WO2012130998A1

WO2012130998A1 - Method for cross-linking polymers, use of the cross-linked polymers, and associated composition

Info

Publication number: WO2012130998A1
Application number: PCT/EP2012/055723
Authority: WO
Inventors: Elina TRUB; Matthieu Sonnati; Olivier CHOULET
Original assignee: Ecoat
Priority date: 2011-03-30
Filing date: 2012-03-29
Publication date: 2012-10-04
Also published as: EP2691447A1; FR2973383A1; FR2973383B1

Abstract

The present invention relates to a method for cross-linking polymers, characterized in that it includes a step of reacting at least one first reactant comprising at least one carbonate function with at least one second reactant comprising at least one protected amine function that is configured to be unprotected so as to be cross-linked with at least one carbonate function of the first reactant during said reaction. The invention applies specifically to alkyd resins or urethane systems. The invention is useful in the field of decorative or industrial coatings.

Description

"Process for crosslinking polymers, use of crosslinked polymers and associated composition"

The present invention relates to a process for crosslinking polymers and macromolecules, the use of crosslinked polymers and an associated composition.

It will find its application for crosslinking using a carbonate function and an amine function, such as for example for alkyd resins or polyurethane systems. The invention is particularly advantageous for coatings intended for example in the fields of decorative coatings, such as paints or varnishes, or industrial coatings.

The invention is particularly advantageous for the preparation of protected bi-component polyurethane used in a pot.

Traditionally, the drying of a paint film formulated from an alkyd resin is carried out by crosslinking obtained by the oxidation of the double bonds of the fatty acids with the oxygen of the air, catalyzed by the Ultra Violet rays and metal salts (cobalt, zirconium, calcium, etc.). This process is called siccativation. All these metals do not act from the Similarly, it is known, for example, that cobalt salts catalyze surface drying where oxygen dissolved in the film is present. Although other metal salts are proposed, even today cobalt salts are essential for the development of a correct drying on the surface and to obtain satisfactory properties including sufficient mechanical strength.

In recent years the use of cobalt salts as siccatives in alkyd resin paints has been strongly questioned because of the carcinogenic classification and labeling of these salts.

JP 4,248,835 discloses a thermosetting resin composition with a polyester-type polymer bearing cyclocarbonate groups. To carry out the crosslinking, it is necessary to add a catalyst which, like any catalyst, increases the reaction rate and is unchanged at the end of the reaction.

Modified isocyanates are known from EP 1 386 626. The document relates more particularly to the branching of cyclocarbonate crosslinking functionality on a polymer via modified isocyanates. It does not seek to propose a system of protection / deprotection of one of the crosslinking functions. The properties of the reagents are not maintained during storage, the crosslinking not being sufficiently controlled.

There is therefore the need to propose an alternative crosslinking process.

An object of the invention is a method for crosslinking polymers, for example of the polyester type or any other macromolecules, alkyd resins and / or polymers of the acrylic, vinyl, styrene, polyurethane or epoxy type, comprising a reaction step between at least a first reagent comprising at least one carbonate function and at least one second reagent comprising at least one amine protected function configured to be deprotected so as to crosslink with at least one carbonate function of the first reactant during said reaction.

Indeed, it has been found that the reaction between these two reagents is sufficient to crosslink the polymers without addition of siccative or in significantly lower amounts while giving once applied to a support to cover mechanical and aesthetic properties at least equivalent to product of the prior art. The present crosslinking process no longer involves oxidation as in the prior art. In addition, the temporary protection, advantageously total, of the amine function allows the storage in a single container of the different reagents.

According to the invention, the protected amine function can therefore only react with the carbonate function once the amine function has been deprotected.

The protection of the function is temporary. Advantageously, the protection of the amine function is carried out by a protection agent. The protection step can be carried out by neutralization with a weak and volatile acid or by separation of the amine function and the carbonate function in two distinct phases, for example emulsions or dispersions, mixed subsequently.

A second object of the invention consists of a com position, for example for decorative or industrial coating, comprising polymers, or macromolecules, for crosslinking characterized in that it comprises a first reagent comprising at least one carbonate function and a second reagent comprising at least one protected amine functional group intended to be deprotected to react with at least one carbonate function of the first reactant, so as to cause the crosslinking of the polymers.

According to variants which may be cumulative or alternatively produced and which are not limiting of the invention, the composition is such that:

the amine function is protected by a protective agent;

the two reagents are stored in the same container, said in a pot;

it comprises at least one weak and volatile acid intended to neutralize the amine function of the second reagent;

the weak and volatile acid is chosen from carbon chain acids from C 1 to C 6 _, and preferentially from carbonic acid, formic acid and acetic acid;

the first reagent and the second reagent are each in the form of an emulsion or dispersion not mutable with the other emulsion or dispersion so as to protect the amine function of the second reagent. Another subject of the invention is the use of the polymers obtained by the crosslinking process as a decorative or industrial coating or as an adhesive, putty or as a hot-melt, that is to say thermoplastics heat-set by example for coatings for roads, or else as additive for plastic or crosslinking agent for the processing of plastics such as ABS (Acrylonitrile Butadiene Styrene), PBT (Polybutylene Terephthalate), SBR (Styrene Butadiene Rubber), PC (Polycarbonate) ), PE (Polyethylene), PP (Polypropylene), PVC (Polyvinyl Chloride).

Another subject of the invention is a coating obtained by application of a composition according to the invention. Advantageously, the coating, obtained by the process, and / or from the composition according to the invention does not contain metals, that is to say it does not contain siccative.

