Controlled RAFT synthesis of side-chain oleic acid containing polymers and their post-polymerization functionalization

Maiti, Binoy; Kumar, Sonu; De, Priyadarsi

doi:10.1039/c4ra08872g

Cited by 32 publications

(45 citation statements)

References 39 publications

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“…In order to overcome this drawback, some research groups focused on the copolymerization of vegetable oils with a more reactive co‐monomer to provide suitable additives for lubricating oil . However, FA could be also functionalized with (meth)acrylate moieties to overcome their poor reactivity in radical polymerization . For instance, Maiti et al .…”

Section: Introductionmentioning

confidence: 99%

Oleic acid‐based poly(alkyl methacrylate) as bio‐based viscosity control additive for mineral and vegetable oils

Lomège

Négrell

Robin

et al. 2018

Polymer Engineering & Sci

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This work described the design of an efficient oleic‐acid based viscosity control additive for lubricating oils as potential alternative to petroleum poly(alkyl)methacrylates (PAMAs) additives. Hence, Poly(2‐(methacryloyloxy)ethyl oleate) (PMAEO) was synthesized by free radical homopolymerization to afford a comb‐like polymer structure similar to common PAMAs. Then, in order to evaluate its efficiency as viscosity control additive, the resulting polymer was mixed at several concentrations from 1%wt to 10%wt with different oil compositions, including a mineral paraffinic oil (MPO) and an organic triglyceride oil (OTO). For all polymer‐solution blends, relative viscosities (RV) measurements showed that addition of PMAEO in MPO had a better contribution on oil viscosity at 100°C than at 20°C (RV = 1.16 at 40°C while RV = 1.25 for 3%wt of PMAEO in MPO). These results were attributed to the coil expansion of polymer chains with increasing temperature. Additionally, rheological studies showed that addition of 3%wt of PMAEO in MPO improved the MPO cold flow properties at −30°C by decreasing the required yield stress to put the oil in motion from 310 mPa to 42 mPa. These results are in total accordance with the common viscosimetric properties of PAMAs‐based viscosity control additives at low and high temperature in mineral oils. POLYM. ENG. SCI., 59:E164–E170, 2019. © 2018 Society of Plastics Engineers

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Section: Introductionmentioning

confidence: 99%

Oleic acid‐based poly(alkyl methacrylate) as bio‐based viscosity control additive for mineral and vegetable oils

Lomège

Négrell

Robin

et al. 2018

Polymer Engineering & Sci

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“…Methacrylic acid, allyl amine, phenethylamine, and triethylamine were purchased from Merck Chemicals (India). MAEO monomer was synthesized as reported earlier . The RAFT chain‐transfer agent (CTA) 2‐cyanopropan‐2‐yl benzodithioate (CPDB) was synthesized by following the standard literature procedure .…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we have polymerized methacrylate monomer 2‐(methacryloyloxy) ethyl oleate (MAEO) containing oleic acid side chains in a controlled fashion by a reversible addition–fragmentation chain‐transfer (RAFT) process. The C=C double bond in oleate side chains of the homopolymer (PMAEO) reacted with various organic thiol compounds in a thermally initiated thiol‐ene reaction . Post‐polymerization functionalization of polymers bearing dual‐functional reactive units in a sequential one‐pot reaction could be an important method for creating single‐reactive polymers to generate a diverse library of functional polymers.…”

Section: Introductionmentioning

confidence: 99%

Functional‐Polymer Library through Post‐Polymerization Modification of Copolymers Having Oleate and Pentafluorophenyl Pendants

Maiti

Haldar

Rajasekhar

et al. 2017

Chemistry A European J

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Poly[2-(methacryloyloxy)ethyl oleate-co-pentafluorophenyl methacrylate] [P(MAEO-co-PFPMA)] random copolymers with oleate and pentafluorophenyl side-chain pendants were synthesized. These copolymers were utilized as dual-reactive polymeric scaffolds in a range of post-polymerization modification strategies involving thiol-ene and para-fluoro-thiol substitution, amidation, trans-esterification, and epoxidation followed by amidation. The 2-(methacryloyloxy)ethyl oleate (MAEO) functional handle in the copolymer is open to functionalization at its internal double bond through thermally initiated thiol-ene reaction, whereas the pentafluorophenyl moiety of the pentafluorophenyl methacrylate (PFPMA) unit undergoes para-fluoro-thiol substitution under basic conditions at room temperature. By means of these modification approaches, the P(MAEO-co-PFPMA) copolymer was orthogonally ligated with thiol compounds having, for example, alkyl, hydroxyl, and protected amine functional groups. Furthermore, different functional groups such as benzyl, allyl, methacrylate, pyrene, and water-soluble poly(ethylene glycol) were easily introduced into the side chain of the P(MAEO-co-PFPMA) copolymer by amidation, trans-esterification, and epoxidation followed by amidation. Functionalization of both the reactive pendants with the various organic substituents was confirmed by H and F NMR spectroscopy, gel permeation chromatography, and fluorescence spectroscopy.

