WO2001085831A2 - Nanocomposites polymeres fonctionnalises - Google Patents

Nanocomposites polymeres fonctionnalises Download PDF

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Publication number
WO2001085831A2
WO2001085831A2 PCT/US2001/014179 US0114179W WO0185831A2 WO 2001085831 A2 WO2001085831 A2 WO 2001085831A2 US 0114179 W US0114179 W US 0114179W WO 0185831 A2 WO0185831 A2 WO 0185831A2
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Prior art keywords
percent
polymer
layered silicate
weight
cation
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PCT/US2001/014179
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WO2001085831A3 (fr
Inventor
Mladen Ladika
Richard F. Fibiger
Chai-Jing Chou
Anna C. Balazs
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Dow Chemical Co
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Dow Chemical Co
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Priority to AU2001259378A priority Critical patent/AU2001259378A1/en
Publication of WO2001085831A2 publication Critical patent/WO2001085831A2/fr
Publication of WO2001085831A3 publication Critical patent/WO2001085831A3/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with nitrogen-containing compounds, e.g. by nitration

Definitions

  • the instant invention relates to a composite material consisting of a delaminated or exfoliated cation exchanging multi-layered silicate material dispersed in a polymer.
  • Such composite materials are known in the art as a "nanocomposite polymers" when at least one dimension of the exfoliated cation exchanging multi-layered silicate material is less than sixty nanometers.
  • Nanocomposite polymers generally have enhanced mechanical property characteristics vs. conventionally filled polymers, for example, increased tensile or flex modulus together with increased impact toughness.
  • the thickness of a single layer of a delaminated cation exchanging multi-layered silicate material is in the range of one to two nanometers while the length and width of such layer can be in the range of, for example, one hundred to one thousand nanometers.
  • Photomicrographs of nanocomposite polymers usually show a dispersion of multiple layer units of the cation exchanging multi-layered silicate material in the polymer, for example, two, three, four and more layer units dispersed in the polymer. It is generally desired to achieve a high degree of exfoliation of the cation exchanging multi-layered silicate material. Ideally the degree of such exfoliation is so extensive that only single layer units are present.
  • the mechanical property improvement of the polymer composite will usually be no better than if a conventional micron sized filler, for example, talc, is dispersed in the polymer.
  • Cation exchanging multi-layered silicate materials have been treated with organic onium ions to facilitate exfoliation when blended with polar polymers such as polyamide polymers, United States Patent 5,973,053, herein fully incorporated by reference.
  • polar polymers such as polyamide polymers
  • non- polar polymers such as polyethylene or polypropylene
  • a compatibalizer by incorporating more than ten percent of a polar substituted main guest molecule as a compatibalizer, it is possible to achieve an effective degree of exfoliation of the onium treated cation exchanging multi-layered silicate material into the non- polar polymer.
  • the instant invention is a nanocomposite material, comprising: a bulk polymer, the bulk polymer being a non-polar polymer; a cation exchanging multi-layered silicate material dispersed in the bulk polymer, the cation exchanging multi-layered silicate material being exfoliated to one, two, three, four and more than four layer units, the number percent of the one, two, three and four layer units being greater than the number percent of the more than four layer units, the cation exchanging multi-layered silicate content of the nanocomposite material being more than one percent and less than thirty percent respectively by weight; and an organic cation, the organic cation having a pendent polymer chain, the polymer of the pendent polymer chain being miscible with the bulk polymer, the average molecular weight of the pendent polymer chain being more than 3000, the organic cation content of nanocomposite material being more than one tenth of one percent and
  • the instant invention is a process for making a nanocomposite material, comprising the step of blending from 98.9 to 70 parts by weight of a molten bulk polymer, 1 to 30 parts by weight of a cation exchanging multi-layered silicate material and 0.1 to 10 parts by weight of an organic cation to form the nanocomposite material, the bulk polymer being a non-polar polymer, the organic cation having a pendent polymer chain, the polymer of the pendent polymer chain being miscible with the bulk polymer, the average molecular weight of the pendent polymer chain being more than 3000, the multi-layered silicate material being exfoliated to one, two, three, four and more than four layer units, the number percent of the one, two, three and four layer units being greater than the number percent of the more than four layer units .