It is recalled that the invention relates to a process for crosslinking polymers, or macro-molecules, characterized in that it comprises a reaction step between at least one first reagent comprising at least one carbonate function and at least one second reagent comprising at least one primary or secondary amine function protected by a protective agent and configured to be deprotected by evaporation of the protective agent so as to crosslink with at least one carbonate function of the first reagent during said reaction, the first reagent and / or or the second reagent being a polymer to be crosslinked.

The following are advantageous embodiments that can be cumulated or alternatively realized and which are not limiting of the invention:

the deprotection is carried out by evaporation of a protective agent;

the amine function is a primary or secondary amine function;

the amine function is protected by neutralization with a weak and volatile acid;

the weak and volatile acid has a pKa of between 1 and 14, preferably 3 and 9; preferentially 3 and 7; the weak and volatile acid has a vapor pressure greater than 10 kPa at a temperature below 100 ° C., preferably below 85 ° C.

the weak and volatile acid is chosen from C1 to C6 carbon chain acids _, and preferentially from carbonic acid, formic acid and acetic acid;

the second reagent is mixed with the weak and volatile acid to protect the amine function and then the first reagent is mixed with the second reagent whose amino function is protected;

prior to the reaction step, between the carbonate function and the amine function, the process comprises a step of evaporation of the weak and volatile acid in the course of which the amine function is deprotected to react with the carbonate function for crosslinking and forming a urethane group;

the first and second reagents are each in emulsion or microemulsion or dispersion form so that they are immiscible in order to protect the amine function of the second reagent.

prior to the reaction step, the method comprises a step of evaporation of water and coalescence of the two emulsions or microemulsions or dispersions respectively containing the first reagent and the second reagent during which the amine function is deprotected for can react with the carbonate function to crosslink and form a urethane group;

the deprotection of the amine function is carried out without the addition of an additional deprotection reagent;

the first reagent is a molecule, linear or branched, bearing at least one, preferably several, carbonate function,

the first reagent is a linear or branched molecule obtained by reaction between a glycerol carbonate and a polybasic carboxylic acid or an anhydride of functionality at least equal to 2, in particular chosen from adipic acid, azelaic acid and citric acid; , diglycolic acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid, succinic acid, sebacic acid, trimellitic acid, terephthalic acid and pyromellitic anhydride,

the second reagent is a molecule, linear or branched, bearing at least one, preferably several, amino function;

the second reagent is a linear or branched molecule obtained by reaction between an amino acid and a polyol,

the first reagent and / or the second reagent are polymers to be crosslinked,

the first reagent is a polymer to be crosslinked bearing at least one, preferably several, carbonate function;

the second reagent is a polymer to be crosslinked bearing at least one, preferably several, amino function;

the first and the second reagents are not isocyanates;

the polymers to be crosslinked are alkyd resins;

said resins are chosen from alkyd resins, conventional or modified polyurethane, silicone, vinyl, polyamide or acrylic resins;

the alkyd resins are polyesters obtained by polycondensation between at least one polyol and at least one polyacid and modified with oils or fatty acids;

for example, the polyol may be chosen from polyols having a functionality of at least 2, in particular such as butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, glycol, glycerol, hexane diol, neopentyl glycol, methyl glucoside, pentaerythritol, pentane diol, polyethylene glycol of molecular weight between 300 and 6000, propylene glycol, 1,3 propane diol, sorbitol, triethylene glycol, trimethylolpropane, trimethylolethane, xylitol, xylose, sugar and cellulosic derivatives;

for example, the polyacid may be chosen from a polycarboxylic acid or an anhydride of functionality at least equal to 2 chosen in particular from adipic acid, azelaic acid, citric acid, diglycolic acid, acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid, succinic acid, sebacic acid, trimellitic acid, terephthalic acid and pyromellitic anhydride,

the oils and fatty acids are chosen from oils and fatty acids comprising a carbon chain of Cs to C32, preferably Cu to

for example, the oils and fatty acids are chosen from unsaturated fatty acids conjugated or otherwise, among 2-ethyl hexanoic acid, linoleic acid, linolenic acid, pinoleic acid, oleic acid, pelargonic acid, alpha-eleostearic acid, alpha-licanic acid, ricinolenic acid, dehydrated ricinolenic acid, fatty acids obtained from sunflower, linseed, soy, dehydrated or non-dehydrated castor oil coconut, cotton, tall oil, tung, oitica, soya, safflower, grape seed, olive, palm, perilla, nut, rapeseed, flaxseed;

for example, the oils and fatty acids are chosen from saturated fatty acids and / or fatty mono-acids chosen from fatty acids obtained from castor oil, coconut oil, cotton, dehydrated castor oil and tall oil , sunflower, safflower, grape seed, olive oitica, palm, tung, walnut perillan, rapeseed, flaxseed, tallow, maize, 2-ethyl hexanoic acid, linoleic linolenic, pinoleic, oleic, pelargonic, rosin, stearic, palmitic, hydrogenated ricinoleic;

for example, the alkyd resins are prepared from non-fatty carboxylic mono-acids chosen, for example, from benzoic, butanoic, para-tert-butylbenzoic, caproic, caprylic, capric, propanoic, pentanoic, abietic and crotonic acids;

said alkyd resins have a viscosity of between 1 and 500,000 Pascal seconds at 25 ° C .; preferably between 100000 and

300000 Pascal seconds at 25 ° C the non-alkyd polymers to be crosslinked are resins of polyurethanes, acrylic, vinyl, styrene, silicone, polyamide resins, with or without butadiene, epoxies;

the first and second reagents are in distinct phases, the amine function of the second reagent being not protected by neutralization with a weak and volatile acid, the first and second reagents are separately dispersed or emulsified or microemulsion, and then mixed together together,

the first and second reagents are in distinct phases, the amine function of the second reagent being protected by neutralization with a weak and volatile acid, the first and second reagents are mixed together, and the mixture is then dispersed or emulsion or microemulsion ,

the first reagent and / or the second reagent are in distinct phases, the amine function not being protected by neutralization with the weak and volatile acid, in the aqueous phase in a dispersion, an emulsion or a microemulsion or in an organic phase in solvent or mass;

the first reagent and / or the second reagent are in identical phase, the amine function being protected by neutralization with the weak and volatile acid, in the aqueous phase in a dispersion, an emulsion or a microemulsion or in an organic solvent or mass phase;

the first and second reagents are based on renewable and / or vegetable materials.

