Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • 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
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
• • 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
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
  • C08K2003/3045—Sulfates
• • 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
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• This patent application relates to improving barrier properties in polymers and polymer-containing products, to reduce the permeation of fluids (where a fluid is meant to include any mobile phase such as a gas or liquid).
• Carbon black is generally included in a highly elastic polymeric material to provide reinforcing properties such as modulus, tensile strength, tear resistance, and aid in obtaining desired processing characteristics.
• a platy filler which is often described as having a high aspect ratio, can be introduced to improve the permeation resistance but comes at the expense of these desired reinforcing properties that carbon black produces.
• the nature of the carbon black can also contribute to the disrupting of the packing of a platy filler thereby reducing its effectiveness. It would be desired to optimize the filler to allow lower fluid permeation rates and/or concomitant reductions in material usage but this has been limited by the need to balance the polymers properties.
• this disclosure provides a composition for reducing fluid permeability through a polymer membrane, the composition comprising a polymer and from about 10 to about 100 parts per hundred of mineral particles, wherein the mineral particles include fine mineral particles with particle sizes between about 0.05 ⁇ and about 1 ⁇ and coarse mineral particles with particle sizes between about 3 ⁇ and about 20 ⁇ , and wherein the weight ratio of the fine mineral particles to the coarse mineral particles is selected from about 0.1 to about 10.
• the composition comprises from about 15 to about 100 parts per hundred of mineral particles, such as from about 40 to about 70 parts per hundred of mineral particles or from about 50 to about 60 parts per hundred of mineral particles.
• the weight ratio is selected from about 0.2 to about 10, such as about 0.2 to about 5, or about 2.5 to about 3.5.
• the weight ratio may be selected to balance gas-barrier and strength properties associated with a particular composition.
• the coarse mineral particles constrain the movement of the fine mineral particles.
• the coarse mineral particles may limit the ability of the fine mineral particles to rotate in the presence of a shear field.
• the coarse mineral particles may cause alignment of the fine mineral particles or vice versa.
• compositions for reducing fluid permeability through a polymer membrane comprising a polymer and mineral particles, wherein:
• the mineral particles possess a bimodal particle-size distribution
• the bimodal particle-size distribution includes a first peak diameter and a first peak population associated with fine mineral particles and a second peak diameter and a second peak population associated with coarse mineral particles;
• the first peak diameter is from about 0.05 ⁇ to about 1 ⁇ ;
• the second peak diameter is from about 3 ⁇ to about 20 ⁇ .
• the weight ratio of the fine mineral particles to the coarse mineral particles is from about 0.1 to about 10.
• the particle-size distribution is measured by laser light scattering, and/or by using the average Stokes-equivalent particle diameters for the fine and coarse mineral particles.
• the first peak population may be smaller or larger than the second peak population.
• the first peak diameter is in the range of about
• the second peak diameter is in the range of about 5 ⁇ to about 10 ⁇ , in some embodiments, such as about 6.5 ⁇ to about 8.5 ⁇ . Larger particles (such as particles larger than 20 ⁇ ) may also be present.
• the mineral particles may have a calculated average specific surface area (measured by laser light) in the range of about 1 m 2 /g to about 5 m 2 /g, such as about 1.5 m 2 /g to about 3.5 m 2 /g, or as measured by BET in the range of 8-28 m 2 /g, such as about 12-22 m 2 /g, for example.
• the mineral particles may be clay mineral particles.
• the mineral particles are selected from the group consisting of ball clay, kaolin, talc, mica, calcite, dolomite, alumina, silica, alumina-silicates, mineral zeolites, pyrophyllite, vermiculite, lime, gypsum, and any polymorph or mixture thereof.
• the mineral particles may be selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al 2 Si 2 0 5 (OH)4. In certain embodiments, the mineral particles consisting essentially of kaolin particles.
• the polymer may be a thermoset elastomer, such as a polymer selected from the group consisting of butyl rubber, halobutyl rubber, nitrile rubber, natural rubber, neoprene rubber, ethylene-propylene-diene-monomer rubber, polybutadiene, poly(styrene-butadiene-styrene), and any combination thereof.
• a thermoset elastomer such as a polymer selected from the group consisting of butyl rubber, halobutyl rubber, nitrile rubber, natural rubber, neoprene rubber, ethylene-propylene-diene-monomer rubber, polybutadiene, poly(styrene-butadiene-styrene), and any combination thereof.
• the polymer is bromobutyl rubber.
• the polymer may be a thermoplastic polymer, such as a polymer selected from the group consisting of homopolymers or co-polymers of
• polypropylene polyethylene, polystyrene, poly(acrylonitrile-butadiene-styrene), poly(methyl methacrylate), poly( vinyl chloride), poly(vinyl acetate), styrene- butadiene block copolymer, polylactide, and any combination thereof.
