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(12) United States Patent % USOO9056940B2 (12) United States Patent (10) Patent No.: US 9,056,940 B2 Beatty et al. (45) Date of Patent: Jun. 16, 2015 (54) ALPHATIC POLYESTERPOLYOLS FROM (56) References Cited CYCLOHEXANE OXDATION BYPRODUCT STREAMS AS PRECURSORS FOR U.S. PATENT DOCUMENTS POLYURETHANE AND 3,365.490 A 1/1968 Arthur POLYISOCYANURATE POLYMERS 4,233,408 A 1 1/1980 Satterly et al. (75) Inventors: Richard P. Beatty, Newark, DE (US); (Continued) Carina Araulo McAdams, Wilmington, NC (US); Yanhui Sun, Wilmington, DE FOREIGN PATENT DOCUMENTS (US); Thomas A. Micka, West Grove, PL 93248 * 5, 1977 PA (US) PL 151999 * 10, 1990 (73) Assignee: INVISTA North America S.a.r.l., (Continued) Wilmington, DE (US) OTHER PUBLICATIONS (*) Notice: Subject to any disclaimer, the term of this International Search Report and Written Opinion received for PCT patent is extended or adjusted under 35 Patent Application No. PCT/US2012/041951, mailed on Nov. 7, U.S.C. 154(b) by 78 days. 2012, 10 pages. (Continued) (21) Appl. No.: 13/493,840 (22) Filed: Jun. 11, 2012 Primary Examiner — Wayne Langel (74) Attorney, Agent, or Firm — Ni Yan (65) Prior Publication Data (57) ABSTRACT US 2013/OO42659 A1 Feb. 21, 2013 The invention provides polyester polyol compositions and Related U.S. Application Data resin blends, useful as components of polyurethane and poly isocyanurate polymers, produced from cyclohexane oxida (60) Provisional application No. 61/496.268, filed on Jun. tion reaction byproducts, such as water extracts and non 13, 2011, provisional application No. 61/496,868, volatile distillation residues from the reaction. Such filed on Jun. 14, 2011. byproducts of industrial processes for preparation of adipic acid and caprolactam, important intermediates in the produc (51) Int. C. tion of various types of nylon, have hitherto largely been used C07C35/00 (2006.01) only as fuels. The present invention provides value-added C05G 3/00 (2006.01) products, methods for making, and methods for using the (Continued) byproduct-derived polyester polyol compositions. For (52) U.S. C. example, the invention provides polyurethane (PU) and/or CPC ............ C08G 18/4222 (2013.01); C07C3 1/18 polyisocyanurate (PIR) polymers made using the polyolcom (2013.01); C05G 3/0029 (2013.01); positions and polyfunctional isocyanates. The PU and PIR polymers can be used as adhesives, binders (e.g., for wood (Continued) fibers), coatings (e.g., for controlled release fertilizers), and (58) Field of Classification Search foams. USPC ............................................. 71/31-63, 64.07 See application file for complete search history. 19 Claims, 1 Drawing Sheet POLYMER DESCRIPTION IS RELATIVE RELEASE PROFILES 20 S. 18 6 % S. 14 S 12 % % 2 RECIPE RECIPE2 RECIPE 3 RECIPE 4 RECIPE5 RELATE AROATC CONTENT RELATEAPHATIC CONTENT HYDROPHOBICCONTENT ->k - 3-DAY RELATYEUREA RELEASE (3-4% COATING) -3-1-DAY RELATYEVREA RELEASE (3-4% COATING) US 9,056,940 B2 Page 2 (51) Int. Cl. 2004.0020254 A1 2/2004 Wynnyk et al. 2004/0045331 A1 3/2004 Geiger et al. C08G 18/42 (2006.01) 2004.0054235 A1 3/2004 Fodor et al. C08G 18/10 (2006.01) 2004/O105877 A1 6/2004 Hargrove et al. C09D 75/06 (2006.01) 2005/0276905 A1 12/2005 Xing et al. CO5C 9/OO (2006.01) 2006, OOOO252 A1 1/2006 Carstens et al. 2006, O115586 A1 6/2006 Xing et al. CO7C3 1/18 (2006.01) 2006/0222735 A1 10, 2006 Rosenthal et al. COSG IOI/OO (2006.01) 2007/O137274 A1 6/2007 Wynnyk et al. (52) U.S. Cl. 2007/0231369 A1 10/2007 Hargrove 2008/0010878 A1 1/2008 Hansen et al. CPC ........... C08G 18/10 (2013.01); C08G 18/4286 2008/0236228 A1 10/2008 Geiger et al. (2013.01); C08G 2101/00 (2013.01); C08G 2010.0011825 A1 1/2010 Ogle et al. 2105/02 (2013.01); C09D 175/06 (2013.01); 2010, 0186470 A1 7/2010 Xing et al. 2010. 0233325 A1 9/2010 Hargrove C05C 9/005 (2013.01) 2010. 0233332 A1 9/2010 Xing et al. 2010/0275665 A1 1 1/2010 Ogle et al. (56) References Cited 2010/030721 1 A1 12/2010 Xing et al. 2010/0326152 A1* 12/2010 Mente ............................... 7 1/27 U.S. PATENT DOCUMENTS 2012,006.4252 A1 3/2012 Beatty 2012/0101009 A1 4/2012 Beatty 4,804,403 A * 2, 1989 Moore .............................. 71 28 2012/0227451 A1* 9/2012 Ogle et al. ........................ 71 28 5,374,292 A 12, 1994 Detricket al. 2012/0240648 A1* 9/2012 Ogle et al. ........................ 71 28 5,435,821 A 7, 1995 Duvdevani et al. 5,538,531 A * 7, 1996 Hudson et al. .................... 