Other objects and advantages will become apparent from the following description of the invention.

The process according to the invention is intended for the crosslinking of polymers. The polymers are of the macro-molecule type, alkyd resins or polyesters, or acrylic, vinylic, styrenic, polyurethane or epoxy polymers.

The method comprises a reaction step between a first reagent comprising at least one carbonate function and a second reagent comprising at least one protected amine function.

By reagent is meant a polymeric reactive compound or an additive. The protection of the amine function makes it possible to control the crosslinking. As long as the amine function is protected, the crosslinking is not initiated. The crosslinking reaction is blocked. Once deprotected amine function, it reacts with the carbonate function and initiates crosslinking. When the amine function reacts with the carbonate function there is formation of a urethane group. Advantageously, the crosslinking process according to the invention does not require the use of catalyst or drying agent.

Preferentially, the amine function of the second reagent is a primary or secondary amine.

According to the invention, the process comprises in advance a step of protecting the amine function of the second reagent. If the second reagent comprises several amino functions, they are all protected, advantageously so as to prevent the crosslinking reaction.

The first and second reagents are prepared separately. The protection step is performed on the second reagent. Once, the amine function of the second protected reagent, the first reagent and the second reagent are mixed.

The amine function can be protected according to different embodiments, applicable alone or in combination. The protection of the amine function is temporary until it is applied as a film of paint, glue or plastic transformation.

According to a first possibility, the amine function is protected by neutralization with a weak and volatile acid. The protective agent is a weak and volatile acid. The amine function is neutralized by mixing a weak and volatile acid with the second reagent. The ammonium ion formed is partially dissociated as a base which equilibrates with the weak acid added. Amine forms a salt with weak and volatile acid. Thus, the amine function does not react with the carbonate function present on the first reagent.

By weak acid is meant an acid having a pKa of between 1 and 14 and more precisely between 3 and 9, more specifically between 3 and 7.

In general, the term "weak and volatile acid" is understood to mean any linear or branched carbon chain acid composed of less than six carbon atoms. The volatility of the acid is its ability to vaporize. Advantageously, the boiling temperature is the temperature for which the atmosphere is composed of 100% of this gas. The atmospheric pressure is 101.3 kPa. A vapor pressure of 10 kPa therefore corresponds to an atmosphere containing 10% of corresponding gas. The temperature given for 10 kPa is therefore the temperature at which the atmosphere contains 10% of this molecule in gaseous form.

According to the invention, the acid is said to be volatile when its vapor pressure is greater than 10 kPa for a temperature below 100 ° C, preferably below 85 ° C, more preferably below 80 ° C.

In this way, during the application of the composition of the first and second reagents, the crosslinking is initiated by the evaporation of the weak and volatile acid. Since the crosslinking reaction is an exothermic reaction, there is an increase in temperature which makes it possible to accelerate the evaporation of the acid, hence of the deprotection and therefore of the crosslinking.

By way of a preferred example, the weak and volatile acid is chosen from carbonic acid, formic acid and acetic acid. Carbonic acid is the weak and volatile acid preferred because of its high volatility.

Advantageously, the method according to the invention comprises a step prior to the reaction step between the first reagent and the second reagent consisting of a deprotection step of the amine function. The stage of deprotection does not include the addition of a deprotection reagent; the invention relates to a composition and a method of crosslinking said in a pot.

According to the present embodiment, the deprotection step comprises evaporation of the weak and volatile acid. A volatile acid having a carbon chain from C 1 to C 6 is chosen so that the evaporation is easy. As a preferred example in the field of paints, during the application of a coating layer, the weak acid evaporates so as to deprotect the amine function thus causing its reaction with the carbonate function. The evaporation of the weak acid will shift the chemical equilibrium and initiate the crosslinking.

The process comprises, preferably after the protection step and before the reaction step, a step of contacting the first reagent with the second reagent. Preferably, this contacting step is preceded by the step of protecting the amine function of the second reagent. The second reagent is contacted with the first reagent after the amine function has been protected to avoid any reaction between the amine function and the carbonate function. Preferably, the mixture of the first and second reagents is in the aqueous phase or in the solvent phase so that the deprotection of the amine function takes place during the application of the composition to the open air, and that the water and or the solvent and the weak and volatile acid evaporate, thus allowing the crosslinking between the first and second reagents through the amine function-carbonate function reaction.

Advantageously, the pH of the emulsion is modified during evaporation of the water, thus improving the deprotection of the amine function.

Advantageously, the first reagent and the second reagent are prepared separately. The second reagent comprising the amine function undergoes a protection step. The protection step may consist of the addition of weak and volatile acid. Then, the first reagent and the second reagent are mixed. The mixture is formed into an emulsion or dispersion. Preferably, the first and second reagents are in separate phases before protection of the amine function. That is, the first and second reagents are first separated and mixed to form a single phase. Preferably, the first and second reagents are in the oily organic phase. The process according to the invention with the amine protected by neutralization with a weak and volatile acid also applies to solutions and to the masses.

