Preparation of α,ω‐telechelic hexyl acrylate polymers with ?OH, ?COOH,and ?NH2 functional groups by RAFT

The design, synthesis, and use of two new, stable, functionalized chain transfer agents (CTA's) containing OH and amine end groups for the RAFT polymerization is reported: 2‐hydroxyethoxy‐carbonylphenylmethyl dithiobenzoate and 2‐(2‐(tert‐butoxycarbonyl)ethylamino)‐2‐oxo‐1‐phenylethyl benzodithioate, respectively. The RAFT polymerization of n‐hexyl acrylate (HA) using those CTA's, were compared to several other functionalized dithiobenzoate esters reported in the literature containing COOH and Ester groups. The performances of the dithiobenzoates were compared in terms of kinetics and molecular weight distribution control. Good control in polymerization of n‐hexyl acrylate with a linear increase of M_n with conversion mantaining polydispersity indices (PDI) below 1.1 was obtained by use of the new functionalized CTA's developed and also by use of some other CTA's tested, to produce well‐defined linear polymers with one specific chain‐end functionality: ? OH, ? COOH or Amine. Using a postpolymerization reaction with functionalized azocompounds in a 5 to 1 ratio, α,ω‐telechelic polymers, with ? OH or ? COOH as functional group at the second end were obtained. By using this synthetic strategy α,ω‐homotelechelic and heterotelechelic polymers were readily prepared. The chemical availability of functional end‐groups in the telechelics was demonstrated by reaction with methacrylic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3033–3051, 2010     

Chain Multiplication of Fatty Acids to Precise Telechelic Polyethylene

Starting from common monounsaturated fatty acids, a strategy is revealed that provides ultra‐long aliphatic α,ω‐difunctional building blocks by a sequence of two scalable catalytic steps that virtually double the chain length of the starting materials. The central double bond of the α,ω‐dicarboxylic fatty acid self‐metathesis products is shifted selectively to the statistically much‐disfavored α,β‐position in a catalytic dynamic isomerizing crystallization approach. “Chain doubling” by a subsequent catalytic olefin metathesis step, which overcomes the low reactivity of this substrates by using waste internal olefins as recyclable co‐reagents, yields ultra‐long‐chain α,ω‐difunctional building blocks of a precise chain length, as demonstrated up to a C₄₈ chain. The unique nature of these structures is reflected by unrivaled melting points (T _m=120 °C) of aliphatic polyesters generated from these telechelic monomers, and by their self‐assembly to polyethylene‐like single crystals.     

An efficient synthesis of telechelic poly (N‐isopropylacrylamides) and its application to the preparation of α,ω‐dicholesteryl and α,ω‐dipyrenyl polymers

Poly(N‐isopropylacrylamide)s (PNIPAMs) with cholesteryl or pyrenyl moieties at each chain end (CH‐PNIPAMs or Py‐PNIPAMs) were prepared via end‐group modification of α,ω‐dimercapto poly(N‐isopropylacrylamides), ranging in molecular weight from ～ 7000 to 45,000 g mol^?1 with a polydispersity index of 1.10 or lower. The telechelic thiol functionalized PNIPAMs were obtained by aminolysis of α,ω‐di(isobutylthiocarbonylthio)‐poly(N‐isopropylacrylamide)s (iBu‐PNIPAMs) obtained by reversible addition‐fragmentation chain transfer (RAFT) polymerization of N‐isopropylacrylamide in the presence of the difunctional chain transfer agent, diethylene glycol di(2‐(1‐isobutyl)sulfanylthiocarbonylsulfanyl‐2‐methyl propionate) (DEGDIM). The self‐assembly of the polymers in water was assessed by fluorescence spectroscopy, using the intrinsic emission of Py‐PNIPAM or the emission of pyrene added as a probe in aqueous solutions of CH‐PNIPAM. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 314–326, 2008     

Synthesis,self‐assembly,and thermosensitivity of amphiphilic POEGMA‐PDMS‐POEGMA triblock copolymers

