WO2012079999A1 - Composites structuraux avec une matrice de polycarbamide continue avec des propriétés fonctionnelles pour applications structurales - Google Patents

Composites structuraux avec une matrice de polycarbamide continue avec des propriétés fonctionnelles pour applications structurales Download PDF

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Publication number
WO2012079999A1
WO2012079999A1 PCT/EP2011/071589 EP2011071589W WO2012079999A1 WO 2012079999 A1 WO2012079999 A1 WO 2012079999A1 EP 2011071589 W EP2011071589 W EP 2011071589W WO 2012079999 A1 WO2012079999 A1 WO 2012079999A1
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reagent
filler
alkyl group
fiber
group
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Domenico De Nardi
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ECOPOLIMERI Srl
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ECOPOLIMERI Srl
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3296—Hydroxyamines being in latent form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/02—Polyureas
    • 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
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a composite material that comprises a polycarbamide resin and a filler, to a method for preparing said composite material and to the elements obtained by means of said composite material.
  • Composite materials comprise a continuous matrix having an organic polymeric base and a dispersed filler.
  • organic matrixes are the ones based on unsaturated polyester resins and the ones based on epoxy resins.
  • the former have been used very widely in all applications requiring large volumes, typically in the construction sector and in the production of large manufactured articles, also thanks to interesting technical characteristics and to their relatively low cost.
  • Their main limitation derives from the considerable environmental impact linked to the use of styrene as liquid monomer, which has the function of fluidifying the preformed unsaturated polyester resin and to take part, therefore, as reactive solvent, in the cross-linking process initiated by free radicals produced in situ.
  • Epoxy resins have no volatile components and are much more eco-compatible in the step of composite production, but their cost is high. Both types of resin in any case yield cross-linked matrixes of the composite and this makes any recycling extremely difficult and onerous, since the resulting molecular structures cannot be melted, are insoluble and also very difficult to degrade by thermal means.
  • the derived composites described in the background art even with high contents of fillers of the inorganic type, have a low flame resistance, because a superficial layer of substantial thickness is constituted by organic substance.
  • the aim of the present invention is to provide a composite material with low environmental impact which comprises a continuous matrix with an organic polymeric base and a dispersed filler.
  • An object of the present invention is to provide a method for preparing said material that is eco-compatible, can be provided on an industrial scale and at low cost.
  • Another object of the present invention is to provide structures and manufactured articles that comprise a micro- or nanostructural composite material that is adapted also for use in the construction of structural manufactured articles, particularly if they are large.
  • a composite material comprising a filler of fiber or powder selected among glass filler, basalt filler, carbon filler and mixtures thereof and a polycarbamide resin obtained by means of a process that comprises reacting a diamine compound of formula A (reagent A) and a diisocyanate compound of formula B (reagent B), to obtain a polycarbamide resin of type C
  • Ri and R 2 can be independently H, an alkyl group unsubstituted or substituted with heteroaromatic groups, an aromatic group, an alkyl or aromatic ester, an alkyl or aromatic ether, siloxane groups or heteroaromatic groups, provided that Ri and R 2 are not both H;
  • X is a linear or branched alkyl group or an aromatic group, which can be optionally substituted with amine functional groups
  • Y is an alkyl group, an aromatic group, a polyisocyanate group
  • m and n are independently an integer comprised between 2 and 20.
  • the aim and objects of the present invention are achieved, moreover, by means of an element made of composite material obtained by depositing successive layers of filler and of a polycarbamide resin obtained by means of a process that comprises reacting a diamine compound of formula A (reagent A) and a diisocyanate compound of formula B (reagent B), to obtain a polycarbamide resin of type C
  • Ri and R 2 can be independently H, an alkyl group unsubstituted or substituted with heteroaromatic groups, an aromatic group, an alkyl or aromatic ester, an alkyl or aromatic ether, siloxane groups or heteroaromatic groups, provided that Ri and R 2 are not both H;
  • X is a linear or branched alkyl group or an aromatic group, optionally substituted with amine functional groups
  • Y is an alkyl group, an aromatic group, a polyisocyanate group; and m and n are independently an integer comprised between 2 and 20.
  • composition that comprises a diisocyanate compound in which at least one additive selected among a glassy, metallic, saline, organic material or mixtures thereof is dispersed and in which the diisocyanate compound has the formula B (reagent B), in which Y is an alkyl group or a polyisocyanate group; and m is an integer comprised between 2 and 20.
