|Publication number||US7193015 B1|
|Application number||US 10/815,544|
|Publication date||Mar 20, 2007|
|Filing date||Mar 31, 2004|
|Priority date||Mar 24, 2000|
|Publication number||10815544, 815544, US 7193015 B1, US 7193015B1, US-B1-7193015, US7193015 B1, US7193015B1|
|Inventors||Joseph M. Mabry, Rene I. Gonzalez, Rusty L. Blanski, Patrick N. Ruth, Brent D. Viers, Joseph J. Schwab, Joseph D. Lichtenhan|
|Original Assignee||Mabry Joseph M, Gonzalez Rene I, Blanski Rusty L, Ruth Patrick N, Viers Brent D, Schwab Joseph J, Lichtenhan Joseph D|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (12), Referenced by (20), Classifications (10), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application claims the benefit of U.S. Provisional Application No. 60/459,357 filed on Mar. 31, 2003, and is a continuation-in-part of U.S. patent application Ser. No. 09/818,265 filed Mar. 26, 2001, now U.S. Pat. No. 6,716,919, which claims the benefit of U.S. Provisional Application No. 60/192,083, filed Mar. 24, 2000.
This invention relates generally to methods for enhancing the properties of thermoplastic and thermoset fluorinated polymer and fluid compositions and, more particularly, to methods for the incorporation of nanostructured chemicals into fluorinated polymers and fluorinated fluids.
This invention also relates to several applications of the fluorinated polymers with improved properties. These applications include space-survivable materials and creep resistant seals and gaskets. Improved polymer surface properties may be useful for applications such as anti-icing or non-wetting surfaces or as low friction surfaces.
It has long been recognized that the properties of polymers can be tailored to a high degree through variables such as polymer sequence, structure, additive and filler incorporation, composition, morphology, thermodynamic and kinetic processing control. It is similarly known that various sizes and shapes of fillers, and particulates (e.g. calcium carbonate, silica, carbon black etc.) can be incorporated into preformed polymers or prepolymers or monomer mixtures to enhance physical and material properties of the resulting formulations.
In their solid state all polymers (including amorphous, semi-crystalline, crystalline, and rubber, etc.) possess considerable amounts of internal and external free volume (see
The accessibility of free volume in a polymer system depends greatly on its morphology and on the size of the agent desired to occupy the free volume. As shown in
Prior art in fluoropolymers has focused on modifications through the formation of an inorganic interpenetrating network that is either partially or fully condensed and is in contact with or dispersed amoungst the fluoropolymer chains. See U.S. Pat. Nos. 5,876,686 and 5,726,247. Similarily modifications have been described that enhance properties through the continuous or discontinuous dispersion of macro, micro and nanoscale particulates of a dissimilar composition (e.g. inorganic) relative to that of the fluoropolymer. In either case the function of the inorganic network or filler particle is to reduce the relative slippage or motion of the fluoropolymer chains and segments relative to each other. The combination of reduced chain motion with the thermally stable inorganic component utlimately enhances physical properties such as dimensional stability, impact resistance, tensile and compressive strengths, thermal stability, electrical properties, abrasion and chemical resistance, shrinkage and expansion reduction. Unfortunately, all of the prior art either suffers from process complexity, a length scale of the reinforcement that is too large to sufficiently access polymer free volume, or reinforcement that lacks sufficient geometrical definition to provide structure regularity and reinforcement at the molecular (10−10 m) and nanoscopic (10−9 m) length scales. As illustrated in
Furthermore, it has been calculated that as filler sizes decrease below 50 nm, they would become more resistant to sedimentation and more effective at providing reinforcement to polymer systems. The full application of this theoretical knowledge, however, has been thwarted by the lack of a practical source of particulate reinforcement or reinforcements which are geometrically well defined, and monodisperse and with diameters below the 10 nm range and especially within the 1 nm to 5 nm range. Particularly desirable are monodisperse, nanoscopically sized chemicals with precise chemical compositions, rigid and well defined geometrical shapes, and which are dimensionally large enough to provide reinforcement of polymer chains. Such nanoscopic chemicals are desirable as they are expected to form the most stable dispersions within polymer systems, would be well below the length scale necessary to scatter light and hence are visually nondetectable when incorporated into fluoropolymers, and would be chemically compatible with fluoropolymers and dissolve into and among the polymer chains, thus eliminating the need for extensive dispersion or reactive self assembly or the complex processing requirements of the prior art.
