Partially renewable copolyesters prepared from acetalized <scp>d</scp>‐glucitol by solid‐state modification of poly(butylene terephthalate)

Gubbels, Erik; Lavilla, Cristina; Ilarduya, Antxon Martı́nez de; Noordover, Bart A. J.; Koning, Cor E.; Muñoz‐Guerra, Sebastián

doi:10.1002/pola.26985

Cited by 20 publications

(16 citation statements)

References 52 publications

(161 reference statements)

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“…A recent study on 479 the use of Glux-diol as comonomer in the solid state modification of PBT has shown 480 that the reactivity of the axially oriented hydroxyl function in transesterification reactions 481 was significantly hindered. 26 However the slight differences in synthesis results attained 482 for the two PBS copolyester series indicate that such hindering effect must not be 483 significant in this case. 484…”

Section: Hydrolytic Degradation and Biodegradation 420mentioning

confidence: 95%

Bio-based PBS copolyesters derived from a bicyclicd-glucitol

et al. 2015

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to other bicyclic sugar-based diols reported in the literature, Glux-diol appeared to be more 22 efficient in both increasing the T g and enhancing the susceptibility to hydrolysis of PBS. 24 Introduction 25A growing interest for chemicals derived from renewable resources which are 26 able to replace oil-based monomers for the production of industrial polymers is 27 noticeable in these last years.1,2 Additionally, environmental pollution has recently 28 become a big problem of both social and technical repercussions due largely to the 29 high impact of plastic wastes.3 The most popular approach followed today to give 30 response to these concerns is to replace the commodity synthetic polymers by bio-31 based polymers. 4,5,6 In fact, polymers made from monomers derived from non-fossil 32 materials are sustainable and also total or partially susceptible to microbial 33 degradation.7 Aliphatic polyesters such as poly (L-lactic biodegradability when compared to PET and PBT. 19b,20b 67The purpose of this work is to explore the effects on properties of PBS caused 68 by the presence of carbohydrate-based diacetalized bicyclic units in the polymer chain, 69 more specifically of 2,4:3,5-di-O-methylene-D-glucitol, abbreviated as Glux-diol. We 70 have very recently reported on PBS copolyesters made from Manx-diol, the 71 stereoisomer of Glux-diol that derives from D-mannose. 21 Both isomers consist of two 72 fused 1,3-dioxane rings structure sharing a C6-segment backbone that bears two 73 hydroxyl functions at the end positions. At difference with Manx-diol, Glux-diol is 74 asymmetric so its two OH groups are spatially and hence chemically different (Scheme 75 1). Random PBS copolyesters containing Manx units could be obtained with M w above 76 30,000, they were semicrystalline for the whole range of compositions and displayed 77 enhanced T g and biodegradability. Since polymerization rate as well as polymer 78 properties are largely depending on monomer symmetry, it is of much conceptual 79 interest to compare Manx and Glux diols as comonomers for the production of PBS 80 copolyesters. Additionally, data obtained from this study can be related to those 81 reported for PBS copolyesters containing isosorbide in order to assess diacetalized 82 and dianhydride bicyclic diols as optional comonomers for their capacity to improve 83 PBS properties. The study is also of practical relevance since Glux-diol is a compound 84 coming from D-glucose, the most available monosaccharide in nature. C NMR spectra were recorded on a Bruker AMX-300 spectrometer at 102 25.0 ºC operating at 300.1 and 75.5 MHz, respectively. Polyesters were dissolved 103 either in deuterated chloroform or in a mixture of deuterated chloroform/ trifluoroacetic 104 acid (TFA) (1/1), and spectra were internally referenced to tetramethylsilane (TMS). 105About 10 and 50 mg of sample dissolved in 1 mL of solvent were used for 1 H and 13 C 106 NMR, respectively. Sixty-four scans were acquired for 1 H and 1,000-10,000 for 13 C with 107 32 and 64-K data points ...

