Classifications

• • 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
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
  • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/42—Amides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/43—Thickening agents
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/48—Thickener, Thickening system
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to a rheology additive based on a fatty diamide derived from 1,5-pentamethylene diamine, preferably biobased, more preferably 100% biobased. It also relates to its uses and more particularly as a rheology additive in binder compositions for applications in coatings, glues or adhesives, molding compositions, sealants or sealants or cosmetics.
• Hexamethylene diamine is a diamine of fossil origin known to be used in rheology additives based on fatty diamides based on 12-hydroxy stearic acid as described for example in WO 2014/053774 and WO 2015/01 1375.
• 1,5-pentamethylene diamine possibly biobased, such as cadaverine to replace all or part of hexamethylene diamine, in the fatty diamides used as rheology additives does not seem to be known in the art. 'state of the art.
• the rheological performance of a fatty diamide is difficult to predict by replacing one component with another. Furthermore, predicting the behavior of a new organogelator still remains one of the major challenges of supramolecular chemistry as described in Langmuir 2009, 25 (15), 8392-8394.
• the physicochemical phenomena involved are very complex and difficult to predict, with the performance of the rheology additive governed by a sum of weak non-covalent interactions (hydrogen bonds, Van der Waals forces, etc.) depending on the molecular structure of this additive.
• the first object of the present invention relates to an additive which, according to option A), consists of a) a symmetrical fatty diamide, preferably biobased, more preferably 100% biobased, based on 1,5-pentamethylene diamine, preferably based on cadaverine, and a hydroxylated fatty acid and according to option B), it comprises said diamide a) and in addition b) a second symmetrical diamide based on a diamine different from the 1,5-pentamethylene diamine, preferably different from cadaverine, and chosen from cycloaliphatic, aliphatic or aromatic and a hydroxylated fatty acid.
• the second object of the invention relates to an organic binder composition, which comprises at least one rheology additive as defined according to the invention.
• the last object of the invention relates to the use of said additive according to the invention in compositions for coatings, glues or adhesives, in particular for molding composites, sealants or sealants or cosmetics.
• the first object of the invention therefore relates to a rheology additive, which according to: A) said additive consists of:
• said additive comprises:
• (AGH), NHCO and CONH having the same definition as that given above in formula (I) and (R) being the residue without amine groups of a diamine other than 1, 5-pentamethylene diamine, preferably other than cadaverine, chosen from a cycloaliphatic, aliphatic or aromatic diamine, preferably a linear cycloaliphatic or aliphatic diamine , more preferably a cycloaliphatic diamine.
• said additive according to the invention is defined according to option A).
• said additive is 100% of fatty diamide a), preferably with a) being biobased, more preferably with a) being biobased at 100%, and therefore at 0% of diamide b) as defined above.
• bio-based means according to the present invention based on raw materials of biological origin with renewable resources. These raw materials can be characterized and distinguished from materials of non-renewable fossil origin by the rate of carbon 14 ( 14 C).
• Raw materials from renewable resources (100% biobased) have a rate of 14 C close to that of the atmosphere while those of fossil origin (0% biobased) have a rate almost zero compared to original materials renewable.
• the 14 C assay also makes it possible to determine the rate of biobased raw material in the final product. For such an analysis, the product or raw material is burned and the analysis is carried out on the C0 2 recovered according to the ASTM D-6866 method.
• said additive according to the invention is defined according to alternative option B).
• said fatty diamide b) is present with said diamide a) in said additive according to the invention.
• said additive of the invention is a mixture of diamide a), preferably biobased, more preferably biobased at 100%), and of fatty diamide b) as defined above.
• said fatty diamide a) is in particular present at a rate by weight relative to a) + b), ranging from 0.5 to 99.5%, preferably from 5 to 75%, more preferably from 7 to 50%, more preferably still from 10 to 45%.
• said fatty diamide a) is in particular present at a rate by weight relative to a) + b), ranging from 0.5 to 99.5% or 1 to 95% or 5 to 75 % or 5 to 50% or 5 to 45% or 7 to 50% or 7 to 45% or 10 to 50% or 10 to 45% or 50 to
• the biobased fatty diamide a) has the advantage of providing excellent synergy and compatibility in the presence of the second fatty diamide b) to allow the application performance to be adjusted according to the usage application.
• the hydroxylated fatty acid R1CO2H can be selected from: 12-hydroxy stearic acid (12HSA), 9-hydroxy stearic acid, 10-hydroxy stearic acid or 14-hydroxy eicosanoic acid or mixtures thereof, preferably binary mixtures.