• the polymer may also be a thermoplastic vulcanizate.
• the composition may further include carbon black, carbon nanotubes, or another form of carbon particles.
• the composition may also include a coupling agent, a dispersing aid, or a viscosity modifier.
• the present disclosure also provides a composition for reducing fluid permeability through a polymer membrane, the composition comprising a bromobutyl polymer, carbon black, and from about 25 to about 100 parts per hundred of mineral particles, wherein the mineral particles include fine mineral particles with particle sizes between about 0.05 ⁇ and about 1 ⁇ and coarse mineral particles with particle sizes between about 3 ⁇ and about 20 ⁇ , and wherein the weight ratio of the fine mineral particles to the coarse mineral particles is selected from about 0.1 to about 10.
• the composition may further comprise stearic acid, magnesium oxide, dimethylalkyl tertiary amine, naphthenic oil, zinc oxide, and sulfur.
• composition as provided herein is
• gas permeability of about 4 ⁇ 10 ⁇ 13 (cm 3 -cm/(cm 2 -sec-Pa)) or less as measured in accordance with ASTM D-1434-82 (2003), Procedure V, using air at a temperature of 70°C, gas pressure of 35 psi, permeation area 66.4 cm 2 , and capillary diameter of 0.0932 cm, on a test sample cured to a gauge of 0.020" for 10 minutes at 160°C.
• the gas permeability may be about 3.3, 3.2, 3.1, 3 ⁇ 10
• composition as provided herein is
• the aged tensile strength is at least 1400 psi, 1450 psi, or 1500 psi, in some embodiments.
• a composition comprising a polymer, carbon particles, and from about 40 to about 70 parts per hundred of fine mineral particles with particle sizes between about 0.05 ⁇ and about 1 ⁇ ; wherein the composition provides a gas permeability of about 4 ⁇ 10 ⁇ 13 (cm 3 -cm/(cm 2 -sec-Pa)) or less as measured in accordance with ASTM D-1434-82 (2003), Procedure V, using air at a temperature of 70°C, gas pressure of 35 psi, permeation area 66.4 cm 2 , and capillary diameter of 0.0932 cm, on a test sample cured to a gauge of 0.020" for 10 minutes at 160°C; and an aged tensile strength of at least 1300 psi as measured in accordance with ASTM D- 412 on a test sample cured for 20 minutes at 160°C and then aged for 48 hours at 100°C in accordance with ASTM D-573.
• a composition comprising a polymer, carbon particles, and from about 40 to about 70 parts per hundred of fine mineral particles with particle sizes between about 0.1 ⁇ and about 1 ⁇ ; wherein the composition provides reduced gas permeability and increased tensile strength compared to an otherwise- equivalent composition without the fine mineral particles.
• the present disclosure additionally provides a polymeric membrane for resisting fluid permeation, the polymeric membrane comprising a composition in accordance the described compositions.
• the fluid whose permeability is reduced is any gas, including but not limited to air, oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, water vapor, or any mixture thereof.
• the fluid whose permeability is reduced is a liquid, such as an aliphatic or aromatic hydrocarbon, a polar hydrocarbon, or a water-based liquid.
• the disclosure also provides products incorporating the disclosed compositions, such as tire innerliners, coatings, plastic extrusions, films, liners, adhesives, paints, hoses, or weather-protection materials or systems.
• This disclosure also provides a method of fabricating a polymeric membrane for resisting fluid permeation, the method comprising:
• the method further comprises introducing a dispersing aid (e.g., an alkyl tertiary amine, polyacrylate, TSPP, silane-based chemicals or other suitable dispersants) into the polymer-particle mixture.
• a dispersing aid e.g., an alkyl tertiary amine, polyacrylate, TSPP, silane-based chemicals or other suitable dispersants
• the method may include liberating freely associated water on the surface of the mineral particles when incorporated into hydrophobic polymers. Liberated water may be replaced by a dispersing aid. In some embodiments, liberating freely associated water prevents blisters or other defects during step (d). In other cases the dispersant may be working to ensure wetting of the surface of the mineral by the polymeric material such that air is not entrained in the final product. It may be necessary as well when processing liquid polymers to remove the air prior to application.
• a dispersing aid e.g., an alkyl tertiary amine, polyacrylate
• the method further comprises introducing a coupling agent into the polymer-particle mixture.
• the method may include chemically treating at least a portion of the mineral particles with one or more functional organic groups.
• Functional organic groups may be selected to repel the fluid, provide crosslinking or adsorption to the polymer, adjust the hydrophilic- lipophilic balance of the polymer, and/or adjust viscosity of the polymer-particle mixture.
• the method may further comprise chemically treating at least a portion of the mineral particles with a silane, a titanate, a grafted maleic anhydride, and any combination thereof.
