# US 10,865,275 B2 · Copolymerization of carbon dioxide and cyclic monomers to form polycarbonates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,865,275 B2 - Document ID: US10865275B2 - Status: Granted - Kind: B2 - Application number: 16/555,052 - Filed: 2019-08-29 - Published: 2019-12-26 - Granted: 2020-12-15 - Earliest claimed: 2015-06-15 - Assignees: King Abdullah University of Science and Technology - Applicants: King Abdullah University of Science and Technology - Inventors: Yves Gnanou; Xiaoshuang Feng; Dongyue Zhang; Yahya Alzahrany; Senthil Boopathi; Nikolaos Hadjichristidis - Web page: https://patentgrep.com/patent/US10865275B2 ## CPC - C08G 64/34: and cyclic ethers - C08G 64/32: using carbon dioxide - C08G 81/00: Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42}) - C08K 5/057: Metal alcoholates {(metal enolates C08K5/0091)} - C08K 5/19: Quaternary ammonium compounds - C08K 5/53: bound to oxygen and to carbon only - C08K 5/5399: Phosphorus bound to nitrogen - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract Embodiments of the present disclosure describe initiating systems comprising an activator and an initiator, wherein the activator includes an alkyl borane or alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen. Embodiments of the present disclosure further describe methods of making a polycarbonate comprising contacting a cyclic monomer and carbon dioxide in the presence of an activator and an initiator to form a polycarbonate, wherein the catalyst is one or more of an alkyl borane and alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen. ## Claims ### Claim 1 A method of making a polycarbonate, comprising: contacting an epoxide monomer and carbon dioxide in the presence of an activator and an initiator to form a polycarbonate, wherein the activator is trialkyl borane, wherein the initiator includes an alkali metal and an organic cation. ### Claim 2 (depends on 1) The method of claim 1, wherein the epoxide monomer is one or more of propylene oxide, cyclohexene oxide, ethylene oxide, styrene oxide, butyl glycidyl ether, and allyl glycidyl ether. ### Claim 3 (depends on 1) The method of claim 1, wherein the activator is one or more of triethyl borane, trimethyl borane, triisobutylborane, and triphenylborane. ### Claim 4 (depends on 1) The method of claim 1, wherein the alkali metal is one or more of lithium, potassium, and sodium. ### Claim 5 (depends on 1) The method of claim 1, wherein the organic cation is one or more of phosphazenium, ammonium, and phosphonium. ### Claim 6 (depends on 1) The method of claim 1, wherein the initiator is characterized by the formula: R-O−{−Li/t-Bu-PY}, where R-O− is an anion of any lithium alkoxide, P is a phosphazene, and Y is 1, 2, or 4. ### Claim 7 (depends on 1) The method of claim 1, wherein the initiator is characterized by the formula: R-C−{+Li/t-Bu-PY}, R-C− is any alkyl, P is a phosphazene, and Y is 1, 2, or 4. ### Claim 8 (depends on 1) The method of claim 1, wherein the initiator is characterized by the formula: X−{+Li/t-Bu-PY}, where X is one or more of Cl, Br, F, and CO3, P is a phosphazene, and Y is 1, 2, or 4. ### Claim 9 (depends on 1) The method of claim 1, wherein the initiator is one or more of n-Bu−{+Li/t-Bu-P4}, n-Bu−{+Li/t-Bu-P2}, sec-Bu−{+Li/t-Bu-P4}, and Cl−{+Li/t-Bu-P4} where P is a phosphazene. ### Claim 10 (depends on 1) The method of claim 1, wherein the polycarbonate is an alternating copolymer of one or more of poly(cyclohexene carbonate), poly(propylene carbonate), poly(ethylene carbonate), poly(styrene carbonate), or poly(tert-butyl carbonate). ### Claim 11 A method of making a block copolymer of polycarbonate, comprising: contacting a first epoxide monomer and carbon dioxide in the presence of an activator including trialkyl borane and an initiator to form a first polycarbonate block, wherein the initiator includes an alkali metal and an organic cation, and adding a second epoxide monomer to form a second polycarbonate block of a block copolymer that is different from the first polycarbonate block. ### Claim 12 (depends on 11) The method of claim 11, wherein the first epoxide monomer and the second epoxide monomer are different. ### Claim 13 (depends on 11) The method of claim 11, wherein the first epoxide monomer and the second epoxide monomer are one or more of ethylene oxide, propylene oxide, 1-butene oxide, 1-hexene oxide, 1-octene oxide, styrene oxide, cyclohexene oxide, allyl glycidyl ether, and butyl glycidyl ether. ### Claim 14 (depends on 11) The method of claim 11, wherein the activator is one or more of triethyl borane, trimethyl borane, triisobutylborane, and triphenylborane. ### Claim 15 (depends on 11) The method of claim 11, wherein the alkali metal is one or more of lithium, potassium, and sodium. ### Claim 16 (depends on 11) The method of claim 11, wherein the organic cation is one or more of phosphazenium, ammonium, and phosphonium. ### Claim 17 (depends on 11) The method of claim 11, wherein the initiator is characterized by the formula: R-O−{+Li/t-Bu-PY}, where R-O− is an anion of any lithium alkoxide, P is a phosphazene, and Y is 1, 2, or 4. ### Claim 18 (depends on 11) The method of claim 11, wherein the initiator is characterized by the formula: R-C−{+Li/t-Bu-PY}, R-C− is any alkyl, P is a phosphazene, and Y is 1, 2, or 4. ### Claim 19 (depends on 11) The method of claim 11, wherein the initiator is characterized by the formula: X−{+Li/t-Bu-PY}, where X is one or more of Cl, Br, F, and CO3, P is a phosphazene, and Y is 1, 2, or 4. ### Claim 20 (depends on 11) The method of claim 11, wherein the block copolymer is an ABA block copolymer, wherein A and B are different.