According to a second additional or alternative possibility, the protection of the amine is carried out by emulsification or microemulsion or dispersion.

Thus, the first reagent and the second reagent are prepared in separate phases. They are each separately emulsified or microemulsion or dispersion. Then they are mixed. The first reagent and the second reagent are then immiscible. The crosslinking reaction is blocked. The first reagent is dispersed in the second reagent or vice versa. The amine function is then unable to react with the carbonate function. Preferably, the first and second reagents are in the oily organic phase. Preferably, the emulsion or dispersion is in the aqueous phase so that the deprotection of the amine takes place during the application of the composition to the open air and the water evaporates allowing the coalescence of the two emulsions, or microemulsions or dispersions, each containing a reagent and thus allowing crosslinking between the first and second reagents through the amine function - carbonate function reaction. The protective agent is water allowing a phase separation.

In one embodiment, the first reagent and the second reagent are prepared in separate phases. The second reagent is mixed with a weak and volatile acid so as to protect the amine function. Then, the first reagent and the second reagent are each separately emulsified or microemulsion or dispersion. Then they are mixed.

The invention also relates to a composition comprising a first reagent bearing at least one carbonate function and a second reagent carrying at least one protected amine function.

Either the composition comprises a weak and volatile acid acting as protector of the amino function, or the composition is in the form of emulsion, microemulsion or dispersion in which the first and second reagents are immiscible. Alternatively, the two protection modes of the amino function can be combined. The composition according to the invention is in the form of an emulsion or microemulsion or dispersion.

The process according to the invention is applicable to any form of composition in emulsion, in dispersion, in microemulsion in aqueous phase or in organic phase in a solvent or bulk medium. The process according to the invention with the amine protected by neutralization with a weak and volatile acid also applies to solutions and to the masses.

The method for crosslinking polymers according to the invention is particularly studied for polymers such as alkyd resins, more specifically alkyd resins modified with carbonate groups and protected amino groups. Alkyd resins are also known as oleoglycerophthalic resins. Conventionally, these alkyd resins are obtained by polyesterification of a polyol, for example glycerol or pentaerythritol, with a polyacid, for example phthalic anhydride modified with fatty acids or oils.

According to the invention, the carbonate function and the protected amine function are carried respectively by a first reagent and a second reagent.

The first and / or second reagent may be linear or branched molecules.

By way of example, the first reagent is a molecule, linear or branched, bearing at least one, preferably several, carbonate function and obtained, for example by reaction between a glycerol carbonate and a polybasic carboxylic acid or an anhydride of at least one functionality. equal to 2 which can be chosen from adipic acid, azelaic acid, citric acid, diglycolic acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid, succinic acid, sebacic acid, trimellitic acid, terephthalic acid and pyromellitic anhydride.

By way of example, the second reagent is a molecule, linear or branched, bearing at least one, preferably several, amine function and obtained, for example by reaction between an amino acid and a polyol.

As an indication and not limiting, the amino acid can be chosen from Alanine, Arginine, Asparagine, Aspartic acid, Cysteine, Glutamic acid, Glutamine, Glycine, Histidine, Isoleucine, Leucine, Lysine, Methionine, Phenylalanine, Proline, Serine, Threonine, Tryptophan, Tyrosine, Valine.

By way of indication and not limitation, the polyol may be chosen from polyols with a functionality of at least 2, such as butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, polyol glycol, glycerol, hexane diol, neopentyl glycol, methyl glucoside, pentaerythritol, pentane diol, polyethylene glycol of molecular weight between 300 and 6000, propylene glycol, 1,3 propane diol, sorbitol , triethylene glycol, trimethylolpropane, trimethylolethane, xylitol, xylose, sugar and cellulosic derivatives.

The first and / or second reagent may be polymers or macromolecules.

Alternatively, the first reagent and the second reagent may be of the same composition before modification by the amine and / or carbonate function. But the first reagent and the second reagent are prepared separately.

The invention is applicable to conventional alkyd resins made from compounds derived from petrochemicals or modified by other polymers: polyurethane, silicone, vinyl polyamide or acrylic. But the invention is particularly advantageous for alkyd bio-sourced resins, that is to say based on renewable raw materials, including plant origin. Currently, there is no plant-based synthon allowing drying qualities and hardness comparable to those obtained by the use of alkyd resins based on phthalic anhydride.

The present process makes it possible to improve the drying of the alkyd resins by crosslinking and thus makes it possible no longer to use metal salts called siccatives for drying alkyd resins.

The alkyd resins are polyesters obtained by polycondensation between at least one polyol and at least one polyacid and modified with oils or fatty acids.

The polyols used for the preparation of bio-sourced or petro-sourced alkyd resin and additives are preferably polyols of functionality at least equal to 2, among which the polyols used By way of example, butylene diol-1,3, diethylene glycol, dipentaerythritol, dipropylene glycol, ethylene glycol, glycerol, hexane diol, neopentyl glycol, pentaerythritol, pentane diol, polyethylene glycol and polypropylene glycol (molecular weight of between 300 and 6000), propanediol-1,3, propylene glycol, sorbitol, triethylene glycol, trimethylolpropane, trimethylolethane, xylose.

It is understood that a mixture of such polyols can also be used.

The polyacids used for the preparation of bio-sourced or petro-sourced alkyd resin and additives are preferably polyacids of functionality at least equal to 2, in carboxylic acid or anhydride form, among which, by way of example, the following polyacids are suitable:

citric acid, isophthalic acid, terephthalic acid, phthalic anhydride, para, meta or ortho, pyromellitic anhydride, trimellitic anhydride, adipic, azelaic, diglycolic, fumaric, maleic, oxalic, succinic, sebacic acid or anhydride.

