Sustainable polyacetals from isohexides

Rajput, Bhausaheb S.; Gaikwad, Shahaji R.; Menon, Shamal K.; Chikkali, Samir H.

doi:10.1039/c4gc00543k

Cited by 47 publications

(31 citation statements)

References 34 publications

(15 reference statements)

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“…polymers with spirocyclic units in the main chain [1][2][3][4][5][6][7]. This cyclic structure restricts conformational flexibility and hence results in an increased thermal stability of the polymers.…”

Section: Introductionmentioning

confidence: 99%

Renewable thermoplastic polyurethanes containing rigid spiroacetal moieties

Lingier

Espeel

Suárez

et al. 2015

European Polymer Journal

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a b s t r a c tUnprecedented polyurethanes with rigid spiroacetal linkages in the backbone were synthesized from renewable resource compounds. First, the large-scale synthesis of a rigid diol monomer containing acetal bonds was established. Subsequently, this diol monomer was combined with seven different diisocyanates to vary the backbone of thermoplastic polyurethanes, leading to a spectrum of chemical and physical properties. The molar masses of the polymers ranged from 8 to 45 kDa and the corresponding polymers were obtained in high yields. DSC and DMTA analysis demonstrated glass transition temperatures up to 85°C. Acid-mediated degradation of the materials was not noticed during hydrolytic stability tests.

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Section: Introductionmentioning

confidence: 99%

Renewable thermoplastic polyurethanes containing rigid spiroacetal moieties

Lingier

Espeel

Suárez

et al. 2015

European Polymer Journal

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“…Thus, significant progress has been made in the synthesis of polymers derived from isohexides; however, degradation of these polymers remains uninvestigated. In our pursuit to address these two issues of reactivity of the isohexides and degradation of the resultant polymers, this group recently reported syntheses of isohexide‐diacetals and their corresponding polyacetals . We also demonstrated that the isohexide derived polyacetals degraded under slightly acidic conditions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Renewable Copolyacetals with Tunable Degradation

Rajput

Chander

Arole

et al. 2016

Macromol. Chem. Phys.

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Acetal metathesis copolymerization (AMCP) of renewable isohexide diacetals and aliphatic long-chain diacetals is reported and access to a small family of copolyacetals has been established. Crucial 1-2D NMR and MALDI-ToF-MS fi ndings unambiguously confi rm the existence of a copolymeric structure. In a stark contrast to the earlier reported isohexide-polyacetals, the current copolyacetals reveal very slow degradation. Hydrolytic degradation of copolyacetal pellets is extremely slow at pH 7, whereas only 30% degradation over a period of 15 d is observed in 9 M hydrochloric acid solution. GPC investigations reveal that with increasing chain-length the rate of degradation reduces, whereas copolyacetals with short-chain aliphatic segments display a faster degradation profi le. The reduced rate of degradation can be attributed to the hydrophobic nature of long-chain acetal segments. In situ NMR spectroscopy reveals the existence of formates, hemiacetals, and diols as degradation products. Thus, the rate of degradation can be tuned by the judicious choice of isohexide-diacetal and linear-diacetals in a copolyacetal.

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“…Even partial replacement of petroleum‐based raw materials by renewable resources is a major contemporary challenge in terms of both economic and environmental aspects . In this context, there has been significant contributions from the scientific community, and various renewable resources have been identified . Several renewable products have been successfully launched such as sugar cane based polyethylene, poly‐lactic acid (PLA), and polyhydroxyalkanoates, to name a few .…”

Section: Introductionmentioning

confidence: 99%

Isomerizing Hydroformylation of Cashew Nut Shell Liquid

2017

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A small library of bisphosphorus ligands was evaluated in the rhodium‐catalyzed isomerizing hydroformylation (I‐HF) of cashew nut shell liquid (CNSL). The rhodium complex of 1,2‐bis((di‐tert‐butylphosphanyl)methyl)benzene (BDTBPMB; L4) outperformed the other bisphosphite and bisphosphine ligands and unveiled a moderate selectivity of 28 % and 50 % in the I‐HF of CNSL monoene and methoxy‐protected monoene, respectively. The resultant aldehyde 16‐(3‐methoxyphenyl)hexadecanal P1′ was isolated and its identity was fully established. Application of bis‐phosphine ligand L4 in the I‐HF of highly challenging CNSL cardanol (S3) and methoxy‐protected CNSL cardanol yielded a linear selectivity of 74 %, although with reduced conversion. To demonstrate the synthetic utility of our strategy, the obtained aldehyde (derived from S3) was subjected to hydrogenation and the resultant 3‐(16‐hydroxyhexadecyl) phenol (P8) was isolated in 89 % isolated yield. High‐pressure NMR investigation revealed selective formation of a bis‐equatorial BDTBPMB–rhodium complex, which might be responsible for the excellent linear selectivity.

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Sustainable polyacetals from isohexides

Cited by 47 publications

References 34 publications

Renewable thermoplastic polyurethanes containing rigid spiroacetal moieties

Renewable thermoplastic polyurethanes containing rigid spiroacetal moieties

Synthesis of Renewable Copolyacetals with Tunable Degradation

Isomerizing Hydroformylation of Cashew Nut Shell Liquid

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