Nickel and cobalt complexes bearing β‐ketoamine ligands: syntheses,structures and catalytic behavior for norbornene polymerization

Late transition metal (nickel, cobalt) complexes (1, 2) with β‐ketoamine ligand (L) based on the pyrazolone derivative are synthesized by condensing 1‐phenyl‐3‐methyl‐4‐benzoyl‐5‐pyrazolone with p‐fluoroaniline, and then treating the β‐ketoamine (L) produced with the respective metal halide. The bis(β‐ketoamine)metal complexes can act as catalyst precursors for norbornene polymerization with activation by methylaluminoxane. The effects of the central metal variation in the complex on catalyst activities and polymer microstructure are described. Copyright © 2005 John Wiley & Sons, Ltd.     

Vinyl polymerization of norbornene by nickel(II) complexes bearing β‐diketiminate ligands

Norbornene polymerizations were carried out using nickel(II) bromide complexes CH{C(R)NAr}₂NiBr ( 1 , R = CH₃, Ar = 2, 6 ? ⁱPr₂C₆H₃; 2 , R = CH₃, Ar = 2, 6‐Me₂C₆H₃; 3 , R = CF₃, Ar = 2, 6 ? ⁱPr₂C₆H₃; 4 , R = CF₃, Ar = 2, 6‐Me₂C₆H₃) in the presence of methylaluminoxane. Compound 3 is the most active norbornene polymerization catalyst of all the nickel complexes tested. The activity of theses catalysts increases with increases in steric bulk of the substituents on the aryl rings. The electronic nature of the ligand backbone also affects the activity. The resulting polynorbornenes are vinyl type by IR and NMR analyses. Copyright © 2007 John Wiley & Sons, Ltd.     

Homo‐ and copolymerization of ethylene and norbornene with bis(β‐diketiminato) titanium complexes activated with methylaluminoxane

Homo‐ and copolymerization of ethylene and norbornene were investigated with bis(β‐diketiminato) titanium complexes [ArNC(CR₃)CHC(CR₃)NAr]₂TiCl₂ (R = F, Ar = 2,6‐diisopropylphenyl 2a; R = F, Ar = 2,6‐dimethylphenyl 2b ; R = H, Ar = 2,6‐diisopropylphenyl 2c ; R = H, Ar = 2,6‐dimethylphenyl 2d) in the presence of methylaluminoxane (MAO). The influence of steric and electric effects of complexes on catalytic activity was evaluated. With MAO as cocatalyst, complexes 2a–d are moderately active catalysts for ethylene polymerization producing high‐molecular weight polyethylenes bearing linear structures, but low active catalysts for norbornene polymerization. Moreover, 2a – d are also active ethylene–norbornene (E–N) copolymerization catalysts. The incorporation of norbornene in the E–N copolymer could be controlled by varying the charged norbornene. ¹³C NMR analyses showed the microstructures of the E–N copolymers were predominantly alternated and isolated norbornene units in copolymer, dyad, and triad sequences of norbornene were detected in the E–N copolymers with high incorporated content of norbornene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 93–101, 2008     

Vinyl polymerization of norbornene catalyzed by a new bis(β‐ketoamino)nickel(II) complex–methylaluminoxane system

A new β‐ketoimine ligand was prepared through traditional condensation of 2‐acetylcyclohexanone with 1‐naphthylamine. Consequently, the new moisture‐ and air‐stable bis(β‐ketoamino)nickel(II) complex Ni[2‐CH₃C(O)C₆H₈(NAr)]₂ (Ar = naphthyl) was synthesized and characterized. The solid‐state structures of the ligand and complex have been determined by single‐crystal X‐ray diffraction. Additionally, the new complex is a highly active catalyst precursor for polymerization of norbornene in combination with methylaluminoxane. Copyright © 2005 John Wiley & Sons, Ltd.     

