WO2009152301A2 - Systèmes de résine contenant des nanoparticules à faible teneur en ions - Google Patents

Systèmes de résine contenant des nanoparticules à faible teneur en ions Download PDF

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Publication number
WO2009152301A2
WO2009152301A2 PCT/US2009/047000 US2009047000W WO2009152301A2 WO 2009152301 A2 WO2009152301 A2 WO 2009152301A2 US 2009047000 W US2009047000 W US 2009047000W WO 2009152301 A2 WO2009152301 A2 WO 2009152301A2
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Prior art keywords
resin system
resin
nanoparticles
silica nanoparticles
curable
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WO2009152301A3 (fr
Inventor
Emily S. Goenner
Travis Q. Gregar
Brant U. Kolb
William J. Schultz
Kristin L. Thunhorst
Andrew M. Hine
James M. Nelson
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3M Innovative Properties Co
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3M Innovative Properties Co
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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present disclosure relates to resin systems containing a curable resin and surface-modified nanoparticles.
  • the resin systems have low ion contents, particularly, low contents of alkali metals and alkaline earth metals.
  • the present disclosure also relates to curable resin systems (e.g., gel coats) containing treated, surface-modified nanoparticles that have low ion contents.
  • the present disclosure provides a resin system comprising a curable resin and at least 10 weight percent surface-modified silica nanoparticles.
  • the resin system comprises no greater than 200 parts per million by weight alkali metal and alkaline earth metal ions based on the total weight of the silica nanoparticles and curable resin.
  • the resin system comprises at least 20 weight percent, or even at least 40 weight percent surface-modified silica nanoparticles.
  • the resin system comprises no greater than 100 parts per million by weight alkali metal and alkaline earth metal ions based on the total weight of the silica nanoparticles and curable resin.
  • the curable resin comprises a vinyl ester, an unsaturated polyester resin, or a (meth)acrylate.
  • the resin system further comprises a reactive diluent.
  • surface-modified silica nanoparticles comprise dual-ion exchanged, surface-modified silica nanoparticle. In some embodiments, the surface- modified silica nanoparticles are end-capped.
  • the present disclosure provides a resin system that comprises at least 20 weight percent surface-modified silica nanoparticles having an average particle size of greater than 50 nm dispersed in a curable resin; wherein a 425 micron thick sample of the resin system has a haze of no greater than 3% as measured by the Optical Property Test Method.
  • the 425 micron thick sample of the resin system has a clarity of at least 99.5 as measured by the Optical Property Test Method.
  • the present disclosure provides a resin system that comprises at least 20 weight percent end-capped, surface-modified silica nanoparticles having an average particle size of greater than 50 nm dispersed in a curable resin system, wherein a 1.5 millimeter thick cured sample of the resin system has a clarity of greater than 50, as measured by the Optical Property Test Method.
  • the curable resin comprises an unsaturated polyester/styrene resin system.
  • the 1.5 millimeter thick cured sample has a clarity of greater than 90, as measured by the Optical Property Test Method.
  • the 1.5 millimeter thick cured sample has a transmission of greater than 60%, as measured by the Optical Property Test Method.
  • the 1.5 millimeter thick cured sample has a haze of no greater than 30%, as measured by the Optical Property Test Method.
  • the present disclosure provides a gel coat comprising one of the resin system according to an embodiment of the present disclosure.
  • the present disclosure provides a method of preparing a curable resin system.
  • the method comprises providing a silica nanoparticle sol comprising no greater than 200 micrograms of sodium per gram of silica as measured by IC Procedure #1; covalently bonding a surface-treatment agent to a surface of the silica nanoparticles to form surface-treated silica nanoparticles; and combining the surface- treated nanoparticles with a curable resin.
  • the method further comprises ionically binding an end-capping agent to the surface of the surface-modified nanoparticles. Curable resin systems made by such methods are also disclosed.
  • FIG. 1 illustrates the increase in viscosity of a resin system containing dual-ion- exchanged, surface-modified nanoparticles.
  • FIG. 2 illustrates the effect of end-capping with DMAEMA on the viscosity of a resin system containing dual-ion-exchanged, surface-modified nanoparticles.
  • FIG. 3 illustrates the effect of end-capping with HMDS on the viscosity of a resin system containing dual-ion-exchanged, surface-modified nanoparticles.
  • FIG. 4A is a TEM image of the nanoparticle-containing resin system of EX-3.
  • FIG. 4B is a TEM image of the nanoparticle-containing resin system of EX-4.
  • FIG. 4C is a TEM image of the nanoparticle-containing resin system of EX-5.
  • agglomerated is descriptive of a weak association of primary particles usually held together by charge or polarity. Agglomerated particles can typically be broken down into smaller entities by, for example, shearing forces encountered during dispersion of the agglomerated particles in a liquid.
