WO2014098637A1 - Émulsions aqueuses réactives pour revêtements composites - Google Patents

Émulsions aqueuses réactives pour revêtements composites Download PDF

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Publication number
WO2014098637A1
WO2014098637A1 PCT/PT2013/000070 PT2013000070W WO2014098637A1 WO 2014098637 A1 WO2014098637 A1 WO 2014098637A1 PT 2013000070 W PT2013000070 W PT 2013000070W WO 2014098637 A1 WO2014098637 A1 WO 2014098637A1
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Prior art keywords
aqueous emulsions
production
reactive aqueous
reactive
organic
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PCT/PT2013/000070
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English (en)
Inventor
Susana Paula S. CARVALHO PIÇARRA GONÇALVES
José Manuel Gaspar MARTINHO
José Paulo Sequeira FARINHA
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Instituto Superior Técnico
Instituto Politécnico De Setúbal
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Publication of WO2014098637A1 publication Critical patent/WO2014098637A1/fr

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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Definitions

  • the present invention relates to the production of reactive aqueous emulsions for the production of composite coatings to be used as paints and varnishes, comprising polymeric micro or nanoparticles (1) with encapsulated metal alkoxides (2) in their monomeric form.
  • Sol-gel is a well-established method for glass preparation without using high temperatures (required by the conventional process of silica fusion) .
  • sol-gel process it is possible to condensate hydrolyzed metal alkoxides or halides in solution at temperatures typically comprehended between 25°C and 60°C.
  • This process occurs in two steps. It begins by the hydrolyzation of the metal alkoxide or halide, forming metal hydroxides, which condensate, in the second step, forming a tridimensional network of a metal oxide [1] .
  • the hydrolysis step can occur both under acid or base catalysis, with the final network properties (such as density or gelation time) depending on the conditions used. At neutral pH the rate of the hydrolysis of the metal alkoxides is very low, leading to very low reaction yields [2] .
  • the first composite coating for protection of facades based on an ORMOSIL (organically modified silicon compound) that was commercially available was Col.9 from BASF [5], which was characterized by forming films comprising silicon nanoparticles evenly spaced in a polymer matrix, showing excellent performances .
  • ORMOSIL organically modified silicon compound
  • Another composite that has been already described in the state of the art [6] is a transparent material (optical clarity of at least 85%, tensile strength of at least 0.1 MPa and an elongation of at least 50%) produced from an aqueous emulsion of silicone.
  • the particles, formed by organosiloxane block copolymers ("resin-linear") originate films comprised by independent, non-crosslinked chains.
  • this material production does not occur in aqueous phase and do not even need the addition of solvents. Frequently, it comprises dehydrating agents to minimize water loss by evaporation during the cure and increase the stability of the final solid.
  • dehydrating agents to minimize water loss by evaporation during the cure and increase the stability of the final solid.
  • emulsions are stable for extended periods of time, comprising a volatile organic compounds' (VOC) content lower than 5%, preferably null, with clear environmental advantages.
  • VOC volatile organic compounds'
  • This emulsion can be classified as reactive because the metal alkoxide plays different roles throughout the various stages of coatings' formation.
  • the disclosed material is characterized by a composite very homogeneous structure, ' comprising organic and inorganic crosslinked chains.
  • the present invention relates to the production of reactive aqueous emulsions comprising organic micro or nanoparticles (1) of organic polymer chains (6) with encapsulated metal alkoxides
  • nH r ns s l i n l R onl v occurs at the desired timincr. after application over the substrate and drying.
  • the final coating presents a composite network (8) structure, comprised by mutually crosslinked organic and inorganic chains, which confers high mechanical, abrasion, and chemical resistance, as well as good malleability and mechanical impact resistance.
  • the disclosed invention relates to the production of reactive aqueous emulsions comprising organic micro or nanoparticles (1) of organic polymer chains (6) with encapsulated monomeric metal alkoxides (2) in their monomeric form, for the production of composite coatings to be used as paints and varnishes on several substrates .
  • the final coatings present a composite network (8) structure formed by mutually crosslinked organic and inorganic chains. It is characterized by high mechanical, abrasion and chemical resistance, as well as good malleability and resistance to mechanical impact.
