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ANAWWWWWWWWW Wwvavawmmowy 04 Wwwwwwwxwwwmw ??? |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 . Application Data Bielawski et al. , “ An “ Endless ” Route to Cyclic Polymers ,” Sci ence , 2002 , vol . 297 , pp . 2041 - 2044 . on Aug . 8 , 2014 , provisional application No . 62 /035 , Bielawski et al. , " Synthesis of Cyclic Polybutadiene via Ring 955 , filed on Aug . 11 , 2014 , provisional application Opening Metathesis Polymerization : The Importance of Removing No. 62 /035 , 962 , filed on Aug . 11 , 2014 . Trace Linear Contaminants , " J . Am . Chem . Soc . , 2003 , 125 , pp . 8424 - 8425 . ( 52 ) U . S . CI. A . Blencowe and G . Qiao “ Ring -Opening Metathesis Polymeriza CPC . .. .. C08G 2261/ 142 (2013 . 01 ) ; C08G tion with the Second Generation Hoveyda -Grubbs Catalyst: An 2261 / 1422 ( 2013 . 01 ) ; C08G 2261/ 3321 Efficient Approach toward High - Purity Functionalized Macrocyclic (2013 . 01) ; C08G 2261/ 3342 (2013 . 01 ) ; C08G Oligo ( cyclooctene )s , " J . Am . Chem . Soc. , 2013 , 135, pp . 5717 5725 . 2261/ 418 ( 2013 .01 ) ; C08G 2261/ 419 Boydston et al. , “ Cyclic Ruthenium - Alkylidene Catalysts for Ring ( 2013 .01 ) ; C08G 2261/ 724 ( 2013 .01 ) ; C08G Expansion Metathesis Polymerization , ” J . Am . Chem . Soc. , 2008 , 2261/ 80 (2013 . 01 ) 130 , pp . 12775 - 12782 . Hillmyer et al. , “ Ring -Opening Metathesis Polymerization of (56 ) References Cited Functionalized Cyclooctenes by a Ruthenium - Based Metathesis Catalyst, ” Macromolecules 1995, 28 , pp . 6311- 6316 . U . S . PATENT DOCUMENTS Marinescu et al ., “ Ethenolysis Reactions Catalyzed by Imido 3 , 963 ,792 A 6 / 1976 Takeshita Alkylidene Monoaryloxide Monopyrrolide (MAP ) Complexes of 5 , 312 , 940 A 5 / 1994 Grubbs et al. Molybdenum ," J . Am . Chem . Soc . , 2009 , 131 , pp . 10840 - 10841 and 5 , 342 , 909 A 8 / 1994 Grubbs et al. supporting information S1- S41 . 5 , 977 , 393 A 11/ 1999 Grubbs et al. S . Monfette and D . Fogg “ Equilibrium Ring - Closing Metathesis, " 6 , 284 , 852 B1 9 / 2001 Lynn et al . Chem . Rev. 2009 , 109 , pp . 3783 - 3816 . 6 ,410 ,666 B1 * 6 / 2002 Grubbs . CO8F 293/ 005 S . Ramakrishnan and T . C . Chung “ Poly ( 5 -hydroxyoctenylene ) and 525 / 326 . 1 Its Derivatives : Synthesis via Metathesis Polymerization of an 6 ,486 ,279 B2 11/ 2002 Lynn et al . Organoborane Monomer ," Macromolecules 1990 , 23 , pp . 4519 6 ,552 , 139 B14 / 2003 Herrmann et al . 4524 . 6 ,613 , 910 B29 / 2003 Grubbs et al. Roe et al. , “ Two- directional ring -opening cross- metathesis ,” Chem . 6 ,635 ,768 B1 10 / 2003 Herrmann et al . 6 ,787 ,620 B2 9 / 2004 Herrmann et al . Commun ., 2009 , pp . 4399 - 4401 . 7 , 294 , 717 B211/ 2007 Herrmann et al. Scherman et a . , “ Synthesis of Well- Defined Poly ( ( vinyl alcohol ) 2 7 ,378 , 528 B2B2 5 / 2008 Herrmann et al. alt -methylene ) via Ring -Opening Metathesis Polymerization , " 7 ,652 , 145 B2 1 / 2010 Herrmann et al. Macromolecules 2002 , 35 , pp . 5366 - 5371. 7 , 671 , 224 B2 3 / 2010 Winde et al . Scholl et al. , " Synthesis and Activity of a New Generation of 7 ,687 , 635 B2 3 / 2010 Verpoort et al . Ruthenium - Based Olefin Metathesis Catalysts Coordinated with 2003 /0055262 A1 3 / 2003 Grubbs et al. 1 , 3 - Dimesityl - 4 ,5 -dihydroimidazol - 2 - ylidene Ligands ,” Org . Let . 