Titanium complexes of dialkanolamine ligands as initiators for living ring‐opening polymerization of ε‐caprolactone

The titanium complexes with one ( 1a , 1b , 1c ) and two ( 2a , 2b ) dialkanolamine ligands were used as initiators in the ring‐opening polymerization (ROP) of ε‐caprolactone. Titanocanes 1a and 1b initiated living ROP of ε‐caprolactone affording polymers whose number‐average molecular weights (M_n) increased in direct proportion to monomer conversion (M_n ≤ 30,000 g mol^?1) in agreement with calculated values, and were inversely proportional to initiator concentration, while the molecular weight distribution stayed narrow throughout the polymerization (M_w/M_n ≤ 1.2 up to 80% monomer conversion). ¹H‐NMR and MALDI‐TOF‐MS studies of the obtained poly(ε‐caprolactone)s revealed the presence of an isopropoxy group originated from the initiator at the polymer termini, indicating that the polymerization takes place exclusively at the Ti–OⁱPr bond of the catalyst. The higher molecular weight polymers (M_n ≤ 70,000 g mol^?1) with reasonable MWD (M_w/M_n ≤ 1.6) were synthesized by living ROP of ε‐caprolactone using spirobititanocanes ( 2a , 2b ) and titanocane 1c as initiators. The latter catalysts, according MALDI‐TOF‐MS data, afford poly(ε‐caprolactone)s with almost equal content of α,ω‐dihydroxyl‐ and α‐hydroxyl‐ω(carboxylic acid)‐terminated chains arising due to monomer insertion into “Ti–O” bond of dialkanolamine ligand and from initiation via traces of water, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1230–1240, 2010     

Efficient catalysts for ring‐opening polymerization of ε‐caprolactone and β‐butyrolactone: Synthesis and characterization of zinc complexes based on benzotriazole phenoxide ligands

A series of efficient zinc catalysts supported by sterically bulky benzotriazole phenoxide ( BTP ) ligands are synthesized and structurally characterized. The reactions of diethyl zinc (ZnEt₂) with ^CMe2PhBTP ‐H, ^t‐BuBTP ‐H, and ^TMClBTP ‐H yield monoadduct [(μ‐ BTP )ZnEt]₂ ( 1 – 3 ), respectively. Bisadduct complex [( ^t‐BuBTP )₂Zn] ( 4 ) results from treatment of ZnEt₂ with ^t‐BuBTP ‐H (2 equiv.) in toluene, but treatment of ^TMClBTP ‐H with ZnEt₂ in the same stoichiometric proportion in Et₂O produces five‐coordinated monomeric complex [( ^TMClBTP )₂Zn(Et₂O)] ( 5 ). The molecular structures of compounds 1 , 4 , and 5 are characterized by X‐ray crystal structure determinations. All complexes 1 – 5 are efficient catalysts for the ring‐opening polymerization of ε‐caprolactone (ε‐CL) in the presence of 9‐anthracenemethanol. Experimental results indicate that complex 3 exhibits the greatest activity with well‐controlled character among these complexes. The polymerizations of ε‐CL and β‐butyrolactone catalyzed by 3 are demonstrated in a “living” character with narrow polydispersity indices (monomer‐to‐initiator ratio in the range of 25–200, PDIs ≤ 1.10). The “immortal” character of 3 provides a way to synthesize as much as 16‐fold polymer chains of poly(ε‐CL) (PCL) with narrow PDI in the presence of a catalyst in a small proportion. The controlled fashion of complex 3 also enabled preparation of the PCL‐b‐poly(3‐hydroxybutyrate) copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Homo‐ and copolymerization of norbornene with styrene catalyzed by a series of copper(II) complexes in the presence of methylaluminoxane

Vinyl‐type polymerization of norbornene as well as random copolymerization of norbornene with styrene was studied using a series of copper complexes‐MAO. The precatalysts used here are copper complexes with β‐ketoamine ligands based on pyrazolone derivatives and the molecular structure of complex 4 was determined using X‐ray analysis. All of these catalyst systems are moderately active for the vinyl‐type polymerization of norbornene and random copolymerization of norbornene with styrene. The random copolymers obtained suggest that only one type of active species is present. Gel permeation chromatography (GPC) and NMR indicate that the copolymers are ‘true’ copolymers. The copolymerization reactivity ratios (r_NBE = 20.11 and r_Sty = 0.035) indicate a much higher reactivity of norbornene, which suggests a coordination polymerization mechanism. The solubility and processability of the copolymers are improved relative to polynorbornene and the thermostability of the copolymers is improved relative to polystyrene. Copyright © 2006 John Wiley & Sons, Ltd.     

