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    • 专利摘要:
    crosslinkable composition, kit, method for preparing a crosslinkable composition, coating compositions, and composite articles. The present invention relates to a crosslinkable composition, crosslinkable by real michael addition reaction (rma), comprising a component with at least 2 activated unsaturated groups (hereinafter referred to as rma acceptor groups) and a component with, at least 2 ch acid protons on activated methylene or methine groups (hereinafter referred to as the rma donor groups) whose components can react to form a cross-linked network. the composition comprises: f. component(s) a having at least 2 c-h acid donor groups on activated methylene or methine and having a pka(a) between 10, 5 and 14; g. component(s) b, having at least 2 activated unsaturated acceptor groups, where the molar ratio r of acceptor groups to donor groups is between 3:1 to 1:6, and which component(s) b react with component( s) by adding real michael to form a reticulated network; H. basic component(s) and being a salt of a basic anion x- from an acidic group x-h containing compound wherein x is n, p, o, s or c; iv. in an amount xc between 0.001 and 1 meq/(g of components a, b, c, d); v. anion x- being a michael addition donor that can react with component b; and saw. anion x is characterized by a pka(c) of the corresponding acid x-h of more than two units less than the pka(a) of the major component a and being less than 10.5; i. optional component(s) d comprising one or more acidic groups x'-h wherein x' is n, p, o, s or c; v. x' being a group the same as or different from group x in component c; saw. the anion x? - being a michael addition donor that can react with component b; vii. the pka(d) of the x'-h group in the d component being more than two units less than the pka(a) of the major component a and being less than 10.5; viii. the equivalent ratio rd/c of acidic x?-h groups in the d component to the basic x anion in the c component is between 1% and 5000%.
    公开号:BR112015025624B1
    申请号:R112015025624-4
    申请日:2014-04-07
    公开日:2021-09-08
    发明作者:Richard Hendrikus Gerrit Brinkhuis；Ferry Ludovicus Thys；Elwin Aloysius Cornelius Adrianus De Wolf
    申请人:Allnex Netherlands B.V；
    IPC主号:
    专利说明:

    [001] The present invention relates to a crosslinkable composition, crosslinkable by Michael Real Addition reaction (RMA), comprising a component with at least 2 activated unsaturated groups (hereinafter referred to as RMA acceptor groups) and a component with at least 2 CH acidic protons in the activated methylene or methine groups (hereinafter, referred to as the RMA donor groups) which components can react to form a crosslinked network.
    [002] The RMA chemistry can be adjusted to give fast curing compositions, also at lower curing temperatures, in compositions with acceptable or good mix lifespans, to achieve good material properties, which makes this chemistry very attractive as a basis for crosslinkable compositions. Details of crosslinkable RMA compositions using a latent base crosslinkable catalyst are described in WO2011/124663.
    [003] Addition of Michael Real is activated by strong bases, but also inhibited by the presence of acidic species that will consume these base catalysts. In line with the reactivity of coating systems, in order to achieve a desirable drying profile, there are several requirements to balance. The drying profile (also referred to as the reaction profile or cure profile) is the crosslinkable reaction progress as a function of time. It is generally necessary for the drying profile to allow mechanical properties to build up as quickly as possible under mild conditions in order to aid productivity. The crosslinkable composition also requires a reasonable period of time, in which it can be used with good application properties, after its formulation, in order to be practical; this time is generally referred to as the pot life. It is further also required to have a drying profile that is robust, i.e. the reactivity (and therefore the resulting drying profile) is not strongly influenced by the presence of accidental low levels of acidic contaminants.
    [004] On the other hand, for coating applications, it is necessary to have a good appearance of the resulting coating. This implies the need for sufficient leveling during the period immediately after application when the curing coating composition is present as a liquid and is capable of such leveling. This also implies the need for the absence of artifacts such as solvent inclusions or gas inclusions or other surface irregularities that can occur if the cure is too fast, especially if it is faster on the surface than deeper layers, which this is often the case if curing occurs on the time scale of solvent evaporation or surface activation of a catalyst. Also, film hardness build-up will be affected under conditions where solvent entrapment occurs.
    [005] The requirements described are somewhat mutually opposed. For a fast cure profile, but also for high robustness against accidental acid contaminants, reasonably high catalyst levels are preferred, while at the same time such high levels of catalysts can create a very fast cure, and negatively influence appearance surface and hardness development as described above. In general, higher catalyst levels can also negatively affect mix life.
    [006] It has been shown in previous publications, WO2011/124663, WO2011/124664 and WO2011/124665, that it is possible to combine fast cure with a long pot life, using carbon dioxide blocked basic catalyst, which becomes active after evaporation of carbon dioxide (CO2) when the composition is applied as a thin film. While this method is usable in creating long mix life/fast cure combinations, it introduces complications in the case of thick film applications where there is a risk of inhomogeneous activation resulting from CO2 escaping from the surface. In addition, applications where there is not a large surface area available to allow CO2 evaporation, such as catalysts locked with CO2, have significant limitations.
    [007] There is also a desire for crosslinkable compositions that can simply be cured under ambient conditions, as opposed to, for example, compositions comprising photolatent amine catalysts known from T. Jung et al Farbe und Lacke Oct 2003. Photo-latent amines, which do not generate a strong base in UV radiation, are not suitable for coating more complex irregular substrates where parts of the surfaces are not reachable with UV or visible light, or for highly pigmented systems.
    [008] The aim of the invention is to provide a crosslinkable RMA composition that provides a better balance between these contradictory requirements.
    [009] According to the invention, at least one of the problems mentioned above was overcome by a crosslinkable composition, crosslinkable by Michael Real Addition reaction (RMA), comprising it. component(s) A having at least 2 activated C-H acid donor groups in methylene or methine and with a pKa(A) between 10.5 and 14.b. component(s) B, having at least 2 activated unsaturated acceptor groups, wherein a molar ratio R of acceptor groups to donor groups is between 3:1 to 1:6, and which component(s) B react(s) with component(s) A by Real Michael Addition (RMA) to form a lattice, c. basic component(s) C being a salt of a basic anion X- from an acidic group X-H containing compound wherein X is N, P, O, S or C,i. in an amount xc between 0.001 and 1 meq/(g of components A, B, C, D),ii. anion X- being a Michael Addition donor that can react with component B eiii. anion X- is distinguished by a pKa(C) of the corresponding acid X-H of more than two units smaller than the pKa(A) of the major component A and being less than 10.5,d. optional component(s) D comprising one or more acidic X'-H groups where X' is N, P, O, S or C,i. X' being the same or different group as the X group in component C,ii. the anion X’- being a Michael Addition donor that can react with component B,iii. the pKa(D) of the X'-H group in the D component being greater than two units less than the pKa(A) of the majority A component and being less than 10.5, iv. the Rd/c equivalent ratio of acidic X’-H groups in component D over the basic anion X- in component C is between 1% and 5000%,e. not including a composition comprising an ethylmalonate-modified polyester based on neopentyl glycol and hexahydrophthalic anhydride, di-trimethiolpropane-tetraacrylate and tetrabutylammonium succinimide and ethylacetoacetate.
