Patent Grant
7601772
The present invention is directed to a nano-composite comprising a clay and a cationic mediator, wherein the cationic mediator comprises a hydrophobic unit and a cationic unit. The invention is further directed to a composition comprising the nano-composite and a polymer. The composition is useful in preparing products such as tires with improved and well-balanced properties including gas impermeability, cure rates, and superior mechanical characteristics, etc.
In manufacturing rubber products such as a tire, one needs to consider a wide range of factors and various balances between them, such as gas permeability, curing properties such as curing time and curing capability, traction characteristics on dry and wet surfaces, rolling resistance, tread-wear resistance, ring tensile, vulcanization plateau, Shore A hardness, rubber damping properties, elongation, strain, specific gravity, reliability, manufacturability, and cost effectiveness, among others. For example, gas impermeability is important for many rubber products where unsaturated bonds can be attacked by atmospheric ozone. These attacks may, over time, lead to oxidative degradation, which may subsequently lead to chain cleavage. As such, there exists a continuous interest in lowering gas permeability of polymers.
Since the discovery of exfoliated nylon/clay nano-composites by Usuki et al. (J. Mater. Res. 1993, 8, 1174), people have made extensive efforts to lower gas permeability by using well-exfoliated layered materials. A common morphology for miscible polymer-layered material dispersions is known as intercalation and exfoliation, which improves polymeric properties such as mechanical, gas barrier/permeability, thermal, and heat distortion temperature. However, for polymers, particularly nonpolar polymers, well-exfoliated polymer-layered material nano-composites are notoriously difficult to obtain. For example, Wang et. al in the Journal of Applied Polymer Science, Vol. 78, 1879-1883 (2000) describe a process of making clay-rubber mixtures by mixing a styrene-vinylpyridine-butadiene latex with a hydrophilic unmodified clay. The expansion of clay gallery was reported to increase only from 1.24 to 1.46 nm. The limited extent of intercalation is not expected to provide substantial property enhancement in rubber materials.
Although organic ammonium salts have shown improved capability in clay exfoliation, they typically have a low decomposition temperature. As an undesirable effect, organo-clays treated by the ammonium salts may damage or retard the cure process of the rubbery material, especially when free radical cure, sulfur cure, or ZnO cure is employed.
Advantageously, the present invention provides nano-composites that are useful in formulating compositions such as rubbers and tire products with improved and well-balanced properties including gas permeability, thermal stability, cure properties, and/or mechanical properties etc.
A first aspect of the present invention provides a nano-composite comprising (i) a clay and (ii) a cationic mediator comprised of a hydrophobic unit and a cationic unit, wherein the clay is exfoliated or intercalated by the cationic mediator.
A second aspect of the present invention provides a composition comprising the nano-composite and a polymer, wherein the clay of the nano-composite is exfoliated or intercalated by the cationic mediator or by a mixture of the cationic mediator and the polymer.
A third aspect of the invention provides a process for making a rubber article such as a tire.
It is to be understood herein, that if a “range” or “group” is mentioned with respect to a particular characteristic, for example, ratio, percentage, chemical group, and temperature etc., it relates to and explicitly incorporates herein each and every specific member and combination of sub-ranges or sub-groups therein. Thus, any specified range or group is to be understood as a shorthand reference to each and every member of a range or group individually as well as each and every possible sub-range or sub-group encompassed therein; and similarly with respect to any sub-ranges or sub-groups therein.
As one aspect the nano-composite comprises (i) a clay and (ii) a cationic mediator comprised of a hydrophobic unit and a cationic unit, wherein the clay is exfoliated or intercalated by the cationic mediator. Herein incorporated into this description are WO9853000; JP08199062; JP Publication Number 2003-95640A; U.S. Pat. Nos. 6,197,849; 5,707,439; J. S. Wikes, J. A. Levisky, B. A. Wilson, Inorg. Chem. 1982, 21, 1263-1264; J N Hay and S J Shaw “A Review of Nanocomposites 2000”; and Gilman, J. W. et al “Recent Advances in Flame Retardant Polymer Nanocomposites”.
The term “cationic mediator” used herein describes a chemical species able to effectively mediate, or compatiblize, immiscible organic polymer and inorganic layered materials such as clay, into a relatively homogenous state without phase separation. Generally, the mediator facilitates the intercalation of organic polymer between the layers of the layered material.
The cationic mediators of the invention may include, but are not limited to, those commonly known as surfactants. The nano-composites of the invention may include, but are not limited to, those commonly known as organo-clay, for example, organo-mica.
In one exemplary embodiment, the cationic mediator comprises at least one cationic unit, which typically is also hydrophilic, that can bind to the layers of inorganic layered material with effectively higher affinity than to an organic, and typically also hydrophobic material, such as butyl rubber or IIR. While a cationic mediator typically binds to an inorganic layered material by hydrophilic interaction or ionic bond, it can also bind or link to an organic material through a variety of physical and chemical forces such as hydrophobic interaction, covalent bonds, π-π stacking interaction, lock-key type interaction, hydrogen bonds, and coordination bonds etc. Accordingly, a cationic mediator of the present invention comprises, in addition to the “at least one cationic unit”, an organic binding unit, for example, a sufficiently long alkyl chain, or a covalently bonded polymeric group etc.
The cationic unit may be monoatomic or polyatomic, and bears one or more elementary positive charges of the proton. Depending upon the specific structure of the cationic mediator, such as the presence or absence of a conjugated system and whether the cationic unit includes the conjugated system, the positive charge(s) can be either localized or delocalized. The cationic mediator can be accompanied by negatively charged species to balance its positive charge and neutralize the overall charge of the system. Although the negatively charged species is typically independent, e.g. a counter ion(s), it is also feasible that the negatively charged species is part of the cationic mediator, by which an inner salt is formed. In various embodiments, the counter ion of the cationic mediators may also be those negatively charged groups of the layers in the layered material, for example, after the cationic mediator has undergone cation exchange with the layered material by intercalating.
Throughout this description, it should be understood that a cationic mediator is typically accompanied by charge-equivalent counter ion(s), which, for simplicity, may not be so explicitly stated. Exemplary counter ions of the cationic mediator may include, but are not limited to, simple anions such as Cl−, Br−, F−, I−, O2−, S2−, Se2−, Te2−, N3−, As3−, and the like; and polyatomic anions such as BF4−, PF6−, CO32−, HCO3−, SO42−, CF3SO3−, SO32−, S2O32−, HSO4−, H2PO4−, HPO42−, PO43−, NO2−, NO3−, C2O42−, C2H3O2−, OH−, O22−, N3−, CrO42−, Cr2O72−, BO33−, MnO4−, AsO43−, SCN−, CN−, CNO−, ClO−, ClO4−, ClO3−, ClO4−, BrO−, BrO2−, BrO3−, BrO4−, IO−, IO2−, IO3−, IO4−, and the like. In one embodiment, the counter ion is Cl− or Br−.