In this article, the synthesis and self‐assembly of a novel well‐defined biocompatible amphiphilic POEGMA‐PDMS‐POEGMA triblock copolymer were studied. The copolymer was synthesized by atom transfer radical polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) using α,ω‐dibromo polydimethylsiloxane macroinitiator (Br‐PDMS‐Br). Br‐PDMS‐Br was synthesized through the esterification of α,ω‐hydroxypropyl polydimethylsiloxane and 2‐bromoisobutyryl bromide. The structures of the copolymers were confirmed by proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The copolymers showed reversible aggregation in response to temperature cycles with a lower critical solution temperature (LCST) between 61 and 66 °C, as determined by ultraviolet‐visible spectrophotometry and dynamic light scattering. The LCST values increased in proportion to the length of the hydrophilic block and were lower than that of the POEGMA homopolymer. The self‐assembly behavior of the copolymers in aqueous solution was investigated by fluorescence spectroscopy and transmission electron microscopy. The critical micelle concentration value (1.08–0.26 10^?6 mol L^?1) decreased as the length of the POEGMA chain increased. The POEGMA‐PDMS‐POEGMA copolymers can easily self‐assemble into spherical micelles in aqueous solution. Such biocompatible block copolymers may be attractive candidates as ‘‘smart'' thermo‐responsive drug delivery systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2684‐2691     

Visible light‐induced thiol‐ene reaction: A new strategy to prepare Α,ω‐dithiol and Α,ω‐divinyl telechelic polythiolether oligomers

A new strategy is developed to prepare both α,ω‐dithiol and α,ω‐divinyl linear telechelic polythiolether oligomers by visible light induced thiol‐ene chemistry in the presence of a fac‐Ir(ppy)₃ photoredox catalyst. Polythiolether oligomers of well‐defined end groups and controlled molecular weights have been successfully synthesized at varying monomer molar ratios of 1,4‐benzenedimethanethiol (BDMT) to diethylene glycol divinyl ether (DEGVE). ¹H NMR and MALDI‐TOF MS analyses demonstrate that as‐prepared polythiolethers possess high end‐group fidelity, which is further supported by the successful polyaddition of polythiolethers bearing α,ω‐dithiol and α,ω‐divinyl groups. For example, with the α,ω‐dithiol‐ (M_n = 1900 g mol^?1, PDI = 1.25) and α,ω‐divinyl‐terminated (M_n = 2000 g mol^?1, PDI = 1.29) polythiolethers as macromonomers, the molecular weight of resulting polythiolether is up to 7700 g mol^?1 with PDI as 1.67. The reactivity of the terminal thiol group is further confirmed by the addition reaction with N‐(1‐pyrenyl)maleimide. UV‐vis spectra and fluorescene measurements suggest that fac‐Ir(ppy)₃ undergo a redox quenching process reacted with BDMT to generate thiyl free radicals. With these results, the mechanism of the thiol‐ene reaction catalyzed by photoredox catalyst is proposed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 740–749     

Synthesis and characterization of hyperbranched polyesters and polyurethane coatings

Polyurethane (PU) coatings are widely used for variety of high‐performance applications in today's coating technology. The emerging hyperbranched polymers having three‐dimensional morphology have opened a new avenue to tailor the architecture of PU coatings. The methodology followed here is based on preparation of PU coatings from hyperbranched polyester. Initially, different hyperbranched polyester polyols (HPs) were synthesized by varying the hydroxyl‐terminated precursors that is, pentaerythritol, trimethylol propane or glycerol and keeping the diacid that is, adipic acid quantity constant at various mole ratios of 1:0.6, 1:0.8, 1:0.9, and 1:1, respectively. The obtained HPs were characterized by nuclear magnetic resonance (NMR) spectroscopy, matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF)‐mass spectrometry, and Fourier transform‐infrared (FTIR) spectroscopy. The degree of branching and the quantity of different structural units present in the various HPs were calculated by integrating the quaternary carbon and carbonyl zone in ¹³C NMR spectroscopy. The extent of condensation in different HPs was also calculated from ¹H NMR spectra. Later on, NCO‐terminated PU prepolymers (NCO‐PU) were synthesized by reacting HPs with isophorone diisocyanate (IPDI) at NCO/OH ratio of 1.6:1. In the third step, the excess NCO content in the NCO‐capped PU prepolymers were reacted with atmospheric moisture and hyperbranched polyurethane (HPU) coatings were formed. The coating films were analyzed by FTIR and dynamic mechanical thermal analysis instruments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2673–2688, 2007     