    [0010] It has been found that it is possible to initiate an effective crosslinking reaction between donor and acceptor components RMA A and B using the specified component C being a salt of a cation and a basic anion X- from a compound containing acidic XH group (deprotonated) where X is N, P, O, S or C and where the X- anion is also a Michael Addition donor that can react with component B and with specific requirements for the pKa(C) of the corresponding XH . The specified X-anion of component C starts the RMA reaction and the X-anion will be covalently bonded to the A component and becomes integrated with the crosslinked network being formed, which is advantageous in view of the mechanical and chemical properties of the resulting crosslinked product . The term compound containing acidic XH group wherein X is N, P, O, S or C means a compound comprising an acidic XH group wherein the acidic proton H is situated on an atom of N, P, O, S or C, in this compound. Although the X herein refers to an atom in the compound, where in the description or claims reference is made to the XH group, the X- anion, the X- group, etc., it is evidently meant to refer to the compound containing the acidic XH or the group X- deprotonated. This applies similarly to X' and X".
    [0011] Whether or not a component is a Michael Addition donor that can react with component B depends on pKa values, as specified, but also on certain molecular parameters. Michael Addition donors are known in the literature and can be easily established by one skilled in the art by a simple experiment, whether or not a component exhibits Michael Addition reactivity to component B. This experiment is also described below. Appropriate X-H group containing components with their pKa values are also described below. Each component A, C, D, and F in the composition is identified by a characteristic range of PKA. The pKa values of both existing compounds are reported in the literature and/or can be easily established by standard routine by the person skilled in the art. In this context, where a component comprises more than one acidic proton, the relevant pKa of said component is the pKa of the first proton of the component; for example, pKa(A) of malonate is 13. In addition, when referring to the pKa of a component, it is implied that reference is made to the pKa of the acidic RMA X-H donor group in this component. Note that the term component(s) means one or more components, which also includes two or more different components.
    [0012] The composition according to the invention provides a well-balanced set of application properties such as application time, drying time, hardness development without solvent entrapment complications and appearance. Starting the RMA reaction does not require a separate base catalyst. In particular, the RMA reaction for the composition of the invention does not require a carbon dioxide blocked base catalyst and therefore has advantages in applications such as composites, adhesives, etc. where carbon dioxide evaporation is problematic or impossible. Furthermore, the composition can be significantly less expensive compared to compositions having a latent base catalyst. One aspect of this lower price is the wider choice of cations that can be used in the C-component of salt, including less expensive cations such as alkali or alkaline earth metal cations, due to better salt solubility of most anions X- compared to a carbonate anion. Yet another advantage of the present invention is that component C is less sensitive to inhibition of the RMA reaction by a polymer containing hydroxyl groups. Therefore, the C salt component can be used in combination with one or more A, B, D and/or F containing hydroxyl functional polymers having a hydroxyl value greater than 61 mg KOH/g and up to 200, 180, 150, 120 100 or 80 mg KOH/g while still having good appearance and hardening properties.
    [0013] In addition to the above composition, one can have a composition comprising a polyester modified with ethylmalonate based on neopentyl glycol and hexahydrophthalic anhydride, di-trimethiolpropane-tetraacrylate, tetrabutylammonium succinimide and ethylacetoacetate. Alternatively, the above composition does not include tetrabutylammonium succinimide as component C in combination with ethylacetoacetate. Alternatively, the composition does not comprise tetrabutylammonium succinimide as component C.
    In a preferred embodiment, the crosslinkable composition comprises component(s) D comprising one or more acidic X'-H groups wherein X' is N, P, O, S or C,i. X' being a group equal to or different from group X in component C,ii. the anion X’- being a Michael Addition donor that can react with component B,iii. the pKa(D) of the group X'-H in component D being greater than two units smaller than the pKa(A) of the majority component A and being less than 10.5, iv. the Rd/C equivalent ratio of acidic X’-H groups in component D over the basic X- anion in component C is between 1 and 5000%.
    [0015] It has surprisingly been found that the presence of component D in the inventive composition creates a drying profile with an induction time, implying that the crosslinking reactivity starts low (allowing for mix life, flow and optional solvent leakage), while still benefiting from the full potential of the C initiator component beyond this induction period, thus creating an acceleration of the reaction in the later stages to complete crosslinking at a high rate. This induction time can be tuned through the quantities and characteristics of components C and D, as will be explained in more detail below.
    [0016] Component D is optional, so the quantity range is between 0% and 5000%. Preferably component D is present and the Rd/c equivalent ratio of acidic X'-H groups in component D over basic anion X-in component C is between 10 and 4000%, more preferably between 20 and 2000%, more preferably between 50 and 500%, 400% or 300% or between 75 and 200%.
    [0017] Without wishing to be bound by theory, it is believed that the reaction mechanism, in essence, is that anion X- in component C reacts with B forming the deprotonated XB- carbanion adduct, which, in turn, deprotonates groups X'-H in component D (the next strong acid available) to form an X'- anion which, in turn, reacts with B to form an X'-B- adduct until the amount of D is depleted and only then does the Strong base X'-B- adduct will react with A (which reacts after D because it is less acidic and has a higher pKa). The last chain reaction reaction is the reaction causing the components A in B to cross-link to form a network. However, the time consuming reaction is the reaction between X- and X'- anion with B to form XB- and X'-B- adduct because the reactivity of X- and X'- anion to B is low, which creates induction time.
    [0018] Yet another advantage of the present invention compared to the prior art CO2-blocked latent base catalyst is that the lower limit of the pKa of the components in the composition can be much lower, because there is no risk of acid decomposition of the catalyst blocked with CO2. The pKa(C) and pKa(D) can be too low. The pKa(C) and pKa(D) can be as low as -2, -1, 0, but preferably at least 1, 2 or 3 in order to achieve sufficient Michael Addition reactivity. Because of this wide pKa range, components C and D can be chosen from a relatively wide range of molecules.
    [0019] The start of the RMA reaction is caused by C components. The composition according to the invention does not need any other basic components to start the RMA reaction. Therefore, it is preferable that the composition comprises less than 50% moles, and more preferably substantially none (i.e. 0% moles) of a basic compound other than C that can initiate or catalyze the RMA crosslinking reaction. Preferably, the composition comprises less than 50, 40, 30, 20, 15, 10.5, 3% by moles relative to the basic components C of a base component other than C which is capable of initiating (directly after unblocking or activate) the RMA reaction between A and B. In particular, it is an advantage of the present invention that the composition comprises substantially no latent base catalyst, more particularly substantially no latent base catalyst blocked with carbon dioxide. This allows for the application of thicker layers or articles. Another base, for example an amine, may be present as long as it is such a weak base that it will not initiate the RMA reaction.
    [0020] In component(s) A, acidic CH donor groups in methylene or methine activated with a pKa(A) between 10.5 and 14 and preferably have a structure according to formula 1:
    wherein R is hydrogen or an alkyl, aralkyl or aryl substituent and Y and Y' are the same or different substituent groups, preferably alkyl, aralkyl or aryl (R*), or alkoxy (-OR*) or wherein the group - C(=O)-Y and/or -C(=O)-Y' is substituted by CN or phenyl. The activated methylene or methine is the -(H)-C(-R)- group between the carbonyl groups in Formula 1. Preferably, the component A RMA donor groups are from malonate or acetoacetate groups and preferably they are predominantly from malonate groups . As these components can be built into a polymer, for example, through transesterification, the ester group in them can be an ester bond with a polymer.
    [0021] In the crosslinkable composition, it is preferred that the majority, preferably at least 50, 60, 70, or even 80% by moles of the CH acidic RMA donor groups in component(s) A are malonate or acetoacetate groups, plus preferably malonate groups. In this case, the malonate or acetoacetate groups are referred to as the dominant component A. The term dominant refers to the compound that provides the most functional RMA reactive acceptor or donor groups; in the case of component A, C, D and F of the type of donor group containing X-H providing the majority of acidic RMA donor groups X-H. In the crosslinkable composition the majority, preferably at least 50, 60, 70 or even 80% by moles of the CH acidic RMA donor groups in component(s) A are malonate groups with the remaining RMA donor groups in component(s) A being substantially only from acetoacetate groups.
