WO2016166397A1

WO2016166397A1 - Composition for the cross-linking of an amine with a vinyl compound α,β- conjugated to a carbonyl group of esters, and subsequent polymerisation of the vinyl compound and corresponding methods

Info

Publication number: WO2016166397A1
Application number: PCT/ES2016/070251
Authority: WO
Inventors: Maria Àngels SERRA ALBET; Xavier Fernández Francos; Xavier Ramis Juan; Josep Maria MORANCHO LLENA
Original assignee: Universitat Politècnica De Catalunya; Universitat Rovira I Virgili
Priority date: 2015-04-17
Filing date: 2016-04-13
Publication date: 2016-10-20
Also published as: ES2538180B2; ES2538180A1

Abstract

The invention relates to a composition for the cross-linking of an amine with a vinyl compound α,β-conjugated to a carbonyl group of esters, and subsequent polymerisation of the vinyl compound, comprising: a) an amine having two or more N-H bonds; b) a vinyl compound, of general formula (I), containing a minimum of two double bonds α,β-conjugated to a carbonyl group of esters - formula (I) - where Y and Z are each independently a hydrogen, aliphatic or aromatic groups or more complex groups, and where X is an aliphatic or aromatic group or a more complex group; and c) a radical photoinitiator or a radical thermal initiator, suitable for starting the cross-linking of said double bonds excess α,β-conjugated to a carbonyl group of esters.

Description

COMPOSITION FOR THE INTERRUPTING OF AN AMINA WITH AN α, β-CONNECTED VINYL COMPOUND TO A CARBONYL ESTER GROUP AND POSTERIOR POLYMERIZATION OF THE VINYL COMPOUND AND CORRESPONDING PROCEDURES

DESCRIPTION

FIELD OF THE INVENTION

The present invention relates to cross-curable compositions by dual curing, in which the first step consists of a Michael addition of an amine to an α, β-conjugated vinyl compound to a carbonyl ester group and the second the polymerization of the same vinyl compound or of another vinyl compound. The invention also relates to a process for obtaining said composition.

The invention also relates to a process for coating substrates and the corresponding substrate, and a process for manufacturing parts by molding and the corresponding part. These procedures consist of bringing the components into contact and activating each of the curing stages, either thermally or by ultraviolet radiation, depending on the components that form the desired final composition and properties. The materials prepared from the compositions of the present invention have properties ranging from those of non-gelled materials to those of highly crosslinked materials, depending on the components of the composition, their functionality and their relative proportions, on the Cure conditions and whether the two stages of cure have been performed or only the first. Also, the materials prepared after the first stage of curing can be stored, for long periods of time without substantially modifying their properties, before the second stage of curing is performed. The present invention has application in all the usual fields of thermosetting materials, although its application in the field of thermosensitive substrate coatings is of particular interest.

BACKGROUND OF THE INVENTION

Unsaturated monomers and oligomers are used in a wide range of applications such as adhesives, matrices for composites, varnishes, surface coatings, dental or structural repair systems, systems of Photo printing and holography. After a cross-linking process, called curing, these materials reach their maximum properties, which depend fundamentally on their chemical structure and the degree of cross-linking achieved. The process of crosslinking vinyl systems generally proceeds according to a radical type mechanism, which can be initiated thermally or by ultraviolet radiation. In the first case, a radical initiator, peroxide, hydroperoxide or azo compound is required, which decomposes producing a radical that initiates polymerization. If you also want the process to take place at room temperature, a promoter should be added that reduces the initiator by forming a radical that will also start the process. As promoters, aromatic tertiary amines or cobalt salts are commonly used. In the case of photoinduced curing, a photoinitiator is needed that generates free radicals during irradiation. There are two families of photoinitiators, those of type I and those of type II, which require to be active of a sensitizer that acts as an electron donor and active species. As type I photoinitiators, 2,2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclo exylphenyl ketone and its derivatives are usually used. Benzophenone is one of the most commonly used type II photoinitiators. A tertiary amine can be used as a sensitizer, which in addition to reacting easily with benzophenone producing an active species, retards the effect of oxygen inhibition on polymerization. While thermal curing requires a high energy consumption, the photo curing takes place at room temperature with low energy consumption, although in many cases the photo-cured materials must be postured to devitrify and achieve their final properties. If the material is not fully reacted, it can modify its properties during its useful life and even change its composition, if there is free monomer without crosslinking that can be volatile.

One of the problems that vinyl systems can present is the need to use solvents. In this case the solvent must be removed during its application, with the consequent energy expenditure and volatile generation. Likewise, the use of cross-linking agents (monomers) of low molecular weight and relatively volatile, styrene type, can present toxicity problems both during its application and during its useful life if it is free without being part of the lattice.

Radical systems present a serious problem that lies in the inhibition that exerts oxygen on the curing process. The oxygen in the air can trap free radicals, generating new non-active radicals, paralyzing or slowing down the curing process. In this case the material may be partially cured or with a certain surface tack, in the area where oxygen may have been more active. Different alternatives are commonly used to solve or minimize this problem, such as increasing the time and intensity of irradiation, working in an inert atmosphere, using high amounts of photoinitiator or adding oxygen scavengers / sequestrants and / or photosensitizers. Most of these alternatives increase the cost and complexity of the formulation and in some cases, such as working in an inert atmosphere, it is a difficult solution to implement in some industrial applications.

Although the processing and curing of many industrial formulations takes place in a single stage, for certain applications such as microelectronics, semiconductors, repair materials or assembly of printed circuit boards (PCBs), where the thermosetting material acts as an adhesive, it can It is useful for curing to take place in two stages. This type of curing, known as dual curing, allows that after a first stage of pre-curing the material can be stored stably, deformed if necessary or simply that the handling is comfortable, before the material reaches its final properties in a second stage of curing, by application of pressure, temperature or any other form of activation. After the first stage the material must be chemically inactive, maintaining a certain latency until the second curing stage is activated. Dual thermosets are typically prepared by two different chemical processes, often one of them photochemical and the other thermal, although this is not essential if the chemistry of each of the processes and the necessary starting materials and curing agents are properly chosen. . Click reactions that have been widely applied in macromolecular engineering can be used in the preparation of thermosets with controlled stoichiometry obtained by dual curing. These reactions are characterized by being fast, highly selective, quantitative, orthogonal and insensitive to oxygen or water. The term orthogonal refers to the fact that two components can react specifically for a certain functional group with high performance in the presence of a large number of other functional groups without affecting them. In this way the reaction is perfectly controlled and the Stoichiometry and reaction conditions allow conversions and defined architectures to be reached that do not depend on processing variables, so the final material is fully reproducible. Within the click reactions is the aza-Michael addition of a primary or secondary amine to an α, β-conjugated vinyl compound with a carbonyl group, which will be used in the first stage of curing of the present invention.

In general, Michael's reaction consists in the catalytic addition of a nucleophile (Michael donor) to an α, β-unsaturated carbonyl compound (Michael acceptor). In the particular case of the aza-Michael addition, the donor group would be the secondary or primary amine. In some systems it has been seen that this reaction proceeds efficiently without the need for a base and in others that the addition of certain Lewis acids also catalyzes it. Hyperbranched polymers are being used recently as toughness modifiers and as crosslinking agents for thermostable systems. The relative ease of its synthesis together with the existence of an increasing amount of commercial hyperbranched polymers has increased its use. The interest of these polymers lies primarily in their low viscosity compared to their linear counterparts, in their great structural versatility, in their good solubility and in the large number of reactive or non-reactive terminal groups. Its usefulness as a curing agent only requires that some of the terminal functional groups can react with the system to crosslink. In the case of the aza-Michael additions of amines to vinyl systems, it is only necessary that the hyperbranched contain reactive terminal amino groups. It is thought that hyperbranched polyethyleneimines containing primary, secondary and tertiary amines would be potential candidates to form Michael adducts with acrylates, with the advantage that tertiary amines could act simultaneously as bases, accelerating the addition, and as oxygen sequestering agents, diminishing the effect of inhibition that this has on the radical cure.

