01479nas a2200121 4500008004100000245006000041210005900101260000800160520104600168100002401214700002601238856009301264 2014 eng d00aIsohexide-diacetal based polymers and a process thereof0 aIsohexidediacetal based polymers and a process thereof cNOV3 a

The present invention discloses isohexide based compounds and their polymers which are derived from renewable resources and are potentially degradable. Also disclosed herein is the synthesis of isohexide based monomers and their polymers from renewable resources which are potentially degradable. Further, the present invention disclose a process for the synthesis of isohexide based copolymers via copolymerization of isohexide based monomers and long chain diols, which are degradable. (FR)Cette invention concerne des composés à base d'isohexide et leurs polymères qui sont dérivés de ressources renouvelables et sont potentiellement dégradables. Cette invention concerne également la synthèse de monomères à base d'isohexide et leurs polymères à partir de ressources renouvelables qui sont potentiellement dégradables. Un procédé de synthèse de copolymères à base d'isohexide par copolymérisation desdits monomères à base d'isohexide et de diols à chaîne longue, qui sont dégradables, est en outre décrit.

1 aChikkali, Samir, H.1 aRajput, Bhausaheb, S. uhttps://library.ncl.res.in/content/isohexide-diacetal-based-polymers-and-process-thereof02037nas a2200277 4500008004100000022001400041245006600055210006600121260007500187300001400262490000800276520113600284653001801420653002401438653001401462653001501476653002301491100002601514700001901540700001901559700002201578700002201600700002001622700002401642856009301666 2016 eng d a1022-135200aSynthesis of renewable copolyacetals with tunable degradation0 aSynthesis of renewable copolyacetals with tunable degradation aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcJUN a1396-14100 v2173 a

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 findings unambiguously confirm 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 profile. 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.

10acopolyacetals10adegradable polymers10adiacetals10aisohexides10arenewable polymers1 aRajput, Bhausaheb, S.1 aChander, Umesh1 aArole, Kailash1 aStempfle, Florian1 aMenon, Shamal, K.1 aMecking, Stefan1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/synthesis-renewable-copolyacetals-tunable-degradation01562nas a2200157 4500008004100000245006700041210006300108260000800171490000600179520101500185100002601200700003501226700002201261700002401283856009701307 2017 eng d00aSynthesis of isohexide-di(ether-ene)s and ADMET polymerization0 aSynthesis of isohexidedietherenes and ADMET polymerization cJUN0 v53 aAs the fossil fuel reserves deplete and the greenhouse gases increase, the scientific community is challenged to provide sustainable solutions. Sugar-based isohexides can be modified to prepare a library of isohexide-diene monomers for polymerization. Such isohexide diene monomers can be subjected to Acyclic Diene Metathesis Polymerization to obtain green materials. Here we report a single step synthetic protocol to access a small family of isohexide-di(ether-ene)s and the corresponding polymers. The isohexide di(ether-ene)s 2a-2c could be isolated in good to excellent yields under optimized conditions. The resultant isohexide-di(ether-ene)s 2a-2c are potential versatile building blocks for pharmaceuticals and material science. The synthetic utility of 2a-2c was demonstrated by subjecting them to ADMET polymerization using Grubbs 1st and 2nd generation catalysts. The resultant viscous material was evaluated using 1H NMR and MALDI-ToF-MS, which suggests the formation of anticipated ADMET polymers1 aRajput, Bhausaheb, S.1 aLekshmy, Kalpakasseril, Girija1 aMenon, Shamal, K.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/synthesis-isohexide-diether-enes-and-admet-polymerization02237nas a2200181 4500008004100000245009800041210006900139260000800208300001400216490000700230520157300237100002601810700001501836700002201851700003101873700002401904856012701928 2018 eng d00aCross-metathesis of biorenewable dioxalates and diols to film-forming degradable polyoxalates0 aCrossmetathesis of biorenewable dioxalates and diols to filmform cJUL a1584-15920 v563 aStarting from commonly available sugar derivatives, a single step protocol to access a small family of isohexide-dioxalates (2a-c) has been established. The synthetic competence of 2a-c has been demonstrated by subjecting them to condensation polymerization. Quite surprisingly, the proton NMR of poly(isomannide-co-hexane)oxalate revealed a 1:2 ratio between isomannide-dioxalate (2a) and 1,6-hexanediol (3a) in the polymer backbone. This intriguing reactivity was found to be an outcome of a cross metathesis reaction between 2a and 3a. The cross metathesis products 3a[2-(2-methoxyacetoxy)ethyl 2-(2-hydroxyethoxy)-2-(3-oxydanylidene)acetate] and 2a(3R,6R)-6-hydroxyhexahydrofuro[3,2-b]-furan-3-yl methyl oxalate were isolated in a control experiment. Based on direct and indirect evidence, and control experiments, an alternative polymerization mechanism is proposed. Polymerization conditions were optimized to obtain polyoxalates P1(2a-3a)-P9(2c-3c) with molecular weights in the range of 14,000-68,000 g/mol, and narrow polydispersities. The identity of the polyoxalates was unambiguously established using 1-2D NMR spectroscopy, MALDI-ToF-MS, and GPC measurements. The practical implication of these polymers is demonstrated by preparing transparent, mechanically robust films. The environmental footprint of the selected polyoxalates was investigated by subjecting them to solution and solid-state degradation. The polyoxalates were found to be amenable to degradation. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1584-15921 aRajput, Bhausaheb, S.1 aRam, Farsa1 aMenon, Shamal, K.1 aShanmuganathan, Kadhiravan1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/cross-metathesis-biorenewable-dioxalates-and-diols-film-forming-degradable-polyoxalates02148nas a2200265 4500008004100000022001400041245010600055210006900161260000900230300001100239490000800250520122800258653002901486653003101515653002401546653001701570653001001587100002601597700002201623700002401645700002401669700003301693700002401726856013201750 2020 eng d a0014-305700aRenewing polyethylene: insertion copolymerization of sugar derived hydrophilic monomers with ethylene0 aRenewing polyethylene insertion copolymerization of sugar derive cJUL  a1097750 v1343 a