    Components A containing both malonate and acetoacetate groups in the same molecule are also suitable. In addition, physical mixtures of components containing malonate and acetoacetate groups are suitable. For example, components A can be a physical blend of a polymer comprising single malonate and acetoacetate molecules. Especially preferred malonate group-containing components for use with the present invention are malonate group-containing oligomeric or polymeric esters, ethers, urethanes and epoxy esters containing 1-50, more preferably 2-10, malonate groups per molecule. In practice, polyesters and polyurethanes are preferred. It is also preferred that such components containing malonate groups have a number average molecular weight (Mn) in the range of about 100 to about 5000, more preferably 250-2500, and an acid number of about 2 or preferably less. Also monomalonates can be used since they have 2 reactive C-H per molecule. Monomeric malonates can furthermore be used as reactive diluents.
    [0023] Component B generally can be ethylenically unsaturated components in which the carbon-carbon double bond is activated by an electron-withdrawing group, eg, a carbonyl group in the alpha-position. Suitable B components are known in the art, for example (meth-)acryloyl esters, (meth)acrylamides, alternatively polyesters based on maleic, fumaric and/or itaconic acid (and maleic and itaconic anhydride and polyesters, polyurethanes, polyethers and/or alkyd resins containing pendant activated unsaturated groups. Acrylates, fumarates and maleates are preferred. More preferably, the dominant B component, preferably providing at least 50, 60, 70, 80 or even at least 90% mole of the RMA acceptor groups , is an unsaturated acryloyl functional component. Preferably, the functionality, defined as the numerical average number of unsaturated RMA acceptor groups per component B molecule, is 2-20, the equivalent weight (EQW: average molecular weight per reactive functional group) is 100 -2000, and the number average molecular weight Mn is preferably 200-5000.
    [0024] The amounts of components A and B must be balanced in terms of their reactive equivalents for an RMA reaction. The equivalent molar ratio of acceptor groups to CH donors in the composition is generally between 3:1 and 1:6, preferably between 2:1 and 1:4, more preferably between 3:2 and 1:3, more preferably less than 1 :1 and preferably more than 1:2. Component A is typically present in the composition in fractions by weight of between 5 and 95% by weight (relative to total resin solids), component B is also normally present in the composition in fractions by weight of between 5 and 95% by weight. In the situation where A and B are present in the same polymer, the fraction by weight of the polymer present in the composition can be at least 80, 90 or 95% by weight and can even reach 99% by weight.
    [0025] Typically, at least one of components A and B is in the form of a polymer, for example a polyester containing malonate groups. It is also possible that both functional groups associated with components (A and B) could be present in the same polymer. Note that the term components A, B, C, D and F refers to the compound that has specified RMA reactive groups with no specific relationship to the molecular architecture. A component can be a single small molecule, a dimer, trimer or tetramer, etc., or an oligomer or a chain polymer to which one or more of the specified RMA reactive groups are attached. For example, Component A can be a single molecule with a single moiety of activated methylene, such as ethylacetate or malonate. These molecules have two acidic C-H donor groups available for RMA reaction. Component A can also be a dimer or trimer comprising 2 or 3 malonates. Component A can also be an oligomer or polymer chain comprising one or more malonates, for example, attached to or incorporated into the chain. The same applies in fact to components B, C, D and F. On the other hand, one or more of components A, B, C, D and F can be combined into a small molecule, oligomer or polymer. The particular choice of shape of the components depends on the expected characteristics of the reticulated network to be formed. Different polymers can also be used in combination in the composition, for example a polyester, polyepoxy, polyurethane or a polyacrylate polymer. It is also envisaged to use combinations of different polymers that are integrated by the RMA reaction in a cross-linked network. Note that components C, D, and F can also comprise two or more acidic donor groups that are Michael Addition donors that can react with component B and therefore can be integrated into the crosslinked network. In general, the molecular weight of the oligomer or polymers carrying components A to F can vary within wide ranges, the choice depending on the specific application envisioned; typically the molecular weight (weight average) Mw is greater than 100, 200 or 500 and less than 200,000, 150,000 or 100,000 50,000 g/mol. As described herein for coating applications, the number average molecular weight (Mn) is preferably in the range of about 100 to about 5000.
    [0026] Preferably, the composition does not contain substantial amounts of acidic components other than components A, C, D and F which are capable of inhibiting the Michael Addition reaction between components A and B.
    [0027] Component C is a salt according to the formula Cat+X-, where Cat+ is a non-acidic cation, with no ability to inhibit the crosslinking reaction of components A and B. This implies that if any protons are associated with the cation, their acidity does not exceed that of the dominant CH functions in component A, by more than two units, preferably not more than 1 and more preferably not more than 0.5 pKa unit. Examples of useful cations include inorganic cations, preferably alkali or alkaline earth metal cations, more preferably K +, Na + and Li +, or organic cations such as tetraalkylammonium and tetraalkylphosphonium salts, but also cations having a proton , but are extremely non-acidic, for example protonated species of strongly basic organic bases, for example DBU, DBN or tetramethylguanidine. These bases would be able to initiate the crosslinking reaction between components A and B, but do not interfere with the reaction (inhibition) in their protonated form. A further advantage of the invention is that component C can be significantly less expensive than the known RMA latent base catalyst. For example, in most circumstances, the cations that are required in the carbon dioxide blocked latent base catalyst are of the tetra-alkylammonium type which are much more expensive. Because of the X- anion, the C component of salt has sufficient solubility, even with simple and inexpensive cations like potassium.
    [0028] Basic component(s) C is(are) a salt of a basic X- anion from a compound containing acidic XH group where X is N, P, O, S or C. The anion X - of component C is essential for the invention. The X- anion must be a Michael Addition donor that can react with component B and is an anion of a corresponding XH acid that is significantly more acidic than the dominant reactive CH species of component A. In particular, the X- anion is distinguished by a pKa(C) of the corresponding acidic X-H of more than two units less than the pKa(A) of the major component A and being less than 10.5. If, for example, these dominant A-component species are a malonate (pKa 13), the pKa of X-H must be less than 10.5. Preferably it is less than 10, more preferably less than 9.5, even more preferably less than 9, most preferably less than 8.5. If the dominant CH species of component A is of another nature (eg acetoacetate, pKa 10.7), the pKa of XH must be at least two units smaller than that of the dominant CH species of component A. Component C may comprise more than one different component within the specified ranges.
    [0029] Furthermore, it is important that X- is reactive with component B according to a Michael Addition reaction, through the site where the acidic proton can be fixed. Through such a reaction, the original X-anion was thus converted into a more basic carbanion, with loss of the ability to reform an X-H species.
    [0030] Finally, it is important that the reactivity of X- species to component B is less than that of the anion of dominant C-H species to component A. This ensures that an effective induction time can be created. Preferably, the reactivity is lower by a factor of at least 3, more preferably 5, more preferably at least 10, even more preferably at least 20, even more preferably at least 40, most preferably at least 100. However, the reactivity should not be too low either, as otherwise the completion of the reaction will be too slow; the reaction should not be slower than the component A anion by a factor greater than 10,000, preferably not more than 5,000, more preferably not more than 2,000, even more preferably not more than 1,000, most preferably not more than 500.
