydroxyl groups.
• Polyetherols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (eg, ethylene oxide and/or propylene oxide) with a starting molecule.
• Suitable starting molecules include water, polyhydroxy functionalized materials, polyester polyols and amines.
• Polyurethane (meth)acrylate oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers") suitable for use in the polymerizable compositions of the present invention include polyester polyol and polyether based urethanes aliphatic, cycloaliphatic and/or aromatic polyols and diisocyanates of aliphatic, cycloaliphatic and/or aromatic polyesters and polyether diisocyanates capped with (meth)acrylate end groups.
• Suitable polyurethane (meth)acrylate oligomers include, for example, aliphatic polyester-based urethane diacrylate and tetraacrylate oligomers, aliphatic polyether-based urethane diacrylate and tetraacrylate oligomers, as well as oligomers of aliphatic polyester/polyether based urethane diacrylate and tetraacrylate.
• Polyurethane (meth)acrylate oligomers can be prepared by reacting aliphatic, cycloaliphatic or aromatic polyisocyanates (e.g.
• diisocyanate, triisocyanate with polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyorganosiloxane polyols (e.g. polydimethylsiloxane polyols), or polydiene polyols (e.g. polybutadiene polyols), OH-terminated, or combinations thereof, to form isocyanate functionalized oligomers which are then react with hydroxyl functionalized (meth)acrylates such as hydroxyethyl acrylate or hydroxyethyl methacrylate to provide terminal (meth)acrylate groups.
• hydroxyl functionalized (meth)acrylates such as hydroxyethyl acrylate or hydroxyethyl methacrylate to provide terminal (meth)acrylate groups.
• polyurethane (meth)acrylate oligomers can contain two, three, four or more (meth)acrylate functional groups per molecule.
• Other orders of addition can also be practiced to prepare the polyurethane (meth)acrylate, as is known in the state of the art.
• hydroxyl-functionalized (meth)acrylate can be first reacted with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which can then be reacted with a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polydimethylsiloxane polyol or a polybutadiene polyol, terminated with an OH group, or a combination thereof.
• a polyisocyanate may first be reacted with a polyol, including any of the previously mentioned types of polyols, to obtain an isocyanate-functionalized polyol, which is then reacted with a hydroxyl-functionalized (meth)acrylate to give a polyurethane (meth)acrylate.
• a polyol including any of the previously mentioned types of polyols
• an isocyanate-functionalized polyol which is then reacted with a hydroxyl-functionalized (meth)acrylate to give a polyurethane (meth)acrylate.
• all of the components can be combined and reacted at the same time.
• Suitable acrylic (meth)acrylate oligomers include oligomers which can be described as substances having an oligomeric acrylic backbone which is functionalized with one or more (meth)acrylate groups (which may be at a terminal of the oligomer or pendent to the acrylic backbone).
• the acrylic backbone can be a homopolymer, a random copolymer or a block copolymer composed of repeating units of acrylic type monomers.
• the acrylic-type monomers can be any monomeric (meth)acrylate such as C 1 -C 6 alkyl (meth)acrylates as well as functionalized (meth)acrylates such as (meth)acrylates bearing hydroxyl groups, carboxylic acid and/or epoxy.
• the acrylic (meth)acrylate oligomers can be prepared using any procedure known in the state of the art, such as the oligomerization of monomers, at least a part of which being functionalized by hydroxyl groups, carboxylic acid and/or epoxy (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, which is then reacted with one or more reactants containing a (meth)acrylate to introduce the desired (meth)acrylate functional groups.
• any procedure known in the state of the art such as the oligomerization of monomers, at least a part of which being functionalized by hydroxyl groups, carboxylic acid and/or epoxy (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, which is then reacted with one
• the polymerizable composition of the invention can comprise 0 to 90%, in particular 5 to 85%, more particularly 10 to 80%, by weight of oligomer functionalized by (meth)acrylate on the basis of the weight of the composition .
• the polymerizable composition can comprise 0 to 60%, or 5 to 60%, or 10 to 60%, or 15 to 60%, or 20 to 60%, by weight of oligomer functionalized by (meth)acrylate on the based on the weight of the composition.
• the polymerizable composition may comprise 50 to 80%, or 55 to 80%, or 60 to 80%, by weight of (meth)acrylate functionalized oligomer based on the weight of the composition.
• the polymerizable composition of the invention can also advantageously comprise a radical or ionic polymerization initiator, and more particularly a photoinitiator or a peroxide.
