WO2011084380A1 - Nanocalcite and vinyl ester composites - Google Patents
Nanocalcite and vinyl ester composites Download PDFInfo
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- WO2011084380A1 WO2011084380A1 PCT/US2010/060082 US2010060082W WO2011084380A1 WO 2011084380 A1 WO2011084380 A1 WO 2011084380A1 US 2010060082 W US2010060082 W US 2010060082W WO 2011084380 A1 WO2011084380 A1 WO 2011084380A1
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- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- 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
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
- C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- 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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present disclosure relates to compositions comprising surface-modified nanocalcite particles dispersed in a curable vinyl ester resin, and to coatings and fibrous composites incorporating such compositions. Methods of preparing nanocalcite composites in a vinyl ester resin are also described.
- Nanoparticle-containing resins have been used as coatings and as the impregnating resin of fibrous composites. Generally, the addition of nanoparticles provides improved strength-to-weight ratios compared to the pure resins. These materials have been used in a wide variety of applications including coatings for vehicles (e.g., marine gel coats) and wind turbine blades, and composite structures used in e.g., sporting goods, wind turbine blades, and vehicle fabrication.
- vehicles e.g., marine gel coats
- wind turbine blades e.g., composite structures used in e.g., sporting goods, wind turbine blades, and vehicle fabrication.
- the present disclosure provides a composition comprising surface-modified nanoparticles dispersed in a curable resin system comprising a vinyl ester resin.
- the surface-modified nanoparticles comprise a calcite core, and the surface- modified nanoparticles comprise a first surface-modifying agent comprising a
- the binding group has a binding energy of at least 0.50 electron volts to calcite as calculated using the Binding Energy Calculation Procedure assuming a calcite rich surface. In some embodiments, at least 90%, of the calcite cores have an average size of less than 400 nm as measured by the Calcite Particle Size Procedure.
- the curable resin system further comprises a reactive diluent.
- the binding group comprises a phosphonic acid, a sulfonic acid, a phosphoric acid, or a combination thereof. In some embodiments, the binding group comprises a carboxylic acid.
- the compatiblizing group comprises at least one of a polyethylene oxide, a polypropylene oxide, and a polyester. In some embodiments, the compatiblizing group comprises a polyetheramine.
- the first surface-modifying agent is a zwitterion. In some embodiments, the first surface-modifying agent further comprises a reactive group capable of reacting with at least one of the vinyl ester resin and the reactive diluent.
- the composition further comprises a second surface- modifying agent bonded to the calcite, wherein the second surface-modifying agent comprises a binding group and a reactive group capable of reacting with at least one of the vinyl ester resin and the reactive diluent, if present.
- the composition comprises at least 10 wt.% nanoparticles based on the total weight of the nanoparticles and the curable resin system. In some embodiments, the composition comprises no greater than 2 wt.%, solvent.
- the present disclosure provides a cured composition comprising a composition of the present disclosure, wherein the vinyl ester resin is cured.
- the first surface-modifying agent is reacted with at least one of the vinyl ester resin and the reactive diluent, if present.
- the cured composition is bonded to at least a portion of the substrate.
- the present disclosure provides a fibrous composite comprising reinforcing fibers impregnated with a composition of the present disclosure.
- at least 90%, of the calcite cores have an average size of less than 400 nm as measured by the Calcite Particle Size Procedure.
- the vinyl ester resin is cured.
- compositions of the present disclosure comprise surface-modified nanoparticles dispersed in a curable resin system comprising a vinyl ester resin.
- resin system refers to the major reactive elements that react or co-react to form the final cured resin.
- the resin systems of the present disclosure comprise at least one curable vinyl ester resin, one or more additional crosslinkable resins, and/or one or more reactive diluents.
- 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.
- vinyl ester resins include those available under the trade names HETRON, DERAKANE, and DERAKANE MOMENTUM epoxy vinyl esters from Ashland, Inc., Covington Kentucky.
- the vinyl ester resin is both soluble in the reactive diluent of the resin system and reacts with the reactive diluent to form a copolymerized network.
- any known reactive diluent may be used.
- Exemplary reactive diluents include styrene, alpha-methylstyrene, vinyl toluene, divinylbenzene, methyl methacrylate, diallyl phthalate, ethylene glycol dimethacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and triallyl cyanurate.
- the surface-modified nanoparticles of the present disclosure comprise calcite cores and a surface-modifying agent bonded to the calcite.