    [0031] Component C is present in an amount of at least 1 μeq/g (microequivalent per gram of solid organic components), preferably more than 5 μeq/g, more preferably more than 10 μeq/g, and preferably not more than 1 meq/g, more preferably not more than 600 μeq/g, more preferably not more than 400 μeq/g. The term organic solid components refers to solid resin-forming components, also referred to as a binder in a coating composition, excluding volatile components, pigments, drip control agents, and other typical paint additives. In particular, the values are expressed in relation to the sum of components A, B, C, and optional D and F that react to form the lattice. Component C is the dominant basic component present, eventually being able to initiate (following a cascade of acid-base reaction steps from the reaction of components A and B. Preferably, no significant amount is present of other basic species being able to directly, or after deblocking a carbon dioxide, start the reaction between components A and B, without being consumed in a Michael Addition reaction (and do not form a covalent bond) with component B. Component C can be a kind of low weight molecular, but can also be part of a polymeric species, and can be combined with component A and/or D in a polymer.
    [0032] It is preferred that, in addition to component C, also a component D is present to allow prolonging the useful life in the mixture. For some applications, quick activation when mixing may not be a problem (or even preferred), for others a long workability window is required after mixing. Component D is an acidic component X'-H, which is similar in characteristics to the corresponding acidic X-H of the anion of component C. X' may be the same as X, or it may be different; component D may also comprise multiple species as per the definition. Thus, the pKa of component D is defined as being less than 10.5 and being 2 units less than pKa(A). Preferably it is less than 10, more preferably less than 9.5, even more preferably less than 9, most preferably less than 8.5. Furthermore, if the dominant CH species of component A are significantly smaller than malonate (eg, acetoacetate, pKa 10.7), the pKa of X'-H must be at least two units less than that of the dominant component A. In general, the pKa of component D X'-H will not be lower than that of XH species related to component C because otherwise an acid change would reverse the roles of species X and X' , as will be recognized by those skilled in the art. X'-, when deprotonating component D, is reactive with component B according to a Michael Addition reaction, through the X' site where the acidic proton is fixed. Through such a reaction, the original X'- anion is thus converted into a D-B adduct carbanion of greater basicity, with loss of the ability to reform an X-H species.
    [0033] The reactivity of X'- species to component B is less than that of the dominant C-H species anion to component A. This ensures that an effective induction time can be created. Preferably it is less by a factor of at least 3, more preferably 5, more preferably at least 10, even more preferably at least 20, even more preferably at least 40, most preferably at least 100. However, it should not be too low either, because otherwise the completion of the reaction will be too slow; the reactivity should not be lower than that of the component A anion by a factor of more than 10,000, preferably no more than 5,000, more preferably no more than 2,000, even more preferably no more than 1,000, the more preferably not more than 500. The same reactivity preference applies to the anion X- in component C.
    [0034] Component C can be prepared by an acid-base reaction of a strong base and an X-H component. Component D (X'-H) can be added separately or, in the case of anions X and X' or chosen from the same, component D can also be formed in combination with component C, reacting a strong base with a molar excess of the component D (XH) to form a mixture of an anion salt XH as Component C and the remaining unreacted excess XH as Component D. Of course, it is possible to add additional D X'-H components, where X' is not the same than the original XH from which component C is formed. In such a combination, it is preferable, in order to improve the pot life of the mixture, that the total molar amount of the original X-H and X'-H species exceed that of the original strong base used.
    [0035] Component D slows the crosslinking reaction between components A and B in the composition and creates an induction time. This also provides an open time in application of a coating layer of the crosslinkable composition; open time being the time when the viscosity is low enough to allow flow and allow trapped air to escape and solvent to evaporate. Large amount and low activity of component D provide longer induction/delay time. The preferred equivalent amount of component D in the composition can be defined as a function of the equivalent amount of anion X- in component C. The preferred molar ratio Rd/c of component D over basic anion X- in component C is dependent on the relative reactivity of the corresponding anion X- to component B relative to anions of component A. The lower this relative reactivity of component C compared to A, the lower preferred ratio may be to provide a good open time; if this relative reactivity is greater, the ratio will be greater. In general, at least 1 equivalent % of component D compared to component C will be needed, preferably more than 10%, more preferably more than 50%, even more preferably over 100%; preferably it is not more than 5000%, more preferably not more than 4000, 3000, 2000, 1000 or 500%.
    [0036] As described above, components C and D can also be combined into a single molecule. An example of such an alternative embodiment is a molecule comprising a functional group containing more than one acid X-H which is reactive by Michael Addition with B, as would for example be the case with a 1,3-diketone, or nitromethane. A salt of such a material in which one or more of the acidic XH groups is in anion form would be considered to contribute one or more equivalents of the C component, but the other one or more non-deprotonated XH groups could give one or more equivalents. (eg, nitromethane 2, and barbituric acid 3) of non-deprotonated X'-H species capable of reacting with component B via Michael Addition (component D). An example of such a molecule having both C and D component is a mono-salt of a compound of formula 1 where R = H. This salt has an acidic CH proton as a D component and a salt component where X = X'. One equivalent of a salt of such X-H (mono-deprotonated) would react with component B, followed by deprotonation of the remaining second acid group (X'-H). This is analogous to the situation where C and D are separated and component C as a salt of a single X-H group reacts with Michael Addition with B followed by deprotonation of an X'-H into the other separate component D. A salt of acidic methylene or methyl groups containing multiple acidic hydrogens should be considered to contribute to both the C and D components, for example, in a 1:1 ratio in the case of methylene or a 1:2 ratio in the case of nitromethane.
    [0037] Component D can be present as low molecular weight species, it can be present as a polymer, it can be present in a molecule together with the functionality of component C, as discussed in the previous paragraph, it can also be combined with component A in a polymeric substance, it can be combined with component B in as substance, and it can be part of a material in which functionalities A, C and D are combined. It is possible that the composition contains less than 30% by weight of resin from other components capable of undergoing Michael Addition reaction with component B not covered by the definitions of components A and D.
    The pKa values reported are aqueous pKa values at ambient conditions (21°C). They can be easily found in the literature and, if necessary, determined in aqueous solution by procedures known to those skilled in the art. A list of pKa values of the relevant components is given below.

    [0039] The relative Michael Addition reactivities of components A, C, D and F to B and reported here can be determined experimentally. The reactivity of anions from various XH species can be derived from model experiments when one of them is tested under comparable conditions in a formulation at room temperature with an excess of model RMA B acceptor groups (eg, butylacrylate), and in the presence of a base at least capable to deprotonate 1% in moles of RMA donor. The consumption of acidic species can be tracked in time by titration, NMR, GC or other appropriate analytical methods known to those skilled in the art.
    [0040] The appropriate components XH (from which the salts of component C can be derived) and X'-H (components D) can be acids in which the acidic proton is attached to a C, N, P, atom O or S, and Michael Addition reactivity occurs through these atoms. Preferably it is attached to a C, N or a P atom, more preferably a carbon or nitrogen atom. X and X' in components C and D are preferably each independently chosen to be C, N or P.
    [0041] Appropriate compounds C and D have X or X'-H originating from methine or methylene activated by two or three substituents, these substituents are selected from ester groups CO2R, ketone groups C(=O)R, cyano groups and groups nitro, or methyl, methylene or methine groups activated by a nitro group. Examples of components, which are suitable as component D or, in their anionic form, as part of component C, are cyanoacetates, 1,3-diketones such as acetylacetone and 1,3-cyclohexanedione, as well as their substituted analogues, such as dimedone and nitroalkanes such as nitromethane, nitroethane 2-nitropropane. A preferred class of X-H and X'-H components C and D includes compounds wherein the X of component C, and/or X' in component D is a carbon-acid compound (X = C); methine, methylene and methyl groups activated by electron removal of substituents such as CO2R esters, ketones, cyano groups and nitro groups, in particular components according to formula 1. Normally at least two of these substituents must be present, although in the case of nitro groups, one substituent may suffice.