Nickel (II) complexes supported by a fluorinated β‐diketiminate backbone ligand: synthesis,catalytic activity toward norbornene polymerization,and the oxygenated species

The reaction of the lithium salt of backbone fluorinated β‐diketiminate ligands, ArNC(CF₃)CHC(CF₃) NArLi, with trans‐[NiCl(Ph)(PPh₃)₂] gives nickel (II) complexes, ArNC(CF₃)CHC(CF₃)NAr(Ph) (PPh₃)Ni (Ar = 2, 6‐Me₂C₆H₃: 1 ; 2, 6‐ⁱPr₂C₆H₃: 2 ). When activated by methylaluminoxane (MAO), both complexes polymerize norbornene rapidly via a vinyl‐type polymerization mechanism. Treatment of nickel complex 1 with oxygen gives rise to intramolecular aerobic hydroxylation. The oxygenated species 3 was characterized by X‐ray crystallography. Copyright © 2006 John Wiley & Sons, Ltd.     

Phosphine (oxide)‐(thio) phenolate palladium complexes: Synthesis,characterization and (co)polymerization of norbornene

A series of palladium complexes ( 2a–2g ) ( 2a : [6‐^tBu‐2‐PPh₂‐C₆H₃O]PdMe(Py); 2b : [6‐C₆F₅–2‐PPh₂‐C₆H₃O]PdMe(Py); 2c : [6‐^tBu‐2‐PPh^tBu‐C₆H₃O]PdMe(Py); 2d : [2‐PPh^tBu‐C₆H₄O] PdMe(Py); 2e : [6‐SiMe₃–2‐PPh₂‐C₆H₃O]PdMe(Py); 2f : [2‐^tBu‐6‐(Ph₂P=O)‐C₆H₃O]PdMe(Py); 2g : [6‐SiMe₃–2‐(Ph₂P=O)‐C₆H₃S]PdMe(Py)) bearing phosphine (oxide)‐(thio) phenolate ligand have been efficiently synthesized and characterized. The solid‐state structures of complexes 2d , 2f and 2g have been further confirmed by single‐crystal X‐ray diffraction, which revealed a square‐planar geometry of palladium center. In the presence of B(C₆F₅)₃, these complexes can be used as catalysts to polymerize norbornene (NB) with relatively high yields, producing vinyl‐addition polymers. Interestingly, 2a /B(C₆F₅)₃ system catalyzed the polymerization of NB in living polymerization manner at high temperature (polydispersity index 1.07, M_n up to 1.5 × 10⁴). The co‐polymerization of NB and polar monomers was also studied using catalysts 2a and 2f . All the obtained co‐polymers could dissolve in common solvent.     

Monoaryloxo ytterbium(III) chlorides supported by β‐diketiminato ligands as novel initiators for the living ring‐opening polymerization of ε‐caprolactone

Ring‐opening polymerization of ε‐caprolactone (ε‐CL) was carried out using β‐diketiminato‐supported monoaryloxo ytterbium chlorides L¹Yb(OAr)Cl(THF) (1) [L¹ = N,N′‐bis(2,6‐dimethylphenyl)‐2,4‐pentanediiminato, OAr = 2,6‐di‐tert‐butylphenoxo‐], and L²Yb(OAr′)Cl(THF) (2) [L² = N,N′‐bis(2,6‐diisopropylphenyl)‐2,4‐pentanediiminato, OAr′ = 2,6‐di‐tert‐butyl‐4‐methylphenoxo‐], respectively, as single‐component initiator. The influence of reaction conditions, such as polymerization temperature, polymerization time, initiator, and initiator concentration, on the monomer conversion, molecular weight, and molecular weight distribution of the resulting polymers was investigated. Complex 1 was well characterized and its crystal structure was determined. Some features and kinetic behaviors of the CL polymerization initiated by these two complexes were studied. The polymerization rate is first order with respect to monomer. The M_n of the polymer increases linearly with the increase of the polymer yield, while polydispersity remained narrow and unchanged throughout the polymerization in a broad range of temperatures from 0 to 50 °C. The results indicated that the present system has a “living character”. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1147–1152, 2006     