In US Patent 3,844,916 the use of the aza-Michael addition to obtain adducts containing tertiary amines and acrylate groups is described, which subsequently, in a completely independent second stage, can be polymerizable by UV radiation. The adducts are prepared by the progressive addition of an amine containing a single hydrogen atom to the low acrylate reflux conditions and constant agitation. The materials obtained do not have mechanical consistency since they are not gelled. The polymerization of these adducts is carried out in a second differentiated stage by adding a photoinitiator to the previous mixture after the addition reaction (that is, with the adducts already formed), in some cases also in the presence of a solvent, and radiating The sample with ultraviolet light.

However, the present inventors, although using the aza-Michael addition and the polymerization of vinyl compounds in their invention, the starting materials, the materials obtained and the process both to obtain the compositions and the one used in the cross-linking thereof, they are completely different than those described in US 3,844,916. As will be appreciated, in the present invention the formulations are prepared in one step (so that the initial composition, before the addition reaction begins, already includes the radical initiator), although curing is done in two steps (dual cure), under well differentiated reaction conditions. The materials at the end of the first curing stage are stable and can be stored for a long time. Aza-Michael adducts are formed in situ within the curable composition. The materials at the end of the first curing stage may or may not be gelled, depending on the functionality of the reactive monomers / oligomers used and the relative amount thereof, depending on the application to be performed. The amines used can be linear or hyperbranched and the vinyl compounds used are not limited only to acrylates, although these vinyl compounds must be activated by a conjugated unsaturated functional group. The aza-Michael addition can proceed completely at room temperature or at a higher temperature, without catalyst or catalyzed by a base or by a Lewis acid. The second stage of curing can be activated by UV radiation or thermally. The materials at the end of the second curing stage can be fully reacted without energy input, if both curing stages are performed at room temperature. As a base tertiary amines can be used, which also act as oxygen sequestrants.

These amines can be added to the composition, generated in situ or form part of the starting materials. Curable compositions may be free of volatile organic compounds and solvents. Therefore, in view of the foregoing, there is a need in the state of the art to provide new compositions and a new process for obtaining vinyl materials, formulated in a single step but crosslinked by curing. dual, that can be stored or handled after the first stage of curing, without the mentioned disadvantages related to oxygen inhibition, solvent use and high energy cost. The versatility of the new compositions, which lead to materials with diverse properties and wide industrial applications, is also a demand of the prior art.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates in one aspect to a composition, hereinafter composition of the invention, for the cross-linking of an amine with an α, β-vinyl compound conjugated to a carbonyl ester group and subsequent polymerization of the vinyl compound, characterized in that it comprises at least: a) a non-aromatic amine or non-aromatic polyamine, with at least two NH bonds, b) a vinyl compound, of general formula (I), containing at least two double α, β-conjugated double bonds to a group ester carbonyl

where Y and Z are each independently a hydrogen, aliphatic or aromatic moieties or more complex groups, and where X is an aliphatic or aromatic moiety or a more complex group, and c) a radical photoinitiator or a radical thermal initiator, suitable for initiating crosslinking said double α, β-conjugated bonds to an excess ester carbonyl group. Indeed, one of the advantages of the composition according to the invention is that the composition, once formed, already has all the necessary components as to perform dual curing, that is, a first curing stage of component a) with component b) and a second curing stage in which the α, β-conjugated double bonds are reacted to a carbonyl ester group that remain unreacted after the first cure. The inclusion, from the beginning, of component c) allows a plurality of applications of the composition according to the invention.

In general, in the present description and claims, it is understood that a polyamine is any compound that comprises more than one amino group, and may or may not have a polymeric character.

In general, any non-aromatic amine or polyamine are viable, the only limitation having at least two N-H bonds, necessary for polymerization. Likewise, the vinyl compound b) of formula (I) can also be very diverse, and the only really relevant requirement is that it contains at least two double α-β-conjugated bonds to a carbonyl ester group, necessary for its polymerization. Depending on the components a) and b) chosen, a plurality of alternatives will be obtained, all of which share the basic advantages of the invention, such as the fact that the composition already includes, at the outset, all the essential components for curing. dual.

It should be taken into account that if low-boiling products are used, some of them may evaporate during curing, the original composition of the formulation being modified and defects may appear. Although not essential, a selection of materials that prevent evaporation is recommended, according to the selected cure time and temperature.

Preferably, the α, β-conjugated double bonds to a carbonyl ester group are in excess of the NH bonds. Strictly speaking it is not necessary that there is an excess of double α, β-conjugated bonds to a carbonyl ester group so that there can be a dual cure, since, in real conditions, it is possible that, even if NH bonds remain unreacted, these do not react with the α, β-conjugated double bonds to an unreacted carbonyl ester group for various reasons. Therefore, the second stage of dual curing can take place even with unreacted NH bonds. However, it is advantageous that there are double α, β- bonds conjugated to an excess ester carbonyl group to ensure that the second stage of cure takes place in a significant proportion.

Preferably Y and Z are each independently a hydrogen, a C1-C20 alkyl radical, linear or branched, substituted or not, a C2-C20 alkenyl or alkynyl radical, linear or branched, substituted or not, a C4- cycloalkyl or cycloalkenyl radical C20, substituted or not, an aryl radical, which may also have alkyl, halogen or other substituents directly attached to the aromatic rings. Advantageously the group X is a C2-C100 alkyl radical, linear or branched, substituted or not, a C2-C40 alkenyl or alkynyl radical, linear or branched, substituted or not, a C4-C20 cycloalkyl or cycloalkenyl radical, substituted or not, an aryl radical, which may also have alkyl, halogen or other substituents directly attached to the aromatic rings, and X may also be linked to several α, β-conjugated ester groups.

Preferably n varies between 2 and 50.

Advantageously component a), that is, the amine or polyamine, is a polyamine with at least three N-H bonds. These three N-H bonds can be provided by primary, secondary amines or combinations of both.

A preferred solution is when the amine or polyamine has between 3 and 5 NH groups, the vinyl compound contains between 2 and 6 α, β-conjugated double bonds to a carbonyl ester group and, advantageously, the ratio between NH and double groups α, β-conjugated bonds to a carbonyl ester group is between 0.05 and 1.

Another preferred solution is when the amine or polyamine has between 6 and 20 NH groups, the vinyl compound contains between 2 and 6 double bonds α, β-conjugated to a carbonyl ester group and, advantageously, the ratio between NH and double groups α, β-conjugated bonds to a carbonyl ester group is between 0.01 and 1.

Particularly advantageous solutions are when Z and Y are hydrogens, that is, when the compound (I) is an acrylate, or when they are respectively a hydrogen and a methyl group, that is, when the compound (I) is a methacrylate. Other particularly advantageous solutions are available when component b) is a mixture of acrylates, a mixture of methacrylates or a mixture of acrylates and methacrylates in any proportion. In this sense, any of the following alternatives are especially interesting:

- component b) is a mixture of bisphenol A-glycerolate diacrylate and 1,6-hexanediol diacrylate. - component b) is a mixture of bisphenol A-glycerolate diacrylate and trimethylolpropane triacrylate.

- component b) is a mixture of bisphenol A-glycerolate diacrylate and triethylene glycol trimethylolpropane dimethacrylate

- component b) is a mixture of bisphenol A-glycerolate dimethacrylate and 1,6-hexanediol diacrylate.

As regards component a), it is particularly advantageous if it is a polyamine of molecular weight between 400 and 25,000. It is also advantageous that it is:

- a polyetheramine,

- a linear or branched poly (ethylenamine), or

- a simple aliphatic amine of molecular weight between 60 and 2,000.

Polyamines marketed under the trade names Jeffamine D-230 and Lupasol FW are two particularly interesting alternatives.

A particularly preferred solution is that the amine or polyamine is diethylenetriamine.

Component c) of the composition is preferably any radical photoinitiator, both type I and type II. In the case of using a type II photoinitiator in the present invention, the advantage is obtained that no sensitizers will be required since the tertiary amines generated in the first stage of curing they react with the type II photoinitiator generating an active species that initiates the second stage photo curing. It is particularly advantageous for the radical photoinitiator to be 2,2-dimethoxy-2-phenyl acetophenone or benzophenone. If it is desired to accelerate the first stage of curing, it is also possible to add both Lewis bases and acids, which are preferably 1,5-diazabicyclo [4.3.0] non-5- ene or ytterbium triflate, or increase the temperature, although The inventors have observed that the aza-Michael addition of an amine to an α, β-vinyl compound conjugated to a carbonyl ester group is relatively little dependent on temperature, curing slightly accelerating but not the degree of reaction achieved by increasing the temperature. Heating during the first stage, although it can be done, does not seem like a preferred option, since it implies a higher energy cost.