- Calcite is the crystalline form of calcium carbonate (i.e., calcite and its polymorphs aragonite and vaterite). Calcium carbonate typically forms well-faceted, columnar or plate-like rhombohedral crystals. However, in some cases, calcium carbonate can form highly anisotropic, irregularly- shaped crystals.
- the nanocalcite containing resins may be desirable to control, e.g., minimize or even eliminate, filtering of the nanocalcite by the fibers. Larger particles or particle aggregates may be filtered or separated from the resin while the mixture is pressured through a highly compressed fiber array in the process of making a continuous fiber composite. This can result in a non-uniform distribution of particles and resin throughout the final composite resulting in decreased physical properties.
- at least 70%, e.g., at least 75% of the calcite cores have an average size of less than 400 nm.
- at least 90%>, in some embodiments, at least 95%, or even at least 98% of the calcite cores have an average size of less than 400 nm.
- the surface-modifying agents of the present disclosure include at least a binding group and a compatiblizing segment:
- Comp. Seg refers to the compatiblizing segment.
- the compatiblizing segment is selected to improve the compatibility of the calcite nanoparticles with the curable resin and ultimately to improve the dispersion of these nanoparticles in the resin.
- the selection of the compatiblizing group depends on a number of factors including the nature of the curable resin, the concentration of the nanoparticles, and the desired degree of compatibility.
- useful compatiblizing agents include polyalkylene oxides, e.g., polypropylene oxides, polyethylene oxides, and combinations thereof.
- Other useful compatiblizing segments include polyesters and polyether amines.
- the compatiblizing segment may be selected to provide a positive enthalpy of mixing for the composition containing the surface-modified nanoparticles and the curable resin. If the enthalpy of mixing is positive, the dispersion of nanoparticles in the resin is typically stable. To ensure a positive enthalpy of mixing, the solubility parameter of the compatiblizing segment can be matched to the solubility parameter of the curable resin.
- solubility parameter of a material such as a compatiblizing segment or a resin.
- the solubility parameter of the material can be determined from measurements of the extent of equilibrium swelling of the material in a range of solvents of differing solubility parameters.
- the solubility parameters of the solvents themselves can be determined from their heats of evaporation.
- ⁇ 00 ⁇ and ⁇ can be calculated from the heat of evaporation of the solvent or from the course of the vapor pressure as a function of temperature.
- a plot of equilibrium swelling of the material versus the solubility parameter of the solvents is generated.
- the solubility parameter of the material is defined as the point on this plot where maximum swelling is obtained. Swelling will be less for solvents having solubility parameters that are less than or greater than that of the material.
- the binding group bonds to the calcite, connecting the surface-modifying agent to the calcite core.
- the surface-modifying agents of the present disclosure are ionically bonded to (e.g., associated with) the calcite.
- binding energies can be predicted using density functional theory calculations.
- the calculated binding energies may be at least 0.5, e.g., at least 0.6, or even at least 0.7 electron volts.
- the greater the binding energy the greater the likelihood that the binding group will remain ionically associated with the particle surface.
- binding energies of at least 0.8, e.g., at least 0.9, or even at least 0.95 electron volts may be useful.
- the binding group comprises a phosphonic acid, e.g., surface-functionalizing agents having a formula:
- the binding group comprises a sulfonic acid, e.g., surface-functionalizing agents having a formula:
- the surface-modifying agent also comprises a reactive group, e.g., a group capable of reacting with the curable resin, e.g., during the curing process.
- a reactive group e.g., a group capable of reacting with the curable resin, e.g., during the curing process.
- the reactive group is selected based on the nature of the curable resin.
- the reactive group may be located on the end of the compatiblizing segment:
- Rx. Group is the reactive group.
- the reactive group may be located along the backbone of, or pendant to, the backbone of the compatiblizing segment. In some embodiments, the reactive group may be located between the compatiblizing segment and the binding group:
- a linking group is present connecting the compatiblizing segment with the binding group:
- the surface-modifying agent comprises a
- polyetheramine examples include those available under the trade name JEFF AMINE® available from Huntsman Corporation, The Woodlands, Texas.
- the polyether serves as a compatiblizing segment, while the amine is the linking group linking the compatiblizing segment with the binding group, e.g., a sulfonic, phosphonic, or carboxylic acid binding group.
- the surface-modifying agent comprises a zwitterion, i.e., a compound carrying a net charge of zero, but which is capable of carrying a formal positive and negative charge on different atoms.
- the formal negative charge is carried by the binding group.
- the formal positive charge is carried on the nitrogen atom of an amine, e.g., an amine linking group. In such embodiments, the amine may serve as both the linking group and the reactive group.
