# US 2013/0158180 A1 · Processes for making polyolefin nanocomposites > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0158180 A1 - Document ID: US20130158180A1 - Status: Published application - Kind: A1 - Application number: 13/329,792 - Filed: 2011-12-19 - Published: 2013-06-20 - Earliest claimed: 2011-12-19 - Assignees: ExxonMobil Research and Engineering Company - Inventors: Andy Haishung Tsou; Shuji Luo; Donna Jean Crowther; Victor DeFlorio - Web page: https://patentgrep.com/patent/US20130158180A1 ## CPC - C08K 3/36: Silica - C08K 3/32: Phosphorus-containing compounds - C08K 7/14: Glass - C08K 9/06: with silicon-containing compounds - C08L 23/0815: {with aliphatic 1-olefins containing one carbon-to-carbon double bond} - C08K 2003/328: {Phosphates of heavy metals} - Y10T 428/2993: Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.] - Y10T 428/2995: Silane, siloxane or silicone coating - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A process for making a silica-polyolefin composite. The process has the steps of (a) reacting silica particles and an alkyl halosilane in the presence of a solvent and a catalyst to form silane-functionalized silica particles and (b) reacting the silane-functionalized silica particles with a vinyl-terminated polyolefin. There are other processes for making a silica-polyolefin composites. There are other processes for making metal phosphate-polyolefin composites. ## Claims ### Claim 1 A process for making a silica-polyolefin composite, comprising: (a) reacting silica particles and an alkyl halosilane in the presence of a first solvent and a catalyst to form silane-functionalized silica particles and (b) reacting the silane-functionalized silica particles with a vinyl-terminated polyolefin in the presence of a second solvent. ### Claim 2 (depends on 1) The process of claim 1, wherein the olefins of the polyolefin of the vinyl-terminated polyolefin have from 2 to 8 carbons per monomeric unit. ### Claim 3 (depends on 2) The process of claim 2, wherein the vinyl-terminated polyolefin is selected from the group consisting of vinyl-terminated polyethylene and vinyl-terminated polypropylene. ### Claim 4 (depends on 1) The process of claim 1, wherein the alkyl halosilane is selected from the group consisting of dimethylchlorosilane and chloro(methyl)phenylsilane. ### Claim 5 (depends on 4) The process of claim 4, wherein the alkyl halosilane is dimethylchlorosilane. ### Claim 6 (depends on 1) The process of claim 1 wherein the silica and halosilane are present in an equivalent concentration ratio (silica/halosilane) of from 0.05 to 20. ### Claim 7 (depends on 1) The process of claim 1 wherein the silane-functionalized silica and vinyl-terminated polyolefin are present in an equivalent concentration ratio (silica/polyolefin) of from 2 to 100. ### Claim 8 (depends on 1) The process of claim 1, wherein the first solvent is selected from the group consisting of toluene, anisole, xylenes, methyl ethyl ketone, dichloromethane, and chlorobenzene. ### Claim 9 (depends on 1) The process of claim 1, wherein the second solvent is selected from the group consisting of toluene, anisole, xylenes, chlorobenzene, and trichlorobenzene. ### Claim 10 (depends on 1) The process of claim 1, wherein the first solvent and the second solvent are the same. ### Claim 11 (depends on 1) The process of claim 1, wherein step (a) is carried out at a temperature of 20° C. to 150° C. and for a time of 0.5 hour to 72 hours. ### Claim 12 (depends on 1) The process of claim 1, wherein step (b) is carried out at a temperature of 80° C. to 150° C. and for a time of 1 hour to 72 hours. ### Claim 13 A process for making a silica-polyolefin composite, comprising: (a) reacting silica particles and a mercapto alkylalkoxysilane in the presence of a first solvent and a catalyst to form thiol-functionalized silica particles and (b) reacting the thiol-functionalized silica particles with a vinyl-terminated polyolefin in the presence of a second solvent. ### Claim 14 (depends on 13) The process of claim 13, wherein the olefins of the polyolefin of the vinyl-terminated polyolefin have from 2 to 8 carbons per monomeric unit. ### Claim 15 (depends on 14) The process of claim 14, wherein the vinyl-terminated polyolefin is selected from the group consisting of vinyl-terminated polyethylene and vinyl-terminated polypropylene. ### Claim 16 (depends on 13) The process of claim 13, wherein the mercapto alkylalkoxysilane is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane. ### Claim 17 (depends on 16) The process of claim 16, wherein the mercapto alkylalkoxysilane is 3-mercaptopropyltrimethoxysilane. ### Claim 18 (depends on 13) The process of claim 13, wherein the silica and mercapto alkylalkoxysilane are present in an equivalent concentration ratio (silica/mercapto alkylalkoxysilane) of from 0.05 to 20. ### Claim 19 (depends on 13) The process of claim 13, wherein the thiol-functionalized silica and vinyl-terminated polyolefin are present in an equivalent concentration ratio (silica/polyolefin) of from 2 to 100. ### Claim 20 (depends on 13) The process of claim 13, wherein the first solvent is selected from toluene, anisole, xylene(s), methyl ethyl ketone, dichloromethane, chlorobenzene. ### Claim 21 (depends on 13) The process of claim 13, wherein the second solvent is selected from toluene, anisole, xylene(s), chlorobenzene, dichlorobenzene, trichlorobenzene. ### Claim 22 (depends on 13) The process of claim 13, wherein the first solvent and the second solvent are the same. ### Claim 23 (depends on 13) The process of claim 13, wherein the catalyst in step (b) is selected from 2,2′-azoisobutyronitrile (AIBN), dicumylperoxide, benzophenone, thioxanthone, camphorquinone, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,2-dimethoxy-2-phenyl acetophenone, trimethylolpropane tris(2-mercaptoacetate). ### Claim 24 (depends on 13) The process of claim 13, wherein step (a) is carried out at a temperature of 20° C. to 150° C. and for a time from 0.5 hour to 72 hours. ### Claim 25 (depends on 13) The process of claim 13, wherein step (b) is carried out at a temperature of 80° C. to 150° C. and for a time from 1 hour to 72 hours. ### Claim 26 A process for making a silica-polyolefin composite, comprising: (a) reacting silica particles and 1-(chlorosilyl)propyl 2-bromoisobutyrate in the presence of a first solvent and a base to form silylpropyl 2-bromoisobutyrate-functionalized silica particles; (b) polymerizing alkyl acrylate at the surfaces of the silylpropyl 2-bromoisobutyrate-functionalized particles in the presence of a second solvent to form polyacrylate-functionalized silica particles; (c) capping the polyacrylate-functionalized silica particles via reaction with acrylic acid in the presence of a third solvent; (d) reacting vinyl-terminated polyolefin with an alkylchlorosilane in the presence of a fourth solvent and a catalyst to form an alkylchlorosilane-functionalized polyolefin; (e) reacting the alkylchlorosilane-functionalized polyolefin and the polyacrylate-functionalized silica particles in the presence of a fifth solvent. ### Claim 27 (depends on 26) The process of claim 26, wherein the vinyl-terminated polyolefin is selected from the group consisting of vinyl-terminated polyethylene and vinyl-terminated polypropylene. ### Claim 28 (depends on 26) The reaction of claim 26, wherein the 1-(chlorosilyl)propyl 2-bromoisobutyrate is prepared by reacting allyl 2-bromo-2-methylpropionate and alkylchlorosilane in the presence of a catalyst. ### Claim 29 (depends on 26) The reaction of claim 26, wherein the alkylchlorosilane is selected from the group consisting of dimethylchlorosilane, and chloro(methyl)phenylsilane. ### Claim 30 (depends on 29) The reaction of claim 29, wherein the alkylchlorosilane is dimethylchlorosilane. ### Claim 31 (depends on 26) The process of claim 26, wherein the 1-(chlorosilyl)propyl 2-bromoisobutyrate and silica are present in an equivalent concentration ratio (1-(chlorosilyl)propyl 2-bromoisobutyrate/silica) of 0.05 to 20. ### Claim 32 (depends on 26) The process of claim 26, wherein the base is selected from the group consisting of hexamethyldisilazane, pyridine, and imidazole. ### Claim 33 (depends on 26) The process of claim 26, wherein the first solvent is selected from the group consisting of methyl ethyl ketone, toluene, and