Crosslinked polynorbornene particles synthesis by ring‐opening metathesis polymerization in dispersion

This article proposes the first report on the synthesis of nanometric crosslinked polynorbornene particles by ring‐opening metathesis polymerization in dispersion using ruthenium‐based complex (PCy₃)₂Cl₂Ru?CHPh as initiator. Stable but raspberry‐shaped particles were obtained. In this study, a particular attention was paid to the influence of the crosslinker nature and addition mode on reaction kinetics and morphology of the latex particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Vinylic polymerization of norbornene by neutral nickel(II)‐based catalysts

Neutral Ni(II) salicylaldiminato complexes activated with modified methylaluminoxane as catalysts were used for the vinylic polymerization of norbornene. Catalyst activities of up to 7.08 × 10⁴ kg_pol/(mol_Ni · h) and viscosity‐average molecular weights of polymer up to 1.5 × 10⁶ g/mol were observed at optimum conditions. Polynorbornenes are amorphous, soluble in organic solvents, highly stable, and show glass‐transition temperatures around 390 °C. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of the reaction parameters such as the Al/Ni ratio, monomer/catalyst ratio, monomer concentration, polymerization reaction temperature, and time. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2680–2685, 2002     

Cyclic poly(ε‐caprolactone) synthesized by combination of ring‐opening polymerization with ring‐closing metathesis,ring closing enyne metathesis,or “click” reaction

This article described the synthesis of cyclic poly(ε‐caprolactone) (PCL) via ring‐closing metathesis (RCM), ring closing enyne metathesis (RCEM), and “click” reaction of different difunctional linear PCL. Linear PCL precursors were prepared by ring‐opening polymerization (ROP) of ε‐caprolactone in bulk using 10‐undecen‐1‐ol or propargyl alcohol as the initiator, followed by reacting with corresponding acyl chloride containing vinyl or azido end group. The subsequent end‐to‐end intramolecular coupling reactions were performed under high dilution conditions. The successful transformation of linear PCL precursor to cyclic PCL was confirmed by Gel permeation chromatography, ¹H NMR, and Fourier transform infrared measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3022–3033, 2009     

Structurally rigid bis(pyrazolyl)pyridine Zn(II) and Cu(II) complexes: Structures and kinetic studies in ring‐opening polymerization of ε‐caprolactone

Four bis(pyrazolyl)pyridine Zn(II) and Cu(II) carboxylate complexes have been structurally elucidated and used as initiators in the ring‐opening polymerization (ROP) of ε‐carprolactone (ε‐CL). Reactions of bis(3,5‐dimethyl‐pyrazol‐1‐yl)pyridine ( L1 ) with the appropriate Zn(II) and Cu(II) carboxylates afforded the corresponding complexes; [Zn(L1)(C₆H₅COO)₂] ( 1 ), [Zn(L1)(2‐Cl‐C₆H₄COO)₂] ( 2 ), [Zn(L1)(OAc)₂] ( 3 ) and [Cu(L1)(OAc)₂] ( 4 ) in moderate to good yields. Molecular structures of compounds 1 , 2 , 3 confirmed the presence of one tridentate bound ligand L1 in the metal coordination sphere and two carboxylate anions to give five coordination number around Zn(II) and Cu(II) atoms. Complexes 1 , 2 , 3 , 4 initiated the ROP of ε‐CL at 110 °C to give polymers of moderate molecular weights. Kinetic analyses of the ROP reactions indicate pseudo ‐first‐order dependency on ε‐CL monomer and initiator. ¹H NMR and mass spectral data established a coordination insertion mechanistic pathway and behaviour of 1 , 2 , 3 , 4 as initiators in the ROP of ε‐CL. Copyright © 2016 John Wiley & Sons, Ltd.     