- compositions of the present disclosure comprise at least 10 wt.%, in some embodiments, at least 20 wt.%, e.g., at least 30 wt.%, at least 40 wt.%, or even at least 50 wt.% of the surface modified nanoparticles based on the total weight of the nanoparticles and the curable resin system.
- it may be useful to have a low viscosity composition e.g., when the composition is to be sprayed (e.g., when applying a coating), or must flow through fibers (e.g., when making fibrous composites).
- Viscosity can be reduced by diluting the composition in solvents, e.g., water, organic solvents, or a combination thereof. If solvents are used, the solvent or
- compositions of the present disclosure comprise no greater than 5 wt.%, optionally no greater than 2 wt.%, no greater than 1 wt.%, or even no greater than 0.5 wt.% solvent.
- certain steps e.g., milling of the nanoparticles or dispersion of the nanoparticles in the curable resin system, may occur in the presence of a solvent. The solvent can then be removed by, e.g., drying, to reduce the residual solvent in the curable composition to the desired level.
- compositions of the present disclosure may include additional additives such as curing agents, cure accelerators, catalysts, crosslinking agents, dyes, pigments, flame retardants, impact modifiers, and flow control agents.
- additional additives such as curing agents, cure accelerators, catalysts, crosslinking agents, dyes, pigments, flame retardants, impact modifiers, and flow control agents.
- the compositions may include tougheners, e.g., rubber tougheners.
- Exemplary rubber tougheners include coreshell rubbers.
- nano- sized coreshell rubber tougheners may be used, i.e., coreshell rubber tougheners having an average size of less than 1 micron.
- the nano-sized coreshell rubber tougheners have an average size of less than 500 nm, less than 250 nm, or even less than 100 nm.
- micron-sized coreshell rubber tougheners may be used, i.e., coreshell rubber tougheners having an average size of greater than 1 micron, e.g., 1 to 10 microns.
- compositions of the present disclosure may be cured. In some embodiments,
- the curable resin is crosslinked. Any known crosslinking method may be used including exposure to thermal energy or actinic radiation (e.g., ultraviolet light and electron beam radiation).
- the curable resin may also react with the surface-modifying agent.
- a reactive group of the surface-modifying agent may react with, e.g., covalently bond with, the curable resin.
- compositions of the present disclosure may be used in a wide variety of applications.
- the compositions may be applied to a surface of an article. Such coating may be cured, e.g., crosslinked.
- the compositions of the present disclosure may be used to form fibrous composites.
- reinforcing fibers may be impregnated with the composition to form a composite article.
- Composites may be formed using any known means including, e.g., resin transfer molding (RTM), filament winding, tow placement, resin infusion processes, pultrusion process, or traditional prepreg processes.
- RTM resin transfer molding
- the resin may then be cured using any known means including exposure to thermal energy and/or actinic radiation.
- any fibers suitable for use in fibrous composites may be used.
- Exemplary fibers include carbon fibers, glass fibers, ceramic fibers, boron fibers, silicon carbide fibers, polyimide fibers, polyamide fibers, and polyethylene fibers. Combinations of materials may also be used. Generally, the form of the fibers is not particularly limited. Exemplary fiber forms include unidirectional array of individual continuous fibers, woven fabric, knitted fabric, yarn, roving, braided constructions and non-woven mat.
- compositions of the present disclosure may used in a wide variety of applications including as coatings on, e.g., wind turbine blades and as gel coats on, e.g., vehicles, e.g., boats; and as composites used in the manufacture of, e.g., sporting goods (e.g., rackets, fishing poles, hockey sticks, baseball bats, sailing masts, and the like); wind turbine blades, vehicles and vehicle parts including automobiles, ships, aircraft, and satellites, and space vehicles.
- sporting goods e.g., rackets, fishing poles, hockey sticks, baseball bats, sailing masts, and the like
- wind turbine blades, vehicles and vehicle parts including automobiles, ships, aircraft, and satellites, and space vehicles.
- Shear Modulus Procedure Shear modulus was determined with an RDA-700 Rheometrics Dynamic Analyzer (available from Rheometrics, Inc., Piscataway, New Jersey) using a torsion rectangular test mode. Test specimens were machined to 5.08 cm x 1.27 cm x 0.16 cm. Data were collected at 5 °C intervals from 35 °C to above the glass transition temperature of the resin at a heating rate of 5 °C per minute with a one minute thermal soak before each measurement was taken. The initial strain was 0.45% and the machine was in the strain adjustment mode. The frequency was 10 radians per second.
