Simple and effective one‐pot synthesis of (meth)acrylic block copolymers through atom transfer radical polymerization

The synthesis of di‐ and triblock copolymers using atom transfer radical polymerization (ATRP) of n‐butyl acrylate (BA) and methyl methacrylate (MMA) is reported. In particular, synthetic procedures that allow for an easy and convenient synthesis of such block copolymers were developed by using CuBr and CuCl salts complexed with linear amines. Polymerizations were successfully conducted where the monomers were added to the reactor in a sequential manner. Poor cross‐propagation between poly(n‐butyl acrylate) (PBA) macroinitiators and MMA was minimized, and therefore control of molecular weights and distributions was realized, by using halogen exchange—a technique involving the addition of CuCl to the MMA during the chain extension of the PBA macroinitiator. High molecular weight (M_n ∼ 90,000) and low polydispersity (M_w /M_n < 1.35) ABA triblock copolymers were also prepared and their structure and properties in bulk have been preliminary characterized indicating the potential of ATRP for the production of all‐acrylic thermoplastic elastomers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2023–2031, 2000     

Cationic copolymerization of indene with styrene derivatives: Synthesis of random copolymers of indene with high molecular weight

Random copolymers with high molecular weights of indene and p‐methylstyrene (pMeSt) were synthesized by cationic polymerization with trichloroacetic acid/tin tetrachloride in CH₂Cl₂ at low temperatures. When indene and pMeSt (1:1 v/v), for example, were polymerized at ?40 °C, both monomers were consumed at very similar rates to give a copolymer with high molecular weight [number‐average molecular weight (M_n): 8–9 × 10⁴]. This is indeed quite unexpected behavior for the combination of these two monomers because pMeSt polymerized over 1000 times faster than indene in the homopolymerization under the reaction conditions previously described. The product copolymer of indene and pMeSt had a random monomer sequence in it that was confirmed by NMR analyses and thermal‐property measurements. In sharp contrast with pMeSt, styrene and p‐chlorostyrene, which have no electron‐donating groups on the phenyl ring, led to low molecular weight polymers (M_n < 10,000) in the copolymerization with indene (1:1 v/v). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2449–2457, 2002     

Synthesis and characterization of poly(phenylacetylenes) featuring activated ester side groups

Four monomers based on 4‐ethynylbenzoic acid have been synthesized, one of those featuring an activated ester. With the metathesis catalytic system WCl₆/Ph₄Sn, these acetylenic monomers could successfully be polymerized yielding conjugated polymers with molecular weights of around 10,000 to 15,000 g/mol and molecular weight distributions M_w/M_n ≤ 2.1. Also the copolymerization of phenylacetylene or methyl 4‐ethynylbenzoate with pentafluorophenyl 4‐ethynylbenzoate as reactive unit was conducted. Polymer analogous reactions of the reactive polymers and copolymers with amines have been investigated and it was found that poly(pentafluorophenyl 4‐ethynylbenzoate) featured a significant reactivity, such that reactions proceeded quantitatively even with aromatic amines. Moreover the UV‐Vis spectra of the activated ester based polymer before and after conversion with aliphatic amines showed a change, indicating an effect on the conjugated backbone of the polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Efficient synthesis of β‐(1,6)‐linked oligosaccharides through microwave‐assisted glycosylation

A microwave‐assisted glycosylation method was developed for efficient synthesis of oligosaccharides. Di‐functional AB monomers, 2,3,4‐tri‐O‐acetyl‐α‐d ‐galactopyranosyl bromide ( 3a ) and 2,3,4‐tri‐O‐acetyl‐α‐d ‐glucopyranosyl bromide ( 3b ) were designed and synthesized as weakly reactive monomers to avoid unwanted glycosylation or degradation during preparation and storage. The glycosylations of these monomers gave low conversions and low molecular weight oligosaccharides at rt, reflux, and under low microwave energy irradiation. However, the glycosylation became very effective when high microwave energy was applied, giving 100% conversion and producing oligosaccharides with M_n = 4.76 kDa for 3a and M_n = 4.05 kDa for 3b. The acetylated oligosaccharides were further subjected to deprotection for structural analysis, which indicated the oligosaccharides contain predominantly linear β‐(1,6)‐glycosyl linkages. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3693–3699     