  • aggregated and aggregates are descriptive of a strong association of primary particles often bound together by, for example, residual chemical treatment, covalent chemical bonds, or ionic chemical bonds. Further breakdown of the aggregates into smaller entities is very difficult to achieve. Typically, aggregated particles are not broken down into smaller entities by, for example, shearing forces encountered during dispersion of the aggregated particles in a liquid.
  • curable resin systems e.g., crosslinkable resin systems
  • a protective layer e.g., gel coats
  • the impregnation resin in composites e.g., fibrous composites
  • Resin systems are often selected based on the desired mechanical properties of the final product including, e.g., hardness, toughness, fracture resistance, and the like.
  • the optical appearance of the finished product may be important such that properties like clarity and haze must be considered.
  • process conditions may lead to preferred ranges of properties affecting processability such as viscosity.
  • the desired end use of the product often leads to additional requirements, e.g., erosion resistance or anti-blistering.
  • any known curable resin may be used in the various embodiments of the present disclosure.
  • the curable resin may be an ethylenically- unsaturated curable resin.
  • an unsaturated polyester resin may be used.
  • the unsaturated polyester resin is the condensation product of one or more carboxylic acids or derivatives thereof (e.g., anhydrides and esters) with one or more alcohols (e.g., polyhydric alcohols).
  • vinyl ester resins are used.
  • the term "vinyl ester” refers to the reaction product of epoxy resins with ethylenically-unsaturated monocarboxylic acids.
  • exemplary epoxy resins include bisphenol A digycidal ether (e.g., EPON 828, available from Hexion Specialty Chemicals, Columbus, Ohio).
  • exemplary monocarboxylic acids include acrylic acid and methacrylic acid.
  • (meth)acrylate resins including, e.g., urethane (meth)acrylates, polyethyleneglycol (multi)(meth)acrylates, and epoxy (multi)(meth)acrylates may be used.
  • the term (meth)acrylate refers to an acrylate and/or a methacrylate, i.e., ethyl (meth)acrylate refers to ethyl acrylate and/or ethyl methacrylate.
  • the resin system may also include a reactive diluent.
  • exemplary reactive diluents include styrene, alpha-methylstyrene, vinyl toluene, divinylbenzene, triallyl cyanurate, methyl methacrylate, diallyl phthalate, ethylene glycol dimethacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and other mono- and multi-functional (meth)acrylates.
  • Curable resins are sometimes used to form gel coats for industrial applications.
  • a "gel coat” is a material used to provide a high quality finish on the visible surface of a fiber-reinforced composite material.
  • the most common gel coats are made from curable resins such as those based on epoxy, unsaturated polyester diluted with styrene, or vinyl ester diluted with styrene resin chemistry.
  • the curable resin is then formulated into a gel coat by adding additional components such as catalysts, air release agents, leveling agents, surfactants, thixotropic agents, wetting agents and pigments.
  • the formulated gel coat may be applied to a mold in the liquid state and cured to form crosslinked polymers that can be subsequently backed up with composite polymer matrices (e.g., unsaturated polyester resin, vinyl ester resin, or epoxy resin with glass and/or carbon fibers).
  • composite polymer matrices e.g., unsaturated polyester resin, vinyl ester resin, or epoxy resin with glass and/or carbon fibers.
  • a thixotropic additive may be included in the gel coat formulation to assist the gel coat's tenacity to vertical portions of the mold while it cures.
  • the manufactured component when sufficiently cured and removed from the mold, presents the gel coat layer as the exposed, visible surface.
  • This gel coat layer is usually pigmented to provide a colored, glossy surface which improves the aesthetic appearance of the article, such as a counter made with cultured marble.
  • the outer layer is often a gel coat, typically 0.5 mm to 0.8 mm in thickness. In some embodiments, gel coats as thick as 1.5 mm have been used. Gel coats are typically designed to be durable and to provide resistance to ultraviolet degradation and hydrolysis.
  • Suitable curable resin chemistries for the manufacture of gel coats vary, but the most commonly encountered are unsaturated polyesters diluted with styrene, vinyl esters diluted with styrene, or epoxies. Within each of these categories, the resin chemistries are further subdivided. Viscosities of the curable resins used to make gel coats are typically 0.2 to 0.4 Pa » s at 25 0 C and a shear rate of 1.0 (I/seconds).
  • surface modified nanoparticles comprise surface treatment agents attached to the surface of a core.
  • sica nanoparticle refers to a nanoparticle having a silica surface. This includes nanoparticles that are substantially, entirely silica, as well nanoparticles comprising other inorganic (e.g., metal oxide) or organic cores having a silica surface.
  • the core comprises a metal oxide. Any known metal oxide may be used. Exemplary metal oxides include silica, titania, alumina, zirconia, vanadia, chromia, antimony oxide, tin oxide, zinc oxide, ceria, and mixtures thereof.
  • the core comprises a non-metal oxide.