Although the preparation of materials at room temperature is preferably considered, for certain applications, if the second stage of curing is required by thermal activation, a thermal radical initiator should be added to the composition, which is preferably methyl ethyl ketone peroxide, and , if it is also desired that the temperature is not very high, a promoter, which is preferably cobalt octoate.

The composition of the invention may optionally contain at least one common adjuvant additive in formulations with unsaturated monomers and oligomers, such as pigments, dyes, plasticizers, reinforcing and non-reinforcing fillers, etc.

A subject of the invention is also a process for obtaining a composition for cross-linking an amine with an α, β-vinyl compound conjugated to a carbonyl ester group and subsequent polymerization of the excess vinyl compound according to the invention, which It comprises the steps of: (i) dissolving the radical photoinitiator or the radical thermal initiator in component b) of the formulation by stirring at room temperature, (ii) adding component a) to the previous mixture, and maintaining the resulting mixture at vacuum for at least 15 minutes at room temperature. Preferably the vacuum is less than 1 00 mm Hg.

In a possible alternative, prior to step (ii), it is dissolved in component a) a base or a Lewis acid.

In another possible alternative, a radical thermal initiator is used and a promoter is added in component b).

A subject of the invention is also a method of coating a substrate characterized in that it comprises the steps of:

I) preparation of a composition according to the invention,

II) application of the composition on a substrate

III) first stage of curing by reaction between compound a) and compound b)

IV) second stage of curing by activating the photoinitiator by ultraviolet radiation or the thermal initiator by means of heat input and the reaction of the remaining α, β-conjugated double bonds to a carbonyl ester group with each other.

In a preferred alternative the composition gels during the first curing stage, although in certain applications it may be advantageous for the composition to gel during the second curing stage. Another object of the invention is a substrate coated with a crosslinked material obtainable by curing a composition following the above procedure.

Additionally, the object of the invention is a method of manufacturing a part by molding characterized in that it comprises the steps of:

I) preparation of a composition according to the invention,

II) filling a mold with composition III) first stage of curing by the reaction between compound a) and compound b) IV) second stage of curing by activating said photoinitiator by ultraviolet radiation or said thermal initiator by means of heat input and the reaction of the remaining α, β-conjugated double bonds to a carbonyl ester group with each other.

As in the previous case, an advantageous alternative is when the composition gels during the first curing stage, although in some cases it may be advantageous for the composition to gel during the second curing stage. Finally, the object of the invention is also a piece of a crosslinked material obtainable by curing a composition following the above procedure.

The inventors have verified that changes in these procedures, in terms of preparation time and temperature, do not alter the final properties of the materials obtained. Although in some applications, the first stage of curing can begin during the preparation of the composition, if the time used is not excessively long and the temperature is not very high, as long as the material does not gel, the materials can be prepared without any difficulty.

Primers can be made on any type of substrate, although it may have special interest when the substrates are heat sensitive, since it is not necessary to heat the samples to reach their final properties. As for the molds, these can be of any material, although when the second stage is photoinduced they must allow the total or partial passage of UV radiation, being able to be for example glass, quartz or some plastic material such as polypropylene and the polyethylene that let some of the radiation pass.

When it is desired to perform the second stage of curing by thermal initiation, instead of a photoinitiator, a thermal initiator and, if desired, a promoter must be added. If a promoter is added, it is advisable to always work at low temperatures and short times, to avoid starting the second stage of curing during the preparation of the mixture or even during the first stage of curing. Special care must be taken if it is required to store the formulation at the end of the first stage. In order to know the optimum amount of promoter so that there are no prepolymerizations, previous tests can be carried out in a calorimeter or in an oven to determine at what temperature and / or at what time the radical curing of the vinyl component

If it is desired to accelerate the first stage of curing by Lewis bases or acids, these are preferably dissolved in the amine, although it is possible to dissolve them in component b) of the invention, depending on the miscibility of the components.

In another aspect the invention relates to a process for cross-linking an amine to an α, β-conjugated vinyl ester compound by dual curing and subsequent polymerization of the excess vinyl compound, hereinafter process of the invention, which It comprises the use of the composition of the invention as defined above.

The process comprises curing said composition by two stages, the first stage is preferably performed at room temperature, although any other temperature is possible. The time required to perform this stage is variable and varies depending on the formulation of the composition of the invention and the curing temperature. The inventors have observed that the temperature of 35 ^and C (is selected as ambient 35 temperature ^and C for the results to be valid even in hot climates), in three hours most formulations have completed the addition aza-Michael and If this is not the case, the progress of this is already very slow. It has also been seen that most of this process takes place during the first 45 minutes, so it is possible to adjust the cure time more if it is considered convenient. The inventors have also observed that the properties of the product at the end of the first curing stage depend fundamentally on the formulation of the starting composition, and little on the curing conditions (time, temperature), as long as the curing is close to full.

Although in the preferred embodiment the first stage is carried out at room temperature for three hours and without accelerators, in particular embodiments and by way of comparison the first stage of curing is carried out for 24 hours and in some cases they have been used as accelerators 1, 5 -diazabicyclo [4.3.0] non-5-eno, or ytterbium triflate, acting respectively as a base and as Lewis acid. The second stage of curing, homopolymerization of excess vinyl compound, is preferably carried out by photoinduced curing by UV radiation. As a photoinitiator, any type of photoinitiator can be used, both type I and Type II, although in the latter case it is not necessary to add any sensitizers. The amount of photoinitiator can be any, although very low amounts can lead to poorly cured materials or the need to use very high irradiation times and intensities. On the contrary, excessively high amounts can lead to materials with a lower glass transition temperature. During the realization of the present invention it has been observed that between 0.5% and 3% (expressed in mass with respect to total mass that can react in the second stage of curing) of initiator are sufficient for the curing to be practically complete and final properties independent of the amount used. In general, any type of lamp, both monochromatic and polychromatic, can be used, provided they emit within the emission range in which the photoinitiator is activated. The time and intensity of the irradiation used can be practically any, since the reaction proceeds very quickly and efficiently. In general, it has been observed that one minute of irradiation with a polychromatic Hg-Xe lamp of intensity between 1 0 and 20 mW / cm ² is sufficient for the material to reach its final properties. In general, trials with longer times have not shown significant changes in the degree of progress of the reaction. With a monochromatic lamp of 365 nm wavelength of intensity 4mW / cm ² the ultimate cure is achieved by radiating 8 J / cm ² . To achieve homogeneous properties, especially in thick samples, it is better to divide the irradiation time between the two sides of the piece. If you want to adjust the irradiation time necessary for a complete cure to a minimum, each particular system should be studied, taking into account the type of lamp to be used, the composition, the photoinitiator used and the thickness of the sample.

If desired, a high temperature post cure can be performed to help complete the cure. The increase in cure is so insignificant that it seems reasonable not to do so, since it involves a higher energy cost and a risk to the thermal stability of the materials.

If desired, the second stage of thermal curing can be performed. In this case, instead of a photoinitiator, a peroxide or hydroperoxide type thermal initiator must be used. In general, these systems require working at high temperatures above 80 ^e C from which the initiator decomposes. The inventors have observed that although any thermal radical initiator serves, some of the benzoyl peroxide type, despite allowing almost complete cure, lead to materials that exhibit defects due to the formation of carbon dioxide. By On the contrary, if methyl ethyl ketone peroxide type initiators are used, almost completely cured materials are obtained without apparent defects. If the reaction is to be accelerated or the cure temperature decreased, a cobalt octoate type promoter should also be added in the case of methyl ketone peroxide or a tertiary amine type A /, A / -dimethylaniline in the case of benzoyl peroxide. Curing times, and amounts of initiator and promoter must be adjusted in each case depending on the cure temperature.