• the disclosure also provides a method of fabricating a polymeric membrane for resisting fluid permeation, the method comprising producing a composition as set forth herein, and then forming the polymeric membrane, at least in part, from the composition.
• FIG. 1 summarizes the compositions according to Examples A, B, and C.
• FIG. 2 shows particle-size data for the kaolins used in Examples B and C.
• FIG. 3 shows experimental data associated with Examples A, B, and C.
• FIG. 4 summarizes the compositions according to Examples D and E.
• FIG. 5 shows particle-size data for the kaolins used in Examples D and E.
• FIG. 6 shows experimental data associated with Examples D and E.
• FIG. 7 lists viscosity test data for Examples A, B, C, D, and E.
• FIG. 8 summarizes the compositions according to Examples F, G, and H.
• FIG. 9 shows experimental data associated with Examples F, G, and H.
• FIG. 10 shows particle- size data for the kaolin particle blends used in Examples F, G, and H.
• FIG. 11 illustrates reduced gas permeability in some embodiments.
• FIG. 12 illustrates enhanced tensile strength in some embodiments.
• the present inventors studied the replacement of carbon black in a bromobutyl rubber formula similar to formulas referenced in the literature (such as, for example, U.S. Patent No. 7,019,063).
• the formula is illustrated in the table of FIG. 1, with the carbon black formula being Example A.
• Examples B and C compare two different delaminated kaolin clays replacing the carbon black at an equal volume replacement in the rubber compound.
• Polyplate® HMT KaMin LLC, Macon, Georgia, US
• FIG. 2 The results are illustrated in FIG. 2. From this graph, we can see that the Polyplate HMT has a higher percentage of larger-diameter particles and less finer particles than the Polyfil DL. It may be that this indicates that the kaolin in Example C is "platier.”
• plaque refers to particle aspect ratio, wherein a platier particle has a higher aspect ratio (plate-like). Platy particles may be naturally platy or may derive from layered structures that are separated mechanically.
• FIG. 3 shows that both platy kaolin-filled bromobutyl compounds have reduced gas permeation relative to that of the carbon black only compound (Example A).
• Example C is found to reduce gas permeation by 34% relative to the smaller platier pigment.
• the tensile strength test shows that both kaolin examples produce lower tensile strength than the carbon black filled Example A.
• bromobutyl would be expected. While this might allow the use of a finer particle kaolin without the impact on strength, historically these types of fine particle materials have been avoided for barrier applications due to the perception that one needed a large plate to create an appropriate barrier. However, fine particles may allow equal performance to be achieved by allowing higher loading level. We examined these types of clays in the formulas in FIG. 4, Examples D and E.
• FIG. 6 reports the testing of the rubber physical properties, rubber membrane air-permeation resistance, and the Malvern particle sizing of the respective kaolins used in Examples D and E. From this data, at the same loading level the fine particle kaolins do not impact the rubber strength as much as the larger kaolins in Examples B and C. Indeed, the tensile strength of Example E is favorably
• Example C One benefit of the coarser kaolin, Polyplate HMT kaolin (Example C), was that it produced a slightly higher uncured viscosity relative to the Polyfil DL kaolin (Example B) rubber compound. This may be a desirable trait as the use of a non-black filler may create the need for accommodating the effect of viscosity on processing for certain types of equipment, in some embodiments.
• the two finer particle kaolins in Example D and E had viscosities similar to the Polyfil DL kaolin, Example B. These measurements are listed in FIG. 7.
• FIGS. 9 and 10 are illustrated in FIGS. 9 and 10.
• the viscosity for these three compounds was reduced from the 100% Polyplate HMT kaolin in Example C but still comparable to the commercial Polyfil DL kaolin in Example B.
• the tensile strength for these blends is surprisingly favorable versus the carbon black (Example A), despite the presence of the coarser material in the blend.
• Example H is a particularly good compound. Without being limited by any particular hypothesis, it is speculated that a small amount of large particles helps keep the smaller platy particles better aligned during the component fabrication on a mill, extruder, or calendar or in application techniques due to flow properties. A model of the flow would be one of constraint. If one models the flow of plate-like particles that are flowing in a constrained space, the larger the particle the better the alignment as the larger particles tend to streamline with the flow. By using some coarser particles, the flow of the finer particles are constrained by keeping them in plane and limiting their ability to rotate in the shear field.
• a proportional amount of large particles may help overcome the layering of platy materials as impacted by the aggregated carbon black.
• Another theory (without limitation of the disclosure) is that the barrier process is driven by maximizing the number of plates in the system. If all plates are similar thickness, then the way get the most in there is to make them as small as possible and get them aligned, using coarse particles and limit the impact on strength.
• Some embodiments are premised on the surprising discovery that a blend of a very fine and a coarse platy material reduce the permeation rate of a fluid through a polymer.
