Organocatalyzed β-pinene polymerization in UV light: Assessment of reaction conditions and material characterization

Rodrigues, Plínio Ribeiro; Gonçalves, Sayeny A; Vieira, Roniérik Pioli

doi:10.1016/j.eurpolymj.2021.110303

Cited by 15 publications

(10 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The monomer conversion (15.10%) was determined gravimetrically in three replicates. Poly(β-pinene) oligomer characterization is reported by Rodrigues et al [28]. More detailed reaction steps and the oligomer molecular weight determination are presented in the Supplementary material.…”

Section: β-Pinene Polymerization and Molecular Weight Determinationmentioning

confidence: 91%

“…Recently, our research group reported the production of poly (β-pinene) oligomers through the controlled polymerization of β-pinene (O-ATRP), a renewable monomer widely distributed in nature and produced by plants as an essential oil constituent. The oligomers synthesized exhibited antioxidant activity more than twice that observed for β-pinene, which represents a very significant advance since essential oil constituents are already known for their very markedly antioxidant activities [28]. Therefore, the incorporation of poly(β-pinene) oligomer in chitosan matrix might imply in the production of efficient active biobased films.…”

Section: Introductionmentioning

confidence: 89%

“…1a) was produced via O-ATRP in bulk reaction. The molar ratio of 200:1:25:5 was used as the reaction condition for monomer (β-pinene), initiator (1-bromoethyl benzene), catalyst (benzophenone), and electron donor amine (PMDETA), respectively [28]. As illustrated in Fig.…”

Section: β-Pinene Polymerization and Molecular Weight Determinationmentioning

confidence: 99%

See 2 more Smart Citations

O-ATRP synthesized poly(β-pinene) blended with chitosan for antimicrobial and antioxidant bio-based films production

Rodrigues

Júnior²,

Souza

et al. 2021

International Journal of Biological Macromolecules

View full text Add to dashboard Cite

Section: β-Pinene Polymerization and Molecular Weight Determinationmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 89%

See 1 more Smart Citation

O-ATRP synthesized poly(β-pinene) blended with chitosan for antimicrobial and antioxidant bio-based films production

Rodrigues

Júnior²,

Souza

et al. 2021

International Journal of Biological Macromolecules

View full text Add to dashboard Cite

“…20 As a result, better antimicrobial and antioxidant capabilities could be observed for the oligomers compared to their precursors, as reported for poly(βpinene). 21,22 Recently, our group reported the synthesis of low-molar-mass poly(limonene) (PL) employing a lightinduced controlled polymerization approach. 20,23 This promising technique allows control of the polymer characteristics such as dispersity and molar mass.…”

Section: Introductionmentioning

confidence: 99%

Incorporation of Limonene Oligomers into Poly(itaconic acid)/Starch Blend Films for Antimicrobial and Antioxidant Packaging Applications

Vianna,

Gonçalves,

Marangoni Júnior

et al. 2024

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

In this study, we devised novel poly(itaconic acid)/ starch (PIA/S)-based films by incorporating both limonene (LIM) and low-molar-mass poly(limonene) (PL) at varying concentrations (3, 6, and 9/100 g of starch). Our investigation centered on evaluating their antimicrobial and antioxidant capabilities with a focus on characterizing the most promising bioactive film formulations. Surprisingly, LIM-incorporated films showed no discernible bioactivity, contrasting with the remarkable outcomes seen in PL-incorporated films. Specifically, the latter demonstrated effectiveness against several pathogenic microorganisms including Bacillus cereus, Clostridium perfringens, Pseudomonas aeruginosa, and Colletotrichum gloeosporioides. Moreover, these films exhibited notable 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity of up to 13.4%, showcasing the hitherto unexplored potential of PL in this domain. This study also highlights the influence of PL incorporation on the general film properties. Overall, the films displayed uniform morphology, reduced tensile strength, and decreased elongation at break, accompanied by an increased moisture content and water solubility. No significant alterations were noted in the water vapor barrier properties. Notably, the introduction of PL also brought about an exceptional ultraviolet (UV)-light barrier effect, raising the prospect of utilizing PIA/S/PL films as innovative active packaging materials in the future.