The process of the invention does not require that dual cure be performed in the absence of oxygen, and can be done in the air without the need for any prevention. The materials are always very close to complete curing and without any superficial tack. The tertiary amino groups of compound a) (if any) together with the tertiary formed during the first stage of curing (aza-Michael addition), minimize the effect of oxygen inhibition on the radical polymerization of excess vinyl groups.

The materials obtained can be stored indefinitely after the first stage of curing, without their properties changing. Only when the sample is irradiated can the second stage of cure begin. In some formulations where the first stage of cure has not been complete, during storage this stage tends to complete slowly but in no case does the second stage begin.

To describe the embodiments of the present invention, the inventors have established the following nomenclature, in terms of the relative amount of the two dual cure stages. Formulations 1/1, 1/2, 1/4 and 1/8 are understood to be those in which the first stage (aza-Michael addition of the amine to the conjugated double bond) represents 100%, 50%, 25% and 12.5% with respect to total cure. The rest up to 100% would correspond to the second stage of curing (homopolymerization of excess vinyl groups) and for the formulations 1/1, 1/2, 1 A and 1/8 equivalent respectively to 0%, 50%, 75 % and 87.5% of total cure.

The inventors have observed that materials with variable compositions can be prepared, ranging from those in which there is only the first curing stage when the formulations are prepared with stoichiometric amounts of amino groups relative to vinyl groups, to formulations where only the second stage of curing (homopolymerization of excess vinyl compound), when not It includes amine in the formulation. Depending on the components used in the formulation and the relative quantity of the two stages, the material has completely different properties. In particular embodiments, using as component b) mixtures of acrylates formed by bisphenol A-glycerolate diacrylate (BGDA) and 1,6-hexanediol diacrylate (HDDA) with a 25/75 weight ratio and as a polyetheramine amine, the Jeffamine D-230, materials with T _g and relaxed modules (50 ^e C above T _g ) have been obtained after the two curing stages ranging from 102 ^e C and 164 MPa for the formulation where there is only homopolymerization of acrylates up to -4 ^e C and 15 MPa when there is only Michael addition. Intermediate formulations with 50%, 25% and 12.5% Michael addition and the rest up to 100% acrylate homopolymerization have _Tg s and intermediate relaxed modules between those of the extreme compositions and proportional to the relative amount of each Curing stage All formulations containing Jeffamine D-230 have, after the first stage of curing, T _g s ranging between - 92 ^e C and -61 ^e C and none gel during this curing phase. For these same formulations it has been surprisingly observed that approximately only half of the amino groups react while practically all the acrylates disappear (examples 1, 2, 3, 4 and 5). It is thought that only the primary amino groups are capable of reacting and that the secondary formed, although potentially reactive, are not capable of doing so, possibly due to the effect of steric hindrances.

The inventors have also observed that the properties of the materials at the end of the first and second curing stages can be significantly modified by changing the type of amine used. In other particular embodiments, a mixture of BGDA / HDDA acrylates with a weight ratio of 25/75 and diethylenetriamine (examples 6, 7, 8 and 9) and a hyperbranched amine of molecular weight 800 have been used as component b) g / mol and trade name Lupaso FG (examples 10, 1 1, 12 and 13). The latter amine has a composition similar to diethylenetriamine but also has tertiary amino groups in its structure. It has been observed that replacing Jeffamine D-230 with diethylenetriamine significantly increases T _g and the relaxed modulus and curing is almost complete after the two stages of curing in almost all formulations. For these same systems, it is observed that formulations with 100%, 50% and 25% Michael addition (formulations 1/1, 1/2 and 1/4) gel during the first stage of curing respectively to total acrylate conversions 62%, 40% and 26%. Also the T _g s after the first stage of curing are significantly higher than those present the formulations with Jeffamine D-230. When the Lupaso FG hyperbranched amine is used, formulations with 100%, 50% and 25% addition Michael gel very quickly at the beginning of the first stage of curing and total acrylate conversions between 15 and 25%, significantly lower than when diethylenetriamine is used. The T _g s after the first stage of cure are superior in the formulations with Lupaso FG than with diethylenetriamine, as are the T _g s and the module relaxed after the second stage of cure. It seems that the greater functionality of Lupaso FG leads to significantly more crosslinked materials and superior properties. Conversions at the end of the first stage of cure are significantly higher than when Jeffamine D-230 is used, although somewhat lower compared to diethylenetriamine systems. In general, it can be said that the reaction rate and the degree of cure of the first stage are strongly influenced by the type of amine used. The addition of aza-Michael in formulations with diethylenetriamine and Lupasol ^® is much faster and with significantly greater progress than those containing Jeffamine D-230. In the case of Lupaso FG, the tertiary amino groups existing in its structure can justify this behavior and in the case of diethylenetriamine, its low viscosity (high mobility) allows the closest to complete cure to be achieved. The inventors have shown that the degree of crosslinking and the final properties of the materials can be increased by partially or totally replacing the diacrylates with more functional acrylates. In particular embodiments using as component b) mixtures of acrylates formed by BGDA, HDDA and trimethylolpropane triacrylate (TMTA) with weight ratios from 25BGDA / 75HDDA to 25BGDA / 75TMTA and as diethylenetriamine amine with a molar ratio between the first and the Second stage of 1/4 (examples 8, 14 and 15), it is observed how the T _g and the relaxed module at the end of both stages of curing increase significantly as the triacrylate content increases. Both parameters increase from 56 ^e C and 73 MPa to 97 ^e C and 246 MPa when 75% of HDDA is completely replaced by 75% of TMTA. There is also a significant increase in T _g after the first stage from -86 ^e C to -42 ^e C. Intermediate formulations have intermediate properties. The samples with triacrylates surprisingly do not gel during the first stage of curing, although when diethylenetriamine is replaced by Lupasol. Using acrylates with a higher content of acrylate groups, such as dipentaerythritol pentaacrylate, allows materials with _Tg s and higher relaxed modules to be obtained but these have certain defects due to excessive system reactivity, especially in formulations with a very high content of this component.

Although in many of the formulations studied the inventors have used acrylates of the type HDDA and BGDA with a weight ratio of 25/75, as this is one of the formulations widely used in industrial applications, they have observed that the invention is applicable to any Composition of these same acrylates or any other α, β-conjugated vinyl compound to a carbonyl ester group. In other particular embodiments using as component b) mixtures of acrylates formed by BGDA and HDDA with weight ratios from 25% BG DA / 75% HDDA up to 75% BG DA / 25% H DDA and as diethylenetriamine amine with a molar ratio between In the first and second stages of 1/4 (examples 8, 16 and 17), researchers have observed how the final T _g of the material increases from 56 ^e C for the formulation containing 25% in BGDA to 67 ^e C for the formulation with 75% in BGDA and the T _g after the first stage from -86 ^e C to -32 ^e C. In all these embodiments Michael's addition of the first stage has been almost complete, while slightly decreasing the Homopolymerization of excess acrylates by increasing the BGDA content, possibly due to certain spatial impediments by increasing the acrylate content of greater size and viscosity. All formulations gel during the first stage of curing at a total conversion of acrylates close to 25%.

When in a formulation containing 25% BGDA and 75% HDDA and Lupasol ^® FG with a molar ratio between the first and second stage of 1/4, the HDDA is completely replaced by triethylene glycol dimethacrylate (TEGDMA) (examples 12 and 18), the T _g increases from 75 ^e C for the formulation containing 75% HDDA to 150 ^e C for the formulation with 75% in TEGDMA. In these embodiments, the reactive process proceeds relatively similarly although the systems with TEGDMA gel much faster and have little homogeneity, due to the low miscibility between the TEGDMA and the Lupasol ^® FG. Also in the formulations with TEGDMA both stages of curing are complete, reacting the acrylates preferably in the first stage and methacrylates in the second. If 25% of BGDA is replaced in the same formulation with its analogous methacrylate, glycerol bisphenol A-dimethacrylate (BGMA), instead of replacing 75% of HDDA, the final properties are modified very little, although in this embodiment both stages of curing, especially the first, are not complete under the conditions of the study (examples 12 and 19).

