Selective single monomer addition in living cationic polymerization: Sequential double end‐functionalization in combination with capping agent

Amine‐functionalized and amine‐carboxylate double‐functionalized polymers ( I and II , respectively) have been synthesized by a selective single addition of a protected 2‐aminoethyl vinyl ether (BocVE) {CH₂ = CH[OCH₂CH₂N(Boc)₂]; Boc = t‐butoxycarbonyl} onto a living cationic poly(n‐butyl vinyl ether) [poly(NBVE)] initiated with the SnCl₄/n‐Bu₄NCl system: ( I ) ‐(NBVE)_n‐ CH₂CH(OCH₂CH₂NH₂)‐H; ( II ) ‐(NBVE)_n‐CH₂CH(OCH₂CH₂NH₂)‐CH₂CO₂H. The single addition was examined with a set of alkene monomers less reactive than NBVE, including BocVE, 2‐chloroethyl vinyl ether, 2‐vinyloxyethylphtalimide, and styrene (St). Upon addition of 10 molar excess of these alkenes onto the living ends, only BocVE led to the intended single adduct, and this was attributed to a chelating interaction of the two carboxylate groups in the terminal BocVE unit with the growing poly(NBVE) terminal, thus sterically hampering further propagation. A simple acid‐catalyzed Boc‐deprotection led to the amino‐functionalized version I . Alternatively, an additional quenching the BocVE‐capped living end (the precursor of I ) with sodium malonate, followed by double deprotection of the Boc and the malonate groups gave the double‐functionalized version II . The selective addition of a single monomer molecule is thus a new method for addressable or site‐specific introduction of functional groups along polymer chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3375–3381, 2010     

Living cationic polymerization of dihydrofuran and its derivatives

Cationic polymerization of 2,3‐dihydrofuran (DHF) and its derivatives was examined using base‐stabilized initiating systems with various Lewis acids. Living cationic polymerization of DHF was achieved using Et_1.5AlCl_1.5 in toluene in the presence of THF at 0 °C, whereas it has been reported that only less controlled reactions occurred at 0 °C. Monomer‐addition experiments of DHF and the block copolymerization with isobutyl vinyl ether demonstrated the livingness of the DHF polymerization: the number–average molecular weight of the polymers shifted higher with low polydispersity as the polymerization proceeded after the monomer addition. Furthermore, this base‐stabilized cationic polymerization system allowed living polymerization of ethyl 1‐propenyl ether and 4,5‐dihydro‐2‐methylfuran at ?30 and ?78 °C, respectively. In the polymerization of 2,3‐benzofuran, the long‐lived growing species were produced at ?78 °C. The obtained polymers have higher glass transition temperatures compared to poly(acyclic alkyl vinyl ether)s. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4495–4504, 2008     

Living cationic polymerization of α‐methyl vinyl ethers using SnCl4

Cationic polymerization of α‐methyl vinyl ethers was examined using an IBEA‐Et_1.5AlCl_1.5/SnCl₄ initiating system in toluene in the presence of ethyl acetate at 0 ～ ?78 °C. 2‐Ethylhexyl 2‐propenyl ether (EHPE) had a higher reactivity, compared to corresponding vinyl ethers. But the resulting polymers had low molecular weights at 0 or ?50 °C. In contrast, the polymerization of EHPE at ?78 °C almost quantitatively proceeded, and the number‐average molecular weight (M_n) of the obtained polymers increased in direct proportion to the EHPE conversion with quite narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ≤ 1.05). In monomer‐addition experiments, the M_n of the polymers shifted higher with low polydispersity as the polymerization proceeded, indicative of living polymerization. In the polymerization of methyl 2‐propenyl ether (MPE), the living‐like propagation also occurred under the reaction conditions similar to those for EHPE, but the elimination of the pendant methoxy groups was observed. The introduction of a more stable terminal group, quenched with sodium diethyl malonate, suppressed this decomposition, and the living polymerization proceeded. The glass transition temperature of the obtained poly(MPE) was 34 °C, which is much higher than that of the corresponding poly(vinyl ether). This poly(MPE) had solubility characteristics that differed from those of poly(vinyl ethers). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2202–2211, 2008     

Living cationic polymerization of vinyl ethers in the presence of a strong base: Poisonous or helpful?

A quite small dose of a poisonous species was found to induce living cationic polymerization of isobutyl vinyl ether (IBVE) in toluene at 0 °C. In the presence of a small amount of N,N‐dimethylacetamide, living cationic polymerization of IBVE was achieved using SnCl₄, producing a low polydispersity polymer (weight–average molecular weight/number–average molecular weight (M_w/M_n) ≤ 1.1), whereas the polymerization was terminated at its higher concentration. In addition, amine derivatives (common terminators) as stronger bases allow living polymerization when a catalytic quantity was used. On the other hand, EtAlCl₂ produced polymers with comparatively broad MWDs (M_w/M_n ～ 2), although the polymerization was slightly retarded. The systems with a strong base required much less quantity of bases than weak base systems such as ethers or esters for living polymerization. The strong base system exhibited Lewis acid preference: living polymerization proceeded only with SnCl₄, TiCl₄, or ZnCl₂, whereas a range of Lewis acids are effective for achieving living polymerization in the conventional weak base system such as an ester and an ether. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6746–6753, 2008     