anisole. ### Claim 34 (depends on 26) The process of claim 26, wherein step (a) is carried out at a temperature of 20° C. to 120° C. and for a time from 0.5 hour to 72 hours. ### Claim 35 (depends on 26) The process of claim 26, wherein the alkyl acrylate is selected from the group consisting of octadecyl acrylate and longer alkyl acrylates. ### Claim 36 (depends on 26) The process of claim 26, wherein the alkyl acrylate and silylpropyl 2-bromoisobutyrate-functionalized silica are present in an equivalent concentration ratio (acrylate/silica) of from 1 to 100. ### Claim 37 (depends on 26) The process of claim 26, wherein second solvent is selected from the group consisting of toluene, anisole, and xylenes. ### Claim 38 (depends on 26) The process of claim 26, wherein step (b) is carried out at a temperature of 50° C. to 120° C. and for a time from 12 hour to 240 hours. ### Claim 39 (depends on 26) The process of claim 26, wherein the acrylic acid and polyacrylate-functionalized silica are present in an equivalent concentration ratio (acrylic acid/silica) of from 0.05 to 2. ### Claim 40 (depends on 26) The process of claim 26, wherein the third solvent is selected from the group consisting of toluene, anisole, and xylenes. ### Claim 41 (depends on 26) The process of claim 26, wherein step (c) is carried out at a temperature of 50° C. to 120° C. and for a time from 1 hour to 72 hours. ### Claim 42 (depends on 26) The process of claim 26, wherein the alkylchlorosilane is selected from the group consisting of chlorodimethylsilane and chloro(methyl)phenylsilane. ### Claim 43 (depends on 26) The process of claim 26, wherein the alkylchlorosilane and vinyl-terminated polyolefin are present in an equivalent concentration ratio (alkylchlorosilane/polyolefin) of from 1 to 100. ### Claim 44 (depends on 26) The process of claim 26, wherein the fourth solvent is selected from the group consisting of toluene, xylenes, chlorobenzene, dichlorobenzene, and trichlorobenzene. ### Claim 45 (depends on 26) The process of claim 26, wherein step (d) is carried out at a temperature of 80° C. to 150° C. and for a time from 1 hour to 72 hours, in the presence of a catalyst. ### Claim 46 (depends on 26) The process of claim 26, wherein the alkylchlorosilane-functionalized polyolefin and polyacrylate-functionalized silica are present in an equivalent concentration ratio (polyolefin/silica) of from 0.05 to 20. ### Claim 47 (depends on 26) The process of claim 26, wherein the fifth solvent is selected from the group consisting of toluene, xylenes, chlorobenzene, dichlorobenzene, and trichlorobenzene. ### Claim 48 (depends on 26) The process of claim 26, wherein step (e) is carried out at a temperature of 80° C. to 150° C. and for a time from 12 hours to 72 hours. ### Claim 49 A process for making a silica-polyolefin composite, comprising reacting silica particles, a mercapto alkylalkoxysilane, and a vinyl-terminated polyolefin together in the presence of a catalyst. ### Claim 50 (depends on 49) The process of claim 49, wherein the olefins of the polyolefin of the vinyl-terminated polyolefin have from 2 to 8 carbons per monomeric unit. ### Claim 51 (depends on 50) The process of claim 50, wherein the vinyl-terminated polyolefin is selected from the group consisting of vinyl-terminated polyethylene and vinyl-terminated polypropylene. ### Claim 52 (depends on 49) The process of claim 49, wherein the mercapto alkylalkoxysilane is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. ### Claim 53 (depends on 49) The process of claim 49, wherein the mercapto alkylalkoxysilane is 3-mercaptopropyltrimethoxysilane. ### Claim 54 (depends on 49) The process of claim 49, wherein the silica and mercapto alkylalkoxysilane are present in an equivalent concentration ratio (silica/mercapto alkylalkoxysilane) of from 0.05 to 20 equivalents; wherein the silica and vinyl-terminated polyolefin are present in an equivalent concentration ratio (silica/polyolefin) of from 1 to 100. ### Claim 55 (depends on 49) The process of claim 49, wherein the process is a reactive extrusion process. ### Claim 56 (depends on 49) The process of claim 49, wherein the catalyst is selected from 