JP2009509030A - Metallized nanostructured chemicals alloyed into polymers - Google Patents

Abstract

  Metallized nanostructured chemicals are incorporated at the molecular level as alloying agents for reinforcement of the microscopic structure of polymers including polymer coils, domains, chains and segments. The direct blending process is effective for compatibility reasons depending on the purpose of the metallized nanostructured chemical and polymer.

Description

  This application claims the benefit of US Provisional Patent Application No. 60 / 709,638, filed Aug. 19, 2005.

FIELD OF THE INVENTION The present invention generally relates to a method for improving the physical properties of a polymer, and more particularly to the incorporation of metallized nanostructured chemicals into a polymer to improve the physical properties of the polymer. It relates to a method for alloying.

BACKGROUND OF THE INVENTION Polymer properties have long been recognized as being highly controllable by variables such as morphology, composition, thermodynamics and process conditions. Similarly, fillers of various sizes and shapes (eg, calcium carbonate, silica, carbon black, rubber, etc.) are inserted into the polymer to provide some control over both the polymer morphology and the resulting physical properties. Or can be blended.

  In the solid state, all polymers (including amorphous, semi-crystalline, crystalline, rubbery, etc.) have a significant amount of internal and external free volumes. (See Fig. 1) The mechanical properties of the polymer chain (eg, reptation, translation, rotation, crystallization) mainly work, as well as density, thermal conductivity, glass transition, melting transition, elasticity Since it is within this volume that affects fundamental properties such as rate, relaxation, stress transfer and surface properties, the free volume of the polymer has a tremendous effect on its physical properties.

  The accessibility of free volume in polymer systems is highly dependent on its morphology. For example, as shown in FIG. 2, denser regions and separation within the polymer can increase or decrease thermodynamic and mechanical access to such regions. Due to the effects of thermodynamics and mechanical properties, polymer morphology is a major factor limiting the ability of conventional fillers to access free volume regions in polymer systems. Because conventional fillers are physically larger than most polymer dimensions, are not chemically similar, and are usually high-melting solids, to force compatibility between fillers and polymer systems Additional processing / compounding efforts are usually required.

  Prior art formulations include macro, micro and nanoscopic particles (eg, inorganic) of a composition similar to that of small low molecular weight molecules (liquid and solid) and polymers (organic) known as plasticizers or plasticizers. ) Has been focused on combining with polymer systems. The function of the plasticizer promotes the displacement of the polymer chains from one another and thus improves the processability and manufacturability of certain polymer systems. Similarly, fillers previously composed of fibrous or particulate solids are combined with polymers to improve physical properties such as dimensional stability, impact resistance, tensile and compressive strength, and thermal stability. I came. Unfortunately, plasticizers are too small to reinforce polymer chains, and conventional fillers are too large to reinforce individual polymer chains and segments. Fillers are conventionally used to macroscopically reinforce closely related or nearby polymer groups rather than individual chains and segments within these polymers.

  It has been expected that as filler sizes are reduced below 50 nm, they become more resistant to sedimentation and more efficiently reinforce the polymer system, resulting in improved control over physical properties. However, the complete application of this theoretical finding has been hampered by the lack of a practical source of particles that are monodisperse and have a diameter below the 50 nm range, especially below the 10 nm range. Particularly desirable are metal particles that are monodispersed or have a controlled narrow particle size distribution that is expected to form the most stable dispersion within the polymer system. In addition, these particles must be well below the length scale that is necessary to disperse the light and therefore must appear transparent when incorporated into plastics.

  Recent developments in nanoscience have shown that specific exact formula, hybrid (inorganic-organic) chemical composition and size of conventional chemical molecules (0.3-0.5 nm) and larger size conventional fillers (50 nm As a result of its large physical size, it is now possible to economically and efficiently produce the materials best described as metallized nanostructured chemicals in commercial quantities.

  Nanostructured chemicals can be based on low cost polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS). Metallized nanostructured chemicals, also known as polyhedral oligomeric metallosesquioxanes (POMS), are those containing one or more metals inside or outside the cage, or one or more metals bound to the cage It is a spear containing. In some examples, the soot may include one or more metal atoms, or multiple types of metal atoms or metal alloys. POMS is illustrated by the representative structure and formula shown in FIG. Note that POMS are structurally and compositionally diverse and may include several polyhedra, polymorphs and compositional variations that can be used to control the physical properties of POMS and the materials in which they are incorporated. Should be (Figure 4).