  • Fig. 1(a) shows a schematic drawing of a monovalent organic cation of the instant invention
  • Fig. 1(b) shows a schematic drawing of a polyvalent organic cation of the instant invention
  • Fig. 1(c) shows a schematic drawing of a polyvalent organic cation of the prior art
  • Fig. 2 shows a drawing of a photomicrograph of a nanocomposite material of the instant invention.
  • the instant invention is a nanocomposite material, comprising: (a) a bulk polymer, the bulk polymer being a non-polar polymer; (b) a cation exchanging multi-layered silicate material dispersed in the bulk polymer, the cation exchanging multi-layered silicate material being exfoliated to one, two, three, four and more than four layer units, the number percent of the one, two, three and four layer units being greater than the number percent of the more than four layer units, the cation exchanging multi-layered silicate material content of the nanocomposite material being more than one percent and less than thirty percent respectively by weight; and (c) an organic cation having a pendent polymer chain, the polymer of the pendent polymer chain being miscible with the bulk polymer, the average molecular weight of the pendent polymer chain being more than 3000, the organic cation content of the nanocomposite material being more than one tenth of one percent and less than ten percent respectively by weight.
  • the term "miscible" in this regard means that the two polymers interpenetrate with each other.
  • the polymer of the pendent polymer chain is the same polymer type as the bulk polymer .
  • the bulk polymer can be a polyolefin such as polyethylene, polypropylene, polyvinylcyclohexane, hydrogenated polystyrene-butadiene-styrene, polypropylene- ethylene or polypropylene-butadiene. It should be understood that such polyolefins may be copolymers with C4 to CIO alpha-olefins, for example, polyethylene may be a copolymer of ethylene and 1-octene.
  • the bulk polymer can also be polystyrene or ethylene-styrene interpolymer or any other non-polar polymer.
  • the preferred polyolefin of the instant invention is polypropylene with or without the addition of maleated polypropylene.
  • the polypropylene nanocomposite material of the instant invention can be blended with a thermoplastic elastomer to prepare the material known in the art as "thermoplastic olefin".
  • cation exchanging multi-layered silicate material is well known in the nanocomposite art and includes phyllosilicate clays and layered silicates .
  • Illustrative of such materials are smectite clay minerals such as montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, and vermiculite clay minerals.
  • This term also includes illite minerals such as ledikite and layered silicates such as magadiite and kenyaite.
  • Preferred cation exchanging multi-layered silicate materials are phyllosilicates of the 2:1 type having a negative charge centers on the layers ranging from 0.25 to 1.5 charge centers per formula unit and a commensurate number of exchangeable cations in the interlayer spaces .
  • Most preferred are smectite clay minerals such as montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, and the layered silicates magadiite, kenyaite, fluoromica and fluorohectorite .
  • cation exchanging layered silicate material also includes the layered fiber silicate materials such as attapulgite, boehmite, imogolite and sepiolite. Such materials exfoliate to produce multi- fiber units (herein multi-layer units) and most preferably they exfoliate to produce single fiber units (herein single layer units) dispersed in the polymer matrix.
  • the organic cation content of nanocomposite material is preferably more than one tenth of one percent and less than ten percent respectively by weight.
  • the molecular weight of the organic cation is preferably in the range of from 5,000 to 300,000.
  • the organic cation can be a polymer having a plurality of cationic sites or a single cation site such as an amine hydrochloride group, a quaternary ammonium group, a sulfonium group or a phosphonium group.
  • the organic cation must have a "pendent polymer chain” .
  • the term "pendent polymer chain” means a polymer chain extending from a cation site that does not terminate with a cation site. Referring now to Fig.
  • a polymer chain 10 having a molecular weight of 3,000 terminating in a nitrogen based cation group such as an amine hydrochloride or a quaternary ammonium group.
  • the polymer chain 10 is a "pendent polymer chain”.
