Marginal miscibility and solvent-dependent phase behavior in solution-blended poly(vinyl methyl ether)/poly(benzyl methacrylate)

Mandal, Tarum K.; Woo, Eamor M.

doi:10.1002/(sici)1521-3935(19990501)200:5<1143::aid-macp1143>3.0.co;2-s

Cited by 16 publications

(10 citation statements)

References 14 publications

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“…A slight difference in 19 F chemical shifts between monomers and polymers enabled simple estimations of monomer conversions using 19 F NMR spectroscopy before polymer isolation. All samples of pPFBMA were powdery solids with a measured glass transition temperature of T g = 65 °C, higher than that of the non-fluorinated analogue poly(benzyl methacrylate) (T g = 54 °C), 50 but lower than that of the reactive styrenic counterpart poly(2,3,4,5,6-pentafluorostyrene) (T g = 95 °C). 51 Figure S10).…”

Section: Roth Et Al Unpublished Workmentioning

confidence: 94%

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

et al. 2017

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A methacrylic polymer undergoing highly efficient para-fluoro substitution reactions\ud is presented. A series of well-defined poly(2,3,4,5,6-pentafluorobenzyl methacrylate) (pPFBMA)\ud homopolymers with degrees of polymerization from 28 to 132 and Ð ≤ 1.29 was prepared by the\ud RAFT process. pPFBMA samples were atactic (with triad tacticity apparent in 1H and 19F NMR\ud spectra) and soluble in most organic solvents. pPFBMA reacted quantitatively through parafluoro\ud substitution with a range of thiols (typically 1.1 equiv thiol, base, RT, < 1h) in the absence\ud of any observed side reactions. Para-fluoro substitution with different (thio)carbonylthio\ud reagents was possible and allowed for subsequent one-pot cleavage of dithioester pendent groups\ud with concurrent thia-Michael side group modification. Reactions with aliphatic amines (typically\ud 2.5 equiv amine, 50–60 °C, overnight) resulted in complete substitution of the para-fluorides\ud without any observed ester cleavage reactions. However, for primary amines, H2NR, double\ud substitution reactions yielding tertiary (–C6F4)2NR amine bridges were observed, which were\ud absent with secondary amine reagents. No reactions were found for attempted modifications of\ud pPFBMA with bromide, iodide, methanethiosulfonate, or thiourea, indicating a highly selective\ud reactivity toward nucleophiles. The versatility of this reactive platform is demonstrated through\ud the synthesis of a pH-responsive polymer and novel thermoresponsive polymers: an\ud oligo(ethylene glycol)-functional species with an LCST in water and two zwitterionic polymers\ud with UCSTs in water and aqueous salt solution (NaCl concentration up to 178 mM)

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Section: Roth Et Al Unpublished Workmentioning

confidence: 94%

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

et al. 2017

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“…Pei et al measured the glass transition temperature of pPPMA to be 2 °C, which was thought to facilitate rearrangement of chains over a wide temperature range . Though notably, as the glass transition temperature is, strictly speaking, a solid state property, plasticization by solvent may increase the mobility of polymer chains of core‐forming block with higher glass transition temperatures, such as pBnMA (T g = 54 °C) …”

Section: Temperature‐responsive Dispersion Pisa Nano‐objectsmentioning

confidence: 99%

Stimulus‐Responsive Nanoparticles and Associated (Reversible) Polymorphism via Polymerization Induced Self‐assembly (PISA)

Pei

Lowe

Roth

2016

Macromol. Rapid Commun.

