Source: http://www.google.com/patents/US7501460?dq=5579430
Timestamp: 2016-08-29 03:46:01
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Matched Legal Cases: ['art 1', 'art 1', 'art 1', 'art 1', 'art 1', 'art 2', 'art 2', 'art 1', 'art 1', 'art 2', 'art 2', 'art 1']

Patent US7501460 - Split-stream process for making nanocomposites - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe present invention is a process to produce a nanocomposite of a elastomer and organic clay, e.g. an exfoliated clay, suitable for use as an air barrier. The process can include the steps of: (a) contacting a solution (10) of butyl rubber in an organic solvent with a halogen (12) to form a halogenated...http://www.google.com/patents/US7501460?utm_source=gb-gplus-sharePatent US7501460 - Split-stream process for making nanocompositesAdvanced Patent SearchPublication numberUS7501460 B1Publication typeGrantApplication numberUS 11/183,361Publication dateMar 10, 2009Filing dateJul 18, 2005Priority dateJul 18, 2005Fee statusPaidAlso published asCA2614911A1, CA2614911C, CN101233177A, CN101233177B, EP1907464A2, EP1907464B1, WO2007011456A2, WO2007011456A3Publication number11183361, 183361, US 7501460 B1, US 7501460B1, US-B1-7501460, US7501460 B1, US7501460B1InventorsWeiqing Weng, Caiguo Gong, Anthony Jay Dias, Robert Norman Webb, James Peter StokesOriginal AssigneeExxonmobile Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (20), Non-Patent Citations (2), Referenced by (12), Classifications (17), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetSplit-stream process for making nanocomposites
US 7501460 B1Abstract
A commercial embodiment of the halogenated butyl rubber of the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney Viscosity is from 27 to 37 (ML 1+8 at 125� C., ASTM 1646, modified), and the bromine content is from 1.8 to 2.2 weight percent relative to the Bromobutyl 2222. Further, cure characteristics of Bromobutyl 2222 are as follows: MH is from 28 to 40 dN�m, ML is from 7 to 1,8 dN�m (ASTM D2084, modified). Another commercial embodiment of the halogenated butyl rubber is Bromobutyl 2255 (ExxonMobil Chemical Company). Its Mooney Viscosity is from 41 to 51 (ML 1+8 at 125� C., ASTM 1646, modified), and the bromine content is from 1.8 to 2.2 weight percent. Further, cure characteristics of Bromobutyl 2255 are as follows: MH is from 34 to 48 dN�m, ML is from 11 to 21 dN�m (ASTM D2084, modified). The invention is not limited to the commercial source of any of the halogenated rubber components.
A commercial embodiment of the SBHR useful in the present invention is Bromobutyl 6222 (ExxonMobil Chemical Company), having a Mooney Viscosity (ML 1+8 at 125� C., ASTM 1646, modified) of from 27 to 37, and a bromine content of from 2.2 to 2.6 weight percent relative to the SBHR. Further, cure characteristics of Bromobutyl 6222 are as follows: MH is from 24 to 38 dN�m, ML is from 6 to 16 dN�m (ASTM D2084, modified).
Polybutadiene (BR) rubber is another desirable secondary rubber useful in the composition of the invention. The Mooney viscosity of the polybutadiene rubber as measured at 100� C. (ML 1+4) may range from 35 to 70, from 40 to about 65 in another embodiment, and from 45 to 60 in yet another embodiment. Some commercial examples of these synthetic rubbers useful in the present invention are NATSYN™ (Goodyear Chemical Company), and BUDENE™ 1207 or BR 1207 (Goodyear Chemical Company). A desirable rubber is high cis-polybutadiene (cis-BR). By “high cis-polybutadiene”, it is meant that 1,4-cis polybutadiene is used, wherein the amount of cis component is at least 95%. An example of a high cis-polybutadiene commercial product useful herein is BUDENE™ 1207.
In still another embodiment, the invention provides for a process to improve the air impermeability of an elastomer comprising contacting at least one elastomer solution, and at least one aqueous slurry comprising an unmodified layered filler (such as inorganic clay for one example) to form a nanocomposite, wherein the oxygen transmission rate of the nanocomposite is 150 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compositions or articles as described herein.
Alternatively, the oxygen transmission rate is 150 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein; the oxygen transmission rate is 140 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein; the oxygen transmission rate is 130 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein; the oxygen transmission rate is 120 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein; the oxygen transmission rate is 110 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein; the oxygen transmission rate is 100 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein; or the oxygen transmission rate is 90 mm.cc/[m2.day] at 40� C. or lower as measured on cured nanocomposite compounds as described herein. This invention also relates to
(a) contacting a solution of butyl rubber in an organic solvent with a halogen to form a halogenated butyl rubber solution; (b) neutralizing the halogenated rubber solution with a base to from a neutralized halogenated butyl rubber solution; (c) contacting a first portion of the neutralized halogenated butyl rubber solution with a functionalizing agent to form a functionalized butyl rubber solution; (d) mixing an aqueous slurry of inorganic clay with the functionalized butyl rubber solution to form an emulsion masterbatch comprising a concentrated polymer-clay nanocomposite; (e) blending the masterbatch with a second portion of the halogenated butyl rubber solution to form a mixture comprising a polymer-clay nanocomposite dispersed in the halogenated butyl rubber; (f) recovering the halogenated butyl rubber—clay nanocomposite from the second emulsion.