  • the originality of the disclosed invention relates not only to the method of production of the resulting coating, where the organic polymer chains (6) and inorganic chains (9), which are to be crosslinked to form the composite network (8), are produced at different times; but also to the initial emulsion composition, comprising metal alkoxides (2) sol-gel precursors, encapsulated inside the micro or nanoparticles (1) that are emulsified in an aqueous solution buffered at neutral pH (5) and kept unreacted till the application; and to the several roles played by the metal alkoxides (2) : (i) kept unreactive in emulsion, (ii) acting as plasticizers during the organic polymer chain (6) diffusion, (iii) as monomers during the polymerization 0
  • the reactive emulsions produced have low environmental impact, with VOC contents lower that 5%, preferably zero, comprising micro or nanoparticles (1) that encapsulate the metal alkoxides (2), avoiding the formation of inorganic chains (9) in emulsion.
  • the micro or nanoparticles (1) pack together (b) and deform into polyhedra (7) due to capillary forces (c) .
  • the organic polymer chains (6) that were initially located inside the micro or nanoparticles (1) interdiffuse, accelerated by the metal alkoxides (2) that act as plasticizers .
  • the interdiffusion of the organic polymer chains (6) between neighbor particles promotes the homogenization of the films by fading the interfaces between them.
  • the metal alkoxides (2) that diffuse with the organic polymer chains (6) meet the required conditions for condensation, forming inorganic chains (9) and crosslinks with the lateral hydroxyl groups (4) randomly distributed throughout the organic polymer chains (6) .
  • the annealing temperature is chosen according to the final application of the coating and depends only on the selection of the hydrophobic polymers or copolymers that comprise the micro or nanoparticles (1) in emulsion.
  • the annealing temperature has to be higher than the Minimum Film Formation Temperature of the organic polymer chains (6) in water so that chain interdiffusion is promoted and the metal alkoxides (2) can act as plasticizers, prior to the formation of the composite network (8) that constitutes the final coating illustrated in Figure 3.
  • the annealing temperature being crucial to the determination of the final coating structure and properties, only depends on the choice of the hydrophobic polymers or copolymers, which are specifically selected to each particular application.
  • the encapsulation of the inorganic precursors - the metal alkoxides (2) - inside the micro or nanoparticles (1) guarantees that these reactive metal alkoxides (2), will be homogeneously distributed in the forming films (c) , originating coatings with a very homogeneous composite network (8) structure (d) , characterized by being transparent or translucent, with a visible radiation transmission higher than 20%, preferably higher than 30% and most preferably higher than 50%.
  • the sol-gel precursors are hydrophobic metal alkoxides (2) with formula R' n M (OR) (4 - ⁇ ) , wherein M is a metal atom, that is preferably selected form the group comprising silicon, tin, aluminum, titanium, zirconium or boron; n ⁇ 2; R is an organic radical and R' another stable organic radical initiated by a sp 3 carbon atom.
  • the sol-gel precursors are metal alkoxides (2) with formula M(OR) 4 .
  • the weight content of metal alkoxides (2) inside the micro or nanoparticles (1) is preferably contained between 2% and 80%.
  • the reaction mixture further comprises a radical initiator, thermally or redox activated, and surfactants, preferably ionic surfactants .
  • the aqueous phase is buffered at neutral pH (5) , between pH 6 and 8, by standard buffer solutions, preferably phosphate buffer .
  • the reactive aqueous emulsion comprises micro or nanoparticles (1) in emulsion, with mean diameters between 30 nm and 1000 nm, preferably between 50 nm and 500 nm, at neutral pH, containing metal alkoxides (2) inside the particles. These metal alkoxides (2) are kept unreacted, in their monomeric form, while the micro or nanoparticles (1) stay in emulsion, as illustrated in Figure 1.
  • the solids content of the micro or nanoparticles (1) emulsion is preferable of 10% to 80% (by weight) .
  • the micro and nanoparticles (1) pack together (b) and deform into polyhedra (7) due to capillary forces (c) .
  • the metal alkoxides (2) play more active roles, acting as plasticizers in a first stage, and later suffer condensation both with other hydrolyzed metal oxides, to form inorganic chains, and with the lateral hydroxyl groups (4) of the organic polymer chains (6), to form an homogeneous composite network (8) comprising crosslinked organic and inorganic chains - represented in Figure 3.
  • dyes, UV stabilizers or other additives can be incorporated in the free volume of the composite network (8) .