  • a diisocyanate compound in which at least one additive selected among a glassy, metallic, saline, organic material or mixtures thereof is dispersed and in which the diisocyanate compound has the formula B (reagent B), in which Y is an alkyl group or a polyisocyanate group; and m is an integer comprised between 2 and 20.
  • Ri and R 2 can be independently H, an unsubstituted alkyl group, an alkyl ester, an alkyl ether or siloxane groups, provided that i and R 2 are not both H;
  • X is a linear or branched alkyl group that can be optionally substituted with amine functional groups
  • n is an integer comprised between 2 and 20 and
  • the aim and objects of the present invention are also achieved by means of a micro- and nanocomposite structural material having a continuous polycarbamide matrix that can be obtained by way of said process.
  • the aim and objects of the present invention are also achieved by using said material to produce manufactured articles (or elements).
  • the aims and objects of the present invention are also achieved by means of a composite material that comprises a filler and said micro- and nanocomposite structural material having a continuous polycarbamide matrix and by means of a panel-shaped structure of composite material obtained by means of a method that comprises the deposition of successive layers of a fiber with weft and of said composite material.
  • filler designates a material that is not chemically reactive with respect to a resin and in suitable physical form, for example as fiber or powder, which can be added to the resin in order to give desired proprieties.
  • suitable physical form for example as fiber or powder
  • fillers of glassy, metallic, saline, organic material and derivatives thereof that can be used in the present invention are: glass fiber, basalt fiber, carbon fiber.
  • nanostructured particle is understood to reference a particle of an organic or inorganic material in which at least one of the dimensions is on the order of nanometers, such as synthetic or natural alumosilicates (montmorillonite) .
  • structural composite material with continuous matrix is understood to reference a two-phase material constituted by a polymeric phase in which fillers are dispersed and on the surface of which adhesive forces occur with respect to the polymer that constitutes the continuous matrix.
  • the expression "coupling agent” is understood to reference a multifunctional molecule with two or more functionalities, added to the formulation of the resin, capable of forming bonds with amine groups and/or isocyanic groups, for example triisocyanates - polyols - carboxylic acids, polyamines.
  • nanocomposite is understood to reference a composite material that comprises particles of nanometric size.
  • alkyl group references a linear or branched chain of saturated aliphatic hydrocarbons C1-C20 and the term “polyisocyanate” references a molecule with more than one isocyanic group -NCO.
  • organophilically modified montmorillonite and “organophilically modified hydrocalcites” respectively designate synthetic and natural alumosilicates treated with alkyl ammonium salts.
  • An aspect of the present invention relates to a composite material that comprises a fiber or powder filler selected among glass filler, basalt filler, carbon filler and mixtures thereof and a polycarbamide resin obtained by means of a process that comprises reacting a diamine compound of formula A and a diisocyanate compound of formula B, to obtain a polycarbamide resin of type C Reagent A Reagent B
  • Ri and R 2 can be independently H, an alkyl group unsubstituted or substituted with heteroaromatic groups, an aromatic group, an alkyl or aromatic ester, an alkyl or aromatic ether, siloxane groups or heteroaromatic groups, provided that Ri and R 2 are not both H;
  • X is a linear or branched alkyl group or an aromatic group, which can be optionally substituted with amine functional groups;
  • Y is an alkyl group, an aromatic group, a polyisocyanate group; and m and n are independently an integer comprised between 2 and 20.
  • the filler has the form of filament or fabric, with dimensions from 1 cm to 100 cm in length.
  • the filler has the appearance of powder with dimensions from 0.1 to 100 nanometers.
  • the filler is contained in a quantity comprised between 1% and 80% by weight on the total weight of the composition.
  • An aspect of the present invention relates to an element made of composite material obtained by means of the deposition of successive layers of filler and of a polycarbamide resin obtained by way of a process that comprises reacting a diamine compound of formula A and a diisocyanate compound of formula B to obtain a polycarbamide resin of type C
  • Ri and R 2 can be independently H, an alkyl group unsubstituted or substituted with heteroaromatic groups, an aromatic group, an alkyl or aromatic ester, an alkyl or aromatic ether, siloxane groups or heteroaromatic groups, provided that Ri and R 2 are not both H;
  • X is a linear or branched alkyl group or an aromatic group, optionally substituted with amine functional groups
  • Y is an alkyl group, aromatic group, a polyisocyanate group; and m and n are independently an integer comprised between 2 and 20.