In all the particular embodiments set forth up to this point in the document, 3% by weight has been used with respect to the total mixture mass of 2,2-dimethoxy-2-phenyl acetophenone (DMPA) as a photoinitiator. The inventors have shown that type II photoinitiators such as benzophenone are equally efficient for the invented compositions. In particular embodiments with formulations containing 25% BGDA and 75% HDDA and diethylenetriamine with a molar ratio between the first and second stages of 1/2, it has been seen that whether DMPA is used or benzophenone is used, both stages of cure are practically complete, being even slightly superior with benzophenone. With benzophenone and DMPA, materials with T _g and practically identical relaxed modules are obtained (examples 7 and 20). An attempt has been made to homopolymerize the same mixture of acrylates with benzophenone, but without the presence of diethylenetriamine and it has been found that this process does not take place (example 21). This result shows that tertiary amines formed during the first stage (aza-Michael addition) act as a sensitizer by activating benzophenone that can initiate homopolymerization of acrylates in the second stage. In the practice of the present invention it has been surprisingly discovered that the addition of Lewis bases or acids only slightly accelerates cure against expectations, although it does increase the degree of conversion achieved. The addition of 2% of 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) to a formulation with 25% BGDA / 75% HDDA and Jeffamine D-230 with a molar ratio between the first and the second stage of 1/4, has allowed to increase the total conversion of acrylate groups from 90% to 98%, as well as the conversion of the first stage of curing by 4% (examples 3 and 22). For mixed formulations acrylates / methacrylates 25% BGDA / 75% TEGDMA and LupasofFG with a molar ratio between the first and second stage of 1/4, the first stage of curing increases its conversion until it is complete when 1% of DBN is added or of triflate of iterbio.

In most of particular embodiments at 35 ^e C the first stage cure was practically complete. In some systems such as those containing Jeffamine D-230, where this stage has not been completed in 3 hours, the inventors have seen that with longer times, curing can be complete. In a particular embodiment with a 25% BG DA / 75% HD DA formulation with Jeffamine D-230 and a molar ratio between the first and second stages of 1/8 (example 4), the Researchers have observed that at 35 ^e C the complete cure in the first stage is reached in 7 hours.

Although it is not the preferred option, if desired, the second curing stage can be performed thermally instead of photoinduced but the photoinitiator must be replaced by a thermal radical initiator. A particular embodiment containing 25% BGDA and 75% TMTA and Lupasol ^® FG with a molar ratio between the first and second stage of 1/4, has been crosslinked using 3% methyl ethyl ketone peroxide as a thermal initiator . After the first stage of curing and after one hour of curing at 150 ^e C the conversion of double bonds is 55%, and this increases up to 73% with a post-cure of 1 hour at 180 ^e C, to reach a cure of 83% with an additional heating of 1 hour of curing at 200 ^e C (example 23). When 0.1% of cobalt octoate was added to the same formulation as a promoter, the conversions achieved at the end of each stage, following the same cure pattern are 65%, 85% and practically complete curing (example 24) . The T _g of the formulation without octoate is 79 ^e C, while the one containing completely cured octoate is 140 ^e C. The inventors have also observed that when working with cobalt octoate the curing temperature could be clearly lower, especially if the promoter content is increased, although post-curing is always required at an elevated temperature above the T _g of the fully cured material. The curing pattern (temperature-time) must be adjusted for each formulation and this depends on the composition of the formulation (T _g of the completely cured material) and the type and amount of initiator and promoter selected. Some of the prepared materials can be degraded at relatively low temperatures, although above cure temperatures. The higher the proportion of aza-Michael addition has the composition, the more thermally degradable the network is since the CN bonds degrade at a lower temperature than the CC. In particular embodiments with 25% BGDA / 75% HDDA formulations and varying amounts of Jeffamine D-230, the temperature at which the material has decomposed 5% ranges from 216 ^e C for the formulation where 100% is aza-Michael addition up to 382 ^e C for formulations where 100% cure is homopolymerization of the conjugated vinyl compounds (examples 1, 2, 3, 4 and 5) The most outstanding advantages of the present invention are:

- Fully crosslinked thermosetting materials without heating, with the consequent energy savings. - Materials free of solvents and other volatile organic components.

- Obtaining these materials in situ in two stages but with a single formulation.

- Stable materials after the first curing stage that may or may not be gelled, where the second curing stage can be activated at will.

- Very versatile materials ranging from elastomers to highly crosslinked thermosets.

- Materials suitable for any industrial application of vinyl systems.

- Variable viscosity formulations that can be used directly as adhesives, in molding, for primers and for coatings.

- Materials suitable for any substrate, with special interest in heat-sensitive materials, such as wood, since their application does not require heating.

- Materials that can be prepared to measure by varying their composition depending on the desired properties.

- Potentially disposable materials in a controlled manner, for the recovery of high value substrates.

All these characteristics indicate that the present invention may have a potential interest in any application of vinyl systems, especially when it is desired to obtain materials with a controlled composition and properties and with low energy cost and without volatile emission.

Below are illustrative examples of the invention that are set forth for a better understanding thereof and in no case should they be considered a limitation of the scope thereof.

EXAMPLES

The following methods and apparatus are used for various determinations in the examples.

In the present invention, the monitoring of the cure in both stages has been carried out by infrared spectroscopy in real time. The infrared spectra were recorded with a Brucker Vertex 70 spectrophotometer with an attenuated total reflectance accessory with thermal control and with a Specac- Teknokroma diamond crystal at a resolution of 4 cm ^"1 and accumulating 20 scans. For preferred formulations of the present invention was placed the fresh sample of a 50 μηι thickness on the surface of the ATR and the following curing pattern was performed: a first curing stage of 3 hours at 35 ^e C, followed by a second stage at 35 ^e C radiating 1 minute with a polygromatic Hg- lamp Xe Hamamatsu Lightningcure LC5. In some particular embodiments where the second stage consists of thermal curing, the procedure has been similar, but in the second stage, instead of irradiating the sample, the surface of the ATR has been placed at the desired temperature.

The conversion of vinyl groups, in the two stages of curing (Michael addition and homopolymerization), has been established from the disappearance of the bands associated with the double bond, using the changes observed in the relative intensities of these bands. As during the first stage of curing, before irradiation, homopolymerization of the vinyl groups cannot take place and they can only react with the amino groups, it is considered that the disappearance of the unsaturations is directly proportional to the Michael addition of the amine to the conjugated double bond. To determine the conversion, in the formulations with acrylates, the absorbance peak close to 1400 cm ^"1 corresponding to the torsion of C = C has been used, and when working with mixtures of methacrylates and acrylates the conversion has been determined using the bands in the region of 800 cm ^"1 (associated with the set of acrylate and methacrylate groups) and 1400 ^{cm" 1} (associated only acrylate groups). As internal standard was used band close carbonyl at 1750 cm ^{" 1} or the characteristic absorption band of the C = C group of aromatic rings in the region of 1600 to 1500 cm ^"1. Gelification of the materials during the first curing stage was determined on a Mettler TMA / SDTA 840 thermomechanical analyzer "Toledo. The samples were impregnated in silanized fiberglass and placed between two rigid silicon oxide discs. The material was cured the same as in the FTIR by an isothermal test at 35 ^and C applying a varying force ble from 0.0025 to 0.01 N. The time at which the material gains mechanical stability and the amplitude of the oscillations is sharply reduced was taken as a gel time. The conversion in gelation (otgei) was determined as the conversion achieved in the FTIR at the same time as it gelled in the thermomechanical analyzer. At the end of the dual cure all the materials were gelled. The gelation was not determined in the second stage of curing since this takes place at very short times and cannot be detected by conventional techniques. The glass transition temperature (T _g ) at the end of the two curing stages has been determined by a Q800 dynamomechanical analyzer from TA Instruments working at 1 Hz frequency and in the three-point flex mode. In this same test, the relaxed module 50 ^e C was determined above the T _g , which is proportional to the degree of cross-linking. As for the samples for the dynamomechanical tests, 20 x 12 x 0.1 mm ³ specimens were prepared in polypropylene or glass molds, with a Teflon spacer to obtain the desired thickness, following the following curing protocol: three hours at 35 ^e C, followed by irradiation at room temperature of 8 J / cm ² (4 J / cm ² per side) with a monochromatic lamp of 365 nm. The photo curing was carried out in a UV stove of Viber Lormat Bio-Link Crosslinker equipped with 6 lamps of 8 W of power emitting at a wavelength of 365 nm. These samples, before the dynamomechanical test, were analyzed by Fourier transform infrared spectroscopy and showed a degree of conversion similar to the samples cross-linked directly in the spectrophotometer.