    [0042] Another preferred class of components XH and X'-H comprises compounds wherein the X of component C, and/or X' in component D is an aza-acid compound (X = N), preferably these NH acid compounds are derived from an Ar-NH- (C = O), - (C = O)- NH- (C = O)- group, or an -NH- (O = S = O)- group or a heterocycle in which nitrogen of the NH group is contained in a heterocyclic ring. Preferred components can be found in the class of imide components, preferably (optionally substituted) cyclic imides such as succinimide and ethosuximide. Substituted hydantoins, uracils, and barbiturates also fall into this category. Another suitable class is formed by aromatic sulfonamides, such as benzenesulfonamide and p-toluenesulfonamide. Saccharin is an example of low pKa in this category.
    [0043] Another preferred class of X-H and X'-H components comprises acidic N-H compounds derived from NH-containing heterocycles as part of the heterocyclic ring. Examples are triazoles, pyrazoles and imidazoles, for example 2-methyl-4-nitro-imidazole. Especially preferred are triazole components such as 1,2,4-triazole and benzotriazole.
    [0044] It has been found that it may be beneficial in view of creating both a high reactivity in combination with a long pot life and an open time if more than one different group involved in the composition as XH is present ( related to component C) and X'-H (component D). The inventors have found it favorable to use a combination of one or more X-H or X-H' groups that have a pKa <8.9 and other X-H or X'-H groups that have a pKa >8.9; the inventors have also found it favorable to combine a component from aza-acid compounds, in particular triazoles, with activated imides or methylenes such as 1,3-diketones. Preferably, in the crosslinkable composition, the pKa(C) is less than 8.9 and pKa(D) is greater than 8.9.
    [0045] Preferably in the crosslinkable composition a. more than 50, preferably more than 60, 70 or even more preferably more than 80% of the RMA donor groups in components A are malonate groups,b. more than 50, preferably more than 60, 70 or even more preferably more than 80% of the RMA acceptor groups in B components are acryloyl groups, c. component C is a benzotriazolide salt, a 1,2,4-triazole salt or a 1,3-cyclohexanedione salt thereof,d. component D is a triazole or benzotriazole, a 1,3-diketone, or an imide.
    [0046] The composition may further comprise as component(s) E, one or more thixotropy inducing additives, in particular sag control agents for use in coating applications and in particular in thick layers.
    The crosslinkable composition may preferably further comprise smaller amounts of component(s) F comprising an acidic X"-H group wherein X" is N, P, O, S or C, which is i) different from components A and D but also a Michael Addition donor that can react with component B. These components can be, for example, components with the same pKa range as components A, but which do not have at least 2 reactive groups to form the network. cross-linked, C-components or acidic NH-component(s) with a pKa greater than 10.5, e.g. imidazoles and pyrazoles. Such component can be used to moderate the reactivity of component A to improve open time. The amount xf of component(s) F is at most 30% by weight, more preferably at most 25, 20, 15 and preferably between 1 - 10 or 1 - 5% by weight with respect to the total weight of the resin-forming components A, B, C, D and F.
    [0048] The crosslinkable composition as described above will not generally be commercially available because the pot life of the mixture is generally very short; the time the composition can be treated before viscosity increase or gelling makes this impossible is very short. Therefore, the crosslinkable composition needs to be finished until the constituent components A F are mixed, just before application. Therefore, the invention also relates to kits of parts, in which the parts comprise combinations of the constituent components of the crosslinkable composition that do not react.
    [0049] In particular, the kit of parts for manufacturing the composition according to the invention comprises 1) a part I.1 comprising component(s) C and a part II.1 not comprising component(s) C or alternatively 2) a kit of parts comprising a part I.2 comprising component B and a part II.2 not comprising component B or alternatively 3) a kit of parts comprising part I.3 comprising instead of component C the corresponding acidic compound XH and a part II.3 comprising a strong base for mixing with part I.3 to convert the acidic compound XH into its corresponding salt component C.
    The inventors have found that a preferred way of combining the components of the crosslinkable composition is to provide a part I.1 comprising component C, preferably in a part of the solvent if necessary, and also preferably at least part of component D and a separate part II.1 not comprising components C and comprising components A, B and optionally D and F. The invention also relates to a kit of parts I.1 and II.1 as described. The invention also relates to a method of forming the crosslinkable composition by adding the part I.1 kit containing component C to a composition containing component A or B.
    [0051] An alternative way of combining the components to form the complete crosslinkable composition is to have an I.2 part, in which component A and component C (and optionally component D) are combined, but not component B and a part II.2 and comprising component B, these parts II.1 and II.2 can be combined immediately before use. The invention also relates to a kit of parts II.1 and II.2 as described, and a method for preparing the crosslinkable composition comprising mixing parts II.1 and II.2.
    [0052] A third usable mode or preparation of the crosslinkable composition is to provide a composition comprising components A, B and optionally D and F and, instead of adding component C as salt, adding the corresponding acid component XH, followed (immediately before application) by adding a strong base, which forms the salt component C in situ. The same can be achieved if XH is added in a molar excess of strong base leaving residual XH as component D. This method requires proper mixing routines, for example, diluting the strong base and/or intense stirring/mixing, so that salt formation can occur prior to unintentional (local) initiation of the RMA reaction of components A and B. This component XH can also be added shortly before application of the crosslinkable composition. Optionally, salt component C is formed ex-situ immediately prior to application, by reacting component X-H with a strong base and adding to the remaining crosslinkable composition components. The invention therefore also relates to a part I.3 comprising components A, B and optionally D and F, and instead of component C as the salt, the corresponding acid component X-H. The invention also relates to its use for the preparation of a crosslinkable composition according to the invention, to a kit of parts comprising part I.3 and a separate part II.3 comprising a strong base and to the process comprising mixing a part I.3 and II.3. The invention also relates to compositions obtained by the processes of mixing components A to C and optionally D, E and F, in any particular order, preferably, in an order as described above. The invention also relates to a method of preparing a crosslinkable composition comprising providing a first composition comprising components A, B, optional D and F, but not component C and, just before use of the crosslinkable composition, forming component C by reaction of a strong base with XH-containing component, either in situ in the first composition or ex-situ, followed by mixing the thus formed component C with the first composition.
    [0053] Note that, in the composition, pKa(D) is greater than pKa(C). However, when component C and D are separated in a kit of parts, this is not necessary, because in mixing an acid-base reaction will take place between X'-H (D) and X(-) (C) and in balance will have XH and X'(-) in the crosslinkable composition.
    [0054] The crosslinkable composition according to the invention may have a gelling time at room temperature of more than 20 minutes. For many applications, after completion of the preparation of the crosslinkable composition, the resulting composition preferably has a gelling time, before application, at room temperature, of more than 20 minutes, more preferably more than 30 minutes, more preferably more than than 60 minutes, most preferably more than 90 minutes. A method for measuring the gelling time is described below. The crosslinkable composition can be cured at different temperatures and it is also possible and advantageous to obtain it at low temperatures, which are generally the most challenging. The composition can be cured at temperatures less than 120, preferably less than 100, 80, 60, 50, 40 and even less than 30°C.
