Synthesis and microphase separation of dendrimer-like block copolymers by anionic polymerization strategies

Hartmann, Frank; Niebuur, Bart‐Jan; Koch, Marcus; Kraus, Tobias; Gallei, Markus

doi:10.1016/j.eurpolymj.2023.111894

Cited by 6 publications

(11 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It could also be compared to the worm-like morphology, which was obtained in our previous publication. 25 Therefore, the observed simulated density distribution of a bicontinuous morphology with no longrange order is proven for this type of dendrimer-like block copolymer. A gyroid morphology is difficult to manifest in simulation and can easily be overlooked at high χN, as recently described by Sańchez-Leija et al 63 The direct observation of the bicontinuous morphology by TEM is still not given.…”

Section: Resultsmentioning

confidence: 67%

“…It was already suggested in our previous work that the domain size is also influenced by the branching points. 25 The small size of the block copolymer domains of the prepared polymer D3 could explain the nonvisibility of the phase separation by TEM investigation. It is known for dendron structures that the order−disorder transition (ODT) occurs above a value for χN of 60.…”

Section: Resultsmentioning

confidence: 97%

“…Earlier reports on similar polymer architectures indicated a lamellar morphology at 50 vol %. 25 The fraction of the PS-blocks was chosen to be at about 60 vol %. This should still result in a lamellar structure for a linear block copolymer, but we consider our polymer architecture would break the morphology into bicontinuous phases.…”

Section: Resultsmentioning

confidence: 99%

“…23 In comparison, the divergent synthesis starts from the central core and grows further to the next dendrimer generations with either the linking of an active functional polymer or the direct growth of the polymer from a multifunctional initiation site. 24 In a recent publication, 25 a second-generation dendrimer-like BCP ((PB-b-PS) 2 PS) 3 was designed by a core-first approach by living anionic polymerization and subsequent coupling procedures. However, the therein chosen synthesis was limited to second-generation dendrimers and did not allow for the preparation of any further architectural generations.…”

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Design and Self-Assembly of Second-Generation Dendrimer-like Block Copolymers

Hartmann,

Dockhorn,

Pusse

et al. 2024

Macromolecules

View full text Add to dashboard Cite

The tailored synthesis of copolymer architectures provides insights into fundamental structure−property relationships for the formation of complex morphologies through microphase separation. In this way, classical areas within the phase diagram can be specifically influenced and also adapted for important applications. The exploration of copolymer architectures also offers the possibility to discover entirely new morphologies. In this study, we design a symmetric dendrimer-like second generation block copolymer by anionic polymerization. The structural design of the polymers influences the curvature of the interfaces to produce, in particular, bicontinuous morphologies and is investigated based on molecular chain architecture. After extensive molecular analysis of the new dendrimer-like block copolymers, the resulting morphology is analyzed using transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering measurements. We further combine the experimentally obtained morphologies with Monte Carlo simulations to better understand the relationship between tailored polymer architecture and the observed morphology. By changing the volume ratio of the copolymers used and also mixing this complex polymer architecture with a linear block copolymer, we gain insights into the polymer behavior at the phase boundaries. This knowledge has an impact on the optical and mechanical properties of thermoplastic elastomers and their corresponding blends.

show abstract

Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Design and Self-Assembly of Second-Generation Dendrimer-like Block Copolymers

Hartmann,

Dockhorn,

Pusse

et al. 2024

Macromolecules

View full text Add to dashboard Cite

show abstract

“…Thermoplastic elastomers (TPEs) are an important kind of macromolecular material with excellent mechanical properties and low cost, which are used in many aspects of our lives, such as automotive, footwear, adhesives, textiles and biomedical applications [17,18]. In addition to the above-mentioned triblock copolymers, they also have many different topologies such as gradient, star, hyperbranched, dendritic, cyclic and graft [19][20][21][22][23]. Studies on these polymers not only facilitate the exploration of materials with new functionalities and properties, but also improve the ability to tune the properties through chemical design [24].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Graft Copolymers with Poly(ε-caprolactone) Side Chain Using Hydroxylated Poly(β-myrcene-co-α-methyl styrene)

Li,

Zhang,

et al. 2024

Molecules

View full text Add to dashboard Cite

Graft copolymers have unique application scenarios in the field of high-performance thermoplastic elastomers, resins and rubbers. β-myrcene (My) is a biomass monomer derived from renewable plant resources, and its homopolymer has a low glass transition temperature and high elasticity. In this work, a series of tapered copolymers P(My-co-AMS)k (k = 1, 2, 3) were first synthesized in cyclohexane by one-pot anionic polymerization of My and α-methyl styrene (AMS) using sec-BuLi as the initiator. PAMS chain would fracture when heated at high temperature and could endow the copolymer with thermal degradation property. The effect of the incorporation of AMS unit on the thermal stability and glass transition temperature of polymyrcene main chain was studied. Subsequently, the double bonds in the linear copolymers were partially epoxidized and hydroxylated into hydroxyl groups to obtain hydroxylated copolymer, which was finally used to initiate the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) to synthesize the graft copolymer with PCL as the side chain. All these copolymers before and after modifications were characterized by proton nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC), thermogravimetry analysis (TGA), and differential scanning calorimeter (DSC).

show abstract

Facile Characterization of Isothermal Crystallization and Microphase Separation Kinetics of Polyamide 6 (PA6)‐Based Thermoplastic Elastomers

Yuan,

Zhang,

Zhang

et al. 2024

Macro Chemistry & Physics

View full text Add to dashboard Cite

The facile characterization of isothermal microphase separation kinetics in polyamide 6 (PA6)‐based thermoplastic elastomers (TPAE‐6) has long posed a challenge for the development of suitable melt spinning processes. In this study, this challenge was addressed through Differential Scanning Calorimetry (DSC) measurements. It was assumed that the enthalpy changes of TPAE‐6 during the isothermal process are a linear superposition of enthalpy changes associated with microphase separation and crystallization of PA6 in hard phases, resembling that of TPAE‐6 without soft segments (TPAE‐6‐0). The study revealed that, as the concentration of soft segments in TPAE‐6 increases, the accelerated dynamics of phase separation become stronger than the dilution of soft segments to PA6 segments during isothermal process, resulting in an increase in the microphase separation rate of TPAE‐6. Furthermore, despite microphase separation, the overall crystallization rate of TPAE‐6 decreased with rising isothermal temperature and varied with increasing soft segment content at different temperatures. Additionally, the crystallization mode of TPAE‐6 followed two‐dimensional, three‐dimensional or a combination of both crystal growth mechanisms, accompanied by a heterogeneous nucleation mechanism.This article is protected by copyright. All rights reserved

show abstract

Synthesis and microphase separation of dendrimer-like block copolymers by anionic polymerization strategies

Cited by 6 publications

References 73 publications

Design and Self-Assembly of Second-Generation Dendrimer-like Block Copolymers

Design and Self-Assembly of Second-Generation Dendrimer-like Block Copolymers

Synthesis and Characterization of Graft Copolymers with Poly(ε-caprolactone) Side Chain Using Hydroxylated Poly(β-myrcene-co-α-methyl styrene)

Facile Characterization of Isothermal Crystallization and Microphase Separation Kinetics of Polyamide 6 (PA6)‐Based Thermoplastic Elastomers

Contact Info

Product

Resources

About