It is understood that a mixture of such polyacids can also be used.

The monoacids used for the preparation of bio-sourced or petro-sourced alkyd resin and additives are preferably monoacids and may also carry other groups such as hydroxyl, amine, among which, for example, the following monoacids are suitable: abietic acid benzoic acid, p-tertbutyl benzoic acid, methyl benzoic acid, butanoic acid, caproic acid, caprylic acid, capric acid, crotonic acid, 2-ethylhexanoic acid lactic acid, lysine, pentanoic acid, propionic acid.

It is understood that a mixture of such monoacids can also be used.

The derived oils and / or fatty acids are also suitable for the preparation of bio-sourced or petro-sourced alkyd resin and additives, among which the oils or fatty acids with carbon chain of Cs to C32, preferably Cu to C22- By way of example, the following compounds are suitable:

unsaturated fatty acids conjugated or unsubstituted by linoleic acid, linolenic acid, alpha-eleostearic acid, alpha-licanic acid, coconut fatty acids, cotton, linseed, linoleic, linolenic, oleic, pinolenic acids , pelargonic, castor, dehydrated castor, soy, tall oil, sunflower, safflower oils, coconut, cotton, flax, grape seed, oiticica, olive, palm, soya, sunflower, castor, dehydrated castor, soy, tung and tall However, it is understood that a mixture of such fatty acids or oils may also be used.

the oils and fatty acids are chosen from saturated fatty acids and / or mono-fatty acids chosen from castor oil, coconut, cotton, dehydrated castor oil, tall oil, 2-ethyl hexanoic acids, linoleic, linolenic, pinoleic, oleic, pelargonic, rosin, castor oil, coconut, cotton, dehydrated castor oil, soybean oil and tall oil.

The oils and / or fatty acids conventionally used in alkyd resins are oils and / or unsaturated fatty acids, that is to say having a certain number of unsaturation.

The presence of these unsaturations is essential for conventional alkyds because they are the ones that allow the drying of the film by the well-known phenomenon of lipid autooxidation.

The more unsaturation an oil and / or fatty acid has, the better its drying performance.

As a result, traditional alkyds favor the use of oils and / or fatty acids containing as much unsaturation as possible in order to give the resin produced the best performance in terms of drying.

In the context of the present invention, drying involves another mechanism which does not require the presence of unsaturation. Therefore, it is possible to consider the use of other oils and / or fatty acids having less or no unsaturation.

The oils and / or fatty acids are often classified according to their number of unsaturation measured by their iodine number which corresponds to the number of grams of iodine absorbed per 100g of oil.

Knowing the iodine value of a vegetable oil, we can predict its drying quality: an iodine number greater than 130 will indicate an oil having good drying properties;

an iodine number between 1 and 130 will indicate an oil having intermediate drying properties.

an iodine value of less than 1 will indicate an oil which does not dry;

In our case, the use of oils and / or fatty acids having an iodine number of less than 1 would be possible.

By way of nonlimiting example, mention may be made of the oils and fatty acids of rapeseed, castor oil, coconut, tallow, carnation, olive, maize, cotton, safflower safflower, soy, sunflower, tall, nuts, perilla, oiticica, tung, flax.

By way of nonlimiting example, mention may be made of palmitic, stearic, oleic, linoleic, α-linoleic, pinolenic, α-oleostearic, alandicic, hydrogenated ricinoleic and dehydrated ricinoleic acids.

According to another possibility, the invention is particularly advantageous for the preparation of protected two-component polyurethane that can be used in a pot. (Mono-components replacing bi-components). More specifically, for two-component polyurethane systems with controlled reactivity whose polyol is modified with carbonate groups and the crosslinking agent is a protected polyamine.

Traditionally, a one-component composite or polyurethane is a blend of a polyol and a polyisocyanate with protected functions during pot life. The deprotection of the isocyanate functions is generally done by raising the temperature. These products are toxic and irritating.

According to the process of the invention, the urethane group is formed by the crosslinking of a first reagent such as a modified polyol to carry at least one carbonate function with a second reagent comprising at least one protected amine function.

Thus, the crosslinking between the carbonate function and the amine function can take place only under certain conditions including in particular as described above during a step of evaporation of the weak and volatile acid which follows a step of applying the emulsion or the mixture of the first and second reagents.

The present invention has the advantage of excluding the use of toxic polyisocyanate. The first and second reagents are not isocyanates. The invention also makes it possible to have a reaction with controlled reactivity between the amine and the carbonate occurring during the reaction stage which is different from the reactions carried out beforehand in the reactor, as is the case for certain reactions, very alternative reagents to the use of polyisocyanates.

The method makes it possible to prepare polyurethanes by two-component reactive system with controlled reactivity in a pot, without the use of toxic polyisocyanate and without metal-based catalyst also having a certain toxicity.

In addition, the crosslinking process according to the invention generates urethane groups which attribute particularly advantageous properties, in particular mechanical properties. Thus, the coatings obtained from alkyd resins according to the invention have improved drying properties or at least equivalent to those of alkyd resins with driers and improved mechanical or aesthetic performance or at least equivalent.

The emulsions according to the invention and the resulting coatings contribute to the respect of the environment and to sustainable development with performances in application that are at least identical or even improved compared to traditional aqueous coatings.

The present invention is further accompanied by storage stability of aldehyde resin dispersion, as well as compliance with environmental regulations with reduced or zero volatile organic compound levels.

