Fine structures of styrene-butadiene block copolymer films cast from toluene solution

Matsuo, Masato; Sagae, Shizue; Asai, Harumi

doi:10.1016/0032-3861(69)90010-x

Cited by 117 publications

(75 citation statements)

References 4 publications

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“…In the background, block copolymers (BCPs) have attracted attention as toughening modifiers for nanostructured epoxy blends in the past years . It is well known that the BCPs consisting of chemically distinct block chains form nano-phase structures in self-assembly [38][39][40]. Hillmyer et al [15] 23 Control of nanostructures generated in epoxy matrices blended with PMMA-b-PnBA-b-PMMA triblock copolymers [16] first reported nanostructured epoxy blends with the amphiphilic BCPs.…”

Section: Introductionmentioning

confidence: 99%

Control of nanostructures generated in epoxy matrices blended with PMMA-b-PnBA-b-PMMA triblock copolymers

Kishi¹,

Kunimitsu²,

Nakashima³

et al. 2015

Express Polym. Lett.

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Abstract. Stability of nanostructures of epoxy/acrylic triblock copolymer blends was studied. PMMA-b-PnBA-b-PMMA triblock copolymers (acrylic BCPs) having several compositions on the ratio of the block chains and the molecular weight were initially prepared and were blended with diglycidyl ether of bisphenol-A epoxy thermosets. The blends were cured using phenol novolac with tri phenyl phosphine (TPP) as the catalyst. Several nanostructures, such as spheres, cylinders, curved lamellae, were observed in the cured blends. The nanostructures were controlled by the molecular weight of the immiscible PnBA-block chain and the ratio of the PnBA in the blends. Moreover, the effect of the gel time to the nanostructures was examined by altering the trace amount of the TPP in the blends. The types of the nanostructures were almost kept irrespective of the gel time of the blends when the composition of the blends was maintained. This suggested the stability of the nanostructures of the epoxy/acrylic BCP blends made via the self-assembly mechanism, therefore a phase diagram of the cured blends was proposed.

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Section: Introductionmentioning

confidence: 99%

Control of nanostructures generated in epoxy matrices blended with PMMA-b-PnBA-b-PMMA triblock copolymers

Kishi¹,

Kunimitsu²,

Nakashima³

et al. 2015

Express Polym. Lett.

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“…The very small difference between the two SAXS profiles is indicative of nearly random orientation of the grains. In these SAXS profiles, scattering peaks located at 3q/q 1 ) 3, 4, 8,11,12,19,20,35, and 36, where q 1 is the smallest q value for the observed peaks, are identified. This is consistent with the F j 43m space group symmetry of the ZnS structure.…”

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confidence: 99%

Giant Zincblende Structures Formed by an ABC Star-Shaped Terpolymer/Homopolymer Blend System

Hayashida¹,

Takano²,

Dotera³

et al. 2008

Macromolecules

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Much attention has been focused on construction of mesoscopic diamond and/or zincblende (ZnS) structures as a result of their most robust photonic band gaps. 1-4 Self-organizing systems of spherical particles such as nanocrystal superlattices 5-8 and colloidal crystals 9-11 are candidates for building blocks of the diamond and ZnS structures. Recently, a ZnS lattice with a 19 nm lattice constant has been reported which has been obtained by fine-tuning of sizes, charges, and surface layers of nanoparticles. 7 However, it is still very difficult to construct the diamond and ZnS structures by the sphere packing plus interaction approach mainly because such structures have non-close-packed lattices.On the other hand, it is well-known that the block copolymers exhibit a large variety of microphase-separated structures within the mesoscopic length scale in a manner that depends on the volume fractions and chain architectures of the molecules. 12-14 Among these materials, ABC star-shaped terpolymers adopt many unique microphase separations, which cannot be formed by linear-type block polymers such as AB, ABA, and ABC, in condensed 15-24 and solution 25-27 states because the three polymer chains are connected at one junction point and because the junction points must be aligned in a single dimension ( Figure 1a, left). We previously reported that cylindrical structures, whose cross sections reveal various periodic tiling patterns consisting of polygons, are predominantly formed by ISP starshaped terpolymers composed of polyisoprene (I), polystyrene (S), and poly(2-vinylpyridine) (P). [16][17][18][19] For example, the I 1 S 1.8 P 0.8 sample (Supporting Information) adopts a (6.6.6) Archimedean tiling pattern, consisting of three kinds of hexagons (Figure 1a, right). 18 This raises the question as to what morphology is adopted by the I 1 S 1.8 P 0.8 sample when the S chains are sufficiently extended. We can imagine that if a sufficient amount of the S component surrounds the I and P chains, the junction points of the ISP star molecules will be aligned annularly (Figure 1b, left). In the microphase-separated structure, the I and P chains are inclined to form spherical domains due to the requirement of minimizing the I/S and P/S interfacial energies (Figure 1b, right). If each spherical domain is packed periodically, mesoscopic CsCl, NaCl, and/or ZnS structures can be formed by proper placement of the I and P domains alternatively. Here we report that an ISP star-shaped terpolymer/homopolymer blend system can build up a giant zincblende structure. A 3K S-homopolymer has been added to the I 1 S 1.8 P 0.8 sample to increase the volume ratio of the S component instead of extending the S chains. The resulting I 1 S 2.3 P 0.8 and I 1 S 2.5 P 0.8 samples have been found to adopt the ZnS structure. In this structure, the I and P components form spherelike domains in mutual contact at the tetrahedral positions while component S covers the I and P components as matrix. Figure 2a illustrates the ZnS lattice for the I 1 S 2.3 P 0.8 sa...

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“…4.3.4) Soft materials consisting of different chemical/ physical species in a molecule such as lipids, 1 amphiphiles, 2 block copolymers, 3 and copolymerbased supramolecules 4 are well known to form periodic structures spontaneously because of their intramolecular segregation and self-assembling nature. In addition to classical structures like BCC-packed spheres, hexagonally packed cylinders, and lamellar structures found in early days, 5 extraordinary periodic structures, i.e., bicontinuous 6 and tricontinuous double Gyroid, 7 plumber's nightmare, 8 etc., have been found one after another for various soft material systems. Summarizing all the results, we notice that the environment of an element, a lipid or a polymer, is almost the same in these systems.…”

mentioning

confidence: 99%

A mesoscopic Archimedean tiling having a new complexity in an ABC star polymer

Takano

Kawashima

Noro

et al. 2005

J Polym Sci B Polym Phys

154

175

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The Archimedean tiling (3 2 .4.3.4) is a regular but complex polygonal assembly of equilateral triangles and squares. This tiling pattern with mesoscopic repeating distance has been found for an ABC star-branched three-component polymer composed of polyisoprene, polystyrene, and poly(2-vinylpyridine). In this structure the environment of a molecule splits into multiple sites and two microdomains with different sizes and shapes are formed for one component. This complexity is the first observation in complex polymer systems and can lead to a new type of mesoscale self-organization. The tiling pattern has been observed for the other materials on much shorter length-scale; therefore, the experimental fact observed in the present study is demonstrating that the complexity is universal over different hierarchies.

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Fine structures of styrene-butadiene block copolymer films cast from toluene solution

Cited by 117 publications

References 4 publications

Control of nanostructures generated in epoxy matrices blended with PMMA-b-PnBA-b-PMMA triblock copolymers

Control of nanostructures generated in epoxy matrices blended with PMMA-b-PnBA-b-PMMA triblock copolymers

Giant Zincblende Structures Formed by an ABC Star-Shaped Terpolymer/Homopolymer Blend System

A mesoscopic Archimedean tiling having a new complexity in an ABC star polymer

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