Selectively degradable alternating copolymers of isobutyl vinyl ether and plant‐derived aldehydes with acyclic side chains: Effects of side group structures on copolymerization behaviors

Side group structures of aldehydes were demonstrated to have decisive effects on cationic copolymerizations with alkyl vinyl ether (VE). Alternating copolymerizations of isobutyl VE (IBVE) and plant‐derived aldehydes with acyclic side chains such as trans‐2,cis‐6‐nonadienal, trans‐2‐nonenal, and citral proceeded under appropriate reaction conditions with the EtSO₃H/GaCl₃ initiating system. In addition, some aldehydes copolymerized in a well‐controlled fashion to yield alternating copolymers with controlled molecular weights and narrow molecular weight distributions. Quantitative and selective acid hydrolysis of the resulting alternating copolymers, based on the acetal structures in the main chains, was also achieved to give other conjugated aldehydes as nearly sole degradation products. Copolymerization results of IBVE and various plant‐derived aldehydes with acyclic or cyclic side groups suggested that electron‐donating ability and bulkiness of the side groups were most likely responsible for the alternating and/or controlled copolymerization behaviors. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4684–4693     

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

A series of exo-methylene 6-membered ring conjugated dienes, which are directly or indirectly obtained from terpenoids, such as β-phellandrene, carvone, piperitone, and verbenone, were radically polymerized. Although their radical homopolymerizations were very slow, radical copolymerizations proceeded well with various common vinyl monomers, such as methyl acrylate (MA), acrylonitrile (AN), methyl methacrylate (MMA), and styrene (St), resulting in copolymers with comparable incorporation ratios of bio-based cyclic conjugated monomer units ranging from 40 to 60 mol% at a 1:1 feed ratio. The monomer reactivity ratios when using AN as a comonomer were close to 0, whereas those with St were approximately 0.5 to 1, indicating that these diene monomers can be considered electron-rich monomers. Reversible addition fragmentation chain-transfer (RAFT) copolymerizations with MA, AN, MMA, and St were all successful when using S-cumyl-S’-butyl trithiocarbonate (CBTC) as the RAFT agent resulting in copolymers with controlled molecular weights. The copolymers obtained with AN, MMA, or St showed glass transition temperatures (T_g) similar to those of common vinyl polymers (T_g ~ 100 °C), indicating that biobased cyclic structures were successfully incorporated into commodity polymers without losing good thermal properties.     

Quenching of metal‐catalyzed living radical polymerization with silyl enol ethers

Various silyl enol ethers were employed as quenchers for the living radical polymerization of methyl methacrylate with the R Cl/RuCl₂(PPh₃)₃/Al(Oi–Pr)₃ initiating system. The most effective quencher was a silyl enol ether with an electron‐donating phenyl group conjugated with its double bond [CH₂C(OSiMe₃)(4‐MeOPh) ( 2a )] that afforded a halogen‐free polymer with a ketone terminal at a high end functionality [F̄_n ∼ 1]. Such silyl compounds reacted with the growing radical generated from the dormant chloride terminal and the ruthenium complex to give the ketone terminal via the release of the silyl group along with the chlorine that originated from the dormant terminal. In contrast, less conjugated silyl enol ethers such as CH₂C(OSiMe₃)Me were less effective in quenching the polymerization. The reactivity of the silyl compounds to the poly(methyl methacrylate) radical can be explained by the reactivity of their double bonds, namely, the monomer reactivity ratios of their model vinyl monomers without the silyloxyl groups. The lifetime of the living polymer terminal was also estimated by the quenching reaction mediated with 2a . © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4735–4748, 2000     

High Tg microspheres by dispersion copolymerization of N‐phenylmaleimide with styrenic or alkyl vinyl ether monomers

