Process for the manufacture of a crosslinkable composition

Abstract
The invention relates to a process for the preparation of a RMA crosslinkable composition comprising at least one crosslinkable component comprising reactive components A and B each comprising at least 2 reactive groups wherein the at least 2 reactive groups of component A are acidic protons C—H in activated methylene or methine groups and the at least 2 reactive groups of component B are activated unsaturated groups C═C and base catalyst C and one or more N—H group containing reactivity moderating component D that are also a Michael addition donor reactable with component B under the action of catalyst C, characterized in that the one or more reactivity moderating components D have a melting temperature above 60° C. and is first dissolved in one or more crosslinkable components comprising reactive components A or B and the obtained pre-dissolved product is later mixed with other components of the RMA crosslinkable composition.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention

The invention relates generally to a process for the preparation of RMA crosslinkable compositions, in particular those compositions comprising at least one crosslinkable component comprising reactive components A and B each comprising at least 2 reactive groups wherein the at least 2 reactive groups of component A are acidic protons (C—H) in activated methylene or methine groups (the RMA donor group), and the at least 2 reactive groups of component B are activated unsaturated groups (C═C) (the RMA acceptor group), to achieve crosslinking by Real Michael Addition (RMA) reaction between said at least one crosslinkable component in the presence of a base catalyst (C) and an X—H group containing reactivity moderating component (D) that is also a Michael addition donor reactable with component B under the action of catalyst C, wherein X is C, N, P, O or S.


2. Description of the Related Art

The above mentioned compositions and preparation processes are described in EP2764035 from the same applicant. In particular a process for the preparation of the composition is described wherein the components A, B, D are mixed with catalyst C shortly before use. The mentioned prior art further describes a kit of parts comprising part 1 comprising components A and B and part 2 comprising component C and D or alternatively a part 1 comprising components A, B and D and part 2 comprising component C. The examples describe a process wherein all components are added together in an organic solvent and mixed or wherein catalyst component C is mixed in a solvent with component D and added to the other components.


BRIEF SUMMARY OF THE INVENTION

However, it has been found that the prior art process sometimes results in compositions with rather poorly reproducible reactivity profile, which translates into poorly reproducible open time, dry to touch time and hardness development. This makes it difficult to guarantee a high minimum pot life in practical use.


The problem underlying the invention is to provide a process for the preparation of RMA crosslinkable compositions comprising a reactivity promotor D which has at least one of the advantages of having better reproducible results in reactivity profile, open time, dry to touch time and hardness development preferably at low concentration of (volatile) organic solvent (low VOC) and preferably also at short mixing times that provide a better process capacity and economy.


According the invention this problem has been solved by a process for the preparation of a RMA crosslinkable composition comprising at least one crosslinkable component comprising reactive components A and B each comprising at least 2 reactive groups wherein the at least 2 reactive groups of component A are acidic protons C—H in activated methylene or methine groups and the at least 2 reactive groups of component B are activated unsaturated groups C═C and base catalyst C and one or more N—H group containing reactivity moderating components D that are also a Michael addition donor reactable with component B under the action of catalyst C, characterized in that the one or more reactivity moderating component D have a melting temperature above 60, 70, 80, or even 90° C. and is first dissolved in one or more crosslinkable components comprising reactive components A or B and the obtained pre-dissolved product is later mixed with other components of the RMA crosslinkable composition.


The inventors have found out that the problem occurs because the dissolution of the solid reactivity moderator D of the type having N—H acidic groups and having a melting temperature above 60, 70, 80, or even 90° C. is not complete. A solution to that problem could be to use considerably higher amounts of organic solvent. However, that would increase the VOC, which is undesirable from the viewpoint of cost and QESH but also because a high organic solvent content requirement results in lower viscosity and thus prevents the use of the composition in applications where a relatively high viscosity is desired or possible.


The process of the invention has a distinct advantage over dissolving in special high boiling solvents as these are not preferred solvents in RMA crosslinkable composition because they do not evaporate from the coating and so deteriorate the coating properties. A particular preferred solvent for RMA crosslinkable composition (for several reasons) is MEK but solubility of reactivity moderators, in particular succinimide in MEK is poor. Extensive grinding may be a way to improve solubility but this does not work too well, requires special equipment that is not available for all users and in any case adds to production costs.


It is preferred that component D is dissolved in the one or more crosslinkable component comprising reactive components A or B at a temperature above its melting temperature. It is preferred to dissolve D in crosslinkable component comprising reactive components A so that the reactive groups in the crosslinkable component A are similar to the reactive groups in D and both reactable with component B so there is no or less risk of side reaction at elevated temperatures, in particular compared to dissolving in component B.


