Thermoset elastomers covalently crosslinked by hard nanodomains of triblock copolymers derived from carvomenthide and lactide: tunable strength and hydrolytic degradability

Jang, Jeongmin; Park, Hyejin; Jeong, Haemin; Mo, Eunbi; Kim, Yongbin; Yuk, Jeong Suk; Choi, Siyoung Q.; Kim, Young‐Wun; Shin, Jihoon

doi:10.1039/c8py01765d

Cited by 18 publications

(16 citation statements)

References 47 publications

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“…The thermal decomposition ( T d,5% = 272–290 °C) of the PIB- g -(P(L)LA–Ac) exhibited an obvious shift, with an increase in the T d,5% range of 16–19 °C. This was greater than PIB- g -(P(L)LA–OH), which means that transesterification was suppressed due to the absence of the terminal hydroxyl group after replacing −OH with −OC(O)CH 3 (Figures b and S2b inset). , …”

Section: Results and Discussionmentioning

confidence: 99%

Thermoplastic Superelastomers Based on Poly(isobutylene)-graft-Poly(l-lactide) Copolymers: Enhanced Thermal Stability, Tunable Tensile Strength, and Gas Barrier Property

Yuk

Kim

et al. 2020

Macromolecules

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A mechanically adjustable reinforced thermoplastic superelastomer system, with tunable gas-permeability, was developed. The superelastomer is based on a graft copolymer structure, using commercial butyl rubbers (or poly(isobutylene-co-isoprene), P(IB-co-I)) and l- or d,l-lactide (LLA or LA) derived from renewable feedstocks, by a “grafting from” controlled polymerization. First, hydroxyl-functionalized PIB (PIB-g-(OH)) macroinitiators were prepared through epoxidation using an economical alternative to m-chloroperoxybenzoic acid and ring-opening reaction. Second, PIB-based graft copolymers with end-hydroxylated poly(lactide) as hard side-chains, PIB-g-(P(L)LA–OH)s, were synthesized to target f P(L)LA of 0.18–0.45, to achieve mechanical reinforcement and an additional gas barrier. They were subsequently acetylated with an acetic anhydride to produce PIB-g-(P(L)LA–Ac)s with improved thermal stability. The well-defined molecular structures indicated controlled P(L)LA lengths, and the resulting superelastomers demonstrated improved thermal stability with increased T d,5%; microphase-separated structures having spherical and/or elongated features; thermoplastic behaviors proved by T ODT, which were much lower than the resulting T d,5%; and superior and adjustable mechanical characterizations, proving to control elastomeric-to-ductile properties. An oxygen permeability value as low as 27 mL mm m–2 day–1 atm–1 was achieved by increasing f P(L)LA to 0.45, comparable to polyethylene terephthalate. The partially biodegradable and processable gas barrier films based on these PIB-g-PLLA thermoplastic superelastomers have great potential for the flexible packaging of food and medical products.

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Section: Results and Discussionmentioning

confidence: 99%

Thermoplastic Superelastomers Based on Poly(isobutylene)-graft-Poly(l-lactide) Copolymers: Enhanced Thermal Stability, Tunable Tensile Strength, and Gas Barrier Property

Yuk

Kim

et al. 2020

Macromolecules

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“…The small differences in degradation rates are likely due to the small differences in hydrophilicity, original molar mass, and PLA content. , A decrease in molar mass was accompanied by the broadening of SEC traces (Figure S27), which is evidence of homogeneous and random chain scission. , 1 H NMR spectra of the degradation products also confirm the structural change of PPDCL and PLA upon hydrolytic degradation (Figure ). The methine proton in PLA (δ ∼ 5.2 ppm, see red triangle region) disappeared almost completely while a new carboxylic acid proton appeared at δ ∼ 10.5 ppm. Methylene protons, assigned as g (δ ∼ 4.0 ppm) and f (δ ∼ 2.2 ppm), were also shifted and broadened, indicative of PPDCL chain scission.…”

Section: Results and Discussionmentioning

confidence: 99%

“…42,43 1 H NMR spectra of the degradation products also confirm the structural change of PPDCL and PLA upon hydrolytic degradation (Figure 9). 45 The methine proton in PLA (δ ∼ 5.2 ppm, see red triangle region) disappeared almost completely while a new carboxylic acid proton appeared at δ ∼ 10.5 ppm. Methylene protons, assigned as g (δ ∼ 4.0 ppm) and f (δ ∼ 2.2 ppm), were also shifted and broadened, indicative of PPDCL chain scission.…”

Section: ■ Introductionmentioning

confidence: 98%

Sustainable Triblock Copolymers as Tunable and Degradable Pressure Sensitive Adhesives

Kim¹,

Jin

Shim

et al. 2020

ACS Sustainable Chem. Eng.