  • the filler is at least a fiber with weft selected among a glass fiber, a basalt fiber or a carbon fiber, comprising a fabric with fibers arranged in a manner that is not prearranged and a fabric with ordered and crossed wefts.
  • the present invention relates to a composition that comprises a diisocyanate compound in which at least one additive selected among a glassy, metallic, saline, organic material or mixtures thereof is dispersed and in which the diisocyanate compound has the formula B (reagent B)
  • Reagent B in which Y is an alkyl group or a polyisocyanate group; and m is an integer comprised between 2 and 20.
  • the additive is present in a quantity comprised between 0.5% and 5% by weight on the total weight of the composition.
  • the filler is at least one among: glass fiber, basalt fiber, carbon fiber.
  • the additive is preferably selected among organophilically modified montmorillonite, sodium montmorillonite, aluminum hydroxide, magnesium hydroxide, organophilically modified hydrocalcites, bohemites, aluminum oxide.
  • the additive is of micrometric size or in nanostructured form, in powder or liquid.
  • the additive is pretreated with a coupling agent, such as an aminosilane, before being dispersed in the reagent B.
  • a coupling agent such as an aminosilane
  • An aspect of the present invention relates to a method for obtaining a material that comprises the following steps:
  • i and R 2 can be independently H, an unsubstituted alkyl group, an alkyl ester, an alkyl ether or siloxane groups, provided that Ri and R 2 are not both H;
  • X is a linear or branched alkyl group that can be optionally substituted with amine functional groups; and n is an integer comprised between 2 and 20 and b) polymerization of the mixture obtained in step a).
  • the diamine compound A has the following formula (I);
  • X is a linear, branched or cyclic alkyl group, optionally substituted with amine functional groups;
  • Rio-Ro equal or mutually different, are selected independently among linear, cyclic or branched aliphatic groups.
  • the reagents A and B comprise no more than two reactive functionalities in the reaction of polymerization per molecule of reagent.
  • the present invention relates to a micro- and nanocomposite structural material with continuous polycarbamide matrix that can be obtained by way of said method.
  • the additive added in dispersion in the reagent B is present in a percentage comprised between 0.1% and 5% by weight on the total weight of the material.
  • the present invention relates to a manufactured article that is suitable for the construction of hulls, pipes, beams, car and motorcycle parts, tanks, which comprises the micro- and nanocomposite structural material with continuous polycarbamide matrix that can be obtained by way of said method or to a composite material that comprises a filler and the micro- and nano composite structural material with continuous polycarbamide matrix that can be obtained by way of said method.
  • the present invention relates to a panel-shaped structure of composite material obtained by means of a method that comprises the deposition of successive layers of a fiber with weft and of the micro- and nanocomposite structural material with continuous polycarbamide matrix that can be obtained by way of said method.
  • the fiber with weft is at least one among a glass fiber, a basalt fiber, a carbon fiber and mixtures thereof, comprising a fabric with fibers arranged in a manner which is not prearranged and a fabric with ordered and crossed wefts.
  • the filler used in the material, in the element, in the structure, in the composition and in the method of the invention may have dimensions that vary from micro (10 "5 to 10 "6 m) to nano (10 "7 to 10 “9 m) and the particles that constitute it may have different shapes (for example spheres, fibers, planar particles).
  • the present invention thanks to the nature of the resins and of the specific steps of synthesis, allows to prepare a composite material using volatile toxic substances in minimal or negligible quantities and therefore can be performed in high eco-compatible production conditions.
  • the method of the present invention allows to prepare composite materials with excellent functional proprieties with the ultimate purpose of obtaining manufactured articles of different kinds, comprising resin ones, thanks also to the considerable efficiency of the polycarbamide resins used in the present invention in bonding as continuous matrixes a large number of reinforcing fillers with ample structural possibility, in particular by varying conveniently the chemical structures of the diamine component, of the diisocyanate component and of the chain extenders and/or cross-linking agents.
  • the diamine and the diisocyanate used in the method of the present invention may both have reactive functionalities in a number of no more than two per molecule.
  • the use of reagents with these characteristics allows to provide a completely thermoplastic continuous matrix.
  • the diamine compound A is a ester derivative of aspartic acid with formula (I)
  • X is a linear alkyl group constituted typically by 6 methylene groups or by the methylene-dicyclohexane group, where X is a linear, branched or cyclic alkyl group, and both can be optionally replaced with other functional groups of formula (II):
  • the groups 10 to R 13 can be mutually identical or different and are selected among aliphatic groups.
