Synthesis and spectral characterization of methyl 9(10)-dialkylphosphonostearates

Bantchev, Grigor B.; Biresaw, Girma; Vermillion, Karl E.; Appell, Michael

doi:10.1016/j.saa.2013.02.039

Cited by 15 publications

(15 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…7. The spectra show peaks only in the 30-40 ppm region, which is consistent with the presence of phosphonates [65][66][67]. The crude product obtained after distillation of the dialkyl phosphite showed no signals in the region of 6-12 ppm.…”

Section: Synthesissupporting

confidence: 59%

Tribological Properties of Limonene Bisphosphonates

Biresaw

Bantchev

2015

Tribol Lett

Self Cite

View full text Add to dashboard Cite

Limonene was chemically modified by reacting it with dialkyl phosphites of varying alkyl structures under inert atmosphere in the presence of free radical initiators. The reaction gave a mixture of mono-and di-adduct products and was optimized to produce only the di-adduct product limonene bisphosphonate by forcing both limonene double bonds to react completely. The product mixture was carefully characterized using a combination of gas chromatography-mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy ( 1 H, 13 C, 31 P). The bisphosphonates were investigated for their physical and tribological properties. The alkyl bisphosphonates displayed density and viscosity that was a function of the alkyl structure (methyl, ethyl, n-butyl) and much higher than the values for the unreacted limonene. They also displayed improved oxidation stability but lower viscosity index and solubility in polyalphaolefin (PAO6) and higholeic sunflower oil (HOSuO) base oils. Tribological characterization of the neat modified oils on a four-ball tribometer showed improved extreme-pressure weld point by all three di-adducts and improved anti-wear coefficient of friction (COF) and wear scar diameter (WSD) by the nbutyl di-adduct only. The limonene bisphosphonates also displayed improved COF and WSD as additives in PAO6 and HOSuO base oils at low concentrations. The effects of chemical modifications on physical and tribological properties can be explained in terms of increased polarity of the modified products, insertion of heavy atoms (from PO 3 ) into the limonene structure, and complete absence of unsaturation in the modified products.

show abstract

Section: Synthesissupporting

confidence: 59%

Tribological Properties of Limonene Bisphosphonates

Biresaw

Bantchev

2015

Tribol Lett

Self Cite

View full text Add to dashboard Cite

show abstract

“…2a). Both the shift and the splitting pattern are typical of carbons bonded directly to a P atom [9,18,19]. 31 P{H} showed seven peaks in the region 37-33.5 ppm (Fig.…”

Section: Nmr Characterizationmentioning

confidence: 98%

“…The detailed NMR spectra of the products are found in the Supplementary Information. The signals in the NMR spectra were assigned based on the previous data on monophosphonate spectra [9].…”

Section: Nmr Characterizationmentioning

confidence: 99%

“…Triglyceride derivatives with incorporated phosphorus atoms (phosphine oxide and phosphonate groups) possess a flame retardant property [7,8]. In our previous work, we synthesized phosphonate derivatives of methyl oleate and limonene using radical dialkyl phosphite (H-phosphonate)-ene reactions [9,10]. The products showed promising antiwear and extreme-pressure properties and had good pour and cloud points [10,11].…”

Section: Introductionmentioning

confidence: 99%

“…The radical-initiated reaction between methyl oleate and dialkyl phosphite was carried out previously [2,9]. Similar dialkyl phosphite-ene reactions between methyl linoleate and dialkyl phosphites proved more challenging, due to the inhibitory effect of the bis-allylic hydrogens.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and Characterization of Phosphonates from Methyl Linoleate and Vegetable Oils

Bantchev

Moser

Murray

et al. 2016

J Americ Oil Chem Soc

Self Cite

View full text Add to dashboard Cite

Phosphonates were synthesized on a medium scale (~200 g) from three lipids—methyl linoleate (MeLin), high‐oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites—methyl, ethyl and n‐butyl, using a radical initiator. A staged addition of the lipid and the initiator was used to achieve good yields. Good results were observed with MeLin (94–99% conversions of the double bonds, as determined by NMR, and 83–99% isolated yields) and HOSO (99–100% NMR conversions, 87–96% isolated yields) using tert‐butyl perbenzoate as the initiator. With SBO, benzoyl peroxide was used as the initiator, due to its capability to generate radicals at a higher rate at slightly lower temperatures, and thus to shorten the reaction time. Conversions of 91–93% (by NMR) and isolated yields of 80–94% were achieved. The progress of the reaction was monitored with GC–MS. The products were characterized using 1H, 13C and 31P NMR, IR and gel permeation chromatography. A prolonged reaction led to some transesterification between the carboxylic and phosphite ester groups. Conditions favoring higher reaction rates led to the formation of more oligomers and benzoate fatty ester byproducts. The benzoate fatty ester byproducts were formed by the attack of a benzoate radical on a double bond. The more double bonds that were present per lipid molecule, the more oligomers were formed: MeLin 2–8%, HOSO 3–9% and SBO 8–29%.

show abstract

Vegetable Oils in Lubrication

Biresaw

2020

Bailey's Industrial Oil and Fat Products

View full text Add to dashboard Cite

Vegetable oils and their derivatives are commercially used in lubricant formulations as both base oils and additives. They are major players in the growing biobased lubricant market because they provide a wide range of benefits, including superior environmental and health properties. Vegetable oils are applied in lubrication in various forms. In the past, vegetable oils have been used directly as base oils in the presence of a variety of additives (e.g. antioxidants), or blended with petroleum base oils, such as polyalphaolefins, to enhance their performance. Vegetable oils are also used in lubrication after undergoing chemical, thermal, or enzymatic modifications to enhance their performance. Examples of such commercial products include epoxidized, heat‐bodied, and blown vegetable oils. More recently, vegetable oils are used to produce fatty acids (FAs) and fatty acid methyl esters (FAMEs), which are used in lubrication directly or after further modifications. Examples of such products include estolides, epoxidized FAMEs, and phosphonated FAMEs. In the latest applications, vegetable oils, their FAs, and FAMEs are used to produce base oils with renewable carbon via various biorefinery processes, where they are subjected to deoxygenation, isomerization, and other processes. These products have similar structures as petroleum‐based oils and can be used as “drop‐in” components to enhance the bio‐content of lubricants to meet regulatory and environmental requirements (e.g. BioPreferred), without affecting performance. Such application of vegetable oils has a significant market potential since petroleum‐based lubricant formulations are extremely affordable and account for >98% of the current global lubricant market.

show abstract

Synthesis and spectral characterization of methyl 9(10)-dialkylphosphonostearates

Cited by 15 publications

References 21 publications

Tribological Properties of Limonene Bisphosphonates

Tribological Properties of Limonene Bisphosphonates

Synthesis and Characterization of Phosphonates from Methyl Linoleate and Vegetable Oils

Vegetable Oils in Lubrication

Contact Info

Product

Resources

About