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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
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/549—Silicon-containing compounds containing silicon in a ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

• This invention relates generally to methods for utilizing metallized nanostructured chemicals as cure promoters, catalysts, and alloying agents to improve the physical, chemical, and electronic properties of a polymer.
• polymers can be controlled to a high degree through variables such as morphology, composition, thermodynamics and processing conditions. It is similarly known that various sizes and shapes of fillers (e.g. calcium carbonate, silica, carbon black, etc.) can be incorporated into a polymer to somewhat control both polymer morphology and the resulting physical properties. Further it is known that metals are utilized to catalyze the cure (connectivity) of polymeric chains. The resulting physical properties of polymers can be controlled by the nature of the catalyst, the extent of cure, and the mechanism of cure. For example, it is well known that polyurethanes, silicones, vinyl esters, and polydienes are commonly cured through the formation of chemical crosslinks catalyzed by metals.
• fillers e.g. calcium carbonate, silica, carbon black, etc.
• metals are utilized to catalyze the cure (connectivity) of polymeric chains.
• the resulting physical properties of polymers can be controlled by the nature of the catalyst, the extent of cure, and the
• Nanostructured chemicals are best exemplified by those based on low-cost Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS).
• Figure 1 illustrates some representative examples of metallized nanostructured chemicals for which the all silicon containing systems are known as POSS and metallized systems are known as POMS.
• POMS polyhedral oligomeric metallosesquioxanes
• cages may contain more than one metal atom, more than one type of metal atom, or even metal alloys.
• POMS contain hybrid (i.e. organic- inorganic) compositions contain internal frameworks that are primarily comprised of inorganic silicon-oxygen bonds but which also contain one or more metal atoms bound to or inside of the cage ( Figure 2).
• organic- inorganic compositions contain internal frameworks that are primarily comprised of inorganic silicon-oxygen bonds but which also contain one or more metal atoms bound to or inside of the cage ( Figure 2).
• the exterior of a POMS nanostructured chemical is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic polymers.
• these metallized nanostructured chemicals have molecular diameters that can range from 0.5 nm to 5.0 nm, are of low density (>2.5 g/ml), highly dispersable into polymers and solvents, exhibit excellent inherent fire retardancy, and possess unique optical and electronic properties.
• the present invention describes methods of preparing polymer compositions by incorporating metallized nanostructured chemicals, most commonly referred to as POMS, into polymers.
• the resulting polymers are wholly useful by themselves, in combination with other polymers to form laminates or interpenetrating networks, or in combination with macroscopic reinforcements such as fiber, clay, glass mineral, nonmetallized POSS cages, metal particulates, and other fillers.
• the resulting polymers are particularly useful for producing polymeric compositions with desirable physical properties such as adhesion to polymeric, composite and metal surfaces, skin and hair, improved hydrophobicity, and surface properties.
• the R groups on the POSS are wholly organic they provide water repellency, reduced melt viscosity, low dielectric constant, resistance to abrasion and fire, biological compatibility, and optical properties.
• compositions presented herein contain two primary material combinations: (1) metallized nanostructured chemicals, metallized nanostructured oligomers, or metal containing nanostructured polymers from the chemical classes of polyhedral oligomeric silsesquioxanes, polyhedral oligomeric silicates, polyoxometallates, carboranes, boranes, and polymorphs of carbon; and (2) all crosslinkable polymer systems such as: styrenics, amides, nitriles, olefins, aromatic oxides, aromatic sulfides, esters, ionomers, acrylics, carbonates, epoxies, ethers, esters, silicones, imides, amides, urethanes, phenolics, cyanate esters, ureas, resoles, analines, fluoropolymers, and synthetic and natural rubber.
• the polymers are inclusive of systems containing functional groups, and semicrystalline, crystalline, amorphous
• incorporation of the metallized nanostructured chemical (POMS) into the polymers is accomplished via blending or mixing the POMS with a polymer, prepolymer or mixture of monomers or oligomers. All types and techniques of blending and mixing, including melt blending, dry blending, solution blending, and reactive and nonreactive blending are effective.
• POMS metallized nanostructured chemical
• the selective incorporation of a nanostructured chemical into a specific region of a polymer can be accomplished by utilizing a metallized nanostructured chemical with a chemical potential (miscibility) compatible with the chemical potential of a region within the polymer. Because of their chemical nature, metallized nanostructured chemicals can be tailored to show compatibility or incompatibility with nearly all polymer systems.
• FIG. 1 illustrates examples of metallized nanostructured chemicals based upon polyhedral oligomeric metallosilsesquioxanes (POMS).
• POMS polyhedral oligomeric metallosilsesquioxanes
• FIG. 2 shows a structural example of a metallized nanostructured chemical.
• FIG. 3 shows thermogravimetric plots for various POMS.
• FIG. 4 provides UV-visible plots showing absorption ranges of POMS.
• FIG. 5 shows preferred POMS compositions for polyurethane catalysts and cure promoters.
• FIG. 6 is a DSC plot comparing onset of cure for POMS and non-POMS BMI.