• the photoinitiator may be a radical photoinitiator, in particular a radical photoinitiator having Norrish I type activity and/or Norrish II type activity, more particularly a radical photoinitiator having Norrish I type activity.
• Non-limiting types of radical photoinitiators suitable for use in the polymerizable compositions of the present invention include, for example, benzoins, benzoin ethers, acetophenones, ⁇ -hydroxyacetophenones, benzil, benzil ketals , anthraquinones, phosphine oxides, acylphosphine oxides, ⁇ -hydroxyketones, phenylglyoxylates, ⁇ -aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline compounds, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, compounds of the acylsilyl or acylgermanyl type, camphorquinones, corresponding polymeric derivatives, and corresponding mixtures.
• 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, benzoins, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, l 'alpha-phenylbenzoin, Michler's ketone, acetophenones such as 2,2-dialkoxybenzophenones and 1-hydroxyphenylketones, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2 -diethyloxyacetophenone, diethyloxyacetophen
• the photoinitiator can be a benzophenone (such as SpeedCure® BP, SpeedCure® 7005, SpeedCure® 7006), a thioxanthone (such as SpeedCure® 7010, SpeedCure® ITX), an ⁇ -hydroxyacetophenone (such as SpeedCure® ® 73), an acylphosphine oxide (such as SpeedCure ® BPO, SpeedCure ® TPO, SpeedCure ® TPO-L).
• the photoinitiator is an ⁇ -hydroxyacetophenone or an acylphosphine oxide.
• the polymerizable composition of the invention may in particular comprise 0 to 20%, in particular 0.1 to 15%, more particularly 1 to 10% by weight of photoinitiator relative to the weight of the composition.
• the polymerizable composition of the invention may comprise other additives chosen from: antioxidants, photostabilizers, light absorbers, polymerization inhibitors, antifoaming agents, antistatic agents, leveling agents, dispersants (wetting agents, surfactants ), slip agents, adhesion promoters, lubricants, pigments, colorants, fillers, chain transfer agents, rheological agents (thixotropic, thickener), matting agents, opacifying agents, impact resistance agents, waxes.
• the polymerizable composition of the invention is a composition of ink, coating (in particular protective coating, electrical insulation coating, decorative coating or coating reactive to external stimuli), material loaded with fibrous or particulate reinforcements which may be carbon nanotubes or graphite (in particular putty, chemical anchor, artificial stone, dental filling or composite), an adhesive composition, molding, ink plate, of binder for an electrode, or a composition for additive manufacturing, in particular for printing 3D or 4D objects.
• an inking plate is a flexible photopolymer plate intended for transferring ink to the support to be printed in rotary letterpress printing or in flexography.
• Additive manufacturing also called 3D printing, consists of creating, from a digital model containing the properties related to the geometry of the object to be produced (mesh of points or surfaces) and possibly the parameters of the materials to use, a (volumetric / three-dimensional) object point by point (called voxels by analogy with the pixels of conventional two-dimensional printing), or by selectively modifying the properties of a loose medium at these points, for example by solidification (polymerization) from a tank of liquid resin, by agglomeration/sintering/fusion-resolidification from a bed of powder, or to be deposited selectively at different points on a surface (also called layer and generally flat) the material continuously (by extrusion) or discontinuously (inkjet), and this, surface after surface.
• a digital model containing the properties related to the geometry of the object to be produced (mesh of points or surfaces) and possibly the parameters of the materials to use, a (volumetric / three-dimensional) object point by point (called voxels by analogy with the
• the surfaces can add up one under the other or on top of the other, as well as from the center outwards, generally from a printing medium, the unmodified material possibly being itself -same medium.
• the general principles of 3D printing are defined in the ISO/ASTM 52900:2015 standard.
• Printing a 4D object can be defined as printing a 3D object that is capable of transforming over time.
• 4D printing is the process by which a 3D printed object can itself modify its structure and change its shape under the influence of external energy such as temperature, light or other environmental stimuli.
• Another object of the present invention relates to a process for the manufacture of a crosslinked product comprising a step of crosslinking a polymerizable composition as defined according to the present invention, in particular by exposing said composition to radiation, and more particularly to UV, near-UV, visible, infrared or near-infrared rays, or to an electron beam.
• the method of the invention is aimed at the manufacture of a crosslinked product chosen from an ink, a coating (in particular a protective coating, an electrical insulation coating, a decorative coating or a coating reactive to stimuli materials), a material filled with fibrous or particulate reinforcements which may be carbon nanotubes or graphite (in particular a putty, a chemical plug, an artificial stone, a dental filling or a composite), an adhesive, a molded material, a ink plate, an electrode binder, or an object obtained by additive manufacturing, in particular an object obtained by 3D or 4D printing.
