Peptide block copolymers by N‐carboxyanhydride ring‐opening polymerization and atom transfer radical polymerization: The effect of amide macroinitiators

The synthesis of polypeptide‐containing block copolymers combining N‐carboxyanhydride (NCA) ring‐opening polymerization and atom transfer radical polymerization (ATRP) was investigated. An amide initiator comprising an amine function for the NCA polymerization and an activated bromide for ATRP was used. Well‐defined polypeptide macroinitiators were obtained from γ‐benzyl‐L ‐glutamate NCA, O‐benzyl‐serine NCA, and N‐benzyloxy‐L ‐lysine. Subsequent ATRP macroinitiation from the polypeptides resulted in higher than expected molecular weights. Analysis of the reaction products and model reactions confirmed that this is due to the high frequency of termination reactions by disproportionation in the initial phase of the ATRP, which is inherent in the amide initiator structure. In some cases selective precipitation could be applied to remove unreacted macroinitiator to yield well‐defined block copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Terpolymerization kinetics of amino acid N‐carboxy anhydrides

Based on their versatility with respect to amino acid type and sequence, polypeptides have become attractive for a number of biological applications such as drug delivery, biomineralization, and drugs. N‐carboxy anhydride (NCA) polymerization is a convenient way to rapidly prepare high‐molecular weight polypeptides with good control over molecular weight and polydispersity. However, the kinetics of the incorporation of NCA monomers into copolypeptides during random copolymerization are poorly understood. Here, kinetic data is presented that allows insight into the NCA polymerization of a terpolymer composed of three commercially relevant amino acids, namely, glutamic acid, lysine, and tyrosine. Furthermore, kinetic data and copolymerization parameters from the copolymerization of binary mixtures of these three amino acid NCAs is used to make predictions of the terpolymer composition. This study provides access to the information necessary to prepare functional copolypeptides with better‐defined sequence architecture that will be essential for the future development of polypeptide‐based materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1228–1236     

Rethinking Cysteine Protective Groups: S‐Alkylsulfonyl‐l‐Cysteines for Chemoselective Disulfide Formation

The ability to reversibly cross‐link proteins and peptides grants the amino acid cysteine its unique role in nature as well as in peptide chemistry. We report a novel class of S‐alkylsulfonyl‐l ‐cysteines and N‐carboxy anhydrides (NCA) thereof for peptide synthesis. The S‐alkylsulfonyl group is stable against amines and thus enables its use under Fmoc chemistry conditions and the controlled polymerization of the corresponding NCAs yielding well‐defined homo‐ as well as block co‐polymers. Yet, thiols react immediately with the S‐alkylsulfonyl group forming asymmetric disulfides. Therefore, we introduce the first reactive cysteine derivative for efficient and chemoselective disulfide formation in synthetic polypeptides, thus bypassing additional protective group cleavage steps.     

Controlled metal‐free polymerization toward well‐defined thermoresponsive polypeptides by polymerization at low temperature

A controlled metal‐free synthetic methodology toward well‐defined thermoresponsive polypeptides by decreasing the reaction temperature to 0 °C has been developed. Good control over the molecular weight in the polymerization of a trithiocarbonate‐functionalized N‐carboxyanhydride (MES‐l ‐Glu‐NCA) monomer was obtained using n‐hexylamine as the initiator at 0 °C. It yielded homopolypeptide macro‐transfer agent (PMESLG) with narrow molecular weight distribution (PDI < 1.3) and controllable chain length. Detailed ¹H NMR and MALDI‐TOF‐MS analysis clearly confirmed that frequently occurring side‐reactions was absent at 0 °C, and the polymerization was controlled. The resultant PMESLG was applied to mediate the reversible addition‐fragmentation chain transfer (RAFT) polymerization of oligo‐ethylene‐glycol acrylate (OEGA) for the metal‐free synthesis of thermoresponsive polypeptides. These thermoresponsive polypeptides have well‐controlled molecular weight, adopted regular α‐helical conformation, and exhibited a lower critical solution temperature between 23 °C and 55 °C. To the best of our knowledge, there are very few reports about the synthesis of well‐defined thermoresponsive graft polypeptides via NCA polymerization and RAFT. Consequently, this provides a new strategy for the synthesis of promising intelligent material for future biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2618–2624     

