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(12) United States Patent (10) Patent No.: US 7,902,403 B2 Karol Et Al

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(12) United States Patent (10) Patent No.: US 7,902,403 B2 Karol Et Al US007902403B2 (12) United States Patent (10) Patent No.: US 7,902,403 B2 Karol et al. (45) Date of Patent: Mar. 8, 2011 (54) DITHIOPHOSPHATE COMPOSITION AND s: A ck E. Redmore et et al al. .............. 558, 152 UTILITY IN RUBBER 4,216,126 A 8/1980 Kay 4,308,072 A * 12/1981 Schneider et al. ....... 106,287.26 (75) Inventors: Thomas J. Karol, Holualoa, HI (US); 4,397,791 A * 8/1983 RE . 558,112 Ronald J. Tepper, Fairfield, CT (US) 4,778,906 A * 10/1988 Love et al. ...................... 556.25 5,464,601 A * 1 1/1995 Griffith et al. ................ 423.303 5,691.406 A 11/1997 Lane et al. (73) Assignee: st Yerbilt Ompany, Inc., 5,726,132 A * 3/1998 Roby et al. .................... 508/287 orwalk, CT (US) 6,242,522 B1 6/2001 Ezawa et al. - 6,761,832 B1* 7/2004 Heiliger et al. .......... 252, 182.17 (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS U.S.C. 154(b) by 0 days. CS 153714 * 3/1974 JP 10045771 * 2/1998 (21) Appl. No.: 12/023,396 SU 682 .526 8, 1979 WO WO 2005/0954.25 * 10/2005 (22) Filed: Jan. 31, 2008 OTHER PUBLICATIONS O O German et al. Oxidation of bis(2-ethylhexyl) hydrogen (65) Prior Publication Data dithiophosphate, Izvestiya Sibirskogo Otdeleniya Akademii Nauk US 2008/O183O18A1 Jul. 31, 2008 SSSR, Seriya Khimicheskikh Nauk (1981), (3), 150-152.* Zimin et al., Reactions of phosphorus dithio acids with chloro-Sub Related U.S. Application Data stituted acetonitriles, Zhurnal Obshchei Khimi (1980), 50(1), 24-30. (60) Provisional application No. 60/887,380, filed on Jan. 31, 2007. * cited by examiner (51) Int. Cl. Primary Examiner — Daniel M Sullivan C07F 9/02 (2006.01) Assistant Examiner — Chukwuma O Nwaonicha (52) U.S. Cl. ....................................... 568/15:568/14 (74) Attorney, Agent, or Firm — Norris McLaughlin & (58) Field of Classification Search .................... 568/15. Marcus, PA. 568/14 (57) ABSTRACT See application file for complete search history. The present invention relates to oligomeric or polymer dithio- 0 (56) References Cited phosphate di- or poly-sulfides and their utility in rubbers. Another aspect of the invention is a method for making oli U.S. PATENT DOCUMENTS gomeric or polymeric dithiophosphates by reacting phospho 2,725,327 A 1 1/1955 Diveley rous pentasulfide with a di- or polyol and a mono alcohol to 2,828.241 A 3, 1958 Birum produce a dithiophosphoric acid, and then oxidizing the 3, 197405 A 7, 1965 Le Suer dithiophosphoric acid with an oxidizing agent to produce an 3,544.465 A 12, 1970 Braid oligomeric or polymeric dithiophosphate. 3,865,906 A 2f1975 Shin et al. 3,883,457 A 5/1975 Lohr, Jr. et al. 15 Claims, No Drawings US 7,902,403 B2 1. 2 DTHOPHOSPHATE COMPOSITION AND but to a wide variety of animal life (The Ortho Group, “Envi UTILITY IN RUBBER ronmental Hazards: This pesticide is toxic to fish, aquatic invertebrates, and aquatic life stage of amphibians.'). Other FIELD OF THE INVENTION references to toxic dithiophosphates are provided in U.S. Pat. No. 2,725,327 Nov. 29, 1955, William R. Diveley; et al., The present invention relates to polymer compositions and which describes Pestisidal composition containing 2-P-Diox methods for producing the composition. More specifically, anethiol S (O,O-dialkylphophorodithioate) and U.S. Pat. the polymer compositions comprise novel polymeric dithio No. 2,828,241 Mar. 25, 1958, Gail H. Birum; et al. which phosphates. describes O,Odialkyl S-arylmercapto phosphorodithioates 10 BACKGROUND OF THE INVENTION compositions and method of destroying insects. It is generally accepted that polymeric materials offer Dithiophosphate accelerators have been used as sulfur improved and lower toxicity over their monomeric forms. donors in the Vulcanization of diene. As compared with con Bonding an additive to a polymer (carrier) would afford ventional accelerators, they offer advantages such as 15 improved environmental safety but dilutes the activity of the improved reversion of natural rubber, heat stability of the molecule by non active polymer (as related to rubber cure). It Vulcanizates or rubber produced, and high solubility in rub has been unexpectedly discovered that forming polymeric bers of varying polarity for curing and producing a product dithiophosphates via bi- or polyfunctional alcohols (utiliza without bleed of additive (“non blooming). tion of di- or polyol alcohol within the reaction with phos Commercially available dithiophosphate additives are (1) phorous pentasulfide to form the oligomer or polymeric Accelerator ZIPPAC from Akrochem. ZIPPAC is a zinc dithiophosphoric acid) can be oxidized to oligomeric or poly amine dithiophosphate complex dispersed in a polymer merdisulfides and subsequently to polysulfides. Alternatively matrix. ZIPPAC, when used in combination with thiazoles the dithiophosphoric acid can be reacted with metal hydrox and thiurams, gives fast cure