• Another object of the present invention relates to a process for the manufacture of a three-dimensional object, comprising a step of additive manufacturing using a polymerizable composition as defined according to the present invention, and in particular a step of printing in continuous or layer by layer.
• a crosslinked product obtained by crosslinking a polymerizable composition as defined according to the present invention or obtained by a process as defined according to the present invention also forms part of the invention.
• the crosslinked product of the invention is advantageously an ink, a coating (in particular a protective coating, an electrical insulation coating, a decorative coating or a coating reactive to external stimuli), a material filled with fibrous reinforcements or particles which may be carbon nanotubes or graphite (including but not limited to putty, chemical anchor, artificial stone, dental filling or composite), adhesive, molded material, ink pad, electrode binder, or an object obtained by additive manufacturing, in particular an object obtained by 3D or 4D printing.
• a coating in particular a protective coating, an electrical insulation coating, a decorative coating or a coating reactive to external stimuli
• a material filled with fibrous reinforcements or particles which may be carbon nanotubes or graphite (including but not limited to putty, chemical anchor, artificial stone, dental filling or composite)
• adhesive molded material
• ink pad ink pad
• electrode binder or an object obtained by additive manufacturing, in particular an object obtained by 3D or 4D printing.
• One of the last objects of the invention relates to the use of a polymerizable composition as defined according to the present invention for obtaining an ink, a coating (in particular a protective coating, 'an electrical insulation coating, a decorative coating or a coating reactive to external stimuli), a material filled with fibrous or particulate reinforcements which may be carbon nanotubes or graphite (in particular a mastic , a chemical anchor, an artificial stone, a dental filling or a composite), an adhesive, a molded material, an ink plate, an electrode binder, or of an object obtained by additive manufacturing, in particular an object obtained by 3D or 4D printing.
• a coating in particular a protective coating, 'an electrical insulation coating, a decorative coating or a coating reactive to external stimuli
• a material filled with fibrous or particulate reinforcements which may be carbon nanotubes or graphite (in particular a mastic , a chemical anchor, an artificial stone, a dental filling or a composite)
• an adhesive
• the invention also relates to the use of an oligomer as defined according to the present invention as a binder in a polymerizable composition.
• the last object of the invention relates to the use of an oligomer as defined according to the present invention in a composition for additive manufacturing, in particular for printing a 3D or 4D object.
• the invention further comprises other provisions which will emerge from the additional description which follows, which relates to examples of synthesis of oligomers according to the invention, and to the evaluation of the application properties of compositions comprising them.
• Noury dynamic viscosity corresponds to the travel time, in the liquid to be characterized, of a steel ball subjected to its gravity, according to the AFNOR XP T51-213 standard which specifies in particular the geometry of the container, the diameter of the ball (2 mm), and the path of the ball (104 mm). Under these conditions, the dynamic viscosity is proportional to the travel time of the ball, with a travel time of 1 second corresponding to a viscosity of 0.1 Pa.s.
• Reactivity The composition was applied with a filmograph to a thickness of 12 ⁇ m on a contrast card (Penoparc charts form 1B ® Leneta), then photopolymerized by exposure to a FUSION mercury vapor lamp (Heraeus) d power of 120 W. The measurement gives the necessary number of passages under the lamp at the minimum running speed (5 m/min), to obtain a film that is dry to the touch.
• Persoz hardness according to standard NF EN ISO 1522. The Persoz hardness was measured after application with a filmograph of a composition with a thickness of 100 ⁇ m on a glass plate, then photo- polymerized by exposure to a FUSION mercury vapor lamp (Heraeus) with a power of 120 W.
• the exposure time was controlled by the speed of a conveyor which takes the substrate under the lamp at a speed of 8 m /min multiplied by the number of passes.
• the measurement indicates the time (in seconds) before the damping of the oscillations (passage from 12o to 4o of amplitude) of a pendulum in contact with the glass plate coated with the composition, after 24 hours of rest in an air-conditioned room at 23oC and 50% relative humidity.
• Pencil hardness The composition was applied in a 100 ⁇ m film on a glass plate, then photopolymerized by exposure to a FUSION mercury vapor lamp (Heraeus) with a power of 120 W. This test makes it possible to evaluate the resistance of the coating to surface scratches.
• Pencils of decreasing hardness were moved over the tested film, according to the ASTM D3363:1992 standard, after 24 hours of rest in an air-conditioned room at 23oC and 50% humidity. relative. The first grade of pencil hardness not to damage the surface determines the hardness of the film.