It is found that the melting of the moderator in the presence of the crosslinkable components, in particular polymer, not only accelerates the dissolution but also stabilizes the solution after the cooling. The moderator may be hindered by the presence of the polymer to crystallise again. The obtained mixture of crosslinkable components and moderator can be easily compounded with the other composition components. It has been found that no moderator D crystallization takes place in the RMA coating composition. The compositions have a good long shelf life.


A suitable way of preparing the solution of the moderator and the crosslinkable components is simply by providing the moderator D and the crosslinkable components, heating at least the moderator to a temperature above the melting temperature of the moderator D and mixing it with the crosslinkable components. As the mount of moderator is relatively small it is more easy to add and mix the solid particulate moderator D to the crosslinkable components that are at a temperature above the melting temperature of the moderator component D and mixed.


In a particularly preferred embodiment of the process, the moderator D is added directly after the synthesis of a polymeric crosslinkable components while they are still at high temperature. In that process the crosslinkable component is a polymer comprising reactive component A or B or both which is synthesised at a temperature above the melting temperature of component D and wherein component D is added directly after the synthesis of said polymer and dissolved therein before cooling to a temperature below the melting temperature of the component D. Herein the crosslinkable component is for example and preferably a polyester comprising reactive components A which is synthesised by forming a polyester polymer using reactive component A as monomer or by transesterification of polyester polymer with a reactive component A. This embodiment provides a cost effective and very efficient way without significant expense or effort to prepare a stable and homogeneous solution of the moderator D which can be used for preparation of the RMA crosslinkable composition. Melting temperatures of components D are reported in literature and suitable solid particulate moderators D can be chosen on the basis of their melting temperature in relation with the envisaged synthesis process


The invention also relates to a solution of moderator D having a melting temperature above 60 C in RMA crosslinkable polymer components as herein described and obtainable by the described preparation processes and its use in the preparation of RMA crosslinkable compositions.


Suitable polymeric crosslinkable components are chosen from the group of polyesters, polyurethanes, polyacrylates, epoxy resins, polyamides and polyvinyl resins which contains components A or B or both in the main chain, pendant, terminal or combinations thereof. The crosslinkable components preferably have a weight average molecular weight Mw of at least 250 gr/mol, preferably a polymer having Mw between 250 and 5000, more preferably between 400 and 4000 or 500 and 3000 gr/mol.


As described in the abovementioned prior art it is preferred that the reactive component A is malonate or acetoacetate and reactive component B is acryloyl. The N—H group in component D preferably has a pKa (defined in aqueous environment) of at least one unit, preferably two units, less than that of the C—H groups in component A, preferably the pKa of the N—H group in component D is lower than 13, preferable lower than 12, more preferably lower than 11, most preferably lower than 10; it is preferably higher than 7, more preferably 8, more preferably higher than 8.5. Thus the moderator will react first with the RMA acceptor in reactive component B and hence slow down the reaction with crosslinkable component A.


The process component D may contain the N—H as part of a group —(C═O)—NH—(C═O)—, or of a group —NH—(O═S═O)— or a heterocycle in which the nitrogen of the N—H group is contained in a heterocyclic ring. Preferably the component D is chosen from the group of an substituted or unsubstituted succinimide, phthalimide, glutarimide, hydantoin, triazole, pyrazole, imidazole or uracil or a mixture thereof, preferably chosen from the group of (mixtures of) succinimides and triazoles.


The component D is preferably present in an amount between 0.1 and 10 wt %, preferably 0.2 and 7 wt %, 0.2 and 5 wt %, 0.2 and 3 wt %, more preferably 0.5 and 2 wt % relative to the total amount of the crosslinkable components A or B and component D and is present in such amount that the amount of N—H groups in component D is no more than 30 mole %, preferably no more than 20, more preferably no more than 10, most preferably no more than 5 mole % relative to C—H donor groups from component A present in the crosslinkable polymer.


The invention also relates to a crosslinkable composition obtainable by the process according to the invention having without additional solvent removal steps, an amount of volatile organic components of no more than 300, preferably no more than 200, 175 or 150 gr/ltr and to the use of such a coating composition having a volatile organic components content of no more than 300, preferably no more than 200, 175 or 150 gr/ltr in an airless spraying application process.