Synthesis and ring‐opening (co)polymerization of L‐lysine N‐carboxyanhydrides containing labile side‐chain protective groups

This contribution describes the synthesis and ring‐opening (co)polymerization of several L ‐lysine N‐carboxyanhydrides (NCAs) that contain labile protective groups at the ?‐NH₂ position. Four of the following L ‐lysine NCAs were investigated: N^?‐trifluoroacetyl‐L ‐lysine N‐carboxyanhydride, N^?‐(tert‐butoxycarbonyl)‐L ‐lysine N‐carboxyanhydride, N^?‐(9‐fluorenylmethoxycarbonyl)‐L ‐lysine N‐carboxyanhydride, and N^?‐(6‐nitroveratryloxycarbonyl)‐L ‐lysine N‐carboxyanhydride. In contrast to the harsh conditions that are required for acidolysis of benzyl carbamate moieties, which are usually used to protect the ?‐NH₂ position of L ‐lysine during NCA polymerization, the protective groups of the L ‐lysine NCAs presented here can be removed under mildly acidic or basic conditions or by photolysis. As a consequence, these monomers may allow access to novel peptide hybrid materials that cannot be prepared from ?‐benzyloxycarbonyl‐L ‐lysine N‐carboxyanhydride (Z‐Lys NCA) because of side reactions that accompany the removal of the Z groups. By copolymerization of these L ‐lysine NCAs with labile protective groups, either with each other or with γ‐benzyl‐L ‐glutamate N‐carboxyanhydride or Z‐Lys NCA, orthogonally side‐chain‐protected copolypeptides with number‐average degrees of polymerization ≤20 were obtained. Such copolypeptides, which contain different side‐chain protective groups that can be removed independently, are interesting for the synthesis of complex polypeptide architectures or can be used as scaffolds for the preparation of synthetic antigens or protein mimetics. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1167–1187, 2003     

Polymerization of N-carboxy–amino acid anhydrides in the solid state. II. Relation between polymerizability and molecular arrangement in L-leucine NCA and L-alanine NCA crystals

The polymerizability of N-carboxy–amino acid anhydrides (NCAs) of L -leucine and L -alanine was examined in the solid state and in solution. L -leucine NCA shows much higher reactivity in the solid state (when immersed in hexane) than in solution (in acetonitrile), but the opposite is true for L -alanine NCA. However, the two NCAs give similar values of apparent activation energy in each polymerization system. Rather high-molecular-weight polypeptides were obtained in the polymerization of L -leucine NCA in the solid state compared with those obtained in solution, while the molecular weight of polymers obtained from L -alanine NCA was higher in solution than in the solid state. IR spectra showed that α helices form mainly in the polymerization of both L -leucine NCA and L -alanine NCA in the solid state; a small amount of the β structure forms in the latter polymerization. X-ray diffraction and electron microscopy revealed that L -leucine NCA polymerizes predominantly along the c axis in the crystal, while the polymer chains grow in random directions in the crystal of L -alanine NCA. The difference can be explained by the molecular arrangement in the crystal. There are two requirements for high reactivity in the solid state: the five-membered rings of the monomer must form a layer structure and the polymer must occupy nearly the same space as the reacting monomer.     