  Like the POSS cage, the POMS system includes a hybrid (ie, organic-inorganic) composition in which the framework of the cage inside is composed primarily of inorganic silicon-oxygen bonds. The exterior of the nanostructure is covered by both reactive and non-reactive organic functional groups (R), ensuring compatibility and adaptability between the nanostructure and the organic polymer. These and other properties of metallized nanostructured POSS chemicals are discussed in detail in US Pat. No. 5,589,562 and by Hanssen, van Santen, and Abbenhuis, 2004 Eur. J. Inorg. Chem. 675-83. However, both are incorporated herein by reference. Unlike metal fillers or particles, these POMS nanostructured chemicals are low density (range 1.17 g / ml to 2.04 g / ml), highly dispersible in polymers and solvents, and have excellent intrinsic properties. Flame retardant, optical, electronic properties and radiation tolerance, and may range from 0.5 nm to 50 nm in diameter.

  Prior art on fillers, plasticizers and polymer morphology has not been able to properly control the movement, optical and electronic properties of polymer chains, coils and segments at the molecular level. In addition, chemical potential incompatibilities (eg, solubility, miscibility, etc.) between hydrocarbon-based polymers and inorganic fillers are similar to oils mixed with water, with a high level of heterogeneity in blended polymers. Gave birth to sex. Thus, there is a need for a properly sized metal-containing drug for polymer systems that have precisely controlled diameter (nanodimension), distribution, and chemical functionality that can be tailored. In addition, it would be beneficial to have a readily compoundable metallized nano-reinforcement that has a similar range of chemical potentials (miscibility) to various polymer systems.

SUMMARY OF THE INVENTION The present invention describes a method for preparing novel polymer compositions by incorporating metallized nanostructured chemicals into the polymer. The resulting nanoalloyed polymer is macroscopically reinforced as such or in combination with other polymers or other fillers including fibers, clays, glass minerals, nanometallized POSS 籠, metal particles and diamond fines. Combined with is completely beneficial. Nanoalloyed polymers are adhesive to polymers, composites and metal surfaces, water repellency, reduced melt viscosity, low dielectric constant, abrasion resistance, fire resistance, biocompatibility, lubricity, gas permeability control, It is particularly beneficial for producing polymer compositions having the desired physical properties such as chemically resistant and optically high quality plastics.

  A preferred composition comprises the following two main material combinations:

(1) Polyhedral oligomeric silsesquioxane, polyhedral oligomeric metallasilsesquioxane, polyhedral oligomeric silicate, polyhedral oligomeric metallosilicate, polyoxometalate, metallized fluorene, carborane, borane And metallized nanostructured chemicals, metallized nanostructured oligomers or metals, including nanostructured polymers from chemical classes such as polymorphic carbon, and (2) acrylic resins, carbonates, epoxies, esters, silicones, polyolefins, poly Conventional amorphous polymer systems such as ethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides and polymers containing functional groups, styrene resins, amides, nitriles, olefins, aromatic oxides, aromatic sulfides and Conventional semi-crystalline and crystalline polymer systems such as esters, ionomers or conventional rubbery polymer systems such as those derived from hydrocarbons and silicones.

  Formulation of the metallized nanostructured chemical into the polymer is preferably accomplished by blending the metallized nanostructure into the polymer system of interest. All types of blending techniques, including melt blends, dry blends and solution blends, as well as reactive and non-reactive blends are useful.

  In addition, the selective incorporation of nanostructured chemicals into a specific region of the polymer can result in metallized nanostructured chemicals that have a chemical potential (miscibility) compatible with the chemical potential of the region within the polymer to be alloyed. This is achieved by blending into the polymer. Due to the presence of reactive groups on the polymer with the metal contained in the nanostructure, the metallized nanostructure may be activated in a similar manner to associate with specific regions of the polymer. The reactive groups typically incorporated into the polymer include olefins, cyanates, acrylic resins, amines, amides, alcohols, carbohydrates, esters, acids, nitriles and boron. The Lewis basicity of these groups is given in relation to the intrinsic Lewis acidity of the metallized nanostructure.

