Can tetraphenylethane (TPE) “iniferter” groups be introduced into polymer chains by coupling TPE diol with diisocyanates?

Grabowski, Mateusz; Kost, Bartłomiej; Gostyński, Bartłomiej; Bednarek, Melania

doi:10.1016/j.polymer.2022.124738

Cited by 4 publications

(5 citation statements)

References 25 publications

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“…First, polylactide diol was prepared via the cationic ring-opening polymerization of L-lactide using a difunctional initiator [21]. TPE-diET diol bearing primary -OH groups was synthesized according to the procedure described in our earlier article [13]. As a result of the preliminary experiments, DMF was chosen as a solvent that was able to solubilize all the substrates and products of polyurethane synthesis, and DBTDL was used as a catalyst for the formation of urethane linkages.…”

Section: Synthesis Of Polylactide-based Polymer Containing Multiple T...mentioning

confidence: 99%

“…Tetraphenyletahane (TPE) was applied as the inifer, which is known as a group that undergoes dissociation into radicals under heating and as being able to initiate radical polymerization [8][9][10][11]. TPE was generated inside the PLA chain from benzophenone fragments [12,13] via a method we elaborated [6] (commercial benzopinacole could not be introduced via the initiation of lactide polymerization due to the insufficient reactivity of tertiary -OH groups, which was proven by us previously [13]). Using a PLA-TPE macroinifer, acrylonitrile (AN) was polymerized at 85 • C, resulting in the triblock copolymer.…”

Section: Introductionmentioning

confidence: 99%

“…We also publish the results of experiments aiming to prove this fact, and we suggested replacing the commercial TPED with a derivative synthesized by us. This derivative was synthesized by coupling benzophenone functionalized with primary hydroxyl group [13].…”

Section: Introductionmentioning

confidence: 99%

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Functionalization of Polylactide with Multiple Tetraphenyethane Inifer Groups to Form PLA Block Copolymers with Vinyl Monomers

Grabowski¹,

Kost²,

Bodzioch³

et al. 2022

IJMS

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In the present contribution, a new strategy for preparing block copolymers of polylactide (PLA), a bio-derived polymer of increasing importance, is described. The method should lead to multiblock copolymers of lactide with vinyl monomers (VM), i.e., monomers that polymerize according to different mechanisms, and is based on the introduction of multiple “inifer” (INItiator/transFER agent) groups into PLA’s structure. As an “inifer” group, tetraphenylethane (TPE, known to easily thermally dissociate to radicals) was incorporated into PLA chains using diisocyanate. PLA that contained TPE groups (PLA-PU) was characterized, and its ability to form initiating radicals was demonstrated by ESR measurements. PLA-PU was used as a “macroinifer” for the polymerization of acrylonitrile and styrene upon moderate heating (85 °C) of the PLA-PU in the presence of monomers. The formation of block copolymers PLA/PVM was confirmed by 1H NMR, DOSY NMR, and FTIR spectroscopies and the SEC method. The prepared copolymers showed only one glass transition in DSC curves with Tg values higher than those of PLA-PU.

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Section: Synthesis Of Polylactide-based Polymer Containing Multiple T...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Functionalization of Polylactide with Multiple Tetraphenyethane Inifer Groups to Form PLA Block Copolymers with Vinyl Monomers

Grabowski¹,

Kost²,

Bodzioch³

et al. 2022

IJMS

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“…We decided to introduce the TPE unit into the PLA chain with the same purpose, i.e., to synthesize the PLA/poly(vinyl monomer) copolymer; however, during our preliminary study, the reaction of isocyanate with tetraphenylethanediol, which contained tertiary -OH groups, was not effective [24]. Other attempts to introduce one TPE unit into the PLA chain by applying TPED as a difunctional initiator of lactide polymerization were also unsuccessful, probably due to the side reactions that occur with benzopinacol in the presence of any catalyst (pinacol rearrangement under acidic conditions [25] or decomposition to benzophenone derivatives under basic conditions) [26].…”