2,2′-azoisobutyronitrile (AIBN), dicumylperoxide, benzophenone, thioxanthone, camphorquinone, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,2-dimethoxy-2-phenyl acetophenone, and trimethylolpropane tris(2-mercaptoacetate). ### Claim 57 (depends on 55) The process of claim 55, wherein the process is carried out at a temperature of 120° C. to 220° C. for a time of 0.5 minute to 1 hour in an extruder operating at RPM 30-100. ### Claim 58 A process for making an alpha zirconium phosphate-polyolefin composite, comprising: (a) reacting a vinyl terminated polyolefin with a peroxyacid in the presence of a first solvent to form an epoxy-terminated polyolefin; (b) reacting the epoxy-terminated polyolefin with an amine-terminated polyalkylene glycol in the presence of a second solvent and a catalyst to form a polyalkylene glycol-terminated polyolefin; (c) reacting the polyalkylene glycol-terminated polyolefin and an alpha zirconium phosphate in the presence of a third solvent. ### Claim 59 (depends on 58) The process of claim 58, wherein the olefins of the polyolefin of the vinyl-terminated polyolefin have from 2 to 8 carbons per monomeric unit. ### Claim 60 (depends on 59) The process of claim 59, wherein the vinyl-terminated polyolefin is selected from the group consisting of vinyl-terminated polyethylene and vinyl-terminated polypropylene. ### Claim 61 (depends on 58) The process of claim 58, wherein the peroxyacid is selected from the group consisting of 3-chloroperbenzoic acid and hydrogen peroxide. ### Claim 62 (depends on 61) The process of claim 61, wherein the peroxyacid is 3-chloroperbenzoic acid. ### Claim 63 (depends on 58) The process of claim 58, wherein the peroxyacid and vinyl-terminated polyolefin are present in an equivalent concentration ratio (peroxyacid/polyolefin) of from 1 to 5. ### Claim 64 (depends on 58) The process of claim 58, wherein the first solvent is selected from toluene, xylenes, chlorobenzene, dichlorobenzene, and trichlorobenzene. ### Claim 65 (depends on 58) The process of claim 58, wherein step (a) is carried out at a temperature of 80° C. to 120° C. and for a time from 1 hour to 72 hours. ### Claim 66 (depends on 58) The process of claim 58, wherein the amine-terminated polyalkylene glycol is selected from the group consisting of di- or poly-amine-functionalized polyethylene glycol, di- or multi-amine-functionalized polypropylene glycol, and poly(ethylene-co-propylene)glycol. ### Claim 67 (depends on 58) The process of claim 58, wherein the amine-terminated polyalkylene glycol and epoxy-terminated polyolefin are present in an equivalent concentration ratio (polyalkylene glycol/polyolefin) of from 1 to 100. ### Claim 68 (depends on 58) The process of claim 58, wherein the second solvent is selected from toluene, xylenes, chlorobenzene, dichlorobenzene, and trichlorobenzene. ### Claim 69 (depends on 58) The process of claim 58, wherein step (b) is carried out at a temperature of 80° C. to 150° C. and for a time of 1 hour to 72 hours. ### Claim 70 (depends on 58) The process of claim 58, wherein the polyalkylene glycol-terminated polyolefin and alpha zirconium phosphate are present in an equivalent concentration ratio (polyolefin/ZrP) of from 0.05 to 20. ### Claim 71 (depends on 58) The process of claim 58, wherein the third solvent is selected from toluene and xylenes. ### Claim 72 (depends on 58) The process of claim 58, wherein step (c) is carried out at a temperature of 80° C. to 150° C. and for a time from 1 hour to 72 hours. ### Claim 73 A process for making an alpha zirconium phosphate-polyolefin composite, comprising: (a) reacting an alpha zirconium phosphate with thioamine in the presence of a solvent to form a thioamine-substituted alpha zirconium phosphate and (b) reacting the thioamine-substituted alpha zirconium phosphate with a vinyl-terminated polyolefin in the presence of a catalyst. ### Claim 74 (depends on 73) The process of claim 73, wherein the olefins of the polyolefin of the vinyl-terminated polyolefin have from 2 to 8 carbons per monomeric unit. ### Claim 75 (depends on 74) The process of claim 74, wherein the vinyl-terminated polyolefin is selected from the group