Cationic Polymerization of β-Pinene Using Keggin Phosphotungstates as Catalysts

Liu, Zu Guang; Zeng, Wei; Zhang, Tai Shun; Wang, Shuo; Zhu, Hua Long; Lei, Fu

doi:10.4028/www.scientific.net/amr.550-553.296

Cited by 5 publications

(3 citation statements)

References 23 publications

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“…The Lewis acid catalyzed carbocationic isomerization polymerization of β-pinene has been explored since the 1950s [ 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 ]. A number of Lewis acids, such as AlCl 3 , AlBr 3 , EtAlCl 2 , Et 2 AlCl, BiCl 3 , SbCl 3 , ZrCl 4 , BF 3 , TiCl 4 , TiCl 3 (O i Pr), SnCl 4 , and ZnCl 2 , and different reaction conditions were used in attempts to carry out the polymerization of β-pinene.…”

Section: Introductionmentioning

confidence: 99%

“…Based in part on environmental considerations, attempts were also made to use various solid acid catalysts (co-initiators) in order to replace classical Lewis acids in the carbocationic polymerization of β-pinene [ 56 , 57 , 58 , 59 , 60 , 61 , 62 ]. For instance, the H 3 PW 12 O 40 acid was reported to have considerably high catalytic activity, but the applied reaction time was rather long (22 h) and the presence of halogenic solvents and low reaction temperature (−10 °C) was necessary to obtain sufficient yields (10–60%) [ 56 , 57 , 58 , 59 ]. The M n values of the resulting polymers were around 700–800 g/mol.…”

Section: Introductionmentioning

confidence: 99%

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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

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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.

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Section: Introductionmentioning

confidence: 99%

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

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“…It is possible to modify their acid-base and catalytic performance by changing their chemical composition (substituted HPAs). In previous paper [20][21][22][23][24], we have used Keggin-type heteropolyacids and their salts as catalysts for the polymerization of pinene and obtained good reaction selectivity and polymers yields. We now report the performance of substituted phosphotungstic acids containing manganese, chromium, molybdenum and vanadium as catalysts for the homo-polymerization of β-pinene to terpene resin.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Substituted Phosphotungstic Acids and their Catalytic Performance on Cationic Polymerization of β-Pinene

Liu

Zhu

Wang

et al. 2013

AMR

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Substituted phosphotungstic acids containing manganese, chromium, molybdenum and vanadium were prepared, and their catalytic performance on cationic polymerization of β-pinene was also investigated. The experimental results show that the substituted phosphotungstic acids are mono-substituted and keep Keggin structure. The substituted phosphotungstic acids containing Mn or Cr exhibit similar catalytic performance as phosphotungstic acid, instead show bad properties if containing Mo or V. The yield of polymer is up to 44.3 %, and the average number molecular weight is about 1200, and molecular weight distribution index is 1.4.

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Reactions of Terpenes Catalyzed by Heteropoly Compounds: Valorization of Biorenewables

Gusevskaya

2014

ChemCatChem

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Heteropoly compounds (HPCs) have already proved their high potential for the clean synthesis of commercially valuable chemicals. However, the use of HPCs for the transformations of terpenic substrates became a research topic only about 20 years ago. Terpenes, natural products available from essential oils, are an important biomass‐based feedstock for the pharmaceutical, flavor, and fragrance industries.

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Cationic Polymerization of β-Pinene Using Keggin Phosphotungstates as Catalysts

Cited by 5 publications

References 23 publications

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

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

Synthesis of Substituted Phosphotungstic Acids and their Catalytic Performance on Cationic Polymerization of β-Pinene

Reactions of Terpenes Catalyzed by Heteropoly Compounds: Valorization of Biorenewables

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