  • surface treatment agents for silica nanoparticles are organic species having a first functional group capable of covalently chemically attaching to the surface of a nanoparticle, wherein the attached surface treatment agent alters one or more properties of the nanoparticle.
  • surface treatment agents have no more than three functional groups for attaching to the core.
  • the surface treatment agents have a low molecular weight, e.g. a weight average molecular weight less than 1000 gm/mole.
  • the surface treatment agent further includes one or more additional functional groups providing one or more additional desired properties.
  • an additional functional group may be selected to provide a desired degree of compatibility between the surface modified nanoparticles and one or more of the additional constituents of the resin system, e.g., one or more of the curable resins and/or reactive diluents.
  • an additional functional group may be selected to modify the rheology of the resin system, e.g., to increase or decrease the viscosity, or to provide non-Newtonian rheological behavior, e.g., thixotropy (shear- thinning).
  • the surface-modified nanoparticles are reactive; that is, at least one of the surface treatment agents used to surface modify the nanoparticles of the present disclosure may include a second functional group capable of reacting with one or more of the curable resin(s) and/or one or more of the reactive diluent(s) of the resin system.
  • Particle size measurements can be based on, e.g., transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the surface-modified nanoparticles have a primary particle size (as determined by TEM) of between about 5 nanometers to about 500 nanometers, and in some embodiments from about 5 nanometers to about 250 nanometers, and even in some embodiments from about 50 nanometers to about 200 nanometers.
  • the cores have an average diameter of at least about 5 nanometers, in some embodiments, at least about 10 nanometers, at least about 25 nanometers, at least about 50 nanometers, and in some embodiments, at least about 75 nanometers.
  • the cores have an average diameter of no greater than about 500 nanometers, no greater than about 250 nanometers, and in some embodiments no greater than about 150 nanometers.
  • silica nanoparticles can have a particle size of ranging from about 5 to about 150 nm.
  • Commercially available silicas include those available from Nalco Chemical Company, Naperville, Illinois (for example, NALCO 1040, 1042, 1050, 1060, 2327 and 2329); Nissan Chemical America Company, Houston, Texas (e.g., SNOWTEX-ZL, -OL, -O, -N, -C, -20L, -40, and -50); and Admatechs Co., Ltd., Japan (for example, SX009-MIE, SX009-MIF, SC1050-MJM, and SC1050-MLV).
  • the core is substantially spherical. In some embodiments, the cores are relatively uniform in primary particle size. In some embodiments, the cores have a narrow particle size distribution. In some embodiments, the core is substantially fully condensed. In some embodiments, the core is amorphous. In some embodiments, the core is isotropic. In some embodiments, the core is at least partially crystalline. In some embodiments, the core is substantially crystalline. In some embodiments, the particles are substantially non-agglomerated. In some embodiments, the particles are substantially non-aggregated in contrast to, for example, fumed or pyrogenic silica.
  • NP-2329 colloidal silica sol (1600 grams (g)) was added to a large jar and stirred, l-methoxy-2-propanol (1800 g), A- 174 (11.14 g), and SILQUEST A-1230 (22.45 g) were mixed together and then added to the stirring colloidal silica. The resulting colloidal silica sol was then heated for sixteen hours at 80 degrees Celsius ( 0 C) to produce a sol of surface-modified silica nanoparticles.
  • Solvents were removed from the sol using rotary evaporation to achieve a concentrated solution containing 70% by weight (70 wt.%) silica.
  • the concentrated solution was then dried according to the procedures described in the U.S. Pat. No. 5,980,697 (KoIb et al.) and U.S. Pat. No. 5,694,701 (Huelsman, et. al.) with a dispersion coating thickness of about 0.25 mm (10 mils) and a residence time of 1.1 minutes (heating platen temperature 107 0 C, and condensing platen temperature 21 0 C) to yield a fine, free- flowing white powder of surface-modified nanoparticles.
  • the dried, surface-modified nanoparticles (233.12 g) were then combined with 316.9 g of HK-I and 1.27 g of 4- hydroxy-TEMPO and mixed with a DISPERMAT laboratory dissolver (BYK-Gardner, Columbia, MD) for ten minutes.
  • the nanoparticle-containing resin system was then milled.
  • Milling Process The dry nanoparticles were first mixed into the resin with a Cowles-blade-type, pneumatically-driven mixing blade. The resin was placed into a wide- mouth jar and the dry nanoparticle powder was added to the resin while stirring. The combination was then mixed more thoroughly with the DISPERMAT dissolver for approximately ten minutes until a uniform consistency was achieved.
  • the nanoparticle/resin mixture was pumped through a peristaltic pump (MASTERFLEX LS, Cole Partner, Vernon Hills, Illinois), and into a MINICER mill (0.15 liter laboratory-sized MINIZETA horizontal mill, Netszch Fine Particle Technology, Exton, PA) equipped with ceramic internal components.