Oxo‐crown‐ethers as comonomers for tuning polyester properties

2‐Oxo‐12‐crown‐4‐ether (OC) was procured in a novel, two‐step procedure in a 37% overall yield. This interesting hydrophilic lactone was effectively polymerized with Novozym 435 as the catalyst: within 10 min, the monomer conversion was greater than 95%. Poly(2‐oxo‐12‐crown‐4‐ether) [poly(OC)] was obtained as a viscous oil with a glass‐transition temperature of approximately ?40 °C, and it was soluble in water. Subsequently, OC was copolymerized with ω‐pentadecanolactone (PDL). A kinetic evaluation of both monomers showed that for OC, the Michaelis–Menten constant (K_M) and the maximal rate of polymerization (V_max) were 2.7 mol/L and 0.24 mol/L min, respectively, whereas for PDL, K_M and V_max were 0.5 mol/L and 0.09 mol/L min, respectively. Although OC polymerized five times faster than PDL, ¹H NMR analysis of the copolymers revealed a random copolymer structure. Differential scanning calorimetry traces of the copolymers showed that they were semicrystalline and that the melting temperature and melting enthalpy of the copolymers linearly decreased with an increasing amount of OC. The melting temperature of the copolymers could be adequately predicted by the Baur equation, and this suggested that poly (OC) was rejected from the poly(ω‐pentadecanolactone) [poly(PDL)] crystals. Solid‐state NMR studies confirmed that the crystalline phase exclusively consisted of poly (PDL), whereas the amorphous phase was a mixture of OC and PDL units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2166–2176, 2006     

Synthesis of AB‐type block copolymers containing benzoxazole and anthracene groups by ATRP and fluorescent property

Two functional monomers, methacrylic acid 4‐(2‐benzoxazol)‐benzyl ester (MABE) containing the benzoxazole group and 4‐(2‐(9‐anthryl))‐vinyl‐styrene (AVS) containing the anthracene group were synthesized by rational design. The MABE was polymerized via atom transfer radical polymerization (ATRP) using ethyl 2‐bromoisobutyrate (EBIB) as initiator in CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) catalyst system; block copolymers poly(MABE‐b‐AVS) was obtained, which was conducted by using poly(MABE) as macro‐initiator, AVS as the second monomer, and CuBr/PMDETA as catalyst. The constitute of two monomers in block copolymers poly(MABE‐b‐AVS) by ATRP could be adjusted, that is the constitute of the benzoxazole group and the anthracene group could be controlled in AB‐type block copolymers. Moreover, the fluorescent properties of homopolymers poly(MABE) and block copolymers poly(MABE‐b‐AVS) were discussed herein. With the excitation at λ_ex = 330 nm, the fluorescent emission spectrum of poly(MABE) solution showed emission at 375 nm corresponding to the benzoxazole‐based part; with the same excitation, the fluorescent emission spectrum of poly(MABE‐b‐AVS) solution showed a broad peek at 330–600 nm when the monomer AVS to the total monomers mole ratio was 0.31, and the fluorescent emission spectrum of poly(MABE‐b‐AVS) in film state only showed one peak at 525 nm corresponding to the anthracene‐based unit that indicated a complete energy transfer from the benzoxazole group to the anthracene group. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3894–3901, 2007     

Synthesis and copolymerization of oligo(lactic acid) derived norbornene macromonomers with amino acid derived norbornene monomer: Formation of the 3D macroporous scaffold

