US009637573B2 (12) United States Patent (10) Patent No.: US 9,637,573 B2 Hlavinka et al. (45) Date of Patent: *May 2, 2017 (54) POLYMER COMPOSITIONS AND METHODS (58) Field of Classification Search OF MAKING AND USING SAME CPC ................ C08F 210/16; C08F 2500/05; C08F 2500/07; C08L 2203/18 (71) Applicant: Chevron Phillips Chemical Company See application file for complete search history. LP, The Woodlands, TX (US) (56) References Cited (72) Inventors: Mark L. Hlavinka, Bartlesville, OK (US); Qing Yang, Bartlesville, OK U.S. PATENT DOCUMENTS (US); William B. Beaulieu, Tulsa, OK 3,161,629 A 12/1964 Gorsich (US); Paul J. Deslauriers, Owasso, OK 3,242,099 A 3/1966 Manyik et al. (US) (Continued) (73) Assignee: Chevron Phillips Chemical Company FOREIGN PATENT DOCUMENTS LP, The Woodlands, TX (US) CN 103.01.2196. A 4/2013 (*) Notice: Subject to any disclaimer, the term of this DE 1959322 A1 7, 1971 patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 0 days. This patent is Subject to a terminal dis OTHER PUBLICATIONS claimer. Alt, Helmut G. et al., “ansa-Metallocenkomplexe des Typs (C13H8-SiR2-C9H6 nR'n)ZrC12 (n=0, 1: R=Me, Ph. Alkenyl: (21) Appl. No.: 15/051,173 R=Alkyl, Alkenyl): Selbstimmobilisierende Katalysatorvorstufen für die Ethylenpolymerisation.” Journal of Organometallic Chem (22) Filed: Feb. 23, 2016 istry, 1998, pp. 229-253, vol. 562, Elsevier Science S.A. (65) Prior Publication Data (Continued) US 2016/O16829O A1 Jun. 16, 2016 Primary Examiner — Rip A Lee (74) Attorney, Agent, or Firm — Conley Rose, P.C.; Related U.S. Application Data Rodney B. Carroll: Chad E. Walter (60) Continuation of application No. 14/684.844, filed on (57) ABSTRACT Apr. 13, 2015, now Pat. No. 9.394,385, which is a A polymer reactor-blend comprising at least a first compo (Continued) nent having a polydispersity index of greater than about 20 (51) Int. C. and is present in an amount of from about 1 wt.% to about CSF2IO/I6 (2006.01) 99 wt.% based on the total weight of the polymer and a CSF IO/4 (2006.01) second component having a polydispersity index of less than about 20 and is present in an amount of from about 1 wt.% (Continued) to about 99 wt.% based on the total weight of the polymer (52) U.S. C. wherein a molecular weight distribution of the second CPC ............ C08F 10/14 (2013.01); C08F 210/16 component lies within a molecular weight distribution of the (2013.01); F16L 9/127 (2013.01); C08F first component. 4/6591.2 (2013.01); (Continued) 20 Claims, 5 Drawing Sheets 140 120 - 100 2 8 O 4. o - X 40 O O 200 400 600 800 Tensile Strain (%) US 9,637,573 B2 Page 2 Related U.S. Application Data 5,455,314 10, 1995 Burns et al. 5,461,127 10, 1995 Naganuma et al. division of application No. 13/753.289, filed on Jan. 5,468,702 11, 1995 Jejelowo 29, 2013, now Pat. No. 9,034,991. 5483,014 1, 1996 Turner et al. 5,496,781 3, 1996 Geerts et al. 5,496,782 3, 1996 Zandona (51) Int. C. 5,498,581 3, 1996 Welch et al. FI6L 9/27 (2006.01) 5,527,867 6, 1996 Bergmeister FI6L 9/12 (2006.01) 5,534.473 T/1996 Welch et al. COSF 4/659 5,541,272 T/1996 Schmid et al. (2006.01) 5,543,376 8, 1996 Bergmeister COSF 4/6592 (2006.01) 5,554,795 9, 1996 Frey et al. (52) U.S. C. 5,556,893 9, 1996 Costa et al. CPC 5,563,284 10, 1996 Frey et al. C08F 4/65927 (2013.01); C08F 2500/05 5,565, 175 10, 1996 Hottovy et al. (2013.01); C08F 2500/09 (2013.01); C08F 5,565,592 10, 1996 Patsidis et al. 2500/10 (2013.01); C08L 2203/18 (2013.01); 5,571,880 11, 1996 Alt et al. C08L 2205/02 (2013.01); F16L 9/12 (2013.01) 5,575,979 11, 1996 Hanson 5,576,259 11, 1996 Hasegawa et al. References Cited 5,587,501 12, 1996 Winter et al. (56) 5,594,078 1/1997 Welch et al. 5,594,080 1/1997 Waymouth