Tuning the conformation of synthetic co‐polypeptides of serine and glutamic acid through control over polymer composition

Ring opening polymerization (ROP) of N‐carboxy anhydride (NCA) amino acids presents a rapid way to synthesize high molecular weight polypeptides with different amino acid compositions. The compositional and functional versatility of polypeptides make these materials an attractive choice for biomaterials. The functional performance of polypeptide materials is equally linked to their conformation which is determined by the amino acid sequence in the polymer chains. Here, the interplay between composition and conformation of synthetic polypeptides obtained by NCA polymerization was explored. Various copolypeptides from Glu(Bzl) and Ser(Bzl) were prepared to investigate how polypeptide composition affected the conformation of the resulting copolymer. Polymerization kinetics indicated that the copolymerization of Glu(Bzl) and Ser(Bzl) preferentially yielded alternating copolymers. Both the polydispersity and the conformation of the polypeptides were dependent on the Ser(Bzl) content in the polymer, demonstrating that polypeptide functionalities could be tuned directly by altering the relative amounts of amino acids in the chain. This work presents the first step toward an improved understanding and control over polypeptide conformation through modulating the amino acid composition of the material. Understanding this sequence–functionality relationship is essential to advancing the use of ROP as a technique to design smart polypeptide based materials with specific functions. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2331–2336     

Are N‐substituted glycine N‐thiocarboxyanhydride monomers really hard to polymerize?

N‐Substituted glycine N‐thiocarboxyanhydrides (NNTAs) are promising cyclic monomers to synthesize polypeptoids with the advantages of easier preparation and higher stability during purification and storage than N‐substituted glycine N‐carboxyanhydrides (NNCAs). NNTAs were commonly considered too stable to polymerize for their low reactivity. In this contribution, we report controlled polymerizations of N‐ethylglycine NTA (NEG‐NTA) and sarcosine NTA (Sar‐NTA) using primary amines as initiator under proper polymerization conditions. The controllability has been fully supported by ¹H NMR end group analyses, MALDI‐ToF mass spectra, kinetic data, block copolymerizations by sequential monomer addition, and low polydispersities (1.14–1.17) of polypeptoids. Variation of the [NNTA]/[initiator] ratio allows well control of the molar mass, and degrees of polymerization (DPs) up to 287 can be reached for poly(N‐ethylglycine) or DPs up to 262 for polysarcosine. NNTAs exhibit excellent activity and they are potential to synthesize polypeptoids with controllable polymerization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 404–410     

Synthesis,characterization, and stability of carbodiimide groups in carbodiimide‐functionalized latex dispersions and films

Cyclohexylcarbodiimidoethyl methacrylate (CCEMA) and t‐butylcarbodiimidoethyl methacrylate (t‐BCEMA) were prepared in a two‐step synthesis. These monomers were then used to prepare carbodiimide‐functionalized PBMA and PEHMA latex particles, employing two‐stage emulsion polymerization, with the carbodiimide–methacrylate monomers being introduced only in the second stage under monomer‐starved conditions. During emulsion polymerization, the carbodiimide moiety ( NCN ) was found to be unstable at pH 4, but stable when the pH of the dispersion was increased to 8, using NaHCO₃ as the buffer. Survival of  NCN group against hydrolysis during the polymerization, and during storage in the dispersion, was enhanced by using EHMA as the comonomer (more hydrophobic) and the t‐butyl carbodiimide derivative. The t‐butyl group provides more steric hindrance to the hydrolysis reaction. A decrease in the reaction temperature from 80°C to 60°C was also found to increase the extent of  NCN group incorporation during emulsion polymerization. Under ideal conditions, more than 98% of the  NCN groups in the monomer feed are successfully incorporated into the latex. When these latex particles are mixed with a  COOH containing latex and allowed to dry, polymer diffusion leading to crosslinking occurs. Films annealed at 60°C reach a gel content of 60% in 10 h. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 855–869, 2000     

Polymerization in the crystalline state. VIII. Polymerization in N-carboxy anhydrides of γ-benzyl glutamate, γ-methyl glutamate,and ϵ-carbobenzoxylysine

The kinetics of the solid-state polymerization of the N-carboxy anhydrides (NCA) of the L - and racemic forms of γ-benzyl glutamate (BG), γ-methyl glutamate (MG), and ?-carbobenzoxylysine (CL) were studied as a function of temperature and aqueous vapor pressure. The reaction of the L -forms of BG and MG was characterized by an induction period, while the CL derivative reached its maximum polymerization rate at the outset of the reaction. Water vapor had only a minor effect in accelerating the reaction and reducing the chain length of the polypeptides formed. The racemic monomers were found to have different crystal structures from those of the L -isomers and the racemic MG and CL derivatives polymerized much more slowly than the corresponding optically active crystals. All polymers gave diffuse x-ray diffraction patterns. Infrared spectra of the L -polypeptides showed that they were largely in the α-helical form. The polymer derived from the racemic BG–NCA had a content of α-helical material which suggested that it consisted of polypeptides with long blocks of D and L residues.     

