US009 109080B2 (12) United States Patent (10) Patent No.: US 9,109,080 B2 Drake et al. (45) Date of Patent: *Aug. 18, 2015 (54) CROSS-LINKED ORGANIC POLYMER FOREIGN PATENT DOCUMENTS COMPOSITIONS AND METHODS FOR CONTROLLING CROSS-LINKING EP O251357 B1 1, 1988 REACTION RATE AND OF MODIFYING GB 2185114 7, 1987 SAME TO ENHANCE PROCESSABILITY (Continued) (71) Applicant: Delsper LP, Kulpsville, PA (US) OTHER PUBLICATIONS (72) Inventors: Kerry A. Drake, Red Hill, PA (US); Andrew F. Nordquist, Whitehall, PA Ladacki et al., “Studies of the Variations in Bond Dissociation Ener (US); Sudipto Das, Norristown, PA gies of Aromatic Compounds. I. Mono-bromo-aryles.” Proc. R. Soc. (US); William F. Burgoyne, Jr., Lond. a, r219, pp. 341-253 (1953). Bethlehem, PA (US); Le Song, Chalfont, (Continued) PA (US); Shawn P. Williams, North Wales, PA (US); Rodger K. Boland, Primary Examiner — Robert S. Loewe Levittown, PA (US) (74) Attorney, Agent, or Firm — Flaster/Greenberg P.C. (73) Assignee: Delsper LP, Kulpsville, PA (US) (*) Notice: Subject to any disclaimer, the term of this (57) ABSTRACT patent is extended or adjusted under 35 The invention includes a cross-linking composition compris U.S.C. 154(b) by 0 days. ing a cross-linking compound and a cross-linking reaction additive selected from an organic acid and/or an acetate com This patent is Subject to a terminal dis pound, wherein the cross-linking compound has the structure claimer. according to formula (IV): (21) Appl. No.: 14/059,064 (22) Filed: Oct. 21, 2013 (IV) (65) Prior Publication Data US 2014/0284.850 A1 Sep. 25, 2014 Related U.S. Application Data (60) Provisional application No. 61/833,351, filed on Jun. ) A. 10, 2013, provisional application No. 61/716,800, filed on Oct. 22, 2012. (51) Int. Cl. () C08G 65/48 (2006.01) C08G 16/00 (2006.01) wherein the cross-linking reaction additive is capable of reacting with the cross-linking compound to form a reactive (Continued) oligomer intermediate, which is capable of cross-linking an (52) U.S. Cl. organic polymer. Also included is an organic polymer com CPC ................ C08G 65/00 (2013.01); C07C35/38 position for use in forming a cross-linked organic polymer, (2013.01); C07C 43/275 (2013.01); C08G comprising a cross-linking compound of Formula (IV), a 65/48 (2013.01); C08L 71/00 (2013.01) cross-linking reaction additive and at least one organic poly (58) Field of Classification Search mer. In one embodiment, the at least one organic polymer has None at least one halogen-containing reactive group and is dehalo See application file for complete search history. genated by reacting with an alkali metal compound. 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Written Opinion for PCT/US14/30666, mailed Jan. 30, 2015–3 8,096.353 B2 1, 2012 Ver Meer pageS. 8,367,776 B2 2, 2013 Noguchi et al. 8,502.401 B2 8, 2013 Burgoyne, Jr. et al. * cited by examiner U.S. Patent Aug. 18, 2015 Sheet 1 of 7 US 9,109,080 B2 4.000E3. 3,500E6; 3,55 O-2 Crosslinker Not treated with glacial acetic acid 2.000E5. 15OOES 1.000E5 bio-2 Crosslinker Treated with glacial acetic acid (5.06.050. 20.025,036,035.046,045,656.0 time (min) F.G. 1 U.S. Patent Aug. 18, 2015 Sheet 2 of 7 US 9,109,080 B2 4:5 3,505 3.500 3,500S hio-2 Crossiker Not treated with glacial acetic acid 2.000E5 C. iii.5 .000E5 feates with OA: it cyclohexafore 4 r. fefix Oil-2 . s / treated with CAC in cyclohexandre 6. refix 65,000 15026,025,036,035.046,045,056.0 time (min) FG. 2 Cure Time, 380C, Oligomer Method 4000----------------------------------------------------------------------- 35 3000 2500 c f 2. g 50 OOO al t :enoopooooooooooo. ---------------------------- (.00 2.0 4, 8, 8.O.O. O. 2.OO 14.00 8.00 reactic irre tooooooo fectic Poiri oooooo G', G" Crossover FG. 2A U.S. Patent Aug. 18, 2015 Sheet 3 of 7 US 9,109,080 B2 OCES 3.500E5 3,500E3 3500E8 OOO No lithin acetate hydrate s 2.OOOES adde: & 1.500E5 1.000E5 500 t try're-cirrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrt S. O. 3.O. 23. 35.0 3.0 38.) 40 45. 80.0 time (min) FG. 3 Delay in Cure vs. '%. Additive 1 5 O {} O e p .8% .50% 50%, 2.0% 2.50%, 3.8% 3.50% %. Additive see G', G" Crossoverroio infection; Point FG. 3A U.S. Patent Aug. 18, 2015 Sheet 4 of 7 US 9,109,080 B2 FG. 4A FG.