et al. U.S. PATENT DOCUMENTS 5,612,271 3, 1997 Zandona 5,631,203 5, 1997 Welch et al. 3.248,179 4, 1966 Norwood 5,631,335 5, 1997 Alt et al. 3,533.738 10, 1970 Rundell et al. 5,643,847 7/1997 Walzer, Jr. 3,946,020 3, 1976 Minato et al. 5,646,322 7/1997 van Beek et al. 4,060,480 11, 1977 Reed et al. 5,648.439 7/1997 Bergmeister et al. 4,070,272 1, 1978 Rausch 5,654.454 8, 1997 Peifer et al. 4,077,904 3, 1978 Noshay et al. 5,668,230 9, 1997 Schertl et al. 4,101,445 7, 1978 Levine et al. 5,670,580 9, 1997 Tazaki et al. 4,279,780 T. 1981 Dombro 5,700,748 12, 1997 Murray 4,452,910 6, 1984 Hopkins et al. 5,703, 181 12, 1997 Tashiro et al. 4476,243 10, 1984 Dombro 5,705,578 1, 1998 Peifer et al. 4,501.885 2, 1985 Sherk et al. 5,705,579 1, 1998 Hawley et al. 4,526,942 7, 1985 Chester et al. 5,714.425 2, 1998 Chabrand et al. 4,547,551 10, 1985 Bailey et al. 5,714,555 2, 1998 Chabrand et al. 4,588,790 5, 1986 Jenkins, III et al. 5,719,241 2, 1998 Razavi et al. 4,596,862 6, 1986 McDaniel et al. 5,726.264 3, 1998 Jung et al. 4,657,998 4, 1987 Malpass 5,739,220 4, 1998 Shamshoum et al. 4,659,685 4, 1987 Coleman, III et al. 5,780,659 7, 1998 Schmid et al. 4,788,171 11, 1988 Klendworth 5,807,938 9, 1998 Kaneko et al. 4,794,096 12, 1988 Ewen 5,854,165 12, 1998 Yabunouchi et al. 4,803.253 2, 1989 McDaniel et al. 5,854,363 12, 1998 Jung et al. 4,806,513 2, 1989 McDaniel et al. 5,861,352 1/1999 Gila et al. 4,808,561 2, 1989 Welborne, Jr. 5,866,497 2, 1999 Murray 4,892,851 1, 1990 Ewen et al. 5,883,036 3, 1999 Fujie et al. 4,939,217 7, 1990 Stricklen 5,886,202 3, 1999 Jung et al. 4.969,522 11, 1990 Whitehurst et al. 5,906,955 5, 1999 Hamura et al. 5,001.204 3, 1991 Klendworth et al. 5,907,021 5, 1999 Turner et al. 5,010, 152 4, 1991 McDaniel et al. 5,919,983 7, 1999 Rosen et al. 5,036,034 7, 1991 Ewen 5,942.459 8, 1999 Sugano et al. 5,037,911 8, 1991 McDaniel et al. 6,034,187 3, 2000 Maehama et al. 5,049,535 9, 1991 Resconi et al. 6,096,677 8, 2000 Wilson, Jr. 5,071,808 12, 1991 Antberg et al. 6,107,230 8, 2000 McDaniel et al. 5,075.467 12, 1991 Desobry 6,114,477 9, 2000 Merrill et al. 5,085,705 2, 1992 Withiam 6,150,544 11/2000 Seki et al. 5,162,278 11, 1992 Razavi 6,165,929 12, 2000 McDaniel et al. 5,171,798 12, 1992 McDaniel et al. 6,169,151 1, 2001 Waymouth et al. 5, 183,868 2, 1993 Nordquest 6,174.981 1, 2001 Bergmeister et al. 5, 191,132 3, 1993 Patsidis et al. 6,180,736 1, 2001 Muhle et al. 5,210,352 5, 1993 Alt et al. 6,187,880 2, 2001 Welch et al. 5,223,467 6, 1993 Razavi 6,201.077 3, 2001 Bergmeister et al. 5,321, 105 6, 1994 Rekers et al. 6,204,346 3, 2001 Bergmeister et al. 5,332,707 T. 1994 Karayannis et al. 6,225.425 5/2001 Dolle et al. 5,347,026 9, 1994 Patsidis et al. 6,239,059 5/2001 Saudemont et al. 5,352,749 10, 1994 DeChellis et al. 6,239,235 5/2001 Hottovy et al. 5,369,196 11, 1994 Matsumoto et al. 6,262,191 T/2001 Hottovy et al. 5,376,611 12, 1994 Shveima 6,262,201 T/2001 Welch et al. 5,399,636 3, 1995 Alt et al. T/2001 Murray et al. 5,401,817 3, 1995 Palackal et al. 6,268.447 5,401,820 3, 1995 McDaniel et al. 6,274,684 8, 2001 Loveday et al. 5,416.228 5, 1995 Ewen et al. 6,291,699 9, 2001 Birmingham et al. 5,420,320 5, 1995 Zenk et al. 6,294,494 9, 2001 McDaniel et al. 5.434,116 7, 1995 Sone et al. 6,300,271 10, 2001 McDaniel et al. 5,436,304 7, 1995 Griffin et al. 6,300.451 10, 2001 Mehta et al. 5,436,305 7, 1995 Alt et al. 6,316,553 11/2001 McDaniel et al. 5.439,995 8, 1995 Bailly et al. 6,333,389 12, 2001 Whiteker et al. 5,444,134 8, 1995 Matsumoto 6,340,651 1, 2002 Licht et al. 5,451,649 9, 1995 Zenk et al. 6,340,652 1, 2002 Sugano et al. US 9,637,573 B2 Page 3 (56) References Cited 7,696,280 B2 4/2010 Krishnaswamy et al.