  • the groups R 10 to R 13 are of linear or branched alkyl nature in beta position with respect to the oxygen of the ester group, more preferably the groups R 10 to R 13 are ethyl groups (Formula II).
  • aliphatic amines that are commercially available with the general formula (III) with n comprised between 1 and 3, Rl and R2 equal independently from H, methyl, ethyl, isopropyl or other linear or branched aliphatic groups that comprise 3 to 8 atoms of carbon
  • the diisocyanate compound B is selected among 1,6-hexamethylene diisocyanate (HDI), l-isocyanate-3- isocyanatomethyl- 3,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI).
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • H12MDI 4,4'-dicyclohexylmethane diisocyanate
  • aliphatic polyisocyanates based on 1,6-hexamethylene diisocyanate (HDI) are:
  • the composite material that can be obtained by way of the method of the invention can be further modulated in its structure and molecular weight and optionally strengthened by means of a post-reaction process, in which suitable non-volatile coupling agents, characterized by the presence of functional groups that are reactive with those of the primary resin, increase the network of the final product, allowing to increase the distortion temperature (HDT) of the final manufactured article to temperatures of 75°C or more.
  • suitable non-volatile coupling agents characterized by the presence of functional groups that are reactive with those of the primary resin, increase the network of the final product, allowing to increase the distortion temperature (HDT) of the final manufactured article to temperatures of 75°C or more.
  • the method for preparing the resin according to the invention comprises the addition to the reaction mixture that comprises the reagents A and B of a non-volatile additive (coupling agent) in order to obtain a composite material with a higher degree of cross-linking.
  • a non-volatile additive coupling agent
  • amine groups and the hydroxyl groups thus formed can then react with amine and/or isocyanate groups that have remained free during polycondensation in stages, leading to an increase in the density of the lattice of the final resin.
  • cross-linking agents that can react in a reversible manner with suitable functional groups present on the main resin so as to provide for the possibility of lowering the molecular weight at the end of the life of the manufactured article, which therefore can be disposed and/or recycled more easily.
  • a derivative of the bismaileimide of formula (VI) can be added, for example, to the formulation and can increase the polymeric network by a Diels-Alder reaction with suitable dienes present in the main resin.
  • the filler selected among at least one glassy, metallic, saline, organic material or mixtures thereof used in the method of the present invention can be based on nanodispersible silicates in a quantity from 1% to 5% by weight on the total weight of the composition, in order to obtain a matrix that belongs to the REI flammability class.
  • Said filler can also be a flame suppressant or flame retardant, for example an organophilic phylosilicate such as montmorillonite, which can be added together with the amine component in a quantity from 1% to 10% by weight on the total weight of the composition.
  • the present invention relates to the use of said material for producing manufactured articles.
  • said composite material is used for the production of manufactured articles for the nautical sector and in particular for forming boat hulls; in the construction sector, with particular reference to light beams, in the transportation sector, for example in the construction of body parts for cars and trains, or in the provision of small manufactured articles for series such as for example car mirrors, motorcycle fairings, spoilers for trucks, and in the industrial field, such as for example for providing pipes for liquids of different types, tanks of different shape and size.
  • the manufactured article of the invention comprises a superficially applied layer of a resin, preferably produced by polymerization of the reagents A and B, comprising a fluorescent color capable of emitting in the visible spectrum.
  • diamine e.g. of formula III
  • polyisocyanate constituted by a mixture that contains diisocyanate and/or cyclic derivatives thereof (e.g. a mixture of equal weights of Biuret, isocyanurate and Uretdione) and nanodispersible silicate- based nano-fillers from 1% to 5% by weight of the total, were mixed with a mechanical agitator machine at room temperature for approximately 1 minute to obtain a polycarbamide matrix that belongs to the REI flammability class. By applying this procedure, complete homogeneity of the mixture is ensured. Cross-linking occurs in 24 hours at the temperature of 25-30°C on a glass support and produces the polycarbamide resin.
  • diamine e.g. of formula III
  • polyisocyanate constituted by a mixture that contains diisocyanate and/or cyclic derivatives thereof (e.g. a mixture of equal weights of Biuret, isocyanurate and Uretdione) and nanodispers
  • the compound will receive the addition, by slow mixing for 1 minute, in the isocyanate component, of 5% to 20% bisoxazolidine derivatives.
  • This matrix is then used to provide composites filled with 30/60% by weight of different inorganic materials, mainly of the glassy type, as described in the examples given hereinafter.
