# US 2010/0168334 A1 · Polymeric Compositions and Polymerization Initiators Using Photo-Peroxidation Process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2010/0168334 A1 - Document ID: US20100168334A1 - Status: Published application - Kind: A1 - Application number: 12/345,525 - Filed: 2008-12-29 - Published: 2010-07-01 - Earliest claimed: 2008-12-29 - Assignees: Fina Technology, Inc. - Inventors: Olga Khabashesku - Web page: https://patentgrep.com/patent/US20100168334A1 ## CPC - C08F 2/50: with sensitising agents - C01B 15/022: Preparation from organic compounds - C08F 279/02: on to polymers of conjugated dienes - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} ## Abstract A rubber-modified polymeric composition having predominately core-shell morphology is disclosed. The rubber-modified polymeric composition can be a polystyrene comprising styrene, polybutadiene, and a high-grafting initiator formed by contacting singlet oxygen with an olefin containing an allylic hydrogen or a diene to form a hydroperoxide or peroxide. The singlet oxygen can be formed by contacting ground state oxygen with a photo catalyst, such a photosensitive dye exposed to light. ## Claims ### Claim 1 A rubber-modified polymeric composition comprising: a matrix phase of a polymer of an aromatic monomer; and a grafted rubber copolymer; the grafted rubber copolymer formed from the grafting of peroxides along a rubber copolymer chain by a high-grafting initiator; the initiator formed by contacting ground-state oxygen with an activated donor to produce singlet oxygen and contacting said singlet oxygen with an olefin containing either an allylic hydrogen or a diene, such that the olefin forms a high-grafting peroxide initiator. ### Claim 2 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the composition exhibits predominately core-shell morphology. ### Claim 3 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the monovinyl aromatic monomer is styrene or a substituted styrene compound. ### Claim 4 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the grafted rubber polymer is polybutadiene or a polymer of a conjugated 1,3-diene. ### Claim 5 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the grafted rubber polymer is predominately 1,4-cis-polybutadiene. ### Claim 6 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the activated donor is obtained by exposing a photosensitive dye to light with a wavelength of from 300 nm to 1400 nm. ### Claim 7 (depends on 6) The rubber-modified polymeric composition of claim 6, wherein the photosensitive dye may be selected from the following: xanthene dye, thiazine dye, acridine dye, or combinations thereof. ### Claim 8 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the olefin is a petrochemically-derived hydrocarbon, selected from the following: 1,3 cyclohexadiene, 1-methyl-1-cyclohexadiene, indene, and dimethyl-2,4,6-octacyclotriene. ### Claim 9 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the olefin is derived from a biorenewable source, and is selected from the following: alpha-terpinene, citronellol, myrcene, limonene, 3-carene, alpha-pinene, soybean oil, and farnesene. ### Claim 10 (depends on 1) The rubber-modified polymeric composition of claim 1, wherein the activated donor is housed in a transparent dry column, through which oxygen may be passed, to form singlet oxygen. ### Claim 11 (depends on 10) The rubber-modified polymeric composition of claim 10, wherein the dry column is connected to a reactor containing styrene, polybutadiene, and an olefin containing either an allylic hydrogen or a diene, such that singlet oxygen formed in the dry column passes into the reactor. ### Claim 12 (depends on 1) An article made from the rubber-modified polymeric composition of claim 1. ### Claim 13 A method for making a rubber-modified polymeric composition comprising: preparing a polymerizable mixture comprising monovinyl aromatic monomer, rubber copolymer, and a high-grafting initiator; and polymerizing the mixture under reaction conditions; wherein the high-grafting initiator is formed by contacting ground-state oxygen with an activated donor to produce singlet oxygen and contacting said singlet oxygen with an olefin containing either an allylic hydrogen or a diene, such that the olefin forms a high-grafting peroxide initiator; wherein the high-grafting initiator facilitates grafting of monovinyl aromatic polymer along the rubber copolymer chain. ### Claim 14 (depends on 13) The method of claim 13, wherein the rubber-modified polymeric composition exhibits predominately core-shell morphology. ### Claim 15 (depends on 13) The method of claim 13, wherein the monovinyl aromatic monomer is styrene or a substituted styrene compound. ### Claim 16 (depends on 13) The method of claim 13, wherein the grafted rubber polymer is polybutadiene or a polymer of a conjugated 1,3-diene. ### Claim 17 (depends on 13) The method of claim 13, wherein the rubber-modified polymeric composition is a high-impact polystyrene. ### Claim 18 (depends on 13) The method of claim 13, wherein the polybutadiene is predominately 1,4-cis-polybutadiene. ### Claim 19 (depends on 13) The method of claim 13, wherein the activated donor molecule is obtained by exposing a photosensitive dye to light with a wavelength of from 300 nm to 1400 nm. ### Claim 20 (depends on 19) The method of claim 19, wherein the photosensitive dye may be selected from the following: xanthene dye, thiazine dye, acridine dye, or combinations thereof. ### Claim 21 (depends on 13) The method of claim 13, wherein the activated donor is housed in a transparent dry column, through which oxygen may be passed, to form singlet oxygen. ### Claim 22 (depends on 21) The method of claim 21, wherein the dry column is connected to a reactor containing styrene and polybutadiene, such that singlet oxygen formed in the dry column passes into the reactor. ### Claim 23 (depends on 13) An article made from the method of claim 13. ### Claim 24 A high-impact polystyrene comprising styrene and polybutadiene having predominately core-shell morphology; wherein the polybutadiene is highly-grafted by contacting ground-state oxygen with an activated donor to produce singlet oxygen; and contacting said singlet oxygen with polybutadiene to form hydroperoxides along the polybutadiene chain. ### Claim 25 (depends on 24) The high-impact polystyrene of claim 24, wherein the activated donor molecule is obtained by exposing a photosensitive dye to light with a wavelength of from 300 nm to 1400 nm. ### Claim 26 (depends on 25) The high-impact polystyrene of claim 25, wherein the photosensitive dye may be selected from the following: xanthene dye, thiazine dye, acridine dye, or combinations thereof. ### Claim 27 (depends on 25) The high-impact polystyrene of claim 25, wherein the activated donor is housed in a transparent dry column, through which oxygen may be passed, to form singlet oxygen. ### Claim 28 (depends on 27) The high-impact polystyrene of claim 27, wherein the dry column is connected to a reactor containing styrene and polybutadiene, such that singlet oxygen formed in the dry column passes into the reactor.