  • the encapsulation of the metal alkoxides (2) inside the micro or nanoparticles (1) can be achieved by different processes involving emulsion polymerization techniaues. in which the* m al alkoxides (2) are previously mixed with the hydrophobic organic monomers or comonomers (3) , before being introduced into the reaction medium.
  • the emulsion polymerization method chosen in each case is determined according to the hydrophobic organic monomers and comonomers (3) to be used, and to the intended diameter of the micro or nanoparticles (1), which depend on the intended annealing temperature and final application of the coating.
  • the emulsion polymerization method can either occur in two steps or by mini-emulsion [13] .
  • the emulsion polymerization reactions occur, for both methods, under inert atmosphere - it is preferable that the inert gas is nitrogen or argon - and at temperatures up to 90°C. Two immiscible phases are always used:
  • One or more hydrophobic organic monomers or comonomers (3) with at least two C C terminal double bonds, comprising divynilbenzene and ethilenoglycol dimethacrylate, preferably with a weight content in the range of 0% to 20%, to introduce crosslinks in the organic polymer chains (6) .
  • d) when the molecular weight of the organic polymer chains (6) has to be controlled, hurirnnhn i .
  • r-.hain transfer aoents can be added, in a weiaht content from 0% to 20%, selected from the group comprising mercaptanes - for example, 1-dodecanothyol -, carbon tetrabromine, or carbon tetrachloride.
  • One or more hydrophobic metal alkoxides (2) preferably silicon, tin, aluminum, titanium, zirconium or boron, of general formula R' n M (OR) ( - n ) , wherein 0 ⁇ n ⁇ 2; R is a stable organic radical and R' another stable organic radical initiated by a sp 3 carbon atom.
  • Some examples are Si(OEt) 4 , Si(0Me) 4 , H 3 C-Si (OMe) 3 , B(OEt) 3 , Al(0-i-Pr) 3 , or
  • An aqueous phase comprising: a) A buffer solution with pH between 6 and 8, selected from the group comprising sodium bicarbonate buffer, phosphate buffer and citric acid/sodium hydrogenphosphate buffer.
  • a water soluble radical initiator comprising persulfates, preferably potassium, sodium or ammonium persulfate, and benzoyl peroxide, or alternatively, a water soluble redox initiator selected from the group comprising persulfate- bisulfite, persulfate-hydrosulfite and persulfate-iron (II).
  • a surfactant - amphiphilic molecules preferably sodium dodecyl sulfate and sodium dodecylbenzenesulfonate .
  • a co-stabilizer for example, hexadecane or hexadecanol in a range of 0% to 20%.
  • UV stabilizers may also be included [16], or other additives, according to the final application of the coating.
  • an emulsion of the organic phase has to be prepared by mechanical shear or sonification, prior to the polymerization .
  • the embodiments that follow the emulsion polymerization in two steps start with the production of primary particles with mean diameters in the range of 20 nm to 500 nm through a batch emulsion polymerization procedure. These particles are used as seeds at the second step of the emulsion polymerization, which
  • metal alkoxides (2) (fully or partially hydrolyzed) , is lower than the rate of interdiffusion of the organic polymer chains (6) .
  • the metal alkoxides (2) diffuse with the organic polymer chains (6), acting as plasticizers. The condensation of metal alkoxides (2) between each other and with
  • the annealing temperature is selected according to the final application of the coating, through a rigorous choice of the organic polymers or copolymers that form the micro or nanoparticles (1) .
  • the proposed method is, as explained, unique and based on the multiple functions performed by the metal alkoxides (2), namely: i) Remain nreacted inside the micro or nanoparticles (1) for long periods of time, contributing to the emulsion stability;
  • the method here disclosed is not only simple, but highly advantageous, allowing the use of a VOC-free stable formulation for the production of composite coatings with a very homogeneous composite network (8) structure, represented in Figure 3.
  • These coatings are hydrophobic, with contact angles higher than 90°, preferably higher than 120°. They are characterized by being resistant to acids, bases and organic solvents, such as tetrahydrofuran, and for presenting good mechanical properties, with Young modulus in the range of 0,1 MPa to 100 Mpa, preferably in the range of 0,1 MPa to 50 MPa, and elongations in the range of 50% to 800%, preferably between 100% and 600%. Therefore, the films produced by the disclosed method simultaneously present good mechanical properties and malleability, showing large resistance to abrasion and mechanical impact.