    The crosslinkable composition according to the invention comprises a network forming components A, B, C, preferably also D and optionally F and optionally comprising solvent, said composition preferably having. component(s) A, preferably an oligomer or polymer, in an amount x between 5 and 95% by weight with respect to the total resin and b. component(s) B, preferably a dimer, trimer or tetramer, oligomer or polymer, in an amount xb between 5 and 95% by weight with respect to the total resin, wherein x plus xb is at least 40, preferably 50, 60 , 70, 80 or 90% by weight with respect to the total resin, c. basic component(s) C in an amount xc between 0.001 and 1meq/(g of total resin)d. preferably component(s) D in an equivalent amount xd such that the ratio Rd/c of acidic X'-H groups in component D to basic anion groups X- in component C is between 1% and 5000%,e. optional component(s) F in an amount xf between 1 and 30% by weight with respect to the total resin,f. optionally, a solvent in an amount between 0.1 and 80% by weight with respect to the total weight of total resin plus solvent.
    [0056] Depending on the intended application, the crosslinkable composition may also contain a certain amount of one or more different solvents, preferably organic solvents. In coating applications, it may be preferred to add organic solvents, preferably less than 80% by weight, more preferably less than 55, 45, 35, 25% by weight. In order to create a better pot life of the mixture, it is preferred that the solvent comprises at least 1% by weight of volatile primary alcohols, more preferably at least 3% by weight, even more preferably at least 5% by weight, most preferably, at least 8% by weight, volatile primary alcohols (with respect to the total weight of ABCD and F and solvent). The boiling point of volatile primary alcohols is preferably less than 140°C, more preferably less than 130, 120, 110 and most preferably less than 100°C. Examples include methanol, ethanol, n-propanol, n-butanol, n-pentanol. The crosslinkable composition may also contain water.
    [0057] The invention makes it possible to provide substantially solvent-free crosslinkable compositions for special applications. Such special embodiments are, for example, powder coating resins or resin for composite materials. Since the molecular weight of components A, B, C, D and F can be chosen very low, the viscosity of the composition can be low enough for applications that require a low viscosity, even without a solvent. Low molecular weight components A to F (Mw <500, 400, 300 or 200) can be used in reactive diluent. For example, mono-acetoacetate or mono-malonate can be used as components A of reactive diluent. The advantage is that the composition has a very low content of volatile organic compounds (VOC) which has a significant environmental advantage. Therefore, in one of the preferred embodiments, the amount of organic solvent added is low and the VOC is less than 5, more preferably less than 3, 2 or even 1% by weight. In this embodiment, it is preferred that resin components A, B, C, D or F have a molecular weight Mw of less than 50,000, 20,000, 10,000, 5000 or even less than 3000 g/mol. This composition can be advantageously used in applications where evaporation of VOC is either impossible or difficult or unacceptable.
    [0058] The components A, B, C, D and F all react with each other and become integrated into the lattice. As described above, components A and B have at least two functional cross-linked groups (the RMA donor and acceptor groups, respectively) to form a cross-linked network. Preferably at least one of components A or B has on average more than 2, preferably at least 2.1 functional crosslinking groups to give a more densely crosslinked network. In addition to components A and B, each of the components C, D and F can also comprise two or more RMA donor groups so that they become fully integrated into the reticulated network. In general, the total amount of components that have two or more crosslinking groups and thus can become fully integrated into the crosslinked network represents at least 40, more preferably at least 50, 60 and 70 and most preferably, at least 80% by weight of the total weight of components A, B, C, D and F. However, it is preferable that components A and B form the majority of the crosslinked network, preferably at least 50, 60 or 70 and more preferably at least 80% by weight of the total weight of resin components A, B, C, D and F.
    [0059] In addition, the crosslinkable composition may contain other components relevant to the specific application envisaged. These can be rheology additives to induce thixotropy to allow vertical application of coatings without dripping; the crosslinkable composition for use as a coating composition can include all kinds of coating additives like pigments, extenders, nanoparticles, fibers, stabilizers, dispersants, wetting additives, anti-foam additives, blowing agents, etc.
    [0060] The crosslinkable composition according to the invention can be used as coating compositions, for coating materials, for example, metal or wood coatings, plastic coatings, automotive coatings, marine and protective applications, whether pigmented or as transparent coating. They can also be useful for applications in the field of printing inks, adhesives, films, foams and composites (such as composite matrix). The invention therefore also relates to coating compositions comprising the crosslinkable composition according to the invention and further additives for paints, preferably a thixotropy control agent, and composite articles comprising a filler material, preferably fibers or particles, more preferably inorganic fibers or particles and as a binding material of the crosslinked composition according to the invention.
    The foregoing more general discussion of the present invention will be further illustrated by the following specific examples, which are exemplary only.
    The following abbreviations were used for the chemicals used in the experiments: DiTMPTA is di-trimethiolpropane-tetraacrylate (obtained from Aldrich (MW = 466 g/mol)) or used as Sartomer SR355 (commercially supplied by Sartomer); Disperbyk 163 is a dispersing agent commercially supplied by Byk; Byk 310 and 315 are additives commercially supplied by ByK; Kronos 2310 is a TiO2 pigment commercially supplied by Kronos, TBAH is tetrabutylammonium hydroxide, TPAH is tetrapropylammonium hydroxide, DBU is 1.8, - diazabicyclo [5.4.0] undec-[7]-ene, C-HD is 1 ,3-cyclohexanedione, EtAcAc is ethylacetoacetate; RT is room temperature, BT is benzotriazole, KBZT solution is potassium benzotriazolide solution in ethanol as described below. Preparation of A malonate polyester
    [0063] In a reactor provided with a distillation column filled with Raschig rings, 17.31 mol of neopentylglycol, 8.03 mol of hexahydrophthalic anhydride and 0.0047 mol of butyl stanoic acid were placed. The mixture was polymerized at 240°C under nitrogen atmosphere at an acid number of 0.2 mg KOH/g. The mixture was cooled to 130°C and 10.44 mol of diethylmalonate was added. The reaction mixture was heated to 170°C and ethanol removed under reduced pressure. The nearly colorless material was cooled and diluted with 420 g of butyl acetate having a solids content of 90%. The final resin had an acid number of 0.3 mg KOH/g solids, an OH value of 20 mg KOH/g solids, and an average molecular weight of 3400 Da. Preparation of base solution C
    [0064] An amount of acid (XH) was dissolved in a solution of strong base in an alcoholic solvent according to Table A (amounts in grams; all base/strong acid molar ratios are equal to 1). The solution was left overnight before use. Table A

    [0065] The foregoing more general discussion of the present invention will be further illustrated by the following specific examples, which are exemplary only.
    [0066] Molecular weights were measured by GPC in THF, and expressed as polystyrene equivalent weights.
    [0067] Determination of gelling time: After mixing base C with the crosslinkable formulation, the formulation was visually checked at regular intervals for increased viscosity and heat development. Gelation time was defined as the time taken to stop the 10 g of crosslinkable formulation in a 40 mL vial from exhibiting any movement when the vial was turned upside down.
    Determination of drying time: Ink was sprayed onto a 19 x 10.5 cm phosphate pretreated steel panel using a Devilbiss spray pad, FF-1 nozzle. 4 with an air pressure of 3.5 bars giving a dry film layer thickness between 67 and 91 µm. Directly after spraying, the paintwork was checked regularly (usually every 2-5 min) manually for tackiness under climate conditions (22°C, 60 ± 2% relative humidity). When the film did not exhibit any more tackiness over manual touch, the film was scored for skin formation and complete drying by touching with greater force and rotation. If no marks were observed after this determination, the ink was defined as dry and the drying time was recorded.
