Asymmetric supramolecular double-comb diblock copolymers: From plasticization, to confined crystallization, to breakout

Hofman, Anton H.; Loos, Katja; Brinke, G. ten

doi:10.1016/j.polymer.2017.05.057

Cited by 8 publications

(6 citation statements)

References 53 publications

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“…The effect of chain architecture in the crystallization of copolymers has been studied employing star [110,111,[239][240][241][242], graft [243][244][245], brush [246][247][248], dendritic [249], comb [135,250] or H shaped [251,252] copolymers. These kinds of systems are very interesting, since in those copolymers confinement can be induced by the composition of the block copolymer as well as by the chain topology, because both parameters affect the final morphology of the copolymer.…”

Section: Effect Of Chain Architecturementioning

confidence: 99%

Fractionated crystallization in semicrystalline polymers

Sangroniz

Wang

et al. 2021

Progress in Polymer Science

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The crystallization of heterogeneously nucleated bulk polymers typically occurs in a single exothermic process, within a narrow temperature range, i.e., a single exothermic peak is detected by Differential Scanning Calorimetry when the material is cooled from the melt. However, when a bulk semicrystalline polymer is subdivided or dispersed into a multitude of totally (or partially) isolated microdomains (e.g., droplets or cylinders), in number comparable to that of commonly available nucleating heterogeneities, several separated crystallization events are typically observed, i.e., fractionated crystallization. This situation is often found for the minor crystallizable component in immiscible blends.When the bulk polymer is dispersed into a number of microdomains that is several orders of magnitude higher than the available number of heterogeneities within it, most microdomains will be heterogeneity-free. In these clean microdomains the nucleation can occur by contact with the interfaces (i.e., surface nucleation) or by homogeneous nucleation inside the microdomain volume. These cases can be easily encountered in cylinders or spheres within strongly segregated block copolymers, or in infiltrated polymers within nanopores of alumina templates.In this work, a comprehensive review of the known cases of fractionated crystallization is provided. The changes upon decreasing microdomain sizes from a dominant single heterogeneous nucleation, through fractionated crystallization, to surface or homogeneous nucleation are critically reviewed. Emphasis is placed on the common features of the phenomenon across the different systems, and thus on the general conclusions that can be drawn from the analysis of representative semicrystalline polymers. The origin of the fractionated crystallization effects and their dramatic consequences on the nucleation and crystallization kinetics of semicrystalline polymers are also discussed.

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Section: Effect Of Chain Architecturementioning

confidence: 99%

Fractionated crystallization in semicrystalline polymers

Sangroniz

Wang

et al. 2021

Progress in Polymer Science

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“…[11][12] The microphase morphology of block copolymers can further be tuned with supramolecular interactions, [13][14][15][16][17] and a few studies have shown that the addition of small hydrogen bonding molecules to block copolymers with hydrogen bond accepting side groups can have diverse effects including plasticization, confined crystallization and breakout crystallization. [18][19] While the relationship between phase segregation and mechanical properties of SPs is well understood and their assembly into various microphases including lamellar and hexagonal phases has been reported, 9,[20][21][22][23][24] little is known about the effects of the hard phase's mass fraction and the role of crystallization on their microphase segregation. One reason for this is the predominance of SPs based on self-complementary supramolecular units, 1 which yield single component systems in which the systematic variation of the volume fractions of two different blocks is not trivial.…”

Section: Introductionmentioning

confidence: 99%

“…In addition to these parameters, the presence of crystallizable blocks introduces additional complexity to the phase behavior of block copolymers. , Thus, a semicrystalline diblock copolymer may assemble in different morphologies when cooled from a microphase segregated melt, depending on the nature of the amorphous phase. If the latter is glassy at the crystallization temperature of the crystallizable block, the crystallization is confined and the microstructure will not be disrupted; however, a rubbery amorphous phase may template the crystallization or it may not, in which case the microstructure would be lost in a so-called breakout crystallization. , The microphase morphology of block copolymers can further be tuned with supramolecular interactions, − and a few studies have shown that the addition of small hydrogen bonding molecules to block copolymers with hydrogen bond accepting side groups can have diverse effects including plasticization, confined crystallization and breakout crystallization. , …”

Section: Introductionmentioning

confidence: 99%

Hard Phase Crystallization Directs the Phase Segregation of Hydrogen-Bonded Supramolecular Polymers

et al. 2019

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A growing body of work shows that the phase behavior of supramolecular polymers assembled from telechelic building blocks featuring binding motifs at the two termini is quite similar to that of conventional block copolymers. However, it remains unclear how crystallization of the phase formed by the binding motifs, which occurs in many supramolecular polymers, affects the phase morphology of such materials. Here we report a systematic investigation of a series of supramolecular polymers based on poly(ethylene-cobutylene) (PEB) telechelics and the complementary H-bonding pair isophthalic acid−pyridine (IPA-Py). These polymers were designed to feature two blocks that assemble into an amorphous low-glass-transition phase formed by the PEB segments and crystalline domains consisting of the binding motifs. The nature of the latter was systematically varied via the choice of the pyridine employed. The influence of the binding motif on the phase morphology and thereby properties of these supramolecular polymers was investigated by means of thermal analysis, polarized optical microscopy, (dynamic) mechanical analyses, small-angle X-ray scattering, and transmission electron microscopy. In the melted state, all materials assembled into hexagonal phases. However, when cooled below the crystallization temperature of the IPA-Py domains, three different scenarios were observed: breakout crystallization resulting in complex morphologies, retention of the melt morphology, and the formation of a lamellar phase.

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“…In the asymmetric complexes, however, crystallization of the surfactant and the tendency of the double-comb to avoid the formation of a curved interface disturbed formation of ordered structures. 28 …”

mentioning

confidence: 99%

“…This supramolecular approach was recently extended to double-comb diblock copolymer complexes by exchanging the PS block for an acrylamide block that could form a supramolecular complex as well, thus resulting in hierarchical morphologies in both polymer phases. , In symmetric diblock copolymer systems, highly unusual double parallel and double perpendicular lamellae- in -lamellae were observed over a wide range of molecular weights. In the asymmetric complexes, however, crystallization of the surfactant and the tendency of the double-comb to avoid the formation of a curved interface disturbed formation of ordered structures …”

mentioning

confidence: 99%

Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers

et al. 2018

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Involving supramolecular chemistry in self-assembling block copolymer systems enables design of macromolecular architectures that are challenging to obtain through conventional all-covalent routes. In this work we present supramolecular double-comb triblock terpolymers in which both outer blocks are able to interact with a surfactant via hydrogen bonding and thereby form a comb-shaped architecture upon complexation. While the neat triblock terpolymer only formed a triple lamellar morphology, multiple hierarchical structures were observed in these supramolecular comb–coil–comb triblock terpolymers by simply adjusting the surfactant concentration. Structures included spheres on tetragonally packed cylinders-in-lamellae and spheres on double parallel lamellae-in-lamellae, as evidenced by electron microscopy and X-ray scattering. Incorporation of a middle coil block thus allowed an even higher macromolecular complexity than the previously reported double-comb diblock copolymers.

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Asymmetric supramolecular double-comb diblock copolymers: From plasticization, to confined crystallization, to breakout

Cited by 8 publications

References 53 publications

Fractionated crystallization in semicrystalline polymers

Fractionated crystallization in semicrystalline polymers

Hard Phase Crystallization Directs the Phase Segregation of Hydrogen-Bonded Supramolecular Polymers

Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers

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