  • a phillosilicate flame suppressant or flame retardant such as sodium montmorillonite added together with the amine component from 1% to 10% by weight with respect to the weight of the resin component in the composite.
  • a layer of polycarbamide resin with a thickness of approximately 1 mm was applied on a base of inert material covered by a PVC or LDPE film with release effect.
  • a layer of glass fiber known as Mat 450 constituted by glass fabric with fibers arranged in a non-prearranged manner, also known as random-type fabric, without size was applied.
  • Mat 450 constituted by glass fabric with fibers arranged in a non-prearranged manner, also known as random-type fabric, without size was applied.
  • a new layer of polycarbamide resin was applied which was compressed with a suitable tool in order to remove any residual air bubbles.
  • a second layer of glass fiber of the random type was applied with the same method.
  • a new layer of polycarbamide resin with montmorillonite was used as a binding agent for the applied fibers.
  • a type of fabric with ordered and crossed wefts of the BAX 800 type is applied to the panel thus obtained, again without size. This material is known as "powder fiber". Again, in order to bind the glass fibers, the polycarbamide resin was deposited and any air bubbles were eliminated.
  • a last layer of random fiber overlapped by a layer of polycarbamide resin allows to obtain the final panel.
  • thermomechanical performance will be reached by adding to the diamine component of the poly carbamide resin adhesive agents (aminosilanes) between the surface of the glass fiber and the matrix itself.
  • the resulting mixture is then combined with the diisocynate and fillers like example 1 for the production of composite.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un matériau composite comprenant une charge de fibres ou de poudre et une résine polycarbamide obtenue au moyen d'un procédé qui comprend une réaction entre un composé diamine et un composé diisocyanate.
PCT/EP2011/071589 2010-12-15 2011-12-02 Composites structuraux avec une matrice de polycarbamide continue avec des propriétés fonctionnelles pour applications structurales Ceased WO2012079999A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2010A002287 2010-12-15
ITMI2010A002287A IT1402930B1 (it) 2010-08-10 2010-12-15 Nuovi compositi strutturali a matrice continua policarbammidica con proprieta' funzionali per applicazioni strutturali.

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WO2012079999A1 true WO2012079999A1 (fr) 2012-06-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20121755A1 (it) * 2012-10-17 2014-04-18 Ecopolimeri S R L Materiale composito a base di una resina policarbammidica e di una carica inorganica.
CN115895235A (zh) * 2022-11-10 2023-04-04 金华市政工程有限公司 一种耐老化沥青再生剂及再生沥青混合料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002016482A2 (fr) * 2000-08-18 2002-02-28 Huntsman International Llc Systeme de polyurethanne thermodurcissable a un composant
WO2009076516A2 (fr) * 2007-12-11 2009-06-18 Campbell Matthew T Articles formés à partir de fibres alignées durcies dans une matrice acide polyaspartique-uréthanne
WO2010120617A2 (fr) * 2009-04-16 2010-10-21 3M Innovative Properties Company Procédé et composition pouvant être utilisés pour le revêtement de conduites d'eau potable
WO2011041643A2 (fr) * 2009-10-01 2011-04-07 University Of Houston System Nanocomposites argile organique-polyurée
WO2012019916A1 (fr) * 2010-08-10 2012-02-16 Ecopolimeri S.R.L. Procédé de préparation d'une résine polycarbamide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002016482A2 (fr) * 2000-08-18 2002-02-28 Huntsman International Llc Systeme de polyurethanne thermodurcissable a un composant
WO2009076516A2 (fr) * 2007-12-11 2009-06-18 Campbell Matthew T Articles formés à partir de fibres alignées durcies dans une matrice acide polyaspartique-uréthanne
WO2010120617A2 (fr) * 2009-04-16 2010-10-21 3M Innovative Properties Company Procédé et composition pouvant être utilisés pour le revêtement de conduites d'eau potable
WO2011041643A2 (fr) * 2009-10-01 2011-04-07 University Of Houston System Nanocomposites argile organique-polyurée
WO2012019916A1 (fr) * 2010-08-10 2012-02-16 Ecopolimeri S.R.L. Procédé de préparation d'une résine polycarbamide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20121755A1 (it) * 2012-10-17 2014-04-18 Ecopolimeri S R L Materiale composito a base di una resina policarbammidica e di una carica inorganica.
CN115895235A (zh) * 2022-11-10 2023-04-04 金华市政工程有限公司 一种耐老化沥青再生剂及再生沥青混合料的制备方法

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