The hydrophobic unit of the cationic mediator may comprise a C≧3 hydrocarbon group or a polymeric group. The symbol C≧3 denotes “containing no less than 3 carbon atoms”. For example, the C≧3 hydrocarbon may include any saturated or unsaturated, substituted or unsubstituted, straight or branched, cyclic or acyclic C3-C50 alkyl or arylalkyl group.
Exemplary C≧3 hydrocarbon groups of the invention include, but are not limited to, 3-phenyl-3-ene-propyl, 6-ene-hexyl, butyl, isobutyl, behenyl, palmitoleyl, oleyl, linoleyl, linelenyl, erucyl, capryl, tallow, n-pentyl, any isopentyl, n-hexyl, any isohexyl, n-heptyl, any isoheptyl, n-octyl, any isooctyl, n-nonyl, any isononyl, n-decyl, any isodecyl, n-undecyl, any isoundecyl, n-dodecyl or lauryl, any isododecyl, n-tridecyl, any isotridecyl, n-tetradecyl, myristyl, any isotetradecyl, n-pentadecyl, any isopentadecyl, n-hexadecyl or cetyl, palmityl, any isohexadecyl, n-heptadecyl, any isoheptadecyl, n-octadecyl, stearyl, any isooctadecyl, n-nonadecyl, any isononadecyl, n-eicosyl, any isoeicosyl, n-henicosyl, any isohenicosyl, n-docosyl, any isodocosyl, n-tricosyl, any isotricosyl, n-tetracosyl, any isotetracosyl, n-pentacosyl, any isopentacosyl, n-hexacosyl, any isohexacosyl, n-heptacosyl, any isoheptacosyl, n-octacosyl, any isooctacosyl, n-nonacosyl, any isononacosyl, n-triacontyl, any isotriacontyl, n-hentriacontyl, any isohentriacontyl, n-dotriacontyl, any isodotriacontyl, n-tritriacontyl, any isotritriacontyl, n-tetratriacontyl, any isotetratriacontyl, n-pentatriacontyl, any isopentatriacontyl, n-hexatriacontyl, any isohexatriacontyl, n-heptatriacontyl, any isoheptatriacontyl, n-octatriacontyl, any isooctatriacontyl, n-nonatriacontyl, any isononatriacontyl, n-tetracontyl, any isotetracontyl, n-hentetracontyl, any isohentetracontyl, n-dotetracontyl, any isodotetracontyl, n-tritetracontyl, any isotritetracontyl, n-tetratetracontyl, any isotetratetracontyl, n-pentatetracontyl, any isopentatetracontyl, n-hexatetracontyl, any isohexatetracontyl, n-heptatetracontyl, any isoheptatetracontyl, n-octatetracontyl, any isooctatetracontyl, n-nonatetracontyl, any isononatetracontyl, n-pentacontyl, isopentacontyl and mixtures thereof.
In certain embodiments, the C≧3 hydrocarbon group is selected from the group consisting of 3-phenyl-3-ene-propyl, n-butyl, 6-ene-hexyl, n-octyl, n-hexadecyl, n-docosyl, and the mixture thereof.
The C≧3 hydrocarbon group can be more specifically selected from the group consisting of n-dodecyl or lauryl, n-tridecyl, n-tetradecyl, myristyl, n-pentadecyl, n-hexadecyl or cetyl, palmityl, n-heptadecyl, n-octadecyl, and the mixture thereof.
The cationic unit of the cationic mediator may comprise a heterocyclic cation or an onium. Exemplary heterocyclic cations of the present invention may include, but are not limited to, imidazolium, 1-arylalkylimidazolium such as 1-benzyl-imidazolium, 1-alkylimidazolium such as 1-methylimidazolium, 1-arylalkyl-2-methyl-imidazolium such as 1-benzyl-2-methyl-imidazolium, 1-alkyl-2-methyl-imidazolium such as 1,2-dimethylimidazolium, 1,3-dialkylimidazolium, 1-arylalky-3-alkyl-limidazolium, 1,3-diarylalkylimidazolium, benzimidazolium, imidazolinium, pyridinium, piperidinium, pyrazinium, piperazinium, pyrrolium, pyrrolidinium, pyrazolium, diazolium, triazolium, pyridazinium, tetrazolium, amidinium, guanidinium, oxazolium, oxadiazolium, oxatriazolium, thiazolium, thiadiazolium, thiatriazolium, quaternary pyrazolidine, quaternary pyrrolidones, indolium, isoindolium, quinolinium, isoquinolinium, quinazolinium, quinoxalinium, derivates thereof, and mixture thereof.
The heterocyclic cation is selected from the group consisting of imidazolium, 1-arylalkylimidazolium such as 1-benzyl-imidazolium, 1-alkylimidazolium such as 1-methylimidazolium, 1-arylalkyl-2-methyl-imidazolium such as 1-benzyl-2-methyl-imidazolium, 1,3-dialkylimidazolium, 1-alkyl-2-methyl-imidazolium such as 1,2-dimethylimidazolium, 1-arylalky-3-alkyl-limidazolium, 1,3-diarylalkylimidazolium, and the like, and the mixture thereof.
The cationic mediators can have the formula (I) shown below:
wherein at least one of R1 and R2 group is any of the C≧3 hydrocarbon group, preferably a C12-C18 hydrocarbon group. In case only one of R1 and R2 groups is a C≧3 hydrocarbon group, the other group may be any univalent group such as methyl or benzyl.
The cationic mediator can further comprise the following formula (I′) compound, which is particularly effective in improving the gas barrier property of a polymeric product.
wherein n=12, 13, 14, 15, 16, 17 or 18.
In other exemplary embodiments, the cationic mediator of the invention may be selected from one or more of the following compounds:
The cationic mediators may be prepared by reacting halogenated C≧3 hydrocarbons with heterocyclic cation precursors. Examples of halogenated C≧3 hydrocarbons include octyl chloride, hexadecyl chloride, 1-cinnamyl chloride, 6-chloro-1-hexene, 1-bromodocosane, 1-chlorobutane, and the like. Examples of heterocyclic cation precursors include 1-methylimidazole, 1-benzylimidazole, 1-benzyl-2-methylimidazole, 1,2-dimethylimidazole, 1-dodecyl-2-methyl imidazole, pyrazine, pyrazole, pyridazine, pyridine, imidazolidine, piperazine, piperidine, pyrazolidine, pyrrolidine, the derivatives thereof, and the mixtures thereof. Advantageously, several of these are environmentally friendly green solvents.