  Because of its chemistry, metallized nanostructured chemicals can be adapted to be compatible or incompatible with almost all polymer systems. Combined with their adaptable suitability, their physical size allows metallized nanostructured chemicals to be selectively incorporated into plastics, controlling the dynamics of coils, blocks, domains and segments, and thus It makes it possible to act advantageously on many physical properties. Advantageously improved properties include thermal strain, creep, compressive strain, strength, toughness, visual appearance, feel and texture, CTE, electrical, radiative and oxidative stability, shrinkage, elasticity, hardness and resistance. Time-dependent mechanical and thermal properties such as friction. In addition to mechanical properties, other advantageously improved physical properties include biocompatibility, antimicrobial activity, thermal and electrical conductivity, adhesion, surface lubrication, laser marking, fire resistance, gas and moisture transmission. Includes control and painting, printing, film and coating properties.

Definition of the Nanostructure Expression For the purpose of understanding the chemical composition of the present invention, polyhedral oligomeric silsesquioxane (POSS), polyhedral oligomeric silicate (POS) and polyhedral oligomeric metallase skies. For the expression of oxane (POMS) and polyhedral oligomeric metallosilicates, the following definitions are made.

In polysilsesquioxane, ∞ represents the degree of molar polymerization, R is an organic substituent (H, siloxy, cyclic or linear aliphatic or aromatic group, and additionally, alcohol, ester, amine, ketone, Reactive functional groups such as olefins, ethers or halides may be included.) A material represented by the formula [RSiO _1.5 ] _∞ . The polysilsesquioxane may be either homoleptic or heteroleptic. A homoleptic system contains only one type of R group, while a heteroleptic system contains more than one type of R group.

[(RSiO _1.5 ) _n ] _{Σ #} for homoleptic compositions
For heteroleptic compositions, [(RSiO _1.5 ) _n (R′SiO _1.5 ) _m ] _{Σ #} (where R and R ′ are different).
For functionalized heteroleptic compositions, [(RSiO _1.5 ) _n (RXSiO _1.0 ) _m ] _{Σ #} (wherein the R groups may be the same or not the same).
For heterofunctionalized heteroleptic compositions, [(RSiO _1.5 ) _n (RSiO _1.0 ) _m (M) _j ] _{Σ #}
For hetero functionalized heteroleptic _{compositions, [(RSiO 1.5) n (} RSiO 1.0) m (ML) j] Σ #
All of the above R are the same as defined above, and X is not limited, but includes OLi, ONa, OK, OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR) ), Amine (NR ₂ ), isocyanate (NCO) and R. The symbol M refers to metal elements in compositions comprising low and high atomic number metals and s and p block metals, including transition, lanthanide and actinide metals, and d and f block metals. In particular, Al, B, Ga, Gd, Ce, W, Fe, Ni, Eu, Y, Zn, Mn, Os, Ir, Ta, Cd, Cu, Ag, V, As, Tb, In, Ba, Ti, Sm, Sr, Pb, Lu, Cs, Tl, Te. The symbol ML represents the metal and the ligand L coordinated to the metal. Various ligands may be coordinated to the metal, either covalently to maintain the proper oxidation state, or a donor bond to maintain the coordination sphere electronics of the metal atom. For example, transition metals containing s, p, d orbitals generally prefer a number of 18 electrons at the metal center, whereas actinides and lanthanides can exceed this rule due to the presence of f orbitals. Typical L groups include solvent molecules such as tetrahydrofuran, pyridine, water or alkoxides, amides, oxides and halides. The symbols m, n and j mean the stoichiometry of the composition. The symbol Σ indicates that the composition forms a nanostructure, and the symbol # indicates the number of silicon atoms contained in the nanostructure. The value of # is usually the sum of m and n, the range of n is typically 1-24, and the range of m is typically 1-12. It should be noted that Σ # should not be confused with the multiplier that determines the stoichiometry, but merely describes the overall nanostructure characteristic of the system (known as the wrinkle size).

Detailed Description of the Invention The present invention relates to metallized nanostructural chemistry as an alloying agent for the enhancement of polymer properties by incorporation of metal atoms and reinforcement of polymer coils, polymer domains, polymer chains, polymer segments at the molecular level. Describes the use of the substance (POMS).

