Selective hydroformylation of polyunsaturated fats with a rhodium‐triphenylphosphine catalyst

Frankel, E. N.; Thomas, Frederick

doi:10.1007/bf02545129

Cited by 42 publications

(23 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The observed rate expressions for the catalyst systems, Rh/Ph 3 P and Rh/(PhO) 3 P, were formulated based on the data collected (Eqs. 2,3): [1] where n Rh is the number of moles of rhodium used, (∆n) re is the number of moles of double bonds reacted at time interval ∆t, and [2] [3]…”

Section: Methodsmentioning

confidence: 99%

“…The chemical composition of vegetable oils consists of TG esters with three dominant FA, oleic, linoleic, and linolenic acids having internal double bonds. Hydroformylation, commonly known as the oxo process, is an environmentally friendly process by which those TG can be converted to polyaldehydes (1)(2)(3)(4). Whereas the kinetics and mechanism of simple olefin hydroformylation over phosphine-or phosphitemodified rhodium catalysts have been reported (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16), the effects of reaction parameters on the reaction rates of unsaturated FA esters, TG, or vegetable oils have not been extensively investigated (17)(18)(19).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Kinetics of the hydroformylation of soybean oil by ligand‐modified homogeneous rhodium catalysis

Kandanarachchi

Guo

Demydov

et al. 2002

J Americ Oil Chem Soc

View full text Add to dashboard Cite

The kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand-modified rhodium catalysts were investigated at 70-130°C and 4000-11,000 kPa. The effects of reaction rates on systematic variations in reaction parameters were evaluated in order to develop an industrial process to convert vegetable oils to polyaldehydes. The activation energies in the presence of triphenylphosphine (Ph 3 P) (61.1 ± 0.8 kJ/mol) (mean ± SD) and triphenyl phosphite [(PhO) 3 P] (77.4 ± 5.0 kJ/mol) were determined. The catalyst was deactivated at temperatures higher than 100°C. An evaluation of the effects of the reaction parameters on initial rates yielded the rate laws for Ph 3 P {rate = k [olefin][Rh(CO) 2 Acac] 1.1 [Ph 3 P] −0.5 (pH 2 + pCO) 1.4 , where Rh(CO) 2 Acac is (acetylacetonato)dicarbonylrhodium (I)} and (PhO) 3 P {rate = [olefin] [Rh(CO) 2 Acac] 1.2 [(PhO) 3 P] −0.8 (pH 2 + pCO) 0.9 at total pressures lower than 7000 kPa, and rate = [olefin] [Rh(CO) 2 Acac] 1.2 [(PhO) 3 P] −0.8 (pH 2 + pCO) 1.7 at total pressures higher than 7000 kPa}.Strategic research in the development of new technologies for the conversion of biobased feedstocks such as vegetable oils to value-added products is important for economic growth in the environmentally conscious, yet highly competitive, global economy. The chemical composition of vegetable oils consists of TG esters with three dominant FA, oleic, linoleic, and linolenic acids having internal double bonds. Hydroformylation, commonly known as the oxo process, is an environmentally friendly process by which those TG can be converted to polyaldehydes (1-4). Whereas the kinetics and mechanism of simple olefin hydroformylation over phosphine-or phosphitemodified rhodium catalysts have been reported (5-16), the effects of reaction parameters on the reaction rates of unsaturated FA esters, TG, or vegetable oils have not been extensively investigated (17)(18)(19).We now report the results of a kinetic investigation of the conversion of soybean oil to polyaldehydes by the hydroformylation reaction using homogeneous rhodium catalysis under the reaction conditions relevant to industrial processes. Scheme 1 shows the hydroformulations of a model TG ester having one (oleic) and two (linoleic) double bonds. EXPERIMENTAL PROCEDURESThe iodine value of soybean oil (ADM, Decatur, IL) was measured, and the oil was used as received. Acetone (HPLC grade), acetonitrile (HPLC grade), triphenylphosphine (Ph 3 P; 99%), and triphenyl phosphite [(PhO) 3 P; 99+%] were purchased from Acros Organics (Fairlawn, NJ), as was toluene (HPLC grade, Fisher, Fairlawn, NJ); these were used as received. FTIR measurements were made as thin films of liquid samples on NaCl windows by a PerkinElmer (Spectra 1000) spectrometer. HPLC analysis was performed by using a Waters 1525 binary pump, a Waters 2410 refractive index, and Waters 2487 dual λ absorbance detectors.A detailed description of the hydroformylation reactor and the kinetic procedure are reported elsewhere (3). The experimental setup used to evaluate t...