Indeed, thanks to the present invention, the mixture of reactive compounds can be stored before its final application without deterioration of its properties.

The polymers obtained according to the process of the present invention are applicable for air drying, forced air drying and oven drying paints.

Advantageously, the process according to the invention is carried out at room temperature. It is applicable also to hot to speed up the reaction and remains applicable to cold because the reaction occurs even at low temperature. The limit for the low temperature is given by the evaporation of water in an aqueous phase system and / or the weak and volatile acid in the case of this type of protection. The process is therefore favorable for winter applications.

As an illustration of the invention, the following examples demonstrate without any limitation, the performance of the compositions according to the invention and coatings obtained.

Raw materials used

at. Acids and polyacids

Index

Reference Functionality

Acid supplier

commercial COOH

(MgKOH / g)

Tall Arizona fatty acids

/ 192-195 1

Oil Chemicals

Fatty acids

/ Uniqema 200 1 sunflower

Fatty acids of oil

dehydrated castor oil Dedico 5981 Uniqema 193-198 1

conjugates

Nouracid fatty acids

Akzo Nobel 202 1 sunflower isomerized HE305

Benzoic acid / DSM 459.5 1

Phthalic Anhydride / BASF 757, 1 2

Fatty Acids Dimers / Uniqema 2

Lysine / 1

Succinic acid / DSM / Rocket 2

Formic acid

Acetic acid b. Alcohols and polyols

Other additives

Supplier Nature / Function

Formic acid

Neutralizing agent (HCOOH)

Acetic acid

Neutralizing agent (CH3COOH)

Ethoxylated fatty alcohol

/ Nonionic surfactant 310E HLB: 17.4

Iso alcohol C10 ethoxylated

/ Nonionic surfactant 410E HLB: 18.3

Maxemul 7201 CRODA Anionic surfactant

Maxemul 7102 CRODA Nonionic surfactant

Lithine (LiOH, H20) Neutralizing agent

SPX THOR Biocide Acticide (CMIT / MIT)

Coatex BR3 Coatex dispersing agent

BYK 028 IMCD Antifoam Agent

Kemira 660 Kemira Titanium Dioxide Pigment

Nuosept 515 N Biocide

Nuosept BMC 422 Anti-foam

Borchi Oxy Coat ® OMG Borchers Siccative

Thickening agent

Acrysol RM 2020 Rohm & Haas

gradient

Thickening agent

Acrysol RM 12 W Rohm & Haas

gradient d. Compositions and characteristics of alkyd resins mass before emulsification

Quantities are expressed by weight.

Reference

A B C D E

Resin Mass

Alkyd resin

Alkyd Resin Bio-sourced Alkyd Resin

Alkyd Resin Alkyd Resin

according to bio-sourced according to

Conventional definition of bio-sourced

invention according to the invention the unmodified

with amine with amine with carbonate

Petrochemical Petrochemical

Nature Agrochemical Agrochemical Agrochemical e e

Fatty acids

18.5 18.5 / / Tall Oil

Fatty acids

18.5 18.5 12.15 / / Sunflower

Fatty acids

of castor oil

/ / 24.3 12.29 16.37 dehydrated

conjugates

Fatty acids

/ / 42,53 46,08 57,3 dimers

Lysine 9.81 / 9.22 /

Pentaerythritol 25.25 23.94 / / /

Sorbitol 70% / / 31, 24 36.43 24.56

Carbonate

/ / / 8.19 glycerol

Acid

18.75 / / / / Benzoic

anhydride

27.48 36.00 / / / Phthalic

Acid

/ / 6.08 15.36 8.19 Succinic 38 (82 with 13 (61 with 17 (77 with

Length

38 38 Acids Acids Oil acids (%)

Dimers) Dimers) Dimers)

Dry extract (%)

> 99> 99> 99> 99> 99 (1 g, 1 H, 125 ° C)

Viscosity

(Noury, 110 ° C, 40 40 30 25 35 dPa.s)

Acid value

12 12 12 12 12 (mgKOH / g)

Index

22 (Index 10 (Index

hydroxyl 60 50 25 amine = 38) amine = 35)

(MgKOH / g)

Functionality f 2 2 1, 97 1, 98 1, 99

Weight

Molecular 4676 4676 3667 3639 4191 theoretical e. Composition of additives before emulsification

Reference

A B C D

Additive

Di di Succinate phthalate

Triester ester tetra ester

Definition pentaerythritol carbonate carbonate sorbitan

glyceryl glyceryl

Nature Agrochemical Agrochemical Petrochemical Agrochemical

Lysine 81, 1 65.2 //

anhydride

/ / 38.5 /

phthalic

Acid

/ / / 33.3

succinic

Pentaerythritol 18.9 / / /

Sorbitol 70% / 34.8 / /

Carbonate

/ / 61, 66.7 glycerol f. Composition and characteristics of emulsions

The compositions according to the invention are the columns B, D, E, F. In compositions, the amine function is protected by a weak and volatile acid. The reagent carrying the amine function is first mixed with the weak and volatile acid and then the reagent carrying the carbonate function is added.

We describe below the preparation of a composition according to the invention. By way of example for composition B, the resin dB is mixed with carbonic acid. The amine function of the resin dB is neutralized by the weak and volatile acid. Then the additive eC carrying the carbonate function which can not react with the protected amine function is added. Then the mixture is emulsified.

In the case of protection by preparation in two distinct phases of the amine function and of the carbonate function, the first or the second reagent is emulsified or dispersed and then only afterwards, the other reagent is added in the other phase.