  The key to enabling POMS to function as a reinforcement and alloying agent at the molecular level is (1) a unique size relative to the polymer chain dimensions and (2) the incompatibility and elimination of nanoreinforcement by polymer chains The ability to be compatible with polymer systems to overcome the repulsive force That is, metallized nanostructured chemicals can be adapted to exhibit preferential affinity / compatibility with the microscopic structure of the polymer by changing the R group on each nanostructure. The metallized nanostructure may be activated to associate with a particular region of the polymer due to the presence of the metals contained in the nanostructure and reactive groups on the polymer. The reactive groups typically incorporated in the polymer include acrylic resins, amines, amides, alcohols, esters, nitriles and boron. The Lewis basicity of these groups provides a bonding site for metal atoms in the nanostructure, depending on the intrinsic Lewis acidity.

  Conversely, POMS can be adapted to become incompatible with the microscopic structure within the polymer, and thus for the selective reinforcement of the microscopic structure of a particular polymer and the modification of surface properties. Transfer to the polymer surface. Thus, the factors that lead to selective nano-reinforcement are the specific nano-size of metallized nanostructured chemicals, the nano-size distribution, and the incompatibility and mismatch between R groups on POMS and polymers, present in certain polymer systems The type of functional group to be.

  Metallized nanostructured chemicals such as the POMS structure illustrated in FIG. 4 are available in both solid and oily forms. The physical shape is mainly controlled by the type of R group on each cage and the topology of the structure. For example, a POMS having a hard structure or a hard R group will generally give a crystalline solid. Both crystalline and amorphous POMS are soluble in solvents, monomers and molten polymers, thus solving the long-standing dispersion problem with conventional particle fillers. Furthermore, since POSS and POMS dissolve in plastics at the molecular level, the forces from solvation / mixing (ie free energy) are micron-sized, as occurs with conventional and other organic functionalized fillers. It sufficiently prevents the formation of coalesced regions. Aggregation of particle fillers has been a problem that has plagued blenders and molders.

Table 1 lists the POSS size range for polymer dimensions and filler size. The size of POSS is roughly the same as most polymer dimensions, so at the molecular level, POSS can effectively alter the movement of polymer chains that work well on physical properties.

  The physical size of POSS and POMS is important to POSS's ability to control chain movement. This is particularly evident when POSS is grafted onto the polymer chain.

See US Pat. No. 5412053, US Pat. No. 5,484,867, US Pat. No. 5,589,562 and US Pat. No. 5,047,492, all incorporated by reference. When POSS nanostructures are incorporated into the polymer, they act to suppress chain movement and T _g , which correlates with improved elastic modulus, hardness and wear resistance, lubricity, hydrophobicity and surface properties, Time-dependent properties such as HDT, creep and curability are greatly improved. The present invention demonstrates that additional property enhancements can be realized by incorporating metallized nanostructured chemicals into plastics. This greatly simplifies the prior art process and gives a higher degree of property control as a direct result of the incorporation of metal atoms into the resulting material.

  In addition, because metallized nanostructured chemicals have a spherical shape similar to the molecular shape (from single crystal X-ray scattering studies) and because they dissolve, they reduce the viscosity of the polymer system. It is also effective. This advantage is similar to that produced by the incorporation of plasticizers into the polymer, but also adds the advantage of reinforcing individual polymer chains due to the nanoscopic nature of the material. Thus, while processability and reinforcement can be obtained by using POMS, the prior art required the use of both POSS and metal filler. In addition, because the metal filler is denser than POMS, cost and weight advantages are realized, and in many cases its atomic properties are more desirable than the inherent properties of any metal particle.

Examples General Process Variables Applicable to All Processes As is typical for chemical processes, there are a number of variables used to control purity, selectivity, speed and process mechanism. Variables affecting the process of incorporating POMS into materials include polymer type and composition, as well as polydispersity, molecular weight and composition of POMS. A preferred approach is to harmonize the polymer system with that of POMS and all related additives (eg, fillers, processing aids, catalysts, stabilizers, etc.) to obtain the desired physical properties. Finally, the kinetics, thermodynamics and processing aids used during the compounding process are also trade tools that can affect the level of usage and the improvement resulting from the incorporation of POMS into the polymer. Blending processes such as melt blending, dry blending and solution blending are all effective in mixing and alloying metallized nanostructured chemicals into plastics.

