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Patent US7514491 - Functionalized isobutylene polymer-inorganic clay nanocomposites and organic ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA nanocomposite of a halogenated elastomer and an inorganic, exfoliated clay, suitable for use as an air barrier, is disclosed. The halogenated elastomer can be a polymer comprising C4 to C7 isoolefin derived units, para-methylstyrene derived units, and para(halomethylstyrene) derived units, or can be...http://www.google.com/patents/US7514491?utm_source=gb-gplus-sharePatent US7514491 - Functionalized isobutylene polymer-inorganic clay nanocomposites and organic-aqueous emulsion processAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS7514491 B2Publication typeGrantApplication numberUS 11/184,000Publication dateApr 7, 2009Filing dateJul 18, 2005Priority dateJul 18, 2005Fee statusPaidAlso published asCA2617766A1, CA2617766C, CN101287778A, CN101287778B, EP1969038A2, EP1969038B1, US20070015853, WO2008045012A2, WO2008045012A3Publication number11184000, 184000, US 7514491 B2, US 7514491B2, US-B2-7514491, US7514491 B2, US7514491B2InventorsWeiqing Weng, Anthony Jay Dias, Carmen Neagu, Beverly Jean Poole, Caiguo Gong, James Richard Ayers, Kriss Randall Karp, Molly Westermann JohnstonOriginal AssigneeExxonmobil Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (21), Non-Patent Citations (1), Referenced by (9), Classifications (16), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetFunctionalized isobutylene polymer-inorganic clay nanocomposites and organic-aqueous emulsion process
Nanocomposites are polymer systems containing inorganic particles with at least one dimension in the nanometer range. Some examples of these are disclosed in U.S. Pat. Nos. 6,060,549, 6,103,817, 6,034,164, 5,973,053, 5,936,023, 5,883,173, 5,807,629, 5,665,183, 5,576,373, and 5,576,372. Common types of inorganic particles used in nanocomposites are phyllosilicates, an inorganic substance from the general class of so called “nano-clays” or “clays”. Ideally, intercalation should take place in the nanocomposite, wherein the polymer inserts into the space or gallery between the clay surfaces. Ultimately, it is desirable to have exfoliation, wherein the polymer is fully dispersed with the individual nanometer-size clay platelets. Due to the general enhancement in air barrier qualities of various polymer blends when clays are present, there is a desire to have a nanocomposite with low air permeability; especially a dynamically vulcanized elastomer nanocomposite such as used in the manufacture of tires.
As used herein, “multiolefin” refers to any monomer having two or more unsaturations (typically double bonds), for example, a multiolefin may be any monomer comprising two conjugated double bonds such as a conjugated diene such as isoprene.
As used herein, “intercalation” refers to the state of a composition in which a polymer is present between the layers of a platelet filler. As is recognized in the industry and by academia, some indicia of intercalation can be the shifting and/or weakening of detection of X-ray lines as compared to that of original platelet fillers, indicating a larger spacing between vermiculite layers than in the original mineral.
As used herein, “exfoliation” refers to the separation of individual layers of the original inorganic particle, so that polymer can surround or surrounds each particle. In an embodiment, sufficient polymer is present between the platelets such that the platelets are randomly spaced. For example, some indication of exfoliation or intercalation may be a plot showing no X-ray lines or larger d-spacing because of the random spacing or increased separation of layered platelets. However, as recognized in the industry and by academia, other indicia may be useful to indicate the results of exfoliation such as permeability testing, electron microscopy, atomic force microscopy, etc.
A commercial embodiment of a halogenated butyl rubber useful in 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 18 dN·m (ASTM D2084, modified). Another commercial embodiment of a halogenated butyl rubber useful in the present invention 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 an 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.
Rubbers of ethylene and propylene derived units such as EPM and EPDM are also suitable as secondary rubbers. Examples of suitable comonomers in making EPDM are ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, as well as others. These rubbers are described in RUBBER TECHNOLOGY 260-283 (1995). Suitable ethylene-propylene rubbers are commercially available under the VISTALON™ tradename (ExxonMobil Chemical Company, Houston Tex.).