show abstract

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Kinetics of the hydroformylation of soybean oil by ligand‐modified homogeneous rhodium catalysis

Kandanarachchi

Guo

Demydov

et al. 2002

J Americ Oil Chem Soc

View full text Add to dashboard Cite

show abstract

“…Materials ttydroformylated vegetable oil esters were prepared as previously reported (6,8). Ethylene glycol (Matheson, Coleman & Bell, Norwood, Ohio; 99+%) and trimethyl orthoformate CH(OCH3)3, (Aldrich Chemical Co., Milwaukee, Wisc.…”

Section: Methodsmentioning

confidence: 99%

Ethylene and dimethyl acetals from hydroformylated linseed, soybean, and safflower methyl esters as plasticizers for polyvinyl chloride

Awl

Frankel

Pryde

et al. 1974

J Americ Oil Chem Soc

Self Cite

View full text Add to dashboard Cite

Dimethyl and ethylene acetals of polyformylated unsaturated fatty esters were prepared, characterized, and evaluated as polyvinyl chloride plasticizers. Dimethyl acetals were prepared with trimethyl orthoformate as a water scavenger in the acid catalyzed acetalation reaction. With ethylene acetals, water was removed azeotropically. Although the acetals prepared were mixtures, molecular distillation gave diacetal esters of 80–90% purity and triacetal esters of 80–95% purity. The samples were characterized by gas liquid chromatography and by IR and NMR spectra. Compared to di‐2‐ethylhexyl phthalate as a plasticizer for polyvinyl chloride, the triacetal esters (both dimethyl and ethylene acetals) gave less migration and at least equivalent volatility characteristics; the triacetals also gave equivalent compatibility and strength, but somewhat less desirable low temperature and heat stability properties. The diacetal esters also had good compatibility, equivalent strength, somewhat better low temperature, but less desirable migration and volatility properties.

show abstract

“…The synthesis of polyols by the hydroformylation of natural oils has been studied previously [1,2]. However, the molecular weight of such polyols is limited by the molecular weight and extent of unsaturation of the starting natural oil.…”

Section: Introductionmentioning

confidence: 99%

Vegetable oil‐based triols from hydroformylated fatty acids and polyurethane elastomers

Petrovìć

Cvetković

Hong

et al. 2010

Euro J Lipid Sci & Tech

View full text Add to dashboard Cite

Novel bio-based polyols were prepared from hydroformylated oleic acid (9/10-hydroxymethyl-octadecanoic acid) methyl esters (HFME) and trimethylolpropane by transesterification. Hydroformylation produces primary hydroxyls, which allow relatively lower transesterification temperatures and better yields than hydroxy fatty acids with secondary hydroxyl groups. These non-crystallizing polyols have no double bonds and their viscosities are acceptable. Polyurethane (PU) elastomers prepared by reaction of these polyols with diphenylmethane diisocyanate had glass transition temperatures from -33 to -56 7C, depending on the molecular weight of the triols. Tensile strength and Shore A hardness were higher, and elongation, swelling and sol fraction lower than those of corresponding networks from polyricinoleic acid polyols. The plasticizing effect of longer dangling chains in HFME-based PU compensated, to a degree, the presence of double bonds in ricinoleic acid, effectively resulting in similar glass transitions between the two families of polyols. Lipid Sci. Technol. 2010, 112, 97-102 97 Practical applicationsNovel triols of high molecular weight, suitable as base polyols for flexible foams, were prepared and tested in cast polyurethane elastomers. The polyols exhibit excellent reactivity, high enough molecular weight and high regularity as well as low glass transitions. The polyurethane networks displayed good elastomeric properties.

show abstract

Selective hydroformylation of polyunsaturated fats with a rhodium‐triphenylphosphine catalyst

Cited by 42 publications

References 7 publications

Kinetics of the hydroformylation of soybean oil by ligand‐modified homogeneous rhodium catalysis

Kinetics of the hydroformylation of soybean oil by ligand‐modified homogeneous rhodium catalysis

Ethylene and dimethyl acetals from hydroformylated linseed, soybean, and safflower methyl esters as plasticizers for polyvinyl chloride

Vegetable oil‐based triols from hydroformylated fatty acids and polyurethane elastomers

Contact Info

Product

Resources

About