Typically, the preparation of these cationic mediators may be conducted at an elevated temperature, such as between about 23° C. to about 500° C., preferably between about 50° C. and about 180° C., more preferably between about 70° C. and about 100° C. During the preparation, the reactants may be mixed with vigorous stirring using e.g. a magnetic stirrer, under the protection of an inert gas such as nitrogen gas. In preferred embodiments, a halogenated C≧3 hydrocarbon may be used to directly dissolve a heterocyclic cation precursor. For example, after heating 1-benzyl imidazole may be dissolved into 1-chlorohexadecane. Typically, the reaction time may last from 0.5 hours to 4 days, preferably from 0.5 day to 3 days, and most preferably from 0.5 days to 2 days. The resultant product may be washed with a suitable solvent such as ethyl acetate, toluene, and/or hexane, for one or more times, followed by vacuum drying at elevated temperature.
The cationic mediator of the invention may work alone or, optionally, in combination with one or more conventional surfactants, in exfoliating clay and forming the nano-composite. Some representative examples of conventional surfactants that can be used include methyl tallow bis-2-hydroxyethyl ammonium salt, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium salt, dimethyl benzyl hydrogenated-tallow ammonium salt, dimethyl dihydrogenated tallow ammonium salt, N-tallow alkyltrimethylenediamine, hydrogenated tallow amine, octadecylamine, octadecylamine and γ-aminopropyltriethoxy silane, polyoxyethylene decycloxypropylamine, n-dodecylpyrrolidone, or their combinations and analogs.
Examples of conventional surfactants include quaternary ammonium surfactants, such as dimethyl ditallow ammonium, trimethyl tallow ammonium, dimethyl dihydrogenated tallow ammonium, methyl ethyl ditallow ammonium, methyl ethyl benzyl tallow ammonium, dimethyl ethyl tallow ammonium, and the like. For example, dimethyl ditallow ammonium may be used first to treat mica, before the cationic mediator of the invention is used.
The cationic mediators can be used to exfoliate a layered material and form useful products such as a nano-composite, or organo-clay, or exfoliated clay, or intercalated clay. “Layered material” means an inorganic material that is in the form of a plurality of adjacent bound layers or plates. Typically, layered materials are those that can give at least one of the cationic mediators access to their interlayer spaces through exchanging, partially or completely, cations with the cationic mediators, a process called intercalation.
In many cases, the layered material is clay, which typically comprises an inorganic phase having layered materials in plates or other shapes with a significantly high aspect ratio. The aspect ratio is defined as the ratio of the largest and smallest dimension of the clay particles.
Exemplary clays include, but are not limited to, mica; synthetic mica; smectites such as montmorillonite (Bentonite), sodium montmorillonite, magnesium montmorillonite, calcium montmorillonite, beidellite, nontronite, hectorite, sodium hectorite, saponite, synthetic saponite, and sauconite; pyrophyllite; glauconites; vermiculites; polygorskines; sepiolites; allophanes; imogolites; talc; fluoro-mica; illites; glauconite; phyllosilicates; volkonskoite; sobockite; stevensite; svinfordite; magadiite; kenyaite; kaolinite; dickite; nacrite; anauxite; ledikite; montronite; silicate; halloysite; metahalloysite; sericite; allophone; serpentine clays; chrysotile; antigorite; attapulgite; sepiolite; palygorskite; Kibushi clay; gairome clay; hisingerite; chlorite; and the like; and mixtures thereof.
Clays may be untreated, or may have been chemically pretreated to make them more compatible with organic materials, as well as the cationic mediators of the invention. For example, a layered silicate clay may be modified with up to about 70 parts by weight of a quaternary ammonium salt surfactant selected from the group consisting of methyl tallow bis-2-hydroxyethyl ammonium halides, methyl tallow bis-2-hydroxyethyl ammonium alkyl sulfates, methyl tallow bis-2-hydroxyethyl ammonium nitrate, methyl tallow bis-2-hydroxyethyl ammonium hydroxide, methyl tallow bis-2-hydroxyethyl ammonium acetate, methyl tallow bis-2-hydroxyethyl ammonium phosphate, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium halides, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium alkyl sulfates, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium nitrate, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium hydroxide, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium acetate, dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium phosphate, dimethyl dehydrogenated-tallow ammonium halides, dimethyl dehydrogenated-tallow ammonium alkyl sulfates, dimethyl dehydrogenated-tallow ammonium nitrate, dimethyl dehydrogenated-tallow ammonium hydroxide, dimethyl dehydrogenated-tallow ammonium acetate, and dimethyl dehydrogenated-tallow ammonium phosphate, among others.
In specific embodiments, mica from Coop Chemical Co. with a trade name ME100 is used as the clay in preparing nano-composites. The aspect ratio of this synthetic mica is over 1000, making it a preferred material for reducing gas permeability of rubber compounds.
In a variety of exemplary embodiments, the weight ratio between the clay and the cationic mediator can be from about 20:80 to about 80:20, preferably from about 40:60 to about 60:40.
The nano-composite comprises a clay and a cationic mediator, which is comprised of a hydrophobic unit and a cationic unit. The clay is exfoliated or intercalated by the cationic mediator.
Typical clays have a layered lamellar structure with a gap of about 0.1 nm between each layer and exchangeable cationic species such as K+, Na+ or Ca2+ on the surface layer and between clay galleries or layers. The cationic species are attached by an ionic interaction with the negatively charged surface of the clay layers, and create a net neutral charge between clay layers.
To exfoliate or intercalate a clay, its lamellar structure is opened to some degree in order to permit the cation exchange reaction to take place with the cationic mediator of the invention. In a variety of embodiments, at least a portion of these exchangeable cationic species are substituted by the cationic mediator.
Any suitable clay exfoliation technique may be used to prepare the nano-composites of the invention. Exemplary clay-exfoliation techniques include, but are not limited to, direct addition method, and slurry method, among others. Direct addition techniques have been described in U.S. Pat. No. 5,334,241 and U.S. Pat. No. 5,616,286, the disclosures of which are incorporated herein by reference in its entirety.
In a slurry method, the clay may be first swelled in water. Swelling takes place because the cations of the clay become solubilized in the water. Presumably, the adjacent clay layers are repulsed by their similar negative charges, resulting in gaps between them. A cationic mediator may then be added to the swollen clay to form an organo-clay or nano-composite. Alternatively, before addition of the cationic mediator, the clay may be pre-exfoliated with a cationic surfactant such as an ammonium salt. In some embodiments, if the cationic mediator used is an ionic liquid, the clay may be directly mixed with the cationic mediator. The cationic mediator is attracted to the negatively charged surface of the clay, keeping the swelling state stable. Preferably, the exfoliated clay will have an average between-layer gap greater than about 0.1 nm, preferably greater than 1.0 nm, and more preferably greater than about 3.0 nm, such as about 5-10 nm. Then, a dewatering step may be taken to dry the exfoliated clay. Optionally, the dried exfoliated clay is washed with an alcohol, such as, but not limited to, isopropanol, propanol, butanol, hexanol, and the like, and the mixture thereof.