Solution and dispersion copolymerizations of N‐phenylmaleimide (PMI) with either styrenics or alkyl vinyl ethers (AVEs), systems with a tendency to give alternating polymers, were investigated with the goal of producing high glass transition particles. Equimolar solution copolymerization of PMI with styrenics gave alternating copolymers, whereas AVEs gave PMI‐rich copolymers (～65:35) except for t‐butyl vinyl ether, which gave copolymers with only a slight excess of PMI. These copolymers had glass transition temperatures (T_gs) ranging from 115 to 225 °C depending on comonomer(s). Dispersion copolymerization in ethanol‐based solvents in the presence of poly(vinylpyrrolidone) as steric stabilizer led to narrow‐disperse microspheres for many copolymers studied. Dispersion copolymeriations of PMI with styrenics required good cosolvents such as acetonitrile or methyl ethyl ketone as plasticizers during particle initiation and growth. Dispersion copolymerizations generally resulted in copolymer particles with compositions and T_gs very similar to those of the corresponding copolymers formed by solution polymerization, with the exception of t‐butyl vinyl ether (tBVE), which now behaved like the other AVEs. Dispersion terpolymerizations of PMI (50 mol %) with different ratios of either n‐butylstyrene and t‐butylstyrene or n‐butyl vinyl ether and tBVE led to polymer particles with T_gs that depended on the ratio of the two butyl monomers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Spontaneous reactions of electron‐accepting substituted quinodimethane with substituted styrenes: Inductive and steric effects on the formation of a zwitterionic intermediate

Spontaneous reactions of an electron‐accepting substituted quinodimethane, 1‐(2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione‐5‐ylidene)‐4‐(dicyanomethylene)‐2,5‐cyclohexadiene, with p‐substituted, α‐substituted, and β‐substituted styrenes were investigated. When p‐substituted styrenes were used as comonomers, no spontaneous reactions took place for styrenes with an electron‐accepting p substituent such as COOMe and CN groups, and both terpolymers and cycloadducts were formed for the other p‐substituted styrenes. When α‐substituted and β‐substituted styrenes were used as comonomers, no reactions occurred for α‐ and β‐substituted styrenes with a bulky phenyl group, and spontaneous reactions took place for those with a smaller methyl group. The reaction products were an alternating copolymer for α‐substituted styrene and both terpolymers and 5‐ethylidene‐2,5‐dimethyl‐1,3‐dioxane‐4,6‐dione for β‐substituted styrenes. The position of the methyl group in the styrenes significantly affected the product formation. This behavior in the spontaneous reactions was discussed on the basis of the ability of formation of the zwitterionic tetramethylene intermediate and its conformation, determined by polar and steric effects of the substituents in the substituted styrenes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5195–5206, 2005     

Novel dialkyl vinyl ether phosphonate monomers: Their synthesis and alternated radical copolymerizations with electron‐accepting monomers

Three new vinyl ether monomers containing phosphonate moieties were synthesized from transetherification reaction. We showed that the yield was dependent on the spacer length between the vinyl oxy group and the phosphonate moieties: when the spacer is a single methylene side reaction may occur, leading to the formation of acetal compounds. Free‐radical copolymerizations of phosphonate‐containing vinyl ether monomers with maleic anhydride were carried out, leading to alternated copolymers of rather low molecular weights (from 1000 to 7000 g/mol). Both gel permeation chromatography and ³¹P NMR analyses enhanced possible intramolecular transfer reactions occurring from the phosphonate moieties. Kinetic investigation showed that the electron‐withdrawing character of the phosphonate moieties tends to decrease the rate of copolymerization. Nevertheless, almost complete monomers conversion was reached after 30 min of reaction with dimethyl vinyloxyethylphosphonate (VEC₂PMe). Then, radical copolymerization of VEC₂PMe with a series of electron‐accepting monomers, that is, dibutyl maleate, dibutylitaconate, itaconic anhydride, butyl maleimide, and methyl maleimide, led to a series of alternated copolymers. From kinetic investigation, we showed that the higher the electron‐accepting effect, the faster the vinyl ether consumption and the higher the molecular weights. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Expanding vinyl ether monomer repertoire for ring-expansion cationic polymerization: Various cyclic polymers with tailored pendant groups