• Flexibility The composition is applied in a 100 ⁇ m film on a smooth steel plate 25/10 mm thick (D-46 ® Q-Panel), then light-cured by exposure to a vapor lamp of mercury FUSION (Heraeus) with a power of 120 W at a speed of 8 m/min. The coated plate is bent on cylindrical mandrels according to ISO 1519.
• the composition is applied in a 12 ⁇ m film on a glass plate, then photopolymerized by exposure to a FUSION mercury vapor lamp (Heraeus) with a power of 120 W at a speed of 8 m/min.
• the coating is then rubbed with a 500 g weight fitted with a cotton wick soaked in acetone, going back and forth over the coating to be tested.
• the result is the time (expressed in seconds) beyond from which the film detaches and/or disintegrates from the support, measured using a Taber® 5750 linear abraser.
• Shore hardness The Shore hardness was measured on a printed object according to the printable object file of Figure 1 according to the ISO 868:2003 standard, using a type A Shore durometer. The measurements were taken after 5 seconds of contact between the measuring tip and the sample.
• the measurements of the storage (G') and loss (G") modules were carried out on a Rheometric Scientific RDA III device controlled by the RSI Orchestrator software, with a temperature rise from -40oC to 180oC, at a speed of 3oC /min, by applying a rectangular torsion stress to a sample printed according to the printable object file of Figure 2 of dimension 80*10*4 mm (useful length between jaws adjustable between 1.5 and 4 cm, this value being taken into account in the calculation of the moduli by the software) with a typical deformation rate of 0.05% and a stress frequency of 1 Hz.
• the samples have previously undergone conditioning for at least 24 hours at a temperature of 23oC +/- 2oC and 50% +/- 10% relative humidity Storage modulus values have been reported at different temperatures including 25oC and 150oC
• the G''/G' ratio is called the loss factor or tangent delta (tan delta)
• the Tg corresponds to the temperature for which the value of this tangent is maximum (T ⁇ ).
• the basicity of the sample was assayed with a solution of perchloric acid in acetic acid with a normal N titer (in Eq/l) of 0.1 N.
• the equivalent point was detected by a glass electrode (filled with a 1 mol/L solution of lithium perchlorate in acetic acid) controlling an automatic burette (“716 DMS Titrino” automatic titrator, Metrohm brand) delivering the equivalent volume VE expressed in mL.
• Products and raw materials are as follows: - CN981: aliphatic urethane diacrylate oligomer having a weight-average molecular mass of 2200 g/mol (Arkema), - IPGA: 2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylate monomer obtained by trans-esterification reaction between isopropylidene glycerol (Augeo SL 191) (Solvay) and methyl acrylate (Arkema), with a acrylate/alcohol molar ratio of 2 to 3, catalyzed with zirconium acetylacetonate (Zr(AcAc) 4 ) (Sachem), - SR238: 1,6-hexanediol diacrylate (HDDA) monomer having a molecular weight of 226 g/mol (Arkema), - SR355: di-tri-trimethyl diacrylate (
• Example 1 Preparation of a urea (meth)acrylate oligomer according to the invention HDDA SR238 (75.00 g) and EMHQ (0.120 g) were introduced at 23° C. into a reactor equipped with a reflux column, two funnels, a thermometer, and a stirrer with inclined blades.
• sec-butylamine (19.64 g) was introduced through a dropping funnel over a period of 5 minutes.
• the reactor was heated to 80°C for 30 minutes and then maintained at this temperature for 2 hours.
• the reactor was then cooled to 40°C.
• Proton NMR analysis showed total consumption of sec-butylamine and absence of tertiary amine.
• IPDI (28.00 g) was added through the second dropping funnel over a 1 hour period. During the introduction, the temperature was maintained at a temperature below 50oC by controlling the exotherm with an ice water bath. The temperature was maintained at 50°C for 15 minutes.
• Examples 2 to 8 Preparation of urea (meth)acrylate oligomers according to the invention The same protocol as in example 1 was repeated by modifying the proportion and the nature of the acrylate, the amine and isocyanate as shown in Table 2 below.
• Example 9 Preparation of an aminoacrylate-acrylate urethane oligomer according to WO 2016/170264 (comparative example) HDDA SR238 (75.00 g), EMHQ (0.100 g), BHT (0.050 g ), triphenylphosphite (0.100 g) and PTZ (0.020 g) were introduced at 23oC into a reactor equipped with a reflux column, two dropping funnels, a thermometer and a stirrer with inclined blades . NMEA (17.80 g) was introduced through a dropping funnel over a period of 30 minutes. The reactor was heated to 50°C in 30 minutes and then maintained at this temperature for 2 hours.