The present invention provides a composition comprising (i) a clay, (ii) a cationic mediator comprised of a hydrophobic unit and a cationic unit, and (iii) a polymer, wherein the clay is exfoliated or intercalated by the cationic mediator or by a mixture of the cationic mediator and the polymer.
When a polymer such as rubber is incorporated with the nano-composites the cationic mediator helps to form a relatively homologous morphology. Preferably, however not necessarily, the polymer will penetrate the clay layers and further separate the layers of the clay, based on the possibility that the added polymer and the cationic mediator can attract each other at, e.g., their hydrophobic portions. Preferably, the large molecule size of the cationic mediator and/or the added polymer may counteract any remaining Van der Waals interactions between the clay layers and the clay can be fully or almost fully exfoliated, i.e. separated into discrete layers.
Based on the total weight of the composition (clay+cationic mediator polymer), the amount of the nano-composite (clay+cationic mediator) may be from about 0.1% (wt) to about 90% (wt), preferably from about 1% (wt) to about 50% (wt), and more preferably from about 1% (wt) to about 30% (wt).
Based on the total weight of the composition, the amount of the polymer may be from about 99.9% (wt) to about 10% (wt), preferably from about 99% (wt) to about 50% (wt), and more preferably from about 99% (wt) to about 70% (wt).
Before the nano-composite (clay+cationic mediator) is added to the polymer in forming the composition, at least about 50% (wt) of the clay, preferably at least about 70% (wt) of the clay, and more preferably at least about 90% (wt) of the clay, is exfoliated. After the nano-composite is blended with the polymer at least about 50% (wt) of the clay, preferably at least about 70% (wt) of the clay, and more preferably at least about 90% (wt) of the clay, is exfoliated.
Before the nano-composite is blended with the polymer in forming the composition, the exfoliated clays may have an average between-layer gap greater than about 3 nm, preferably greater than 5 nm, and more preferably greater than about 10 nm. After the nano-composite is blended with the polymer in forming the composition, the exfoliated clays may have an average between-layer gap greater than about 3 nm, preferably greater than 7 nm, and more preferably greater than about 15 nm.
There is no specific limitation on suitable polymers. However, preferred polymers are those that can intercalate between clay layers more effectively with than without the aid of the cationic mediator as demonstrated above. The polymer can have a saturated or unsaturated polyvinyl-type (i.e., carbon-chain) backbone, such as polychloroprene, polyethylene, isobutene-isoprene rubber (butyl rubber, IIR), halogenated butyl rubber (HIIR) such as CIIR and BrIIR, neoprene rubber, nitrile rubber (NBR), 1,2-polybutadiene, polyallene, polybutadiene (butadiene rubber, BR), polyisobutylene (PIB), polyisoprene, 3,4-polyisoprene, poly(methyl acrylate), poly(methyl vinyl ketone), ethylene-propylene elastomer, polystyrene (PS), polyacrylamide, poly(acrylamide oxime), polypropylene (PP), styrene-butadiene rubber (SBR), poly(methyl methacrylate), acrylonitrile-butadiene-styrene terpolymer (ABS), poly(vinyl chloride) (PVC), poly(vinylidene chloride), poly(vinyl pyridine), poly(vinyl pyrrolidone), poly(acrylic anhydride), polyacrylonitrile, styrene-acrylonitrile copolymer (SAN), ethylene-vinyl acetate copolymer (EVA), and the like. Of course, the polymer in the composition can possess a backbone with one or more functional groups such as carbonyl, or a non-carbon element such as N, S or O etc. (i.e. heterochain polymer). Exemplary heterochain polymers include, but are not limited to, polyether such as poly(oxyethylene), polyformadehyde, poly(phenylene oxide) or polyacetaldehyde; polyacrolein, polysulfide, polysulfone, poly(alkylene polysulfide), polyester, polycarbonate, polyphosphate ester, polyamide, polyurea, polyurethane, heterocyclic polymer, polyhydrazides, polyimide, melamine-formaldehyde resin (MF), polysaccharides, phenol-formaldehyde resin (PF), and polyanhydride etc. The polymer can also be an inorganic or inorganic/organic polymer such as polysiloxane, polysilane, carborane polymer, and organometallic polymer etc.
In a variety of exemplary embodiments, the composition of the invention may be used to manufacture articles such as tires. Rubber materials can be made by polymerization or copolymerization of a wide range of monomers, which include, but are not limited to, conjugated dienes such isoprene, butadiene, and the like; alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and the like; vinylidene monomers having one or more terminal vinyl groups; vinyl aromatics such as styrene, α-methylstyrene, t-butylstyrene, bromostyrene, chlorostyrene, fluorostyrene, and the like; α-olefins such as ethylene, propylene, 1-butene, and the like; vinyl halides, such as vinylbromide, chloroethane (vinylchloride), vinylfluoride, vinyliodide, 1,2-dibromoethene, 1,1-dichloroethene (vinylidene chloride), 1,2-dichloroethene, and the like; vinyl esters such as vinyl acetate; α,β-olefinically unsaturated nitriles, such as acrylonitrile and methacrylonitrile; α,β-olefinically unsaturated amides, such as acrylamide, N-methyl acrylamide, N,N-dimethylacrylamide, methacrylamide, and the like.
In some embodiments, vinyl aromatic monomers are incorporated into polydiene rubbers. Such vinyl aromatic monomers are selected so as to be copolymerizable with the conjugated diolefin monomers being utilized. Generally, any vinyl aromatic monomer which is known to polymerize with organolithium initiators can be used. Such vinyl aromatic monomers typically contain from 8 to 20 carbon atoms. Usually, the vinyl aromatic monomer will contain from 8 to 14 carbon atoms. Some examples of vinyl aromatic monomers that can be utilized include styrene, 1-vinyinaphthalene, 2-vinylnaphthalene, α-methylstyrene, 4-phenylstyrene, 3-methylstyrene, t-butylstyrene, and the like.
In a variety of exemplary embodiments, the polymer may be synthesized by emulsion polymerization, solution polymerization, vapor phase polymerization or bulk polymerization. The polymerization process can be conducted as a batch, semi-continuous, or continuous process. Examples of useful rubber materials include butyl rubber, epichlorohydrin rubber, natural rubber, isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, butadiene rubber, styrene-butadiene rubber, acrylic rubber, urethane rubber, fluoro rubber and silicone rubber, among others.
The invention also provides a process for making a rubber article such as tire comprising the steps of (1) kneading (a) a polymer; (b) a nano-composite as described above; and (c) conventional rubber compounding ingredients to produce a mixture; (2) forming an article from the mixture; and (3) vulcanizing the article.
