Synthesis and structural characterization of block and random low molecular weight copolymers composed of L-lactic acid and isosorbide succinate moieties

Abstract

Resíduos de succinato de isosorbídeo foram incorporados na cadeia principal de poli(L-lactídeo) (PLLA) visando a obtenção de uma nova classe de polímeros biodegradáveis com propriedades melhoradas. Este artigo descreve a síntese e caracterização de quatro tipos de copolímeros de baixa massa molar. O copolímero I foi obtido da mistura dos monômeros L-lactídeo, isosorbídeo e anidrido succínico; II do oligo(L-lactídeo) (PLLA), isosorbídeo e anidrido succínico; III do oligo(succinato de isosorbídeo) (PIS) e L-lactídeo; e IV de reações de transesterificação entre PLLA e PIS. Análises de MALDI-TOFMS e 13 C-NMR apresentaram evidências de que cooligomerização foi alcançada em todos os casos. Os dados sugerem que o produto I é um cooligômero aleatório e que os produtos II-IV são cooligômeros em bloco.Isosorbide succinate moieties were incorporated into poly(L-lactide) (PLLA) backbone in order to obtain a new class of biodegradable polymer with enhanced properties. This paper describes the synthesis and characterization of four types of low molecular weight copolymers. Copolymer I was obtained from monomer mixtures of L-lactide, isosorbide, and succinic anhydride; II from oligo(L-lactide) (PLLA), isosorbide, and succinic anhydride; III from oligo(isosorbide succinate) (PIS) and L-lactide; and IV from transesterification reactions between PLLA and PIS. MALDI-TOFMS and 13 C-NMR analyses gave evidence that co-oligomerization was successfully attained in all cases. The data suggested that the product I is a random co-oligomer and the products II-IV are block co-oligomers.

Applications of MALDI-TOF-MS in structural characterization of synthetic polymers

“…Random copolymers of l -lactic acid and isosorbide succinate moieties, 96 styrene oxide (SO) and allylglycidyl ether (AGE), propylene oxide (PO) or isopropyl glycidyl ether (IPGE) 97 and poly(styrene- co -4-vinylpyridine) 98 were verified by MALDI-TOF-MS. Schubert reported characterization of different poly(2-oxazoline) block copolymers by MALDI-TOF-MS, and revealed the desired polymer structure and possible polymerization mechanisms. 99 The crossover reaction during ROMP block copolymerization of 3-methyl-3-phenylcyclopropene and norbornene derivatives was investigated using MALDI-TOF-MS by Binder et al 100 Samperi et al applied MALDI-TOF-MS to characterize the linear-hyperbranched hybrid poly(butylene adipate) (HPBA) copolymers.…”

“…85 This MS technique was also used for monitoring other homopolymers with different structures, such as poly(dendrimer)s, 86 poly(2-oxazoline), 87 poly(ethylene glycol), and allyl(1-ethoxyethoxy)-PEG-OH, 88 as well as uorotelomer-based acrylate polymers (FTACPs), 89,90 trimethylene carbonate, 91 poly(methyl methacrylate) (PMMA), 92 linear 3-polylysine, 93 poly(butoxycarbonylaminomethyl acrylate) (PtBAMA) homopolymer, 94 poly(1.2-butylene oxide)-diol (PBOdiol) 95 and so on. Random copolymers of L-lactic acid and isosorbide succinate moieties, 96 styrene oxide (SO) and allylglycidyl ether (AGE), propylene oxide (PO) or isopropyl glycidyl ether (IPGE) 97 and poly(styrene-co-4-vinylpyridine) 98 were veried by MALDI-TOF-MS. Schubert reported characterization of different poly(2oxazoline) block copolymers by MALDI-TOF-MS, and revealed the desired polymer structure and possible polymerization mechanisms. 99 The crossover reaction during ROMP block copolymerization of 3-methyl-3-phenylcyclopropene and norbornene derivatives was investigated using MALDI-TOF-MS by Binder et al 100 Samperi et al applied MALDI-TOF-MS to characterize the linear-hyperbranched hybrid poly(butylene adipate) (HPBA) copolymers.…”

Preparation and mechanical properties of a copolycarbonate composed of bio-based isosorbide and bisphenol A

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Isosorbide is obtained by dehydration of D-sorbitol and produced worldwide at a rate of 650 000 tons per annum. 16,17 Isosorbide is thermally stable, available in large quantities and useful for the synthesis of bio-based polymers, such as polyesters, [18][19][20][21][22][23][24][25][26][27][28] polyamides 29 and polyurethanes. [30][31][32][33][34][35][36] A polycarbonate derived from petroleum is a bisphenol A-based polycarbonate (BPAPC).…”

Synthesis and characterization of isosorbide-based α,ω-dihydroxyethersulfone oligomers

“…[1][2][3][4] Many studies reported the synthesis of functional monomers and oligomers based on isosorbide (IS), which belongs to 1,4;3,6-dianhydrohexitols, [5][6][7][8] known as renewable and sustainable OH-functional monomers. [9][10][11][12] The scope of this study is the synthesis of new bio-based dihydroxy functional oligomers of polyethersulfones (PES) based on IS as precursor of biomaterials.…”