Herein, we clarified the ring-expansion cationic polymerization with a cyclic hemiacetal ester (HAE)-based initiator was versatile in terms of applicable vinyl ether monomers. Although there was a risk that higher reactive vinyl ethers may incur β-H elimination of the HAE-based cyclic dormant species to irreversibly give linear chains, the polymerizations were controlled to give corresponding cyclic polymers from various alkyl vinyl ethers of different reactivities. Functional vinyl ether monomers were also available, and for instance a vinyl ether monomer carrying an initiator moiety for metal-catalyzed living radical polymerization in the pendant allowed construction of ring-linear graft copolymers through the grafting-from approach. Furthermore, ring-based gel was prepared via the addition of divinyl ether at the end of the ring-expansion polymerization, where multi HAE bonds cyclic polymers or fused rings were crosslinked with each other. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3082–3089     

Synthesis and polymerization of new di‐octadecyl ester derivatives of α‐hydroxymethyl acrylate: A structure‐property correlation for their copolymers with methyl methacrylate

New ether dimer (ED‐Od) and diester (ODE) derivatives of α‐hydroxymethylacrylate, each having two octadecyl side chains, were synthesized and (co)polymerized to evaluate the effects of differences in the structures of the monomers on final (co)polymer properties, particularly glass transition temperature. The free radical polymerizations of both monomers yielded high‐molecular weight polymers. Cyclopolymer formation of ED‐Od was confirmed by ¹³C NMR analysis and the cyclization efficiency (0.95 or greater) was found to be as high as the cyclization efficiencies of the cyclopolymerizations of ether dimers of various alkyl α‐hydroxymethylacrylates synthesized previously. Copolymers of both ED‐Od and ODE with methyl methacrylate (MMA) showed significant T_g decreases over PMMA due to octadecyl side groups causing “internal” plasticization. Comparison of the T_g's of the copolymers of octadecyl methacrylate, ED‐Od and ODE with MMA revealed that the impacts of these monomers on depression of T_g's are identical. That is, the magnitude of decrease in T_g's was quantitatively related to the number of the octadecyl side groups in the copolymers rather than their placement on the same or randomly incorporated repeat units. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7785–7793, 2008     

Donor–acceptor complexes in copolymerization. XLIX. Cationic polymerization of donor monomers in presence of polar solvents and acrylic monomers. A revised mechanism for polymerization of comonomer complexes

α-Methylstyrene (MS) and isobutyl vinyl ether (VE) readily polymerize, styrene (S) polymerizes to a small extent, and isobutylene (IB), butadiene (BD), and isoprene (IP) fail to polymerize in the presence of catalytic amounts of AlCl₃ when propionitrile, ethyl propionate, and methyl isobutyrate are used as reaction media. MS polymerizes readily and S polymerizes with difficulty in the presence of AlCl₃ to yield homopolymers when acrylonitrile (AN) is present and copolymers with ethyl acrylate (EA) and methyl methacrylate (MMA). VE readily homopolymerizes, while IB, BD, and IP fail to polymerize in the presence of AlCl₃ and the acrylic monomers. VE readily homopolymerizes, S and MS polymerize to a very small extent, and IB, BD, and IP do not polymerize in the presence of ethylaluminum sesquichloride (EASC) in polar solvents. VE readily homopolymerizes in the presence of EASC and the acrylic monomers. MS polymerizes to a small extent in the presence of EASC and the acrylic monomers to yield equimolar copolymers with EA and MMA and a mixture of cationic homopolymer and equimolar copolymer with AN. S yields equimolar copolymers in low yield in the presence of EASC and the acrylic monomers. IB, BD, and IP in the presence of EASC do not polymerize to any significant extent when EA is present, form AN-rich copolymers and yield poly(methyl methacrylate) in the presence of MMA. A revised mechanism is presented for the formation of cationic, radical, random, and alternating copolymers as well as alternating copolymer graft copolymers in the copolymerization of donor and acceptor monomers.     