show abstract

“…Polymerizations of β-pinene by processes other than cationic polymerization were also attempted. Recently, Vieira et al [ 67 , 68 , 69 , 70 ] reported on the atom transfer radical polymerization (ATRP) of this monomer, leading to low molecular weight oligomers. Coordination polymerization by Schiff-base nickel complex catalysts [ 71 ] was also accomplished.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Cationic Polymerization of β-Pinene, a Bio-Based, Renewable Olefin, with TiCl4 Catalyst from Cryogenic to Energy-Saving Room Temperature Conditions

Verebélyi

Szabó

Réti

et al. 2023

IJMS

View full text Add to dashboard Cite

Polymers based on renewable monomers are projected to have a significant role in the sustainable economy, even in the near future. Undoubtedly, the cationically polymerizable β-pinene, available in considerable quantities, is one of the most promising bio-based monomers for such purposes. In the course of our systematic investigations related to the catalytic activity of TiCl4 on the cationic polymerization of this natural olefin, it was found that the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4/N,N,N′,N′-tetramethylethylenediamine (TMEDA) initiating system induced efficient polymerization in dichloromethane (DCM)/hexane (Hx) mixture at both −78 °C and room temperature. At −78 °C, 100% monomer conversion was observed within 40 min, resulting in poly(β-pinene) with relatively high Mn (5500 g/mol). The molecular weight distributions (MWD) were uniformly shifted towards higher molecular weights (MW) in these polymerizations as long as monomer was present in the reaction mixture. However, chain–chain coupling took place after reaching 100% conversion, i.e., under monomer-starved conditions, resulting in considerable molecular weight increase and MWD broadening at −78 °C. At room temperature, the polymerization rate was lower, but chain coupling did not occur. The addition of a second feed of monomer in the polymerization system led to increasing conversion and polymers with higher MWs at both temperatures. 1H NMR spectra of the formed polymers indicated high in-chain double-bond contents. To overcome the polarity decrease by raising the temperature, polymerizations were also carried out in pure DCM at room temperature and at −20 °C. In both cases, rapid polymerization occurred with nearly quantitative yields, leading to poly(β-pinene)s with Mns in the range of 2000 g/mol. Strikingly, polymerization by TiCl4 alone, i.e., without any additive, also occurred with near complete conversion at room temperature within a few minutes, attributed to initiation by adventitious protic impurities. These results convincingly prove that highly efficient carbocationic polymerization of the renewable β-pinene can be accomplished with TiCl4 as catalyst under both cryogenic conditions, applied widely for carbocationic polymerizations, and the environmentally benign, energy-saving room temperature, i.e., without any additive and cooling or heating. These findings enable TiCl4-catalyzed eco-friendly manufacturing of poly(β-pinene)s, which can be utilized in various applications, and in addition, subsequent derivatizations could result in a range of high-added-value products.

show abstract

Organocatalyzed β-pinene polymerization in UV light: Assessment of reaction conditions and material characterization

Cited by 15 publications

References 63 publications

O-ATRP synthesized poly(β-pinene) blended with chitosan for antimicrobial and antioxidant bio-based films production

O-ATRP synthesized poly(β-pinene) blended with chitosan for antimicrobial and antioxidant bio-based films production

Incorporation of Limonene Oligomers into Poly(itaconic acid)/Starch Blend Films for Antimicrobial and Antioxidant Packaging Applications

Highly Efficient Cationic Polymerization of β-Pinene, a Bio-Based, Renewable Olefin, with TiCl4 Catalyst from Cryogenic to Energy-Saving Room Temperature Conditions

Contact Info

Product

Resources

About