Example 1. Alloying POMS to Polycarbonate A series of POMS was compounded in Bayer Makrolon® polycarbonate 2405 using a twin screw extruder. POMS and polymer were dried before compounding to ensure the best alloyed state. After compounding, POMS reinforced samples were then molded into disks, dog bones and other specimens and characterized. The optical characterization of POMS polycarbonate is particularly important for the application of polycarbonate as an optical resin. The optical properties were retained. (Example, (a) [(phenyl _{SiO 1.5) 4} (phenyl _{SiO 2) 3 Al] Σ8,} (b) [( isobutyl _{SiO 1.5) 4} (isobutyl _{SiO 2) 3} SnCH _3] Σ8 and (c ) [(Isobutyl SiO _1.5 ) ₄ (isobutyl SiO ₂ ) ₃ B] _Σ8 , polycarbonate containing 2% by weight of use)
Furthermore, incorporation of [( _{phenylSiO 1.5} ) ₄ ( _{phenylSiO 2} ) ₃ Al] _Σ8 POMS into polycarbonate increased the Young's modulus by 6% without reducing impact and thermal properties. POMS can be used in combination with POSS to improve other properties. For example, incorporating POSS into a PC results in improved hardness and reduced penetration damage. (Table 2)

  It is observed that changes in the composition, size and usage level of POMS have a clear effect on the degree of improvement in various physical properties. It is observed that this mechanism of improvement is related to chain movement and the free volume between the POMS and polymer chains.

  In addition, the incorporation of POMS provides an improved hydrophobic surface that allows for improved hydrophobicity and weatherability of the PC. Of particular importance to the polycarbonate was the incorporation of POMS containing metals such as cerium that provide UV stability. Depending on the desired wavelength to be absorbed, the incorporation of metal atoms into POMS can be highly efficient. For example, incorporation of cerium and titanium atoms into the corners of the POMS can protect the polymer against UV causing chain cleavage and decolorization.

Example 2. Alloying gadolinium POMS of POMS into the thermoplastic resin [(phenyl _{SiO 1.5) 4} (phenyl _{SiO 2) 3 Gd] Σ8,} [( isobutyl _{SiO 1.5) 4} (isobutyl _{SiO 2) 3} Gd] Σ8 and boron POMS [(Phenyl SiO _1.5 ) ₄ (Phenyl SiO ₂ ) ₃ B] _Σ8 , [(Isobutyl SiO _1.5 ) ₄ (Isobutyl SiO ₂ ) ₃ B] _Σ8 is an extrusion and single pot low shear blending technology Was blended into a hot melt wax. A clear compatibility with visible solubility was found in the range of 0.1 to 80% by weight in the hot wax. Similar levels of compatibility were observed between POMS and other polymers. The compatibility between the nanoscopic material and the polymer is important to achieve improved properties and reliable dispersibility. For POMS, its compatibility is controlled by the R group on the POSS / POMS cage, the type of functional group on the polymer and the amount of shear force used in the mixing process. Table 3 summarizes the wax type thermoplastic resins suitable for alloying by POMS.

  The combination of polyamides, polyurethanes, polyolefins and POSS and POMS in the formulation is highly desirable since polyamides and polyurethanes provide a wide range of adhesive properties, while polyolefins provide low cost and low melting point. POSS / POMS provides improved compatibility and physical properties between the two resin systems. POSS / POMS is also particularly beneficial to improve the chemical and oil resistance of the finish formulation. POSS / POMS is also particularly beneficial for improving the compatibility of dissimilar polymer systems. Zhang et al. Reported in 35 Macromolecule 8029-38 (2002) in 2002 that methacrylate POSS adapted polymethacrylate and polystyrene on a microscopic scale. POMS is now becoming a practice for the formulation of dissimilar polymer systems.

  Most polymers, especially polyamides and polyurethanes, are susceptible to oxidation and must be stabilized with antioxidants. Although there are various stabilizer packages, the most common antioxidants used are hindered phenols, phosphites, phosphates and hindered aromatic amines. Incorporation of POSS and POMS into the polymer also promotes stabilization by controlling reactivity with the oxidant as well as permeation / barrier properties. For example, the corner metal of POMS is oxyphilic and reacts to form a metal oxide. Therefore, POSS and POMS can be used to obtain a synergistic effect with conventional stabilizers and perfumes, pigments, dyes and processing agents.