2) Test methods:

at. Dry extract :

Determination according to ISO 3251 under the conditions: 1 g, 1 H, 125 ° C expressed as a percentage.

b. Viscosity:

Determination of the Noury viscosity at 110 ° C. of the mass resin according to the AFNOR XPT 51213 standard expressed in dPa.s.

Evaluation of the Brookfield viscosity at 23 ° C., 10 rpm with the mobiles 2 and 3 with a Brookfield RVDVE-230 viscometer according to the ISO 2555 standard.

vs. Particle size:

Determination with a Zetasizer Device from Malvern Instruments Ltd. The sample is diluted to 1% in deionized water for measurement.

d. Acid number:

Determination according to ISO 3682.

e. Hydroxylate number:

Determination according to the NFT 30-403 standard.

f. Drying time: ASTM D 1640

boy Wut. Hardness :

Determination with a Persoz pendulum, on a film of wet thickness of 100pm, applied on a glass plate, according to the ISO 1522 standard. h. Yellowing:

Determination with a Dr Lange Micro Color LMC spectrocolorimeter. Measurements of the yellow index according to ASTM D 1925 on dry films as a function of time. The 100 μm thick films are applied to Leneta with a filmograph.

i. Brilliant:

Determination with a Trigloss micro-gloss meter at 20 ° C or 60 ° C after drying of 100 μm wet films applied to glass plates according to ISO 2813.

3) Preparation and characterization of the emulsions:

at. Process for the preparation of resin mass: the polymers or the macromolecules are prepared according to the techniques of the prior art. When it is an alkyd resin, all the reagents (polyols, polyacids, fatty acids) are mixed and brought to 230 ° C for reaction by eliminating the water formed. When the oil is used, a preliminary step of preparing monoglycerides or acidolysis is necessary. The progress of the reaction is monitored by the measurement of the acid number and the viscosity as a function of time.

b. Process for the preparation of additive It is in this case molecules obtained by conventional acid catalyzed esterification (APTS, AMS) at the temperature between 100 and 150 ° C by removing the water formed by distillation.

vs. Emulsification process The most used method is that by phase inversion. The polymer or macromolecule (resin) to be emulsified is heated to 80 ° C. and then neutralized, and surfactants are added with stirring. Then the water is introduced until phase inversion and then to the desired level of solids. 4) Evaluation of prepared emulsions.

Paint formulations based on aqueous emulsions and film performances.

The performance evaluation of the modified alkyd resin emulsions prepared previously is made on the glossy paint films formulated from these emulsions. Cobalt siccative is used in a formulation to compare performance with and without siccative.

General procedure for the preparation of paints.

Preparation of the grinding base:

In a metal tank (cooled if necessary) introduce successively:

- Water with moderate agitation

- Biocide

- dispersing agent

- Anti-foam

- Titanium dioxide

- Part of the thickening agent with high shear gradient

Then increase the speed of the disperser (about 4000rpm or more) to obtain an effective dispersion of the pigments. Leave stirring for 20-30 minutes.

- Introduce the grinding base in the alkyd resin emulsion with or without driers.

The complement of thickening agents is then added to adjust the viscosities at high and low shear rates.

Composition of the formulations: Example of formulation of a resin. A composition according to the prior art comprises a siccative whereas according to the invention the drying agent is removed because it is no longer necessary. Drying occurs according to the crosslinking process according to the invention.

Component / Reference

Function Parts in commercial weight

Thinner 12

Orotan 1124 Dispersant (carboxylate) 0.35

BYK 028 Anti-foam 0.2

Kemira 660 Titanium Dioxide Pigment 24,22 Nuosept 515N Biocide 0.03

Nuosept BMC 422 Antifoam 0, 15

Binding Alkyd Resin Emulsion 60.5

Acqua 421® Siccatif 0.2

Coapur 3025 High gradient thickening agent 2

Acrysol RM 12 W Thickening Agent Low Gradient 0.35

Total 100

Characteristics of Prepared Paintings: These characteristics are obtained in a substantially equivalent manner for a composition and a process according to the invention for a composition containing a drying agent and a crosslinking process according to the prior art.

Characteristics Units Values

Viscosity ICI 10000s-1 dPa.s 2.2

Viscosity Brookfield mPa.s 4000

PH +/- 6.0

Brightness 90 @ 60

Density Kg / I 1.29

Dry extract% 55

VOC (Volatile Organic Compound) g / i 2.66

CMIT / MIT

ppm 7.5

Chloro / Methyl iso-thiazolone

P / L Report Pigment on Binder 0.4

Claims

1. Process for crosslinking polymers, or macro-molecules, characterized in that it comprises a reaction step between at least one first reagent comprising at least one carbonate function and at least one second reagent comprising at least one protected primary or secondary amine function by a protective agent and configured to be deprotected by evaporation of the protective agent so as to crosslink with at least one carbonate function of the first reactant during said reaction, the first reagent and / or the second reagent being a polymer to be crosslinked .

2. The method of claim 1 wherein the amine function is protected by neutralization with a weak and volatile acid.

3. Method according to the preceding claim wherein the weak and volatile acid has a pKa between 1 and 14, preferably between 3 and 9.

4. Method according to one of the two preceding claims wherein the weak and volatile acid has a vapor pressure greater than 10 kPa at a temperature below 100 ° C, preferably below 85 ° C.

5. Process according to any one of the three preceding claims, in which the weak and volatile acid is chosen from C1 to C6 carbon chain acids _, and preferentially from carbonic acid, formic acid, and acid. acetic.

6. Process according to any one of the preceding claims, comprising, prior to the reaction step, a step of evaporation of the weak and volatile acid during which the amine function is deprotected to be able to react with the carbonate function for crosslink and form a urethane group.