Ring opening polymerization of α‐amino acid N‐carboxyanhydrides catalyzed by rare earth catalysts: Polymerization characteristics and mechanism

Five rare earth complexes are first introduced to catalyze ring opening polymerizations (ROPs) of γ‐benzyl‐L ‐glutamate N‐carboxyanhydride (BLG NCA) and L ‐alanine NCA (ALA NCA) including rare earth isopropoxide (RE(OiPr)₃), rare earth tris(2,6‐di‐tert‐butyl‐4‐methylphenolate) (RE(OAr)₃), rare earth tris(borohydride) (RE(BH₄)₃(THF)₃), rare earth tris[bis(trimethylsilyl)amide] (RE(NTMS)₃), and rare earth trifluoromethanesulfonate. The first four catalysts exhibit high activities in ROPs producing polypeptides with quantitative yields (>90%) and moderate molecular weight (MW) distributions ranging from 1.2 to 1.6. In RE(BH₄)₃(THF)₃ and RE(NTMS)₃ catalytic systems, MWs of the produced polypeptides can be controlled by feeding ratios of monomer to catalyst, which is in contrast to the systems of RE(OiPr)₃ and RE(OAr)₃ with little controllability over the MWs. End groups of the polypeptides are analyzed by MALDI‐TOF MS and polymerization mechanisms are proposed accordingly. With ligands of significant steric hindrance in RE(OiPr)₃ and RE(OAr)₃, deprotonation of 3‐NH of NCA is the only initiation mode producing a N‐rare earth metallated NCA ( i ) responsible for further chain growth, resulting in α‐carboxylic‐ω‐aminotelechelic polypeptides after termination. In the case of RE(BH₄)₃(THF)₃ with small ligands, another initiation mode at 5‐CO position of NCA takes place simultaneously, resulting in α‐hydroxyl‐ω‐aminotelechelic polypeptides. In RE(NTMS)₃ system, the protonated ligand hexamethyldisilazane (HMDS) initiates the polymerization and produces α‐amide‐ω‐aminotelechelic polypeptides. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hydroxyl‐tolerated polymerization of N‐phenoxycarbonyl α‐amino acids: A simple way to polypeptides bearing hydroxyl groups

Differing from the moisture‐sensitive α‐amino acid N‐carboxyanhydrides (AA‐NCAs) monomers, N‐phenoxycarbonyl α‐amino acids (AA‐NPCs) can be prepared and stored in open air. In this contribution, we report that the controlled polymerizations of AA‐NPC monomers of O‐tert‐butyl‐dl ‐serine (BRS‐NPC), N^ε‐benzyloxycarbonyl‐l ‐lysine (ZLL‐NPC) and N^ε‐trifluoroacetyl‐l ‐lysine (FLL‐NPC) initiated by amines are surprisingly able to tolerate common nucleophilic impurities such as water and alcohols at a level of monomer concentration. The structures of polypeptides synthesized in the presence of water or alcohols agree well with the designed ones in the case of repeated chain extensions. Detailed mechanism study and density functional theory calculation reveal that the low concentration of AA‐NCA and the high activity of amines are the key factors to the controllability of AA‐NPC polymerizations. The water‐ and alcohol‐tolerant property in polymerizations of AA‐NPCs encourages the following studies on unprotected (phenolic) hydroxyl groups containing AA‐NPCs. The controllable polymerizations of N‐phenoxycarbonyl l ‐tyrosine (LT‐NPC) and N‐phenoxycarbonyl S‐(3‐hydroxypropyl)‐l ‐cysteine (HLC‐NPC) initiated by amines are confirmed and reported for the first time, which extends the library of AA‐NPCs and polypeptides as well. All the universality of library, the convenience of monomer preparation, and the controllability and water‐ and alcohol‐tolerant property of polymerization of AA‐NPCs significantly enhance the feasibility of polypeptide synthesis, making AA‐NPC approach a promising synthetic method of polypeptides. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 907–916     