  • Figure 1 schematically represents one of the micro or nanoparticles (1) in emulsion, with encapsulated metal alkoxides (2), that can remain in the monomeric form for very long times, typically months.
  • These micro or nanoparticles (1) comprise organic polymer chains (6) that are formed by repeating units resulting from the polymerization of hydrophobic organic monomers or comonomers (3) similar or distinct between each other, and comonomers with a lateral hydroxyl group (4), that become randomly distributed throughout the organic polymer chain (6) .
  • the micro or nanoparticles (1) are emulsified in aqueous medium, buffered at neutral pH (5) .
  • Figure 2 schematically represents the composite network (8) homogeneous film formation process.
  • the aqueous emulsion of micro or nanoparticles (1) is applied on the substrate (a) the micro or nanooarticles (1) remain in the emulsion, buffered at neutral pH (5), and keep their original constitution, comprising organic polymer chains (6) and encapsulated metal alkoxides (2) in their monomeric form.
  • micro and nanoparticles (1) pack together (b) and deform into polyhedra (7) due to capillary forces (c) .
  • the metal alkoxides (2) act as plasticizers, contributing to the interdiffusion of the organic polymer chains (6) between neighbor particles and to the fading of the interfaces. Later on, the hydrolyzed metal alkoxides (2) suffer condensation reactions and form inorganic chains (9) crosslinked to the organic polymer chains (6) through their lateral hydroxyl groups (4) .
  • the final structure is a very homogeneous composite network (8) (d) .
  • Figure 3 schematically represents the homogeneous composite network (8) structure (d) of the films obtained after annealing. It comprises organic polymer chains (6) that are crosslinked to the chains produced through the metal alkoxides sol-gel reactions, which are inorganic chains (9) .
  • the crosslinking points correspond to the monomeric units with lateral hydroxyl groups (4) contained in the organic polymer chains (6).
  • Figure 4 presents the infrared spectrum obtained for a film produced from an emulsion of micro or nanoparticles without introducing any metal alkoxide (10) and the infrared spectra of a film produced from the emulsion of micro or nanoparticles with encapsulation of a silicon alkoxide (Si (OR) 4 ) , collected before annealing (11) and after 5 h (12) and 10 h of annealing (13), at 3 nrnnpr f-Ainnsratnrp. . All sDftni-.ra were obtained in DRIFT mode and are normalized at the carbonyl band (14), which is present in all repeating units of the organic polymer chain (6) of that coating.
  • Si (OR) 4 silicon alkoxide
  • the xx axis identified by Kubelka-Munk/a . u. , refers to the intensity of the Kubelka-Munk function expressed in arbitrary units and the yy axis refers to the wavenumber, expressed in cm -1 .
  • Figure 5 presents an amplification of the same infrared spectra obtained in DRIFT mode, presented in Figure 4, in the range from 600 to 450 cm -1 . It is possible to observe the band attributed to the O-C-C deformation in symmetrically substituted silicons (that corresponds to the unreacted metal alkoxide (2) in its initial Si(OR) form). This band, which is not present in the infrared spectrum of the film produced from the emulsion of micro or nanoparticles without introducing any metal alkoxide (10), shows maximum intensity in the IR spectrum of the film produced with in the presence of encapsulated silicon alkoxide before annealing (11) .
  • the xx axis identified by Kubelka-Munk/a.u. , refers to the intensity of the Kubelka-Munk function expressed in arbitrary units and the yy axis refers to the wavenumber, expressed in cm "
  • Figure 6 presents an amplification of the same infrared spectra obtained in DRIFT mode, presented in Figure 4, in the range from 3700 to 2500 cm -1 . It is possible to observe the bands related to the elongation of the silanol O-H groups, present in the partially or fully hydrolyzed alkoxides (at 3432 cm -1 and around 3300 cm -1 ) . These bands are not present in the IR spectra of the film produced from the emulsion of micro or nanoparticles without introducing anv metal alkoxide (1 ⁇ .
  • the band shows the highest intensity after 5 h (12) of annealing, decreasing after 10 h of annealing (13) - the decrease on the intensity of these bands suggests the occurrence of condensation reactions.
  • silica bands (located between 1100 and 1300 cm -1 ) are not observed in the IR spectra presented in Figure 4, because they are overlapped with the bands of the repeating units of the organic polymer chains.