Conventional rubber compounding ingredients may be selected from the group consisting of curing agents, cure accelerators, cure activators, curing aids such as sulfur, processing aids, conventional fillers, fatty acid, zinc oxide, waxes, reinforcing agents, oils, cure retarders, resins including tackifying resins, peptizing agents, extenders, stabilizers, plasticizers, antidegradants, antioxidants, antiozonants, pigments, fragrances, and the mixture thereof.
Specific examples of useful antioxidants and stabilizers include 2-(2′-hydroxy-5′-methylphenyl) benzotriazole, nickel di-butyl-di-thiocarbamate, tris(nonylphenyl)phosphite, 2,6-di-t-butyl-4-methylphenol, and the like. Other representative antioxidants may be, for example, diphenyl-p-phenylenediamine and those disclosed in The Vanderbilt Rubber Handbook(1978), Pages 344 through 346.
Exemplary fillers and pigments include silica, carbon black, titanium dioxide, iron oxide, and the like. In some embodiments, it will be beneficial to utilize a combination of silica and carbon black as the filler. It is to be appreciated that the silica coupler may be used in conjunction with a carbon black (namely, pre-mixed with a carbon black prior to addition to the composition). Talc can also be included as a portion of the filler to reduce cost.
Suitable reinforcing materials are inorganic or organic products of high molecular weight. Examples include glass fibers, asbestos, boron fibers, carbon and graphite fibers, whiskers, quartz and silica fibers, ceramic fibers, metal fibers, natural organic fibers, and synthetic organic fibers. Suitable processing aids can include, for example, aromatic, napthenic, and/or paraffinic processing oils. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates.
The kneading may be conducted in a bulk thermomechanical mixer at a temperature within the range of from about 25° C. to about 250° C., preferably from about 50° C. to about 200° C., more preferably from about 70° C. to about 180° C.
In one embodiment, the nano-composite can be incorporated into butyl rubber by any method known to a skilled artisan, for example, wet/solvent method or a dry mixing method under mild mixing conditions. Such mild mixing conditions are similar to those normally used in butyl rubber mixing. The mixing may be accomplished, for example, by using any integral mixing device such as a Brabender mixer, a twinscrew extruder or a kneader, at a mixing rate of from about 20 to about 200 rpm, at a temperature of about 25° C. to about 250° C. for a period of about 3˜30 minutes. The mixing conditions for example include mixing in a Brabender mixer at about 60 rpm at a temperature of about 70° C. for about three minutes. The vulcanization is conducted in the presence of a sulfur-vulcanizing agent. Examples of suitable sulfur vulcanizing agents include elemental sulfur (free sulfur) or sulfur donating vulcanizing agents, for example, an amine disulfide, polymeric polysulfide or sulfur olefin adducts. Preferably, the sulfur-vulcanizing agent is elemental sulfur.
The polymer composition can be used in tire treads in conjunction with ordinary tire manufacturing techniques. After the tire has been built, it can be vulcanized using a normal tire cure cycle. Tires made in accord with this invention can be cured over a wide temperature range. However, it is generally preferred for the tires of this invention to be cured at a temperature ranging from about 100° C. to about 250° C. It is generally preferred for the cure cycle used to vulcanize the tire to have a duration of about 5 minutes to about 60 minutes with a cure cycle of about 10 minutes to about 40 minutes being preferred.
Experimentation has shown occurrences of improved tensile strength, gas permeability, and cure properties including cure capability and cure time etc. for various rubber compounds including the nano-composite of the present invention.
In one embodiment, the present compounds can be used for tire inner liners, sidewall, tread rubber, hose and containers. The technology can provide good cure systems and low gas permeability materials as well as BR-IIR. In some exemplary embodiments, the butyl rubber composition is useful in the formation of inner liners for automobile tires and in applications requiring good damping characteristics, such as engine mounts. Other uses for the butyl rubber include use in air cushions, pneumatic springs, air bellows, accumulator bags, tire-curing bladders, high temperature service hoses, and conveyor belts for handling hot materials.
The following examples are included to provide additional guidance to those skilled in the art in practicing the claimed invention. The examples provided are merely representative of the work that contributes to the teaching of the present application. Accordingly, these examples are not intended to limit the invention, as defined in the appended claims, in any manner.
103 g of 1-benzylimidazole (Aldrich) and 170 g of 1-chlorohexadecane were added into a 2000 ml three-neck round-bottom flask. A refluxing/cooling condenser was set on the left neck. A thermometer was set on the right neck. A rubber stopper was set on the middle neck. Nitrogen gas was breathed into the liquid phase through the needle from the middle neck. The reactants were mixed with vigorous stirring using a magnetic stirrer. Temperature was kept between 70° C. and 80° C. After heating up, 1-benzyl imidazole dissolved into 1-chlorohexadecane. The solution in the flask turned into red brown solution. The reaction was continued for three days. Then, the product was cooled down. The white product came out of the solution. The product was washed with ethyl acetate five times. After that, it was dried in vacuum for seven hours at about 50° C.
The procedure of Example 1 was repeated with minor changes. 868 g of 1-chlorohexadecane and 570 g of 1-methylimidazole were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 95 to 100° C. After four hours the milk-like solution transferred into homogenous solution. The reaction was continued for three days. Then, the product was washed with ethyl acetate five times and toluene three times. After that, it was dried under vacuum for three days.
The procedure of Example 1 was repeated with minor changes. 51.0 g of 6-chloro-1-hexene (Aldrich) and 35.3 g of 1-methylimidazole (Aldrich) were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After four hours the milk-like solution transferred into a homogenous solution. The reaction was continued for three days. Then, the product was washed with ethyl acetate five times. After that, it was dried under vacuum for three days.
The procedure of Example 1 was repeated with minor change. 427 g of 1-chlorohexadecane (Aldrich) and 280 g of 1-benzyl-2-methyl imidazole (Shikoku Chemicals Corp. 1B2MZ) were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After four hours the milk-like solution transferred into a homogenous solution. The reaction was continued for four days. Then, the product was washed with ethyl acetate five times. After that, it was dried under vacuum for three days.
The procedure of Example 1 was repeated with minor changes. 199 g of 1-cinnamyl chloride (Acros) and 108 g of 1-methyl imidazole (Aldrich) was added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After one hour, the gel appeared. The reaction was continued for four days. Then, the product was washed with ethyl acetate three times. After that, it was dried under vacuum for three days.
The procedure of Example 1 was repeated with minor changes. 269 g of 1-chlorohexadecene (Aldrich) and 256 g of 1-dodecyl-2-methyl imidazole (Shikoku Chemicals Corp. SZ) were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After seven days a white product appeared. The reaction was continued for ten days. Then, the product was washed with toluene two times and n-hexane three times. After that, it was dried in vacuum for three days.