118

131

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"smart" materials rely on very distinct material responses on a macroscopic and/or microscopic level. This can be achieved by crafting stimulus-responsive polymers into nanostructured materials, including smart nanoparticles, which are receiving increasing attention specifically in the biomedical field. [2,3] Amphiphilic block copolymers are well-known to undergo self-directed assembly in selective solvents providing access to a range of soft matter nanoparticles [4][5][6][7] with applications in coatings, [8] electronics, [9] drug delivery, [10] and cancer therapy, [11,12] among others. Traditionally, the preparation of such nanoparticles has been accomplished by initial synthesis and molecular dissolution of well-defined parent copolymers which are subsequently "processed", often via time-consuming step-wise dialysis, to give the targeted nano-object. Another drawback of this well-established approach is the generally low concentration of the final copolymer nanoparticles (≤1.0 wt% is common) which limits industrial application and study of such nanoparticles in areas where high Polymerization-induced self-assembly (PISA) is an extremely versatile method for the in situ preparation of soft-matter nanoparticles of defined size and morphologies at high concentrations, suitable for large-scale production. Recently, certain PISA-prepared nanoparticles have been shown to exhibit reversible polymorphism ("shape-shifting"), typically between micellar, worm-like, and vesicular phases (order-order transitions), in response to external stimuli including temperature, pH, electrolytes, and chemical modification. This review summarises the literature to date and describes molecular requirements for the design of stimulus-responsive nano-objects. Reversible pH-responsive behavior is rationalised in terms of increased solvation of reversibly ionized groups. Temperature-triggered order-order transitions, conversely, do not rely on inherently thermo-responsive polymers, but are explained based on interfacial LCST or UCST behavior that affects the volume fractions of the core and stabilizer blocks. Irreversible morphology transitions, on the other hand, can result from chemical post-modification of reactive PISA-made particles. Emerging applications and future research directions of this "smart" nanoparticle behavior are reviewed.

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“…They have pointed out that poly(methyl acrylate) (PMAcr) is immiscible with PVME, but poly(ethyl acrylate) (PEAcr) is miscible with PVME with LCST at 221 °C, and that poly(propyl acrylate) (PPAcr) or poly(butyl acrylate) (PBAcr) is also miscible with PVME but with no LCST. In extension, one of our previous studies4 found miscibility with relatively low LCST in poly(benzyl methacrylate) (PBzMA)/PVME and poly(phenyl methacrylate)/PVME blends, whose phase behavior is strongly affected by solvents and casting temperatures owing to the kinetic process of formation of blends and these factors were found to lead to different outcome of phase structure of the PBzMA/PVME blend. When cast from methylene chloride or chloroform (at ambient or 45 °C), the blends appeared to be phase separated.…”

Section: Introductionmentioning

confidence: 86%

Comparison of glass transition and interpretation on miscibility in blends of amorphous poly(vinyl methyl ether) with highly crystallizable versus less‐crystallizable polyesters

Chiang

Woo

2007

J Polym Sci B Polym Phys

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Various phase behavior of blends of poly(vinyl ether)s with polyesters of two types (highly crystalline and less crystalline with different main-chains) were examined using differential scanning calorimetry (DSC) and optical microscopy (OM). Effects of varying the main-chain polarity of the constituent polyesters on the phase behavior of the blends were analyzed. Miscibility in PVME/polyester blends was found only in polyesters with backbone CH 2 /CO ratio ¼ 3.5 to 7.0). T g -composition relationships for blends of PVME with highly crystalline polyesters (PBA, PHS) were found to differ significantly from those for PVME blends with less-crystalline polyesters (PTA, PEAz). Crystallinity of highly crystalline polyester constituents in blends caused significant asymmetry in the T g -composition relationships, and induced positive deviation of blends' T g above linearity; on the other hand, blends of PVME with less crystalline polyesters exhibit typical Fox or Gordon-Taylor types of relationships.The v parameters for the miscible blends were found to range from À0.17 to À0.33, reflecting generally weak interactions. Phase behavior was analyzed and compared among blends of PVME with rapidly crystallizing vs. less-crystallizing polyesters, respectively. Effects of polyesters' crystallinity and structures on phase behavior of PVME/polyester blends are discussed.

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Marginal miscibility and solvent-dependent phase behavior in solution-blended poly(vinyl methyl ether)/poly(benzyl methacrylate)

Cited by 16 publications

References 14 publications

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

Stimulus‐Responsive Nanoparticles and Associated (Reversible) Polymorphism via Polymerization Induced Self‐assembly (PISA)

Comparison of glass transition and interpretation on miscibility in blends of amorphous poly(vinyl methyl ether) with highly crystallizable versus less‐crystallizable polyesters

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