- Calcite Concentration Procedure A 20 to 50 milligram sample of calcite in resin was placed in a TA Instruments TGA 500 thermogravimetric analyzer. The sample temperature was ramped up in air at 30 °C per minute from 50 °C to 900 °C, and then held at 900 °C for 3 minutes. The residual weight was assumed to be the CaO remaining in the sample after volatilizing all organics and carbon dioxide from the calcite. The calcite concentration in the original sample was calculated by dividing the weight percent CaO residue by 0.56.
- Calcite Particle Size Procedure The particle size of the calcite was measured by laser diffraction using a HORIBA LA-950 laser diffraction particle size analyzer, including its accompanying software (available from Horiba Instruments, Inc., Irvine, California). The calcite dispersion was diluted to approximately 1% solids with methyl ethyl ketone. The sample was then added to the measurement cell, which was filled with methyl ethyl ketone, until the transmittance was between the recommended levels of 85% to 95%.
- the optical model for the calculation used a refractive index of 1.6000 for calcite and 1.379 for the methyl ethyl ketone solvent, and assumed spherical particles.
- the second differential method was used for smoothing and was based on 150 iterations.
- the reported values of percent average particle size less than 400 nm (% less than 400 nm) were based on volume fraction averages and static light scattering.
- surface-modifying agents include a compatiblizing group to aide in dispersing the nanoparticles in resin, and a binding group to associate the compatiblizing group with the nanoparticles.
- the binding energy to calcite of various common and potential binding groups can be determined using density functional theory calculations. Details regarding such calculations are available in Pendrew, J.P.; Burke, K.J.; Ernzerhof, M; Phys. Rev. Lett. 1996, 3865, 77.
- Binding Energy Calculation Procedure The binding energies of different functional groups to the surface of nanocalcite with periodic boundary condition density functional theory (PBC-DFT) were calculated.
- PBC-DFT periodic boundary condition density functional theory
- the surface of the nanoparticle was represented a 2D-periodic slab.
- the calculations were actually periodic in three dimensions, but a 20 Angstrom layer of vacuum was included to prevent the slabs from interacting with each other in the z-direction. As such, the slab had 2D periodicity.
- the slabs included three to four layers and were cleaved along a Miller plane. For the case of nanocalcite, the surface was cleaved along the ⁇ 1014 ⁇ surface.
- Two potential surfaces were modeled, a stoichiometric surface and a calcium rich surface.
- the under-coordinated calcium ions on the surface were terminated with hydroxyl groups.
- the isolated molecules were calculated in a periodic box that had an edge length of 11 or 12 Angstroms. The distance was large enough to prevent the molecules from interacting with each other.
- BE E(Slab) + E(Molecule) - E(Slab+Molecule) (1) wherein, E(Slab+Molecule), E(Slab), and E(Molecule) are the electronic energies of the complex, isolated slab, and isolated molecule, respectively. In all cases, the geometries were optimized to their respective minima.
- BE E(Slab) + E(Molecule) + E(Water) - E(Slab+Molecule) (2) wherein E(Slab+Molecule), E(Slab), and E(Molecule) are defined above and E(Water) is the electronic energy of an isolated water molecule.
- Ligand A Polyetheramine Sulfonate Ligand.
- Mn poly(ethylene glycol) methyl ether
- thionyl chloride 152.8 g (1.284 mol) of thionyl chloride
- a mixture of 150.0 g (0.430 mol) of the crude chloride prepared above and 214.0 g (1.290 mol) of triethyl phosphite was heated at 170 °C. After 3 days, an additional 100.0 g (0.600 mol) of triethyl phosphite was added, and the reaction temperature was increased to 180 °C. After an additional 2 days at 180 °C, a third portion of 100.0 g (0.600 mol) of triethyl phosphite was added, and heating at 180 °C was continued. After an additional 2 days, 13C NMR analysis of the reaction mixture indicated the absence of the starting chloride at 43 ppm.
- triethylphosphite was heated at 135 °C for 16 hours. An additional 50.0 g (300 mmol) of triethylphosphite was added, and heating at 135 °C was continued for an additional 17 hours. Volatiles were distilled from the mixture at 0.1 mm to a bath temperature of 110 °C, affording the desired diethylphosphonate ester, which was used without further purification.
- the solution was cooled to room temperature, filtered through Celite and concentrated to a soft, tan solid.
- the solid was triturated in 1 L of hexanes, and filtration provided 27.1 g of 11-phosphonoundececyl acrylate as an off- white solid.
- the 1H, 13C, and 3 IP NMR spectra of the final product and all intermediates were consistent with the structures of the target compounds.