Section: Introductionmentioning

confidence: 99%

A New Approach to The Synthesis of Polylactide/Polyacrylonitrile Block Copolymers

et al. 2022

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As a result of the search for alternatives to the known methods for the synthesis of PLA/vinyl polymer block copolymers, a new approach based on the “iniferter” concept was demonstrated in this article. In this approach, the introduction of a group that was capable of forming radicals and initiating radical polymerization into the polylactide (PLA) chain was conducted. Then, the obtained functional PLA was heated in the presence of a radically polymerizable monomer. The tetraphenylethane (TPE) group was chosen as a group that could dissociate to radicals. PLA with a TPE group in the middle of the chain was prepared in several steps as follows: (1) the synthesis of 4-(2-hydroxyethoxy)benzophenone (HBP-ET); (2) the polymerization of lactide, which was initiated with HBP-ET; and (3) the coupling of HBP-ET chains under UV radiation to form TPE-diET_PLA. A “macroiniferter”, i.e., TPE-diET_PLA, was used to initiate the polymerization of acrylonitrile (AN) by heating substrates at 85 °C. 1H and 13C NMR and SEC analyses of the products indicated that the triblock copolymer PLA-PAN-PLA formed and thus confirmed the assumed mechanism of the initiation of AN polymerization, which relied on the addition of the radical that formed from TPE (linked with the PLA chain) to the monomer molecule. Copolymerizations were performed with the application of prepared TPE-diET_PLA with three different Mn’s (1400, 2200, and 3300) and with different AN/PLA ratios, producing copolymers with varied compositions, i.e., with AN/LA ratios in the range of 2.3–11.1 and Mn’s in the range of 5100–9400. It was shown that the AN/LA ratio in the copolymer was increasable by the applied excess of AN with respect to the PLA macroiniferter in the feed and that more AN monomer was able to be introduced to PLA with shorter chains.

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“…PLA‐based networks were prepared by coupling PLA stars containing TPE groups in the core using aliphatic diisocyanate in the amount 1.1:1 in respect to PLA terminal (primary) OH groups (OH groups linked with the formed TPE groups are not reactive with diisocyanate at applied conditions 33 ). The reaction was performed in DCE solution, which after dissolving all components was poured into a Petri dish to obtain a network film suitable for further analysis.…”

Section: Resultsmentioning

confidence: 99%

Reversible polymer networks based on polylactide with tetraphenylethane thermally dissociating groups in crosslinks

Bednarek,

Grabowski,

Lipińska

et al. 2024

Polymers for Advanced Techs

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Polylactide (PLA)‐based reversible/dynamic polymer networks were synthesized by coupling 4‐arm PLA stars containing reversible tetraphenylethane (TPE) groups in the core using diisocyanate. Star‐shaped PLAs with molecular weights of 3200 and 6400 g/mol were obtained by the original method involving UV coupling of linear PLAs containing benzophenone moieties in the chain middle. The efficient formation of networks with gel content close to 100% was confirmed by FTIR spectroscopy. Networks with different densities of reversible groups exhibited tensile strength in the range of 35–50 MPa. Their reversible character was demonstrated by stress relaxation measurements performed at different temperatures (120–150°C). The prepared networks were capable of very fast stress relaxation due to radical exchange reactions between TPE groups placed in crosslinks, in contrast to a reference network without TPE groups. It was shown in the repairing experiment that networks were capable of processing.

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Can tetraphenylethane (TPE) “iniferter” groups be introduced into polymer chains by coupling TPE diol with diisocyanates?

Cited by 4 publications

References 25 publications

Functionalization of Polylactide with Multiple Tetraphenyethane Inifer Groups to Form PLA Block Copolymers with Vinyl Monomers

Functionalization of Polylactide with Multiple Tetraphenyethane Inifer Groups to Form PLA Block Copolymers with Vinyl Monomers

A New Approach to The Synthesis of Polylactide/Polyacrylonitrile Block Copolymers

Reversible polymer networks based on polylactide with tetraphenylethane thermally dissociating groups in crosslinks

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