Synthesis of Aliphatic Polyesters by Direct Polyesterification of Dicarboxylic Acids with Diols under Mild Conditions Catalyzed by Reusable Rare-Earth Triflate

Takasu, Akinori; Oishi, Yoshika; Iio, Yoshitaka; Inai, Yoshihito; Hirabayashi, Tadamichi

doi:10.1021/ma021462v

Cited by 110 publications

(83 citation statements)

References 11 publications

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“…De acordo com a literatura [26][27][28][29], grupos hidroxila podem reagir com grupos carboxila, via policondensação, para formar poliésteres, essa reação é capaz de gerar um grupo éster, onde a carbonila do ácido acrílico passa a compor esse grupo. Estando presente, essa reação contribui para aumento do peso molecular e então do torque dos sistemas PCL/PEgAA.…”

Section: Resultsunclassified

Comportamento reológico do Bio-PE e do PCL na presença do PEgAA e PEgMA

et al. 2017

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RESUMOO reômetro de torque é um equipamento que reproduz em escala laboratorial o processamento de polímeros. Neste equipamento, a velocidade de rotação dos rotores, temperatura e tempo de processamento são parâme-tros predeterminados e impostos ao sistema investigado; avalia-se o torque necessário para a fusão, mistura e homogeneização da amostra. Através do gráfico do torque em função do tempo e do gráfico da temperatura em função do tempo de processamento, cujos valores estão relacionados com as propriedades reológicas, estrutura e massa molar das amostras, é possível obter informações sobre o comportamento dos polímeros em fluxo, ou seja, durante o processamento. Neste trabalho, foi investigado o efeito do polietileno graftizado com ácido acrílico (PEgAA) e do polietileno graftizado com anidrido maléico (PEgMA) no biopolietileno (Bio-PE) e no poli(ε-caprolactona) (PCL) por reometria de torque. Foi verificado que o PEgAA e o PEgMA promoveram aumento no torque dos sistemas Bio-PE/PEgAA, Bio-PE/PEgMA, PCL/PEgAA e PCL/PEgMA, possivelmente resultante de interações e/ou reações químicas ocorridas nesses sistemas poliméricos. Espectros de FTIR evidenciaram possíveis interações e/ou reações químicas entre os grupos funcionais dos políme-ros grafitizados e o Bio-PE e o PCL. Valores de torque mais altos foram observados nos sistemas com parâ-metros de solubilidade (δ) mais próximos, corroborando com os cálculos propostos por Hansen. Palavras-chave:Bio-PE, PCL, PEgAA, PEgMA, reometria de torque, parâmetro de solubilidade. ABSTRACTThe torque rheometer is equipment that enables to simulate the polymer processing in a laboratory scale. A set of parameters, i.e., rotor speed, temperature and processing time are predefined and imposed to the compounds under analysis. The necessary torque for melting and mixing the compound is measured. Through the plots of torque as a function of time and temperature, which are linked to the rheological properties, microstructure and molar weight of the samples, it is possible to acquire information regarding the flow behavior of polymers, meaning during processing. In this work, the effect of acrylic acid-grafted polyethylene (PEgAA) and maleic anhydride-grafted polyethylene (PEgMA) in bio-polyethylene (Bio-PE) and in poly(ε-caprolactone) (PCL) was performed by torque rheometry. PEgAA and PEgMA increased the torque rheometry values of the polymeric systems under investigation, i.e, Bio-PE/PEgAA, Bio-PE/PEgMA, PCL/PEgAA and PCL/PEgMA, possibly due to chemical interaction and/or reactions occurred during the processing. FTIR spectra presented possible interactions and/or chemical reactions between the functional groups of grafted polymers and Bio-PE and PCL. Higher torques were observed for the systems with similar solubility parameters agreeing with the mathematical calculations provided by Hansen.

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Section: Resultsunclassified

Comportamento reológico do Bio-PE e do PCL na presença do PEgAA e PEgMA

et al. 2017

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“…Under these conditions it is known that Sc(OTf) 3 is able to catalyze reactions; also good performance of this catalyst has been reported for both higher and lower reaction temperatures. 19 Regarding TBD and DBTO, polymerization reactions are usually carried out at higher temperatures, and a temperature of 100 °C may be not high enough for adequate active performance. 15 For this reason, in the second set of experiments the reactions were performed at temperatures at which the selected catalysts are known to exhibit their optimum catalytic activity: 60 °C for Sc(OTf) 3 , 11 120 °C for TBD, 16 and 140 °C for DBTO.…”

Section: Synthesis Of Sorbitol-based Polyesters Using Different Catalmentioning

confidence: 99%

“…Ether formation by the Lewis acid Sc(OTf) 3 has been also reported for polycondensation reactions using 1,3-PD and methylsuccinic acid at 80 °C. 19 At 60 °C (entry c), 10% of the 1,3-PD units within the polymer chain (excluding end groups) are linked to another 1,3-PD unit by an ether linkage. When raising the temperature up to 100 °C, this amount increases to 33% (entry b).…”

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confidence: 99%

Green and selective polycondensation methods toward linear sorbitol‐based polyesters: enzymatic versus organic and metal‐based catalysis

et al. 2016

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This is the peer reviewed version of the following article: "Gustini, L., Lavilla, C., Janssen, W., Martínez de Ilarduya, A., Muñoz-Guerra, S. FULL PAPER Green and selective polycondensation methods toward linear sorbitol-based polyesters: enzymatic vs. organic and metal-based catalysisLiliana Gustini [a,b] , Cristina Lavilla * [a] , William W.T.J. Janssen [a] , Antxon Martínez de Ilarduya [c] , Sebastián Muñoz-Guerra [c] , Cor E. Koning [a,d] Abstract: Renewable polyesters derived from a sugar alcohol, i.e. sorbitol, were synthesized by solvent-free polycondensation. The aim was to prepare linear polyesters with pendant hydroxyl groups along the polymer backbone. The performance of the sustainable biocatalyst SPRIN liposorb CALB and the organo-base catalyst triazobiciclodecene were compared with two metal-based catalysts, viz. scandium trifluoromethanesulfonate and dibutyl tin oxide. For the four catalytic systems, the efficiency and selectivity for the implementation of sorbitol were studied, mainly via 13 C and 31 P NMR spectroscopies, while side reactions such as ether formation and dehydration of sorbitol were evaluated via MALDI-ToF-MS. Especially the biocatalyst SPRIN liposorb CALB succeeded in incorporating sorbitol in a selective way without side reactions, leading to close-to-linear polyesters. By using a renewable hydroxylreactive curing agent based on L-lysine, transparent and glossy poly(ester urethane) networks were successfully synthesized offering a tangible example of bio-based coatings.

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“…The polymers were made using scandium (III) triflate as a catalyst under solvent-free conditions [29][30][31][32][33] and evaluated for drugloading via nanoprecipitation in the presence of coumarin-6 dye. The polymer exhibiting the highest dye loading was tested for colloidal and hydrolytic stability when formulated into nanoparticles (NPs).…”

Section: Introductionmentioning

confidence: 99%