- DISPERB YK D- 111 (Ligand D) is a phosphoric acid polyester ligand, commercially available from BYK-Chemie GmbH.
- Calcium carbonate has been used as a filler in resin systems.
- most commercially available fillers have a large average particle size, e.g., 1 to 10 microns.
- Even commercially available calcium carbonate material based on nanometer-sized primary particle sizes typically contain aggregates of such primary particles leading to an effective particle size significantly greater than the primary particle size. Even with common surface treatments, such aggregated particles may result in highly viscous resin systems at higher particle loadings.
- 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.
- aggregated particles are not broken down into smaller entities by, for example, shearing forces encountered during dispersion of the aggregated particles in a liquid.
- agglomerated and agglomerates are 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.
- the reduction in aggregate size of the as-received nanoparticles can be important to achieving the desired mechanical properties.
- common procedures for blending fillers such as calcium carbonate into a resin rely on low shear processes, e.g., air mixing, that are sufficient to provide the desired dispersion, but provide insufficient energy to reduce the aggregate sizes.
- the milling procedures used in the present application provided sufficient energy to reduce the aggregate size and disperse them in the resin.
- the nanocomposite mixture was circulated through the mill using a peristaltic pump at 250 ml/min. In each case, milling was performed until greater than 99% of the calcite particles had an average size of less than 400 nm, as determined according to the Calcite Particle Size Procedure.
- Examples EX- 1 and EX-2 These examples illustrate the surface modification and compounding of calcite nanoparticles with a resin system containing a reactive diluent using solventless milling.
- the samples were prepared according to the Vinyl Ester Nanocomposite Preparation Procedure. The compositions and milling conditions are summarized in Table 3.
- Table 3 Composition of calcite modified with Ligand A and compounded.
- Examples EX-3 and EX-4 These examples illustrate the surface modification and compounding of calcite nanoparticles with a resin system containing a reactive diluent using solventless milling.
- the samples were prepared according to the Vinyl Ester Nanocomposite Preparation Procedure. The compositions and milling conditions are summarized in Table 4.
- Table 4 Calcite modified with Ligands B and C and compounded.
- Example EX-5 This Example illustrates solventless milling with a reactive diluent and a commercially available ligand (Ligand D) to disperse calcite in a vinyl ester resin.
- a composition containing 857 g of VE-1398-5 vinyl ester, 234 g of styrene, 35 g of Ligand D (DISPERBYK-111 , phosphoric acid polyester), and 700 g of SOCAL 31 nanocalcite were compounded according to the Vinyl Ester Nanocomposite Preparation.
- the composition was milled at 57 °C for three hours.
- the resulting surface-modified nanoparticles were dispersed in the resin system and greater than 99% of the calcite particles had an average size of less than 400 nm, as determined according to the Calcite Particle Size Procedure.
- Example 1 The milled product of Example 1 (270 g) was mixed with two peroxide curatives, i.e., PERKADOX 16 (1.62 g) and TRIGONOX 121 (1.62 g), in a SpeedMixer container. The container was sealed and the contents mixed at 2000 revolutions/minute (rpm) for 30 seconds using a SpeedMixerTM dual asymmetric centrifuge (Model DAC 600 FVZ-sp, available from Flack Tek, Incorporated, Landrum, South Carolina).
- a SpeedMixerTM dual asymmetric centrifuge Model DAC 600 FVZ-sp, available from Flack Tek, Incorporated, Landrum, South Carolina.
- Comparative Example CE-1 Comparative Example CE-1.
- a sample was prepared without the surface-modified nanocalcite material.
- 270 g of VE-1398-5 vinyl ester resin was mixed with PERKADOX 16 peroxide curative (2.70 g) and TRIGONOX 121 peroxide curative (2.70 g) in a SpeedMixer container.
- the container was sealed and the contents mixed at 2000 revolutions/minute (rpm) for 30 seconds using a SpeedMixerTM dual asymmetric centrifuge (Model DAC 600 FVZ-sp, available from Flack Tek,
- SOCAL 31 nanocalcite was dispersed into VE-1398-5 vinyl ester using the Vinyl Ester Nanocomposite Preparation Procedure.
- the ligands used are summarized in Table 6.
- a comparative example containing no ligand was also prepared.
- the ligand concentration, also reported in Table 6, was adjusted during the milling process and greater than 99% of the calcite particles in the milled composition had an average size of less than 400 nm, as determined according to the Calcite Particle Size Procedure.