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

Organocatalysis offers a number of prospects in the polymer community and presents advantages over metal based and bio‐organic methods. The use of organic molecules for performing chemical reactions is not a new concept, and any research into organocatalytic reactions builds on a respected history. Compared to the organocatalysis of large lactones, which began in the early 2000s, the examples presented here will demonstrate that few metal‐free initiating systems had been applied to β‐lactones well before the beginning of the current millennium. These metal‐free initiating systems present indisputable advantages over metal‐based processes. In the following paper, ring‐opening polymerizations (ROPs) of various β‐lactones for the preparation of poly(hydroxyalkanoate)s will be presented, as will the types of mechanisms involved, that is, zwitterionic and anionic, and cationic or supramolecular‐based ROPs. The advantages and drawbacks of the different technics will be discussed in the domain, which, for us, is important in the overall production of bioplastics. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 657–672     

Copolymerization of norbornene and 5‐norbornene‐2‐yl acetate using novel bis(β‐ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3 catalytic system

Vinyl‐type copolymerization of norbornene (NBE) and 5‐NBE‐2‐yl‐acetate (NBE‐OCOMe) in toluene were investigated using a novel homogeneous catalyst system based on bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃/AlEt₃. The copolymerization behavior as well as the copolymerization conditions, such as the levels of B(C₆F₅)₃ and AlEt₃, temperature, and monomer feed ratios, which influence on the copolymerization were examined. Without combination of AlEt₃, the catalytic bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃ exhibited very high catalyst activity for polymerization of NBE. Combination of AlEt₃ in catalyst system resulted in low conversion for polymerization of NBE. For copolymerization of NBE and NBE‐OCOMe, involvement of AlEt₃ in catalyst is necessary. Slight addition of NBE‐OCOMe in copolymerization of NBE and NBE‐OCOMe gives rise to significant increase of catalyst activity for catalytic system bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃/AlEt₃. Nevertheless, excess increase of the NBE‐OCOMe content in the comonomer feed ratios results in decrease of conversion as well as activity of catalyst. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of FTIR, ¹H NMR, and ¹³C NMR spectra. ¹³C NMR studies further revealed the composition of the copolymer and the incorporation rate was 7.6–54.1 mol % ester units at a content of 30–90 mol % of the NBE‐OCOMe in the monomer feeds ratios. TGA analysis results showed that the copolymer exhibited good thermal stability (T_d > 410 °C) and failed to observe the glass transitions temperature over 300 °C. The copolymers are confirmed to be noncrystalline by WAXD analysis results and show good solubility in common organic solvents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3990–4000, 2009     

Synthesis and characterization of aluminum(III) and tin(II) complexes supported by diiminophosphinate ligands and their application in ring‐opening polymerization catalysis of ε‐caprolactone

A series of Al(III) and Sn(II) diiminophosphinate complexes have been synthesized. Reaction of Ph(ArCH₂)P(?NBu^t)NHBu^t (Ar = Ph, 3 ; Ar = 8‐quinolyl, 4 ) with AlR₃ (R = Me, Et) gave aluminum complexes [R₂Al{(NBu^t)₂P(Ph)(CH₂Ar)}] (R = Me, Ar = Ph, 5 ; R = Me, Ar = 8‐quinolyl, 6 ; R = Et, Ar = Ph, 7 ; R = Et, Ar = quinolyl, 8 ). Lithiated 3 and 4 were treated with SnCl₂ to afford tin(II) complexes [ClSn{(NBu^t)₂P(Ph)(CH₂Ar)}] (Ar = Ph, 9 ; Ar = 8‐quinolyl, 10 ). Complex 9 was converted to [(Me₃Si)₂NSn{(NBu^t)₂P(Ph)(CH₂Ph)}] ( 11 ) by treatment with LiN(SiMe₃)₂. Complex 11 was also obtained by reaction of 3 with [Sn{N(SiMe₃)₂}₂]. Complex 9 reacted with [LiOC₆H₄Bu^t‐4] to yield [4‐Bu^tC₆H₄OSn{(NBu^t)₂P(Ph)(CH₂Ph)}] ( 12 ). Compounds 3–12 were characterized by NMR spectroscopy and elemental analysis. The structures of complexes 6 , 10 , and 11 were further characterized by single crystal X‐ray diffraction techniques. The catalytic activity of complexes 5–8 , 11 , and 12 toward the ring‐opening polymerization of ε‐caprolactone (CL) was studied. In the presence of BzOH, the complexes catalyzed the ring‐opening polymerization of ε‐CL in the activity order of 5 > 7 ≈ 8 > 6 ? 11 > 12 , giving polymers with narrow molecular weight distributions. The kinetic studies showed a first‐order dependency on the monomer concentration in each case. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4621–4631, 2006     

