Enzyme-catalyzed polymerizations at higher temperatures: Synthetic methods to produce polyamides and new poly(amide-co-ester)s

Ragupathy, Laks; Ziener, Ulrich; Dyllick‐Brenzinger, Rainer; Vacano, Bernhard von; Landfester, Katharina

doi:10.1016/j.molcatb.2011.11.019

Cited by 49 publications

(64 citation statements)

References 27 publications

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“…Reaction temperatures were set between 130 °C, which is the minimum value required for melting the reactants, and 150 °C, which is the maximum value compatible with enzyme activity. The capacity of CALB to retain polymerization catalytic activity at high temperatures has been reported in several occasions . In this work, an activity test has been carried out to confirm that such capacity is effective under the reaction conditions here used.…”

Section: Resultsmentioning

confidence: 72%

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

Morales‐Huerta

Ilarduya

Muñoz‐Guerra

2017

J. Polym. Sci. Part A: Polym. Chem.

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Cyclic oligo(butylene 2,5‐furandicarboxylate) and ɛ‐caprolactone were copolymerized in bulk at 130–150 °C by enzymatic ring opening polymerization using CALB as catalyst. Copolyesters within a wide range of compositions were thus synthesized with weight‐average molecular weights between 20,000 and 50,000, the highest values being obtained for equimolar or nearly equimolar contents in the two components. The copolyesters consisted of a blocky distribution of the ɛ‐oxycaproate (CL) and butylene furanoate (BF) units that could be further randomized by heating treatment. The thermal stability of these copolyesters was comparable to those of the parent homopolyesters (PBF and PCL), and they all showed crystallinity in more or less degree depending on composition. Their melting and glass‐transition temperatures were ranging between those of PBF and PCL with values increasing almost linearly with the content in BF units. The ability of these copolyesters for crystallizing from the melt was evaluated by comparative isothermal crystallization and found to be favored by the presence of flexible ɛ‐oxycaproate blocks. These copolyesters are essentially insensitive to hydrolysis in neutral aqueous medium but they became noticeably degraded by lipases in an extend that increased with the content in CL units. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 290–299

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Section: Resultsmentioning

confidence: 72%

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

Morales‐Huerta

Ilarduya

Muñoz‐Guerra

2017

J. Polym. Sci. Part A: Polym. Chem.

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“…32,33 Only few synthetic polyamides are successfully prepared via enzymatic polymerization. [34][35][36][37] This is mainly due to the high melting temperatures (T m ) and low solubility of polyamides. 33 In our laboratory the hydrolase-catalyzed polymerization is actively investigated and therefore various polyesters and polyamides are successfully produced via enzymatic polymerization, e.g., saturated and unsaturated aliphatic polyesters, [38][39][40] glucose-based polyesters, 41 furan-based polyesters, 42,43 semi-aromatic oligoamides, 44 oligo(amino acid)s, 45 aliphatic polyamides [46][47][48] and poly(amide-co-ester)s. 49 The previous studies reported by our laboratory revealed that Novozym 435 (N435), which is an immobilized form of Candida antarctica Lipase B (CALB) on acrylic resin, is a robust biocatalyst for polyester and polyamide synthesis; and N435 works well with FDCA derivatives in biocatalytic polyester synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…On the one hand, the low reaction speed of enzymatic amidation/transamidation can result in the removal of 1,8-OAD, which will lead to low molecular weights. Landfester et al37 …”

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confidence: 99%

Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides

Jiao¹,

Maniar²,

Woortman³

et al. 2015

Biomacromolecules

115

124

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Furan-2,5-dicarboxylic acid (FDCA)-based furanic-aliphatic polyamides can be used as promising sustainable alternatives to polyphthalamides (semiaromatic polyamides) and be applied as high performance materials with great commercial interest. In this study, poly(octamethylene furanamide) (PA8F), an analog to poly(octamethylene terephthalamide) (PA8T), is successfully produced via Novozym 435 (N435)-catalyzed polymerization, using a one-stage method in toluene and a temperature-varied two-stage method in diphenyl ether, respectively. The enzymatic polymerization results in PA8F with high weight-average molecular weight (M̅(w)) up to 54000 g/mol. Studies on the one-stage enzymatic polymerization in toluene indicate that the molecular weights of PA8F increase significantly with the concentration of N435; with an optimal reaction temperature of 90 °C. The temperature-varied, two-stage enzymatic polymerization in diphenyl ether yields PA8F with higher molecular weights, as compared to the one-stage procedure, at higher reaction temperatures. MALDI-ToF MS analysis suggests that eight end groups are present in the obtained PA8F: ester/amine, ester/ester, amine/amine, acid/amine, ester/acid, acid/acid, ester/amide, and no end groups (cyclic). Compared to PA8T, the obtained PA8F possesses a similar Tg and similar crystal structures, a comparable Td, but a lower Tm.