In one embodiment of the invention, a so called semi-crystalline copolymer (“SCC”) is present as the secondary “rubber” component. Useful Semi-crystalline copolymers are described in WO00/69966. Generally, the SCC is a copolymer of ethylene or propylene derived units and α-olefin derived units, the α-olefin having from 4 to 16 carbon atoms in one embodiment, and in another embodiment the SCC is a copolymer of ethylene derived units and α-olefin derived units, the α-olefin having from 4 to 10 carbon atoms, wherein the SCC has some degree of crystallinity. In a further embodiment, the SCC is a copolymer of 1-butene derived units and another α-olefin derived unit, the other α-olefin having from 5 to 16 carbon atoms, wherein the SCC also has some degree of crystallinity. The SCC can also be a copolymer of ethylene and styrene.
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.
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 were 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 of ZnO (Kadox 911 obtained from CP 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 was around 15 mil (38.1 microns). Using an Arbor press, 2-in. (5 cm) 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 vacuum grease. Ten psig (0.07 MPa(g)) nitrogen was kept on one side of the disk, whereas the other side was 10 psig (0.07 MPa(g)) oxygen. Using the oxygen sensor on the nitrogen side, the increase in oxygen concentration was monitored over time. The time required for oxygen to permeate through the disk, or for oxygen concentration on the nitrogen side to reach a constant value, was 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 rate results are given for each sample.
For Examples 1-10, a mixture of BIMS 03-1 (10 weight percent PMS, 0.8 mole percent Br) was dissolved in cyclohexane in a 2-liter reactor. The polymer cement was heated to a temperature between 60 and 80° C., after which an amine was added to the solution. An aqueous slurry of clay and water was prepared separately by stirring the clay and water at room temperature for 12 hours. The aqueous slurry of clay was then added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for a period of time, after which the product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours. The permeability of the dried nanocomposite was then tested as described above.
CLOISITE ® Na+;
CLOISITE ® Na+,
(mm · cc/m2 · day,
Fifty grams of BIMS 03-1 (10 weight percent PMS, 0.8 mole percent Br) were dissolved in 600 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 70° C., and 0.5 grams of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) were added. The reaction was kept at 70° C. for 3 hours. An aqueous slurry of CLOISITE® Na+ (2 g) and water (500 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 weight percent PMS, 0.8 mole percent Br) were dissolved in 600 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 70° C., and 0.5 grams of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) were added. The reaction was kept at 70° C. for 1 hour. An aqueous slurry of CLOISITE® Na+ (106 g of 2.83 wt % slurry from Southern Clay) and water (400 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 weight percent PMS, 0.8 mole percent Br) were dissolved in 600 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 70° C., and 0.5 grams of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) were added. The reaction was kept at 70° C. for 3 hours. An aqueous slurry of CLOISITE® Na+ (4 g) and water (500 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 600 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 70° C., and 0.125 grams of N,N-dimethylhexyl amine (Aldrich) were added. The reaction was kept at 70° C. for 2 hours. An aqueous slurry of CLOISITE® Na+ (2 g) and water (500 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
One hundred grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 75° C., and 2.0 grams of PIB-amine (KEROCOM PIBA 03 from BASF) were added. The reaction was kept at 75° C. for 1 hour. An aqueous slurry of CLOISITE® Na+ (5.7 g) and water (600 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
One hundred grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 75° C., and 0.25 grams of N,N-dimethylhexyl amine (Aldrich) were added. The reaction was kept at 75° C. for 1 hour. An aqueous slurry of CLOISITE® Na+ (5.7 g) and water (600 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
One hundred grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2 Liter reactor. The polymer cement was heated to 75° C., and 1.2 grams of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) were added. The reaction was kept at 75° C. for 1 hour. An aqueous slurry of SOMASIF ME-100 (4 g) and water (600 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
One hundred grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2 Liter reactor. The polymer cement was heated to 75° C., and 1.2 grams of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) were added. The reaction was kept at 75° C. for 1 hour. Aqueous slurry of SOMASIF ME-100 (8 g) and water (600 mL) were prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 600 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 70° C., and 1.5 grams of PIB-amine (KEROCOM PIBA 03 from BASF) were added. The reaction was kept at 70° C. for 1 hour. An aqueous slurry of SOMASIF ME-100 (8 g) and water (600 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for one hour. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
One hundred grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2-Liter reactor. The polymer cement was heated to 75° C., and 1.0 grams of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) were added. The reaction was kept at 75° C. for 1 hour. An aqueous slurry of Kenyaite (8 g) and water (600 mL) was prepared separately by stirring the slurry at room temperature for 12 hours. The aqueous slurry of clay was added to the polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed in the reactor for 30 minutes, and then mixed in a blender at high speed for 2 minutes. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Procedure A: BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) was dissolved in 800 mL of cyclohexane at room temperature. To the solution were added: 200 mL water, clay (CLOISITE® Na+, 3.4 g) and N,N dimethylhexyl amine (Aldrich), as indicated. The solution was heated to 70° C. and stirred for 30 minutes. After cooling to room temperature, the solution was poured out and the solvent was evaporated. The product was dried under vacuum at 100° C. overnight. The permeability of the resulting nanocomposite was tested as described above.