Synthesis of fluorine‐containing star‐shaped poly(vinyl ether)s via arm‐linking reactions in living cationic polymerization

Various types of fluorine‐containing star‐shaped poly(vinyl ether)s were successfully synthesized by crosslinking reactions of living polymers based on living cationic polymerization. Star polymers with fluorinated arm chains were prepared by the reaction between a divinyl ether and living poly(vinyl ether)s with fluorine groups (C₄F₉, C₆F₁₃, and C₈F₁₇) at the side chain using cationogen/Et_1.5AlCl_1.5 in a fluorinated solvent (dichloropentafluoropropanes), giving star‐shaped fluorinated polymers in high yields with a relatively narrow molecular weight distribution. The concentration of living polymers for the crosslinking reaction and the molar feed ratio of a bifunctional vinyl ether to living polymers affected the yield and molecular weight of the star polymers. Star polymers with block arms were prepared by a linking reaction of living block copolymers of a fluorinated segment and a nonfluorinated segment. Heteroarm star‐shaped polymers containing two‐ or three‐arm species were synthesized using a mixture of different living polymer species for the reaction with a bifunctional vinyl ether. The obtained polymers underwent temperature‐induced solubility transitions in various organic solvents, and their concentrated solutions underwent sol–gel transitions, based on the solubility transition of a thermoresponsive fluorinated segment. Furthermore, a slight amount of fluorine groups were shown to be effective for physical gelation when those were located at the arm ends of a star polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Precise synthesis of end‐functionalized thermosensitive poly(vinyl ether)s by living cationic polymerization

A series of poly(2‐methoxyethyl vinyl ether)s with narrow molecular weight distributions and with perfectly defined end groups of varying hydrophobicities was successfully synthesized by base‐assisting living cationic polymerization. The end group was shown to greatly affect the temperature‐induced phase separation behavior of aqueous solutions (lower critical solution temperature‐type phase separation) or organic solutions (upper critical solution temperature‐type phase separation) of the polymers. The cloud points were also influenced largely by the molecular weight and concentration of the polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Rapid living cationic polymerization of vinyl ethers by a single‐molecular initiating system

Initiated by an organic molecule trifluoromethanesulfonimide (HNTf₂) without any Lewis acid or Lewis base stabilizer, cationic polymerization of isobutyl vinyl ether (IBVE) takes place rapidly and the polymerization is proved to be in a controlled/living manner. The conversion of IBVE could easily achieve 99% in seconds. The product poly(isobutyl vinyl ether) is narrowly distributed and its molecular weight increases linearly with time and fits well with the corresponding theoretical value. This single‐molecular initiating system also works well in the living cationic polymerization of ethyl vinyl ether. HNTf₂ is considered playing multiple roles which include initiator, activator, and stabilizer in the polymerization. It is quite different from the hydrogen halide‐catalyzed polymerizations of vinyl ethers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1373‐1377     

Living cationic polymerization of amide‐functional vinyl ethers: Specific properties of SnCl4‐based initiating system

Living cationic copolymerization of amide‐functional vinyl ethers with isobutyl vinyl ether (IBVE) was achieved using SnCl₄ in the presence of ethyl acetate at 0 °C: the number–average molecular weight of the obtained polymers increased in direct proportion to the monomer conversion with relatively low polydispersity, and the amide‐functional monomer units were introduced almost quantitatively. To optimize the reaction conditions, cationic polymerization of IBVE in the presence of amide compounds, as a model reaction, was also examined using various Lewis acids in dichloromethane. The combination of SnCl₄ and ethyl acetate induced living cationic polymerization of IBVE at 0 °C when an amide compound, whose nitrogen is adjacent to a phenyl group, was used. The versatile performance of SnCl₄ especially for achieving living cationic polymerization of various polar functional monomers was demonstrated in this study as well as in our previous studies. Thus, the specific properties of the SnCl₄ initiating system are discussed by comparing with the Et_xAlCl_3?x systems from viewpoints of hard and soft acids and bases principle and computational chemistry. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6129–6141, 2008     

Synthesis of dual pH/temperature‐responsive polymers with amino groups by living cationic polymerization

For the precision synthesis of primary amino functional polymers, cationic polymerization of a phthalimide‐containing vinyl ether monomer precursor, 2‐vinyloxyethyl phthalimide (PIVE), was examined using a base‐assisting initiating system. Living polymerization of PIVE in CH₂Cl₂ in the presence of 1,4‐dioxane as an added base yielded nearly monodispersed polymers (M_w/M_n < 1.1) and higher molecular weight polymers, which have never been obtained using other initiating systems. Furthermore, block copolymers with hydrophobic or hydrophilic groups could be prepared. The deprotection of the pendant phthalimide groups gave well‐defined pH‐responsive polymers with pendant primary amino groups. Dual‐stimuli–responsive block copolymers having a pH‐responsive polyamine segment and a thermosensitive segment self‐assembled in water in response to both pH and temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1207–1213, 2010     