  • Fig. 1(b) therein is shown a polymer chain 11 having a molecular weight of 15,000 terminating adjacent a nitrogen based cation group such as an amine hydrochloride or a quaternary ammonium group and then another polymer chain 12 terminating adjacent another nitrogen based cation group.
  • the polymer chain 11 is a "pendent polymer chain”. Referring now to Fig.
  • polymer chain 13 terminating at each end with a nitrogen based cation group.
  • the polymer chain 13 is not a "pendent polymer chain” and is similar to the organic cation shown in Fig. 5 of United States Patent 5,973,053.
  • the "pendent polymer chain” may be linear or branched.
  • the cation exchanging multi-layered silicate content of the nanocomposite material is preferably more than one percent and less than thirty percent respectively by weight. More preferably, the multi-layered silicate content of the nanocomposite material is more than two percent and less than twenty percent respectively by weight. Even more preferably, the multi-layered silicate content of the nanocomposite is more than three percent and less than ten percent respectively by weight.
  • the cation exchanging multi-layered silicate has been treated with either an onium ion, a nonionic surfactant or hydrogen ion so that the onium ion and/or hydrogen ion is ionically bonded to more than one half of the anionic sites of the cation exchanging multi- layered silicate, the onium ion having a molecular weight of less than 3000.
  • the specific onium ion used is not critical in the instant invention and can be any conventional onium ion as taught in, for example, United States Patent 5,973,053.
  • the cation exchanging multi-layered silicate has been treated with either an onium ion or hydrogen ion so that the onium ion and/or hydrogen ion is ionically bonded to ninety percent or more of the anionic sites of the cation exchanging multi-layered silicate.
  • Such residual cation content of an acid and/or onium treated cation exchanging multi- layered silicate material can be determined by repeated washing with an acid solution followed by analysis of the wash solution for the amount of exchanged residual cation.
  • FIG. 2 therein is shown a drawing reproduction of a photomicrograph of a nanocomposite polymer of the instant invention, showing a cross- sectional representative view of one, two, three, four, five and twelve layer units of exfoliated cation exchanging multi-layered silicate material dispersed in the bulk polymer 14.
  • the number of one, two, three and four layer units shown in Fig. 2 is fifteen.
  • the number of more than four layer units shown in Fig. 2 is three (two five layer units and one twelve layer unit) .
  • the number percent of one, two, three and four layer units is greater than number percent of the more than four layer units (about 83 percent one, two, three and four layer units vs. about 17 percent more than four layer units) .
  • An organic cation of the type shown in Fig. 1(a) can be prepared using the hydroboration procedure outlined by Chung and Rhubright in J. Polymn. Sci., Part A, Polym. Chem., 1993, 31, 2759.
  • An organic cation of the type shown in Fig. 1(b) can be prepared by reacting commercially available maleated polypropylene with N,N- dimethylethylenediamine in the presence of chlorobenzene at 130 degrees Celsius for 4 hours to produce an imine- amine functionalized polypropylene that can then be converted to, for example, the amine hydrochloride form by reaction with hydrochloric acid.
  • the process of the instant invention comprises the step of blending from 98.9 to 70 parts by weight of the molten bulk polymer, from 1 to 30 parts by weight of the cation exchanging multi-layered silicate material and from 0.1 to 10 parts by weight of the organic cation. It should be understood that the process of the preceding sentence is practiced even when one or more components are pre-mixed.
  • the cation exchanging multi- layered silicate material is pre-reacted with the organic cation to form an organic cation treated cation exchanging multi-layered silicate material which is then blended with the molten bulk polymer, or, for example, when the cation exchanging multi-layered silicate material has been treated with either an onium ion or a nonionic surfactant and then is pre-reacted with the organic cation to form an organic cation treated multi-layered silicate material which is then blended with the molten bulk polymer, or, for example, when the molten bulk polymer is blended with an amine terminated polymer and an acid treated cation exchanging multi-layered silicate material (the acid of the acid treated cation exchanging multi-layered silicate material reacting with the amine terminated polymer to produce the organic cation in situ, see Example 6 and 7 below) .