  • the flowrate through the peristaltic pump was 150 ml/min.
  • the milling media was 0.5 millimeter diameter yttria-stabilized zirconia milling media (Torayceram AGB-K-0.5, Toray International America, New York, NY). The mill run rate was set to 4320 rpm.
  • CE-2 was prepared as follows. NP -2329 colloidal silica sol (1625 g) was added to a large jar and stirred. AMBERLITE IR-120plus(H) cation exchange resin (11.35 g) was added to the stirring colloidal silica sol and stirred for 30 minutes until the pH was 3.0. The cation exchange resin was filtered out and 1185 g of l-methoxy-2-propanol was added to the stirring colloidal silica sol. Ammonium hydroxide (30%) was added to the stirring colloidal silica sol until the pH was 9.5. The concentration of silica was 22.58 wt.%.
  • Example 1 EX-I was prepared as follows.
  • NP-2329 colloidal silica sol (1625 g) was added to a large jar and stirred.
  • DOWEX MONOSPHERE 550A(OH) anion exchange resin (88 g) was added to the jar and stirred for 30 minutes until the pH was 9.5. The anion exchange beads were filtered out.
  • 140 g of DOWEX MONOSPHERE 650C(H) cation exchange resin was added to the jar and stirred for 30 minutes until the pH was 3.0.
  • the cation exchange beads were filtered out and 600 g of l-methoxy-2-propanol was added to the jar while stirring.
  • Ammonium hydroxide (30%) was slowly added to the stirring colloidal silica sol until the pH was 9.5.
  • the concentration of silica was 25.71 wt.%.
  • the dried, surface-modified nanoparticles (233.12 g) were then combined with 316.9 g of HK-I and 1.27 g of 4- hydroxy-TEMPO and mixed with a DISPERMAT dissolver for ten minutes.
  • the nanoparticle-containing resin system was then milled as described for Comparative Example 1 , except the flow rate through the peristaltic pump was 200 ml/minute.
  • the calculated amount of vinyl ester resin was weighed out, and initiated with 1.25 wt.% methyl ethyl ketone peroxide (LUPEROX DDM-9, available from Sigma- Aldrich, Milwaukee, WI).
  • One-third of the vinyl ester resin was poured evenly onto the cured gel coat layer.
  • the first ply of chopped strand mat was placed on top of the vinyl ester resin and allowed to soak up the resin.
  • a ridged roller was used to roll out the vinyl ester resin and remove air bubbles.
  • An additional one -third of the vinyl ester resin was poured on top of the first ply, spread out, and covered with a second ply of chopped strand mat. This middle ply was rolled out, and then the last one-third of the vinyl ester resin was poured on top of the middle ply and spread out.
  • the third ply of chopped strand mat was laid up and rolled out.
  • This 3-ply construction was allowed to cure in a vented hood for 24 hours at room temperature. Then, while still on the glass, it was put into a 70 0 C (158 0 F) oven for 4 hours. After removal from the oven, the glass and panel are allowed to cool for one hour before the panel is removed from the glass, exposing the gel coat layer. The panel was cut into as many 7 cm by 7 cm (2.75 inch x 2.75 inch) square test specimens as possible.
  • Example 10 was prepared as follows.
  • NP-LMS colloidal silica sol 1201.6 g was added to a large jar and stirred.
  • the surface modified silica sol was dried to a powder in an oven at 80 0 C. Next, 475.1 g of the dried powder and H lO g acetone were mixed in ajar and high shear mixed for 10 minutes using a SILVERSON 4LR high shear mixer. HK-3 curable resin (615.0 g), 4-hydroxy-TEMPO (2.5 g) and 2-(Dimethyl amino)ethyl methacrylate (DMAEMA) (3.5 g) were added to the surface modified silica dispersed in acetone. Acetone was removed via rotary evaporation. Gas chromatography confirmed no acetone remained in the sample. MMA (28.41 g) and styrene (114.3 g) were added back to the sample. The sample contained approximately 40 wt.% Si ⁇ 2-
  • nanoparticle-containing, curable resin system of EX-10 was used to prepare flat, gel-coated, 3-ply, fiber-reinforced composite test panels according to Panel Preparation Procedure 2.
  • the nanoparticle-containing curable resin system (“gel coat") was promoted with 1.00 wt% cobalt solution (JK 8033, available from HK Research (Hickory, NC)) and was initiated with 2.0 wt.% methyl ethyl ketone peroxide (MEKP B0410 46-702, available from HK Research (Hickory, NC )).
  • the MEKP was mixed into the curable resin system using a SPEEDMIXER DAC 600 FVZ available from FlackTek, Inc. (Landrum, SC) for 15 seconds at 2000 rpm.
  • a 30.5 cm (12 inch) wide adjustable gap knife coater was set to a gap of 0.89 millimeters (0.035 inch) and used to coat 50 to 80 grams of the initiated gel coat across a mold-released glass plate.
