Synthesis and characterization of functional polyethylene with regularly distributed thioester pendants via ring‐opening metathesis polymerization

Song, Shaofei; Zhang, Zhen; Liu, Xiaoyu; Fu, Zhisheng; Xu, Jun‐Ting; Fan, Zhiqiang

doi:10.1002/pola.28870

Cited by 14 publications

(9 citation statements)

References 67 publications

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“…76 Thioester-containing polypentenamers with similar pendant alkyl groups showed higher T g and T m but reduced thermal stability. 77 Our group's entry point to polypentenamers research came from the ROMP of 4-phenylcyclopentene (5) to produce a precision styrenic rubber (P4PCP) or ethylene-styrene (ES) "like" copolymer (H 2 −P4PCP) following hydrogenation ( Figure 6). 51 Here we reemphasize that, due to the 5-carbon phenyl branch spacing, accessing this microstructure through ES copolymerization is not possible.…”

Section: Acs Macro Lettersmentioning

confidence: 99%

“…With synthetic progress taking large strides, exploration of thermal and physical properties toward potential applications for functionalized polypentenamers is highly needed. Fan and co-workers recently reported a series of homoallylic ester or thioester-substituted CPs where they systematically increased the size of the ester pendant alkyl group. − The T g of the resulting polymers was shown to decrease from −26 °C to −65 °C as the ester pendant was increased from methyl to n -octyl . With n -dodecyl pendants and higher, semicrystalline properties arose from the long alkyl chains .…”

Section: Challenges With Admetmentioning

confidence: 99%

“…With n -dodecyl pendants and higher, semicrystalline properties arose from the long alkyl chains . Thioester-containing polypentenamers with similar pendant alkyl groups showed higher T g and T m but reduced thermal stability …”

Section: Challenges With Admetmentioning

confidence: 99%

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Polypentenamer Renaissance: Challenges and Opportunities

2018

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This Viewpoint highlights the viability and increasing variety of functionalized polypentenamers as unique and valuable materials created through enthalpydriven ring-opening metathesis polymerization (ROMP) of low ring strain cyclopentene monomers. The terms "low ring strain" and "enthalpy-driven" are typically conflicting ideologies for successful ROMP; however, these monomers possess a heightened sensitivity to reaction conditions, which may be leveraged in a number of ways to provide performance elastomers with good yield and precise functional topologies. Over the last several years, a rekindled interest in these systems has led to a renaissance of research aimed at improving their synthesis and exploring their potential. Their chemistry, applications, and future outlook are discussed. Figure 7. (a) Sulfonation of H 2 −P4PCP produces a precision polyelectrolyte similar to polystyrenesulfonate (PSS) but with precise 5-carbon distances along the chain. This material has an accessible T g (109°C) allowing it to be thermally molded (inset). Adapted with permission from ref 86. Copyright 2018 John Wiley and Sons. (b) Design of a polypentenamer bottlebrush polymer from ROMP of BIB-functionalized CP followed by ATRP. Block polymer grafts of PS and PMMA, monitored by SEC traces, produce a core−shell polymer visualized by AFM (inset). Adapted with permission from ref 57.

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Section: Acs Macro Lettersmentioning

confidence: 99%

Section: Challenges With Admetmentioning

confidence: 99%

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Polypentenamer Renaissance: Challenges and Opportunities

2018

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“…ROMP of cyclopentene (CP) derivatives has been largely overshadowed due to their low ring strain, [Δ H p ] = ∼23 kJ mol –1 , which reduces polymerization kinetics and limits high conversions due to the thermodynamics of the equilibrium ROMP. However, ROMP of CP and derivatives has received heightened interest within the last several years. − Recently, we reported a method to achieve high conversion, targeted molar mass, and low dispersity ( Đ ) PCP by altering the temperature during ROMP . This method, which we termed variable temperature ROMP (VT-ROMP), initiates polymerization at warm temperature and propagates CP to high conversion by cooling after initiation is complete.…”

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confidence: 99%

Well-Defined and Precision-Grafted Bottlebrush Polypentenamers from Variable Temperature ROMP and ATRP