The T _g after the first curing stage has been determined by differential scanning calorimetry, using a Mettler DSC-822e calorimeter with a TS0801 RO robot in aluminum capsules and under nitrogen atmosphere. The samples placed in the capsules have been heated to 10 ^e C / min after an oven cure for 3 hours at 35 ^e C and the temperature of the midpoint of the heat capacity jump has been taken as T _g when the material changes from the vitreous state to the amorphous.

The thermal stability of the crosslinked materials was determined under a nitrogen atmosphere with a flow of 200 cm ³ / min (measured under normal conditions) in a TGA / DSC 1 thermobalance from Mettler-Toledo. Samples of approximately 10 mg were degraded between 30 and 700 ^e C by heating at 10 ^e C / min. The temperature at which the material had lost 5% of weight has been taken as the decomposition temperature.

Example 1 (mass ratio BGDA / HDDA 25/75, Jeffamine D-230 with a molar ratio between the first and second stage of 1/1, 3% DMPA)

A cross-linking composition at room temperature of a mixture of acrylates with an amine was prepared, homogeneously mixing 2.5 g of BGDA and 7.5 g of HDDA. Then 3 g of DMPA was added and stirred until DMPA was completely dissolved. Finally 4,596 g of Jeffamine D-230 was added, stirred and held for 15 minutes under vacuum. Three parts of the prepared composition were placed a in a mold, another in a DSC capsule and another on the surface of the ATR / FTIR and kept for 3 hours at 35 ^e C. Finally, the samples of the mold and the FTIR were irradiated as explained. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of -4 ^e C, a relaxed modulus of 1 5 MPa and a decomposition temperature of 216 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 48% that directly represents 48% of the aza-Michael addition at the end of the first curing stage and 97% of acrylates at the end of the second. The material did not gel during the first curing stage and showed at the end of this stage a glass transition temperature of -61 ^e C.

Example 2 (mass ratio BGDA / HDDA 25/75, Jeffamine D-230 with a molar ratio between the first and second stage of 1/2, 3% DMPA)

The procedure was as in Example 1 but half of Jeffamine D-230, 2,298 g was added. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 1 0 ^e C, a relaxed modulus of 26 MPa and a decomposition temperature of 230 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing they showed a 32.5% acrylate conversion that directly represents 65% of the aza-Michael addition at the end of the first curing stage and 92% of acrylates at the end of the second. The material did not gel during the first curing stage and showed at the end of this stage a glass transition temperature of -71 ^e C.

Example 3 (mass ratio BGDA / HDDA 25/75, Jeffamine D-230 with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1 but a quarter of Jeffamine D-230, 1, 149 g was added. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 48 ^e C, a relaxed modulus of 58 MPa and a decomposition temperature of 258 ^e C. The Fourier transform infrared spectroscopy spectra recorded during Curing showed a 13% acrylate conversion that directly represents 52% of the aza-Michael addition at the end of the first curing stage and 90% of acrylates at the end of the second. The material did not gel during the first curing stage and showed at the end of this stage a glass transition temperature of -84 ^e C.

Example 4 (mass ratio BGDA / HDDA 25/75, Jeffamine D-230 with a molar ratio between the first and second stage of 1/8, 3% DMPA) The procedure was as in Example 1 but one eighth of Jeffamine D-230, 0.5745 g was added. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 67 ^e C, a relaxed modulus of 86 MPa and a decomposition temperature of 307 ^e C. The Fourier transform infrared spectroscopy spectra recorded during Curing showed a conversion of 6.25% acrylates that directly represents 50% of the aza-Michael addition at the end of the first curing stage and 87% of acrylates at the end of the second. The material did not gel during the first curing stage and showed at the end of this stage a glass transition temperature of -92 ^e C.

Comparison example 5 only photo-cured without addition aza-Michael (mass ratio BGDA / HDDA 25/75, 3% DMPA)

The procedure was as described in example one but without adding amine and without performing the first curing stage (aza-Michael addition). The crosslinked material at the end of the curing showed a glass transition temperature of 102 ^e C, a relaxed modulus of 164 MPa and a decomposition temperature of 382 ^e C. The recorded Fourier transform infrared spectroscopy spectra showed a conversion of acrylates of the 88% at the end of the curing. Example 6 (mass ratio BGDA / HDDA 25/75, diethylenetriamine with a molar ratio between the first and second stage of 1/1, 3% DMPA)

The procedure was as in Example 1, but the mass of Jeffamine D-230 was replaced by 1.5964 g of diethylenetriamine. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 16 ^e C, a relaxed modulus of 33 MPa and a decomposition temperature of 232 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 72% that directly represents 72% of the aza-Michael addition at the end of the first curing stage and 94% of acrylates at the end of the second. The material gelled in 45 minutes and achieved a conversion in gelation of 62% acrylates during the first curing stage. The material also showed at the end of this stage a glass transition temperature of -45 ^e C.

Example 7 (mass ratio BGDA / HDDA 25/75, diethylenetriamine with a molar ratio between the first and second stage of 1/2, 3% DMPA)

The procedure was as in example 1, but the mass of Jeffamine D-230 was replaced by 0.7882 g of diethylenetriamine (half as in example 6). The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 39 ^e C, a relaxed module of 44 MPa and a decomposition temperature of 242 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 45% that directly represents 90% of the addition aza-Michael at the end of the first stage of curing and 93% of acrylates at the end of the second. The material gelled in 96 minutes and achieved a conversion in gelation of 40% acrylates during the first curing stage. At the end of this stage, the material also showed a glass transition temperature of -65 ^e C. Example 8 (mass ratio BGDA / HDDA 25/75, diethylenetriamine with a molar ratio between the first and second stages of 1/4, 3 % DMPA)

The procedure was as in example 1, but the mass of Jeffamine D-230 was replaced by 0.3991 g of diethylenetriamine (a quarter as in example 6). The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 56 ^e C, a relaxed modulus of 73 MPa and a decomposition temperature of 275 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 24% that directly represents 96% of the aza-Michael addition at the end of the first curing stage and 89% of acrylates at the end of the second. The material gelled in 127 minutes during the first curing stage and reached a conversion in gelation of 26% acrylates and showed at the end of this stage a glass transition temperature of -86 ^e C.

Example 9 (mass ratio BGDA / HDDA 25/75, diethylenetriamine with a molar ratio between the first and second stage of 1/8, 3% DMPA)

The procedure was as in example 1, but the mass of Jeffamine D-230 was replaced by 0.16555 g of diethylenetriamine (the eighth part as in example 6). The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 70 ^e C, a relaxed modulus of 92 MPa and a decomposition temperature of 335 ^e C. The Fourier transform infrared spectroscopy spectra recorded during Curing showed a 12.5% acrylate conversion that directly represents 100% of the aza-Michael addition at the end of the first curing stage and 88% of acrylates at the end of the second. The material did not gel during the first curing stage and showed at the end of this stage a glass transition temperature of -93 ^e C.

Example 10 (mass ratio BGDA / HDDA 25/75, Lupaso FG with a molar ratio between the first and second stage of 1/1, 3% DMPA)

The procedure was as in Example 1, but the mass of Jeffamine D-230 was replaced by 2.58 g of Lupaso FG. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 33 ^e C, a relaxed modulus of 44 MPa and a decomposition temperature of 249 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 62% that directly represents 62% of the aza-Michael addition at the end of the first curing stage and 85% of acrylates at the end of the second. The material gelled in 2 minutes and reached a conversion in gelation of 25% acrylates during the first stage of curing. The material also showed at the end of this stage a glass transition temperature of -33 ^e C.