    [0069] Persoz hardness measurement: Persoz pendulum hardness was measured in an air-conditioned room at 23°C, and 55 +/- 5% relative humidity. Hardness is measured with an acc pendulum. Persoz, as described in ASTM D 4366. Layer thicknesses were measured with a Fischer Permascope MP40E-S at five times at different locations on the panel and averaged.
    [0070] Wavescan Analysis: Panels as described above were analyzed using Wavescan II from Byk Instruments. Data were stored using Byk's Autochart software. The analysis was performed in the direction perpendicular to the thickness gradient. In this instrument, small laser diode light is reflected off the surface of the sample under an angle of 60% and the reflected light is detected at the brightness angle (opposite 60°). During measurement, the wave-scan is moved across the surface of the sample over a scan length of approximately 10 cm, with a data point being recorded every 0.027 mm. The surface structure of the sample modulates the light from the laser diode. The signal is divided into 5 wavelength ranges in the range of 0.1-30 mm and processed by mathematical filtration. For each of the five ranges, a characteristic value (Wa 0.1-0.3mm, Wb 0.31.0mm, Wc 1.0-3.0mm, Wd 3.0-10mm, We 10-30mm) well as typical long-wave (LW, approx. 1-10mm) and short-wave (SW, approx. 0.3-1mm) “wave-scan” values are calculated. Low values mean a smooth surface structure. In addition, an LED light source is installed in “wave-scan” DOI and illuminates the surface under 20 degrees after passing through an opening. Scattered light is detected and a so-called haze value (du, <0.1 mm) is measured. Using the three shortwave band values Wa, Wb and du, a DOI value is calculated. (see Osterhold ea, Progress in Organic Coatings, 2009, vol. 65, no4, pp. 440-443).

    [0071] Crosslinkable formulations were prepared according to Table B (values in grams). Components A, B and D were added and mixed. Subsequently, basic solution C was added and the formulation was mixed again. Gelation time was recorded as described above and the results are included in Table B.
    [0072] The gel times in the table clearly demonstrate that very fast gelation was observed when malonate polyester and Sartomer SR355 were mixed with base component C only (Examples 1, 3). The reaction was also found to be strongly exothermic. Furthermore, when EtAcAc was added, gelling was very fast, despite the slightly inferior functionality (Examples 2, 4). Interestingly, when an excess of component D was added (Examples 5, 6), a significant delay in gelling was observed. The delay was longer when component D was benzotriazole compared to component D 1,2,4-triazole, probably due to the low reactivity of benzotriazolide as a Michael donor. Table C

    [0073] Crosslinkable formulations from Table C were prepared and tested similarly compared to formulations from Table B. Comparison of examples 7 - 9 showed that salts with other neutral cations in the RMA reaction can be used as initiators to achieve gelation of these formulations. Again, addition of an excess of component D (benzotriazole) resulted in longer gelling times.
    [0074] The base salt of nitrogen DBU and benzotriazole resulted in a similar observation (Example 10), ie, gelation occurred at a similar time to that observed for other samples containing component D. Interestingly, if a more base was used weak nitrogen, such as tributylamine, no gelation was observed (Comparative 1). This can be explained by the higher acidity of the tributylammonium cation compared to DBU-H+, that is, the former significantly inhibited the deprotonation of malonates, while the latter did not.
    [0075] A special case is the use of 1,3-cyclohexanedione (Example 11), because this compound has two acidic CH bonds. In its mono-potassium salt form, an acidic CH bond and potentially reactive RMA will still be present. Therefore, it will act as both component C and component D. This compound can also be used to initiate the gelation of this crosslinkable composition. However, due to its low pKa value and low potential reactivity in RMA reactions, a long gelling time was found. Table D
    Table E

    [0076] Formulations of examples 12-17 were prepared as pigmented paints, having compositions as shown in Table X (values in grams).
    [0077] The pigment ink was first prepared by grinding Kronos 2310, Disperbyk 163 and Sartomer SR355 together to a pigment paste (3 first components from table D). The KBZT solution was obtained by dissolving 7 g of KOH and 14.86 g of benzotriazole (1:1 molar ratio) in 63 g of ethanol, obtaining a solution of 1.47 meq/g of potassium benzotriazolide. For pigment paste, malonate resin, plus Sartomer SR355, EtAcAc, 310/315 Byk blend, benzotriazole, acetyl acetone, n-propanol and butyl acetate were added in amounts according to Table D. All components were mixed. Subsequently, the KBZT solution was added, the paint now ready for spraying was mixed and sprayed as described above within 5 minutes after the addition of the KBZT solution.
    [0078] Dry layer thickness (mm), drying time (min), gelling time (min), hardness after 24 h RT, short wave and long wave were measured in these formulations as described above. The results are included in Table E.
    [0079] It can be seen from the comparison of examples 12, 13, 14, that increasing the amount of acetyl acetone in the formulations resulted in an increase in drying times, as well as longer gelling times, without much affecting hardness . Comparison of Example 14 and Example 15 demonstrates that increasing the benzotriazole level further delays drying and gelling time. However, when a very similar formulation (Example 16), containing less compared to KBZT solution from Example 15, was applied at a lower layer thickness, good results were obtained with respect to drying time, drying time balance /gelation and hardness. Finally, Example 17 shows that succinimide is very effective in prolonging drying time, but this resulted in a high short wave value. Example 18. Determination of reactivity Michael's addition of succinimide
    [0080] 5 grams of succinimide (50.5 mmols) were dissolved in a mixture of 42 grams of butylacrylate and 42 grams of methanol, and kept at room temperature as such, or after addition of a strong base (9.82 grams of a 1.12 meq/g solution of tetrabutylammonium hydroxide in methanol, 11 meq). Subsequently, the succinimide concentration is determined as a function of time, taking samples, neutralizing with a known excess of HCl in water, and a back-titration with KOH solution. Neither baseline initiation nor significant loss of succinimide NH in this solution is observed within two weeks. With the added base, the concentration of succinimide can be seen to decrease over time, as illustrated in Table F below. Succinimide concentration is expressed as % of theoretical level based on amounts used. Table F

    [0081] At this catalyst level ([succinimide]/[base] = 5), 23% of the succinimide acid protons were consumed in approximately 1 hour.
    [0082] Using the same method, also the reactivity of several other components was determined; as a reference a similar set for the reactivity of dimethylmalonate under these conditions (only in this case, the level of remaining DMM was determined by GC). Table G lists the results of the relative Michael Addition reactivities, expressed as a number indicating the initial increase in % conversion per minute under these conditions. Note that, in all cases, this intrinsic reactivity is significantly lower than that of malonate, but still present. Table G. Relative Conversion Rates
    权利要求:
    Claims (15)
    [0001]
    1. Crosslinkable composition being crosslinkable by real Michael Addition (RMA) reaction, characterized by the fact that it comprises it. component(s) A having at least 2 acid donor C-H groups in activated methylene or methine and with a pKa(A) between 10.5 and 14.b. component(s) B, having at least 2 activated unsaturated acceptor groups, wherein the molar ratio R of acceptor groups to donor groups is between 3:1 to 1:6, and whose component(s) B reacts (m) with component(s) A by Michael Real Addition (RMA) to form a lattice,c. basic component(s) C being a salt of a basic anion X- from an acidic group X-H containing compound wherein X is N, P, O, S or C,i. in an amount xc between 0.001 and 1 meq/(g of components A, B, C, D),ii. anion X- being a Michael Addition donor that can react with component B,iii. the anion X- being distinguished by a pKa(C) of the corresponding acid X-H of more than two units less than the pKa(A) of the major component A and being less than 10.5, the composition further comprising:d. optional component(s) D comprising one or more acidic X'-H groups where X' is N, P, O, S or C,i. X' being the same or different group as the X group in component C,ii. the anion X’- being a Michael Addition donor that can react with component B,iii. the pKa(D) of the X'-H group in the D component being more than two units smaller than the pKa(A) of the majority A component and being less than 10.5, iv. the equivalent Rd/c ratio of acidic X’-H groups in component D over basic anion X- in component C is between 10 and 3000%,e. not including a composition comprising an ethylmalonate-modified polyester based on neopentyl glycol and hexahydrophthalic anhydride, di-trimethylolpropane-tetraacrylate and tetrabutylammonium succinimide and ethylacetoacetate.
