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Sanders et al. 37742. Producing Polyurethane Foamfrom Natural OilAaron Sanders, David Babb, Robbyn Prange, Mark Sonnenschein, Van Delk,Chris Derstine and Kurt OlsonAbstractThe Dow Chemical Company, 2301 N Brazosport Blvd., Freeport, TX, 77541awsanders@dow.comAs part of the effort to reduce our dependence on fossil fuels, The Dow ChemicalCompany has been developing a seed oil based polyol to be used as a replacement toconventional petrochemical based polyether polyols in the production of flexiblepolyurethane foam. The general process for making natural oil polyols consists offour steps. In the first step, a vegetable oil (triglyceride) is transesterified withmethanol, liberating glycerin, and forming fatty acid methyl esters or FAMEs. In thesecond step the FAMEs are hydroformylated giving a complex mixture of FAMEsthat contain 0-3 formyl groups per chain. In the third step, the aldehydes and theremaining unsaturates are hydrogenated to yield a mixture of FAMEs that contain0-3 hydroxymethyl groups. Finally, the poly(hydroxymethyl)fatty esters aretransesterified onto a suitable initiator to produce the natural oil polyol.IntroductionThe preparation of polyester polyols from seed oils for the production of a variety ofpolyurethane products has been previously reported (1,2). The development ofprocess and product technology that is sufficiently robust to compensate for inherentvariability in products derived from natural resources is key to successfulimplementation. Product variability is primarily due to genetic variety in feedstocksand seasonal inconsistency, such as regional rainfall totals or pests and disease.Process technology that may be applied to a wide variety of potential feedstockswould be highly desirable.Dow’s process for producing natural oil polyols consists of four steps and isshown in Figure 1. In the first step, a vegetable oil (triglyceride) is transesterifiedwith methanol, liberating glycerin and forming fatty acid methyl esters (FAMEs). Inthe second step the FAMEs are hydroformylated to create a complex mixture ofFAMEs that contain 0-3 formyl groups per chain. In the third step, the aldehydesand the remaining unsaturation are hydrogenated to yield a mixture of FAMEs thatcontain 0-3 hydroxymethyl groups. In the final step the poly(hydroxymethyl)fattyesters are transesterified onto a suitable initiator to produce the natural oil polyol.This paper will review the process, emphasizing the catalysts employed in each step.
378 Polyurethane from Natural OilMethanolysis: Triglyceride + MeOHOH -OO(FAMEs)+ glycerineHydroformylation:OOH2 + COCatalystOOOHydrogenation:OOOH2 / CatalystOOMonomerOHOOOOOROHnRPolymerization: Monomer + Initiator Catalyst+ MeOHFigure 1. Process for producing natural oil polyolsROHnOHOnResults and DiscussionThe composition of seed oil triglycerides is well understood. Triglycerides are fattyacid esters of glycerin, and the composition depends on the source of the oil (Figure2). The nomenclature used is standard in the fats and oils industry, with the numberof carbons in the fatty acid indicated first, followed by the number of sites ofunsaturation in parentheses.OC16(0) - PalmiticOOMeC18(0) - StearicC18(1) - OleicC18(2) - LinoleicC18(3) - LinolenicFigure 2. Methyl esters of common fatty acids found in vegetable oilsOOOOMeOMeOMeOMe
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Catalysis ofOrganic Reactions
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14. Catalyst Manufacture: Laborator
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62. Catalysis of Organic Reactions,
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108. Metal Oxides: Chemistry and Ap
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CRC PressTaylor & Francis Group6000
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xiii14. The Transformation of Light
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xviien Catalisis y Petroquimica (UN
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xix56. Transition Metal Removal fro
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xxiiiChronology of Organic Reaction
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To Zsuzsanna and Tim
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Jones et al. 31. On the Use of Immo
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Jones et al. 5three-phase tests in
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Jones et al. 7In the HKR of rac-epi
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Jones et al. 9term performance char
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Jones et al. 115. A. S. Gruber, D.
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Moses et al. 132. Supported Re Cata
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Moses et al. 15perrhenate, followed
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Moses et al. 17SnCOSnMe 4≡SiOReO
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Moses et al. 19(AlOSi) of the cube.
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Moses et al. 212.510 3 k obs / s -1
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Wang et al. 233. Catalytic Hydrogen
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Wang et al. 25The rate expressions
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Wang et al. 27Schiff’s base forma
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Wang et al. 29AcknowledgementsWe gr
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32Halophosphite LigandsIn 1970, Pru
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34Halophosphite LigandsThe ligands,
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36Halophosphite LigandsTable 2 Temp
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38Halophosphite Ligands3. P. W. N.