  • EXAMPLE 3 Ninety three and eight tenths grams of polypropylene (Dow grade H705-04Z) , six grams of the bis (octadecyl) dimethyl ammonium bromide treated onium ion treated magadiite and 0.2 gram of amine terminated 15,000 molecular weight polypropylene (the amine being in the hydrochloride form, see Fig. 1(a)) are blended at 180 degrees Celsius using a Haake Brand blender for 5 minutes at 60 rpm.
  • X-ray diffraction and electron microscopic analysis of the resulting blend indicates significant exfoliation of the onium treated magadiite into one, two, three, four and more than four layer units, the number percent of the one, two, three and four layer units being greater than the number percent of the more than four layer units .
  • X-ray diffraction and electron microscopic analysis of the resulting blend indicates significant exfoliation of the onium treated magadiite into one, two, three, four and more than four layer units, the number percent of the one, two, three and four layer units being greater than the number percent of the more than four layer units.
  • EXAMPLE 7 Ninety five grams of polypropylene (Dow grade H705- 04Z) , three grams of acid treated montmorillonite (Fluka grade K 20) and two grams of amine terminated 15,000 molecular weight polypropylene are blended at 180 degrees Celsius using a Haake Brand blender for 5 minutes at 60 rpm. Electron microscopic analysis of the resulting blend indicates significant exfoliation of the onium treated magadiite into one, two, three, four and more than four layer units, the number percent of the one, two, three and four layer units being greater than the number percent of the more than four layer units . The resulting blend is then formed into test bars. The flex modulus of the resulting blend using ASTM method D-790 is 1,537,600 KPa (223,000 pounds per square inch) . The impact toughness of the resulting blend using ASTM method is 2.06 joules (18.2 inch pounds) .
  • COMPARATIVE EXAMPLE 4 Thirty and six tenths grams of polypropylene (Amoco grade 9934) and five and four tenths grams of onium ion treated sepiolite (bis (hydrogenated tallow) dimethyl ammonium chloride treated) are blended at 180 degrees Celsius using a Haake Brand blender for 5 minutes at 150 rpm. An electron microscopic analysis of the resulting blend indicates little exfoliation of the onium treated sepiolite. The resulting blend is then formed into test bars. The tensile modulus (using a test method ASTM D 638) of the resulting blend is 2,9167,000 KPa (423,000 pounds per square inch) .
  • An electron microscopic analysis of the resulting blend indicates substantial exfoliation of the onium treated sepiolite into one, two, three, four, and more than four fiber units, the number percent of one, two, three, and four fiber units being greater than the number percent of the more than four fiber units.
  • the resulting blend is then formed into test bars.
  • the tensile modulus (using a test method ASTM D 638) of the resulting blend is 3,399,000 Kpa (493,000 pounds per square inch) .
  • amine terminated 15,000 molecular weight polypropylene (the amine being in the hydrochloride form, see Fig. 1 (a)) are blended at 185 degrees Celsius using a Haake Brand blender for 5 minutes at ' 150 rpm.
  • An electron microscopic analysis of the resulting blend indicates substantial exfoliation of the onium treated sepiolite into one, two, three, four, and more than four fiber units, the number percent of one, two, three, and four fiber units being greater than the number percent of the more than four fiber units .
  • the resulting blend is then formed into test bars.
  • the tensile modulus (using a test method ASTM D 638) of the resulting blend is 3,599,00 KPa (522,000 pounds per square inch) .
  • COMPARATIVE EXAMPLE 7 Thirty two and six tenths grams of polypropylene (Amoco grade 9934) and seven and four tenths grams of onium ion treated fluormica (bis (hydrogenated tallow) dimethyl ammonium chloride treated) are blended at 180 degrees Celsius using a Haake Brand blender for 5 minutes at 100 rpm. The resulting blend is then formed into test bars. The flex modulus (using a test method ASTM D 790) of the resulting blend is 2,475,000 KPa (359,000 pounds per square inch) .
