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RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

ABSTRACT: RAFT solution polymerization of N-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA₆₃-PNMEP _x diblock copolymers. High conversions (?92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M_n with increasing PNMEP DP. A gradual increase in M_w/M_n was also observed when targeting higher DPs. However, this problem could be minimized (M_w/M_n < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both ¹H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA₆₃-PNMEP _x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA₈₅-PNMEP _x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ? 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses.

SUBMITTER: Cunningham VJ

PROVIDER: S-EPMC4928143 | biostudies-literature | 2016 Jun

REPOSITORIES: biostudies-literature

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RAFT Aqueous Dispersion Polymerization of <i>N</i>-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

Cunningham Victoria J VJ Derry Matthew J MJ Fielding Lee A LA Musa Osama M OM Armes Steven P SP

Macromolecules 20160608 12

RAFT solution polymerization of <i>N</i>-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was c ...[more]

PMID: 27375300

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Project description:A near-monodisperse poly(stearyl methacrylate) macromolecular chain transfer agent (PSMA macro-CTA) was prepared via reversible addition-fragmentation chain transfer (RAFT) solution polymerisation in toluene. This PSMA macro-CTA was then utilised as a stabiliser block for the RAFT dispersion polymerisation of a highly polar monomer, N-2-(methacryloyloxy)ethyl pyrrolidone (NMEP), in n-dodecane at 90 °C. 1H NMR studies confirmed that the rate of NMEP polymerisation was significantly faster than that of a non-polar monomer (benzyl methacrylate, BzMA) under the same conditions. For example, when targeting a PSMA14-PNMEP100 diblock copolymer, more than 99% NMEP conversion was achieved within 30 min, whereas only 19% BzMA conversion was obtained on the same time scale for the corresponding PSMA14-PBzMA100 synthesis. The resulting PSMA-PNMEP diblock copolymer chains underwent polymerisation-induced self-assembly (PISA) during growth of the insoluble PNMEP block to form either spherical micelles, highly anisotropic worms or polydisperse vesicles, depending on the target DP of the PNMEP chains. Systematic variation of this latter parameter, along with the solids content, allowed the construction of a phase diagram which enabled pure morphologies to be reproducibly targeted. Syntheses conducted at 10% w/w solids led to the formation of kinetically-trapped spheres. A monotonic increase in particle diameter with PNMEP DP was observed for such PISA syntheses, with particle diameters of up to 462 nm being obtained for PSMA14-PNMEP960. Increasing the copolymer concentration to 15% w/w solids led to worm-like micelles, while vesicles were obtained at 27.5% w/w solids. High (≥95%) NMEP conversions were achieved in all cases and 3 : 1 chloroform/methanol GPC analysis indicated relatively high blocking efficiencies. However, relatively broad molecular weight distributions (Mw/Mn > 1.50) were observed when targeting PNMEP DPs greater than 150. This indicates light branching caused by the presence of a low level of dimethacrylate impurity. Finally, PSMA14-PNMEP49 spheres were evaluated as Pickering emulsifiers. Unexpectedly, it was found that either water-in-oil or oil-in-water Pickering emulsions could be obtained depending on the shear rate employed for homogenisation. Further investigation suggested that high shear rates lead to in situ inversion of the initial hydrophobic PSMA14-PNMEP49 spheres to form hydrophilic PNMEP49-PSMA14 spheres.

Project description:Poly(N-vinylpyrrolidone) (PNVP) is a well-known, highly polar, nonionic water-soluble polymer. However, N-vinylpyrrolidone (NVP) usually exhibits strongly non-ideal behavior when copolymerized with methacrylic or styrenic monomers. Moreover, NVP is not particularly well-controlled under living radical polymerization conditions. For these reasons, alternative pyrrolidone-based monomers have been investigated. For example, the reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-(N-methacryloyloxy)ethylpyrrolidone (NMEP) has been recently investigated using various polymerization formulations. However, PNMEP homopolymers are significantly less hydrophilic than PNVP and exhibit inverse temperature solubility in aqueous solution. In the present work, we studied the RAFT aqueous solution polymerization of 2-(N-acryloyloxy)ethylpyrrolidone (NAEP) using either AIBN at 70 °C or a low-temperature redox initiator at 30 °C. PNAEP homopolymers are obtained in high yield (>99%) with good control (M w/M n < 1.20) for target degrees of polymerization (DP) of up to 400 using the latter initiator, which produced relatively fast rates of polymerization. However, targeting DPs above 400 led to lower NAEP conversions and broader molecular weight distributions. 2-Hydroxyethyl acrylate (HEA) and oligo(ethylene glycol) methyl ether acrylate (OEGA) were chain-extended using a PNAEP x macro-CTA via RAFT aqueous solution polymerization, yielding double-hydrophilic acrylic diblock copolymers with high conversions (>99%) and good control (M w/M n < 1.31). In addition, a PNAEP95 macro-CTA was chain-extended via RAFT aqueous solution polymerization of N-isopropylacrylamide (NIPAM) at 22 °C. Dynamic light scattering (DLS) analysis indicated that heating above the lower critical solution temperature of PNIPAM led to so-called "anomalous micellization" at 35 °C and the formation of near-monodisperse spherical micelles at 40 °C. Finally, 2-(diethylamino)ethyl methacrylate (DEA) was polymerized using an N-morpholine-functionalized trithiocarbonate-based RAFT chain transfer agent and subsequently chain-extended using NAEP to form a novel pH-responsive diblock copolymer. Above the pK a of PDEA (?7.3), DLS and 1H NMR studies indicated the formation of well-defined PDEA-core spherical micelles.

Project description:A poly(2-(dimethylamino)ethyl methacrylate) (PDMA) chain transfer agent (CTA) is used for the reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization of benzyl methacrylate (BzMA) in ethanol at 70 °C. THF GPC analysis indicated a well-controlled polymerization with molecular weight increasing linearly with conversion. GPC traces also showed high blocking efficiency with no homopolymer contamination apparent and Mw/Mn values below 1.35 in all cases. 1H NMR studies confirmed greater than 98% BzMA conversion for a target PBzMA degree of polymerization (DP) of up to 600. The PBzMA block becomes insoluble as it grows, leading to the in situ formation of sterically stabilized diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA). Fixing the mean DP of the PDMA stabilizer block at 94 units and systematically varying the DP of the PBzMA block enabled a series of spherical nanoparticles of tunable diameter to be obtained. These nanoparticles were characterized by TEM, DLS, MALLS, and SAXS, with mean diameters ranging from 35 to 100 nm. The latter technique was particularly informative: data fits to a spherical micelle model enabled calculation of the core diameter, surface area occupied per copolymer chain, and the mean aggregation number (Nagg). The scaling exponent derived from a double-logarithmic plot of core diameter vs PBzMA DP suggests that the conformation of the PBzMA chains is intermediate between the collapsed and fully extended state. This is in good agreement with 1H NMR studies, which suggest that only 5-13% of the BzMA residues of the core-forming chains are solvated. The Nagg values calculated from SAXS and MALLS are in good agreement and scale approximately linearly with PBzMA DP. This suggests that spherical micelles grow in size not only as a result of the increase in copolymer molecular weight during the PISA synthesis but also by exchange of individual copolymer chains between micelles and/or by sphere-sphere fusion events.

Dataset Information

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

Publications

RAFT Aqueous Dispersion Polymerization of <i>N</i>-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

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