• the hydroxylated fatty acid R1CO2H is preferably 12-hydroxy stearic acid (12HSA).
• diamine H 2 NR-NH 2 on which the second fatty diamide is based b when the latter is present in the rheology additive according to the invention, it can be cycloaliphatic, linear or aromatic aliphatic, preferably cycloaliphatic or linear aliphatic, more preferably cycloaliphatic.
• cycloaliphatic primary diamines cycloaliphatic meaning comprising in its structure at least one ring saturated with Ce
• the residue (R) of the fatty diamide b) is the residue of 1,3-bis (aminomethyl) cyclohexane.
• the proportion by weight of the fatty diamide a) relative to the weight a) + b) can in particular range from 5 to 50% or 5 to 45% or 7 to 50% or 7 to 45% or 10 to 50% or 10 to 45% or 50 to 95% or 55 to 95% or 60 to 95% or 70 to 95% or 50 to 90% or 55 to 90% or 60 to 90% or 70 to 90%, the limits upper and lower of the ranges indicated can be combined with each other.
• linear aliphatic primary diamines there may be mentioned the primary diamines ethylene diamine, diethylene triamine, 1, 3-propylene diamine, 1, 4-butylene diamine, 1, 6-hexamethylene diamine.
• the residue (R) of the fatty diamide b) is the residue of 1,6-hexamethylene diamine.
• the proportion by weight of the fatty diamide a) relative to the weight a) + b) may in particular range from 30 to 70% or 35 to 65% or 40 to 60% or 45 to 55%, the limits upper and lower of the indicated ranges can be combined with each other, the upper and lower limits of the indicated ranges can be combined with each other.
• aromatic diamines aromatic meaning comprising in its structure at least one aromatic ring
• aromatic diamines aromatic meaning comprising in its structure at least one aromatic ring
• o-, m- and p-phenylene diamine o-, m- and p-xylylene diamine, preferably m -xylylene diamine.
• the preparation of the fatty diamides a) and b) is carried out according to synthesis methods well known to those skilled in the art by reacting the hydroxylated fatty acid with the diamine or the mixture of diamines in the molten state at a temperature between 135 and 180 ° C with elimination of the condensation water.
• the ratio of amine / carboxy equivalents is in a range around the stoichiometry (0.95 / 1.05).
• the reaction is considered finished when the amine number or the acid number is less than 8, preferably less than 5 mg KOH / g.
• the final molten fatty diamide is cooled and then ground in a micronizer and put into the form of micronized powder before final use.
• the rheology additive according to the invention is in the form of micronized powder having a particle size corresponding to a volume average size ranging from 1 to 15 ⁇ m, measured by dry particle size.
• the particle size was determined in accordance with ISO 13320: 2009 using the Malvern Mastersizer S. This technique is based on the principle that particles passing through a laser beam diffract light at a different angle depending on their size. : particles of small sizes diffract at large angles, while particles of larger sizes diffract at small angles.
• the second object of the present invention relates to an organic binder composition, which comprises at least one rheology additive as defined above.
• said organic binder composition is a composition of coatings, glues or adhesives, molding, in particular composite, sealants or sealants or cosmetics.
• the coating compositions are chosen from paints, varnishes and inks in a non-reactive solvent medium and so-called “gel coats” surface coatings in a reactive solvent medium.
• Said organic binder can be selected from: epoxy resins, unsaturated and saturated polyesters, vinyl esters, alkyds, silane (or silylated) resins, polyurethanes, polyester-amides, acrylic solvents, monomers and / or multifunctional acrylic oligomers or acrylic resins acrylic with reactive diluent or inert resins diluted in reactive or non-reactive solvent.
• said binder can comprise silylated polyurethanes, silylated polyethers and polyesters, silylated polybutadienes.
• Another subject of the invention relates to the use of the rheology additive as defined according to the invention, in compositions for coatings, glues or adhesives, molding, in particular composites, sealants or d sealants or cosmetics.
• part of the invention is a finished product chosen from a coating film, an adhesive joint, an adhesive joint, a sealant joint, a sealant joint, a cosmetic product or a part.