- the milled product (270 g) was mixed with PERKADOX 16 peroxide curative (1.62 g) and TRIGONOX 121 peroxide curative (1.62 g) in a SpeedMixer container.
- the container was sealed and the contents mixed at 2000 revolutions/minute (rpm) for 30 seconds using a SpeedMixerTM dual asymmetric centrifuge (Model DAC 600 FVZ-sp, available from Flack Tek, Incorporated, Landrum, South Carolina).
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CN201080055289.7A CN102639623B (en) | 2009-12-17 | 2010-12-13 | Nanocalcite and vinyl ester composites |
US13/502,891 US10023726B2 (en) | 2009-12-17 | 2010-12-13 | Nanocalcite and vinyl ester composites |
EP10812968A EP2513214A1 (en) | 2009-12-17 | 2010-12-13 | Nanocalcite and vinyl ester composites |
JP2012544683A JP5823979B2 (en) | 2009-12-17 | 2010-12-13 | Nanocalcite and vinyl ester composites |
KR1020127018506A KR101793303B1 (en) | 2009-12-17 | 2010-12-13 | Nanocalcite and Vinyl Ester Composites |
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CN105452349B (en) | 2013-08-13 | 2022-09-27 | 3M创新有限公司 | Nanocomposites comprising silica nanoparticles and dispersants, composites, articles, and methods of making the same |
WO2015055433A1 (en) * | 2013-10-15 | 2015-04-23 | Basell Poliolefine Italia S.R.L. | Highly filled soft polyolefin composition for roofing membrane |
US20200140722A1 (en) | 2016-12-29 | 2020-05-07 | 3M Innovative Properties Company | Curable compositions |
US20210198535A1 (en) | 2017-12-22 | 2021-07-01 | 3M Innovative Properties Company | Multilayered polyetherketoneketone articles and methods thereof |
EP3788117B1 (en) * | 2018-05-03 | 2022-11-09 | Merck Patent GmbH | Crosslinked ligands |
CN110564127B (en) * | 2019-08-27 | 2020-11-13 | 珠海格力电器股份有限公司 | Anti-static composite material, preparation method, anti-static shell and purifier |
US11485833B2 (en) | 2019-10-23 | 2022-11-01 | Hexcel Corporation | Thermoplastic toughened matrix resins containing nanoparticles |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5648407A (en) * | 1995-05-16 | 1997-07-15 | Minnesota Mining And Manufacturing Company | Curable resin sols and fiber-reinforced composites derived therefrom |
US20040076574A1 (en) * | 2000-10-02 | 2004-04-22 | Xu Peter W.Q. | Surface-modified Ca(CO3) and polymers containing same |
JP2006188552A (en) * | 2004-12-28 | 2006-07-20 | Toho Earthtech Inc | Viscous resin composition |
WO2010080459A1 (en) * | 2008-12-19 | 2010-07-15 | 3M Innovative Properties Company | Nanocalcite composites |
WO2011050121A2 (en) * | 2009-10-21 | 2011-04-28 | 3M Innovative Properties Company | Solventless functionalization, milling, and compounding process with reactive diluents |
Family Cites Families (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4478963A (en) | 1980-08-08 | 1984-10-23 | The B. F. Goodrich Company | Filler particles coated with reactive liquid polymers in a matrix resin |
JPS58500251A (en) | 1981-01-15 | 1983-02-17 | バテル デイベロプメント コ−ポレイシヨン | Photocurable composition for coating a support with an abrasion-resistant transparent or translucent film |
DE3141955A1 (en) | 1981-10-22 | 1983-05-05 | Siemens AG, 1000 Berlin und 8000 München | REACTION RESIN AND MOLDS MADE THEREOF |
JPS59138267A (en) * | 1983-01-29 | 1984-08-08 | Nitto Funka Kogyo Kk | Surface treatment of calcium carbonate powder |
JPS62135528A (en) * | 1985-12-10 | 1987-06-18 | Dainippon Ink & Chem Inc | Molding composition |
JPH06107937A (en) * | 1992-09-28 | 1994-04-19 | Hitachi Chem Co Ltd | Unsaturated polyester resin composition and production of sheetlike molding material and fiber-reinforced plastic molding |