Synthesis of periodic copolymers via ring‐opening copolymerizations of cyclic anhydrides with tetrahydrofuran using nonafluorobutanesulfonimide as an organic catalyst and subsequent transformation to aliphatic polyesters

To synthesize polyesters and periodic copolymers catalyzed by nonafluorobutanesulfonimide (Nf₂NH), we performed ring‐opening copolymerizations of cyclic anhydrides with tetrahydrofuran (THF) at 50–120 °C. At high temperature (100–120 °C), the cyclic anhydrides, such as succinic anhydride (SAn), glutaric anhydride (GAn), phthalic anhydride (PAn), maleic anhydride (MAn), and citraconic anhydride (CAn), copolymerized with THF via ring‐opening to produce polyesters (M_n = 0.8–6.8 × 10³, M_n/M_w = 2.03–3.51). Ether units were temporarily formed during this copolymerization and subsequently, the ether units were transformed into esters by chain transfer reaction, thus giving the corresponding polyester. On the other hand, at low temperature (25–50 °C), ring‐opening copolymerizations of the cyclic anhydrides with THF produced poly(ester‐ether) (M_n = 3.4–12.1 × 10³, M_w/M_n = 1.44–2.10). NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra revealed that when toluene (4 M) was used as a solvent, GAn reacted with THF (unit ratio: 1:2) to produce periodic copolymers (M_n = 5.9 × 10³, M_w/M_n = 2.10). We have also performed model reactions to delineate the mechanism by which periodic copolymers containing both ester and ether units were transformed into polyesters by raising the reaction temperature to 120 °C. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Cationic copolymerization behavior of cyclic ether monomers with norbornene‐containing cyclic carbonate or spiro–orthoether structure

Cationic ring‐opening copolymerizations of various cyclic ether compounds with volume expanding monomers bearing norbornene backbones [norbornene‐spiro orthocarbonate (N‐SOC) and norbornene‐cyclic carbonate (N‐CC)] were carried out in the presence of a thermally latent initiator 1 . The 10% weight loss decomposition temperatures (T_d10) and the volume changes on the copolymerizations were measured for these resultant products. In the comparison between copolymerizations of bifunctional epoxide 2 with N‐SOC and with N‐CC, it was found that N‐CC served as a more useful volume controllable comonomer than N‐SOC. The copolymerizations with N‐CC yielded the products with a decrease in the volume change (volume shrinkage) and with an increase in the monomer feed ratio of N‐CC; T_d10 was relatively similar to the homopolymer of epoxide 2 and was observed except when the proportion of N‐CC was more than 20% in the monomer feed ratio of N‐CC. In contrast, similar copolymerizations with N‐SOC did not exhibit such tendencies, probably because of the low efficiency of the copolymerization derived from the low miscibility of N‐SOC for the epoxide. The other copolymerization systems of other bi‐ and monocyclic ether compounds ( 3 – 6 and phenyl glycidyl ether) with N‐CC also indicated an almost similar tendency toward that of the copolymerization with epoxide 2 . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5113–5120, 2004     

Photoinitiated alternating copolymerization of dialkyl maleates and fumarates with vinyl ethers

A systematic study of the free radical photoinitiated alternating crosslinking copolymerizations of dialkyl maleates and furmarates with multifunctional vinyl ethers was carried out. The photocopolymerizations were fast and highly efficient when carried out using a variety of α‐cleavage photoinitiators. The effects of the structures of the both the unsaturated esters and the vinyl ether monomers were examined. Dialkyl maleates were observed to be more reactive than the corresponding fumarate esters. The photopolymerization rates of several of these comonomer pairs were compared with standard diacrylate and dimethacrylate monomers. A range of different physical properties can be obtained by varying the length of the alkyl chain on alcohol portion of the unsaturated ester monomer. Prospects for the use of these comonomer systems in UV curable coatings, adhesives, printing inks, and composites are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of poly(β‐pinene)‐g‐poly(meth)acrylate by the combination of living cationic polymerization and atom transfer radical polymerization