71 28 5,547,486 A 8, 1996 Detricket al. FOREIGN PATENT DOCUMENTS 5,599,374 A 2, 1997 Detrick 5,803,946 A 9, 1998 Petcavich et al. PL 162632 * 12/1993 5,851.261 A * 12, 1998 Markusch et al. ........... T1/64.07 WO 2009/022432 A1 2, 2009 6,338,746 B1 1, 2002 Detricket al. WO 2010/088227 A1 8, 2010 6,537,611 B1 3, 2003 Detricket al. WO 2010/115759 A2 10/2010 6,663,686 B1 12, 2003 Geiger et al. WO 2012, 173938 A1 12/2012 6,682,751 B1 1, 2004 Hargrove et al. OTHER PUBLICATIONS 7,267,707 B2 9, 2007 Rosenthal et al. 7,544,736 B2 6, 2009 Zhou et al. 7,682,656 B2 3, 2010 Xing et al. International Preliminary Report on Patentability received for PCT 7,713,326 B2 5, 2010 Carstens et al. Patent Application No. PCT/US2012/041951, mailed on Jan. 3, 7,771.505 B2 8, 2010 Ogle et al. 2014, 8 pages. 8,759,594 B2 6, 2014 Abillard et al. 2004, OO16276 A1 1, 2004 Wynnyk et al. * cited by examiner U.S. Patent Jun. 16, 2015 US 9,056,940 B2 S-Old S.W. N.W. rs cran cd US 9,056,940 B2 1. 2 ALPHATIC POLYESTERPOLYOLS FROM oxidation of cyclohexane, followed by nitric acid conversion CYCLOHEXANE OXDATION BYPRODUCT to diacids, such as adipic acid, and processing of byproduct STREAMS AS PRECURSORS FOR wastestreams. This contacting, or extraction results in a two POLYURETHANE AND phase mixture that, after phase separation, yields a purified POLYSOCYANURATE POLYMERS cyclohexane stream containing K, A, and CHHP (which can be subjected to known high-yield processes to convert CHHP CROSS-REFERENCE TO RELATED to KA) and a byproduct water stream. The byproduct water APPLICATIONS stream (“Water Wash') contains various mono- and di-acids, hydroxy-acids, and other oxidation byproducts formed dur This application claims the benefit of priority of U.S. pro 10 ing the initial oxidation of cyclohexane. visional applications 61/496.268, filed Jun. 13, 2011, and Regardless of whether a water wash is performed as an 61/496,868, filed Jun. 14, 2011, the disclosures of which are intermediate step, the stream containing K, A, and CHHP is incorporated herein by reference in their entireties. further processed by methods well known in the art, to com plete conversion of CHHP to K and A. The resulting mixture BACKGROUND 15 is then refined, again by methods well known in the art, to recover unconverted cyclohexane for recycle and to obtain As petroleum-based materials escalate in price and envi purified K and A for Subsequent oxidation to adipic acid or ronmental pressures increase, there is a growing need to conversion to caprolactam. To Summarize, the byproduct responsibly utilize, to the greatest extent possible, all prod streams, sometimes referred to herein as “by-product’ ucts from petrochemical processes, which includes the streams, available from a cyclohexane oxidation process byproducts that are unavoidably formed along with the include “Water Wash' (the aqueous stream produced by water desired main products. Reaction byproducts are often mix extraction of cyclohexane oxidate) and “NVR (the high tures that may be complex in composition, difficult to use boiling distillation bottoms from KA refining), CAS Registry directly, and difficult and/or costly to purify. They are fre Number 6841 1-76-7. Concentration of “Water Wash” by quently treated as materials of little or no value, for example 25 removal of at least some of the water produces a stream being discarded or burned for fuel value. known as “COP Acid.” CAS Registry Number 68915-38-8. It is known in the manufacture of adipic acid or caprolac See also published US patent applications US2004/0054235 tam from cyclohexane that byproduct streams result because describing production of “non-volatile residue', high-boiling the chemical transformations do not proceed perfectly in distillation bottoms from distillative recovery of cyclohexane 100% yield. These byproduct streams contain a variety of 30 oxidation products cyclohexanol and cyclohexanone, termed molecules having functionalities which include, among oth “NVR, having low chromium content, more suitable for ers, one or more alcohol, alkene, carboxylic acid, lactone, combustion, US2012/0064252 and US2012/0101009, incor ester, and ketone groups, and combinations thereof. These porated herein by reference, describing processing of NVR, byproduct streams are complex mixtures. It is known to use Water Wash, or COP acid through conversion of free acid Some byproduct streams for their fuel value. In Such uses, 35 functional groups to monomeric esters and oligomeric esters, there is little or no recognition or recovery of value for the and converting oligomeric esters to monomeric esters. functionality present in the byproduct stream. As a result, “Water Wash”, “COP Acid, and “NVR are known to most of the byproduct stream from adipic acid manufacture contain both mono- and poly-functional materials (functional remains underutilized. monomers), mainly with the functional groups comprising Manufacture of adipic acid from cyclohexane generally 40 acids, peroxides, ketones, alcohols, and esters. Other func involves two steps.
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