Recent developments in nanoscience have enabled the ability to cost effectively manufacture commercial quantities of materials that are best described as nanostructured chemicals due to their specific and precise chemical formula, hybrid (inorganic-organic) chemical composition, large physical size relative to the size of traditional chemical molecules (0.3–0.5 nm), and small physical size relative to larger sized traditional fillers (>50 nm).
Nanostructured chemicals are best exemplified by those based on low-cost Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS).
These systems contain hybrid (i.e., organic-inorganic) compositions in which the internal frameworks are primarily comprised of inorganic silicon-oxygen bonds. The exterior of a nanostructure is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic polymers. These and other properties of nanostructured chemicals are discussed in detail in U.S. Pat. Nos. 5,412,053 and 5,484,867, both are expressly incorporated herein by reference in their entirety. These nanostructured chemicals are of low density, exhibit excellent inherent fire retardancy, and can range in diameter from 0.5 nm to 5.0 nm.
Prior art associated with fillers, plasticizers, interpenetrating networks, and polymer morphology has not been able to adequately control polymer chain, coil and segmental motion at the 1 nm–10 nm level. Furthermore, the mismatch of chemical potential (e.g., solubility, miscibility, etc.) between fluoro-based polymers and inorganic-based fillers and chemicals results in a high level of heterogeneity in compounded polymers that is akin to oil mixed with water. Therefore, there exists a need for appropriately sized chemical reinforcements for polymer systems with controlled diameters (nanodimensions), distributions and with tailorable chemical functionality. In addition, it would be desirable to have easily compoundable nanoreinforcements that have chemical potential ranges (misibilities) similar to the various fluorinated polymer and fluorinated fluid systems.
The present invention describes methods of preparing new polymer compositions by incorporating nanostructured chemicals into polymers. The resulting nano-alloyed polymers are wholly useful by themselves or in combination with other polymers or in combination with macroscopic reinforcements such as fiber, clay, glass mineral and other fillers. The nano-alloyed polymers are particularly useful for producing polymeric compositions with desirable physical properties such as adhesion to polymeric, composite and metal surfaces, water repellency, reduced melt viscosity, low dielectric constant, resistance to abrasion and fire, biological compatibility, and optical quality plastics. The preferred compositions presented herein contain two primary material combinations: (1) nanostructured chemicals, nanostructured oligomers, or nanostructured polymers from the chemical classes of polyhedral oligomeric silsesquioxanes, polysilsesquioxanes, polyhedral oligomeric silicates, polysilicates, polyoxometallates, carboranes, boranes, and polymorphs of carbon; and (2) fluorinated polymer systems such as: PFA, MFA, PVDF, semicrystalline, crystalline, glassey, elastomeric, oils, and lubricants thereof as derived from hydrocarbons, or silicones and fluoropolymers or copolymers thereof.
Preferably, the method of incorporating nanostructured chemicals into such fluoropolymers is accomplished via blending of the chemicals into the polymers. All types and techniques of blending, including melt blending, dry blending, solution blending, reactive and nonreactive blending are effective.
In addition, selective incorporation of a nanostructured chemical into a specific region of a polymer can be accomplished by compounding into the polymer a nanostructured chemical with a chemical potential (miscibility) compatible with the chemical potential of the region within the polymer to be alloyed. Because of their chemical nature, nanostructured chemicals can be tailored to show compatibility or incompatibility with selected sequences and segments within polymer chains and coils. Their physical size in combination with their tailorable compatibility enables nanostructured chemicals to be selectively incorporated into fluoroplastics and control the dynamics of coils, blocks, domains, and segments, and subsequently favorably impact a multitude of physical properties. Properties most favorably improved are time dependent mechanical and thermal properties such as heat distortion, creep, compression set, shrinkage, modulus, hardness and abrasion resistance. In addition to mechanical properties, other physical properties are favorably improved, including lower thermal conductivity, improved fire resistance, and improved oxygen permeability, improved oxidative stability, improved electrical properties and printability.