Degradable multisegmented polymers synthesized by consecutive radical addition‐coupling reaction of α,ω‐macrobiradicals and nitroso compound

A consecutive radical addition‐coupling reaction induced by spin‐trapping agent is applied to produce degradable multisegmented polymer using α,ω‐dibromo polymer as a precursor. The macroradical generated by single electron transfer process catalyzed by Cu/PMDETA from α,ω‐dibromo polymer can be efficiently captured by 2‐methyl‐2‐nitrosopropane (MNP), which results in nitroxide radical. The in situ formed nitroxide radical immediately undergoes cross‐coupling reaction with polymeric radical, generating block polymer bridged with alkoxyamine moiety. The consecutive radical addition‐coupling reaction generates multisegmented polymer via step‐growth mechanism. Different multisegmented polymers have been prepared from α,ω‐dibromo‐PS, PtBA, and PtBA‐PS‐PtBA. The block number of multisegmented polymers can be tailored by varying the feed ratio of α,ω‐dibromo precursor to MNP. The multisegmented polymer can be degraded in the presence of hydrogen atom donor or air, and the molecular weight distribution transformed back into shape of its original precursor as it is conjugated by alkoxyamine moieties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of perfectly bifunctional polyacrylates by single‐electron‐transfer living radical polymerization

Poly(methyl acrylate)s, poly(ethyl acrylate)s, and poly(butyl acrylate)s with α,ω‐di(bromo) chain ends and M_n from 8500 to 35,000 were synthesized by single‐electron‐transfer living radical polymerization (SET‐LRP). The analysis of their chain ends by a combination of ¹H and 2D‐NMR, GPC, MALDI‐TOF MS, chain end functionalization, chain extension, and halogen exchange experiments demonstrated the synthesis of perfectly bifunctional polyacrylates by SET‐LRP. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4684–4695, 2007     

Amino acid‐based bioanalogous polymers. Synthesis,and study of regular poly(ester amide)s based on bis(α‐amino acid) α,ω‐alkylene diesters,and aliphatic dicarboxylic acids

The purpose of this research was to synthesize new regular poly(ester amide)s (PEAs) consisting of nontoxic building blocks like hydrophobic α‐amino acids, α,ω‐diols, and aliphatic dicarboxylic acids, and to examine the effects of the structure of these building block components on some physico‐chemical and biochemical properties of the polymers. PEAs were prepared by solution polycondensation of di‐p‐toluenesulfonic acid salts of bis‐(α‐amino acid) α,ω‐alkylene diesters and di‐p‐nitrophenyl esters of diacids. Optimal conditions of this reaction have been studied. High molecular weight PEAs (M_w = 24,000–167,000) with narrow polydispersity (M_w/M_n = 1.20–1.81) were prepared under the optimal reaction conditions and exhibited excellent film‐forming properties. PEAs obtained are mostly amorphous materials with T_g from 11 to 59°C. α‐Chymotrypsin catalyzed in vitro hydrolysis of these new PEA substrates was studied to assess the effect of the building blocks of these new polymers on their biodegradation properties. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 391–407, 1999     

Precision synthesis of sustainable thermoplastic elastomers from lysine‐derived monomers