2005 / 0014916 Al * 1 / 2005 Sakamoto .. .. C07D 233 /02 1999 , vol . 1 , No. 6 , pp . 953 -956 . 526 / 172 Schwab et al ., “ Synthesis and Applications of 2005 /0113540 Al 5 / 2005 Weaver et al. RuC12 ( = CHR ') ( PR3 ) 2 : The Influence of the Alkylidene Moiety on 2006 / 0293526 AL 12 / 2006 Koehler et al. Metathesis Activity , " J . Am . Chem . Soc ., 1996 , 118 , pp . 100 - 110 . 2007 /0043188 AL 2 / 2007 Schaubroeck et al . R . Tuba and R . Grubbs “ Ruthenium catalyzed equilibrium ring 2008 /0293905 A9 11/ 2008 Schaubroeck et al . opening metathesis polymerization of cyclopentene , ” Polym . 2009 /0170692 AL 7 / 2009 Ying et al. 2009 / 0264672 Al 10 / 2009 Abraham et al. Chem ., 2013 , 4 , pp . 3959 - 3962. 2010 /0210515 AL 8 / 2010 Nash et al . D . Valenti and K . Wagener “ Direct Synthesis of Well - Defined 2014 / 0370318 A1 * 12 / 2014 Stephen .. .. .. .. C08G 61/ 08 Alcohol- Functionalized Polymers via Acyclic Diene Metathesis 428 /523 ( ADMET ) Polymerization ,” Macromolecules 1998 , 31, pp . 2764 2773 . Xia et al. , “ Ring - Expansion Metathesis Polymerization : Catalyst FOREIGN PATENT DOCUMENTS Dependent Polymerization Profiles, ” J . Am . Chem . Soc. , 2009 , 131, EP 1757613 B11 / 2011 pp . 2670 - 2677 . EP | 1577282 B1 6 / 2011 Xia et al. , " Synthesis and Direct Imaging of Ultrahigh Molecular JP H03200806 A 9 / 1991 Weight Cyclic Brush Polymers, ” Angew . Chem . Int. Ed . 2011, 50 , WO 02 /079208 A2 10 / 2002 pp . 5882 -5885 . WO 03 /011455 A1 2 / 2003 Zhang et al. , “Gels Based on Cyclic Polymers, ” J . Am . Chem . Soc. , WO 2004 / 013198 A2 2 / 2004 2011 , 133 , pp . 4140 -4148 . WO 2008 /066306 A1 6 / 2008 Partial Supplementary European Search Report in EP Application WO 2010 / 037550 A1 4 / 2010 No . 14842763 . 6 , dated Mar . 28 , 2017 . wo 2011 / 069134 A2 6 / 2011 Buschhaus et al ., “ Transformations of Cyclic Olefins Mediated by WO WO 2011/ 069134 * 9 / 2011 Tungsten Nitrosyl Complexes, ” Organometallics , 2008 , 27 , pp . 4724 - 4738 . OTHER PUBLICATIONS Alois Fuerstner and Klaus Langemann , “ Macrocycles by Ring Closing Metathesis , ” Synthesis , Jul. 1997 , vol. 7 , pp . 792 - 803 . International Preliminary Report on Patentability of International K . J . Ivin and J . C . Mol, “ Ring - Opening Metathesis Polymerization : Application No . PCT/ US2014 / 054158 , dated Mar. 17 , 2016 . General Aspects , ” in “ Olefin Metathesis and Metathesis Polymer PUBCHEM CID 548949 , Mar. 27 , 2005 , pp . 1 - 3 (online ), retrieved ization , ” 1997 , Academic Press , pp . 224 - 231 . on Oct . 15 , 2014 from the internet < URL :https : // pubchem .ncbi . nlm . Amon Shani “ Studies of the CIS , CIS -Cyclodeca - 1 , 6 - Diene Sys nih . gov / summary / summary . cgi ? cid = 548949 > ; p . 1 , formula . tem , ” Israel Journal of Chemistry , vol. 13 , No. 1 ., 1975 , pp . 35 -52 . Allen et al . , “ Well -Defined Silica - Supported Olefin Metathesis Catalysts , " Org . Let . 2009 , vol. 11 , No. 6 , pp . 1261 - 1264 . * cited by examiner atent Feb . 13 , 2018 Sheet 1 of 15 US 9 ,890 , 239 B2 Fig . 1 (5 ) (0 . 4 mol % ) toluene, 55 °C 1 . 6 . 5 equiv TSH , 2020h h xylene, reflux , 4 h ; - - O - si - tBu ó ó 2 . TBAF ?? ?? . tBu tButBu THF , DMF , 75 °C , 40 h U . S . 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 .
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