The procedure of Example 1 was repeated with minor changes. 311 g of 1-bromodocosane (Aldrich) and 67 g of 1-methyl imidazole (Aldrich) were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After a day, a black product appeared. The reaction was continued for three days. Then, the product was washed with n-hexane five times. After that, it was dried in vacuum for three days.
The procedure of Example 1 was repeated with minor changes. 549 g of 1-chlorobutane and 487 g of 1-methylimidazole were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After four hours, the milk-like solution transferred into homogenous solution. The reaction was continued for three days. Then, the product was washed with ethyl acetate five times. After that, it was dried in vacuum for three days.
The procedure of Example 1 was repeated with minor changes. 654 g of 1-chlorooctane and 360 g of 1-methylimidazole were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After four hours, the milk-like solution transferred into homogenous solution. After two days, 60 g of 1-chlorooctane was added into the reactor. The reaction was continued for three days. Then, the product was washed with ethyl acetate five times and toluene three times. After that, it was dried in vacuum for three days.
Preparation of Organo-Mica
80 g of the product from Example 1, 40 g of ME100 (Coop Chemical, Co.) and 800 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 50.31% of the inorganic residue.
80 g of the product from Example 2, 40 g of ME100 (Coop Chemical, Co.) and 800 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 48.57% of the inorganic residue.
44 g of Example A and 600 g of isopropanol were mixed together in a bottle and tumbled for four hours. The solution was filtered and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 68.34% of inorganic residue.
60 g of Example B and 600 g of isopropanol were mixed together in a bottle and tumbled for four hours. The solution was filtered, and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 68.89% of inorganic residue.
80 g of the product from Example 8, 40 g of ME100 (Coop Chemical, Co.) and 800 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 85.06% of the inorganic residue.
80 g of the product from Example 9, 40 g of ME100 (Coop Chemical, Co.) and 800 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 79.38% of the inorganic residue.
80 g of the product from Example 3, 40 g of ME100 (Coop Chemical, Co.) and 800 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, it was dried in vacuum. TGA analysis showed that the treated mica contained 84.25% of the inorganic residue.
300 g of the product from Example 4, 150 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered and the treated mica was collected. Then, about 300 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then, the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 67.05% of the inorganic residue.
300 g of the 1-benzyl-2-methyl-3-dodecyl imidazolium chloride (Shikoku Chemicals Corp. SFZ), 150 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 300 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 70.01% of the inorganic residue.
300 g of the Cetyl pyridimium chloride, 150 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 300 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 70.94% of the inorganic residue.
30 g of the product from Example 5, 100 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 200 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 84.05% of the inorganic residue.
300 g of the product from Example 6, 150 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 250 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 64.03% of the inorganic residue.
57 g of the product from Example 7, 100 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 800 g of the treated mica containing water and 1700 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 63.63% of the inorganic residue.
56 g of the 1,3-dibenzyl-2-methyl imidazolium chloride (Shikoku Chemicals Corp. DB2MZ-CI), 100 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 400 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 83.34% of the inorganic residue.
Rubber Mixing
Compounds A-F were prepared according to the formulation and the mixing conditions shown at Tables 1 and 2. Results were summarized at Table 3.
After sheeting, rubber compounds were cured for 30 minutes at 165° C. Gas permeability was measured at 100° C. by GTR-30ABS (GTR TEK Co LTD). Freon gas (F-134a) was used as test gas.
Experimental results shown at Table 3 indicated that the excess surfactants affected badly to gas permeability, cure properties and ring tensile.
Compounds G-N were prepared according to the formulation and the mixing conditions shown at Tables 2, 4 and 5. Results were summarized at Tables 6, 7 and
103 g of 1-benzylimidazole (Aldrich) and 170 g of 1-chlorohexadecane were added into a 2000 ml three-neck round-bottom flask. A refluxing/cooling condenser was set on the left neck. A thermometer was set on the right neck. A rubber stopper was set on the middle neck. Nitrogen gas was breathed into the liquid phase through the needle from the middle neck. The reactants were mixed with vigorous stirring using a magnetic stirrer. Temperature was kept between 70 and 80° C. After heating up, 1-benzyl imidazole dissolved into 1-chlorohexadecane. The solution in the flask turned into red brown solution. The reaction was continued for three days. Then, the product was cooled down. The white product came out the solution. The product was washed with ethylacetate five times. After that, it was dried in vacuum for seven hours at about 50° C.
The procedure of Example 10 was repeated with minor changes. 269 g of 1-chlorohexadecene (Aldrich) and 256 g of 1-dodecyl-2-methyl imidazole (Shikoku Chemicals Corp. SZ) were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After seven days, a white product appeared. The reaction was continued for ten days. Then, the product was washed with toluene two times and n-hexane three times. After that, it was dried in vacuum for three days.
The procedure of Example 10 was repeated with minor changes. 311 g of 1-bromodocosane (Aldrich) and 67 g of 1-methyl imidazole (Aldrich) were added into a 2000 ml three-neck round-bottom flask. The reaction temperature was set from 75 to 80° C. After a day, a black product appeared. The reaction was continued for three days. Then, the product was washed with n-hexane five times. After that, it was dried in vacuum for three days.
Preparation of Organo-Mica
100 g of the product from Example 10, 50 g of ME100 (Coop Chemical, Co.) and 1000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 240 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 67.13% of the inorganic residue.
300 g of the product from Example 11, 150 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 250 g of the treated mica was collected. Then, about 250 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 64.03% of the inorganic residue.
56 g of the 1,3-dibenzyl-2-methyl imidazolium chloride (Shikoku Chemicals Corp. DB2MZ-CI), 100 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered, and the treated mica was collected. Then, about 400 g of the treated mica containing water and 2000 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 83.34% of the inorganic residue.
57 g of the product from Example 12, 100 g of ME100 (Coop Chemical, Co.) and 3000 g of deionized water were mixed together in a bottle and tumbled overnight. The solution was filtered and the treated mica was collected. Then, about 800 g of the treated mica containing water and 1700 g of isopropanol were mixed together and tumbled for four hours. Then the solution was filtered, and the treated mica was collected. After that, it was dried in vacuum. TGA analysis showed that the treated mica contained 63.63% of the inorganic residue.
Compounds O-U were prepared according to the formulation and the mixing conditions shown at Tables 8 and 9. Results were summarized at Table 10.
After sheeting, rubber compounds were cured for 30 mins. at 165° C. Gas permeability was measured at 100° C. by GTR-30ABS (GTR TEK Co LTD). Freon gas (F-134a) was used as test gas.
While the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. As such, further modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as defined by the following claims. All patents and publications cited herein are incorporated herein by reference.