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“…86 O processo adotado para a síntese do polímero também pode influenciar suas propriedades. Ragupathy et al 87 fizeram uma comparação entre diferentes processos para a síntese de poliamida utilizando a enzima Novozym 435 como catalisador. Os diferentes processos e condições estão na Tabela 1.…”

Section: Poliamidas E Polipeptídeosunclassified

Applications of Enzymes in Synthesis and Modification of Polymers

Albuquerque¹,

Ribeiro²,

Rabelo³

et al. 2014

Química Nova

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Recebido em 07/06/2013; aceito em 10/12/2013; publicado na web em 21/03/2014 APPLICATIONS OF ENZYMES IN SYNTHESIS AND MODIFICATION OF POLYMERS. Enzymes are biological catalysts that offer great potential for use in the synthesis and modification of polymers, being more specific and greener than chemical catalysts. In this work, enzymes from the classes of hydrolases (lipase, cutinase and protease) and of oxidoreductases (horseradish peroxidase, manganese peroxidase and laccase) were identified as the main biocatalysts responsible for the synthesis of polymers. Biocatalysis can potentially be part of the life cycle of several polymers, including polyesters, polyurethanes, polycarbonates, polyamides, functionalized polysaccharides and polystyrene, allowing the synthesis of specialty macromolecules for fine applications and with higher added-value than commodity polymers.Keywords: enzyme polymerization; biocatalysis; lipase. INTRODUÇÃOProcessos de polimerização representam uma das principais transformações químicas industriais da atualidade, sendo, em sua maioria, conduzidos na presença de catalisadores químicos não renováveis e sob elevadas temperaturas, demandando, em alguns casos, a proteção e desproteção de grupos funcionais, de forma a evitar a ocorrência de reações indesejadas. 1 Há cerca de 20 anos, a catálise enzimática tem sido apontada como uma estratégia de grande potencial para a síntese de políme-ros, por ser ambientalmente amigável e em geral bastante seletiva, permitindo assim a obtenção de macromoléculas com propriedades diferenciadas e de maior valor agregado.2 As enzimas para a síntese e também modificação de polímeros estão nas classes das hidrolases (como lipases, proteases e esterases) e das oxidorredutases. 3A biocatálise pode ser empregada tanto para a síntese de polí-meros naturais como de polímeros sintéticos, e dentre suas maiores vantagens está a elevada seletividade (enantio-, quimio-, éstereo-e régio-seletividade), levando à obtenção de polímeros perfeitamente estruturados na maioria dos casos. Além disso, a catálise enzimática ocorre em geral de forma bastante eficiente sob condições mais brandas de temperatura e pressão, 4 demanda reduzida (ou nenhuma) quantidade de solventes orgânicos, 5 não proporciona a formação de produtos secundários e os produtos finais são de fácil separação e recuperação.6-8 Tais vantagens ficam claras especialmente quando são empregados biocatalisadores na forma imobilizada, a qual é uma técnica amplamente reportada pela literatura.9,10 A biocatálise foi reconhecida na década de 1990 como uma área nova na síntese de polímeros de precisão. 11Dessa forma, o objetivo desse artigo é apresentar um panorama das principais enzimas e condições de processo que podem ser utilizadas para a síntese e a modificação de polímeros de interesse industrial. O reconhecimento da importância do tema se traduz pela existência hoje de livros inteiramente dedicados à polimerização enzimática. 12-14 APLICAÇÕES DE ENZIMAS NA SÍNTESE DE POLÍMEROS PoliésteresOs poliésteres estão dentre ...

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Enzyme-catalyzed polymerizations at higher temperatures: Synthetic methods to produce polyamides and new poly(amide-co-ester)s

Cited by 49 publications

References 27 publications

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides

Applications of Enzymes in Synthesis and Modification of Polymers

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