Example 11 (mass ratio BGDA / HDDA 25/75, Lupasol ^® FG with a molar ratio between the first and second stage of 1/2, 3% DMPA)

The procedure was as in example 1, but the mass of Jeffamine D-230 was replaced by 1.29 g of Lupaso FG (half as in example 10). The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 53 ^e C, a relaxed modulus of 65 MPa and a decomposition temperature of 257 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 33% that directly represents 60% of the aza-Michael addition at the end of the first curing stage and 86% of acrylates at the end of the second. The material gelled in 16 minutes and achieved a conversion in gelation of 21% acrylates during the first curing stage. The material also showed at the end of this stage a glass transition temperature of -60 ^e C.

Example 12 (mass ratio BGDA / HDDA 25/75, Lupasol ^® FG with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in example 1, but the mass of Jeffamine D-230 was replaced by 0.645 g of Lupaso FG (the fourth part than in example 10). The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 64 ^e C, a relaxed modulus of 87 MPa and a decomposition temperature of 306 ^e C. The Fourier transform infrared spectroscopy spectra recorded during The curing showed a 20% acrylate conversion that directly represents 80% of the aza-Michael addition at the end of the first curing stage and 87% of acrylates at the end of the second. The material gelled in 48 minutes and reached a conversion in gelation of 16% of acrylates during the first stage of curing. The material also showed at the end of this stage a glass transition temperature of -61 ^e C.

Example 13 (mass ratio BGDA / HDDA 25/75, Lupaso FG with a molar ratio between the first and second stage of 1/8, 3% DMPA)

The procedure was as in example 1, but the mass of Jeffamine D-230 was replaced by 0.645 g of Lupaso FG (the eighth part than in example 10). The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 72 ^e C, a relaxed modulus of 100 MPa and a decomposition temperature of 341 ^e C. The Fourier transform infrared spectroscopy spectra recorded during Curing showed a 10% acrylate conversion that directly represents 80% of the aza-Michael addition at the end of the first curing stage and 87% of acrylates at the end of the second. The material gelled in 445 minutes and achieved a conversion in gelation of 12.5% acrylates during the first stage of curing. The material also showed at the end of this stage a glass transition temperature of -92 ^e C.

Example 14 (mass ratio BGDA / TMTA 37.5 / 37.5, diethylenetriamine with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1, but using 5 g of BGDA and 5 g of TMTA as a mixture of acrylates and 0.407 g of diethylenetriamine The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 76 ^e C , a relaxed module of 157 MPa and a decomposition temperature of 318 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed a 22% acrylate conversion that directly represents 88% of the aza-Michael addition at the end of the first stage of curing and 80% of acrylates at the end of the second. The material showed a glass transition temperature of -62 ^e C at the end of the first curing stage. Example 15 (mass ratio BGDA / TMTA 25/75, diethylenetriamine with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1, but using 2.5 g of BGDA and 7.5 g of TMTA as a mixture of acrylates and 0.430 g of diethylenetriamine The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 97 ^e C, a relaxed module of 246 MPa and a decomposition temperature of 368 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed a 20% acrylate conversion that It directly represents 80% of the aza-Michael addition at the end of the first curing stage and 78% of acrylates at the end of the second. The material showed a glass transition temperature of -42 ^e C at the end of the first curing stage. Example 16 (mass ratio BGDA / HDDA 50/50, diethylenetriamine with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1, but using 5 g of BGDA and 5 g of HDDA as a mixture of acrylates and 0.327 g of diethylenetriamine. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 76 ^e C, a relaxed modulus of 157 MPa and a decomposition temperature of 324 ^e C. The Fourier transform infrared spectroscopy spectra recorded during Curing showed a 25% acrylate conversion that directly represents 100% of the aza-Michael addition at the end of the first curing stage and 82% of acrylates at the end of the second. The material gelled in 123 minutes and achieved a conversion in gelation of 24% acrylates during the first curing stage. Also, the material showed at the end of this stage a glass transition temperature of -68 ^e C.

Example 17 (mass ratio BGDA / HDDA 75/25, diethylenetriamine with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1, but using 7.5 g of BGDA and 2.5 g of HDDA as a mixture of acrylates and 0.276 g of diethylenetriamine. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 67 ^e C, a relaxed modulus of 28 MPa and a decomposition temperature of 325 ^e C. The Fourier transform infrared spectroscopy spectra recorded during Curing showed a 25% acrylate conversion that directly represents 100% of the aza-Michael addition at the end of the first curing stage and 76% of acrylates at the end of the second. The material showed a glass transition temperature of -32 ^e C at the end of the first curing stage.

Example 18 (mass ratio BGDA / TEGDMA 25/75, Lupaso FG with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1, but using 2.5 g of BGDA and 7.5 g of TEGDMA as a mixture of acrylates and methacrylates and 0.501 g of Lupaso FG. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 1 50 ^e C, a relaxed modulus of 83 MPa and a decomposition temperature of 324 ^e C. The infrared spectroscopy spectra by Fourier transform recorded during curing showed an acrylate / methacrylate conversion of 22% (of which 19% are acrylates and 3% methacrylates) which directly represents 88% of the aza-Michael addition at the end of the first stage of Cured and 99% acrylates / methacrylates at the end of the second. The material gelled in the first stage very quickly and at a low conversion that could not be determined and showed a very wide glass transition temperature difficult to determine.

Example 19 (mass ratio BGMA / HDDA 25/75, Lupasol ^® FG with a molar ratio between the first and second stage of 1/4, 3% DMPA)

The procedure was as in Example 1, but using 2.5 g of BGMA and 7.5 g of HDDA as a mixture of acrylates and methacrylates and 0.601 g of Lupaso FG. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 75 ^e C, a relaxed modulus of 86 MPa and a decomposition temperature of 344 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed a conversion of acrylates / methacrylates of 1 1% (of which 10% are acrylates and 1% methacrylates) which directly represents 44% of the aza-Michael addition at the end of the first curing stage and 90 % acrylates / methacrylates at the end of the second. The material did not gel during the first stage of curing and showed a glass transition temperature of -82 ^e C at the end of this stage.

Example 20 (mass ratio BGDA / HDDA 25/75, diethylenetriamine with a molar ratio between the first and second stage of 1/2, 3% benzophenone)

The procedure was as in Example 7, but the DMPA mass was replaced by 3 g of benzophenone. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 39 ^e C, a relaxed modulus of 44 MPa and a decomposition temperature of 242 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed an acrylate conversion of 44% that directly represents 88% of the aza-Michael addition at the end of the first curing stage and 90% of acrylates at the end of the second.

Comparison example 21 only photo-cured without addition aza-Michael (mass ratio BGDA / HDDA 25/75, 3% benzophenone)

The procedure was as described in example 20 but without adding diethylenetriamine and without performing the first curing stage (aza-Michael addition). The material at the end of photo curing had not intersected. Registered Fourier transform infrared spectroscopy spectra showed an acrylate conversion of 0% after 1 minute of irradiation and 3% after 15 minutes. Example 22 (mass ratio BGDA / HDDA 25/75, Jeffamine D-230 with a molar ratio between the first and second stage of 1/4, 3% DMPA, 2% 1, 5- diazabicyclo [4.3.0] non-5-eno)

The procedure was as in Example 3 but 2 g of 1, 5-diazabicyclo [4.3.0] non-5-ene was also added. Although the properties of this formulation were not measured because they were expected to be similar to those of example 3, if by means of the Fourier transform infrared spectroscopy spectra recorded during curing, an acrylate conversion of 17% was observed, which directly represents 68% of the aza-Michael addition at the end of the first curing stage and 98% acrylates at the end of the second.

Example 23 (mass ratio BGDA / TMTA 25/75, Lupaso FG with a molar ratio between the first and second stage of 1/4, 3% methyl ethyl ketone peroxide) Proceed as in example 12, but using 2 , 5 g of BGDA and 7.5 g of TMTA as a mixture of acrylates and replacing the DMPA mass with 3 g of methyl ethyl ketone peroxide. The second stage of curing instead of the usual protocol consisted of the following heat treatment sequence: 1 hour at 150 ^e C, followed by 1 hour at 180 ^e C, to end with 1 hour at 200 ^e C. The material crosslinked at the end of the two stages of dual curing showed a glass transition temperature of 79 ^e C, a relaxed module of 129 MPa and a decomposition temperature of 310 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed a conversion of 17% acrylates directly representing 68% of the aza-Michael addition at the end of the first curing stage, 55% of acrylates at the end of heating for 1 hour at 150 ^e C, 73% of acrylates at the end 1 hour heating at 180 ^e C and 83% acrylates at the end of 1 hour heating at 200 ^e C.