  • the calculated amount of vinyl ester resin was weighed out, initiated with 2.0 wt.% cumyl peroxide (NOROX CHM-50, available from HK Research (Hickory, NC)).
  • One-third of the vinyl ester resin was poured evenly onto the cured gel coat layer.
  • the first ply of chopped strand mat was placed on top of the vinyl ester resin and allowed to soak up the resin.
  • a ridged roller was used to roll out the vinyl ester resin and remove air bubbles.
  • An additional one-third of the vinyl ester resin was poured on top of the first ply, spread out, and covered with a second ply of chopped strand mat. This middle ply was rolled out, and then the last one-third of the vinyl ester resin was poured on top of the middle ply and spread out.
  • the third ply of chopped strand mat was laid up and rolled out.
  • This 3 -ply construction was allowed to cure in a vented hood for 24 hours at room temperature. Then, while still on the glass, it was put into a 70 0 C (158 0 F) oven for 4 hours. After removal from the oven, the glass and panel are allowed to cool for one hour before the panel is removed from the glass, exposing the gel coat layer. The panel was cut into as many 7 cm by 7 cm (2.75 inch x 2.75 inch) square test specimens as possible.
  • Boiling Blister Test A A 5-liter, 3-necked flask was cut in half at the equator and an 8.9 cm (3.5 inch) wide cylindrical band was inserted. Portholes were cut into this band, each with a glass extension tube attached. These 7.6 cm (3 inch) diameter ports extended out from the flask about 7.6 cm (3 inches) and had a flange at the end. This flange accepted a 7.6 cm (3 inch) diameter by 6.4 mm (0.25 inch) thick O-ring onto which a flat test specimen can be clamped with a spring-loaded U-clamp. The apparatus had four ports spaced evenly around the equator of the flask.
  • the flask was placed in a heating mantle controlled by a Vari-AC set at 100% (of 120 VAC).
  • One neck of the flask contained a glass stopper and was used for pouring water into the flask.
  • the center neck contained a condenser which was cooled by circulating cold water and returned vaporized water to the flask.
  • the third neck contained a mercury thermometer inserted into the water.
  • Boiling chips were put into the bottom of the flask. Deionized water was preheated in a microwave oven and poured into the flask. Enough preheated water was added to bring the water level up to the bottom of the ports. When the water started to boil, the test specimens, which have been carefully weighed, were clamped onto the ends of the ports with the cured experimental resin layer side toward the water. More hot deionized water was added until the ports were completely filled.
  • test was continued for up to 100 hours.
  • test specimens were re-clamped to the ends of the ports, the flask refilled with pre-heated deionized water, and timing restarted when the water began to boil. All water was replaced after 100 hours of testing.
  • IC Procedure #1 Ultra-pure (18 mega ohm) water was added to samples of various nanoparticle sols to obtain 2x, 10x, 5Ox, and 10Ox dilutions that were centrifuged at 10,000 rpm for 45 minutes to remove the solids. The remaining supernatant was analyzed by ion-exchange chromatography (IC). Aliquots (25 microliter) of each dilution were injected into a DIONEX ICS-3000 dual channel ion chromatograph. CS12A and CG12A columns, isocratic 20 mM methanesulfonic acid eluent, a CSRS suppressor, and conductivity detection were used for cation chromatography.
  • the system was standardized with the DIONEX 6-cation standard (in dilutions).
  • AS 18 and AGl 8 columns, gradient KOH eluent, an ASRS suppressor, and conductivity detection were used for anion chromatography.
  • the system was standardized with the DIONEX 6-cation and 7-anion standards (in dilutions). Data were obtained as microgram per milliliter. Conversion of these data to parts per million (PPM) was done by dividing the reported data by percent solids and density of the original solution. The reported numbers are micrograms of ion per gram of Si ⁇ 2-
  • Table 3 Ion content of silica sols determined by the IC Procedure #1.
  • CE-3 was prepared as follows. The surface-modified silica sol of CE-I (50.16 g) was combined with polyethylene glycol acrylate (12 g), and A- hydroxy-TEMPO (0.05 g) in a round bottom flask. Water and alcohol were removed with rotary evaporation until less than 1% water/methoxypropanol as measured by gas chromatography remained in the surface-modified nanoparticle-containing resin system.
  • CE-4 was prepared as follows. The cation-exchanged, surface-modified silica sol of CE-2 (43.86 g) was combined with polyethylene glycol acrylate (12 g), and 4- hydroxy-TEMPO (0.05 g) in a round bottom flask. Water and alcohol were removed with rotary evaporation until less than 1% water/methoxypropanol as measured by gas chromatography remained in the surface-modified nanoparticle- containing resin system.