Norbornene macromonomers 2 and 3 bearing 10‐ and 20‐mers of lactide were synthesized by ring‐opening polymerization of lactide using 5‐norbornene‐2, 3‐exo‐exo‐dimethanol as an initiator and DBU as a catalyst. Macromonomers 2 and 3 were copolymerized with amino acid derived norbornene monomer 1 , using the Grubbs 2nd generation ruthenium catalyst. The random and block copolymers with M_n's ranging from 28,000 to 180,000 were obtained almost quantitatively where the M_n's of the block copolymers were higher than those of the random ones. Three‐dimensional macroporous structure polymers with average pore size of 10 µm could be found in poly( 1 ) and the block co‐polymer of 1 and 2 or 1 and 3 at the high ratio of 1 . Meanwhile, poly( 2 ) and poly( 3 ) along with block and random copolymers with low ratio of 1 exhibit much larger pores in the range of 50–300 µm. The porosity increased with increase in the unit ratio of 1 . The compressive strength of the porous structure of poly( 2 ) and poly( 3 ) was improved by the copolymerization with 1 . © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1660–1670     

Living cationic polymerization of vinyl ethers with a urethane group

To study the possibility of living cationic polymerization of vinyl ethers with a urethane group, 4‐vinyloxybutyl n‐butylcarbamate ( 1 ) and 4‐vinyloxybutyl phenylcarbamate ( 2 ) were polymerized with the hydrogen chloride/zinc chloride initiating system in methylene chloride solvent at ?30 °C ([monomer]₀ = 0.30 M, [HCl]₀/[ZnCl₂]₀ = 5.0/2.0 mM). The polymerization of 1 was very slow and gave only low‐molecular‐weight polymers with a number‐average molecular weight (M_n) of about 2000 even at 100% monomer conversion. The structural analysis of the products showed occurrence of chain‐transfer reactions because of the urethane group of monomer 1 . In contrast, the polymerization of vinyl ether 2 proceeded much faster than 1 and led to high‐molecular‐weight polymers with narrow molecular weight distributions (MWDs ≤ ～1.2) in quantitative yield. The M_n's of the product polymers increased in direct proportion to monomer conversion and continued to increase linearly after sequential addition of a fresh monomer feed to the almost completely polymerized reaction mixture, whereas the MWDs of the polymers remained narrow. These results indicated the formation of living polymer from vinyl ether 2 . The difference of living nature between monomers 1 and 2 was attributable to the difference of the electron‐withdrawing power of the carbamate substituents, namely, n‐butyl for 1 versus phenyl for 2 , of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2960–2972, 2004     

The effect of structure on the thermoresponsive nature of well‐defined poly(oligo(ethylene oxide) methacrylates) synthesized by ATRP

Statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO₂MA) and tri(ethylene glycol) methyl ether methacrylate (MEO₃MA) were synthesized by atom transfer radical polymerization (ATRP) providing copolymers with controlled composition and molecular weights ranging from M_n = 8,300–56,500 with polydispersity indexes (M_w/M_n) between 1.19 and 1.28. The lower critical solution temperature (LCST) of the copolymers increased with the mole fraction of MEO₃MA in the copolymer over the range from 26 to 52 °C. The average hydrodynamic diameter, measured by dynamic light scattering, varied with temperature above the LCST. These two monomers were also block copolymerized by ATRP to form polymers with molecular weight of M_n = 30,000 and M_w/M_n from 1.12 to 1.21. The LCST of the block copolymers shifted toward the LCST of the major segment, as compared to the value measured for the statistical copolymers at the same composition. As temperature increased, micelles, consisting of aggregated PMEO₂MA cores and PMEO₃MA shell, were formed. The micelles aggregated upon further heating to precipitate as larger particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 194–202, 2008     

Synthesis and characterization of novel poly(cycloalkyl methacrylate) bearing fused‐ring structure and its copolymers

A new family of cycloaliphatic fused‐ring acrylic polymers based on 8‐hydroxymethyltricyclo[5.2.1.0^2,6]decane (TCD) has been synthesized by free‐radical polymerization. TCD‐methacrylate (TCD‐MA) was synthesized by reacting TCD with methacrylic acid in toluene via transesterification with p‐toluenesulfonic acid as a catalyst. TCDMA was polymerized in toluene with benzoyl peroxide as a free‐radical initiator at 80 °C. Copolymers were synthesized by polymerizing TCDMA with styrene and methyl methacrylate. The composition of the comonomers was varied from 0 to 100%. Homo‐ and copolymers were characterized by Fourier transform infrared (FTIR) and ¹³C NMR spectroscopy. Molecular weight determination by gel permeation chromatography showed that the polymers were obtained in very high molecular weights in the range of M_n > 50,000 and M_w > 80,000 with relatively low polydispersity. The composition analysis of both the copolymer series were determined by ¹H NMR. The thermal properties of the homo‐ and copolymers were studied with differential scanning calorimetry and all the polymers were found to be amorphous. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5617–5626, 2004     