  In relation to the melting point for various thermoplastic resins, the thermal stability of POMS was investigated to determine whether soot would undergo degradation when incorporated into a molten polymer. POMS was found to be unaffected by temperatures below 250 ° C. and could be extruded over the full range of commercially available waxes and thermoplastics (FIG. 6).

  B and Gd containing thermoplastics are highly desirable as coatings for shielding electronic components against x-rays, thermal neutrons, protons and electrons.

Example 3 Alloy aromatic to thermosetting resin POMS [(phenyl _{SiO 1.5) 4} (phenyl _{SiO 2) 3} Gd] Σ8 and aliphatic [(isobutyl _{SiO 1.5) 4} (isobutyl SiO _{2) 3} Gd] _{Σ8 together} with aromatic [( _{phenylSiO 1.5} ) ₄ ( _{phenylSiO 2} ) ₃ Al] _Σ8 and aliphatic [(isobutylSiO _1.5 ) ₄ (isobutylSiO ₂ ) ₃ Al] _Σ8 It was dissolved in aliphatic polycarbonate at a usage level of 70% by weight. (FIG. 7) An optically clear mixture and plaques were obtained from aromatic POMS, while aliphatic POMS formed a translucent mixture. Greater amount of the POMS, of 5-15 wt% [(methacryloxypropyl _{SiO 1.5) 8]} can be obtained by co-incorporation of _Shiguma8 POSS was observed. [(Methacryloxypropyl SiO _1.5 ) ₈ ] _Σ8 is an adaptation between metal and POMS for the adaptation of two dissimilar polymer systems as reported by Zhang et al. Acts as an agent. (Gd POMS thermosetting coating comprising 50 wt% [(phenyl SiO _1.5 ) ₄ (phenyl SiO ₂ ) ₃ Gd] _Σ8 and 5 wt% [(methacryloxypropyl SiO _1.5 ) ₈ ] _Σ8 Demonstrated by transparency.) Gd-containing thermosetting resins are highly desirable as insulating protective coatings for shielding electronic components against X-rays, thermal neutrons, protons and electrons.

Example 4 X-ray emission barrier in a cross-linked coating To determine its efficiency of providing shielding from X-ray radiation, a series of X-ray absorption measurements were made on a Gd POMS coating. The advantages of Gd POMS coating are its ductility, quick and inexpensive coating method, light weight and electrical insulation properties. The results confirm the ability of the Gd POMS coating to shield 35 KeV x-rays. The resulting summary is shown in Table 4.

  A comparison of shielding effectiveness for metallic lead and aluminum is shown in FIG. The plot shows that Pb does not pass X-rays, but GdPOMS is as good as solid metal Al.

Example 5 Neutron radiation barrier [(isobutyl SiO _1.5 ) ₄ (isobutyl SiO ₂ ) ₃ Gd] _Σ8 in a thermoplastic coating was formulated into a hydrocarbon resin system at various usage levels. A gold (Au) foil is sandwiched between two [(isobutyl SiO _1.5 ) ₄ (isobutyl SiO ₂ ) ₃ Gd] _Σ8 layers and the sample is then subjected to a Watt fission neutron spectrum (energy range: 1- 20 MeV, average: ˜1 MeV). Only thermal (0.0253 eV) and non-thermal (greater than 0.5 eV) neutron fluxes were measured. Total neutron flux was measured using high purity gold foil. The reactions involved are:

Cadmium cover was used to measure the thermal component of the total neutron flux. The absolute flux was measured from the activity measured and induced on the gold foil. Attenuation of neutron flux as a result of absorption by [(isobutyl _{SiO 1.5) 4} (isobutyl _{SiO 2) 3} Gd] Σ8 was increased linearly with weight% of Gd POMS loaded into the resin. (Fig. 9)
Attenuation of thermal neutrons 2/3 penetrating the semiconductor, the isotopic abundance 50% by weight of a natural [(isobutyl _{SiO 1.5) 4} (isobutyl SiO _{2) 3} Gd] coating 1mm thickness equivalent including _Σ8 It was calculated that would be achieved from If isotope rich Gd157 is incorporated into POMS, a 2/3 attenuation of penetrating neutrons could be obtained with a coating of only 0.1 mm thickness. Similar results were obtained for the boron and samarium POMS systems. Thus, protection of electrical components from thermal neutral damage can be achieved using coatings containing B, Sm, or Gd POSS additives.