This application claims the benefit of U.S. Provisional Application No. 60/751,787, Filed Dec. 20, 2005, which is incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2493318 | Shonle et al. | Jan 1950 | A |
| 2531396 | Carter et al. | Nov 1950 | A |
| 3972963 | Schwab et al. | Aug 1976 | A |
| 4233409 | Bulkley | Nov 1980 | A |
| 4247434 | Vanderhoff et al. | Jan 1981 | A |
| 4338206 | Hammond et al. | Jul 1982 | A |
| 4463129 | Shinada et al. | Jul 1984 | A |
| 4543403 | Isayama et al. | Sep 1985 | A |
| 4598105 | Weber et al. | Jul 1986 | A |
| 4602052 | Weber et al. | Jul 1986 | A |
| 4659790 | Shimozato et al. | Apr 1987 | A |
| 4665963 | Timar et al. | May 1987 | A |
| 4764572 | Bean, Jr. | Aug 1988 | A |
| 4773521 | Chen | Sep 1988 | A |
| 4788254 | Kawakubo et al. | Nov 1988 | A |
| 4829130 | Licchelli et al. | May 1989 | A |
| 4829135 | Gunesin et al. | May 1989 | A |
| 4837274 | Kawakubo et al. | Jun 1989 | A |
| 4837401 | Hirose et al. | Jun 1989 | A |
| 4870144 | Noda et al. | Sep 1989 | A |
| 4871814 | Gunesin et al. | Oct 1989 | A |
| 4904730 | Moore et al. | Feb 1990 | A |
| 4904732 | Iwahara et al. | Feb 1990 | A |
| 4906695 | Blizzard et al. | Mar 1990 | A |
| 4920160 | Chip et al. | Apr 1990 | A |
| 4942209 | Gunesin | Jul 1990 | A |
| 4956107 | Gutierrez et al. | Sep 1990 | A |
| 5034018 | Gutierrez et al. | Jul 1991 | A |
| 5036138 | Stamhuis et al. | Jul 1991 | A |
| 5075377 | Kawakubo et al. | Dec 1991 | A |
| 5100947 | Puydak et al. | Mar 1992 | A |
| 5112507 | Harrison | May 1992 | A |
| 5120379 | Noda et al. | Jun 1992 | A |
| 5130377 | Trepka et al. | Jul 1992 | A |
| 5169914 | Kaszas et al. | Dec 1992 | A |
| 5178702 | Frerking, Jr. et al. | Jan 1993 | A |
| 5219945 | Dicker et al. | Jun 1993 | A |
| 5227419 | Moczygemba et al. | Jul 1993 | A |
| 5229020 | Gutierrez et al. | Jul 1993 | A |
| 5237015 | Urban | Aug 1993 | A |
| 5238466 | Gutierrez et al. | Aug 1993 | A |
| 5241008 | Hall | Aug 1993 | A |
| 5247021 | Fujisawa et al. | Sep 1993 | A |
| 5256736 | Trepka et al. | Oct 1993 | A |
| 5262502 | Fujisawa et al. | Nov 1993 | A |
| 5290873 | Noda et al. | Mar 1994 | A |
| 5290875 | Moczygemba et al. | Mar 1994 | A |
| 5290878 | Yamamoto et al. | Mar 1994 | A |
| 5308364 | Gutierrez et al. | May 1994 | A |
| 5331035 | Hall | Jul 1994 | A |
| 5336712 | Austgen, Jr. et al. | Aug 1994 | A |
| 5385684 | Gutierrez et al. | Jan 1995 | A |
| 5395902 | Hall | Mar 1995 | A |
| 5399628 | Moczygemba et al. | Mar 1995 | A |
| 5405903 | Van Westrenen et al. | Apr 1995 | A |
| 5421866 | Stark-Kasley et al. | Jun 1995 | A |
| 5436298 | Moczygemba et al. | Jul 1995 | A |
| 5438103 | DePorter et al. | Aug 1995 | A |
| 5447990 | Noda et al. | Sep 1995 | A |
| 5462994 | Lo et al. | Oct 1995 | A |
| 5476521 | Gutierrez et al. | Dec 1995 | A |
| 5496383 | Franz et al. | Mar 1996 | A |
| 5514753 | Ozawa et al. | May 1996 | A |
| 5525639 | Keneko et al. | Jun 1996 | A |
| 5527870 | Maeda et al. | Jun 1996 | A |
| 5530052 | Takekoshi et al. | Jun 1996 | A |
| 5567845 | Franz et al. | Oct 1996 | A |
| 5576372 | Kresge et al. | Nov 1996 | A |
| 5576373 | Kresge et al. | Nov 1996 | A |
| 5580925 | Iwahara et al. | Dec 1996 | A |
| 5587423 | Brandstetter et al. | Dec 1996 | A |
| 5594072 | Handlin, Jr. et al. | Jan 1997 | A |
| 5614579 | Roggeman et al. | Mar 1997 | A |
| 5627252 | De La Croi Habimana | May 1997 | A |
| 5633326 | Patil et al. | May 1997 | A |
| 5665183 | Kresge et al. | Sep 1997 | A |
| 5688856 | Austgen, Jr. et al. | Nov 1997 | A |
| 5707439 | Takekoshi et al. | Jan 1998 | A |
| 5728791 | Tamai et al. | Mar 1998 | A |
| 5733975 | Aoyama et al. | Mar 1998 | A |
| 5739267 | Fujisawa et al. | Apr 1998 | A |
| 5763551 | Wunsch et al. | Jun 1998 | A |
| 5773521 | Hoxmeier et al. | Jun 1998 | A |
| 5777037 | Yamanaka et al. | Jul 1998 | A |
| 5807629 | Elspass et al. | Sep 1998 | A |
| 5811501 | Chiba et al. | Sep 1998 | A |
| 5834563 | Kimura et al. | Nov 1998 | A |
| 5847054 | McKee et al. | Dec 1998 | A |
| 5849847 | Quirk | Dec 1998 | A |
| 5855972 | Kaeding | Jan 1999 | A |
| 5883173 | Elspass et al. | Mar 1999 | A |
| 5891947 | Hall et al. | Apr 1999 | A |
| 5905116 | Wang et al. | May 1999 | A |
| 5936023 | Kato et al. | Aug 1999 | A |
| 5955537 | Steininger et al. | Sep 1999 | A |
| 5986010 | Clites et al. | Nov 1999 | A |
| 5994468 | Wang et al. | Nov 1999 | A |
| 6011116 | Aoyama et al. | Jan 2000 | A |
| 6013699 | Freeman et al. | Jan 2000 | A |
| 6020446 | Okamoto et al. | Feb 2000 | A |
| 6025416 | Proebster et al. | Feb 2000 | A |