The invention also relates to a coating composition comprising the crosslinking composition according to the invention and one or more coating additives like pigments, co-binders, diluents. High solid contents are desired and diluents are added only for achieving desired handling properties like spray viscosity.


As described the invention also relates to a moderator composition for use in a process for the preparation of an RMA crosslinkable composition according to the invention comprising a N—H group containing reactivity moderating component D having a melting temperature above 60, 70, 80, or even 90° C. dissolved in one or more RMA crosslinkable components comprising reactive components A or B, not comprising catalyst C, in particular a moderator composition consisting essentially of a polymer with malonate as reactive components, between 1 and 2 wt % of a dissolved succinimide or a triazole moderator and less than 300, preferably no more than 200, 175 or 150 gr/ltr of an organic solvent.


The RMA composition is characterized by an excellent combination of long pot-life with high curing reactivity and speed, but the potlife is not so long that the mentioned parts can be sold in admixture. Therefore the RMA crosslinkable composition is prepared shortly before use by mixing a first part comprising the moderator composition comprising moderator D and the crosslinkable components comprising reactive components A and/or B, a second part comprising the catalyst C and optional third and further parts comprising all other remaining RMA components and additives. The invention therefore also relates to a kit of parts comprising a first part comprising the moderator composition and a second part comprising catalyst C and optional further parts comprising remaining components of the RMA composition and additives







DETAILED DESCRIPTION OF THE INVENTION

Reference is made to EP2764035 for detailed description of all components A, B C or D, their preparation, the amounts used in the RMA crosslinkable composition as well as for measurement methods and definitions and is hereby incorporated by reference.


Crosslinkable components can be monomers or polymers having 2 or more reactive groups for crosslinking. Polymers are considered to be compounds having at least 2 repeat units and typically have a weight average molecular weight (determined by GPC) of more than 250 gr/mol. The upper limit can be as high as 100000 or 200000 but for the application as coating resin the RMA crosslinkable compositions in view of viscosity are preferably between 250 (preferably 300, 400 or 500) and 5000 (preferably 4500 or 4000) gr/mol (GPC). The reactive components A and B can be pending, terminal or build into a polymer chain.


Monomeric compounds can also be used as crosslinkable components A or B. For example diethylmalonate has 2 C—H groups that can react and hence can be used as crosslinkable component A. Trimethylolpropane triacrylate (TMPTA) has only one repeat unit but 3 reactive C═C groups for crosslinking. These monomer components A or B or mixtures thereof can react to form an RMA crosslinked network and can also be used as reactive diluents together with polymeric crosslinkable components comprising A, B or both to replace organic solvent and reduce VOC of the RMA crosslinkable composition. Optionally also monomer components A or B can be included in the RMA composition that have only 1 RMA reactive C—H or C═C group.


Preferred crosslinkable components are A group containing polymers such as, for example, polyesters, polyurethanes, polyacrylates, epoxy resins, polyamides and polyvinyl resins containing groups A in the main chain, pendant or both. Component A preferably is malonate or acetoacetate. Components containing both malonate and acetoacetate groups in the same molecule are also suitable. Additionally, physical mixtures of malonate and acetoacetate group-containing components are suitable. The RMA reactive donor components A preferably predominantly originate are malonate groups, i.e. more than 50%, 75% or even 90% of reactive components A are malonate groups.


Reactive component B generally can be ethylenically unsaturated components in which the carbon-carbon double bond is activated by an electron-withdrawing group, e.g. a carbonyl group in the alpha-position. Suitable components B are known in the art, for example acryloyl esters, acrylamides, alternatively polyesters based upon 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. Most preferably, the component B is an unsaturated acryloyl functional component. Further preferences regarding the crosslinkable component comprising reactive component B are described in EP2764035.


Typically, the concentrations of the functional groups in components A and B, and their relative stoichiometry, are chosen such that good film properties following cure may be expected, with efficient use of these functional groups. Typically, stoichiometries C═C/C—H are chosen to be from 0.1 to 10, preferably 0.5 to 3, more preferably 0.7 to 3, most preferably 0.8/1.5. For this ratio, the N—H of component D is added to the C—H groups of component A.


