skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Random copolymerization of macromonomers as a versatile strategy to synthesize mixed‐graft block copolymers
Abstract The random copolymerization of norbornene‐functionalized macromonomers was explored as a method of synthesizing mixed‐graft block copolymers (mGBCPs). The copolymerization kinetics of a model system of polystyrene (PS) and poly(lactic acid) (PLA) macromonomers was first analyzed, revealing a gradient composition of side chains along the mGBCP backbone. The phase separation behavior of mGBCPs with PS and PLA side chains of various backbone lengths and side chain molar ratios was investigated, and increasing the backbone length was found to stabilize the phase‐separated nanostructures. The graft architecture was also demonstrated to improve the processability of the mGBCP, compared to a linear counterpart. Investigations of mGBCPs comprised of polydimethylsiloxane and poly(ethylene oxide) side chains exemplified the diverse self‐assembled morphologies, including a Frank‐Kasper A15 phase, that can be obtained with mGBCPs synthesized by random copolymerization of macromonomers. Lastly, a ternary mGBCP was synthesized by the copolymerization of three macromonomers.  more » « less
Award ID(s):
2003875
PAR ID:
10365165
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Journal of Polymer Science
Volume:
59
Issue:
21
ISSN:
2642-4150
Format(s):
Medium: X Size: p. 2571-2580
Size(s):
p. 2571-2580
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Multicomponent nanostructured materials assembled from molecular building blocks received wide attention due to their precisely integrated multifunctionalities. However, discovery of these materials with desirable composition and morphology was limited by their low synthetic scalability and narrow structural tuning window with given building blocks. Here, we report a scalable and diversity‐oriented synthetic approach to hierarchically structured nanomaterials based on a few readily accessible building blocks. Mixed‐graft block copolymers containing sequence‐defined side chains were prepared through ring‐opening metathesis copolymerization of three or four types of macromonomers. Intramolecularly defined interfaces promoted the formation of ordered hierarchical structures with lattice sizes tunable across multiple length scales. The same set of macromonomers were arranged and combined in different ways, providing access to diverse morphologies in the resultant structures. 
    more » « less
  2. A series of model poly((±)-lactide) (PLA) graft copolymers was synthesized by ring-opening metathesis polymerization and used to probe the star-to-bottlebrush transition in shear and extensional flows. Ten samples with backbone degrees of polymerization 11 ≤ Nbb ≤ 420 were investigated using small-amplitude oscillatory shear (SAOS) and extensional rheometry measurements. Each contained one PLA side chain of length Nsc = 72 per two backbone repeating units on average (graft density of z = 0.5). The star-like to bottlebrush transition was identified at Nbb = 50–69 using SAOS. In extension, melt strain hardening is absent in the star-like melts (Nbb ≤ 50) but is prominent in the bottlebrush limit (Nbb > 69). The onset of melt strain hardening occurs at a time scale equivalent to the Rouse time of the backbone. A molecular interpretation of these results builds upon recent conjectures related to strain-induced increases in interchain friction in bottlebrush polymers. These findings will be useful in designing bottlebrush melts that strain harden, which is critical in various types of processing methods involving extensional flows, including foaming, 3D printing, and film-blowing. 
    more » « less
  3. Abstract Amphiphilic graft copolymers were prepared via a grafting through approach to yield materials with a hydrophilic backbone and hydrophobic arms. The thermally responsive macromonomers were designed to contain a Diels–Alder adduct such that cyclo‐reversion would cleave the arms from the backbone thus altering polymer topology, composition and solubility. The macromonomers were prepared via light‐inducted atom transfer radical polymerization followed by post‐polymerization modification to install a polymerizable functionality. Next, free radical polymerization was employed to yield thermally responsive amphiphilic graft copolymers, whose solution state characteristics were extensively characterized by UV/Vis spectroscopy and fluorimetry. Due to the amphiphilic nature of the graft copolymer, some unexpected results occurred because of aggregation and solubility limitations. Furthermore, it was discovered that poly(N‐isopropyl acrylamide) exhibited distinct and unique aggregation properties by itself. 
    more » « less
  4. Graft polymers are gaining increasing interest because of their unique architectural characteristics. We recently reported a novel type of depolymerizable graft polymer based on poly(trans-cyclobutane fused cyclooctene), in an effort to address the trade-off between depolymerizability and controlled grafting-through polymerization. In this work, we examine the thermal, mechanical, and morphological properties of a graft copolymer thermoplastic material prepared by copolymerizing poly(L-lactide) and margaric acid-based macromonomers. A copolymerization kinetics study reveals that the two macromonomers are incorporated almost randomly and that the domain spacing measured from small-angle X-ray scattering is consistent with the random distribution. An investigation of the crystallization behavior suggests that proper thermal treatment is required to maximize, or to even observe crystallinity. The physical states of the soft and hard domains, whether melt, glassy, or semicrystalline, significantly impact the tensile properties of the resulting copolymer materials. Finally, the rheological properties and morphological features are discussed. 
    more » « less
  5. Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chain chemistries. Specifically, we synthesized bottlebrush polymers with either poly(styrene- ran -methyl methacrylate) side chains or with a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains. The bottlebrush additives were matched in terms of PS and PMMA compositions, and they were blended with linear PS or PMMA chains that ranged in length from shorter to longer than the bottlebrush side chains. Experiments revealed similar behaviors of the two types of bottlebrushes, with a slight preference for mixed side-chain bottlebrushes at the film surface. SCFT simulations were qualitatively consistent with experimental observations, predicting only slight differences in the segregation of bottlebrush additives driven by side chain microstructures. Specifically, these slight differences were driven by the chemistries of the bottlebrush polymer joints and side chain end-groups, which were entropically repelled and attracted to interfaces, respectively. Using SCFT, we also demonstrated that the interfacial behaviors were dominated by entropic effects with high molecular weight linear polymers, leading to enrichment of bottlebrush near interfaces. Surprisingly, the SCFT simulations showed that the chemistry of the joints connecting the bottlebrush backbones and side chains played a more significant role compared with the side chain end groups in affecting differences in surface excess of bottlebrushes with random and mixed side chains. This work provides new insights into the effects of side chain microstructure on segregation of bottlebrush polymer additives. 
    more » « less