Creep Resistant Seals and Gaskets
While many fluoropolymers, such as polytetrafluoroethylene (PTFE or Teflon) and fluorinated ethylene/propylene (FEP) are resistant to organic fuels and fluids, creep is often a problem. Creep is the change in dimensions of a molded part resulting from cold flow incurred by continual loading and can cause a polymer press-fit to loosen to an unacceptable condition or even fail. Tensile strength is an important factor in controlling the amount of cold flow in plastics. The higher the tensile strength, the more resistant the plastic is to cold flow and creep. PTFE, for example, has a very low tensile strength. In addition to improving thermal and mechanical properties of fluoropolymers, blended fluorinated POSS reduces the amount of creep. The processing temperature of nearly all fluoropolymers is sufficient to allow the blending of POSS materials. A notable exception is PTFE. While the processing temperature of PTFE is too high to allow conventional blending, supercritical methods may allow fluorinated POSS to be incorporated into PTFE.
Space-survivable Fluorinated Materials
Fluorinated POSS can be blended into several fluoropolymers, including poly(vinylidinefluoride) (PVDF) and FEP, both of which are used in spacecraft coatings. These compounds significantly improve oxidation resistance due to a rapidly forming ceramic-like, passivating and self-healing silica layer when exposed to high incident fluxes of atomic oxygen (AO). AO is the predominant species in low earth orbit (LEO) responsible for material degradation. This is because the collision energy of AO (˜5 eV) exceeds the bond strength of carbon—carbon bonds in fluoropolymers (˜4.3 eV). The silicon-oxygen bonds present in the POSS cage have stronger bond dissociation energies (˜8.3 eV). The POSS cage is not destroyed by the AO, but forms a passivating self-rigidizing/self-healing silica layer, which protects the underlying virgin polymer.
Anti-icing or Non-wetting Applications
Fluorinated POSS films show remarkable surface properties. The contact angle of water on a spin-cast surface of fluorodecyl POSS is 140° in an unoptimized process. Surprisingly, this is 30 degrees higher than PTFE. A higher the contact angle indicates lower surface energy. These fluorinated POSS compounds have the potential to form ultrahydrophobic surfaces and also reduce the surface energy of the fluoropolymers into which they are blended. This also leads to increased abrasion resistance and lubricity. Anti-icing or non-wetting applications may be possible using this technology. Lubricants and low friction surfaces can also be developed. These surfaces would be further enhanced by the creep reduction mentioned above.
For the purposes of understanding this invention's chemical compositions the following definitions for formula representations of Polyhedral Oligomeric Silsesquioxane (POSS) and Polyhedral Oligomeric Silicate (POS) nanostructures are made.
Polysilsesquioxanes are materials represented by the formula [RSiO1.5]∞ where ∞ represents molar degree of polymerization and R=represents organic substituent (H, siloxy, cyclic or linear aliphatic or aromatic groups that may additionally contain reactive functionalities such as alcohols, esters, amines, ketones, olefins, ethers or halides or which may contain fluorinated groups). Polysilsesquioxanes may be either homoleptic or heteroleptic. Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group.
POSS and POS nanostructure compositions are represented by the formula:
[(RSiO1.5)n]Σ# for homoleptic compositions
[(RSiO1.5)n(R′SiO1.5)m]Σ# for heteroleptic compositions (where R≠R′)
[(RSiO1.5)n(RXSiO1.0)m]Σ# for functionalized heteroleptic compositions (where R groups can be equivalent or inequivalent)
In all of the above R is the same as defined above and X includes but is not limited to OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR2) isocyanate (NCO), and R. The symbols m and n refer to the stoichiometry of the composition. The symbol Σ 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 Σ# 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 nanostructured chemicals as alloying agents for the reinforcement of polymer coils, domains, chains, and segments at the molecular level.