The base catalyst C can in principle be any known catalyst suitable for catalyzing RMA reactions. Preferably, in view of achieving good pot-life in combination with low temperature curing, the cross-linking composition comprises a catalyst system C comprising a strong based blocked by a volatile acid which is activated by evaporation of this acid. A suitable catalyst system C comprises a strong based blocked by a carbon dioxide, or the blocked catalytic species are of formula ROCO2-, R being an optionally substituted alkyl, preferably C1-C4 radical or hydrogen, preferably the catalyst comprises a blocked base anion and a quaternary ammonium or phosphonium cation. It is preferred that the crosslinking catalyst is utilized in an amount ranging between 0.001 and 0.3 meq/g solids, preferably between 0.01 and 0.2 meq/g solids, more preferably between 0.02 and 0.1 meq/g solids (meq/g solids defined as mmoles base relative to the total dry weight of the crosslinkable composition, not counting particulate fillers or pigments). Further preferences regarding the crosslinkable component comprising reactive component C are described in EP2764035


The crosslinking composition can comprise a solvent, preferably an organic solvent. For CO2 deblocking catalyst systems, the inventors further found that advantages can be achieved in pot life if in the crosslinkable composition at least part of the solvent is a primary alcohol solvent. The solvent can be a mixture of a non-alcoholic solvent and an alcohol solvent.


In summary the crosslinkable composition according to the invention comprises between 5 and 95 wt % of a crosslinkable component, preferably said polymeric component, comprising reactive component A with at least 2 acidic protons C—H in activated methylene or methine, and between 5 and 95 wt % of a crosslinkable component, preferably a low molecular weight component, comprising reactive component B with at least 2 activated unsaturated groups (wt % relative to the total weight of the crosslinkable composition) and a catalyst system C that contains, or is able to generate a basic catalyst capable of activating the RMA reaction between components A and B, at levels of 0.0001 and 0.5 meq/g solid components, wherein component D is present in quantities of at least 10, 20, 30, 40 or maybe even 50 mole % relative to base catalyst component C or base generated by catalyst component C, and preferably less than 30 mole % of C—H active groups from component A optionally a sag control agent (SCA), optionally between 0.1 and 80 wt % of solvent (preferably less than 45 wt %), preferably containing at least 1 wt % of a primary alcohol, optionally at least 0.2 wt % water.


The crosslinkable composition typically and preferably is a 2K composition which is only formed shortly before the actual use, the invention also relates to a kit of parts for the manufacture of the composition according to the invention comprising a part 1 and part 2 wherein one part comprises the catalyst and the other does not comprise the catalyst C.


The composition of the invention comprises component D as an additive for the improvement of the open time of the crosslinkable composition and for the improvement of the appearance and hardness of the resulting cured composition, in particular a coating.


The N—H group in component D has a higher acidity than the C—H groups in component A, preferably being characterized in that component D has a pKa (defined in aqueous environment) of at least one unit, preferably two units, less than that of component A. Preferably the pKa of the N—H group in component D is lower than 13, preferable lower than 12, more preferably lower than 11 most preferably lower than 10. An excessive acidity may create problems with components in the catalyst system; therefore hence the pKa is preferably higher than 7, more preferably 8, more preferably higher than 8.5. The acidity difference assures that on application of the coating, component D is activated (deprotonated) preferentially over component A.


In the cross-linking composition, the N—H groups in component D are present in an amount corresponding to at least 10, 20, 30 40, or even 50 mole %, preferable at least 100 mole %, most preferably at least 150 mole % relative to the amount of base to be generated by catalyst C. The appropriate amount is very much determined by the acid base characteristics of component D relative to component A, and the reactivity of the corresponding anions relative to B, so may vary for different systems. Typically the N—H groups in component D are present in an amount corresponding to no more than 30 mole %, preferably no more than 20, more preferably no more than 10, most preferably no more than 5 mole % relative to C—H donor groups from component A. Preferably, the N—H functionality (number of groups per molecule) of component D is low, preferably less than 4, more preferably less than 2, most preferably it is 1.


The invention also relates to crosslinkable composition obtainable according to the invention. This composition can be used to prepare a paint composition.


EXAMPLES

The following is a description of certain embodiments of the invention, given by way of example only and with reference to the drawings.


Example 1

The malonate functional resin PE is a polyester resin which has been trans-esterified with diethylmalonate. This resin is prepared as follows: Into a reactor provided with a distilling column filed with Raschig rings were brought 382 g of neopentyl glycol, 262.8 g of hexahydrophthalic anhydride and 0.2 g of butyl stannoic acid. The mixture was polymerised at 240° C. under nitrogen to an acid value of 0.2 mg KOH/g. The mixture was cooled down to 130° C. and 355 g of diethylmalonate was added. The reaction mixture was heated to 170° C. and ethanol was removed under reduced pressure. When the viscosity at 100° C. reached 0.5 Pa·s the material was cooled down to 140° and 11.2 grams of solid succinimide were added. This mixture was stirred until all succinimide was dissolved. The resin was further cooled and diluted with butyl acetate to 85% solids. After 6 month of storage at 4° C. no precipitate was formed.


