Polymers with multiple functions: α,ω-macromolecular photoinitiators/chain transfer agents used in aqueous photoinitiated polymerization-induced self-assembly

Jia, Shuai; Zhang, Li; Chen, Ying; Tan, Jianbo

doi:10.1039/d2py00606e

Cited by 6 publications

(7 citation statements)

References 93 publications

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“…Over the past thirteen years or so, polymerization‐induced self‐assembly (PISA) has become an efficient and versatile approach for the synthesis of various block copolymer assemblies at high polymer concentrations (10—50 wt%). [ 5‐43 ] PISA involves the growth of a second block from a soluble precursor block that forms a block copolymer. The second block becomes insoluble as increasing the molar mass, which drives in situ self‐assembly of the block copolymer during polymerization.…”

Section: Background and Originality Contentmentioning

confidence: 99%

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents^†

2023

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Here, we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization, to access branched block copolymers as well as well-defined branched block copolymer assemblies. Two types of branched macro-RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization, and subsequently utilized in RAFT dispersion polymerization. It was found that only branched macro-RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well-defined morphologies. Reaction conditions including monomer concentration, degree of polymerization (DP) of the core-forming block, and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail. Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro-RAFT agents. This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well-defined structures.

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Section: Background and Originality Contentmentioning

confidence: 99%

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents^†

2023

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“…Nowadays, attributing to the excellent thermal stability and specific solubleness of most macromolecular photoinitiators, especially its thermal decomposition temperature is higher than the spinning temperature ($290 C), 10 and part of the macromolecular photo initiator could be soluble in spinning solvents at high temperature while not dissolve in them at low temperature. 11,12 a new hypothesis was inducing the macromolecular photoinitiator to spinning solvent directly and then irradiating the fiber after high-ratio drawing. This way avoided the long time soaking and improved the production efficiency, which was beneficial to production in the pilot line.…”

Section: Introductionmentioning

confidence: 99%

Structure and properties evolution of UV crosslinked ultra‐high molecular weight polyethylene fiber during processing

Dong,

Niu,

Qiang

et al. 2024

Journal of Polymer Science

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With the development of heat and creep‐resistant UHMWPE fiber via UV crosslinking, its structure‐properties evolution during processing needs attention. The structures of UHMWPE fiber in different forms, the pre‐oriented yarn (POY), the full stretch yarn (FDY) and UV crosslinked FDY (UVFDY), obtained from our pilot line were systematically studied with differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and solid‐state 13C NMR. Additionally, the heat and creep resistance of UVFDY were evaluated by the temperature at break (Tb), glass transition temperature (Tg), time at break (tb) for a given aging temperature, and creep elongation (Lc). The results demonstrated that UVFDY possessed high gel content (89.0%), high crystallinity (84.2%), and high orientation (91.7%). These characteristics caused UVFDY not only with excellent mechanical properties but also process extraordinary heat and creep resistance, especially for its much higher Tb (220 °C), Tg (−75.7 °C) and tb (20 h) while lower Lc (7.8%), comparing with FDY (Tb = 158 °C, Tg = −86.8 °C, tb = 1.3 h and Lc = 38.2%). This work provides insights into the structure‐properties relationship of UVFDY, which will aid in the development of UV crosslinked UHMWPE fiber with better heat and creep resistance.

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“…To enhance the LC ordering effect, one rational strategy is decreasing the reaction temperature to a temperature that is below the transition temperature. Recently, our group and others − have developed novel PISA formulations via photoinitiation that can perform at temperatures ranging from 0 to 70 °C, offering new opportunities for the scalable preparation of fluorinated cylindrical micelles.…”

Section: Introductionmentioning

confidence: 99%

Scalable Preparation of Cylindrical Block Copolymer Micelles with a Liquid-Crystalline Perfluorinated Core by Photoinitiated Reversible Addition-Fragmentation Chain Transfer Dispersion Polymerization

Lin

Zhang

et al. 2023

Macromolecules

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One-dimensional block copolymer micelles have exhibited considerable promise in various fields. However, the large-scale preparation of one-dimensional block copolymer micelles is always challenging. Here, we report the preparation of cylindrical block copolymer micelles up to 30% w/w solids by photoinitiated reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of 2-(perfluorooctyl)ethyl methacrylate (FMA) in ethanol. Because of the liquid-crystalline ordering effect of the PFMA core-forming block at low temperatures, cylindrical micelles could be obtained over a wide range of degree of polymerization of PFMA. The length of cylindrical micelles could be roughly controlled by changing the molar mass of the macromolecular chain transfer agent (macro-CTA). Finally, the concept of seeded growth was successfully incorporated into photoinitiated RAFT dispersion polymerization, allowing the epitaxial growth of cylindrical micelles from seeds. We expect that this method will offer considerable opportunities for the large-scale preparation of well-defined cylindrical micelles that may find applications in some specific areas.

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Polymers with multiple functions: α,ω-macromolecular photoinitiators/chain transfer agents used in aqueous photoinitiated polymerization-induced self-assembly

Abstract: A series of α,ω-functionalized polymers with a photoinitiator end group and a RAFT end group were synthesized and employed as macromolecular photoinitiators/chain transfer agents in aqueous photoinitiated polymerization-induced self-assembly.

Cited by 6 publications

References 93 publications

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents^†

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents^†

Structure and properties evolution of UV crosslinked ultra‐high molecular weight polyethylene fiber during processing

Scalable Preparation of Cylindrical Block Copolymer Micelles with a Liquid-Crystalline Perfluorinated Core by Photoinitiated Reversible Addition-Fragmentation Chain Transfer Dispersion Polymerization

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Polymers with multiple functions: α,ω-macromolecular photoinitiators/chain transfer agents used in aqueous photoinitiated polymerization-induced self-assembly

Abstract: A series of α,ω-functionalized polymers with a photoinitiator end group and a RAFT end group were synthesized and employed as macromolecular photoinitiators/chain transfer agents in aqueous photoinitiated polymerization-induced self-assembly.

Cited by 6 publications

References 93 publications

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents†

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents†

Structure and properties evolution of UV crosslinked ultra‐high molecular weight polyethylene fiber during processing

Scalable Preparation of Cylindrical Block Copolymer Micelles with a Liquid-Crystalline Perfluorinated Core by Photoinitiated Reversible Addition-Fragmentation Chain Transfer Dispersion Polymerization

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Product

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In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents^†

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents^†