Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
  • C09J167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
  • C08K5/1565—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

• the present invention relates to a process for crosslinking polymers and macromolecules, the use of crosslinked polymers and an associated composition.
• 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.
• 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.
• 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.
• 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.
• the temporary protection, advantageously total, of the amine function allows the storage in a single container of the different reagents.
• 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.
• 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.
• 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;
• 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.
• 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.
• 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 deprotection is carried out by evaporation of a protective agent
• the amine function is a primary or secondary amine function
• 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;
• 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.
• 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 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;
• 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;
• 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,
• oils and fatty acids are chosen from oils and fatty acids comprising a carbon chain of Cs to C32, preferably Cu to
• 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;
• 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;
• 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
• 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.
• 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.
• 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.
• the crosslinking process according to the invention does not require the use of catalyst or drying agent.
• the amine function of the second reagent is a primary or secondary amine.
• 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.
• 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.
• the amine function does not react with the carbonate function present on the first reagent.
• weak acid an acid having a pKa of between 1 and 14 and more precisely between 3 and 9, more specifically between 3 and 7.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the pH of the emulsion is modified during evaporation of the water, thus improving the deprotection of the amine function.
• 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.
• the first reagent and the second reagent are mixed.
• the mixture is formed into an emulsion or dispersion.
• 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.
• the first and second reagents are in the oily organic phase.
• the protection of the amine is carried out by emulsification or microemulsion or dispersion.
• 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.
• the first and second reagents are in the oily organic phase.
• 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.
• 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.
• 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
• a composition comprising a first reagent bearing at least one carbonate function and a second reagent carrying at least one protected amine function.
• composition comprises a weak and volatile acid acting as protector of the amino function
• composition is in the form of emulsion, microemulsion or dispersion in which the first and second reagents are immiscible.
• 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.
• alkyd resins are also known as oleoglycerophthalic resins.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• polyols with a functionality of at least 2, such as butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, polyol glycol
• the first and / or second reagent may be polymers or macromolecules.
• 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
• 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.
• 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.
• 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.
• 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-
• the following compounds are suitable:
• 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.
• 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.
• 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.
• 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.
• 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
• oils and / or fatty acids having an iodine number of less than 1 would be possible.
• 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.
• 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.
• 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.
• 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.
• the crosslinking process according to the invention generates urethane groups which attribute particularly advantageous properties, in particular mechanical properties.
• 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.
• 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.
• 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.
• Nonionic surfactant 310E HLB 17.4
• Nonionic surfactant 410E HLB 18.3
• Kemira 660 Kemira Titanium Dioxide Pigment
• compositions according to the invention are the columns B, D, E, F.
• 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.
• 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.
• the additive eC carrying the carbonate function which can not react with the protected amine function is added.
• the mixture is emulsified.
• the first or the second reagent is emulsified or dispersed and then only afterwards, the other reagent is added in the other phase.
• Trigloss micro-gloss meter Determination with a Trigloss micro-gloss meter at 20 ° C or 60 ° C after drying of 100 ⁇ m wet films applied to glass plates according to ISO 2813.
• 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.
• 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 Paint formulations based on aqueous emulsions and film performances.
• 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.
• Characteristics of Prepared Paintings 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.
• VOC Volatile Organic Compound

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• 2011
  • 2011-03-30 FR FR1152663A patent/FR2973383B1/fr active Active
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