Novel renewable thermoplastic elastomers were synthesized by sequential polymerization of lysine‐ and itaconic acid‐derived monomers. Ring‐opening polymerization of lysine‐based O‐carboxyanhydride monomer using diethylene glycol as an initiator gave well‐defined α,ω‐dihydroxy functionalized lysine‐derived polyesters. The M _n of these polyesters increased with the monomer conversion while retaining relatively narrow molecular weight distributions. Based on the successful controlled polymerization and esterification of α,ω‐dihydroxy with 2‐bromoisobutyryl bromide, the resultant Br‐PL‐Br macroinitiator was used for the atom transfer radical polymerization of N‐phenylitaconimide (PhII). Three poly(N‐phenylitaconimide)‐b‐polyester‐b‐poly(N‐phenylitaconimide) triblock copolymers were prepared containing 12 ? 25 mol% PPhII, as determined by ¹H NMR spectroscopy. The properties of the obtained triblock copolymer are evaluated as high‐performance and renewable thermoplastic elastomer materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 349–355     

Synthesis and characterization of polylactide‐block‐polyisoprene‐block‐polylactide triblock copolymers: new thermoplastic elastomers containing biodegradable segments

Anionic polymerization of isoprene initiated by an alkyl lithium containing a silyl ether protected hydroxyl functionality followed by termination with ethylene oxide gave α,ω‐functionalized polyisoprene with narrow molecular weight distribution and prescribed molecular weight in high yield. Deprotection resulted in α,ω‐hydroxyl polyisoprene (HO‐PI‐OH) that was reacted with triethylaluminium to form the corresponding aluminium alkoxide macroinitiator. The macroinitiator was used for the controlled polymerization of lactide to yield polylactide‐block‐polyisoprene‐block‐polylactide triblock copolymers with narrow molecular weight distributions and free of homopolymer (HO‐PI‐OH) contamination. Microphase separation in these novel triblock copolymers was confirmed by SAXS and DSC.     

Straightforward preparation of polymers based on oligodimethylsiloxane and alkylamine

Novel oligodimethylsiloxane‐based polymers with alkyl side chain were synthesized in bulk by step‐growth polymerization between α,ω‐glycidyl ether oligodimethylsiloxanes and a monoalkylamine in the absence of catalyst and at temperatures ranging between 80 and 180 °C. Matrix assisted laser desorption ionization time of flight results attested for the high reactivity of the amine functions with the glycidyl groups and revealed that the main polymer structure was (A₂B₂)_n type with alkyl moieties as dangling chains. No etherification was observed during the reaction even at high temperatures and the nature of the end groups strongly depended on the molar ratio between glycidyl and amine functions. Polymerization reactions were followed by ¹H NMR and the kinetics of the glycidyl‐amine reaction pointed out the dependence of temperature, molar ratio, and the molar mass of the oligodimethylsiloxane. High conversion rates were obtained, especially with the lowest molecular weight oligodimethylsiloxane. An optimized kinetic model derived from the Horie's model was discussed and permitted to correctly fit the experimental data. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003     

Synthesis and thermal crosslinking of benzophenone‐modified poly(dimethylsiloxane)s

Dihydridocarbonyltris(triphenylphosphine)ruthenium catalyzes the regiospecific anti‐Markovnikov addition of an ortho C? H bond of benzophenone across the C? C double bonds of α,ω‐bis(trimethylsilyloxy)copoly(dimethylsiloxane/vinylmethylsiloxane) (99:1), α,ω‐bis(vinyldimethylsilyloxy)poly(dimethylsiloxane), and 1,3‐divinyltetramethyldisiloxane to yield α,ω‐bis(trimethylsilyloxy)copoly[dimethylsiloxane/2‐(2′‐benzophenonyl)ethylmethylsiloxane]), α,ω‐bis[2‐(2′‐benzophenonyl)ethyldimethylsilyloxy]poly(dimethylsiloxane), and 1,3‐bis[2‐(2′‐benzophenonyl)ethyl]tetramethyldisiloxane, respectively. These materials have been characterized with ¹H, ¹³C, and ²⁹Si NMR and IR spectroscopy. Their molecular weight distributions have been determined by gel permeation chromatography. The thermal stability of the polymers has been measured by thermogravimetric analysis, and their glass‐transition temperatures (T_g's) have been determined by differential scanning calorimetry. The molecular weight distribution, thermal stability, and T_g's of the modified polysiloxanes are similar to those of the precursor polymers. The molecular weights of these materials can be significantly increased via heating to 300 °C for 1 h. This may be due to crosslinking, by pyrocondensation, of pendant anthracene groups, which are produced by the pyrolysis of the attached ortho‐alkyl benzophenones. UV spectroscopy of the pyrolysate of 1,3‐bis[2‐(2′‐benzophenonyl)ethyl]tetramethyldisiloxane has confirmed the presence of pendant anthracene groups. Thermal crosslinking by the pyrocondensation of pendant anthracene groups has been verified by the pyrolysis of α,ω‐bis(trimethylsilyloxy)copoly[dimethylsiloxane/2‐(9′‐anthracenyl)ethylmethylsiloxane] (97:3). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5514–5522, 2004     