(a) a process of preparing a halogenated rubber composition comprising: (1) contacting a solution of butyl rubber in an organic solvent with a halogen to form a halogenated butyl rubber solution; (2) neutralizing the halogenated rubber solution with a base to form a neutralized halogenated butyl rubber solution; and (3) removing liquid from the neutralized halogenated butyl rubber solution to recover the halogenated butyl rubber composition; (b) withdrawing a rubber slipstream at a takeoff from the process in (a) upstream from the recovery; (c) admixing clay in the rubber slipstream to form a masterbatch; and (d) introducing the masterbatch into the process in (a) whereby the recovered composition comprises clay nanocomposite.
For each of the following examples, the nanocomposites formed were analyzed for permeability properties using the following method. In certain embodiments, 36 grams of the clay-rubber mixture was loaded into a Brabender� mixer at a temperature of 130-145� C. and mixed with 20 grams of carbon black (N660) for 7 minutes. The mixture was further mixed with a curatives package of 0.33 g stearic acid, 0.33 g ZnO (Kadox 91 lavailable from C. P. Hall (Chicago, Ill.)), and 0.33 g MBTS at 40� C. and 40 rpm for 3 minutes. The resulting rubber compounds were milled, compression molded and cured at 170� C. All specimens were compression molded with slow cooling to provide defect free pads. A compression and curing press was used for rubber samples. Typical thickness of a compression molded pad is around 15 mil (8.1 microns). using an Arbor press, 2″ diameter disks were then punched out from molded pads for permeability testing. These disks were conditioned in a vacuum oven at 60� C. overnight prior to the measurement. The oxygen permeation measurements were done using a Mocon OX-TRAN 2/61 permeability tester at 40� C. under the principle of R. A. Pasternak et. al. in 8 JOURNAL OF POLYMER SCIENCE: PART A-2 467 (1970). Disks thus prepared were mounted on a template and sealed with a vacuum grease. 10 psi (0.07 MPa) nitrogen was kept on one side of the disk, whereas the other side is 10 psi (0.07 MPa) oxygen. Using the oxygen sensor on the nitrogen side, increase in oxygen concentration on the nitrogen side with time could be monitored. The time required for oxygen to permeate through the disk, or for oxygen concentration on the nitrogen side to reach a constant value, is recorded and used to determine the oxygen permeability. Permeability was measured as oxygen transmission rate on a Mocon WX-TRAN 2/61 at 40� C. Where multiple samples were prepared using the same procedure, permeation rates are given for each sample.
Polymer Part 1: Four grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of hexane in a 2-liter reactor. The polymer cement was heated to 75� C. for 2 hours. Aqueous slurry of Cloisite Na+ (2 g) and water was prepared separately. The aqueous slurry of clay was added to the polymer cement with high shear mixing and 1 g of ethoxylated (5)cocoalkylamine (Ethmeen C/15 from Akzo Nobel) was added to give a stable emulsion.
Polymer Part 1: Six grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of hexane in a 2-liter reactor. The polymer cement was heated to 75� C. for 2 hours and 0.8 g of dimethylethanol amine (Aldrich) were added. The reaction was kept at 75� C. for 2 hours. Aqueous slurry of Cloisite Na+ (2 g) and water was prepared separately. The aqueous slurry of clay was added to the polymer cement with high shear mixing and 1 g of ethoxylated (5)cocoalkylamine (Ethmeen C/15 from Akzo Nobel) was added to give a stable emulsion.
Polymer Part 1: Six grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) was dissolved in 800 mL of toluene in a 2-liter reactor. Then, 0.8 g of dimethylethanol amine (Aldrich) were dissolved in 100 mL isopropanol and added to the polymer cement. The reaction was heated to and kept at 80� C. for three hours. Aqueous slurry of Cloisite Na+ (2 g) and water was prepared separately. The aqueous slurry of clay was added to the polymer cement with high shear mixing and 2 g of ethoxylated (5)cocoalkylamine (Ethmeen C/15 from Akzo Nobel) was added to give a stable emulsion. The emulsion was mixed for 15 minutes.
Polymer Part 1: Four grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 800 mL of toluene in a 2-liter reactor. Then, 0.5 g of dimethylethanol amine (Aldrich) were dissolved in 10 mL of isopropanol and added to the polymer cement. The polymer cement was heated to and kept at 80� C. for 3 hours. Aqueous slurry of Cloisite Na+ (2 g) and water was prepared separately. The aqueous slurry of clay was added to the polymer cement with high shear mixing and 2 g of ethoxylated (5)cocoalkylamine (Ethmeen C/15 from Akzo Nobel) was added to give a stable emulsion.