Examples of a paint formulation (i.e. a coating composition) are given below and are based on DTMPTA (di-trimethylolpropane tetra acrylate) as acryloyl acceptor (Miramer M410 mentioned in Table 1 is DTMPTA). The catalyst used is a mixture of tetra-butyl ammonium bicarbonate, diethylcarbonate and n-propanol with a concentration of 0.928 meq/g.


Example 2

Formulation 1 was prepared as described in Table 1, using the succinimide containing resin as described in example 1. After pre-dissolving the 1,2,4-triazole in n-propanol, only liquid materials needed to be mixed. The resulting paint was applied on a metal panel with a dry film thickness of 60 μm, giving the results as described in Table 2, showing that this paint performed similarly compared to paints containing succinimide dissolved in n-propanol and butyl acetate as solvent.


Example 3

Example 2 was repeated, but then after aging the succinimide modified resin for 6 months at room temperature. Similar results were obtained (Table 2).


Comparative Example 1

Formulation 2 was prepared according to Table 1. Here, 2.3 grams of succinimide was dissolved along with 5.1 grams of 1,2,4-triazole in 65.6 grams of n-propanol and 43.7 grams of butyl acetate using an ultrasonic bath for 30 minutes. The resulting paint was applied on a metal panel, giving the results as described in Table 2.


Comparative Example 2

Formulation 2 was prepared according to Table 1. Here, 2.3 grams of succinimide was dissolved along with 5.1 grams of 1,2,4-triazole in 65.6 grams of n-propanol and 43.7 grams of butyl acetate by magnetic stirring overnight. The resulting paint was applied on a metal panel, giving the results as described in Table 2.













TABLE 1







Component
Formulation 1
Formulation 2




















Part 1





Malonate functional PE
139.4
328.9



Succinimide containing
192.2
0



malonate functional PE



Pigment paste*
565.5
565.5



Pre-dissolve:



Succinimide
0
2.3



1,2,4-triazole
4.8
4.8



Butyl acetate
0
40.0



n-propanol
27.0
65.9



Subsequently add



Byk 310:315 1:4
2.8
2.8



Tinuvin 292
4.6
4.6



Part 2



catalyst
24.9
24.9



n-propanol
38.9



Dilute to spray



viscosity



Butyl acetate
55.3
15.7







*mix 32.0% of Miramer M410 with 65.1% of Kronos 2310 and 2.9% of disperbyk 163 and grind until the particle size is smaller than 10 μm


















TABLE 2







Ex. 2
Ex. 3
Comp. Ex. 1
Comp. Ex. 2




















Drying time (min)
40
39
43
37


Persoz hardness (60 μm,
167
175
173
170


after 1 day)


Gloss at 60°
90
90
90
90


Haze
9
10
11
9


VOC of Part 1 (g/L)
121
121
222
222









The examples illustrate the advantages of the invention:


1) There is no need any more for time consuming and elaborate dissolving of component D in solvents. Instead, 2 liquid resins can simply and quickly be mixed.


2) Because the solid component D does not need to be dissolved any more, less solvent is needed in the A-component of the paint (Part 1 in Table 1). Instead, the ratio of part 1 and part 2 can be adapted more flexibly. This is relevant for application where the mixing ratio between part 1 and part 2 can be critical. Alternatively, the paint could be diluted to higher spray viscosities. In this way, the invention contributes to decreasing the VOC of the paint. The invention therefore also relates to crosslinkable composition obtainable according to the process of the invention, in particular to low VOC compositions.


Thus, the invention has been described by reference to certain embodiments discussed above. It will be recognized that these embodiments are susceptible to various modifications and alternative forms well known to those of skill in the art. For example, the succinimide may be any component D, in particular any N—H acidic component having a low solubility in organic solvents, in particular triazoles or imides. Further modifications in addition to those described above may be made to the structures and techniques described herein without departing from the spirit and scope of the invention. Accordingly, although specific embodiments have been described, these are examples only and are not limiting upon the scope of the invention.