  • Example 2 was prepared as follows. The dual-ion-exchanged, surface- modified silica sol of EX-I (42.22 g) was combined with polyethylene glycol acrylate (12 g), and 4- hydroxy-TEMPO (0.05 g) in a round bottom flask. Water and alcohol were removed with rotary evaporation until less than 1 wt.% of water/methoxypropanol as measured by gas chromatography remained in the surface-modified nanoparticle- containing resin system.
  • Optical Property Test Method Various uncured, nanoparticle-containing resins were tested for optical transmission, clarity, and haze using a BYK GARDNER HAZE- GARD PLUS (catalog no. 4723, supplied by BYK Gardner, Silver Spring, Maryland). The transmission, clarity, and haze levels were defined according to ASTM-D 1003-00, titled "Standard Test Method for Haze and Luminous Transmittance for Transparent Plastics". The instrument was referenced against air during the measurements. Light transmission (T) measurements are provided as a percentage of transmitted light based on the incident light. Haze is the scattering of light by a specimen responsible for the reduction in contrast of objects viewed through it.
  • Haze, H is presented as the percentage of transmitted light that is scattered so that its direction deviates more than a specified angle from the direction of the incident beam. Clarity is evaluated using a ring detector and comparing the small-angle scattered light component to the specularly transmitted component.
  • Example 3 was prepared as follows. NP-2329 (3406 g) was added to a large jar and stirred. DOWEX MONOSPHERE 550A(OH) anion exchange resin (184 g)was added to the jar and stirred for 30 minutes until the pH was 9.5. The anion exchange beads were filtered out. Next, 257.9 g of DOWEX MONOSPHERE 650C(H) cation exchange resin was added to the jar and stirred for 30 minutes until the pH was 3.0. The cation exchange beads were filtered out and ammonium hydroxide (30%) was added while slowly stirring until the pH was 9.5. The ion exchanged sol contained 35.6 wt.% silica.
  • the concentrated solution was then dried according to the procedures described in the U.S. Pat. No. 5,980,697 (KoIb et al.) and U.S. Pat. No. 5,694,701 (Huelsman, et al.) with a dispersion coating thickness of about 0.25 mm (10 mils) and a residence time of 1.1 minutes (heating platen temperature 107 0 C, and condensing platen temperature 21 0 C) to yield a fine, free-flowing white powder.
  • a suitable amount of resin was placed in the center of the lower plate. Care was taken to avoid entrainment of air in the resin.
  • the upper fixture (cone) was lowered into the resin until the gap was filled with resin. With the motor off, the lower fixture was slowly turned by hand while the upper fixture was lowered until a gap of 0.0465 mm was obtained. During this gap-setting process, excess resin was gently scraped off the lower plate as it squeezed out.
  • the dual-ion-exchanged nanoparticles of EX- 3 resulted in significantly higher viscosities across the range of shear rates relative to the untreated nanoparticles of CE-I.
  • this increase in viscosity may be tolerable or even desirable.
  • the increase in viscosity may be undesirable, e.g., lower viscosities may be required when spraying coatings (e.g., gel coats) or when infusing fibrous substrates to produce composites.
  • spraying coatings e.g., gel coats
  • fibrous substrates to produce composites.
  • the present inventors discovered that the dual-ion-exchange protocol resulted in an unexpected increase in viscosity of a resin containing such nanoparticles.
  • the present inventors explored whether free silanol groups (Si-OH) remained at the surface of the nanoparticle.
  • Si-OH groups may contribute to the observed increase in viscosity due to, e.g., hydrogen bonding either particle to particle bonding or particle to resin bonding.
  • the present inventors experimented with the addition of low-molecular weight compounds in attempt to displace protons from the silanol groups and associate these compounds with the remaining surface Si-O- groups. This process is referred to herein as "end-capping," and the low molecular weight compounds are referred to as "end-capping agents.”
  • Some end-capping agents associate with the nanoparticles by ionically-bonding with Si-O- groups at the surface of the nanoparticle.
  • 2-(Dimethyl amino)ethyl methacrylate (DMAEMA) is one example of a low molecular weight, ionically-bonding, end-capping agent.
  • Other ionically bonding end-capping agents include other amines such as triethylamine, and pyridines (e.g., vinyl pyridine).
  • Some end-capping agents associate more strongly with the nanoparticles by covalently bonding with the Si-O- groups at the surface of the nanoparticles.
  • Hexamethyl disilazane (HMDS) is one example of a low molecular weight, covalently-bonding, end- capping agent.
  • the end-capping agent may include a functional group capable of reacting with another component of the resin system, for example the curable resin or a reactive diluent.
  • the reactive functional group may be selected based on the characteristic of the resin into which the end-capped, surface-modified nanoparticles are to be added.
  • Example 4 was prepared as follows. Dried, surface-modified nanoparticles were prepared as described above for Example 3. These dried surface- modified nanoparticles (509.18 g) were combined with 690.8 g of HK-2, and 2.26 grams of DMAEMA and mixed with a DISPERMAT dissolver for ten minutes. The nanoparticle-containing resin system was then milled as described for Comparative Example 1.