  • COMPARATIVE EXAMPLE 8 Thirty two and six tenths grams of polypropylene (Dow grade DC 112) and seven and four tenths grams of onium ion treated fluormica (bis (hydrogenated tallow) dimethyl ammonium chloride treated) are blended at 180 degrees Celsius using a Haake Brand blender for 5 minutes at 100 rpm. The resulting blend is then formed into test bars. The flex modulus (using a test method ASTM D 790) of the resulting blend is 1,538,000 KPa (223,000 pounds per square inch) .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne un matériau nanocomposite renfermant divers composants indispensables. Le premier composant est constitué de 98,9 à 70 parties en poids d'un polymère en masse, ledit polymère étant un polymère non polaire, tel que le polyéthylène ou le polypropylène. Le deuxième composant est constitué de 1 à 30 parties en poids d'un matériau silicaté multicouche échangeur de cations, tel qu'une montmorillonite ou une sépiolite traitée à l'acide ou à l'ammonium quaternaire, dispersé dans le polymère en masse, ledit matériau silicaté multicouche échangeur de cations comportant plusieurs sites anioniques, et ledit matériau silicaté multicouche étant exfolié en une, deux, trois, quatre couches, voire plus, le pourcentage en nombre des une, deux, trois et quatre couches étant supérieur au pourcentage en nombre des couches au-delà de quatre. Le troisième composant est constitué de 0,1 à 10 parties en poids d'un cation organique, tel qu'un polyéthylène ou un polypropylène à terminaison à groupe amine. Ledit cation organique comporte une chaîne polymère latérale dont le polymère est miscible avec le polymère en masse, le poids moléculaire moyen de la chaîne polymère latérale étant supérieur à 3000. Le matériau nanocomposite selon l'invention s'obtient par le mélange du polymère en masse fondu avec le matériau silicaté multicouche échangeur de cations et le cation organique.
PCT/US2001/014179 2000-05-05 2001-05-03 Nanocomposites polymeres fonctionnalises Ceased WO2001085831A2 (fr)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006062572A1 (fr) 2004-12-03 2006-06-15 Exxonmobil Chemical Patents Inc. Charges stratifiees multicouches modifiees et utilisation dans des compositions nanocomposites
US7288585B2 (en) 2003-06-24 2007-10-30 Ciba Specialty Chemicals Corp. Acrylic dispersing agents in nanocomposites
US7408000B2 (en) 2004-03-26 2008-08-05 Sanyo Chemical Industries, Ltd. Dispersant or coatability improver
US7498381B1 (en) 2006-08-02 2009-03-03 Exxonmobil Chemical Patents Inc. Low permeability elastomeric-metal phosphate nanocomposites
US7501460B1 (en) 2005-07-18 2009-03-10 Exxonmobile Chemical Patents Inc. Split-stream process for making nanocomposites
US7514491B2 (en) 2005-07-18 2009-04-07 Exxonmobil Chemical Patents Inc. Functionalized isobutylene polymer-inorganic clay nanocomposites and organic-aqueous emulsion process
US7632886B2 (en) 2005-12-02 2009-12-15 Exxonmobil Chemical Patents Inc. Elastomer nanocomposites comprising isobutylene and multifunctional oligomers
US7638573B2 (en) 2006-04-07 2009-12-29 Exxonmobil Chemical Patents Inc. Butyl nanocomposite via low Mw elastomer pre-blend
US7837899B2 (en) 2003-03-03 2010-11-23 Polymers Australia Pty. Ltd. Dispersing agents in nanocomposites
US7905263B2 (en) 2004-12-29 2011-03-15 Exxonmobil Chemical Patents Inc. Processable filled, curable halogenated isoolefin elastomers
US7906600B2 (en) 2004-12-29 2011-03-15 Exxonmobil Chemical Patents Inc. Processable filled, curable halogenated isoolefin elastomers
US8048947B2 (en) 2005-11-08 2011-11-01 Exxonmobil Chemical Patents Inc. Nanocomposites and methods for making the same