2018

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Polypentenamer macroinitiators are synthesized through variable temperature ring opening metathesis polymerization of 3-cyclopentenyl α-bromoisobutyrate, which has sufficient ring strain (ΔH p = −22.6 kJ mol −1 ) to produce targeted molar mass (<5% from theoretical), low dispersity (1.17 ≤ Đ ≤ 1.23), and high conversion (∼72%). An initiation site for atom-transfer radical polymerization at every fifth backbone carbon allows "grafting-from" of styrene with quantitative initiation and linear molar mass increase with time. These bottlebrushes retain a low dispersity (Đ ≤ 1.34) at varying graft degrees of polymerization (5 ≤ N sc ≤ 49) and have a glass transition temperature highly sensitized to graft length. Extension of the grafts with methyl methacrylate produces a core−shell brush polymer with high molar mass (>1000 kg mol −1 ) and Đ = 1.33. This system exhibits high synthetic versatility and control with a unique flexible backbone to expand the suite of densely grafted polymers.

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“…They showed good thermal properties such as 5% weight loss temperature (T 5 ) in the range 307–301 °C and T g s in the range 65–110 °C due to the introduction of alicyclic and ester groups in the polymer chains, which endow chain rigidity. Song et al [ 64 ] prepared a functional polyethylene carrying thioester pendants via ring-opening metathesis polymerization (ROMP) of alkyl cyclopent-3-enecarbothioate catalyzed by a ruthenium-based catalyst. They investigated the thermal properties of obtained materials and they reported that the thioester groups were decomposed at 300–400 °C to release volatile fragments of the side groups, and decomposition of polymer backbone was initiated at temperature above 400 °C.…”

Section: Resultsmentioning

confidence: 99%

Cross-Linked Polythiomethacrylate Esters Based on Naphthalene—Synthesis, Properties and Reprocessing

2020

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Two structurally different aromatic dithioesters were synthesized from two dithiols and methacryloyl chloride. The polymer networks based on methyl methacrylate and/or styrene and the new dimethacrylates were subsequently prepared. The polymerization yields of copolymers were in the range of 95–99%. The thermal and mechanical properties of the copolymers were determined by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TG/DTG), and Shore D hardness. The addition of dithioesters—1,5-NAF-S-Met (or 1,4(1,5)-NAF-CH2S-Met) (from 0.5% to 5%) to MMA- or ST-based polymers results in lowering the glass transition temperature (Tg) by about 8 °C. The thioester-containing polymers based on MMA exhibit lower thermal stability than those with ST. The polythioesters are stable up to 250 °C. The UV/vis spectra and refractive indexes of prepared liquid compositions were also measured. The 1,5-NAF-S-Met (and 1,4(1,5)-NAF-CH2S-Met) improved the refractive index values of ST and MMA compositions. The double bond conversion was also determined for all synthesized materials. The swelling studies of polymers with 20% addition of thioester crosslinkers were investigated. For all polymeric materials with 20% addition of thioesters, depolymerization of the network was carried out by thiol-thioester exchange. The depolymerization products were re-reacted in a thiol-ene reaction with 2-hydroxyethyl methacrylate by thermal initiation. The thiol-ene procedure enabled reprocessing of starting polymers and obtaining new materials characterized by distinctly different thermal, mechanical, and swelling properties. The thiol-ene materials exhibit a lower Shore hardness in the range of 20–50 °Sh, as well as decreased Tg values when compared to starting copolymers. Due to these possible exchange reactions, one can facilely manipulate the properties of the polymers which could lead to the manufacturing of the new products with the desired features. Degradation of the cross-linked structure and recycling of copolymers were also discussed.

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Synthesis and characterization of functional polyethylene with regularly distributed thioester pendants via ring‐opening metathesis polymerization

Cited by 14 publications

References 67 publications

Polypentenamer Renaissance: Challenges and Opportunities

Polypentenamer Renaissance: Challenges and Opportunities

Well-Defined and Precision-Grafted Bottlebrush Polypentenamers from Variable Temperature ROMP and ATRP

Cross-Linked Polythiomethacrylate Esters Based on Naphthalene—Synthesis, Properties and Reprocessing

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