Procedure B: Step 1. Clay (CLOISITE® Na+, 3.4 g) and dodecyltrimethyl ammonium chloride (Arquad® 12-37W, Akzo Nobel) are mixed in 200 mL water at 80° C. for 1.5 hours. The mixture was loaded into the reactor and the mixture container was washed with 80 mL water; the washing solution was also added to the reactor. Step 2. To the reactor was added a polymer solution (80 g BIMS 03-1 in 800 mL cyclohexane). The solution container was washed with 10 mL cyclohexane; the washing solution, and if necessary, N,N-dimethylhexylamine, were added to the reactor. Step 3. The solution was heated to 70° C. and stirred for 30 minutes. After cooling to room temperature, the solution was poured out and the solvent was evaporated. The product was dried under vacuum at 100° C. overnight. The permeability of the resulting nanocomposite was tested as described above and the results are presented in Table 3.
Nanocomposites formed with the emulsifier Arquad ®
12–37 W.
(mm · cc/
12–37 W
m2 · day @
EXXPRO™ (BIMS 03-1, 80 g) and PIBSA (polyisobutylene succinic anhydride) were dissolved in 700 mL cyclohexane in a glass container. The solution was transferred into a mantled reactor. The container was washed with 100 mL of cyclohexane and the washing solution was also added to the reactor. Then, 200 mL water was added with proper pH values (for pH=5, HCl solution was used; for pH=9, NaOH solution was used). After stirring the mixture at 70° C., 3.4 g of CLOISITE® Na+ was added, and the mixture was stirred for 30 minutes. The mixture was poured out and the solvent was evaporated. The sample was dried under vacuum for 24 hours at 100° C. The permeability of the resulting nanocomposite was tested as described above and the results are presented in Table 4.
EXXPRO™ (BIMS 03-1 80 g) and PIBSA 48 (INFINEUM, USA) were dissolved in 700 mL cyclohexane in a glass container. The solution was transferred into a glass reactor at 50° C. The container was washed with 100 mL cyclohexane and the washing solution was added to the reactor. Then 200 mL water were added with proper pH values (for pH=5, HCl solution was used; for pH=9, NaOH solution was used). After the solution was mixed with clay for 30 minutes, the solution was precipitated with isopropanol. The product was dried under vacuum for 24 hours at 100° C. The permeability of the resulting nanocomposite was tested as described above and the results are presented in Table 5.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of hexane in a 2-L reactor. The polymer cement was heated to 70° C., and 0.05 g of dimethylhexylamine (Aldrich) was added. The reaction was kept at 70° C. for 30 min. Aqueous slurry of Cloisite Na+ (145 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 30 min. The aqueous slurry of clay and 1.0 g of Propomeen T/12(Akzo Nobel) were added to polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed for 15 minutes in reactor, and then mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of Exxpro™ polymer (BIMS 03-1: 10 wt % of PMS, 0.85 mol % Br) were dissolved in 1000 mL of hexane in a 2-L reactor. The polymer cement was heated to 70° C., and 0.6 g of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) was added. The reaction was kept at 70° C. for 30 min. Aqueous slurry of Cloisite Na+ (145 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 30 min. The aqueous slurry of clay and 1.0 g of Ethomeen C/12 (Akzo Nobel) were added to polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed for 15 minutes in reactor, and then mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of hexane in a 2-L reactor. The polymer cement was heated to 70° C., and 0.05 g of dimethylhexylamine (Aldrich) was added. The reaction was kept at 70° C. for 30 min. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 30 min. The aqueous slurry of clay and 1.0 g of Ethomeen C/12 (Akzo Nobel) were added to polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed for 15 min in reactor, and then mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of hexane in a 2-L reactor. The polymer cement was heated to 70° C., and 0.6 g of dimethyl hydrogenated tallowalkyl amine (Armeen DMHTD from Akzo Nobel) was added. The reaction was kept at 70° C. for 30 min. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 30 min. The aqueous slurry of clay and 1.0 g of Ethomeen C/12 (Akzo Nobel) were added to polymer cement with vigorous mixing to give a stable emulsion. The emulsion was mixed for 15 min in reactor, and then mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Permeation measurement results for Examples 33–36.