  A preferred method of incorporating Gd POMS into a semiconductor is to alloy Gd POMS into a hot melt adhesive and then cast the alloy into the appropriate shape for the application. For example, alloyed polymer rods can be incorporated into a hot melt glue injector and the Gd POMS / polymer can be applied directly to the exposed tip or die thereof, thereby allowing ionized thermal neutrons It can be completely protected against X-rays and moisture.

  In addition to being used to shield electronic components, Gd and BPOMS are able to efficiently capture neutrons and fit soft tissue when R = isooctyl and hard tissue when R = phenyl. Therefore, it can also find application in fast neutron tumor diagnosis.

Example 6 Metallized POSS for improved oxidative stability
[(Phenyl SiO _1.5 ) ₄ (Phenyl SiO ₂ ) ₃ Al] _{Incorporation} of _{Σ8 into} the epoxy polymer is an amount in the range of 0.1 to 40% by weight to the epoxy resin component to obtain a clear solution. Of [(phenyl SiO _1.5 ) ₄ (phenyl SiO ₂ ) ₃ Al] _Σ8 .

Epon 162 epoxy resin with 20 wt% [(Glycidal SiO _1.5 ) ₈ ] _Σ8 is preferred. Alloyed resin is then curing agent POMS catalyst is mixed with (5 wt% [(phenyl _{SiO 1.5) 4} (phenyl _{SiO 2) 3 Al] Σ8)} , resulting resins are tested Cast into suitable plaque. POSS alloyed and POMS catalyzed epoxy resins show improved resistance to water vapor and ozone. After 100 ozone sterilization cycles, a total weight loss of 20% was observed for the POSS / POMS alloyed resin, compared to a total weight loss of 40% for similar systems cured with imidazole curing agents. . After 50 steam sterilization cycles, a 5% total weight gain was observed for the POSS / POMS alloyed resin compared to a 10% total weight gain for a similar system cured with commercial imidazole. Additionally, the POSS / POMS alloyed resin retains the inherent optical clarity, texture and bond strength over similar systems without POSS / POMS. Incorporation of [( _{phenylSiO 1.5} ) ₄ ( _{phenylSiO 2} ) ₃ Al] _Σ8 into the epoxy resin acts as an antioxidant based on the electrophilicity of Al atoms, while POSS _籠 It is oxidized by exposure to water vapor and forms a nanoscopic thin surface glass that protects against further oxidation.

Example 7 POMS for improved flame retardancy
_{Incorporation of} [(isobutyl SiO _1.5 ) ₄ (isobutyl SiO ₂ ) ₃ Al] _Σ8 and [(isobutyl SiO _1.5 ) ₄ (isobutyl SiO ₂ ) ₃ Al] _{Σ8 into} the polymer during polymer combustion It has been shown to be effective in increasing the amount of charcoal produced. As a result, less fuel reaches the combustion surface, and a reduction in heat release rate and even a reduction in total heat can be achieved. Theoretical and experimental studies indicate that oxidation maximum retardation and flame retardancy can be achieved by incorporation of aluminum and silicon components into the surface coal. Other oxyphilic metals incorporated into the charcoal are also effective in reducing surface oxidation.

In a similar manner [(isobutyl _{SiO 1.5) 4} (isobutyl SiO _{2) 3} Gd] incorporation into _Σ8 paraffin wax in the flame retardancy as represented by slowing the rate of weight loss during heating Show improvement. The thermogravimetric plot in FIG. 10 shows that at 250 ° C., pure paraffin loses its total weight due to melting and subsequent evaporation. Contrary to pure paraffin, 70% [(isobutyl SiO _1.5 ) ₄ (isobutyl SiO ₂ ) ₃ Gd] _Σ8 / 30% paraffin alloy retains its mass at about 300 ° C. and higher temperatures, As a result, it loses mass at a much slower rate.

  While certain representative embodiments and detailed descriptions have been presented to illustrate the present invention, various changes may be made in the methods and apparatus disclosed herein without altering the scope of the invention as defined in the claims. It will be apparent to those skilled in the art that other modifications can be made.