ES2165517T3 (en) | 1995-09-18 | 2002-03-16 | Minnesota Mining & Mfg | COMPONENT SEPARATION SYSTEM THAT INCLUDES A CONDENSATION MECHANISM. |
US5694701A (en) | 1996-09-04 | 1997-12-09 | Minnesota Mining And Manufacturing Company | Coated substrate drying system |
FR2759704B1 (en) * | 1997-02-18 | 2003-08-15 | Centre Nat Rech Scient | FUNCTIONALIZED ALKYLENE POLYOXIDE COMPOUND AND USE AS A DISPERSING AGENT FOR CARBON BLACKS |
JP3623646B2 (en) * | 1997-04-04 | 2005-02-23 | 丸尾カルシウム株式会社 | Body pigment for water-based paint |
DE19738481C2 (en) | 1997-09-03 | 1999-08-12 | Solvay Alkali Gmbh | Calcium carbonate coated in aqueous systems with surface-active substances and process for the controlled bimolecular coating of calcium carbonate ponds |
US6616794B2 (en) | 1998-05-04 | 2003-09-09 | Tpl, Inc. | Integral capacitance for printed circuit board using dielectric nanopowders |
FR2780409B1 (en) * | 1998-06-30 | 2001-07-13 | Omya Sa | PROCESS FOR TREATING A MINERAL FILLER WITH A PHOSPHATE, MINERAL FILLER THUS PROCESSED, POLYURETHANE FOAMS AND COMPOSITE POLYURETHANES USING THE SAME, MOLDED OR NON-CONTAINING OBJECTS |
DK1155078T3 (en) | 1999-02-19 | 2005-11-14 | Du Pont | High modulus reinforced polyamides |
EP1227781B9 (en) | 1999-10-28 | 2006-03-08 | 3M Innovative Properties Company | Dental materials with nano-sized silica particles |
JP2002003726A (en) * | 2000-06-21 | 2002-01-09 | Shiraishi Kogyo Kaisha Ltd | Resin composition for sealing |
US6890968B2 (en) | 2001-05-16 | 2005-05-10 | Kerr Corporation | Prepolymerized filler in dental restorative composite |
TWI283235B (en) * | 2001-11-16 | 2007-07-01 | Maruo Calcium | Surface-treated calcium carbonate, production method thereof, and resin composition containing the calcium carbonate |
DE10200928A1 (en) | 2002-01-12 | 2003-09-25 | Basf Coatings Ag | Organic dispersions of surface-modified nanoparticles, processes for their production and their use |
DE60305611T2 (en) | 2002-11-14 | 2007-05-24 | Rohm And Haas Co. | Curable clay composition: composition, method and uses thereof |
EP1557442A1 (en) * | 2004-01-23 | 2005-07-27 | SOLVAY (Société Anonyme) | Method for surface treatment of precipitated calcium carbonate |
US20060076574A1 (en) | 2004-10-12 | 2006-04-13 | Liang-Wen Wu | Gallium-nitride based light-emitting diodes structure with high reverse withstanding voltage and anti-ESD capability |
ITMI20051464A1 (en) | 2005-07-28 | 2007-01-29 | Macri Chemicals Srl | COMPOSITIONS OF PAINTS AND THEIR USE FOR THE COATING OF SUBSTRATE SURFACES |
DE102005040157A1 (en) | 2005-08-25 | 2007-03-01 | Degussa Ag | Nanoscale powder and dispersant paste |
WO2007025932A2 (en) | 2005-09-02 | 2007-03-08 | Ciba Specialty Chemicals Holding Inc. | Process for preparation of a novel pigmented composition for use in gravure inks |
FR2891546B1 (en) | 2005-10-04 | 2010-09-03 | Solvay | USE OF CALCIUM CARBONATE PARTICLES IN TRANSPARENT POLYMERIC COMPOSITIONS, TRANSPARENT POLYMERIC COMPOSITIONS AND PROCESS FOR THE PRODUCTION THEREOF |
JP4707553B2 (en) * | 2005-12-22 | 2011-06-22 | 丸尾カルシウム株式会社 | Surface treated calcium carbonate filler for plastisol, its production method and plastisol comprising the filler |
WO2007108217A1 (en) | 2006-03-20 | 2007-09-27 | Kotobuki Industries Co., Ltd. | Process for producing nanoparticle dispersion, nanoparticle dispersion, and apparatus for producing nanoparticle dispersion |
US8530573B2 (en) | 2006-05-10 | 2013-09-10 | Designer Molecules, Inc. | Modified calcium carbonate-filled adhesive compositions and methods for use thereof |
CN101511950A (en) | 2006-08-29 | 2009-08-19 | 3M创新有限公司 | Resin systems including reactive surface-modified nanoparticles |
