Synthesis by nitroxide-mediated aqueous dispersion polymerization, characterization, and physical core-crosslinking of pH- and thermoresponsive dynamic diblock copolymer micelles

Delaittre, Guillaume; Save, Maud; Gaborieau, Marianne; Castignolles, Patrice; Rieger, Jutta; Charleux, Bernadette

doi:10.1039/c2py20084h

Cited by 44 publications

(48 citation statements)

References 129 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…27 At this pH the polyacrylic acid (PAA) segment may roughly mimic the charged POM unit, even though their respective conformations cannot be compared. 23,27 Interestingly, for hybrid PP15-T possessing a very short polymer chain (M n = 15 kg mol -1 ), no unimers were detected by DLS ( Figure SI aggregates. The observed changes in size can thus not be attributed to the variation in polymer length -as no effect of the M n has been observed for PDEAAm-C 12 -and can only be explained by the presence of the POM to which hydrophobic counterions are associated ( Table 5).…”

Section: B44mentioning

confidence: 99%

“…18,22,23 Independently of the molar mass, all PDEAAm-C 12 samples showed a TT of about 30 °C, determined at the onset of the transition (Table 3 and Figure SI-1). In addition, the transition enthalpy ∆H (in kJ mol polymer -1 ) increased as expected with increasing molar mass of PDEAAm (P30 to P90), i.e.…”

Section: Thermal Characterization Of Pdeaam-c 12 Samples (P30 P55 Amentioning

confidence: 99%

See 1 more Smart Citation

Study of the temperature-induced aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

Haye

Costa

Pembouong

et al. 2015

Polymer

Self Cite

View full text Add to dashboard Cite

ABSTRACT. In this article, we study the temperature-induced phase transition of aqueous solutions of tailor-made Dawson polyoxometalate-poly(N,N-diethylacrylamide) hybrids (POMPDEAAm) by means of differential scanning calorimetry, dynamic light scattering and cryo-TEM microscopy. Generally, the typical thermoresponsive aggregation of the PDEAAm in water was transferred to the hybrids. The organization of the compounds in solution below and above the transition temperature was studied, and precious insights in the aggregation mechanisms were obtained. The impact of the polymer chain-ends, the nature of the counterions of the negatively charged POM subunits and the weight fraction of the POM was elucidated, revealing a strong influence of the POM's counter-ions. Temperature and nature of the cations are thus two external factors that can be used to control the properties of the conjugates.

show abstract

Section: B44mentioning

confidence: 99%

Section: Thermal Characterization Of Pdeaam-c 12 Samples (P30 P55 Amentioning

confidence: 99%

Study of the temperature-induced aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

Haye

Costa

Pembouong

et al. 2015

Polymer

Self Cite

View full text Add to dashboard Cite

show abstract

“…There are examples of aqueous dispersion polymerisation, [156][157][158] but monomers applicable to this technique are rare. ScCO2 provides a more universal solvent for dispersion polymerisation, since it is dissolves most monomers, but all polymers with the exception of highly fluorinated polymers, 159 siloxane-based polymers 160 and a small subset of hydrocarbon polymers, [161][162][163] are insoluble.…”

Section: Nmpmentioning

confidence: 99%

“…158 DEAA polymerisation exhibited good control/livingness at different temperatures (112 and 120 °C) and solids contents (20 -39 wt%), 158 and MBA (<3% of DEAA) was added after 1h of reaction to cross-link the PDEAA core during chain extension whilst avoiding macrogelation. 225 The group also revealed that PMAA-SG1 showed a higher initiating efficiency than PAA-SG1 when chain extending with MMA or St, 171, 172 a result that is parallel to findings with the analogous macro-RAFT agents.…”

Section: D Nmp In Emulsion/dispersionmentioning

confidence: 99%

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

et al. 2016

View full text Add to dashboard Cite

Nanostructured soft materials open up new opportunities in material design and application, and block copolymer self-assembly is one particularly powerful phenomenon that can be exploited for their synthesis. The advent of controlled/living radical polymerisation (CLRP) has greatly simplified block copolymer synthesis, and versatility towards monomer types and polymer architectures across the different forms of CLRP has vastly expanded the range of functional materials accessible. CLRP-controlled synthesis of block copolymers has been applied in heterogeneous systems, motivated by the numerous process advantages and the position of emulsion polymerisation at the forefront of industrial latex synthesis. In addition to the inherent environmental advantages of heterogeneous routes, the incidence of block copolymer self-assembly within dispersed particles during polymerisation leads to novel nanostructured materials that offer enticing prospects for entirely new applications of block copolymers. Here, we review the range of block copolymers prepared by heterogeneous CLRP techniques, evaluate the methods applied to maximise purity of the products, and summarise the unique nanoscale morphologies resulting from in situ self-assembly, before discussing future opportunities within the field.2

show abstract

“…With increasing pH from 4.5 to approximately 5-7, the LCST of the PNIPAM increased from 29 to 35 • C [77]. In a system applying similar NMP techniques that was used here, PAA-b-poly(diethyl acrylamide) (PAA-b-PDEAAm) was made in dispersion and the hydrodynamic radius was measured as a function of pH at different temperatures (15, 25 and 50 • C) [78]. In that study, the aggregate size was greater when the temperature exceeded the cloud point temperature of the PDEAAm block (about 35 • C).…”

Section: Block Copolymers With Both Ph and Temperature Sensitivitiesmentioning

confidence: 99%

Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

2017

View full text Add to dashboard Cite

Nitroxide-mediated polymerization using the succinimidyl ester functional unimolecular alkoxyamine initiator (NHS-BlocBuilder) was used to first copolymerize tert-butyl methacrylate/ 2-vinylpyridine (tBMA/2VP) with low dispersity (Đ = 1.30-1.41) and controlled growth (linear number average molecular M n versus conversion, M n = 3.8-10.4 kg·mol −1 ) across a wide composition of ranges (initial mol fraction 2VP, f 2VP,0 = 0.10-0.90). The resulting statistical copolymers were first de-protected to give statistical polyampholytic copolymers comprised of methacrylic acid/2VP (MAA/2VP) units. These copolymers exhibited tunable water-solubility due to the different pKas of the acidic MAA and basic 2VP units; being soluble at very low pH < 3 and high pH > 8. One of the tBMA/2VP copolymers was used as a macroinitiator for a 4-acryloylmorpholine/4-acryloylpiperidine (4AM/4AP) mixture, to provide a second block with thermo-responsive behavior with tunable cloud point temperature (CPT), depending on the ratio of 4AM:4AP. Dynamic light scattering of the block copolymer at various pHs (3, 7 and 10) as a function of temperature indicated a rapid increase in particle size >2000 nm at 22-27 • C, corresponding to the 4AM/4AP segment's thermos-responsiveness followed by a leveling in particle size to about 500 nm at higher temperatures.

show abstract

Synthesis by nitroxide-mediated aqueous dispersion polymerization, characterization, and physical core-crosslinking of pH- and thermoresponsive dynamic diblock copolymer micelles

Cited by 44 publications

References 129 publications

Study of the temperature-induced aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

Study of the temperature-induced aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

Contact Info

Product

Resources

About