    [0002]
    2. Crosslinkable composition according to claim 1, characterized in that it comprises. component(s) D comprising one or more acidic X'-H groups where X' is N, P, O, S or C,i. X' being a group equal to or different from the group X in component C,ii. the anion X’- being a Michael Addition donor that can react with component B,iii. the pKa(D) of the X'-H group in component D being more than two units smaller than the pKa(A) of the major component A and being less than 10.5, iv. the Rd/C equivalent ratio of acidic X’-H groups in component D over the basic anion X- in component C is between 10 and 3000%.
    [0003]
    3. Crosslinkable composition according to claim 1 or 2, characterized in that pKa(D) is equal to or greater than pKa(C).
    [0004]
    4. Crosslinkable composition according to any one of claims 1 to 3, characterized in that it further comprises component(s) F comprising an acidic X"-H group in which X" is N, P, O, S or C i. different from components A and D,ii. F being a Michael Addition donor who can react with component B.
    [0005]
    5. Crosslinkable composition according to any one of claims 1 to 4, characterized in that the composition comprises less than 50% by moles and preferably substantially 0% by moles in relation to the basic components C of another basic compound other than C which can initiate or catalyze the RMA crosslinking reaction.
    [0006]
    6. Crosslinkable composition according to any one of claims 1 to 5, characterized in that it comprises. component(s) A in an amount x between 5 and 95% by weight and b. component(s) B, in an amount xb of between 5 and 95% by weight, wherein x plus xb is at least 40% by weight, c. basic component(s) C in an amount xc between 0.001 and 1 meq/(total g resin), d. component(s) D in an amount xd such that the ratio of Rd/c equivalents of acidic X’-H groups in component D over the basic anion groups X- in component C is between 10 and 2000%,e. component(s) F in an amount xf between 0 and 30% by weight, wherein the % by weight is relative to the total resin forming components A, B, C, D and F ef. optionally, a solvent in an amount between 0.1 and 80% by weight with respect to the total weight of total resin plus solvent.
    [0007]
    7. Crosslinkable composition according to any one of claims 1 to 6, characterized in that at least 50% in moles of the RMA donor groups in the component(s) A are malonate or acetoacetate groups, more preferably malonate groups and wherein the RMA acceptor component B groups are acryloyl or maleate groups or mixtures thereof, preferably acryloyl groups.
    [0008]
    8. Crosslinkable composition according to any one of claims 1 to 7, characterized in that X- and X'- anions in components C and D have a lower Michael Addition reactivity for component B than an anion in the major component A by a factor of at least 3, but no greater than 10,000.
    [0009]
    9. Crosslinkable composition according to any one of claims 1 to 8, characterized in thata. more than 50% mol of RMA donor groups in components A are malonate groups,b. more than 50 mol% of the RMA acceptor groups of the B components are acryloyl groups, c. component C is a benzotriazolide salt, a 1,2,4-triazole salt or a 1,3-cyclohexanedione salt,d. component D is benzotriazole or a triazole, a 1,3-diketone, or an imide.
    [0010]
    10. Crosslinkable composition according to any one of claims 1 to 9, characterized in that the X- anion in component C, and/or the X' group in component D is an aza-acid compound (X = N), preferably comprising an NH-containing molecule as part of a -(C=O)-NH-(C=O)- group, or an -NH- (O = S = O)- group, or a cyclic imide, preferably, an optionally substituted succinimide or a triazole component, preferably benzotriazole or 1,2,4-triazole, or wherein the anion X- of component C, and/or the group X' in component D is a carbon-acid compound (X = C), preferably comprising a molecule containing a methine or methylene activated by two or three substituents, these substituents being selected from ester groups CO2R, ketone groups C (=O) R , cyano groups and nitro groups, or a methyl group, methylene or methine activated by a nitro group, preferably a 1,3-diketone, preferably acetylacetone or 1,3-cyclohexanedione, or version substituted thereof, or wherein the anion X- in component C, and/or the group X' in component D are derived from an aromatic sulfonamide, preferably benzenesulfonamide or toluenesulfonamide.
    [0011]
    11. Crosslinkable composition according to any one of claims 1 to 10, characterized in that component C is a triazole and component D is an imide or a 1,3-diketone.
    [0012]
    12. Kit of parts for the manufacture of the composition as defined in any one of claims 1 to 11, characterized in that it comprises 1) a part I.1, comprising component C and preferably also at least part of component D and a part II.1 not comprising component C and comprising components A, B and optionally D and F or alternatively 2) a kit of parts comprising a part I.2 comprising component C, component A, optional solvents and optionally at least one part component D, but not comprising component B and part II.2 comprising component B and optional other components D and F or alternatively a kit of parts or alternatively 3) a kit of parts comprising part I.3 comprising components A, B optionally D and F and instead of component C, the corresponding acid compound XH and a part II.3 comprising a strong base for mixing with part I.3.
    [0013]
    13. Method for preparing a crosslinkable composition as defined in any one of claims 1 to 11, characterized in that it comprises providing a kit of parts according to claim 12 and mixing parts with I.1 with part II.1 or , alternatively part I.2 with part II.2 or alternatively part I.3 with II.3.
    [0014]
    14. Use of a crosslinkable composition as defined in any one of claims 1 to 11 characterized in that it is in the preparation of a coating, paint, film, adhesive, foam or composite matrix composition.
    [0015]
    15. Coating compositions, characterized in that they comprise the crosslinkable composition as defined in any one of claims 1 to 11 and other paint additives, preferably a thixotropy control agent.
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    同族专利:
    公开号 | 公开日
    US10017607B2|2018-07-10|
    EP2984133A1|2016-02-17|
    JP2016514760A|2016-05-23|
    US10604622B2|2020-03-31|
    WO2014166880A1|2014-10-16|
    NO2984133T3|2018-08-25|
    PL2984133T3|2018-07-31|
    KR20150143556A|2015-12-23|
    CN105324426A|2016-02-10|
    US20180282477A1|2018-10-04|
    EP2984133B1|2018-03-28|
    KR102176800B1|2020-11-11|
    ES2669524T3|2018-05-28|
    CN105324426B|2018-07-03|
    DK2984133T3|2018-05-28|
    JP6373965B2|2018-08-15|
    BR112015025624A2|2017-07-18|
    SI2984133T1|2018-06-29|
    US20160060389A1|2016-03-03|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-06-05| B25D| Requested change of name of applicant approved|Owner name: ALLNEX NETHERLANDS B.V. (NL) |
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-15| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-08-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/04/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13162819.0|2013-04-08|
    EP13162819|2013-04-08|
    PCT/EP2014/056953|WO2014166880A1|2013-04-08|2014-04-07|Composition crosslinkable by real michael additionreaction|
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