US8080613B2 (en) 2002-11-08 2011-12-20 Advanced Polymerik Pty Ltd Process for the preparation of polyolefin nanocamposites
US8110626B2 (en) 2005-09-27 2012-02-07 Advanced Polymerik PTY. Limited Dispersing agents in composites
WO2014099219A1 (fr) * 2012-12-17 2014-06-26 Dow Global Technologies Llc Structure à plusieurs couches et procédé d'étanchéité ou de mise en forme au moyen d'une structure à plusieurs couches
US8765863B2 (en) 2007-11-14 2014-07-01 Exxonmobil Chemical Patents Inc. Triethylamine functionalized elastomer in barrier applications

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472344A3 (en) * 1990-08-14 1992-09-30 Ube Industries, Ltd. Reinforced elastomer composition and polypropylene composition containing same
US6060549A (en) * 1997-05-20 2000-05-09 Exxon Chemical Patents, Inc. Rubber toughened thermoplastic resin nano composites
US5910523A (en) * 1997-12-01 1999-06-08 Hudson; Steven David Polyolefin nanocomposites

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8080613B2 (en) 2002-11-08 2011-12-20 Advanced Polymerik Pty Ltd Process for the preparation of polyolefin nanocamposites
US7837899B2 (en) 2003-03-03 2010-11-23 Polymers Australia Pty. Ltd. Dispersing agents in nanocomposites
US7288585B2 (en) 2003-06-24 2007-10-30 Ciba Specialty Chemicals Corp. Acrylic dispersing agents in nanocomposites
US7408000B2 (en) 2004-03-26 2008-08-05 Sanyo Chemical Industries, Ltd. Dispersant or coatability improver
US7825181B2 (en) 2004-12-03 2010-11-02 Exxonmobil Chemical Patents Inc. Modified layered fillers and their use to produce nanocomposite compositions
WO2006062572A1 (fr) 2004-12-03 2006-06-15 Exxonmobil Chemical Patents Inc. Charges stratifiees multicouches modifiees et utilisation dans des compositions nanocomposites
US7906600B2 (en) 2004-12-29 2011-03-15 Exxonmobil Chemical Patents Inc. Processable filled, curable halogenated isoolefin elastomers
US7905263B2 (en) 2004-12-29 2011-03-15 Exxonmobil Chemical Patents Inc. Processable filled, curable halogenated isoolefin elastomers
US7501460B1 (en) 2005-07-18 2009-03-10 Exxonmobile Chemical Patents Inc. Split-stream process for making nanocomposites
US7514491B2 (en) 2005-07-18 2009-04-07 Exxonmobil Chemical Patents Inc. Functionalized isobutylene polymer-inorganic clay nanocomposites and organic-aqueous emulsion process
US8110626B2 (en) 2005-09-27 2012-02-07 Advanced Polymerik PTY. Limited Dispersing agents in composites
US8048947B2 (en) 2005-11-08 2011-11-01 Exxonmobil Chemical Patents Inc. Nanocomposites and methods for making the same
US7632886B2 (en) 2005-12-02 2009-12-15 Exxonmobil Chemical Patents Inc. Elastomer nanocomposites comprising isobutylene and multifunctional oligomers
US7638573B2 (en) 2006-04-07 2009-12-29 Exxonmobil Chemical Patents Inc. Butyl nanocomposite via low Mw elastomer pre-blend
US7498381B1 (en) 2006-08-02 2009-03-03 Exxonmobil Chemical Patents Inc. Low permeability elastomeric-metal phosphate nanocomposites
US8765863B2 (en) 2007-11-14 2014-07-01 Exxonmobil Chemical Patents Inc. Triethylamine functionalized elastomer in barrier applications
WO2014099219A1 (fr) * 2012-12-17 2014-06-26 Dow Global Technologies Llc Structure à plusieurs couches et procédé d'étanchéité ou de mise en forme au moyen d'une structure à plusieurs couches
US9427938B2 (en) 2012-12-17 2016-08-30 Dow Global Technologies Llc Multi-layered structure and a method of sealing or shaping using a multi-layered structure

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WO2001085831A3 (fr) 2002-05-23

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