| 6025445 | Chiba et al. | Feb 2000 | A |
| 6034164 | Elspass et al. | Mar 2000 | A |
| 6060559 | Feng et al. | May 2000 | A |
| 6087016 | Feeney et al. | Jul 2000 | A |
| 6087456 | Sakaguchi et al. | Jul 2000 | A |
| 6106953 | Zimmermann et al. | Aug 2000 | A |
| 6117932 | Hasegawa et al. | Sep 2000 | A |
| 6121379 | Yamanaka et al. | Sep 2000 | A |
| 6147151 | Fukumoto et al. | Nov 2000 | A |
| 6180693 | Tang et al. | Jan 2001 | B1 |
| 6191217 | Wang et al. | Feb 2001 | B1 |
| 6197849 | Zilg et al. | Mar 2001 | B1 |
| 6204354 | Wang et al. | Mar 2001 | B1 |
| 6225394 | Lan et al. | May 2001 | B1 |
| 6255372 | Lin et al. | Jul 2001 | B1 |
| 6268451 | Faust et al. | Jul 2001 | B1 |
| 6277304 | Wei et al. | Aug 2001 | B1 |
| 6348546 | Hiiro et al. | Feb 2002 | B2 |
| 6359075 | Wollum et al. | Mar 2002 | B1 |
| 6383500 | Wooley et al. | May 2002 | B1 |
| 6420486 | DePorter et al. | Jul 2002 | B1 |
| 6437050 | Krom et al. | Aug 2002 | B1 |
| 6472460 | Okamoto et al. | Oct 2002 | B1 |
| 6486253 | Gilmer et al. | Nov 2002 | B1 |
| 6489378 | Sosa et al. | Dec 2002 | B1 |
| 6573330 | Fujikake et al. | Jun 2003 | B1 |
| 6598645 | Larson | Jul 2003 | B1 |
| 6612351 | Zanzig | Sep 2003 | B1 |
| 6617020 | Zhou et al. | Sep 2003 | B2 |
| 6649702 | Rapoport et al. | Nov 2003 | B1 |
| 6689469 | Wang et al. | Feb 2004 | B2 |
| 6706804 | Resendes | Mar 2004 | B2 |
| 6706813 | Chiba et al. | Mar 2004 | B2 |
| 6727311 | Ajbani et al. | Apr 2004 | B2 |
| 6750297 | Yeu et al. | Jun 2004 | B2 |
| 6759464 | Ajbani et al. | Jul 2004 | B2 |
| 6777500 | Lean et al. | Aug 2004 | B2 |
| 6780937 | Castner | Aug 2004 | B2 |
| 6818693 | Heinrich et al. | Nov 2004 | B2 |
| 6835781 | Kondou et al. | Dec 2004 | B2 |
| 6849680 | Knudson, Jr. et al. | Feb 2005 | B2 |
| 6858665 | Larson | Feb 2005 | B2 |
| 6861462 | Parker et al. | Mar 2005 | B2 |
| 6872785 | Wang et al. | Mar 2005 | B2 |
| 6875818 | Wang | Apr 2005 | B2 |
| 6908958 | Maruyama et al. | Jun 2005 | B2 |
| 7019063 | Wada et al. | Mar 2006 | B2 |
| 7241829 | Chung et al. | Jul 2007 | B2 |
| 7371793 | Gong et al. | May 2008 | B2 |
| 7388033 | Nagy et al. | Jun 2008 | B2 |
| 20020045714 | Tomalia et al. | Apr 2002 | A1 |
| 20020095008 | Heinrich et al. | Jul 2002 | A1 |
| 20020144401 | Nogueroles Vines et al. | Oct 2002 | A1 |
| 20030004250 | Ajbani et al. | Jan 2003 | A1 |
| 20030032710 | Larson | Feb 2003 | A1 |
| 20030124353 | Wang et al. | Jul 2003 | A1 |
| 20030130401 | Lin et al. | Jul 2003 | A1 |
| 20030149185 | Wang et al. | Aug 2003 | A1 |
| 20030198810 | Wang et al. | Oct 2003 | A1 |
| 20030225190 | Borbely et al. | Dec 2003 | A1 |
| 20040059057 | Swisher et al. | Mar 2004 | A1 |
| 20040127603 | Lean et al. | Jul 2004 | A1 |
| 20040143064 | Wang | Jul 2004 | A1 |
| 20040147639 | Tsou et al. | Jul 2004 | A1 |
| 20040198917 | Castner | Oct 2004 | A1 |
| 20040226643 | Yagi et al. | Nov 2004 | A1 |
| 20040249045 | Goodman et al. | Dec 2004 | A1 |
| 20050027057 | Dias et al. | Feb 2005 | A1 |
| 20050027062 | Waddell et al. | Feb 2005 | A1 |
| 20050090611 | Huffer et al. | Apr 2005 | A1 |
| 20050098252 | Muraoka et al. | May 2005 | A1 |
| 20050101743 | Stacy et al. | May 2005 | A1 |
| 20050137288 | Maruo et al. | Jun 2005 | A1 |
| 20050203248 | Zheng et al. | Sep 2005 | A1 |
| 20050215693 | Wang et al. | Sep 2005 | A1 |
| 20050222335 | Jones et al. | Oct 2005 | A1 |
| 20060100339 | Gong et al. | May 2006 | A1 |
| 20060173115 | Wang et al. | Aug 2006 | A1 |
| 20060205916 | Takekoshi et al. | Sep 2006 | A1 |
| 20060235128 | Wang et al. | Oct 2006 | A1 |
| 20070293684 | Fudemoto et al. | Dec 2007 | A1 |
| Number | Date | Country |
|---|---|---|
| 3434983 | Apr 1986 | DE |
| 0143500 | Jun 1985 | EP |
| 0265142 | Apr 1988 | EP |
| 0590491 | Apr 1994 | EP |
| 1099728 | May 2001 | EP |
| 1125927 | Aug 2001 | EP |
| 1134251 | Sep 2001 | EP |
| 1273616 | Jan 2003 | EP |
| 1321489 | Jun 2003 | EP |
| 1279943 | Jan 1989 | JP |
| 1955517 | Aug 1989 | JP |
| 5132605 | May 1993 | JP |
| 08199062 | Aug 1996 | JP |
| 3356001 | Oct 2002 | JP |
| 2003-095640 | Apr 2003 | JP |
| 9104992 | Jul 1991 | WO |
| 9853000 | Nov 1998 | WO |
| 9942518 | Aug 1999 | WO |
| 0187999 | Nov 2001 | WO |
| 02031002 | Jul 2002 | WO |
| 02081233 | Oct 2002 | WO |
| 02100936 | Dec 2002 | WO |
| 03085040 | Oct 2003 | WO |
| 2004058874 | Jul 2004 | WO |
| 2005065430 | Aug 2004 | WO |
| 2005095506 | Oct 2005 | WO |
| 2007149842 | Dec 2007 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20070161734 A1 | Jul 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60751787 | Dec 2005 | US |