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Pressure sensitive adhesives (PSAs) are widely used in a variety of applications (e.g., sticky note and packing tape). As for most commercial polymer products, current PSA materials are primarily derived from fossil resources and not readily degradable; this has negative environmental consequences. The design of new PSA materials from sustainable resources that possess competitive adhesion properties and degradability is attractive for addressing sustainability concerns. In this work, we prepared a new aliphatic polyester with a long alkyl substituent, poly(pentadecyl caprolactone) (PPDCL), from cashewnut shell liquid derived lactones by ring opening transesterification polymerization in a controlled fashion. The PPDCL was used as the central block in a symmetric triblock copolymer with poly(lactide) end blocks. A series of ABA triblock copolymers were blended with a renewable tackifier to produce sustainable PSA materials. The resultant PSAs showed competitive adhesion properties with many common commercial adhesives. In addition, the ABA triblock copolymers hydrolytically degraded at 50 °C under acidic conditions suggesting they could be attractive as sustainable and degradable PSA materials.

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“…The molecular structure of elastomers contains partially crosslinked networks, unlike that of other thermosetting materials, which contain highly crosslinked networks. This partially crosslinked structure typically allows elastomers to behave as amorphous polymers or thermosets 4 . However, elastomers can also be copolymerized or physically mixed to perform in similar fashion to thermoplastics, which suit some applications as they are easy to use in manufacturing, for example, injection or compression molding 5,6 .…”

Section: Introductionmentioning

confidence: 99%

“…This partially crosslinked structure typically allows elastomers to behave as amorphous polymers or thermosets. 4 However, elastomers can also be copolymerized or physically mixed to perform in similar fashion to thermoplastics, which suit some applications as they are easy to use in manufacturing, for example, injection or compression molding. 5,6 Currently, these materials are exploited in a wide range of applications such as seals and hoses in the oil and gas industry, 7,8 automotive, agricultural, and medical applications, [9][10][11] soft robotics, 12,13 and wearable devices.…”

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confidence: 99%

Shape memory elastomers: A review of synthesis, design, advanced manufacturing, and emerging applications

Prathumrat

Nikzad

Hajizadeh

et al. 2022

Polymers for Advanced Techs

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Shape memory elastomers (SMEs) are a class of intelligent materials characterized by their ability to deform and recover shapes under applied force and external stimuli. Heat and ultraviolet radiation are examples of the most common external stimuli. With the emerging prevalence of internet of things devices and the ensuing need for smart materials and structures, SMEs provide significant opportunities to support the development of novel applications in robotics, remotely actuated systems, and packages, including those promised for the space industry. To harness the immense potential in the emerging applications of these materials, one approach is the systematic multi‐scale modeling coupled with artificial intelligence‐assisted design leading to the development of next‐generation intelligent systems. This review covers several aspects of the synthesis/materials chemistry and applications of SMEs with a view towards enabling such an approach. The synthesis procedures emphasizing dynamic covalent bond reactions are reviewed. Then, liquid crystalline elastomers are introduced as a specific elastomeric material class that exhibits excellent shape memory characteristics and distinctive transition temperatures. The utilization of advanced manufacturing methods such as additive manufacturing, three‐dimensional printing, and the emerging four‐dimensional printing technologies assisted by machine learning are detailed in producing and predicting SMEs. Finally, the current trends in the use of SMEs are summarized in areas of industrial and space engineering and biomedical applications.

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Thermoset elastomers covalently crosslinked by hard nanodomains of triblock copolymers derived from carvomenthide and lactide: tunable strength and hydrolytic degradability

Abstract: Sustainable, mechanically reinforced, and hydrolytically degradable thermoset elastomers were synthesized by one-pot, three-step synthesis & crosslinking.

Cited by 18 publications

References 47 publications

Thermoplastic Superelastomers Based on Poly(isobutylene)-graft-Poly(l-lactide) Copolymers: Enhanced Thermal Stability, Tunable Tensile Strength, and Gas Barrier Property

Thermoplastic Superelastomers Based on Poly(isobutylene)-graft-Poly(l-lactide) Copolymers: Enhanced Thermal Stability, Tunable Tensile Strength, and Gas Barrier Property

Sustainable Triblock Copolymers as Tunable and Degradable Pressure Sensitive Adhesives

Shape memory elastomers: A review of synthesis, design, advanced manufacturing, and emerging applications

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