  • Example 5 was prepared in the same manner as EX-4, except that 4.53 grams of DMAEMA were used.
  • Figure 4 A is a TEM image of the dual-ion exchanged nanoparticle-containing resin system of EX-3, which was not end-capped.
  • Figure 4B is a TEM image of the dual- ion exchanged nanoparticle-containing resin system of EX-4, which was end-capped with 0.03 millimoles (mmol) DMAEMA per gram of silica.
  • Figure 4C is TEM image of the dual-ion exchanged nanoparticle-containing resin system of EX-5, which was end-capped with 0.06 mmol DMAEMA per gram of silica. All images are at 10,000X magnification. The improvement in particle dispersion resulting from the use of an end-capping agent is apparent from a comparison FIG.
  • FIGS. 4B and 4C illustrate increasingly well-dispersed, non-aggregated, non- agglomerated nanoparticles as the concentration of DMAEMA was increased.
  • REF-3 and REF-4 Two reference examples (REF-3 and REF-4) were also prepared using the unsaturated polyester/styrene resin system (GDW 8082 from HK Research Corp.) without nanoparticles.
  • the resin sample was promoted with 1.00 wt% cobalt solution (JK 8033, available from HK Research (Hickory, NC)) and was initiated with 1.25 wt.% methyl ethyl ketone peroxide (MEKP B0410 46-702, available from HK Research (Hickory, NC )).
  • the MEKP was mixed into the gel coat using a SPEEDMIXER DAC 600 FVZ available from FlackTek, Inc. (Landrum, SC) for 30 seconds at 2000 rpm.
  • the liquid sample was poured between two pieces of mold-release-coated glass held apart by a spacer.
  • the resin-glass-spacer construction was allowed to cure in a vented hood for 24 hours at room temperature. Then, the resin-glass-spacer construction was put into a 70 0 C (158 0 F) oven for 4 hours. After removal from the oven, the glass and sample were allowed to cool for one hour before the cured sample was removed from the glass.
  • the resin sample of REF-4 was pre -heated for 10 minutes at 80 0 C prior to being prepared according to the process used to prepare REF-3.
  • Table 5 Effects of end-ca in on o tical ro erties avera e of 5-7 sam les .
  • Example 6 was prepared as follows. Dual-ion-exchanged nanoparticles were prepared as follows. NP -2329 (3235 g) was added to a large jar and stirred. DOWEX MONOSPHERE 550A(OH) anion exchange resin (175 g) was added to the jar and stirred for 30 minutes until the pH was 9.5. The anion exchange beads were filtered out. Next, 203.5 g of DOWEX MONOSPHERE 650C(H) cation exchange resin was added to the jar and stirred for 15 minutes until the pH was 3.0. The cation exchange beads were filtered out and ammonium hydroxide (30%) was added while slowly stirring until the pH was 9.5. The dual-ion-exchanged sol contained 35.4 wt.% silica. This process was repeated to double the batch size available for the next step.
  • HMDS-treated, concentrated solution was then dried according to the procedures described in the U.S. Pat. No. 5,980,697 (KoIb et al.) and U.S. Pat. No. 5,694,701 (Huelsman, et al.) with a dispersion coating thickness of about 0.25 mm (10 mils) and a residence time of 1.1 minutes (heating platen temperature 107 0 C, and condensing platen temperature 21 0 C) to yield a fine, free-flowing white powder.
  • Example 7 was prepared as follows. First, 1205.5 g of NP-136 low ion content silica sol were added to a large jar and stirred. 837 g l-methoxy-2-propanol, 7.73 g A- 174 and 6.18 g phenyl trimethoxy silane were mixed together and then added to the stirring colloidal silica and the mixture was then heated for 16 hours at 80 0 C. Next, 562.95 g of this mixture, 86.20 g of HK-3, 0.34 g of 4-hydroxy-TEMPO, and 0.4 g DMAEMA were added to a round bottom flask. Water and alcohol were removed via rotary evaporation. Gas chromatography confirmed no methoxy-propanol remained in the sample.
  • Example 8 was prepared as follows. First, 1202.4 g NP-135 were added to a large jar and stirred. Next, 736.8 g l-methoxy-2-propanol, 9.40 g A- 174 and 7.52 g phenyl trimethoxy silane were mixed together and then added to the stirring colloidal silica and the mixture was then heated for 16 hours at 80 0 C. Next, 440.35 g of this mixture, 86.20 g of HK-3, 0.34 g of 4-hydroxy-TEMPO, and 0.4 g DMAEMA were added to a round bottom flask. Water and alcohol were removed via rotary evaporation. Gas chromatography confirmed no methoxy-propanol remained in the sample.