New graft copolymers of β‐pinene with methyl methacrylate (MMA) or butyl acrylate (BA) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization (ATRP). β‐Pinene polymers with predetermined molecular weights and narrow molecular weight distributions (MWDs) were prepared by living cationic polymerization with the 1‐phenylethyl chloride/TiCl₄/Ti(OiPr)₄/nBu₄NCl initiating system, and the resultant polymers were brominated quantitatively by N‐bromosuccinamide in the presence of azobisisobutyronitrile, yielding poly(β‐pinene) macroinitiators with different bromine contents (Br/β‐pinene unit molar ratio = 1.0 and 0.5 for macroinitiators a and b , respectively). The macroinitiators, in conjunction with CuBr and 2,2′‐bipyridine, were used to initiate ATRP of BA or MMA. With macroinitiator a or b , the bulk polymerization of BA induced a linear first‐order kinetic plot and gave graft copolymers with controlled molecular weights and MWDs; this indicated the living nature of these polymerizations. The bulk polymerization of MMA initiated with macroinitiator a was completed instantaneously and induced insoluble gel products. However, the controlled polymerization of MMA was achieved with macroinitiator b in toluene and resulted in the desired graft copolymers with controlled molecular weights and MWDs. The structures of the obtained graft copolymers of β‐pinene with (methyl)methacrylate were confirmed by ¹H NMR spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1237–1242, 2003     

Perfluorocyclohexenyl aryl ether polymers via polycondensation of decafluorocyclohexene with bisphenols

A novel class of semifluorinated perfluorocyclohexenyl (PFCH) aryl ether homo/copolymers was successfully synthesized with high yield through the step‐growth polymerization of commercially available bisphenols and decafluorocyclohexene in the presence of a triethylamine base. The synthesized polymers exhibit variable thermal properties depending on the functional spacer group (R). PFCH aryl ether copolymers with random and alternating architectures were also prepared from versatile bis‐perfluorocyclohexenyl aryl ether monomers. The PFCH polymers show high thermal stabilities with a 5% decomposition temperature ranging from 359 to 444 °C in air and nitrogen atmosphere. These semifluorinated PFCH aromatic ether polymers contain intact enchained PFCH olefin moieties, making further reactions such as crosslinking and application specific functionalization possible. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 232–238     

Facile,efficient functionalization of polyethylene via regioselective copolymerization of ethylene with cyclic dienes

The copolymerizations of ethylene with cyclic dienes [dicyclopentadiene (DCPD) and 2,5‐norbornadiene (NBD)] using bis(β‐enaminoketonato)titanium complexes [PhN = C(R₂)CHC(R₁)O]₂TiCl₂ ( 1a : R₁ = CF₃, R₂ = CH₃; 1b : R₁ = t‐Bu, R₂ = CF₃; 1c : R₁ = Ph, R₂ = CF₃) have been investigated. In the presence of modified methylaluminoxane, these complexes exhibited high catalytic activities in the copolymerization of ethylene with DCPD or NBD, affording high molecular weight copolymers with unimodal molecular weight distributions. ¹H and ¹³C‐NMR spectra reveal ethylene/DCPD copolymerizations by catalysts 1a – c proceeds through the enchainment of norbornene ring. Catalysts 1a and 1c showed a tendency to afford alternating copolymers. More noticeably, catalysts 1b and 1c bearing bulky substituents on the ligands promote ethylene/NBD copolymerization without crosslinking, affording the copolymer containing intracyclic double bonds. The NBD incorporation as high as 27.2 mol % has been achieved by catalyst 1c . Moreover, the microstructures of the copolymers were further confirmed by the measurement of reactivity ratios and dyad monomer sequences as well as mean sequence lengths. The intracyclic double bonds of ethylene/DCPD or ethylene/NBD copolymers can be fully converted into polar groups such as epoxy, amine, silane, and hydroxyl groups under mild conditions. Convenient synthesis of hydroxylated polyethylene can be provided for the first time through the ring opening reaction of epoxide. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1764–1772, 2010     

Graft polymerization of epoxide and alternating graft copolymerization of epoxide–acid anhydride onto a polystyrene backbone having an aminimide moiety