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“…Then, the vial was put in a preheated reaction block, which was already set at 60 °C for 10 h. Polymerization reaction was quenched by cooling the vial in ice‐water bath, and the polymer was purified by reprecipitation in MeOH at least five times (from acetone solution) and dried under high vacuum at room temperature to obtain a yellowish sticky material. The average degree of polymerization (DP n ) for this PMAEO macroCTA has been calculated as 14 via 1 H NMR spectroscopy by comparing the signal integration ratio of oxyethylene protons (4H) of PMAEO repeating units at 4.03–4.39 ppm to the chain end peak from CDP moiety at 2.5 ppm …”

Section: Methodsmentioning

confidence: 99%

“…In our earlier report, we showed that the oleic acid derived methacrylate monomer (having one chemoselective pendant double bond) was dormant during the RAFT polymerization and molecular weight control was obtained up to ∼30,000 g/mol. Double bonds in oleate side‐chains in the polymer were reactive under some specific post‐polymerization conditions to afford a set of functionalized polymers with well‐defined macromolecular characteristics . With this knowledge of RAFT tolerance of oleate moiety, herein we prepared its corresponding homopolymer of definite chain length (macroCTA), and exploited as steric stabilizer for non‐polar RAFTDP of BzMA.…”

Section: Introductionmentioning

confidence: 99%

Surface functionalized nano‐objects from oleic acid‐derived stabilizer via non‐polar RAFT dispersion polymerization

Maiti

Bauri

Nandi

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Surface functionalization in a nanoscopic scaffold is highly desirable to afford nano‐particles with diversified features and functions. Herein are reported the surface decoration of dispersed block copolymer nano‐objects. First, side‐chain double bond containing oleic acid based macro chain transfer agent (macroCTA), poly(2‐(methacryloyloxy)ethyl oleate) (PMAEO), was synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization and used as a steric stabilizer during the RAFT dispersion block copolymerization of benzyl methacrylate (BzMA) in n‐heptane at 70 °C. We have found that block copolymer morphologies could evolve from spherical micelles, through worm to vesicles, and finally to large compound vesicles with the increase of solvophobic poly(BzMA) block length, keeping solvophilic chain length and total solid content constant. Finally, different thiol compounds having alkyl, carboxyl, hydroxyl, and protected amine functionalities have been ligated onto the PMAEO segment, which is prone to functionalization via its reactive double bond through thiol‐ene radical reactions. Thiol‐ene modification reactions of the as‐synthesized nano‐objects retain their morphologies as visualized by field emission‐scanning electron microscopy. Thus, the facile and modular synthetic approach presented in this study allowed in situ preparation of surface modified block copolymer nano‐objects at very high concentration, where renewable resource derived oleate surface in the nanoparticle was functionalized. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 263–273

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Controlled RAFT synthesis of side-chain oleic acid containing polymers and their post-polymerization functionalization

Abstract: We report the synthesis and characterization of well-defined polymers from oleic acid as the bio-renewable resource. Double bonds in oleate side-chains in the polymer are further modified by thiol-ene reaction, epoxidation, and cross-linking.

Cited by 32 publications

References 39 publications

Oleic acid‐based poly(alkyl methacrylate) as bio‐based viscosity control additive for mineral and vegetable oils

Oleic acid‐based poly(alkyl methacrylate) as bio‐based viscosity control additive for mineral and vegetable oils

Functional‐Polymer Library through Post‐Polymerization Modification of Copolymers Having Oleate and Pentafluorophenyl Pendants

Surface functionalized nano‐objects from oleic acid‐derived stabilizer via non‐polar RAFT dispersion polymerization

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