Interfacial geometry in particle-forming phases of diblock copolymers

2022 ◽  
Vol 6 (1) ◽  
Author(s):  
Ryan P. Collanton ◽  
Kevin D. Dorfman
Keyword(s):  
Author(s):  
S.D. Smith ◽  
R.J. Spontak ◽  
D.H. Melik ◽  
S.M. Buehler ◽  
K.M. Kerr ◽  
...  

When blended together, homopolymers A and B will normally macrophase-separate into relatively large (≫1 μm) A-rich and B-rich phases, between which exists poor interfacial adhesion, due to a low entropy of mixing. The size scale of phase separation in such a blend can be reduced, and the extent of interfacial A-B contact and entanglement enhanced, via addition of an emulsifying agent such as an AB diblock copolymer. Diblock copolymers consist of a long sequence of A monomers covalently bonded to a long sequence of B monomers. These materials are surface-active and decrease interfacial tension between immiscible phases much in the same way as do small-molecule surfactants. Previous studies have clearly demonstrated the utility of block copolymers in compatibilizing homopolymer blends and enhancing blend properties such as fracture toughness. It is now recognized that optimization of emulsified ternary blends relies upon design considerations such as sufficient block penetration into a macrophase (to avoid block slip) and prevention of a copolymer multilayer at the A-B interface (to avoid intralayer failure).


Author(s):  
David M. Anderson ◽  
Tomas Landh

First discovered in surfactant-water liquid crystalline systems, so-called ‘bicontinuous cubic phases’ have the property that hydropnilic and lipophilic microdomains form interpenetrating networks conforming to cubic lattices on the scale of nanometers. Later these same structures were found in star diblock copolymers, where the simultaneous continuity of elastomeric and glassy domains gives rise to unique physical properties. Today it is well-established that the symmetry and topology of such a morphology are accurately described by one of several triply-periodic minimal surfaces, and that the interface between hydrophilic and hydrophobic, or immiscible polymer, domains is described by a triply-periodic surface of constant, nonzero mean curvature. One example of such a dividing surface is shown in figure 5.The study of these structures has become of increasing importance in the past five years for two reasons:1)Bicontinuous cubic phase liquid crystals are now being polymerized to create microporous materials with monodispersed pores and readily functionalizable porewalls; figure 3 shows a TEM from a polymerized surfactant / methylmethacrylate / water cubic phase; and2)Compelling evidence has been found that these same morphologies describe biomembrane systems in a wide range of cells.


1990 ◽  
Vol 51 (2) ◽  
pp. 185-200 ◽  
Author(s):  
Zhen-Gang Wang ◽  
S.A. Safran

2019 ◽  
Author(s):  
Jacob Ishibashi ◽  
Yan Fang ◽  
Julia Kalow

<p>Block copolymers are used to construct covalent adaptable networks that employ associative exchange chemistry (vitrimers). The resulting vitrimers display markedly different nanostructural, thermal and rheological properties relative to those of their statistical copolymer-derived counterparts. This study demonstrates that prepolymer sequence is a versatile strategy to modify the properties of vitrimers.</p>


2019 ◽  
Author(s):  
Yanchun Tang ◽  
Kohzo Ito ◽  
Hideaki Yokoyama

In this study, we prepared ultrafiltration membranes with a decoupled responses of filtration property to temperature and pH. The membrane preparation method was developed based on our previous work. We utilized methanol-supercritical carbon dioxide (methanol-scCO<sub>2</sub>) selective swelling method to introduce nanopores to block copolymers containing poly(diethylene glycol) methyl ether methacrylate (PMEO<sub>2</sub>MA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and polystyrene (PS) blocks. Formation of the mesoporous barrier layer with PS being the mechanically stable part of the matrix was driven by selective swelling of the PMEO<sub>2</sub>MA-b-PDMAEMA domains. Due to the selective swelling of PMEO<sub>2</sub>MA or PDMAEMA domains to introduce pores, the interior of the pores are covered with PMEO<sub>2</sub>MA or PDMAEMA blocks after pore formation. The PMEO<sub>2</sub>MA-b-PDMAEMA polymer brushes are naturally attached on the pore walls and worked as functional gates. PMEO<sub>2</sub>MA is a non-toxic, neutral thermo-responsive polymer with LCST at 26 ᴼC. PDMAEMA is a typical weak polyelectrolyte with pK<sub>a</sub> value at 7.0-7.5 and also a thermo-responsive polymer revealed a LCST of 20-80 °C in aqueous solution. Therefore, these membranes were expected to have multi dimensions as function of the combination of temperature and pH. Moreover, to understand the detail of the temperature and pH depended conformation transitions of PMEO<sub>2</sub>MA-b-PDMAEMA brushes, those diblock copolymers were end-tethered on flat substrates and analyzed via neutron reflectivity (NR).


2021 ◽  
Vol 23 (3) ◽  
pp. 1248-1258
Author(s):  
Shannon M. North ◽  
Steven P. Armes

An atom-efficient, wholly aqueous one-pot synthesis of zwitterionic diblock copolymers has been devised. Such copolymers can serve as highly effective aqueous dispersants for nano-sized transparent yellow iron oxide particles.


Synlett ◽  
2021 ◽  
Author(s):  
Quentin Michaudel ◽  
Samuel J. Kempel ◽  
Ting-Wei Hsu

AbstractOlefin metathesis has tremendously impacted all fields of synthetic chemistry. However, the control of the olefin stereochemistry during this process remains a grand challenge. Recent innovations in catalyst design have permitted control of the stereochemistry of the olefin product. Here, we discuss the development of stereoretentive olefin metathesis, with an emphasis on the synthesis of stereodefined polyalkenamers through ring-opening metathesis polymerization (ROMP). We then present our application of this unique reaction manifold to the preparation of all-cis poly(p-phenylene vinylene)s (PPVs). A dithiolate Ru catalyst was found to deliver perfect cis selectivity for the polymerization of a paracyclophane diene monomer. By using optimized conditions, all-cis PPVs with narrow dispersities and predictable molar masses were obtained by varying the ratio of monomer to catalyst. The high chain fidelity of the stereoretentive ROMP with a paracyclophane diene monomer enabled the preparation of well-defined diblock copolymers with a norbornene co-monomer. Photochemical isomerization of all-cis to all-trans PPVs was effected with both homopolymers and diblock copolymers. This process was shown to be selective for the PPV block, and resulted in changes in optical properties, polymer size, and solubility. Stereoretentive ROMP provides a promising platform for synthesizing polymers with unique properties, including photoresponsive all-cis PPVs with living characteristics.1 Introduction2 Synthetic Applications of Stereoretentive Olefin Metathesis3 Stereocontrol of Polyalkenamers through Stereoretentive ROMP4 Stereoretentive ROMP To Access All-cis Poly(p-phenylene vinylene)s5 Conclusion


1998 ◽  
Vol 31 (26) ◽  
pp. 9281-9294 ◽  
Author(s):  
H. D. Bijsterbosch ◽  
M. A. Cohen Stuart ◽  
G. J. Fleer

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