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Section: Hydrolytic Degradation and Biodegradation 420mentioning

confidence: 95%

Bio-based PBS copolyesters derived from a bicyclicd-glucitol

et al. 2015

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“…However, copolymerization entails a significant reduction in the crystallinity and crystallizability of PBT, which is in most cases undesirable. Modification in the solid state (SSM) is an interesting rather recent method that allows increasing the T g of this polymer without much decreasing its crystallinity . On the other hand, PBT is quite resistant to hydrolysis and the replacement of terephthalic units by aliphatic ones by copolymerization has been reported as an alternative to enhance its hydrolytic degradation or even its biodegradation .…”

Section: Copolyesters and Blendsmentioning

confidence: 99%

“…On the other hand, PBT is quite resistant to hydrolysis and the replacement of terephthalic units by aliphatic ones by copolymerization has been reported as an alternative to enhance its hydrolytic degradation or even its biodegradation . NMR has been again the technique of choice in all the above referenced works to characterize the PBT copolyesters including the precise determination of their compositions and microstructures …”

Section: Copolyesters and Blendsmentioning

confidence: 99%

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

Ilarduya

Muñoz‐Guerra

2014

Macro Chemistry & Physics

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The use of NMR spectroscopy in solution to investigate the chemical structure of engineering poly(alkylene terephthalate)s such as poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT) is reviewed. Chemical defects present in the polyester chain, such as oxydialkylene units, as well as accompanying side products such as cyclic oligomers generated in the polycondensation, are well detected in 1H NMR spectra. The technique is also demonstrated to be effective for identifying, and even for quantifying in certain cases, the end groups of these polyterephthalates, including those that are generated in small amounts as a consequence of thermal degradation. The application of NMR to the study of the chemical microstructure of copolyesters derived from such polyterephthalates is also reviewed for its unique ability to determine comonomeric sequence lengths and degree of randomness (R). Copolyesters synthesized by either melt polycondensation or entropically driven ring opening polymerization, in addition to those prepared by solid‐state modification or melt blending, are the object of this review.

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“…Some of the sugar‐based polymers exhibit high glass transition temperatures to allow their potential uses as alternatives of petroleum‐based polymers, by virtue of the successful designs of conformationally constrained monomers that can be obtained by the selective chemical transformations of naturally occurring compounds. Promising candidates involves those synthesized from isohexides that are accessible from abundant monosaccharides and those synthesized from protected sugars …”

Section: Introductionmentioning

confidence: 99%

Rigid triol and diol with adamantane-like core derived from naturally occurringmyo-inositol and their polyaddition with diisocyanates

Okamoto

Onoue

Kobayashi

et al. 2014

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

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Two orthoester derivatives 1 and 2 that are easily accessible from naturally occurring myo-inositol were exploited as new triol-and diol-type monomers bearing a rigid adamantane-like structure to polyaddition with diisocyanates that gave the corresponding networked and linear polyurethanes. DSC analysis of the networked polyurethanes revealed their high glass transition temperatures ranging from 155 to 248 C, suggesting the contribution of the rigidity of the adamantane-like structure introduced at the nodes of the networked polyurethanes 6. Besides, the polyaddition of 2 with diisocyanates gave the corresponding linear polyurethanes 4, of which glass transition temperatures were high, ranging from 105 to 177 C, presumably by virtue of the rigidity of the adamantane-like structure introduced into the main chains. T g s of the networked polyurethanes 6 were higher than those of the linear polyurethanes 4.

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Partially renewable copolyesters prepared from acetalized d‐glucitol by solid‐state modification of poly(butylene terephthalate)

Cited by 20 publications

References 52 publications

Bio-based PBS copolyesters derived from a bicyclicd-glucitol

Bio-based PBS copolyesters derived from a bicyclicd-glucitol

Chemical Structure and Microstructure of Poly(alkylene terephthalate)s, their Copolyesters, and their Blends as Studied by NMR

Rigid triol and diol with adamantane-like core derived from naturally occurringmyo-inositol and their polyaddition with diisocyanates

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