• a composition for reducing fluid permeability through a polymer membrane comprising a polymer and from about 10 to about 100 parts per hundred of mineral particles, wherein the mineral particles include fine mineral particles with particle sizes between about 0.1 ⁇ and about 1 ⁇ and coarse mineral particles with particle sizes between about 3 ⁇ and about 20 ⁇ .
• the weight ratio of fine mineral particles to coarse mineral particles is selected from about 0.1 to about 10.
• the ratio can be adjusted to make up for any changes in the particle sizes themselves.
• the particles do not have a very broad particle size, to avoid significant strength loss. In some embodiments, enough coarse particles are introduced to force alignment of fine particles, without negatively impacting strength.
• thermoset elastomers examples include but are not limited to: halobutyl, butyl, EPDM, BR, neoprenes, natural rubber, polybutadienes, styrene-butadiene, etc.
• thermoplastics polymers examples include but are not limited to: homopolymers or copolymers of polypropylene, polyethylene, polystyrene, ABS, PMMA, PVC, PVA, SBR, etc.
• thermoplastic vulcanizates which are polymeric blends of thermoset and thermoplastic polymers.
• ком ⁇ онент particles of other composition such as talc, mica, etc. used in a similar blend would also produce a similar improvement in permeation resistance.
• the blend could be with two or more types of platy materials as well such as kaolin and talc, kaolin and mica, or mica and talc, for example.
• Other fine fillers may work to help the coarser fillers pack in more tightly.
• the surface of the fillers should be compatible with the matrix.
• Multi-pigment blends may also work to enhance performance. Very fine particles help maintain strength.
• the platy materials can be treated with silanes, titanates, grafted maleic anhydride, etc.
• the inorganic side of the material would either bond or adsorb onto the platy filler blend and the other functional side would be chosen to reduce the compatibility of the platy filler surface to that fluid.
• the chemical treatment could be a blend of different types of chemical treatments (inorganic side) and could be a blend of different functional organic end to combine: repelling the permeating gas or fluid, provide crosslinking or strong adsorption to the polymer system to reduce swelling of the capillary path, and to control the hydrophilic-lipophilic balance functionality of the filler surface for processing viscosity during production (as an example).
• Surface treatment can help retard permeation rates by not wicking permeate, by crosslinking into matrix to help minimize swelling of capillary path.
• a dispersing aid instead of a coupling agent as described above may be used in the formulation to improve the wetting out of the platy filler in the organic polymer complex.
• Dimethylalkyl tertiary amine is one such dispersing aid; for those skilled in the art, a number of materials could be used for this modification.
• the mixing protocol may be adjusted to allow for the liberation of the freely associated water on the surface the surface of the platy filler.
• the temperature of the mix is above 100°C for sufficient time to liberate the associated moisture and allow replacement by the dispersing aid.
• the dispersing aid dosage should be proportional to the surface area of the total platy filler being used that is hydrophilic and cover enough of the platy material surface to maintain the contained moisture below a level where blisters or other type of defects may form during subsequent fabrication steps of component or final product. If the platy filler is hydrophilic, steps may need to be taken to remove adsorbed water for defect free processing (e.g. blisters).
• Dispersing aids include traditional dispersing aids or inorganic and organic nature including but not limited to: sodium silicate, sodium phosphate, lignin based dispersents, organic wetting agents and surfactants, polyacrylates, silane (traditionally used as coupling agents but can also be thought of as dispersants), animal and vegetable based oils and fats and fatty acids, proteins etc. In fact any product that allows the kaolin to be more compatible with the surround matrix may serve as a dispersant.
• Carbon forms that may be suitable include, for example, carbon black; natural graphites, such as flaky graphite, plate-like graphite, and other types of graphite; high-temperature sintered carbon products obtained, for example, from petroleum coke, coal coke, celluloses, saccharides, and mesophase pitch; artificial graphites, including pyrolytic graphite; carbon blacks, such as acetylene black, furnace black, Ketjen black, channel black, lamp black, and thermal black; asphalt pitch, coal tar, active carbon, mesophase pitch, and polyacetylenes; carbon nanostructures such as carbon nanotubes; or graphene-based carbon structures.
• natural graphites such as flaky graphite, plate-like graphite, and other types of graphite
• high-temperature sintered carbon products obtained, for example, from petroleum coke, coal coke, celluloses, saccharides, and mesophase pitch
• artificial graphites including pyrolytic graphite
• carbon blacks such as ace

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• 2012
  • 2012-06-20 JP JP2014517107A patent/JP6089030B2/ja not_active Expired - Fee Related
  • 2012-06-20 EP EP12802433.8A patent/EP2723804A4/en not_active Withdrawn
  • 2012-06-20 KR KR1020147002153A patent/KR101641493B1/ko active Active
  • 2012-06-20 WO PCT/US2012/043214 patent/WO2012177679A1/en not_active Ceased
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