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40Monolithic Bioreactorstrength for
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42Monolithic BioreactorMenten equat
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Gőbölös et al. 456. Highly Selec
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Gőbölös et al. 47was practically
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Gőbölös et al. 49noteworthy that
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Gőbölös et al. 51Figure 2 NMR sp
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Gőbölös et al. 53internal TMS in
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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Mantilla, Tzompantzi, Torres and G
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68Synthesis of MIBKwe examined the
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70Synthesis of MIBK1412Conversion (
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72Synthesis of MIBK4,4’-dimethyl
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74Synthesis of MIBKobtained for MIB
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Ardizzi et al. 7710. The Control of
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Ardizzi et al. 79type acidity at th
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Ardizzi et al. 81procedure describe
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84Phenol Benzoylationconsecutive Fr
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86Phenol BenzoylationThis does not
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92Oxidation with Microchannel Immob
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100 Propylene Partial OxidationThe
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102 Propylene Partial OxidationSiO
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104 Propylene Partial Oxidation0.01
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106 Propylene Partial Oxidation0.02
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108 Propylene Partial OxidationRefe
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110Oxidation of n-Pentanemethacryli
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112Oxidation of n-PentaneFReqox1ox2
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114Oxidation of n-Pentanethe presen
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116Oxidation of n-PentaneIn the mec
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118Oxidation of n-PentaneReferences
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120TEMPO Oxidation of Alcoholsthe u
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122TEMPO Oxidation of AlcoholsThe r
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124TEMPO Oxidation of Alcoholsany d
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126TEMPO Oxidation of Alcoholsconce
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128TEMPO Oxidation of AlcoholsMNT :
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130TEMPO Oxidation of Alcoholsuptak
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132Aminoalcohols to Aminocarboxylic
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142Bromine-Free TEMPO-Based Catalys
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148CO OxidationP25 TiO 2 , respecti
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150CO Oxidation0.02(a)21802110(b)21
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152CO Oxidationcarboxylate species
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Yamauchi 15519. 2006 Murray Raney A
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Yamauchi 157transformation is schem
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Yamauchi 159The X-ray diffraction p
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Yamauchi 161was -0.0009, -0.0032 an
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Yamauchi 163shown in Fig. 12. It wa
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Yamauchi 165These fine particles we
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168Nitrobenzene Hydrogenationfurthe
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170Nitrobenzene Hydrogenationhydrog
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172Nitrobenzene HydrogenationThe co
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174Nitrobenzene HydrogenationHence
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176Nitrobenzene Hydrogenation10. G.
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178 Hydrogenation of Dehydrolinaloo
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198 Fructose HydrogenationHOHCCH 2O
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200 Fructose HydrogenationTable 1.
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202 Fructose Hydrogenationmmol form
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206 Fructose Hydrogenationcleave th
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208 Fructose Hydrogenationfulfills
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Ostgard et al. 231metal atoms. Thes
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Kuusisto, Mikkola and Salmi 23526.
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Kuusisto, Mikkola and Salmi 237100A
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242 1-Phenyl-1-Propyneof cis-β-met
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244 1-Phenyl-1-Propynealkene. When
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Angueira and White 275F igure 4 - c
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294Chiral Ferrocene Ligandsnew Twin
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296Chiral Ferrocene LigandsTable 1.
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298Chiral Ferrocene Ligandsprevents
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300Chiral Ferrocene LigandsConclusi
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302Chiral Ferrocene Ligandsextracte
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304 Catalyst Library DesignIn gas p
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306 Catalyst Library Designd−(b 0
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308 Catalyst Library DesignBasic Pr
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310 Catalyst Library DesignD in com
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312 Catalyst Library DesignCatalyst
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314 Catalyst Library Design27. S. H
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316 Dendrimer TemplatesWe are devel
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318 Dendrimer TemplatesThe differen
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320 Dendrimer TemplatesWe encounter
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322 Dendrimer TemplatesThe 100 cm -
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Page 375 and 376: 348Heteropoly AcidsSOOO O+ +OS1 2 3
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Marincean et al. 431neutralize all
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Kocal 43748. Developing Sustainable
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Kocal 441metallurgy in parts of the
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448Propylene Oxidation to POSupercr
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450Propylene Oxidation to POTable 1
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452Propylene Oxidation to PO
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Riermeier et al. 459Reaction of the
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464 Chiral 2-Amino-1-Phenylethanolp
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466 Chiral 2-Amino-1-PhenylethanolI
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468 Chiral 2-Amino-1-Phenylethanola
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470 t-Butanol DehydrationResults an
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472 t-Butanol Dehydrationcomprises
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482 Reductive AlkylationSince the p
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484 Reductive AlkylationTable 2. Re
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502 Electroreductive Catalytic Ullm
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504 Electroreductive Catalytic Ullm
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Catalysis of Organic Reactions 507A
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Catalysis of Organic Reactions 509K
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Catalysis of Organic Reactions 511T
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514 Keyword Indexcarboncarbon dioxi
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516 Keyword Indexethanolamine 16 13
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518 Keyword IndexNi, activated 25 2
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520 Keyword Indexsuccinimido ketone
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