Synthesis of high glass transition temperature copolymers based on poly(vinyl chloride) via single electron transfer—Degenerative chain transfer mediated living radical polymerization (SET‐DTLRP) of vinyl chloride in water

α,ω‐di(iodo) poly(isobornyl acrylate) macroiniators (α,ω‐di(iodo)PIA) with number average molecular weight from M _n,TriSEC = 11,456 to M _n,TriSEC = 94,361 were synthesized by single electron transfer‐degenerative chain transfer mediated living radical polymerization (SET‐DTLRP) of isobornyl acrylate (IA) initiated with iodoform (CHI₃) and catalyzed by sodium dithionite (Na₂S₂O₄) in water at 35 °C. The plots of number average molecular weight vs conversion and ln{[M]₀/[M]} vs time are linear, indicating a controlled polymerization. α,ω‐di(iodo) poly(isobornyl acrylate) have been used as a macroinitiator for the SET‐DTLRP of vinyl chloride (VCM) leading to high T_g block copolymers PVC‐b‐PIA‐b‐PVC. The dynamic mechanical thermal analysis of the block copolymers suggests just one phase indicating that copolymer behaves as a single material. This technology provides the possibility of synthesizing materials based on PVC with higher T_g in aqueous medium. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Polysiloxanes with chlorobenzyl groups as precursors of new organic‐silicone materials

Various polysiloxanes bearing chlorobenzyl side groups were synthesized by the hydrolytic polycondensation of the 73:27 mol/mol mixture of [2‐(4‐chloromethylphenyl)ethyl] methyldichlorosilane and [1‐(4‐chloromethylphenyl)ethyl] methyldichlorosilane followed by the cationic equilibration or coequilibration with octamethylcyclotetrasiloxane, D₄. 1,3‐Divinyltetramethyl‐disiloxane was used as the chain end blocker to obtain a vinyl–Si ended chlorobenzyl‐substituted polysiloxane. In some cases, the polymer was additionally treated with dimethylvinylchlorosilane to achieve full substitution of chain ends by the vinyl group. Cohydrolysis of the chlorobenzylic monomer mixture with dimethyldichlorosilane was also practiced. Multiblock copolymers were obtained by polyhydrosilylation of the α,ω‐divinylsilyl chlorobenzyl‐substituted polysiloxanes with α,ω‐dihydrosilyl polydimethylsiloxanes. All these polymers and copolymers containing reactive chlorobenzylic groups were demonstrated to be convenient precursors of functional polysiloxanes of potential practical use. Some specific functional groups, such as quaternary ammonium salt groups of biocidal activity or azobenzene groups making the polymer sensitive to external stimuli by light, may be readily generated on polysiloxane under mild conditions. The chlorobenzylic substituted polysiloxanes may be also used as macroinitiators of the atom transfer radical polymerization, to obtain polysiloxanes with grafted organic polymers, such as styrene, 4‐chloromethylstyrene, and n‐butylacrylate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1682–1692, 2004     

Ultrafast single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of acrylates initiated with iodoform in water at room temperature and catalyzed by sodium dithionite