The keys that enable nanostructured chemicals to function as molecular level reinforcing and alloying agents are: (1) their unique size with respect to polymer chain dimensions, and (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. That is, nanostructured chemicals can be tailored to exhibit preferential affinity/compatibility with some polymer microstructures through variation of the R groups on each nanostructure. At the same time, the nanostructured chemicals can be tailored to be incompatible with other microstructures within the same polymer, thus allowing for selective reinforcement of specific polymer microstructure. Therefore, the factors to effect a selective nanoreinforcement include specific nanosizes of nanostructured chemicals, distributions of nanosizes, and compatabilities and disparities between the nanostrucutured chemical and the polymer system.
Nanostructured chemicals, such as the POSS Molecular Silicas illustrated in
Table 1 below relates the size range of POSS cages relative to polymer dimensions and filler sizes. The size of POSS is roughly equivalent to that of most polymer dimensions, thus at a molecular level POSS can effectively alter the motion of polymer chains.
Relative sizes of POSS, polymer dimensions, and fillers.
Random Polymer Coils
The ability of POSS to control chain motion is particularly apparent when POSS is grafted onto a polymer chain. See U.S. Pat. Nos. 5,412,053; 5,484,867; 5,589,562; and 5,047,492, all expressly incorporated by reference herein. When POSS nanostructures are covalently linked to the polymer chain they act to retard chain motion and greatly enhance time dependent properties such as Tg, HDT, Creep and Set, which correlate to increased modulus, hardness, and abrasion resistance. The present invention now shows that similar property enhancements can be realized by the direct blending of nanostructured chemicals into plastics. This greatly simplifies the prior art processes.
Furthermore, because POSS nanostructured chemicals possess spherical shapes (per single crystal X-ray diffraction studies), like molecular spheres, and because they dissolve, they are also effective at reducing the viscosity of polymer systems. This benefit is similar to what is produced through the incorporation of plasticizers into polymers, yet with the added benefits of reinforcement of the individual polymer chains due to the nanoscopic nature of the chemicals (see
As is typical with chemical processes there are a number of variables that can be used to control the purity, selectivity, rate and mechanism of any process. Variables influencing the process for the incorporation of nanostructured chemicals (e.g. POSS/POS etc.) into plastics include the size and polydispersity, and composition of the nanostructured chemical. Similarly the molecular weight, polydispersity and composition of the polymer system must also be matched with that of the nanostructured chemical. Finally, 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 nanostructured chemical into plastics.
(Heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (6.10 g), deionized water (0.27 g), and potassium hydroxide (2.088 mg) were added to a 10 mL volumetric flask. The balance of the volume to 10 mL was filled with ethanol. The contents were transferred to a 25 mL round bottom flask with a Teflon covered magnetic stir bar. The contents were stirred at room temperature overnight under nitrogen. A fine white powder was formed. The product was rinsed with ethanol and dried. A 92.3% yield of pure [(RSiO1.5)8]Σ8) was obtained. 29Si NMR δ:—66.76 ppm.
(Tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (5.10 g), deionized water (0.27 g), and potassium hydroxide (2.088 mg) were added to a 10 mL volumetric flask. The balance of the volume to 10 mL was filled with ethanol. The contents were transferred to a 25 mL round bottom flask with a Teflon covered magnetic stir bar. The contents were stirred at room temperature overnight under nitrogen. A fine white powder was formed. The product was rinsed with ethanol and dried. A 92% yield of pure [(RSiO1.5)8]Σ8) was obtained. 29Si NMR δ:—66.69 ppm.
Poly(vinylidene fluoride) (PVDF) was used. PVDF (Hylar 460) was obtained from Solvay Solexis. The melting temperature determined by differential scanning calorimetry (DSC) was in the range of 150–164° C. [(3,3,3-TrifluoropropylnSiO1.5)n]Σn was blended into PVDF using a twin screw extruder (MicroCompounder, DACA Instruments). The PVDF and POSS were mixed thoroughly for 3 minutes at 177° C. Three samples were prepared with POSS weight percents of 2.5%, 5%, and 10%, respectively.