rates to ENB type EPDM's. ides or oxides. The resulting product will function as an Compared to Akrochem’s other thiophosphate accelerator, 25 Accelerator VS, ZIPPAC provides a much faster cure. ZIP “additive' which can offer high activity, excellent Vulcaniza PAC cures exhibit high modulus and low compression set, tion and/or stabilization properties to rubbers and offer due to a high degree of crosslinking. Vulcanizates are usually improved handling and environmental (“green') consider non-blooming. Hotairaging properties are usually better than ation due to their polymeric additive form (as compared to the those obtained with other thiophosphate accelerators. ZIP 30 monomeric type additives). PAC does not form harmful nitrosoamines (Zippac forms only unstable primary amines that rapidly decompose) and is SUMMARY OF THE INVENTION a useful accelerator in low nitroSoamine generating formulas where its high crosslink density and fast cure overcome nor Dithiophosphate disulfides, dithiophosphate polysulfides, mal problems associated with safe nitroSoamine cure sys 35 tems; (2) Royalac 136 from Crompton-Uniroyal Chemical is and Zinc dithiophosphates are known accelerators, and their a zinc thiophosphate (zinc phosphorodithioate); (3) Meramid chemistry is illustrated below. P a zinc dialkyl dithiophosphate under CAS number 68457 79-4; (4) Deovulc EG 187 from D.O.G. which is described as a synergistic combination of Thiazole- and basic accelerators 40 S together with a zinc dialkyldithiophosphate (ZDTP) as the | alia main components; (5) Vocol ZBPD from Flexsys is described 4. ROH + P2S5 -its 2 R-07 Ns. "?" - as Zinc O,O-Dibutylphosphorodithioate. Elastomer and uti / lized in NR, EPDM, LATEX rubber and non-blooming accel R erator for EPDM cures and also improves reversion resistance 45 S S in NR; (6) VANAX(R) 196 from R. T. Vanderbilt Company, which is a dithiophosphate disulfide; (7) Rhenocure AP-6 R-O11S Ys-S1 -N NO-R from Rhine Chemie, which is described as dithiophosphate O O polysulfides; (8) Rheinocure(R) TP/S from Rhine Chemie / V R R which is described as a Dithiophosphate, sulfur source; (9) 50 Rheinocure(R) SDT/S from Rhine Chemie which is described S S as a phosphoryl polysulfide, sulfur source: (10) Rheinocure | Sulful r SDT/G from Rhine Chemie which is also is described as a R-o1 Ys-s1 No-R - O O phosphoryl polysulfide, sulfur source; and (12) RhenogranR) / V SDT-50 from Rhine Chemie which is described as a polymer 55 R R bound phosphory polysulfide. S S Nitrosoamine reduction in rubbers has become important due to the carcinogenic properties linked to nitroSoamines. l l Dithiophosphate accelerators have a renewed interest due to R-07 Ys--si-s1 So-R lack of nitrogen in the chemical structure, which is pre-req 60 / V uisite of nitroSoamine formation. A common expression for R R having better environmental properties is “green” and efforts S are in way to produce more and more green additives. ZnOl One concern over dithiophosphate technology is that 2 R-07 Ns S although it can not form harmful nitroSoamines, the technol 65 / ogy has the ability to be a toxin. Malathion is a widely avail R able dithiophosphate insecticide. It is not only toxic to insects US 7,902,403 B2 3 4 -continued One embodiment of the present invention utilizes diol in S S combination with alcohols (mono-alcohols), reacted with the phosphorous pentasulfide to produce polydithiophosphos R-O11N YS-Zn-S1 - 'NNO-R phoric acid with higher molecular weight. Oxidative coupling O O / V of the thiol group of the dithiophosphoric acid produces the R R disulfide linkage, essentially multiplying the molecular weight of the oligomer by the extent of disulfide coupling. Polymers are widely and generally considered low or non The molecular weight of the product can be controlled by toxic as compared to monomeric or non-polymeric forms varying the ratio of the mono alcohol to the diol. It is believed primarily due to their higher molecular weight (polymeric 10 to be advantageous to eliminate all of the dithiophosphoric properties) which reduces volatility and the likelihood that acid which at the same time forms higher molecular weights. they will cross biological membranes. Additionally these oli Additionally any part of the disulfide moieties can be con gomeric or polymeric disulfides can be converted to the verted to the di-, tri-, tetra-, or poly-sulfide (or mixtures polysulfides by reaction with elemental sulfur and the polysulfides are part of the diversity of the invention. Dithio 15 thereof), by elemental sulfur insertion (typically done by phosphates are utilized in many elastomers which include heating with disulfide with elemental sulfur at sufficient tem natural rubber (NR), ethylene propylene diene monomer rub perature to induce the reaction). ber (EPDM), EPDM/butyl and Latex cure (NR Latex and In an another embodiment of the present invention, the Chloroprene Latex), polybutadiene resin and styrene-butadi mono-alcohol is substituted with a second diol of the same or ene rubber stabilization.
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