Synthesis of ferrocene‐containing N‐aryloxo β‐ketoiminate lanthanide complexes and polymerization of ε‐caprolactone

The synthesis, characterization and ε‐caprolactone polymerization behavior of lanthanide amido complexes stabilized by ferrocene‐containing N‐aryloxo functionalized β‐ketoiminate ligand FcCOCH₂C(Me)N(2‐HO‐5‐Bu^t‐C₆H₃) (LH₂, Fc = ferrocenyl) are described. The lanthanide amido complexes [LLnN(SiMe₃)₂(THF)]₂ [Ln = Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] were synthesized in good yields by the amine elimination reactions of LH₂ with Ln[N(SiMe₃)₂]₃(µ‐Cl)Li(THF)₃ in a 1:1 molar ratio in THF. These complexes were characterized by IR spectroscopy and elemental analysis, and ¹H NMR spectroscopy was added for the analysis of complex 4 . The definitive molecular structures of complexes 1 and 3 were determined by X‐ray diffraction studies. Complexes 1 – 4 can initiate the ring‐opening polymerization of ε‐caprolactone with moderate activity. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of norbornenes containing cationic mono‐ and di(cyclopentadienyliron)arene complexes and their ring‐opening metathesis polymerization

A number of classes of polynorbornenes containing cationic iron moieties within their side chains were prepared via ring‐opening metathesis polymerization with a ruthenium‐based catalyst. The iron‐containing polymers displayed excellent solubility in polar organic solvents. The weight‐average molecular weights of these polymeric materials were estimated to be in the range of 18,000–48,000. Thermogravimetric analysis of these polymers showed two distinct weight losses. The first weight loss was in the range of 204–260 °C and was due to the loss of the metallic moieties, whereas the second weight loss was observed at 368–512 °C and was due to the degradation of the polymer backbone. Cyclic voltammetry studies of the iron‐containing polymers showed that the 18 e^? cationic iron centers underwent a reduction to give the neutral 19 e^? complexes at half‐wave potential (E_1/2) = ?1.105 V. Photolysis of the metallated polymers led to the isolation of the norbornene polymers in very good yields. Differential scanning calorimetry studies showed a sharp increase in the glass‐transition temperatures up to 91 °C when rigid aromatic side chains were incorporated into the norbornene polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3053–3070, 2006     

Cationic ring‐opening polymerization of monothiocarbonate with a norbornene group

This work deals with the cationic ring‐opening polymerization of cyclic thiocarbonates with a norbornene or norbornane moiety, that is, 5,5‐(bicyclo[2.2.1]hept‐2‐ene‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC1 ) or 5,5‐(bicyclo[2.2.1]heptane‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC2 ), respectively. The reaction of TC1 initiated by trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), boron trifluoride etherate (BF₃OEt₂), or triethyloxonium tetrafluoroborate (Et₃OBF₄) afforded unidentified products; however, TC1 underwent cationic ring‐opening polymerization with methyl iodide as an initiator to afford polythiocarbonate because the propagating end was stabilized by the covalent‐bonding property. The polymerization of TC2 initiated by TfOH, TfOMe, BF₃OEt₂, or Et₃OBF₄ afforded polythiocarbonate with good solubility in common organic solvents and a narrow molecular weight distribution because of the absence of a double‐bond moiety. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1698–1705, 2002