Precise synthesis of pH‐responsive copolymers with naphthoic acid side groups via living cationic polymerization

pH‐Responsive homopolymers and copolymers with naphthoic acid side groups were synthesized via base‐assisting living cationic polymerization. To this end, the feasibility of the living cationic polymerization of ethyl 6‐[2‐(vinyloxy)ethoxy]‐2‐naphthoate (EVEN) was first examined using a base‐assisting initiating system. Et_1.5AlCl_1.5 as a Lewis acid catalyst induced the living cationic polymerization of EVEN in the presence of ethyl acetate or 1,4‐dioxane in CH₂Cl₂ at 0 °C. In contrast, the use of naphthoxyethyl vinyl ether (NpOVE), which is a nonsubstituted counterpart, resulted in a poorly controlled polymerization under these conditions. The presence of the carboxy ester was most likely critical in preventing side reactions. A subsequent alkaline hydrolysis of the side‐chain esters quantitatively yielded a carboxy‐containing polymer. Aqueous solutions of this polymer underwent pH‐driven phase separation at pH 7.0. Well‐defined random and block copolymers were also prepared with various functional segments, and their stimuli‐responsive behaviors were investigated in terms of solution transmittance and aggregate size. Block copolymers containing two different pH‐responsive segments formed micelle‐like structures between the two phase‐separated pH values, and dual stimuli‐responsive copolymers containing a pH‐responsive polyacid segment and a thermosensitive segment self‐assembled in the water in response to both the pH and temperature. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5239–5247     

Thermoresponsive NIPAM block copolymers containing densely grafted poly(vinyl ether) brushes synthesized by a combination of living cationic polymerization and RAFT polymerization

Diblock copolymers consisting of a multibranched polymethacrylate segment with densely grafted poly[2‐(2‐methoxyethoxy)ethyl vinyl ether] pendants and a poly(N‐isopropylacrylamide) segment were synthesized by a combination of living cationic polymerization and RAFT polymerization. A macromonomer having both a poly[2‐(2‐methoxyethoxy)ethyl vinyl ether] backbone and a terminal methacryloyl group was synthesized by living cationic polymerization. The sequential RAFT copolymerizations of the macromonomer and N‐isopropylacrylamide in this order were performed in aqueous media employing 4‐cyanopentanoic acid dithiobenzoate as a chain transfer agent and 4,4′‐azobis(4‐cyanopentanoic acid) as an initiator. The obtained diblock copolymers possessed relatively narrow molecular weight distributions and controlled molecular weights. The thermoresponsive properties of these polymers were investigated. Upon heating, the aqueous solutions of the diblock copolymers exhibited two‐stage thermoresponsive properties denoted by the appearance of two cloud points, indicating that the densely grafted poly[2‐(2‐methoxyethoxy)ethyl vinyl ether] pendants and the poly(N‐isopropylacrylamide) segments independently responded to temperature. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Front velocity dependence on vinyl ether and initiator concentration in radical-induced cationic frontal polymerization of epoxies

Formulations containing vinyl ethers and epoxy were successfully polymerized through a radical-induced cationic frontal polymerization mechanism, using an iodonium salt superacid generator with a peroxide thermal radical initiator and fumed silica as a filler. It was found that an increase of vinyl ether content resulted in higher front velocities for divinyl ethers in formulations with trimethylolpropane triglycidyl ether. However, increased hydroxymonovinyl ether either decreased the front velocity or suppressed frontal polymerization. The kinetic effects of the superacid generator and thermal radical initiator with varying vinyl ether content were also studied. It was observed that increasing concentrations of initiators increased the front velocity, with the system exhibiting higher sensitivity to the superacid generator concentration.     

Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust,reusable, and environmentally benign initiating systems

Cationic polymerization of isobutyl vinyl ether (IBVE) was examined using a variety of metal oxides in conjunction with IBVE–HCl adduct as a cationogen in toluene at 0 °C. Iron oxides (α‐Fe₂O₃, γ‐Fe₂O₃, and Fe₃O₄) induced living polymerization in the presence of an added base, ethyl acetate or 1,4‐dioxane, to give polymers with very narrow molecular weight distributions (MWDs). Conversely, with other metal oxides such as Ga₂O₃, In₂O₃, ZnO, Co₃O₄, and Bi₂O₃, polymers with bimodal MWDs, including long‐lived species along with uncontrolled higher molecular weight portions, were produced in the presence of an added base. A small amount of nBu₄NCl or 2,6‐di‐tert‐butylpyridine (DTBP) suppressed the uncontrolled portion to induce controlled reactions with Ga₂O₃, In₂O₃, and ZnO. The roles of these reagents are discussed in terms of the nature of the active sites of the catalyst surface and the polymerization mechanisms. In addition, the reusability of the catalyst, the effect of stirring before and during polymerization, and the estimation of the number of active sites are also described. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 916–926, 2010