Although highly desirable, insertion copolymerization of renewable resource derived functional olefins with ethylene has been rarely investigated. Herein, we report insertion copolymerization of challenging sugar derived isohexide mono-enes with ethylene in the presence of Pd-phosphinesulfonate acetonitrile catalyst (C1). Thus, copolymerization of ethylene with isomannide mono-ene (2a), isosorbide mono-ene (2b'), isoidide mono-ene (2c) and methacryl-2,3,4,6-tetra-O-acetyl-D glucopyranoside (2d) afforded corresponding functionalized polyethylene (P2a-1 to P2d-1). High temperature proton NMR investigations revealed enchainment of 2a-2c in polyethylene backbone and the highest incorporation of 1.45% was observed for 2c. The high temperature proton NMR results were further corroborated by solid state C-13 NMR and IR spectroscopy. Gel permeation chromatography analysis displayed weight average molecular weight in the range of 13.0-27.2 x 10(3) g/mol. The thus prepared copolymers revealed melting temperature in the range of 117-126 degrees C. Relatively reduced melting temperature compared to neat polyethylene may suggest an irregular arrangement of pendant functional group on polyethylene main chain.

10aHydrophilic polyethylene10ainsertion copolymerization10aIsohexide mono-enes10aPolyethylene10aSugar1 aRajput, Bhausaheb, S.1 aPawal, Sandip, B.1 aBodkhe, Dnyaneshwar1 aRao, Nagamalleswara1 aSainath, Annadanam, V. Sesha1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/renewing-polyethylene-insertion-copolymerization-sugar-derived-hydrophilic-monomers-ethylene01736nas a2200169 4500008004100000022001400041245008100055210006900136260000800205300001400213490000700227520114900234100002201383700002601405700002401431856011101455 2021 eng d a1463-926200aRefining plant oils and sugars to platform chemicals, monomers, and polymers0 aRefining plant oils and sugars to platform chemicals monomers an cMAY a4255-42950 v233 a

As fossil resources continue to dwindle and environmental concerns are magnified, finding sustainable alternatives is the only way to mitigate resource availability and derisk the planet. The principles of Green Chemistry may provide guidance in this case, and renewable resources can be converted into useful platform chemicals, monomers, and polymers. This critical review examines the possibility of utilizing renewable plant oils and sugars to produce feedstock chemicals, monomers, and polymers. Among the seven isomerizing functionalization reactions of plant oils, isomerizing alkoxycarbonylation displays the highest terminal selectivity. Despite the low reactivity of sugar-derived isohexides, new strategies have been deployed to convert isohexides into difunctional monomers and polymers. The commercialization of isohexides and a few polymers derived from these building blocks has just commenced. Thus, challenges associated with isomerizing functionalization of plant oils and the use of sugar-derived isohexides in chemical syntheses have been summarized, and the potential of these renewable resources has been evaluated.

1 aPandey, Swechchha1 aRajput, Bhausaheb, S.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/refining-plant-oils-and-sugars-platform-chemicals-monomers-and-polymers