The method of any of the preceding claims wherein the first reagent and the second reagent are each in emulsion or microemulsion or dispersion form so that they are immiscible to protect the amine function of the second reagent.

8. Method according to the preceding claim comprising, prior to the reaction step, a step of evaporation of water and coalescence of the two emulsions or microemulsions or dispersions containing respectively the first reagent and the second reagent during which the amine function is deprotected to be able to react with the carbonate function to crosslink and form a urethane group.

9. Process according to any one of the preceding claims wherein the deprotection of the amine function is carried out without the addition of an additional deprotection reagent.

10. Process according to any one of the preceding claims, in which the first reagent is a linear or branched molecule obtained by reaction between a glycerol carbonate and a polycarboxylic acid or an anhydride of functionality at least equal to 2.

1 1. A process according to any one of the preceding claims wherein the second reagent is a linear or branched molecule obtained by reaction between an amino acid and a polyol.

The process of any of the preceding claims wherein the first and second reagents are not isocyanates.

13. Process according to any one of the preceding claims, in which the polymers to be crosslinked are alkyd resins.

14. Process according to the preceding claim, in which the alkyd resins are polyesters obtained by polycondensation between at least one polyol and at least one polyacid and modified with oils or fatty acids.

15. Method according to the preceding claim wherein the oils and fatty acids are chosen from oils and fatty acids comprising a carbon chain of 8 to 32 carbon atoms, preferably 14 to 22.

16. Process according to any one of the two preceding claims, in which the oils and fatty acids are chosen from conjugated or unsaturated unsaturated fatty acids chosen from linoleic acid, linolenic acid and alpha-eleostearic acid. alpha licanic acid, oleic, pinolenic, pelargonic, ricinolenic, dehydrated ricinolenic acids, safflower, coconut, cotton, linseed, grapeseed, oitica, olive, palm, soya, sunflower, castor, dehydrated castor oil , tung, tall oil, perilla, nuts, rapeseed and flax.

17. Process according to any one of the three preceding claims, in which the oils and fatty acids are chosen from the acids saturated fats and / or mono-fatty acids chosen from 2-ethylhexanoic acid, linoleic acid, linolenic acid, pinoleic acid, oleic acid, pelargonic acid, rosin, stearic acid, palmitic acid, hydrogenated ricinoleic acid, flaxseed oil, sunflower oil, safflower oil, grape seed, oïticica, olive, palm, tung, perilla, nut, rape, flax, tallow, maize, castor oil, coconut, cotton, dehydrated castor, soy and tall oil.

18. Process according to any one of the four preceding claims, in which the alkyd resins are prepared from mono acids chosen from benzoic, butanoic, para-tert-butylbenzoic, caproic, caprylic, capric, propanoic, pentanoic and abietic acids. and crotonic.

19. A process according to any one of claims 10 or 14 to 18 wherein the polyacid is a polycarboxylic acid or an anhydride of functionality at least 2 which may be selected from adipic acid, azelaic acid, citric acid, diglycolic acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid, succinic acid, sebacic acid, trimellitic acid, terephthalic acid and pyromellitic anhydride.

20. Process according to any one of claims 1 1 or 14 to 19 wherein the polyol is a polyol with a functionality of at least 2 which may be chosen from butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, glycol, glycerol, hexane diol, neopentyl glycol, methyl glucoside, pentaerythritol, pentane diol, polyethylene glycol of molecular weight between 300 and 6000, propylene glycol, 1,3 propane diol, sorbitol, triethylene glycol, trimethylolpropane, trimethylolethane, xylitol, xylose, sugar and cellulose derivatives.

21. Process according to claims 13 to 20 wherein said alkyd resins have a viscosity of between 1 and 500000 Pascal seconds at 25 ° C, preferably between 100000 and 300000 Pascal seconds at 25 ° C.

22. Process according to any one of the preceding claims, in which the polymers to be crosslinked are polyurethane, silicone, vinyl, polyamide, acrylic, epoxy or styrenic polymers.

23. A method according to any one of the preceding claims wherein the first reagent and / or the second reagent are in a dispersion, an emulsion or a microemulsion in aqueous phase or in organic phase in a solvent or bulk medium.

24. Process according to any one of the preceding claims, in which the first and second reagents are based on renewable and / or vegetable raw materials.

25. Composition comprising polymers intended to crosslink characterized in that it comprises a first reagent comprising at least one carbonate function and a second reagent comprising at least one amine function protected by a protective agent and intended to be deprotected to react with less a carbonate function of the first reagent, the first and / or the second reagent being a polymer to be crosslinked.

26. Composition according to the preceding claim comprising a weak and volatile acid for neutralizing the amine function of the second reagent.

27. Composition according to the preceding claim wherein the weak and volatile acid is selected from C1 to C6 carbon chain acids _, and preferably from carbonic acid, formic acid, acetic acid.

28. Composition according to any one of claims 25 to 27 wherein the first reagent and the second reagent are each in the form of emulsion or dispersion immiscible with the other emulsion or dispersion so as to protect the amine function of the second reagent. .

29. Composition according to any one of claims 25 to 28 wherein the first and the second reagent are based on renewable and / or vegetable raw materials.

30. Composition according to any one of claims 25 to 29 which does not comprise added reagent for deprotecting the amine function.

31. Use of the crosslinked polymers obtained by the process according to one of claims 1 to 24 as a decorative or industrial coating.

32. Use of the crosslinked polymers obtained by the method according to one of claims 1 to 24 as an adhesive, putty or hot melt.

33. Use of the crosslinked polymers obtained by the method according to one of claims 1 to 24 as a plastic additive or crosslinking agent for the processing of plastics.