(mm · cc/m2 · day, 40° C.)
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 750 mL of toluene in a 2-L reactor. The polymer cement was heated to 80° C. N-methyldiethanolamine (0.5 g, from Aldrich) was dissolved in 100 mL of isopropanol and added to polymer cement. The reaction was kept at 80° C. for 3 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (225 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 750 mL of toluene in a 2-L reactor. The polymer cement was heated to 80° C. N-methyldiethanolamine (0.25 g, from Aldrich) was dissolved in 100 mL of isopropanol and added to polymer cement. The reaction was kept at 80° C. for 3 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (225 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 800 mL of toluene in a 2-L reactor. The polymer cement was heated to 80° C. N,N-dimethylethanolamine (0.1 g, from Aldrich) was dissolved in 100 mL of isopropanol and added to polymer cement. The reaction was kept at 80° C. for 3 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (225 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 nL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 750 mL of toluene in a 2-L reactor. The polymer cement was heated to 80° C. N,N-dimethylethanolamine (0.05 g, from Aldrich) was dissolved in 100 mL of isopropanol and added to polymer cement. The reaction was kept at 80° C. for 3 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (225 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2-L reactor. The polymer cement was heated to 70° C. Triethanolamine (2 g, from Aldrich) was added to polymer cement. The reaction was kept at 70° C. for 2 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2-L reactor. The polymer cement was heated to 70° C. N-methyldiethanolamine (2 g, from Aldrich) was added to polymer cement. The reaction was kept at 70° C. for 2 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Fifty grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 1000 mL of cyclohexane in a 2-L reactor. The polymer cement was heated to 70° C. N,N-dimethylethanolamine (2 g, from Aldrich) was added to polymer cement. The reaction was kept at 70° C. for 2 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) and water (350 mL) was prepared separately by mixing the slurry with a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The aqueous slurry of clay was added to polymer cement to give an emulsion, and the emulsion was mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 20 min. The product was precipitated by adding 2000 mL of isopropyl alcohol to the polymer/clay emulsion. The resulting polymer/clay nanocomposite was dried in a vacuum oven at 80° C. for 16 hours.
Permeation Results for Examples 37–43.
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.
The cement of Polymer Part 2 was mixed with the emulsion of Part 1 in a high shear mixer 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: 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) was 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) were dissolved in 800 mL of toluene in a 2-liter reactor. 0.8 g of dimethylethanol amine (Aldrich) was 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. 0.5 g of dimethylethanol amine (Aldrich) was 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.
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 80° C. N,N-dimethylethanol amine (0.6 mL, Aldrich) was dissolved in 200 mL of isopropanol and added to the polymer cement. The reaction was kept at 80° C. for 4 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) in water (400 mL) was prepared separately. The aqueous slurry of clay was added to polymer cement and mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min to give a stable emulsion.
Polymer Part 2: 45 g of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) was dissolved in 500 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 toluene in a 2-L reactor. The polymer cement was heated to 80° C. N-methyldiethanol amine (0.8 mL, Aldrich) was dissolved in 200 mL of isopropanol and added to the polymer cement. The reaction was kept at 80° C. for 4 hours. Aqueous slurry of Cloisite Na+ (75 g of 2.83 wt % slurry from Southern Clay) in water (400 mL) was prepared separately. The aqueous slurry of clay was added to polymer cement and mixed in a high-shear mixer (Silverson L4RT) at 6000 RPM for 15 min to give a stable emulsion.
Polymer Part 2: Forty-five grams of BIMS 03-1 (10 wt % of PMS, 0.8 mol % Br) were dissolved in 500 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.
Permeation Rate Measurements for Examples 44–49.
(mm · cc.m2 · day, 40° C.)
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