Block Copolymers by Anionic Polymerization: Recent Synthetic Routes and Developments

Theodosopoulos, Georgios; Pitsikalis, Marinos

doi:10.1007/978-4-431-54186-8_12

Cited by 7 publications

(9 citation statements)

References 288 publications

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“…The rest of the reaction mixture was precipitated in 500 mL of methanol, filtered by a glass filter, and dried in vacuo at 45°C for 12 h. 1 The common method to prepare block copolymers by anionic ROP is via one-pot sequential monomer addition using a common catalyst. 33 We employed this method to prepare PPDL-b-PCL with BnOH:t-BuP 4 :PDL:CL molar ratio of 1:1:100:100 (entry 1, Table 1). BnOH was mixed with t-BuP 4 in toluene followed by the addition of PDL (dissolved in toluene) at 80°C.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

et al. 2018

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Poly(macrolactones) (PMLs) can be considered as biodegradable alternatives of polyethylene; however, controlling the ring-opening polymerization (ROP) of macrolactone (ML) monomers remains a challenge due to their low ring strain. To overcome this problem, phosphazene (t-BuP 4), a strong superbase, has to be used as catalyst. Unfortunately, the one-pot sequential block copolymerization of MLs with small lactones (SLs) is impossible since the high basicity of t-BuP 4 promotes both intra-and intermolecular transesterification reactions, thus leading to random copolymers. By using ROP and the "catalyst-switch" strategy [benzyl alcohol, t-BuP 4 /neutralization with diphenyl phosphate/(t-BuP 2)], we were able to synthesize different well-defined PML-b-PSL block copolymers (MLs: dodecalactone, ω-pentadecalactone, and ωhexadecalactone; SLs: δ-valerolactone and ε-caprolactone). The thermal properties and the phase behavior of these block copolymers were studied by differential scanning calorimetry and X-ray diffraction spectroscopy. This study shows that the thermal properties and phase behavior of PMLs-b-PSLs are largely influenced by the PMLs block if PMLs components constitute the majority of the block copolymers.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

et al. 2018

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“…The employment of novel catalysts, linking, termination, and transfer agents, along with the use of recent advances in organic chemistry, e.g., Suzuki coupling, click chemistry, photochemical reactions etc., have led to the synthesis of complex well-defined macromolecular architectures [11][12][13]. An endless number of structures with numerous combinations of different polymer chains, topologies, and stereo-chemistries have emerged over the years, which shows that the macromolecular architecture can greatly affect the material properties both in solution and in the solid state [14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Triblock Copolymers Through the Formation of Hydrogen Bonds: Synthesis, Characterization, Association Effects in Solvents of Different Polarity

2020

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Anionic polymerization techniques were employed for the synthesis of linear polystyrene (PS) and block copolymer of PS and polyisoprene (PI) PS-b-PI bearing end hydroxyl groups. Following suitable organic chemistry transformation, the –OH end groups were converted to moieties able to form complementary hydrogen bonds including 2,6-diaminopurine, Dap, thymine, Thy, and the so-called Hamilton receptor, Ham. The formation of hydrogen bonds was examined between the polymers PS-Dap and PS-b-PI-Thy, along with the polymers PS-Ham and PS-b-PI-Thy. The conditions under which supramolecular triblock copolymers are formed and the possibility to form aggregates were examined both in solution and in the solid state using a variety of techniques such as 1H-NMR spectroscopy, size exclusion chromatography (SEC), dilute solution viscometry, dynamic light scattering (DLS), thermogravimetric analysis (TGA), differential thermogravimetry (DTG), and differential scanning calorimetry (DSC).

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“…ere is a continuous effort towards the synthesis of novel polymeric materials to cover the needs for modern everyday life and for specialty applications as well [1,2]. Towards this goal, the employment of new monomers as the source of novel polymers is limited and therefore the research is directed to the combination of different monomers with diverse properties, leading to the synthesis of copolymers with various architectures [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. Both parameters, that is, the macromolecular architecture and the coexistence in the same structure of two or more monomer units, may dramatically influence the solid state and solution properties [18,19].…”

Section: Introductionmentioning

confidence: 99%

Thermal Stability and Kinetics of Thermal Decomposition of Statistical Copolymers of N-Vinylpyrrolidone and Alkyl Methacrylates Synthesized via RAFT Polymerization

Gikarakis

Pappas

Arvanitaki

et al. 2021

Journal of Chemistry

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The thermal stability and the kinetics of thermal decomposition of statistical copolymers of N-vinylpyrrolidone (NVP) with the alkyl methacrylates, hexyl methacrylate (HMA) and stearyl methacrylate (SMA), were studied by Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG). Statistical copolymers of different compositions were studied, and their thermal decomposition behavior was compared to the corresponding homopolymers. The activation energies of the thermal decomposition were calculated using the Ozawa-Flynn-Wall, the Kissinger, and the Kissinger-Akahira-Sunose methodologies. The effects of the nature of the methacrylate monomer, the copolymer composition, and the rate of heating are discussed.

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Block Copolymers by Anionic Polymerization: Recent Synthetic Routes and Developments

Cited by 7 publications

References 288 publications

Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

Supramolecular Triblock Copolymers Through the Formation of Hydrogen Bonds: Synthesis, Characterization, Association Effects in Solvents of Different Polarity

Thermal Stability and Kinetics of Thermal Decomposition of Statistical Copolymers of N-Vinylpyrrolidone and Alkyl Methacrylates Synthesized via RAFT Polymerization

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