The relative position of the internal free volume and external free volume of the polymer is indicated. Illustrates different regions of the microscopic structure of phase-separated polymers. The nanostructure [(RSiO _1.5 ) ₄ (RSiO ₂ ) ₃ M] _Σ8 of the _{sample POMS} is illustrated. Illustrates representative structures of POMS nanostructured chemicals. Illustrates representative structures of POMS nanostructured chemicals. Illustrates representative structures of POMS nanostructured chemicals. Various [(RSiO _1.5 ) ₄ (RSiO ₂ ) ₃ M] _Σ8 POMS shows ultraviolet and visible light transmission. [(RSiO _1.5 ) ₄ (RSiO ₂ ) ₃ M] _{Includes a} thermogravimetric plot showing decomposition and carbon yield of _Σ8 POMS. The components of an acrylic GdPOMS thermosetting coating are shown. A comparison of 40 wt% GdPOMS for X-ray shielding of Pd and Al is shown. Measured results from [(isobutyl _{SiO 1.5) 4} (isobutyl _{SiO 2) 3} Gd] Σ8, also illustrates the calculated thermal neutron attenuation. FIG. 5 is a thermogravimetric plot for paraffin wax versus 70 wt% [(isobutylSiO _1.5 ) ₄ (isobutylSiO ₂ ) ₃ Gd] _Σ8 / 30% paraffin alloy.

Claims (20)

  Acrylic resin, carbonate, epoxy, ester, silicone, polyolefin, polyether, polyester, polycarbonate, polyamide, polyurethane, polyimide, styrene resin, amide, nitrile, olefin, aromatic oxide, aromatic sulfide, ester and ionomer or hydrocarbon and A method of blending a metallized nanostructured chemical selected from the group consisting of a polyhedral oligomeric metallaseskioxane and a polyhedral oligomeric metallosilicate into a polymer selected from a rubber-like polymer derived from silicone, Incorporating a metallized nanostructured chemical into the polymer by reactive or non-reactive blending.   The method of claim 1, further comprising formulating a non-metallized nanostructured chemical selected from the group consisting of POSS and POS in the polymer.   The method of claim 1, wherein a plurality of metallized nanostructured chemicals are incorporated into the polymer.   The method of claim 2, wherein a plurality of metallized nanostructured chemicals are incorporated into the polymer.   The method of claim 4, wherein a plurality of non-metallized nanostructured chemicals are incorporated into the polymer.   The method of claim 1 wherein the polymer is in a physical state selected from the group consisting of amorphous, semi-crystalline, crystalline, elastomeric and rubbery.   The method of claim 1, wherein the polymer comprises a chemical arrangement and an associated polymer microstructure.   The method of claim 1, wherein the polymer is selected from the group consisting of a polymer coil, a polymer domain, a polymer chain, and a polymer segment.   The method of claim 1, wherein the metallized nanostructured chemical reinforces the polymer at the molecular level.   The method of claim 1, wherein the formulation is non-reactive.   The method of claim 1, wherein the formulation is reactive.   The method of claim 1, wherein the physical properties of the polymer are improved as a result of incorporation of the metallized nanostructured chemical into the polymer.   Physical properties include adhesion to polymer surface, adhesion to composite surface, adhesion to metal surface, water repellency, density, low dielectric constant, thermal conductivity, glass transition, viscosity, melting transition, storage elasticity 13. The method of claim 12, wherein the method is selected from the group consisting of rate, relaxation, stress transfer, abrasion resistance, fire resistance, biocompatibility, gas permeability, porosity, optical quality and radiation shielding.   The method of claim 1 wherein compounding is done by blending metallized nanostructured chemicals into the polymer.   15. The method of claim 14, wherein the compounding is done by a blending process selected from the group consisting of melt blending, dry blending and solution blending.   The method of claim 1, wherein the metallized nanostructured chemical performs at least one function selected from plasticizers, fillers, compatibilizers, antioxidants, and stabilizers.   The method of claim 2, wherein the metallized and non-metallized nanostructured chemicals serve as compatibilizers.   The method of claim 1, wherein the metallized nanostructured chemical is selectively formulated into the polymer such that the metallized nanostructured chemical is incorporated into a predetermined region of the polymer.   The method of claim 18, wherein physical properties are improved as a result of incorporation of the metallized nanostructured chemical into the polymer.   20. The method of claim 19, wherein the property is selected from the group consisting of Tg, HDT, elastic modulus, creepability, curability and permeability.

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