Preparation of nanoparticles of double‐hydrophilic PEO‐PHEMA block copolymers by AGET ATRP in inverse miniemulsion

Atom transfer radical polymerization with activators generated by electron transfer initiating/catalytic system (AGET ATRP) of 2‐hydroxyethyl methacrylate (HEMA) was carried out in inverse miniemulsion. Water‐soluble ascorbic acid as a reducing agent and mono‐ and difunctional poly(ethylene oxide)‐based bromoisobutyrate (PEO‐Br) as a macroinitiator were used in the presence of CuBr₂/tris[(2‐pyridyl)methyl]amine (TPMA) and CuCl₂/TPMA complexes. The use of poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide) as a polymer surfactant resulted in the formation of stable HEMA cyclohexane inverse dispersion and PHEMA colloidal particles. All polymerizations were well‐controlled, allowing for the preparation of well‐defined PEO‐PHEMA and PHEMA‐PEO‐PHEMA block copolymers with relatively high molecular weight (DP > 200) and narrow molecular weight distribution (M_w/M_n < 1.3). These block copolymers self‐assembled to form micellar nanoparticles being 10–20 nm in diameter with uniform size distribution, and aggregation number of ～10 confirmed by atomic force microscopy and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4764–4772, 2007     

Polyisobutylene‐b‐Poly(N,N‐diethylacrylamide) well‐defined amphiphilic diblock copolymer: Synthesis and thermo‐responsive phase behavior

Polyisobutylene‐b‐poly(N,N‐diethylacrylamide) (PIB‐b‐PDEAAm) well‐defined amphiphilic diblock copolymers were synthesized by sequential living carbocationic polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization. The hydrophobic polyisobutylene segment was first built by living carbocationic polymerization of isobutylene at ?70 ° C followed by multistep transformations to give a well‐defined (M_w/M_n = 1.22) macromolecular chain transfer agent, PIB‐CTA. The hydrophilic poly(N,N‐diethylacrylamide) block was constructed by PIB‐CTA mediated RAFT polymerization of N,N‐diethylacrylamide at 60 ° C to afford the desired well‐defined PIB‐b‐PDEAAm diblock copolymers with narrow molecular weight distributions (M_w/M_n ≤1.26). Fluorescence spectroscopy, transmission electron microscope, and dynamic light scattering (DLS) were employed to investigate the self‐assembly behavior of PIB‐b‐PDEAAm amphiphilic diblock copolymers in aqueous media. These diblock copolymers also exhibited thermo‐responsive phase behavior, which was confirmed by UV‐Vis and DLS measurements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1143–1150     

Synthesis of well‐defined cyclodextrin‐core star polymers

The synthesis of 21‐arm methyl methacrylate (MMA) and styrene star polymers is reported. The copper (I)‐mediated living radical polymerization of MMA was carried out with a cyclodextrin‐core‐based initiator with 21 independent discrete initiation sites: heptakis[2,3,6‐tri‐O‐(2‐bromo‐2‐methylpropionyl]‐β‐cyclodextrin. Living polymerization occurred, providing well‐defined 21‐arm star polymers with predicted molecular weights calculated from the initiator concentration and the consumed monomer as well as low polydispersities [e.g., poly(methyl methacrylate) (PMMA), number‐average molecular weight (M_n) = 55,700, polydispersity index (PDI) = 1.07; M_n = 118,000, PDI = 1.06; polystyrene, M_n = 37,100, PDI = 1.15]. Functional methacrylate monomers containing poly(ethylene glycol), a glucose residue, and a tert‐amine group in the side chain were also polymerized in a similar fashion, leading to hydrophilic star polymers, again with good control over the molecular weight and polydispersity (M_n = 15,000, PDI = 1.03; M_n = 36,500, PDI = 1.14; and M_n = 139,000, PDI = 1.09, respectively). When styrene was used as the monomer, it was difficult to obtain well‐defined polystyrene stars at high molecular weights. This was due to the increased occurrence of side reactions such as star–star coupling and thermal (spontaneous) polymerization; however, low‐polydispersity polymers were achieved at relatively low conversions. Furthermore, a star block copolymer consisting of PMMA and poly(butyl methacrylate) was successfully synthesized with a star PMMA as a macroinitiator (M_n = 104,000, PDI = 1.05). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2206–2214, 2001     