Claims
  • 1. A moderator composition comprising: one or more RMA crosslinkable polymer components comprising one or more reactive components A comprising at least 2 acidic protons C—H in activated methylene or methine groups, and dissolved therein one or more N—H groups containing reactivity moderating components D that are a Michael addition donor reactable with a reactive component B comprising activated unsaturated groups C═C under the action of a base catalyst C, said reactivity moderating components D having a melting temperature above 60° C. and less than 300 gr/ltr of an organic solvent,said moderator composition being obtained by a process wherein the one or more RMA crosslinkable polymer components comprising the reactive component A are synthesized at a temperature above the melting temperature of the components D and the components D are added directly after the synthesis of said polymer and dissolved therein before cooling to a temperature below the melting temperature of the components D.
  • 2. The moderator composition of claim 1, consisting essentially of the RMA crosslinkable polymer components comprising the reactive components A, wherein the reactive components A are malonate, comprising between 0.5 and 5 wt % of a dissolved succinimide or a triazole moderator D relative to the total amount of the RMA crosslinkable components comprising the reactive components A and the components D and comprising less than 300 gr/ltr of an organic solvent.
  • 3. The moderator composition of claim 1, wherein the one or more RMA crosslinkable polymer components comprise a polymer chosen from the group of polyesters, polyurethanes, polyacrylates, epoxy resins, polyamides and polyvinyl resins, which contains the reactive components A in the main chain, pendant, terminal, or combinations thereof.
  • 4. The moderator composition of claim 1, wherein the one or more RMA crosslinkable polymer components comprising the reactive components A have a weight average molecular weight Mw of at least 250 gr/mol.
  • 5. The moderator composition of claim 1, wherein the one or more RMA crosslinkable polymer components comprising the reactive components A have a weight average molecular weight Mw between 300 and 5000 gr/mol.
  • 6. The moderator composition of claim 1, wherein the one or more RMA crosslinkable polymer components comprise a polyester comprising the reactive components A which are synthesised by forming a polyester polymer using the reactive components A as monomer or by transesterification of polyester polymer with the reactive components A.
  • 7. The moderator composition of claim 1, wherein the reactive components A are malonate or acetoacetate.
  • 8. The moderator composition of claim 1, wherein the one or more RMA crosslinkable polymer components comprise both malonate and acetoacetate in the same molecule.
  • 9. The moderator composition of claim 8, wherein more than 50% of the reactive components A are malonates.
  • 10. The moderator composition of claim 1, wherein the N—H group in the components D has a pKa (defined in aqueous environment) of at least one unit less than that of the C—H groups in the reactive components A.
  • 11. The moderator composition of claim 1, wherein the pKa of the N—H group in the components D is lower than 13.
  • 12. The moderator composition of claim 1, wherein the components D comprise a molecule containing the N—H as part of a group —(C═O)—NH—(C═O)—, or of a group —NH—(O═S═O)— or a heterocycle in which the nitrogen of the N—H group is contained in a heterocyclic ring.