89.6/94.4
96.9/96.5
103.4/99.4 4
84.9/90.0
Polymer Part 1: Five grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 500 mL of toluene in a 2-L reactor. The polymer cement was heated to 70� C. N,N-dimethylethanol amine (1.0 mL, Aldrich) was dissolved in 150 mL of isopropanol and added to the polymer cement. The reaction was kept at 70� C. for 3 hours. A slurry of modified clay Cloisite 20A (4 g, from Southern Clay) and toluene (400 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min. The slurry of clay was added to polymer cement and mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min.
Polymer Part 2: Forty-five grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) was dissolved in 400 mL of toluene. The cement of Polymer Part 2 was mixed with emulsion of Polymer Part 1 in a high-shear mixer (Silverson L4RT) for 15 min. The polymer/clay nanocomposite was precipitated by addition of isopropyl alcohol, and dried in a vacuum oven at 85� C. for 16 hours.
Polymer Part 1: Five grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 500 mL of hexane in a 2-L reactor. The polymer cement was heated to 70� C. N,N-dimethylethanol amine (1.0 mL, Aldrich) was dissolved in 150 mL of isopropanol and added to the polymer cement. The reaction was kept at 70� C. for 3 hours. A slurry of modified clay Cloisite 20A (4 g, from Southern Clay) and hexane (400 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min. The slurry of clay was added to polymer cement and mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min.
Polymer Part 2: Forty-five grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) was dissolved in 400 mL of hexane. The cement of Polymer Part 2 was mixed with emulsion of Polymer Part 1 in a high-shear mixer (Silverson L4RT) for 15 min. The polymer/clay nanocomposite was precipitated by addition of isopropyl alcohol, and dried in a vacuum oven at 85� C. for 16 hours.
95.40; 85.86
95.22; 94.40
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No. 11/184,000, filed Jul. 18, 2005, Weng et al., "Functionalized Isobutylene Polymer-Inorganic Clay Nanocomposites and Organic-Aqueous Emulsion Process".Referenced byCiting PatentFiling datePublication dateApplicantTitleUS8476352Jun 26, 2009Jul 2, 2013Exxonmobil Chemical Patents Inc.Elastomeric compositions comprising hydrocarbon polymer additives having improved impermeabilityUS8598261 *Oct 14, 2008Dec 3, 2013Exxonmobil Chemical Patents Inc.Polymer-clay nanocomposite and process for preparing the sameUS8883906Nov 30, 2010Nov 11, 2014Exxonmobil Chemical Patents Inc.Elastomeric nanocomposites, nanocomposite compositions, and methods of manufactureUS9273154Jan 17, 2011Mar 1, 2016Lanxess International SaProcess for production of halobutyl ionomersUS20100036025 *Feb 11, 2010Rodgers Michael BElastomeric Compositions Comprising Hydrocarbon Polymer Additives Having Improved ImpermeabilityUS20110152422 *Jun 23, 2011Rodgers Michael BElastomeric Nanocomposites, Nanocomposite Compositions, and Methods of ManufactureUS20110250372 *Oct 14, 2008Oct 13, 2011Weiqing WengPolymer-Clay Nanocomposite and Process for Preparing the SameUS20130217833 *Mar 23, 2011Aug 22, 2013Lanxess International SaProcess for the production of rubber ionomers and polymer nanocompositesWO2011089083A1Jan 17, 2011Jul 28, 2011Lanxess International SaProcess for production of halobutyl ionomersWO2011117277A1Mar 23, 2011Sep 29, 2011Lanxess International SaProcess for the production of rubber ionomers and polymer nanocompositesWO2012050657A1Aug 17, 2011Apr 19, 2012Exxonmobil Chemical Patents Inc.Hydrocarbon polymer modifiers for elastomeric compositionsWO2012050667A1Aug 25, 2011Apr 19, 2012Exxonmobil Chemical Patents Inc.Silane-functionalized hydrocarbon polymer modifiers for elastomeric compositions* Cited by examinerClassifications U.S. Classification523/351, 524/446, 524/447, 524/445International ClassificationC08J3/20Cooperative ClassificationC08J2423/00, C08J2323/28, C08J3/226, C08J5/005, C08J3/215, B82Y30/00, C08K9/04European ClassificationB82Y30/00, C08J3/22L, C08J3/215, C08J5/00N, C08K3/34BLegal EventsDateCodeEventDescriptionSep 2, 2005ASAssignmentOwner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXASFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WENG, WEIQING;GONG, CAIGUO;DIAS, ANTHONY JAY;AND OTHERS;REEL/FRAME:016724/0206;SIGNING DATES FROM 20050825 TO 20050830May 19, 2009CCCertificate of correctionAug 28, 2012FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services