Synthesis of well-defined di- and triblock acrylic copolymers consisting of hard poly(dicyclopentanyl acrylate) and soft poly(alkyl acrylate) segments by organocatalyzed group transfer polymerization and their glass transition behavior

Jia, Qun; Yan, Zhi-Chao; Li, Yanan; Liu, Junfeng; Ding, Yuansheng; Liu, Yujian; Li, Jian; Chen, Yougen

doi:10.1039/d1py00192b

Cited by 4 publications

(3 citation statements)

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“…Toluene was distilled over Na/benzophenone and degassed by three freeze–pump–thaw cycles under an argon atmosphere prior to use. 1-Methoxy-1-triisopropylsiloxy-2-methylpropene (MTS i Pr ) was synthesized according to a previous report . All other chemicals were used as received.…”

Section: Methodsmentioning

confidence: 99%

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Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties

Liu

Chen

2021

Macromolecules

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The current work presents the organocatalyzed group transfer polymerization (GTP) of alkyl sorbate, the postpolymerization modification at the double bond of the poly(alkyl sorbate) (PAS) backbone, and its thermal properties. The selected alkyl sorbate includes ethyl, n-hexyl, and n-octadecyl sorbate with the carbon number of the n-alkyl side chain being three times between every two neighboring monomers. The polymerization kinetics and mechanisms are briefly discussed for both the t-Bu-P4- and Me3SiNTf2-catalyzed GTPs of ethyl sorbate. Both of the two GTPs only undergo 1,4-addition to produce trans-rich PASs in which the former affords 81.9–85.4% trans content and the latter a much higher value as trans > 96%. The hydrogenation and epoxidation of the internal double bond turn out to be quantitative to provide the hydrogenated and epoxidized polymers, PAS-H2 and PAS-epoxy. The hydrogenation process makes the diastereochemistry and stereoregular structures of the two chiral carbons in the monomeric unit distinguishable by 13C NMR spectra, from which we know that the t-Bu-P4-catalyzed GTP produces erythro-rich PASs (erythro content = ca. 64%), while the Me3SiNTf2-catalyzed GTP gives relatively threo-rich PASs (threo content = 56–58%). However, the diisotactic/disyndiotactic ratios determined by 13C NMR spectra do not show an obvious difference between each other. Thermogravimetric analyses suggest that PAS-H2 shows the highest thermal stability and PAS-epoxy the lowest, due to the different polarity of the newly formed C–C bond in the main chain before and after the chemical modification of the internal double bond. For the amorphous poly(ethyl sorbate) (PES) and poly(n-hexyl sorbate) (PHS), change of the ethyl side group to n-hexyl greatly decreases the glass transition temperature (T g). As for the same PES/PHS series polymers, either the hydrogenation or the epoxidation of the internal double bond drastically changes the T g value of the final polymer product. In addition, the ca. 10% difference in the trans-cis composition for unmodified PES or PHS almost has no effect on T g values, while the erythro/threo content shows a prominent influence for the chemically modified polymers as the T g value can be changed from several to tens of Celsius degree when the same polymer changes from erythro-rich to threo-rich. On the contrary, crystallizable poly(n-octadecyl sorbate) (PODS) and its modified polymers possess melting points (T m) in a pretty narrow temperature range of 34.7–41.4 °C, which is almost the same as the T m of n-octadecyl sorbate. It is likely that the T m values of PODS and its derivative polymers are only determined by the crystallization of the long n-octadecyl side chain, almost irrespective of the chain length, the trans-cis isomerization, the diastereochemistry, and the stereochemistry of the main chain.

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Section: Methodsmentioning

confidence: 99%

“…1-Methoxy-1-triisopropylsiloxy-2-methylpropene (MTS iPr ) was synthesized according to a previous report. 25 All other chemicals were used as received.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties

Liu

Chen

2021

Macromolecules

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“…34,35 The rigid polymer blocks have higher self-cohesion and therefore tend to form crystalline domains, resulting in phase separation from the self-assembly of the flexible polymer blocks. [36][37][38] The key design principle of such inhomogeneous membranes is to strike a balance between the miscibility and immiscibility of different membrane-forming components. 39 In terms of reversible membrane permeability or shape, the blending of rigid and flexible blocks with different mechanical or chemical properties may present more versatile transformation forms.…”

Section: Introductionmentioning

confidence: 99%

Designing polymersomes with inhomogeneous membranes by co-assembly of block copolymers for controlled morphological reversibility

Wang

Fu²,

Zhu

et al. 2022

Phys. Chem. Chem. Phys.

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Poly(β‐trimethylsilyloxy ester): A Degradable Polymer Based on Retro Mukaiyama Aldol Reaction

Pan

Chen

2022

Macromol. Rapid Commun.

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Herein, a new type of degradable poly(𝜷-trimethylsilyloxy ester) prepared by the organocatalyzed Mukaiyama aldol polyaddition between bis(silyl ketene acetal)s and dialdehydes is reported. Specifically, the t-Bu-P 4 -catalyzed polyaddition between 1,2-bis[2-methyl-1-(trimethylsiloxy)prop-1enyloxy]ethane (MTS 2 ) and 4,4′-biphenyldicarboxaldehyde (BPDA) or butane-1,4-diyl bis(4-formylbenzoate) (BDA) can produce poly(𝜷-trimethylsilyloxy ester)s with number-average molar mass greater than 10 kg mol −1 . For the first time, it is found that these poly(𝜷-trimethylsilyloxy ester)s are degradable in solution in the presence of nucleophiles such as fluoride and cyanide anions. It is also found that the degradation behavior of poly(𝜷-trimethylsilyloxy ester)s is highly dependent on the nature of the used catalyst and the bond scission in polymer is fundamentally rooted in the retro Mukaiyama aldol reaction mechanism.

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Synthesis of well-defined di- and triblock acrylic copolymers consisting of hard poly(dicyclopentanyl acrylate) and soft poly(alkyl acrylate) segments by organocatalyzed group transfer polymerization and their glass transition behavior

Abstract: A series of well-defined di- and triblock acrylic copolymers consisting of hard poly(dicyclopentanyl acrylate) (PdcPA) and soft poly(alkyl acrylate) (PAA) blocks are synthesized by the N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (Me3SiNTf2) catalyzed group transfer...

Cited by 4 publications

References 59 publications

Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties

Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties

Designing polymersomes with inhomogeneous membranes by co-assembly of block copolymers for controlled morphological reversibility

Poly(β‐trimethylsilyloxy ester): A Degradable Polymer Based on Retro Mukaiyama Aldol Reaction

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