  • the xx axis identified by Kubelka-Munk/a.u. , refers to the intensity of the Kubelka-Munk function expressed in arbitrary units and the yy axis refers to the wavenumber, expressed in cm -1 .
  • Example 1 One of the preferred embodiments of the present invention is an aqueous emulsion of poly (butyl methacrylate) as organic polymer chains (6) and tetra orthosilicates as metal alkoxide (2), produced through a two-steps emulsion polymerization procedure.
  • a mixture is introduced inside a reactor equipped with mechanical stirring and a reflux condenser, comprising:
  • aqueous solution buffered at neutral pH (5) for example, using a phosphate buffer prepared from sodium hydrogen phosphate 0,1 M and sodium dihydrogen phosphate 0,1 M, with pH between 6 and 8;
  • the mixture is degassed and heated under mechanical stirring till 80°C.
  • Another mixture is added to this one, all at once, comprising: - 1 to 20 %(w/w) of butyl methacrylate; - 0.1 to 15 % (w/w) of ethylene glycol dimethacrylate,
  • the organic phase is also prepared in a separate vessel by mixing:
  • Both aqueous and organic phases are kept in separate vessels and degassed.
  • the reactor is also degassed and, under mechanical stirring and inert atmosphere, is heated to 80°C. Then, both aqueous and organic phases are continuously added to the reactor, at distinct rates, so that the total addition time would be from 4 to 8 h.
  • the reactor is stirred at 80°C under inert atmosphere for an additional 0.5 to 4 h after the addition of the two phases is completed.
  • the obtained emulsion is completely stable, comprising micro or nanoparticles (1) with hydrodynamic diameters in the range of 30
  • This emulsion is stable for 18 months, preferably for 10 months, given that the infrared spectra of films produced with this emulsion, presented in Figure 4, reveal the presence of unreacted tetraethyl orthosilicates, confirmed in Figure 5, 10 months after being prepared.
  • Example 2
  • Other preferred embodiment of the present invention is the preparation of a composite emulsion of the same organic polymer chains (6) - poly (butyl methacrylate) - and the same metal alkoxide (2) - tetraethyl orthosilicates - through a mini- emulsion process.
  • the procedure begins by dissolving 0.01 to 5% (w/w) of sodium dodecyl sulfate in 50 to 90% (w/w) deionized water.
  • 5 to 40% (w/w) of butyl methacrylate is added to 1 to 30% (w/w) of tetraethyl orthosilicate and 0.01 to 19% (w/w) of hexadecane, at 0°C during 30 min.
  • the first mixture is added very slowly and under magnetic stirring to the second and the obtained mixture sonicated at 0°C between 1 to 40 min.
  • the obtained mini-emulsion is transferred into a reactor equipped with a mechanical stirrer and reflux condenser. After being degassed, the mini-emulsion is heated under stirring till 80°C and added a solution comprising 0.001 to 0.5 % (w/w) of potassium persulfate dissolved in 0.1 to 5 % (w/w) of deionized water. The reaction proceeds for no less than 5 h.
  • the final mixture comprises micro or nanoparticles (1) with a mean hydrodynamic diameter of 50 to 500 nm, characterized by Dynamic Light Scattering. References :

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Abstract

La présente invention concerne la production d'émulsions aqueuses réactives comprenant des micro ou nanoparticules organiques comportant des alcoxydes métalliques encapsulés dans leur forme monomère, pour la production de revêtements composites destinés à être utilisés en tant que peintures et vernis. Ces émulsions sont réactives dans le sens où la formation de chaînes inorganiques et d'agents réticulants ne se produit qu'au moment souhaité, après application sur un substrat et séchage. Le revêtement final présente une structure de réseau composite, constituée de chaînes organiques et inorganiques mutuellement réticulées, qui confère au revêtement une résistance mécanique, à l'abrasion et chimique élevée, ainsi qu'une bonne malléabilité et une bonne résistance aux impacts mécaniques.
PCT/PT2013/000070 2012-12-21 2013-12-20 Émulsions aqueuses réactives pour revêtements composites WO2014098637A1 (fr)

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PT106709A PT106709B (pt) 2012-12-21 2012-12-21 Emulsões aquosas reativas para revestimentos compósitos
PT106709 2012-12-21

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