|HAO WAKAT IAKIT US009890239B2 DI RIALLA MADOA TUTTO (12 ) United States Patent ( 10 ) Patent No. : US 9 , 890 ,239 B2 Tuba et al. ( 45 ) Date of Patent: Feb . 13 , 2018 ( 54 ) FUNCTIONALIZED LINEAR AND CYCLIC (52 ) U . S . CI. POLYOLEFINS CPC . .. .. .. .. C08G 61/ 08 (2013 . 01 ) ; C08G 61/ 12 ( 2013 .01 ) ; C08L 65 / 00 ( 2013 .01 ) ; @(71 ) Applicant : CALIFORNIA INSTITUTE OF (Continued ) TECHNOLOGY , Pasadena , CA (US ) (58 ) Field of Classification Search None @( 72 ) Inventors : Robert Tuba, Veresegyhaz (HU ) ; Robert H . Grubbs , South Pasadena , See application file for complete search history. CA (US ) ( 56 ) References Cited ( 73 ) Assignee : CALIFORNIA INSTITUTE OF U . S . PATENT DOCUMENTS TECHNOLOGY, Pasadena , CA ( US ) 3 , 816 , 382 A 6 / 1974 Streck et al. ( * ) Notice : Subject to any disclaimer , the term of this 3 , 952 ,070 A 4 / 1976 Nowak et al. patent is extended or adjusted under 35 (Continued ) U . S . C . 154 ( b ) by 0 days . FOREIGN PATENT DOCUMENTS (21 ) Appl. No. : 14 /915 , 822 ?? 2292584 Al 1 / 1999 EP 1598384 Al 11 / 2005 (22 ) PCT Filed : Sep . 4 , 2014 ( Continued ) ( 86 ) PCT No .: PCT/ US2014 / 054158 OTHER PUBLICATIONS $ 371 ( c ) ( 1 ) , ( 2 ) Date : Mar . 1 , 2016 International Search Report and Written Opinion of International Application No . PCT/ US2014 /054158 , dated Nov . 25 , 2014 . ( 87) PCT Pub . No. : WO2015 /035097 (Continued ) PCT Pub . Date : Mar. 12 , 2015 Primary Examiner — Robert C Boyle ( 74 ) Attorney , Agent, or Firm — J. A . Lindeman & Co ., (65 ) Prior Publication Data PLLC US 2016 /0215089 A1 Jul . 28 , 2016 (57 ) ABSTRACT This invention relates to methods and compositions for Related U . S . Application Data preparing linear and cyclic polyolefins. More particularly , the invention relates to methods and compositions for pre (60 ) Provisional application No . 61/ 873 ,701 , filed on Sep . paring functionalized linear and cyclic polyolefins via olefin 4 , 2013 , provisional application No . 62 /035 ,307 , filed metathesis reactions. Polymer products produced via the (Continued ) olefin metathesis reactions of the invention may be utilized (51 ) Int . Cl. for a wide range of materials applications . The invention has C08G 61 / 08 ( 2006 . 01 ) utility in the fields of polymer and materials chemistry and C08G 61 / 12 ( 2006 .01 ) manufacture . C08L 65 /00 ( 2006 . 01 ) 4 Claims, 15 Drawing Sheets Sisi supponsupport Wix AYWA ANAWWWWWWWWWaf WWVAVAWMmowy 04 WwwwwwwxWWWMW ??? W MM US 9 ,890 , 239 B2 Page 2 Related U . S . 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Patent Feb . 13 , 2018 Sheet 2 of 15 US 9 ,890 , 239 B2 Fig . 2 RA1* [ Cat. ] gameRA1* that 1 : RA1 * = H 3 : RAT" = H : polypentenamer 2 : RA1 * = OH 4 : RAI1 "* = OH : poly (vinylalcohol - alt - propenylene ) atent Feb . 13 , 2018 Sheet 3 of 15 | US 9 , 890 , 239 B2 Fig . 3 . PCy3 Mes - N N - Mes Mes -IN JN - Mes Mes - N N - Mes Rus | cl - Hue CV , PCya / | < X : H , Br as5 is |as U. S . Pateratent Feb . 13 , 2018 Sheet 4 of 15 US 9 ,890 ,239 B2 Waktus ???? Ringstrain VOT 0467 3 wwwwwwwwwwwwwwwwwwwwwww 208 * *. 107 * .* * .* 911.89331323028/412on .* * q?piopuogESTMEETTUSETITWT*MTSWTMETNETETESETATet * .* *. *. 1920 .* . .* .* . 0.72$20-* .* .* .* *. *. CHA COXWV * Fig.4 atent Feb . 13, 2018 Sheet 5 0f15 US 9 ,890 , 239 B2 ? Fig. 5 ?? - 0. 70 . - 0 . 80 - 0 . 90 . _ - 1 . 00 .. - 1 .10 . [M]ur - 1 . 20 . y = - 3 . 120x + 9 .532 Rº = 0 . 994 - 1 . 30 . - L .40 . ? - 1 . 50 . - 1 . 60 . www -170 . ?????? "" " " 3 .25 _ 3 .30 _ 3 .35 3 . 40 _ 3 .45 _ 3 .50 _ 3 .55 _ 3 .60 1 { T * 103 ( 1 / K ) atent Feb . 13 , 2018 Sheet 6 of 15 US 9 , 890 ,239 B2 Fig . 6 OH OH 6 or 7 6 or 7 THF -da , RT, 2h THF -ds , RT, 2h ?? - C2H4 2 ( ? U .