Synthesis and polymerization studies of N-cyanomethanimine monomers

New imine monomers containing C-aryl and N-cyano substituents were synthesized and polymerized by both radical and anionic initiation. Homopolymerization yielded low molecular weight polymers (M_n < 2100). Higher yields were obtained with anionic initiation rather than radical initiation. Radical initiated copolymerization with p-methoxystyrene gave low yields of low molecular weight copolymers. Radical initiated copolymerization with methyl acrylate gave copolymers of 15,000–,32,000 molecular weight in moderate yields, but with rather low incorporation of the imine monomer. The C-substituent affected the anionic and free radical reactivity similarly. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2703–2710, 1997     

Synthesis and characterization of copoly(amide triazole)s derived from d‐Glucose

Copoly(amide triazole)s, abbreviated as PGBM_n, have been prepared by copolymerization of 6‐azido‐6‐deoxy‐2,3,4‐tri‐O‐methyl‐N‐(prop‐2‐yn‐1‐yl)‐d ‐gluconamide and 6‐azido‐6‐deoxy‐2,3,4‐tri‐O‐benzyl‐N‐(prop‐2‐yn‐1‐yl)‐d ‐gluconamide by catalyst‐ and solvent‐free 1,3‐dipolar Huisgen cycloaddition reaction. The resulting copolymers have a diblock or a random distribution of the monomeric units along the polymer chain. Their molecular weights are in the range of 70,000–90,000 and they were characterized by GPC and IR and NMR spectroscopies. Thermal studies revealed them to be amorphous and stable up to 200 °C under nitrogen. Their qualitative solubilities in various solvents and their water sorption have also been investigated. The copolymers are hydrophilic, one of them being water soluble. The in vitro hydrolysis of this copoly(amide triazole) was studied. The degradation study was carried out at 80 °C in buffered solution at pH 10, and was monitored by GPC, and NMR spectroscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 413–421     

Atom transfer radical copolymerization of n‐hexylmaleimide and styrene in an ionic liquid

Dendritic polyarylether 2‐bromoisobutyrates of different generations (Gn‐Br, n = 1–3) as macroinitiators for the atom transfer radical copolymerization of N‐hexylmaleimide and styrene in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate, were investigated. The copolymerization carried out in the ionic liquid with CuBr/pentamethyldiethylenetriamine as a catalyst at room temperature afforded polymers with well‐defined molecular weights and low polydispersities (1.18 < M_w/M_n < 1.36, where M_w is the weight‐average molecular weight and M_n is the number‐average molecular weight), and the resultant copolymers possessed an alternating structure over a wide range of monomer feeds (f₁ = 0.3–0.8). Meanwhile, the copolymerization was also conducted in anisole at 110 °C under similar conditions so that the effect of the reaction media on the polymerization could be evaluated. The monomer reactivity ratios showed that the tendency to form alternating copolymers for the two monomers was stronger in ionic liquids than in anisole. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3360–3366, 2002     

Facile one‐pot synthesis and thermal cyclopolymerization of aryl bistrifluorovinyl ether monomers bearing reactive pendant groups