Synthesis of charged hybrid particles via dispersion polymerization in nonpolar media for color electrophoretic display application

Direct synthesis of charged hybrid particles in non‐polar media has not been widely described in the literature but can lead to many applications such as electrophoretic displays. In this work, we propose a way to synthesize charged hybrid particles within the electrophoretic medium (Toluene or Isopar G) in the presence or not of additives (Charge Control Agent, CCA). The particles synthesis was performed by Nitroxide‐mediated Radical Polymerization (NMRP) via dispersion polymerization in aliphatic hydrocarbon solvents leading to stable chargeable particles with a good size control. Hybrid particles are successfully charged by reaction with functional monomers or addition of CCA to obtain electrophoretic particles. The performance of a dual‐color red/white ink in a display was demonstrated with a test‐cell. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 338–348     

Living polymerization of α‐amino acid‐N‐carboxyanhydrides

This article reviews recent developments in the polymerization of α‐amino acid‐ N‐carboxyanhydrides (NCAs) to form polypeptides. Traditional methods used to polymerize these monomers are described, and limitations in the utility of these systems for the preparation of polypeptides with controlled molecular weights and narrow molecular weight distributions are discussed. The development of transition‐metal‐based initiators, which activate the monomers to form covalent active species, permits the formation of polypeptides via the living polymerization of NCAs. In these systems, polymer molecular weights are controlled by monomer‐to‐initiator stoichiometry, polydispersities are low, and block copolypeptides can be prepared. The scope and limitations of these initiators and their key features and mode of operation are described in detail in this highlight. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3011–3018, 2000     

Synthesis of phosphorescent iridium-containing acrylic monomers and their room-temperature polymerization by Cu(0)-RDRP

A series of acrylic monomers based on cyclometalated iridium(III) complexes have been synthesized based on common phosphorescent emitters for organic light-emitting diodes. A simple room-temperature polymerization procedure for these materials was developed using Cu(0) reversible deactivation radical polymerization, providing polymers with low dispersities of 1.08–1.14 at conversions from 81 to 93% when the Ir complexes are copolymerized with a carbazole-based acrylic host. These methods were also found to be suitable for the preparation of high-molecular-weight polymers with M _n approaching 40,000 Da, as well as block copolymers formed in one pot from the chain extension of methyl acrylate. This scalable room-temperature synthesis of iridium-containing copolymers and block copolymers provides a useful route to optoelectronic materials, which we anticipate can be readily adapted to a broad range of acrylic metallopolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2539–2546     

Influence of monomer type on miniemulsion polymerization systems stabilized by graphene oxide as sole surfactant

Based on a recent report [J. Polym. Sci. Part A. Polym. Chem. 2013 , 51, 47–58] whereby we demonstrated the synthesis of polystyrene nanoparticles by miniemulsion polymerization stabilized by graphene oxide (GO) nanosheets as sole surfactant, we hereby report the synthesis of hybrid polymer nanoparticles of several members of the (meth)acrylate family as well as the cross‐linker divinylbenzene via the same approach. The nature of the resultant emulsion is strongly linked to the polarity of the monomer used; monomers with a relatively small polar component (based on Hansen solubility parameters) such as lauryl methacrylate and benzyl methacrylate, in addition to styrene, generate stable emulsions that can be effectively polymerized. Particularly polar monomers (e.g., methyl acrylate and methyl methacrylate) formed kinetically stable emulsions in the presence of GO, however rapid coagulation occurred during polymerization. Electron microscopy analysis reveals the formation of polymer nanoparticles with size distribution between 200 and 1000 nm with roughened surface morphologies, indicative of GO sheets adsorbed at the interface. The results of this work demonstrate the applicability of this synthetic route for specific monomers in the preparation of novel graphene‐based polymeric materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5153–5162     