• POSS and POS nanostructure compositions are represented by the formula: [(RSiO 1 .5) n ] ⁇ # for homoleptic compositions
• R is the same as defined above and X includes but is not limited to ONa, OLi, OK, OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR 2 ) isocyanate (NCO), and R.
• the symbol M refers to metallic elements within the composition that include high and low Z metals including s and p block metals, d and f block transition, lanthanide, and actinide metals.
• m, n and j refer to the stoichiometry of the composition.
• the symbol ⁇ indicates that the composition forms a nanostructure and the symbol # refers to the number of silicon atoms contained within the nanostructure.
• the value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12. It should be noted that ⁇ # is not to be confused as a multiplier for determining stoichiometry, as it merely describes the overall nanostructural characteristics of the system (aka cage size).
• the present invention teaches the use of metallized nanostructured chemicals as catalysts, cure promoters and alloying agents for the reinforcement of polymer coils, domains, chains, and segments of curable polymers.
• the keys that enable metallized nanostructured chemicals to function as molecular level reinforcing agents, and as cure promoters are: (1) their unique size with respect to polymer chain dimensions, (2) their ability to be compatibilized with polymer systems to overcome repulsive forces that promote incompatibility and expulsion of the nanoreinforcing agent by the polymer chains, and (3) their ability to contain and distribute catalytically active metal atoms and alloys homogeneously in polymers, oligomers, and monomers.
• Metallized nanostructured chemicals can be tailored to exhibit preferential affinity/compatibility with polymer microstructures through variation of the R groups on each cage or via association of the metal atom with functionality contained within the polymer ( Figure 2).
• metallized nanostructured chemicals can be tailored to be incompatible with microstructures within the same polymer, thus allowing for selective reinforcement of specific polymer microstructure. Therefore, the factors to effect a selective nanoreinforcement include specific cage sizes, distributions of sizes, and compatibilities and disparities between the metallized nanostrucutured chemical and the polymer system.
• the catalytic activity and cure promotion attributes of metallized nanostructured chemicals can be controlled through the nature of the metal or number of metal atoms attached to or near the cage, the steric and electronic properties of the cage, and the dispersion characteristics of the cage. It is possible to control physical properties through variation of R group and POSS cage size and topology.
• Nanostructured chemicals such as the metallized POMS illustrated in Figure 1
• Both forms dissolve in molten polymers and solvents, thus solving the long-standing dispersion problem associated with traditional particulate fillers and cure promoting agents.
• the forces (i.e. free energy) from solvation/mixing are sufficient to prevent cages from forming agglomerated domains as occurs with traditional and other organofunctionalized fillers. Agglomeration of particulate fillers and catalysts has been a problem that has traditionally plagued compounders, molders, and resin manufacturers.
• Table 1 lists the size range of POMS relative to polymer dimensions and filler sizes. The size of POMS is roughly equivalent to that of most polymer dimensions, thus at a molecular level the cages can effectively alter the motion of polymer chains.
• POSS and POMS cages to control chain motion and to promote extent of cure is particularly apparent when they are grafted onto a polymer chain. See U.S. Pat. Nos. 5,412,053; U.S. Pat. No. 5,484,867; U.S. Pat. No. 5,589,562; and U.S. Pat. No. 5,047,492, all incorporated by reference.
• POMS nanostructures associate with a polymer chain they act to promote the degree of cure and retard chain motion and thereby greatly enhance time dependent properties such as T 9 , HDT, creep, modulus, hardness, and set, which correlate to increased modulus, hardness, and abrasion resistance, and durability.
• the present invention demonstrates that significant property enhancements can be realized by the incorporation of catalytically active metallized nanostructured chemicals into plastics as catalysts, cure promoters, and alloying agents. This greatly simplifies the prior art. Prior art catalysts did not function as reinforcing agents nor as alloying agents within polymer morphology.
• metallized POSS nanostructured chemicals are single chemical entities and have discreet melting points, and dissolve in solvents, monomers and plastics, they are also effective at reducing the viscosity of polymer systems.
• the latter is similar to what is produced through the incorporation of plasticizers into polymers, yet with the added benefit of promoting the cure of polymers and reinforcement of the individual polymer chains due to the nanoscopic nature of the chemicals.
• ease of processability and reinforcement effects are obtainable through the use of metallized nanostructured chemicals (e.g. POMS) where the prior art would have required the use of both plasticizers and fillers or the covalent linking of POSS to the polymer chains.
• metallized nanostructured chemicals e.g. POMS
• the size, polydispersity, and composition of the nanostructured chemical e.g. POMS
• the molecular weight, polydispersity, and composition of the polymer system must also be matched with that of the nanostructured chemical.
• the kinetics, thermodynamics, and processing aids used during the compounding process are also tools of the trade that can impact the loading level and degree of enhancement resulting from incorporation of nanostructured chemicals into polymers.
• Blending processes such as melt blending, dry blending and solution mixing blending are all effective at mixing and alloying metallized nanostructured chemical into plastics.
• the thermal stability of POMS was examined to determine if it could maintain its ability to catalytically promote polymer cure while not undergoing decomposition.