Example 24 (mass ratio BGDA / TMTA 25/75, Lupasol ^® FG with a molar ratio between the first and second stage of 1/4, 3% methyl ethyl ketone peroxide, 0.1% cobalt octoate)

The procedure was as in example 23, but also adding 0.1 g of cobalt octoate. The crosslinked material at the end of the two stages of dual curing showed a glass transition temperature of 140 ^e C, a relaxed module of 223 MPa and a Decomposition temperature of 313 ^e C. The Fourier transform infrared spectroscopy spectra recorded during curing showed a 20% acrylate conversion that directly represents 80% of the aza-Michael addition at the end of the first curing stage, 65% of acrylates at the end of 1 hour heating at 150 ^e C, 85% of acrylates at the end of 1 hour heating at 180 ^e C and 95% of acrylates at the end of 1 hour heating at 200 ^e C .

Claims

1 - Composition for the cross-linking of an amine with an α, β-conjugated vinyl compound to a carbonyl ester group and subsequent polymerization of the vinyl compound, characterized in that it comprises at least: a) a non-aromatic amine or non-aromatic polyamine, with at least two NH bonds, b) a vinyl compound, of general formula (I), containing at least two α, β-conjugated double bonds to a carbonyl ester group

where Y and Z are each independently a hydrogen, aliphatic or aromatic moieties or more complex groups, and where X is an aliphatic or aromatic moiety or a more complex group, and c) a radical photoinitiator or a radical thermal initiator, suitable for initiating crosslinking said double α, β-conjugated bonds to an excess ester carbonyl group.

2 - Composition according to claim 1, characterized in that said α, β-conjugated double bonds to a carbonyl ester group are in excess of said N-H bonds.

3 - Composition according to one of claims 1 or 2, characterized in that Y and Z are each independently a hydrogen, a linear or branched C1-C20 alkyl radical, substituted or not, a linear C2-C20 alkenyl or alkynyl radical or branched, substituted or not, a C4-C20 cycloalkyl or cycloalkenyl radical, substituted or not, a aryl radical, which preferably also has alkyl, halogen or other substituents directly attached to the aromatic rings.

4 - Composition according to any one of claims 1 to 3, characterized in that the group X is a C2-C100 alkyl radical, linear or branched, substituted or not, a C2-C40 alkenyl or alkynyl radical, linear or branched, substituted or not , a C4-C20 cycloalkyl or cycloalkenyl radical, substituted or not, an aryl radical, which preferably also has alkyl, halogen or other substituents directly attached to the aromatic rings, preferably X is also linked to several α, β-conjugated ester groups .

5 - Composition according to any one of claims 1 to 4, characterized in that n varies between 2 and 50. 6 - Composition according to any one of claims 1 to 5, characterized in that said amine or polyamine is a polyamine with at least three bonds NH.

7 - Composition according to any one of claims 1 to 6, characterized in that said amine or polyamine has between 3 and 5 NH groups, said vinyl compound contains between 2 and 6 double α, β-conjugated double bonds to a carbonyl ester group and, preferably, the ratio between NH groups and α, β-conjugated double bonds to a carbonyl ester group is between 0.05 and 1.

8 - Composition according to any of claims 1 to 6, characterized in that said amine or polyamine has between 6 and 20 NH groups, said vinyl compound contains between 2 and 6 double α, β-conjugated double bonds to a carbonyl ester group and, preferably, the ratio between NH groups and α, β-conjugated double bonds to a carbonyl ester group is between 0.01 and 1. 9 - Composition according to any of claims 1 to 8, characterized in that

Z and Y are hydrogens.

1 0 - Composition according to any one of claims 1 to 8, characterized in that Z and Y are respectively a hydrogen and a methyl group. 1 - Composition according to any one of claims 1 to 8, characterized in that component b) is a mixture of acrylates, a mixture of methacrylates or a mixture of acrylates and methacrylates in any proportion. 1 - Composition according to claim 1, characterized in that component b) is a mixture of bisphenol A-glycerolate diacrylate and 1,6-hexanediol diacrylate.

1 3 - Composition according to claim 1, characterized in that the component b) is a mixture of bisphenol A-glycerolate diacrylate and trimethylolpropane triacrylate.

14 - Composition according to claim 1, characterized in that component b) is a mixture of bisphenol A-glycerolate diacrylate and triethylene glycol trimethylolpropane dimethacrylate 1 - Composition according to claim 1, characterized in that component b) is a mixture of bisphenol A-glycerolate dimethacrylate and 1,6-hexanediol diacrylate.

1 - Composition according to any one of claims 1 to 1, characterized in that said amine or polyamine is a polyamine of molecular weight between 400 and 25,000.

1 - Composition according to any one of claims 1 to 1 6, characterized in that said amine or polyamine is a polyetheramine or a linear or branched poly (ethylenamine). 1-8 - Composition according to any one of claims 1 to 1, characterized in that said amine or polyamine is a simple aliphatic amine of molecular weight between 60 and 2,000.

1 9 - Composition according to any one of claims 1 to 1, characterized in that said amine or polyamine is diethylenetriamine.

20 - Composition according to any one of claims 1 to 9, characterized in that component c) is a radical photoinitiator. 21 - Composition according to claim 20, characterized in that the radical photoinitiator is 2,2-dimethoxy-2-phenyl acetophenone or benzophenone. 22 - Composition according to any one of claims 1 to 21, characterized in that it additionally comprises a Lewis base or acid.

23 - Composition according to claim 22, characterized in that said base or said Lewis acid is 1,5-diazabicyclo [4.3.0] non-5-eno or ytterbium triflate.

Composition according to any one of claims 1 to 9, characterized in that component c) is a radical thermal initiator. 25 - Composition according to claim 24, characterized in that the radical initiator is methyl ethyl ketone peroxide.

26 - Composition according to one of claims 24 or 25, characterized in that it additionally comprises a promoter.

27 - Composition according to claim 26, characterized in that said promoter is cobalt octoate.

28 - Method for obtaining a composition for the cross-linking of an amine with an α, β-conjugated vinyl compound to a carbonyl ester group and subsequent polymerization of the excess of vinyl compound, according to any one of claims 1 to 27, comprising the steps of: (i) dissolving the radical photoinitiator or the radical thermal initiator in component b) of the formulation by stirring at room temperature, (ii) adding component a) to the previous mixture, and keeping the resulting mixture in vacuo at least for 15 minutes at room temperature.

29 - Method for obtaining a composition according to claim 28, characterized in that said vacuum is less than 1 00 mm Hg.

30 - Method for obtaining a composition according to one of claims 28 or 29, characterized in that prior to said step (ii), a Lewis base or acid is dissolved in said component a). 31 - Procedure for obtaining a composition according to one of claims 28 or 29, characterized in that a radical thermal initiator is used and a promoter is added in component b). 32 - Method of coating a substrate characterized in that it comprises the steps of: I) preparation of a composition according to any one of claims 1 to 27,

II) application of said composition on a substrate

III) first stage of curing by reaction between said compound a) and said compound b)

IV) second stage of curing by activating said photoinitiator by ultraviolet radiation or said thermal initiator by means of heat input and the reaction of the remaining α, β-conjugated double bonds to a carbonyl ester group with each other.

33 - Method according to claim 32, characterized in that said composition gels during said first curing stage. 34 - Method according to claim 32, characterized in that said composition gels during said second curing stage.

35 - Substrate coated with a crosslinked material obtainable by curing a composition following the procedure of any one of claims 32 to 34.

36 - Method of manufacturing a part by molding characterized in that it comprises the steps of: I) preparation of a composition according to claims 1 to 27,

II) filling a mold with said composition

37 - Method according to claim 36, characterized in that said composition gels during said first curing stage.

38 - Method according to claim 36, characterized in that said composition gels during said second curing stage.

39 - Piece of a crosslinked material obtainable by curing a composition following the procedure of any one of claims 36 to 38.