US20080153963A1 (en) * | 2006-12-22 | 2008-06-26 | 3M Innovative Properties Company | Method for making a dispersion |
JP5214148B2 (en) * | 2007-01-09 | 2013-06-19 | 中国塗料株式会社 | Container for marine transportation, manufacturing method thereof and coating material used therefor |
US7596986B2 (en) | 2007-03-01 | 2009-10-06 | 3M Innovative Properties Company | Method of testing liquid drop impact and apparatus |
TW200904518A (en) * | 2007-03-28 | 2009-02-01 | Lubrizol Ltd | Dispersant composition |
EP2036944A1 (en) | 2007-09-14 | 2009-03-18 | SOLVAY (Société Anonyme) | Polymer compositions |
FR2923834B1 (en) * | 2007-11-20 | 2011-01-21 | Rhodia Operations | NOVEL HYDRODISPERSIBLE POLYSICOCYANATE COMPOSITIONS. |
JP5356729B2 (en) * | 2008-05-26 | 2013-12-04 | 株式会社カネカ | Primer composition |
-
2010
- 2010-12-13 KR KR1020127018506A patent/KR101793303B1/en active IP Right Grant
- 2010-12-13 EP EP10812968A patent/EP2513214A1/en not_active Withdrawn
- 2010-12-13 JP JP2012544683A patent/JP5823979B2/en not_active Expired - Fee Related
- 2010-12-13 CN CN201080055289.7A patent/CN102639623B/en not_active Expired - Fee Related
- 2010-12-13 US US13/502,891 patent/US10023726B2/en active Active
- 2010-12-13 WO PCT/US2010/060082 patent/WO2011084380A1/en active Application Filing
- 2010-12-16 TW TW099144265A patent/TWI530520B/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5648407A (en) * | 1995-05-16 | 1997-07-15 | Minnesota Mining And Manufacturing Company | Curable resin sols and fiber-reinforced composites derived therefrom |
US20040076574A1 (en) * | 2000-10-02 | 2004-04-22 | Xu Peter W.Q. | Surface-modified Ca(CO3) and polymers containing same |
JP2006188552A (en) * | 2004-12-28 | 2006-07-20 | Toho Earthtech Inc | Viscous resin composition |
WO2010080459A1 (en) * | 2008-12-19 | 2010-07-15 | 3M Innovative Properties Company | Nanocalcite composites |
WO2011050121A2 (en) * | 2009-10-21 | 2011-04-28 | 3M Innovative Properties Company | Solventless functionalization, milling, and compounding process with reactive diluents |
Non-Patent Citations (8)
Title |
---|
"Handbook of Thermoset Plastics", 1998, WILLIAM ANDREW PUBLISHING, pages: 122 |
"Their Numerical Estimation and Prediction from Additive Group Contributions", vol. 7, 1990, ELSEVIER SCIENCE PUBLISHERS B.V., pages: 189 - 225 |
DATABASE WPI Week 200663, Derwent World Patents Index; AN 2006-604835, XP002638016 * |
KRESSE, G.; FURTHMUELLER, J., COMPUT. MATER. SCI., vol. 15, 1996, pages 6 |
KRESSE, G.; FURTHMUELLER, J., PHYS. REV. B, vol. 11, no. 169, 1996, pages 54 |
KRESSE, G.; HAFNER, J. PHYS. REV. B, vol. 251, 1994, pages 49 |
KRESSE, G.; HAFNER, J. PHYS. REV. B, vol. 588, 1993, pages 47 |
PERDEW, J. P.; BURKE, K.; ERNZERHOF, M., PHYS. REV. LETT., vol. 3865, 1996, pages 77 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130253139A1 (en) * | 2010-12-13 | 2013-09-26 | Em Innovative Properties Company | Dry, Surface-Modified Nanocalcite |
EP2651814A4 (en) * | 2010-12-13 | 2015-03-04 | 3M Innovative Properties Co | Dry, surface-modified nanocalcite |
US9512264B2 (en) * | 2010-12-13 | 2016-12-06 | 3M Innovative Properties Company | Dry, surface-modified nanocalcite |
Also Published As
Publication number | Publication date |
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US10023726B2 (en) | 2018-07-17 |
CN102639623B (en) | 2014-11-05 |
TW201137007A (en) | 2011-11-01 |
KR20120104607A (en) | 2012-09-21 |
KR101793303B1 (en) | 2017-11-02 |
CN102639623A (en) | 2012-08-15 |
TWI530520B (en) | 2016-04-21 |
JP2013514437A (en) | 2013-04-25 |
US20120244338A1 (en) | 2012-09-27 |
JP5823979B2 (en) | 2015-11-25 |
EP2513214A1 (en) | 2012-10-24 |
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