• the POMS were found to be unaffected by low temperatures and exhibited thermal stabilities up to 250 0 C (48O 0 F) and 55O 0 C (1022°F) (Figure 3).
• POMS cages are additionally beneficial in polymers because of their radiation absorbing characteristics (Figure 4).
• the absorption wavelength is tunable over a wide range and highly dependant upon the nature of the R group on the cage and type of metal atom.
• the absorptive range coupled with the high thermal stability exceeds the performance of wholly organic absorbers and provides a new opportunity for protection of high temperature polymers, composites, and coatings from UV damage.
• compositions for polyurethanes are [(RSiO L s) 7 (HOTiO 1 , 5 )] ⁇ 8, [(RSiO 1 . S ) 7 (APrOPyIOTiO 1 . 5 )] ⁇ 8 , and [(RSiO 1 -5 )T(Me 3 SiO)(A propyiO) 2 TiO 0 . 5 )fc8 as shown in Figure 5.
• the activity of POMS to polyurethane cure is possible over a range of POMS loading from 0.001 % to 50 wt% with a preferred loading of 0.1% to 10%.
• Organometallic complexes are rarely considered as viable alternatives to existing polyurethane catalyst systems such as tin, amines, or mixtures thereof.
• the main reason that organometallic complexes are not widely used is their poor hydrolytic stability and consequently short pot-life. This is especially true for polyurethane foam systems where often 0.5 wt% or greater of water is present.
• [(RSiO L g) 7 (Me 3 SiO)(A propylO) 2 TiO 0 .5)] ⁇ 8 POMS exhibited excellent hydrolytic stability.
• the bulky and hydrophobic R groups on the cage effectively provide hydrophobicity to the metal atom while maintaining a high level of catalytic activity. Additionally, the R groups on the cage provide for solubilization of the POMS into the resin components. For aliphatic resin systems, aliphatic R groups on POMS are preferred while for aromatic resins, aromatic groups on POMS are preferred. POMS derivatives containing Sn are also highly active toward polyurethane cure.
• the activity of POMS toward epoxy cure is possible over a range of POMS loading from 0.001% to 50 wt% with a preferred loading of 0.1 % to 10%.
• Cure of a Vantico 2-component epoxy comprised of araldite GY 764 BD bisphenol A epoxy resin (100 parts) and araldur 42 cycloaliphatic amine (23 parts) was carried out by mixing the appropriate ratio of components followed by addition and thorough mixing of the POMS component.
• the epoxy resins were suitable for use as coatings, monoliths, prepregs, VARTMable resin or filament winding. While all catalysts promoted cure within 24- 120 hours, the [(PhSiOL 5 )I 4 (AIOL 5 )S]IiS system produced a preferred resin with optical transparency and minimal color.
• POMS can be utilized to homopolymerize epoxy resins into a network polymer with similar thermomechanical properties to conventional cure systems.
• the resulting polymer contains polyether linkages which provided superior moisture performance.
• thermomechanical data in Table 2 shows the POMS cured systems are equivalent to the properties resulting from amine cure with the additional advantage of improved hydrophobicity. The data also show that properties improve as POMS concentration increases. This correlates to findings that POMS loading levels of approximately 0.75 mol % result in 80% conversion of available epoxide groups.
• the [(PhSiOi. 5 )i 4 (AIOi. 5 )2] ⁇ i8 POMS is extremely active towards the cure of cycloaliphatic epoxies. All cycloaliphatic epoxy resin can be cured.
• a preferred composition is Shell ERL4221 and Hybrid Plastics EP0408 containing [(epoxycyclohexyethylSiOi. 5 )8] ⁇ 8 [(epoxycyclohexyethylSiOi. 5 )io] ⁇ io, [(epoxycyclohexyethylSiOi.
• Effective POMS loadings range from 0.01 wt% to 10 wt%, with preferred loadings of 0.1% to 3%.
• the POMS is added to the cycloaliphatic resin with mixing and promotes room temperature polymerization to render an optically clear and hard resin with outstanding thermal properties and resistance to moisture and oxidizing agents such as steam, ozone, hydrogen peroxide.
• the use of POMS and cycloaliphatic epoxy resins is ideal for medical devices requiring sterilization or for electronic adhesives such as underfills and encapsulating agents.
• the [(PhSiOi. 5 )i 4 (MeZn) 2 (ZnOi. 5 ) 2 ] ⁇ 18 POMS is also effective in these resin systems.
• POMS was compounded into Cytec BMI resin 5250- 4 in amounts ranging from 0.001% to 50% with preferred loadings of 0.1- 5%.
• the POMS was added to premixed BMI resin via stirring and was utilized as a 1- component system, although use as a 2-component system is also envisioned.
• a standard cure procedure was followed to result in a BMI resin with improved thermomechanical properties.
• a specific advantage resulting from addition of POMS was the catalytic promotion of cure at lower temperature and more complete cure of the resin system as exhibited by direct scanning calorimetry (Figure 6).
• the use of POMS to enable faster, lower temperature, and more complete cure of the resin is advantageous to realize lower cost processing and improved high temperature properties.

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• 2006
  • 2006-09-28 TW TW095135999A patent/TW200738822A/zh unknown
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