Glycopolypeptides via living polymerization of glycosylated-L-lysine N-carboxyanhydrides

The preparation of new glycosylated-L-lysine-N-carboxyanhydride (glyco-K NCA) monomers is described. These monomers employ C-linked sugars and amide linkages to lysine for improved stability without sacrificing biochemical properties. Three glyco-K NCAs were synthesized, purified, and found to undergo living polymerization using transition metal initiation. These are the first living polymerizations of glycosylated NCAs and were used to prepare well-defined, high molecular weight glycopolypeptides and block and statistical glycocopolypeptides. This methodology solves many long-standing problems in the direct synthesis of glycopolypeptides from N-carboxyanhydrides relating to monomer synthesis, purification, and polymerization and gives polypeptides with 100% glycosylation. These long chain glycopolypeptides have potential to be good mimics of natural high molecular weight glycoproteins.     

Phosgene‐free synthesis of polypeptides: Useful synthesis for hydrophobic polypeptides through polycondensation of activated urethane derivatives of α‐amino acids

We report a useful synthetic method of polypeptides using a series of urethane derivative of α‐amino acids (l ‐leucine, l ‐phenylalanine, l ‐valine, l ‐alanine, l ‐isoleucine, l ‐methionine), which are readily synthesized by N‐carbamoylation of tetrabutylammonium salts of α‐amino acids with diphenyl carbonate. Heating these urethane derivatives in N,N‐dimethylacetamide in the presence of n‐butylamine successfully gave the corresponding polypeptides with well‐defined structures through polycondensation with the elimination of phenol and CO₂. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry investigation showed that the resulting polypeptides had an n‐BuNH₂‐incorporated initiating end and an amino group at propagating end. These results strongly indicated that primary amines served as an initiator in this polycondensation system. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3726–3731     

One‐stage synthesis of narrowly dispersed polymeric core‐shell microspheres

A method of one‐stage soap‐free emulsion polymerization to synthesize narrowly dispersed core‐shell microspheres is proposed. Following this method, core‐shell microspheres of poly(styrene‐co‐4‐vinylpyridine), poly(styrene‐co‐methyl acrylic acid), and poly[styrene‐co‐2‐(acetoacetoxy)ethyl methacrylate‐co‐methyl acrylic acid] are synthesized by one‐stage soap‐free emulsion polymerization of a mixture of one or two hydrophobic monomers and a suitable hydrophilic monomer in water. The effect of the molar ratio of the hydrophobic monomer to the hydrophilic one on the size, the core thickness, and the shell thickness of the core‐shell microspheres is discussed. The molar ratio of the hydrophobic and hydrophilic monomers and the hydrophilicity of the resultant oligomers of the hydrophilic monomer are optimized to synthesize narrowly dispersed core‐shell microspheres. A possible mechanism of one‐stage soap‐free emulsion polymerization to synthesize core‐shell microspheres is suggested and coagglutination of the oligomers of the hydrophilic monomers on the hydrophobic core is considered to be the key to form core‐shell microspheres. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1192–1202, 2008     

Synthesis and physical properties of poly(urethane)s using vicinal diols derived from acrylate and styrene monomers

We describe the utilization of four kinds of diol derivatives, representing structural similarity to the well‐known and commercially available vinyl monomers such as acrylate, acrylamide, styrene, and N‐substituted maleimide. The vinyl monomers are readily converted by dihydroxylation reaction to afford the vicinal diol. The synthesis of poly(urethane)s was performed by the reaction of the vicinal diol with two model diisocyanates, including methylene diphenyl isocyanate (MDI) and hexamethylene diisocyanate (HDI) in the presence of dibutyltin dilaurate to form a series of poly(urethane)s, and the effect of vicinal diol containing a side chain inherited from vinyl monomers on their thermal and mechanical properties was investigated using thermogravimetric analysis, differential scanning calorimetry, and tensile test. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 799–805