• Example 1 diamide according to definition a) of the invention: 12-HSA-PMDA-12-HSA
• Example 2 Diamide according to the state of the art: 12-HSA-1 .3BAC-12HSA
• Example 3 Diamide according to the state of the art: 12-HSA-HMDA-12-HSA
• Example 4 mixture a) + b) according to the invention with diamide of Example 1 (diamide according to a)) + diamide of Example 2 (diamide according to b))
• Example 5 comparative mixture according to the state of the art: diamide of example 2 + diamide of example 3
• Example 6 mixture according to the invention: diamide of example 1 + diamide of example 3
• diamide of example 1 diamide of example 3
• 425.22 g 12-hydroxystearic acid (1.36 moles, 2 eq) are added.
• the mixture is heated to 180 ° C under an inert atmosphere.
• the eliminated water accumulates in the Dean Stark from 150 ° C.
• the reaction is controlled by the acid and amine index. When the acid and amine numbers are less than 5 respectively, the reaction is stopped.
• the reaction mixture is cooled to 140 ° C. and is discharged into a silicone mold. A bis cooled to room temperature the product and transformed into scales.
• Example 7 mixture according to the invention: diamide of example 1 + diamide of example 3
• Example 4 is reproduced by introducing 55.69 g of 1,5-pentamethylene diamine
• Example 8 comparative mixture according to the state of the art: diamide of example 2 + diamide of example 3
• Example 5 is reproduced by introducing 62.38 g of 1.6-hexamethylene diamine (0.54 moles, 0.8 eq), 19.08 g of 1.3-bis (aminomethyl) cyclohexane (0.13 moles , 0.2 eq) and 418.25 g of 12-hydroxystearic acid (1.34 moles, 2 eq).
• the amides prepared were evaluated in formulations of epoxy paints with a high solids content (or high solids content) in xylene.
• the formulation is again dispersed using a 4 cm blade at 3000 rpm.
• the diamide to be evaluated is introduced into the millbase and activated in situ at 55 ° C for 20 mirutes and at 3000 rpm.
• the evaluation is carried out only 24 hours after activation and 30 minutes after the hardener diluted in xylene has been added to the millbase (see Table 3) and the paints thus obtained are adjusted in paint application viscosity with a xylene / butanol mixture (1/1 by weight) at approximately 0.4 P or approximately 400 mPa.s (more precisely 0.37-0.38 P or 370-380 mPa.s) measured on the cone 4 to 25 ° C at 2500 s-1 using a Brookfield CAP ® 1000. the proportions of the hardener and the 10 mixture of solvents are defined in table 4 below.
• the amount of 1/1 xylene / butanol mixture used for viscosity adjustment may vary, but generally less than 1% from test to test. After adjustment, the paint is mixed / homogenized at 1500 rpm for 25 minutes, then left to stand for 30 minutes before the evaluation 24 hours after.
• the mixture of the diamide of example 1 based on PMDA and the diamide of example 3 based on HMDA shows a positive synergy in the sag resistance test in comparison with each diamide taken individually (cf. comparison of Examples 1 and 3 compared to Example 6).
• the partial replacement of 1,6-hexamethylene diamine by 1,5-pentamethylene diamine improves the rheological performance in the system studied.
• the mixture of the diamide of example 1 based on PMDA with another diamide shows a positive synergy in the test for resistance to sagging in comparison with a comparative mixture comprising the diamide of example 3 based on HMDA, in the same proportions (cf. comparison of example 5 according to the invention with comparative example 4 or comparison of example 7 according to l invention with Comparative Example 8).
• an additive based on 1,5-pentamethylene diamine preferably biobased, not only makes it possible to respond to an environmental issue but also to contribute to obtaining excellent rheological performances, in particular in paint formulations with high dry extract.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Veterinary Medicine (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
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• Wood Science & Technology (AREA)
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• Engineering & Computer Science (AREA)
• Dermatology (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Cosmetics (AREA)
• Sealing Material Composition (AREA)
• Paints Or Removers (AREA)

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• 2018
  • 2018-10-26 FR FR1859908A patent/FR3087779B1/fr active Active
• 2019
  • 2019-10-18 EP EP19813376.1A patent/EP3870642A1/fr active Pending
  • 2019-10-18 US US17/288,100 patent/US20210380527A1/en active Pending
  • 2019-10-18 CN CN201980070556.9A patent/CN112955501B/zh active Active
  • 2019-10-18 JP JP2021522411A patent/JP7447106B2/ja active Active
  • 2019-10-18 KR KR1020217015095A patent/KR20210084510A/ko active Search and Examination
  • 2019-10-18 WO PCT/FR2019/052478 patent/WO2020084231A1/fr unknown
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