consisting of vinyl-terminated polyethylene and vinyl-terminated polypropylene. ### Claim 76 (depends on 73) The process of claim 73, wherein the thioamine is selected from the group consisting of cysteamine, 3-mercapto-N-nonylpropionamide, 11-azido-1-undecanethiol, cysteamine hydrochloride, 3-amino-1-propanethiol hydrochloride, 6-amino-1-propanethiol hydrochloride, and (11-mercaptoundecyl)-N,N,N-trimethylammonium bromide. ### Claim 77 (depends on 76) The process of claim 76, wherein the thioamine is cysteamine. ### Claim 78 (depends on 73) The process of claim 73 wherein the thioamine and alpha zirconium phosphate are present in an equivalent concentration ratio (thioamine/ZrP) of 1 to 100. ### Claim 79 (depends on 73) The process of claim 73, wherein the solvent is selected from water and ethanol. ### Claim 80 (depends on 73) The process of claim 73, wherein step (a) is carried out at a temperature of 20° C. to 50° C. and for a time of 1 hour to 72 hours. ### Claim 81 (depends on 73) The process of claim 73, wherein the vinyl-terminated polyolefin and thioamine-substituted alpha zirconium phosphate are present in an equivalent concentration ratio (polyolefin/ZrP) of from 0.05 to 20. ### Claim 82 (depends on 73) The process of claim 73, wherein step (b) is a reactive extrusion process. ### Claim 83 (depends on 73) The process of claim 73, wherein the catalyst is selected from 2,2′-azoisobutyronitrile (AIBN), dicumylperoxide, benzophenone, thioxanthone, camphorquinone, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,2-dimethoxy-2-phenyl acetophenone, trimethylolpropane tris(2-mercaptoacetate). ### Claim 84 (depends on 83) The process of claim 83, wherein the catalyst is dicumyl peroxide. ### Claim 85 (depends on 73) The process of claim 73, wherein step (b) is carried out at a temperature of 120° C. to 220° C. and for a time of 1 minute to 1 hour in an extruder operating at an RPM of 30 to 100. ### Claim 86 A process for making an alpha zirconium phosphate-polyolefin composite, comprising reacting alpha zirconium phosphate particles, a thioamine, and a vinyl-terminated polyolefin together (a) in the presence of a catalyst in a solvent or (b) in an extruder with the vinyl-terminated polyolefin in a molten state in the presence of a catalyst. ### Claim 87 (depends on 86) The process of claim 86, wherein the vinyl-terminated polyolefin is a vinyl-terminated polyethylene. ### Claim 88 (depends on 86) The process of claim 86, wherein the thioamine is selected from the group consisting of cysteamine, 3-mercapto-N-nonylpropionamide, 11-azido-1-undecanethiol, cysteamine hydrochloride, 3-amino-1-propanethiol hydrochloride, 6-amino-1-propanethiol hydrochloride, and (11-mercaptoundecyl)-N,N,N-trimethylammonium bromide. ### Claim 89 (depends on 88) The process of claim 88, wherein the thioamine is cysteamine. ### Claim 90 (depends on 86) The process of claim 86, wherein the thioamine and alpha zirconium phosphate are present in an equivalent concentration ratio (thioamine/ZrP) of 1 to 100. ### Claim 91 (depends on 86) The process of claim 86, wherein the vinyl-terminated polyolefin and thioamine-substituted alpha zirconium phosphate are present in an equivalent concentration ratio (polyolefin/ZrP) of 0.05 to 20. ### Claim 92 (depends on 86) The process of claim 86, wherein the catalyst is selected from 2,2′-azoisobutyronitrile (AIBN), dicumylperoxide, benzophenone, thioxanthone, camphorquinone, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,2-dimethoxy-2-phenyl acetophenone, trimethylolpropane tris(2-mercaptoacetate). ### Claim 93 (depends on 92) The process of claim 92, wherein the catalyst is dicumyl peroxide. ### Claim 94 (depends on 86) The process of claim 86, wherein the solvent is selected from the group consisting of toluene and xylenes. ### Claim 95 (depends on 86) The process of claim 86, wherein process (a) is carried out at a temperature of 100° C. to 160° C. and for a time of 0.5 minute to 24 hours. ### Claim 96 (depends on 86) The process of claim 86, wherein process (b) is carried out at a temperature of 160° C. to 220° C. and for a time of 0.5 minute to 30 minutes, wherein an extruder is operated at 30 to 500 RPM.