A diverse pool of aryl bistrifluorovinyl ether (BTFVE) compounds with reactive pendant groups were prepared in a facile, high yielding three step “one‐pot” synthesis from commercial 4‐bromo(trifluorovinyloxy)benzene. Monomers were confirmed from ATR–FTIR, ¹H, ¹³C, and ¹⁹F NMR, and HRMS analysis. Aryl BTFVE compounds were thermally polymerized to afford perfluorocyclobutyl (PFCB) aryl ether polymers with high number–average molecular weight (M_n) for homopolymers (17,050–27,090) and copolymers with 4,4′‐bis(trifluorovinyloxy)biphenyl monomers (27,860–56,500). The PFCB aryl ether homo‐ and copolymers collectively possess high thermal stability (>299 °C in N₂) and are readily solution processable producing optically transparent films. The thermal polymerization was achieved and reactive moieties remained intact, aside from those functionalized with acrylates. In the case with acrylate functionalized polymers, orthogonal polymerization was achieved by first photopolymerizing the acrylates followed by thermal curing of the aryl trifluorovinyl ether endgroups. Preliminary results in this study produced the successful preparation of photodefinable PFCB aryl ether material. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1887–1893, 2010     

Synthesis,characterization, and structure–property investigation of conformationally rigid regioisomers of poly(p‐phenylene ethynylene)s

A series of rigid poly(p‐phenylene ethynylene)s ( PPE1 – PPE4 ) with biphenyl‐ ( M1–M3 ) and phenyl‐ ( M4 ) side groups is prepared from appropriately functionalized monomers. Herein, the solution and solid state absorption studies show the polymers have adopted twisted and rigid conformations, as supported by deep HOMO energy levels (?5.76 to ?5.81 eV). The absorption maxima of PPE1–PPE3 are shifted to shorter wavelength (λ_max = 375–381 nm) as compared to linear poly(p‐phenylene ethynylene)s (446 nm), implying a nonplanar conformation. The self‐assembly of polymers into fibers is examined using scanning electron microscopy. The fibers are not observed in PPE4 with short phenyl side group, suggesting the important role of the interplay between rigidity, position, and size of the side chains toward the formation of fibers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3652–3662     

Influence of ortho‐substituents on the synthesis and properties of poly(phenylacetylene)s

The phenylacetylene derivatives (4‐decyloxyphenyl)acetylene ( M1 ), (4‐decyloxy‐2‐methylphenyl)acetylene ( M2 ), and (4‐decyloxy‐2,6‐dimethylphenyl)acetylene ( M3 ) were polymerized by the well‐defined Schrock‐type initiator Mo[N‐2,6‐i‐Pr₂C₆H₃)(CHCMe₂Ph)[OCMe(CF₃)₂]₂ ( I1 ) and by the ill‐defined quaternary system MoOCl₄–n‐Bu₄Sn–EtOH–quinuclidine (1:1:2:1) ( I2 ). Comparison of the compatibility of the initiators with the different monomers revealed a correlation of the size of the ortho‐substituents and the polymerizability of the monomers. M1 and M2 readily polymerized employing I1 , but conversion of the sterically demanding monomer M3 remained incomplete. However, the use of I2 led to high monomer conversions and polymer yields only in case of M2 and M3 . The steric bulkiness of the ortho‐substituents also decisively affected the maximum effective conjugation length (N_eff) of the polymers and hence their absorption maximum (λ_max) as well as their solution stability as shown by UV–vis and GPC studies, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4466–4477, 2004     

On the anionic homo‐ and copolymerization of ethyl‐ and butyl‐2‐cyanoacrylates

Ethyl‐(ECA) and butyl‐2‐cyanoacrylate (BCA) monomers of high purity and acidic stabilization were synthesized and anionically polymerized to homo‐ and copolymers in two different ways: by piperidine‐catalyzed bulk polymerization leading to transparent, brittle films (method A) and by polymerization in aqueous medium in the presence of sodium bicarbonate to obtain white powders (Method B). The molecular structure of the synthesized monomers, homopolymers and copolymers were corroborated by spectral methods. The polymers were studied further by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), size exclusion chromatography (SEC) and proton nuclear magnetic resonance (¹H NMR). Controlling the composition of the monomer feed and the way the polymerization was performed, it was possible to obtain phase separated or homogeneous cyanoacrylate copolymers with glass transitions varying between the T_g of polyECA and that of polyBCA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5142–5156, 2008