Sodium dithionite in the presence of NaHCO₃ in water acts as a single‐electron‐transfer agent and facilitates the single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization (SET–DTLRP) of acrylates initiated with iodoform at room temperature. The resulting α,ω‐di(iodo)polyacrylates can be used as macroinitiators for the SET–DTLRP of other acrylates. Ultrahigh‐molar‐mass poly(tert‐butyl acrylate) can be synthesized via the SET–DTLRP of tert‐butyl acrylate and has a very low weight‐average molecular weight/number‐average molecular weight ratio of 1.15. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2178–2184, 2005     

Cyclopolymerization of α,ω‐heterodifunctional monomers containing styrene and maleimide moieties

A series of α,ω‐heterodifunctional monomers with styrene (St) and maleimide moieties bridged by a varied length of oligo‐ethylene glycol (OEG) linkers were synthesized. Cyclopolymerizations of these monomers through reversible addition–fragmentation chain transfer‐mediated alternating radical copolymerization between intramolecular St and maleimide moieties were investigated. For the monomers with three or more ethylene glycol (EG) units, their cyclopolymerizations can be realized properly in low monomer feeding concentrations, affording well‐defined cyclopolymers with crown ether encircled in their main chains. Importantly, the cyclopolymerizations of monomers with six or seven EG units in the presence of KPF₆ could be enhanced by the supramolecular effects between the OEG linkers and the potassium metal ion. Thus, the monomer feeding concentration could be largely improved, which may benefit preparation of the cyclopolymers with high degrees of copolymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 330–338     

Identification of very long chain fatty acids by atmospheric pressure chemical ionization liquid chromatography‐mass spectroscopy from green alga Chlorella kessleri

A method is described for the enrichment of very long chain fatty acids (VLCFAs) from total fatty acids of heterotrophically cultivated green freshwater alga Chlorella kessleri and their identification as picolinyl esters by means of liquid chromatography‐mass spectrometry with atmospheric pressure chemical ionization (LC‐MS with APCI). The method is based on the use of preparative reversed phase HPLC of hundred‐milligram amounts and their subsequent identification by microbore APCI LC‐MS. A combination of these two techniques was used to identify unusual VLCFAs up to C₄₇, both saturated and monounsaturated, with two positional isomers (ω‐9 and ω‐26).     

Biodegradable polymers based on renewable resources. VII. Novel random and alternating copolycarbonates from 1,4:3,6‐dianhydrohexitols and aliphatic diols

Novel copolycarbonates containing 1,4:3,6‐dianhydro‐D ‐glucitol or 1,4:3,6‐dianhydro‐D ‐mannitol units, with various methylene chain lengths, were synthesized by bulk and solution polycondensations, of several combinations of carbonate‐modified sugar derivatives and aliphatic diols. Bulk polycondensations of 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(phenoxycarbonyl)‐D ‐glucitol or 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(phenoxycarbonyl)‐D ‐mannitol with four α,ω‐alkanediols having methylene chain lengths of 4, 6, 8, and 10, respectively, at 180 °C afforded the corresponding copolycarbonates with number‐average molecular weight (M_n) values up to 19.₂ × 10³. ¹³C NMR analysis disclosed that these polymers had scrambled structures in which the sugar carbonate and aliphatic carbonate moieties were nearly randomly distributed along a polymer chain. However, solution polycondensations between 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(p‐nitrophenoxycarbonyl)‐D ‐glucitol or 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(p‐nitrophenoxycarbonyl)‐D ‐mannitol, and the α,ω‐alkanediols in sulfolane or dimethyl sulfoxide at 60 °C gave well‐defined copolycarbonates having regular structures consisting of alternating sugar carbonate and aliphatic carbonate moieties with M_n values up to 33.₈ × 10³. Differential scanning calorimetry demonstrated that all the copolycarbonates were amorphous with glass‐transition temperatures ranging from 1 to 65 °C, which decreased with increasing lengths of the methylene chain of the aliphatic diols. Additionally, all the copolycarbonates were stable up to 310–330 °C as estimated by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2312–2321, 2003