Graft polymerization of glycidyl phenyl ether (GPE) and alternating graft copolymerization of GPE–succinic anhydride (SA) onto a polymer‐supported aminimide were examined. The polymer‐supported aminimide was synthesized by radical polymerization of 1,1‐dimethyl‐1‐(2‐hydroxy‐3‐(4‐vinylbenzyloxy)propyl)amine 2‐benzoylimide, which was prepared by the reaction of methyl benzoate with equimolar amounts of 1,1‐dimethyl hydrazine and 4‐glycidylmethylstyrene. This aminimide could initiate the polymerization of GPE and alternating copolymerization of GPE with SA to give the corresponding graft copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1041–1048, 1999     

Asymmetric cyclopolymerization of N‐tert‐butyl‐N‐allylacrylamide in the presence of β‐cyclodextrin

The radical polymerization of N‐tert‐butyl‐N‐allylacrylamide (t‐BAA) was carried out in a dimethyl sulfoxide/H₂O mixture in the presence of β‐cyclodextrin (β‐CD). The polymerization proceeded with the complete cyclization of the t‐BAA unit and yielded optically active poly(t‐BAA). The IR spectrum of the obtained polymer showed that the cyclic structure in the polymer was a five‐membered ring. The optical activity of poly(t‐BAA) increased with an increasing molar ratio of β‐CD to the t‐BAA monomer. The interaction of β‐CD with t‐BAA was confirmed by ¹H NMR and ¹³C NMR analyses of the polymerization system. It is suggested that interaction of the t‐BAA monomer with the hydrophobic cavity of β‐CD plays an important role in the asymmetric cyclopolymerization of t‐BAA. The radical copolymerization of t‐BAA with styrene (St), methyl methacrylate, ethyl methacrylate, or benzyl methacrylate (BMA) also produced optically active copolymers with a cyclic structure from the t‐BAA unit. St and BMA carrying a phenyl group were predicted to compete with t‐BAA for interaction with β‐CD in the copolymerization system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2098–2105, 2000     

Anionic alternating copolymerization of α‐arylacrylates with methyl methacrylate: Effect of monomer sequence on fluorescence

Anionic polymerizations of acrylates possessing 1‐pyrenyl (Py1), 1‐naphthyl (Np1), 2‐naphthyl (Np2), and 2‐fluorenyl (Fl2) groups as α‐substituents were investigated as well as the properties of the obtained polymers. Py1 and Np1 did not undergo polymerization, whereas Np2 and Fl2, annulated α‐phenylacrylates at 3,4‐position of the phenyl group, afforded homo‐oligomers and alternating copolymers with methyl methacrylate (MMA). The oligomer of Fl2 [oligo(Fl2)] exhibited strong excimer emission in diluted solution. In contrast, dominant monomer emission was observed for the alternating copolymer with MMA [poly(Fl2‐co‐MMA)]. In the alternating copolymer, MMA units could function as spacers preventing the association of pendant fluorene moieties to suppress the excimer formation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2806–2814     

Copolymerizations of tetraethyl vinylidene phosphonate. Bisphosphonate units in the main polymer chain. II

This is the second part of the article with a subtitle “… The First Synthesis” published by us previously. For this, second part, we have chosen copolymers with low proportion of (‐b‐) units, as well as random copolymers with substantial proportions of (‐b‐) units. This is in contrast to the part I, in which we mostly described alternating copolymerization. In this article, radical copolymerization of tetraethyl vinylidene phosphonate (B) with several vinyl/ethylenic monomers (M₂), namely acrylamide, methacrylamide, methyl methacrylate, n‐butyl acrylate, n‐butyl methacrylate, and styrene has been described and reactivity ratios of monomers as well as the average length of the comonomer blocks (n) have been determined (r₁ = 0). It has been found, that (as it should be) there is a proportionality between r₂ (=k_m2M2/k_m2B) and n. Moreover, there is a proportionality between r₂ (or n) and the comonomer (M₂) “reactivity,” defined as the rate constant of M₂ addition to the styrene radical. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1614–1621     

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