# US 8,541,503 B2 · Polymeric core-shell nanoparticles with interphase region > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,541,503 B2 - Document ID: US8541503B2 - Status: Granted - Kind: B2 - Application number: 12/374,883 - Filed: 2007-07-27 - Published: 2010-01-07 - Granted: 2013-09-24 - Earliest claimed: 2006-07-28 - Assignees: Bridgestone Corporation - Applicants: Xiaorong Wang; Georg Böhm; Sandra Warren; Xiao-Dong Pan; James E. Hall - Inventors: Xiaorong Wang; Georg Böhm; Sandra Warren; Xiao-Dong Pan; James E. Hall - Web page: https://patentgrep.com/patent/US8541503B2 ## CPC - C08L 51/006: {grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds} - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - C08F 257/02: on to polymers of styrene or alkyl-substituted styrenes - C08F 285/00: Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers - C08L 21/00: Compositions of unspecified rubbers - C08L 51/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence)} - C08L 53/005: {Modified block copolymers} - C08K 2201/011: Nanostructured additives - C08L 53/02: of vinyl-aromatic monomers and conjugated dienes - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract A polymeric nanoparticle composition is provided. The nanoparticle may be of a core/shell configuration with an interphase region connecting the core and the shell. The mean average diameter of the polymer nanoparticles may be less than about 250 nm. The size, composition, and/or configuration of the interphase region may be varied to achieve desired physical and/or chemical properties of the resulting polymeric nanoparticles, and of the compositions into which the nanoparticles are compounded. ## Claims ### Claim 1 A method of making a polymeric nanoparticle, comprising: polymerizing at least one shell monomer and a second monomer to form a shell and an interphase region; attaching to the interphase region a core by copolymerizing at least one core monomer different than the at least one shell monomer and at least one crosslinking agent in the presence of the shell; and, crosslinking at least the core with the at least one crosslinking agent, thereby forming the polymeric nanoparticle; wherein the interphase region separates and connects the core and the shell; wherein one of the following steps is performed: a. the shell and interphase region are polymerized by adding the shell monomer, subsequently adding the initiator, and subsequently adding a simultaneous charge of the shell monomer and the second monomer; or b. the core is polymerized through incremental addition, by multiple charges or metering, of simultaneous amounts of core monomer and crosslinking agent. ### Claim 2 (depends on 1) The method of claim 1, wherein the at least one shell monomer is a conjugated diene. ### Claim 3 (depends on 2) The method of claim 2, wherein the conjugated diene is 1,3-butadiene. ### Claim 4 (depends on 1) The method of claim 1, wherein the at least one core monomer is an alkenylbenzene. ### Claim 5 (depends on 4) The method of claim 4, wherein the alkenylbenzene is styrene. ### Claim 6 (depends on 1) The method of claim 1, wherein the at least one crosslinking agent is divinylbenzene. ### Claim 7 (depends on 1) The method of claim 1, wherein the at least one crosslinking agent IS a divinylbenzene mixture comprising at least two benzenes chosen from ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene, ortho-ethylvinylbenzene, meta-ethylvinylbenzene, and para-ethyl vinylbenzene. ### Claim 8 (depends on 1) The method of claim 1, wherein at least one of the core, the shell, and the interphase region comprises at least one additional monomer. ### Claim 9 (depends on 1) The method of claim 1, wherein the at least one interphase region is at least 1 nm. ### Claim 10 (depends on 1) The method of claim 1, wherein the at least one interphase region is from about 1 nm to about 100 nm. ### Claim 11 (depends on 10) The method of claim 10, wherein the at least one interphase region is from about 10 to about 50 nm. ### Claim 12 (depends on 1) The method of claim 1, wherein the hardness modulus of the at least one interphase region is less than the hardness modulus of the core and is greater than the hardness modulus of the shell. ### Claim 13 (depends on 1) The method of claim 1, wherein the volume fraction of the at least one interphase region is from about 1% to about 99%. ### Claim 14 (depends on 1) The method of claim 1, wherein the volume fraction of the at least one interphase region is from about 5% to about 95%. ### Claim 15 (depends on 1) The method of claim 1, wherein the volume fraction of the at least one interphase region is from about 10% to about 80%. ### Claim 16 (depends on 1) The method of claim 1, wherein the nanoparticle is one of spherical, substantially spherical, string, flower, or ellipsoid in shape. ### Claim 17 (depends on 1) The method of claim 1, wherein before crosslinking, the polymers from the second polymerization self-assemble to form micelle structures. ### Claim 18 (depends on 1) The method of claim 1, wherein the second polymerization and the crosslinking occur in the same step. ### Claim 19 A method of making a polymeric nanoparticle, comprising: polymerizing conjugated diene monomers in the presence of at least one anionic initiator to form a shell; attaching to the shell a core and an interphase region by copolymerizing alkenylbenzene monomer and a divinylbenzene mixture in the presence of the shell; and, crosslinking the core and the interphase region with the divinylbenzene mixture, thereby forming the polymeric nanoparticle; wherein the interphase region connects and separates the core and the shell and has a greater crosslinking density than the core, and wherein the divinylbenzene mixture comprises para-divinylbenzene and at least one benzene chosen from ortho-divinylbenzene, meta-divinylbenzene, ortho-ethylvinylbenzene, meta-ethylvinylbenzene, and para-ethylvinylbenzene; wherein one of the following steps is performed: a. the shell and interphase region are polymerized by adding the shell monomer, subsequently adding the initiator, and subsequently adding a simultaneous charge of the shell monomer and the second monomer; or b. the core is polymerized through incremental addition, by multiple charges or metering, of simultaneous amounts of core monomer and crosslinking agent. ### Claim 20 (depends on 1) The method of claim 1 wherein the shell and interphase region are polymerized by adding the shell monomer, subsequently adding the initiator, and subsequently adding a simultaneous charge of the shell monomer and the second monomer. ### Claim 21 (depends on 1) The method of claim 1, wherein the core is polymerized through incremental addition, by multiple charges or metering, of simultaneous amounts of core monomer and crosslinking agent. ### Claim 22 (depends on 19) The method of claim 19 wherein the shell and interphase region are polymerized by adding the shell monomer, subsequently adding the initiator, and subsequently adding a simultaneous charge of the shell monomer and the second monomer. ### Claim 23 (depends on 19) The method of claim 19, wherein the core is polymerized through incremental addition, by multiple charges or metering, of simultaneous amounts of core monomer and crosslinking agent.