  • 13. The moderator composition of claim 1, wherein the components D are selected from the group consisting of a substituted or unsubstituted succinimide, phthalimide, glutarimide, hydantoin, triazole, pyrazole, imidazole, uracil, and mixtures thereof.
  • 14. The moderator composition of claim 1, wherein the components D are present in an amount between 0.1 and 10 wt %, relative to the total amount of the RMA crosslinkable polymer components comprising the reactive component A and the components D.
  • 15. The moderator composition of claim 1, wherein the components D are present in such amount that the amount of N—H groups in the components D is no more than 30 mole %, relative to C—H donor groups from the reactive components A in the RMA crosslinkable polymer components.
  • 16. The moderator composition of claim 1, comprising less than 200 gr/ltr of an organic solvent.
  • 17. The moderator composition of claim 1, comprising less than 175 gr/ltr of an organic solvent.
  • 18. A kit of parts comprising a first part comprising the moderator composition of claim 1 and a second part comprising a base catalyst C.
Priority Claims (1)
Number Date Country Kind
2014666 Apr 2015 NL national
US Referenced Citations (54)
Number Name Date Kind
2635100 Werntz Apr 1953 A
2759913 Hulse et al. Aug 1956 A
4217396 Heckles Aug 1980 A
4223072 Baney et al. Sep 1980 A
4408018 Bartman et al. Oct 1983 A
4529487 Hsu et al. Jul 1985 A
4602061 Akkerman Jul 1986 A
4749728 Craun et al. Jun 1988 A
4851294 Buter et al. Jul 1989 A
4871822 Brindöpke et al. Oct 1989 A
4938980 Arciszewski et al. Jul 1990 A
5017649 Clemens May 1991 A
5039720 Saatweber et al. Aug 1991 A
5084536 Brindöpke et al. Jan 1992 A
5959028 Brinkhuis Sep 1999 A
5973082 Elmore Oct 1999 A
5990224 Raynolds et al. Nov 1999 A
6201048 Raynolds et al. Mar 2001 B1
6262169 Helmer et al. Jul 2001 B1
6265029 Lewis Jul 2001 B1
6706414 Dammann et al. Mar 2004 B1
6878845 Sheridan Apr 2005 B2
6989459 Walker Jan 2006 B2
7524435 Bernhard Apr 2009 B2
7851530 Brinkhuis et al. Dec 2010 B2
8013068 Beckley et al. Sep 2011 B2
8124688 Meijer et al. Feb 2012 B2
8569440 Spyrou et al. Oct 2013 B2
8829151 Meijer et al. Sep 2014 B2
8962725 Brinkhuis et al. Feb 2015 B2
9181452 Brinkhuis Nov 2015 B2
9181453 Brinkhuis Nov 2015 B2
9260626 Brinkhuis Feb 2016 B2
9284423 Brinkhuis Mar 2016 B2
9534081 Brinkhuis Jan 2017 B2
9587138 Brinkhuis et al. Mar 2017 B2
9834701 Brinkhuis et al. Dec 2017 B2
20030023108 E. Walker Jan 2003 A1
20030195305 Kuo et al. Oct 2003 A1
20040072979 Sheridan et al. Apr 2004 A1
20050137275 Nefzger et al. Jun 2005 A1
20050143575 Bernard Jun 2005 A1
20060078742 Kauffman et al. Apr 2006 A1
20090143528 Mestach et al. Jun 2009 A1
20090226729 Niimoto et al. Sep 2009 A1
20110003937 Kontani Jan 2011 A1
20110251338 Kim et al. Oct 2011 A1
20130053505 Brinkhuis et al. Feb 2013 A1
20130210986 Brinkhuis et al. Aug 2013 A1
20130317156 Yu Nov 2013 A1
20140088233 Kann Mar 2014 A1
20140221542 Brinkhuis et al. Aug 2014 A1
20140228507 Brinkhuis et al. Aug 2014 A1
20160115344 Brinkhuis et al. Apr 2016 A1
Foreign Referenced Citations (141)
Number Date Country
86101015 Aug 1986 CN
1309683 Aug 2001 CN
1637031 Jul 2005 CN
1723242 Jan 2006 CN
1757656 Apr 2006 CN
1816597 Aug 2006 CN
1910234 Feb 2007 CN
1964997 May 2007 CN
1976972 Jun 2007 CN
101012291 Jul 2007 CN
101103060 Jan 2008 CN
101107289 Jan 2008 CN
101213230 Jul 2008 CN
101268149 Sep 2008 CN
101869844 Oct 2010 CN
101879457 Nov 2010 CN
102834436 Dec 2012 CN
102834437 Dec 2012 CN
103562328 Feb 2014 CN
103974999 Aug 2014 CN
835809 Apr 1952 DE
3041223 May 1981 DE
0192304 Aug 1986 EP
0198519 Oct 1986 EP
227454 Jul 1987 EP
0161697 Mar 1988 EP
0310011 Sep 1988 EP
0326723 Aug 1989 EP
0448154 Sep 1991 EP
0501223 Sep 1992 EP