• Example 10 Preparation of a urea (meth)acrylate oligomer according to the invention HDDA SR238 (75.00 g) and EMHQ (0.120 g) were introduced at 23° C. into a reactor equipped with a reflux column, two funnels, a thermometer, and a stirrer with inclined blades. Sec-butylamine (17.33 g) was introduced through a dropping funnel over a period of 5 minutes. The reactor was heated to 55°C for 10 minutes, then to 75°C and maintained at this temperature for 1 hour. The reactor was then cooled to 40°C.
• IPDI (21.95 g) was added through the second dropping funnel over a 1 hour period. During the introduction, the temperature was maintained at a temperature below 50oC by controlling the exotherm with an ice water bath. The temperature was maintained at 50°C for 15 minutes.
• Examples 11 to 13 Preparation of urea (meth)acrylate oligomers according to the invention The same protocol as in example 10 was repeated by modifying the proportion and the nature of the amine and of the isocyanate as shown in Table 3 below. [0154] [Table 3] The molar quantity of isocyanate functions introduced was constant in all the examples of Table 3, so that the latter are strictly comparable.
• Example 11 shows that mechanical properties equivalent to those of the reference can be obtained without the presence of a cycle.
• the comparison between Examples 9 and 11 is proof that the urea function present in the oligomer of the invention is preferable to a urethane function, at an equivalent concentration.
• the invention offers the possibility of synthesizing oligomers having isocyanate/amine R2 ratios close to 1, which is not possible for the reference.
• examples 12 and 13 show that the compromise between viscosity and Persoz hardness is very clearly to the advantage of the oligomers of the invention.
• Example 14 Preparation of an intermediate with secondary diamine 2(2-ethoxyethoxy)-ethyl acrylate SR256 (60.00 g) and EMHQ (0.100 g) were introduced at 23° C. into a reactor equipped with a reflux column, two funnels, a thermometer and a stirrer with inclined blades. 4,4'-methylenebis(cyclohexylamine) (33.51 g) was introduced through a dropping funnel over a period of 5 minutes. The reactor was heated at 90°C for 3 hours. The reactor was then cooled to 65° C., 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 ambient temperature.
• Example 15 Preparation of an HDI-pentaerythritol triacrylate adduct intermediate HDI (29.66 g), BHT (0.050 g) and EMHQ (0.050 g) were introduced at 23° C. into a reactor equipped with a reflux column, a dropping funnel, a thermometer and a stirrer with inclined blades. Pentaerythritol triacrylate SR444D (91.69 g) was added through the dropping funnel over 20 minutes. The reactor was heated to 80°C until an isocyanate index of 82 mgKOH/g was obtained. After cooling to room temperature, the intermediate is kept for 30 minutes (it is never kept for more than 24 hours).
• Example 16 Preparation of a urea-urethane (meth)acrylate oligomer according to the invention 50.00 g of the intermediate with secondary diamine prepared in Example 14 and BHT (0.100 g) were introduced at 23oC in a reactor equipped with a reflux column, a dropping funnel, a thermometer and a stirrer with inclined blades. The reactor was heated to 50°C until complete solubilization of the BHT. 96.54 g of the HDI-pentaerythritol triacrylate adduct intermediate prepared in Example 15 were introduced through the dropping funnel over 30 minutes.
• Example 17 Preparation of a urea-urethane (meth)acrylate oligomer according to the invention Under dry nitrogen bubbling at a flow rate of 20 mL/minute, DEM (28.21 g) was introduced at 23oC into a reactor equipped with a reflux column, two funnels, a thermometer and a stirrer with inclined blades.
• Example 18 Preparation and Evaluation of Polymerizable Compositions Based on Urea (meth)acrylate Oligomers According to the Invention Compositions were prepared from the urea (meth)acrylate oligomers of Examples 1, 2 and 3 of invention. The oligomers were preheated to 65°C, then, with manual stirring, a photoinitiator was introduced and dissolved. The mixtures were then left to come to room temperature (25°C). The compositions appear in Table 5 below (the amounts are indicated in grams).

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• 2021
  • 2021-12-31 FR FR2114723A patent/FR3131587A1/fr active Pending
• 2022
  • 2022-12-15 KR KR1020247025435A patent/KR20240123392A/ko active Pending
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