PVDF was used in this study. [(1H,1H,2H,2H-heptadecafluorodecylnSiO1.5)n]Σn was blended into PVDF using a twin screw extruder. The PVDF and POSS were mixed thoroughly for 3 minutes at 177° C. Three samples were prepared with POSS weight percents of 2.5%, 5%, and 10%, respectively.
Perfluoroalkoxy polymer (PFA) was used in this study. PFA was obtained from duPont. The melting temperature determined by DSC was in the range of 311–319° C. [(1H,1H,2H,2H-heptadecafluorodecylnSiO1.5)n]Σn was blended into PFA using the twin screw extruder. The PFA and POSS were mixed thoroughly for 3 minutes at 375° C. Two samples were prepared with POSS weight percents of 2.5% and 10%, respectively.
PFA was used in this study. [(c-pentyl)SiO1.5)7(c-pentyl)(OH)SiO1.0)3]Σ7 was blended into PFA using the twin screw extruder. The PFA and POSS were mixed thoroughly for 3 minutes at 750° C. A sample was prepared with a POSS weight percent of 2%.
PFA was used in this study. [(c-pentyl)SiO1.5)7(H)SiO1.5)3]Σ8 was blended into PFA using the twin screw extruder. The PFA and POSS were mixed thoroughly for 3 minutes at 750° C. A sample was prepared with a POSS weight percent of 5%.
A series of Nanostructured POSS Chemicals were compounded into fluoropolymer at the 1 wt %–50 wt % level using a twin screw melt extruder operating at 80–120 rpm and 190° C. Both POSS and the polymer were dried prior to compounding to ensure a maximum state of alloying. After compounding, the POSS-reinforced samples were then molded into discs, dogbones and other test specimens and subjected to analysis and characterization. The viscoelastic response as represented by the values for storage modulus (E*) relative to temperature (° C.) of the POSS-reinforced fluoropolymer is shown in
Various sizes of POSS molecular silicas were observed to have a pronounced effect on the degree to which the modulus was retained at elevated temperatures. Overall it was observed that the Octameric [(RSiO1.5)8]Σ8 and dodecametic [(RSiO1.5)12]Σ12 POSS were most effective at retaining the modulus at elevated temperatures. The fracture toughness and other mechanical properties and physical properties of the POSS-alloyed fluoropolymers were also noticeably improved. The mechanism for this enhancement was observed to be the restriction of the motion of the polymer segments and subsequent polymer chains in the fluoropolymer (see
Alternate Method: Solvent Assisted Formulation. POSS can be added to a vessel containing the desired polymer, prepolymer or monomers and dissolved in a sufficient amount of an organic solvent (e.g. hexane, toluene, dichlormethane, etc.) or fluorinated solvent to effect the formation of one homogeneous phase. The mixture is then stirred under high shear at sufficient temperature to ensure adequate mixing for 30 minutes and the volatile solvent is then removed and recovered under vacuum or using a similar type of process including distillation. Note that supercritical fluids such as CO2 can also be utilized as a replacement for the flammable hydrocarbon solvents. The resulting formulation may then be used directly or for subsequent processing.
Nanostructured POSS was compounded into fluoropolymer fluids in the amounts ranging from 1%, to 50%, and various physical properties of the alloyed fluids were measured and compared with the same physical properties of the base fluorpolymer fluid (Table 3). The enhanced properties of POSS-reinforced fluoropolymer fluid are apparent. Similar levels of enhancements were observed with other fluoro polymer fluids and from the incorporation of POSS fluoropolymer fluids into other polymers.
The mechanism for the physical property enhancements is attributed to the restriction of motion of the polymer chains (see
A transmission electron micrograph was taken of a fractured POSS fluoropolymer monolith of that was composed of 10% [(RSiO1.5)8]Σ8) (see
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|U.S. Classification||525/101, 525/104|
|Cooperative Classification||B82Y30/00, C08K2201/011, C08K5/549, C08G77/045, C08L27/12, C08L27/16|
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