  • EX-9 was prepared as follows. First, 1294.0 NP-MJM, 841.7g of HK-3 and 3.4 g of 4-hydroxy-TEMPO were added to a round bottom flask. Methyl-ethyl ketone was removed via rotary evaporation. Gas chromatography confirmed no solvent remained in the sample. Then, 38.5 g MMA and 107.7 g styrene were added back to the sample to produce EX-9. The sample contained approximately 40 wt.% silica.
  • IC Procedure #2 Extractable anions: The sample was weighed (50-100 mg) into a small glass vial and dissolved in 200 mL dry acetonitrile. 1 mL ultrapure MiIIiQ water was added and the vials vigorously shaken. The contents were transferred to 1.5 mL microcentrifuge tubes. The tubes were placed in a microcentrifuge at 10,000 rpm for 10 minutes to settle the particles. An aliquot of the supernatant was transferred to an autosampler vial and injected onto a DIONEX ICS-3000 dual-channel ion chromatograph with suppressed conductivity detection. A ramp/step hydroxide gradient profile was applied, and the analysis was performed on AG 18/AS 18 columns.
  • Panels were prepared from the resin systems of EX-7, EX- 8, and EX-9 according to Panel Preparation 2 and tested according to Boiling Blister Test B. Ion contents and boil resistance are summarized in Table 6.
  • Boiling Blister Test B is the same as Boiling Blister Test A with the exception that, the test was continued for up to 6 days. In order to extend the testing after the 24 test, the test specimens were re-clamped to the ends of the ports, the flask refilled with preheated DI water, and timing restarted when the water began to boil. All water was replaced after 6 days of testing.
  • Table 6 Comparison of low and high ion content resin systems as measured by IC Procedure #2. (Ion content in micrograms of ion per gram of total silica and resin.)
  • curable resin systems with 40 wt.% surface-treated nanoparticles should contain no greater than 200 ppm, in some embodiments, no greater than 100 ppm, of total alkali metals and alkaline earth metals based on the total weight of silica and resin.
  • the curable resin systems with 40 wt.% surface-modified nanoparticles having a total alkali and alkaline earth metal ion content of less than 100 ppm by total weight of silica and resin produced good boil performance.
  • the sodium content for the curable resin of REF-I in Table 6 we can predict the sodium ion content contribution from the resin only in a curable resin system with varying nanoparticle loading.
  • the additional sodium contribution arising from the addition of nanoparticles to the curable resin system can also be calculated.
  • a curable resin system containing 10 wt.% of the low metal silica nanoparticles would contain 81 ppm of sodium ion originating from the resin (i.e., 90 ppm Na/gram resin* 0.9 wt fraction resin) and an additional 15 ppm sodium ion originating from the NP-LMS sol nanoparticles (151 ppm Na/gram silica * 0.1 wt fraction silica). This yields a total sodium ion content of 96 ppm per total weight silica and resin.
  • the other alkali and alkaline earth metal ions are not reported in Table 3, it is reasonable to expect that there would be some additional ion content contributions from those other species in the curable resin system from EX-10 which passed the Boiling Blister Test A.
  • a resin system comprising a curable resin and at least 10 wt.%, in some embodiments, at least 20 wt.%, or even at least 40 wt.% surface-modified silica nanoparticles; wherein the resin system comprises no greater than 200 parts per million, and in some embodiments, no greater than 100 parts per million, by weight alkali metal and alkaline earth metal ions based on the total weight of the silica nanoparticles and curable resin.
  • the treated, surface-modified nanoparticles of the present disclosure and the resin systems containing such nanoparticles may be used in a wide variety of applications, including as coatings and as the resin system of composite articles (e.g., glass and/or carbon fiber composites).
  • the resin systems of the present disclosure may be useful as gel coats, e.g., gel coats for the marine industry.

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Abstract

L'invention porte sur divers procédés de traitement de nanoparticules modifiées en surface. L'invention porte sur des procédures de double échange d'ions (échange d'anions et échange de cations), ainsi que l'application d'un revêtement de coiffage subséquente. Des agents de revêtement de coiffage liés de façon ionique et liés de façon covalente sont tous deux examinés. L'invention porte également sur les nanoparticules modifiées en surface traitées à faible teneur en ions, en particulier à faible teneur en ions de métaux alcalins et d'oxydes de métaux alcalins, résultantes, y compris de telles nanoparticules dans un système de résine. Les effets de la faible teneur en ions sur diverses propriétés du système de résine résultant, dont la résistance au cloquage, la transparence optique et la rhéologie sont compris.
PCT/US2009/047000 2008-06-12 2009-06-11 Systèmes de résine contenant des nanoparticules à faible teneur en ions Ceased WO2009152301A2 (fr)

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JP4631119B2 (ja) * 2000-01-28 2011-02-16 Ｊｓｒ株式会社 疎水化コロイダルシリカの製造方法
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