0651023 May 1995 EP
0808860 Nov 1997 EP
1541606 Dec 2004 EP
1593727 Nov 2005 EP
1761582 Jan 2006 EP
1513900 Feb 2006 EP
1640388 Mar 2006 EP
1838747 Jul 2006 EP
2072520 Jun 2009 EP
1813630 Mar 2010 EP
2374836 Apr 2010 EP
1641887 Oct 2010 EP
1902081 Dec 2010 EP
2374836 Oct 2011 EP
1641888 Feb 2012 EP
2556108 Jul 2014 EP
2764035 Aug 2014 EP
3085748 Oct 2016 EP
0227454 Jul 1987 ER
1596638 Aug 1981 GB
2093472 Sep 1982 GB
2010879 Jul 1997 GB
2405149 Feb 2005 GB
53141369 Dec 1978 JP
H01121376 May 1986 JP
62-223204 Oct 1987 JP
01204919 Aug 1989 JP
8501124 Feb 1996 JP
8319437 Dec 1996 JP
H1045993 Feb 1998 JP
10330690 Dec 1998 JP
2000119353 Apr 2000 JP
2001505948 May 2001 JP
2001-207631 Aug 2001 JP
2001516787 Oct 2001 JP
2001516789 Oct 2001 JP
2002514673 May 2002 JP
2002285100 Oct 2002 JP
2003522817 Jul 2003 JP
2004018859 Jan 2004 JP
2004211090 Jul 2004 JP
2005-034687 Feb 2005 JP
2005-505653 Feb 2005 JP
2006-089743 Apr 2006 JP
2006525402 Nov 2006 JP
2011-099744 May 2011 JP
2011-208371 Oct 2011 JP
2012505926 Mar 2012 JP
2013-091982 May 2013 JP
2013-108339 Jun 2013 JP
2013528670 Jul 2013 JP
2014533948 Dec 2014 JP
2015120769 Jul 2015 JP
5910952 Apr 2016 JP
100232793 Dec 1999 KR
8203502 Apr 1984 NL
2275403 Apr 2006 RU
2346016 Feb 2009 RU
2415167 Mar 2011 RU
2484113 Jun 2013 RU
2532909 Nov 2014 RU
11201401321 Apr 2013 SG
200613500 May 2006 TW
94017148 Aug 1994 WO
9641833 Dec 1996 WO
9825989 Jun 1998 WO
9914275 Mar 1999 WO
9914278 Mar 1999 WO
9914279 Mar 1999 WO
9958608 Nov 1999 WO
0004106 Jan 2000 WO
0112708 Feb 2001 WO
02053613 Jul 2002 WO
2003031502 Apr 2003 WO
03089479 Oct 2003 WO
2004035632 Apr 2004 WO
2004099329 Nov 2004 WO
2005048866 Jun 2005 WO
2005104694 Nov 2005 WO
2006003044 Jan 2006 WO
2006074895 Jul 2006 WO
2006075000 Jul 2006 WO
2006081079 Aug 2006 WO
2007000335 Jan 2007 WO
2007002328 Jan 2007 WO
2007035255 Mar 2007 WO
2008070022 Jun 2008 WO
2008157468 Dec 2008 WO
2010046240 Apr 2010 WO
2011124663 Oct 2011 WO
2011124664 Oct 2011 WO
2011124665 Oct 2011 WO
2012002095 Jan 2012 WO
2012175622 Dec 2012 WO
WO 2013050624 Jan 2013 WO
2013050574 Apr 2013 WO
2013050622 Apr 2013 WO
2013050623 Apr 2013 WO
2013071012 May 2013 WO
2014125589 Aug 2014 WO
2005021672 Oct 2014 WO
2014166880 Oct 2014 WO
2016054367 Apr 2016 WO
2016166334 Oct 2016 WO
2016166361 Oct 2016 WO
2016166365 Oct 2016 WO
2016166369 Oct 2016 WO
2016166371 Oct 2016 WO
2016166381 Oct 2016 WO
2016166382 Oct 2016 WO
2019145472 Aug 2019 WO
Non-Patent Literature Citations (10)
Entry
Brinkhuis, R.; Schutyser, J.; Thys, F.; De Wolf, E.; Buser, T.; Kalis, J.; Magnus, N.; Van Wijk, F. Taming the Michael Addition Reaction. European Coatings Journal 2015, 34-40. (Year: 2015).
AZO Materials, “A_Guide_to_Silane_Solutions_Adhesives”, Sep. 7, 2012, Internet Article, https://www.azom.com/article.aspx?ArticleID=6777.
T. Jung et al.—Farbe und Lacke Oct. 2003.
International Search Report of PCT/EP2012/069904.
Braun, D. et al., Polymer Synthesis: Theory and Practice, 4th ed., 2005, pp. 64-66.
Noomen, Arie: “Applications of Michael addition chemistry in coatings technology”, Progress in Organic Coatings, 32 (1997), pp. 137-142.
Krishnadas, Shashikiran et al., “Rapid Setting Epoxy Primer System with the Addition of Blocked Catalyst”, Indian Journal of Advances in Chemical Science 2 (2014), pp. 55-60.
Lösungen, Römpp online 4.0, Mar. 1, 2002.
“The Basics of Airless Spraying, Information on Basic Components, Spray Techniques and Safety”, 2014.
“ETPPAAc Solutions Ethyltriphenylphosphonium Acid Acetate”, Apr. 20, 2007, pp. 1-2.
Related Publications (1)
Number Date Country
20200347263 A1 Nov 2020 US
Divisions (1)
Number Date Country
Parent 15563952 US
Child 16934086 US